METHODS OF PROCESSING OF LINGNOCELLULOSIS MATERIALS

专利摘要:
lignocellulosic materials processing methods. The present invention relates to lignocellulosic material processing methods for obtaining hemicellulose sugars, cellulose sugars, lignin, cellulose and other high value products. Hemicellulose sugars, cellulose sugars, lignin, cellulose and other high value products are also provided.
公开号:BR112014027477B1
申请号:R112014027477-0
申请日:2013-05-03
公开日:2019-06-25
发明作者:Robert Jansen；Claire Gregoire；philip Travisano；Lee Madsen；Neta Matis；Yael Har-Tal；Shay Eliahu；James Alan Lawson；Noa Lapidot；Luke Burke；Aharon M. Eyal；Timothy Allen Bauer；Hagit Sade；Paul McWilliams；Ziv-Vladimir Belman；Bassem Hallac；Yelena Gershinsky；Adam Carden
申请人:Virdia, Inc.；
IPC主号:

专利说明:

"PROCESSING METHODS OF LINGNOCELLULOSIC MATERIALS 'CROSS REFERENCE
The present application claims the benefit regulated by Article 35, § 119 (e), of Provisional Patent Application No. 61 / 642,338, filed May 3, 2012, Provisional Patent Application No. 61 / 662,830 , filed June 21, 2012, U.S. Provisional Patent Application No. 61 / 693,637, filed August 27, 2012, U.S. Provisional Patent Application No. 61 / 672,719, filed July 17, 2012, Provisional US 61 / 720,313, filed October 30, 2012, U.S. Provisional Patent Application No. 61 / 680,183, filed August 6, 2012, U.S. Provisional Patent Application No. 61 / 680,661, filed December 7, August 2012, U.S. Provisional Patent Application No. 61 / 720,325, filed October 30, 2012, U.S. Provisional Patent Application No. 61 / 785,891, filed March 14, 2013, U.S. Provisional Patent Application No. 61 No. 6,681,181, filed August 6, 2012, U.S. Provisional Patent Application No. 61 / 681,299, filed August 9, 2012, U.S. Provisional Patent Application No. 61 / 715,703, filed October 18, 2012, and U.S. Provisional Patent Application No. 61 / 786,169, filed March 14, 2013, each of which is hereby incorporated by reference. incorporated herein by reference in its entirety.
STATEMENT OF RESEARCH SPONSORED BY GOVERNMENT
The present invention has been made with government support linked to the Concession No. DE-EE0005003 granted by the Department of Energy. The government has certain rights in invention.
REFERENCE TITLE
All publications, patents, and patent applications mentioned in this descriptive report are incorporated by reference to the same extent, as if incorporation by quotation of each individual publication, patent, or patent application was indicated specifically and individually.
FIELD OF THE INVENTION
The invention relates to the processing of lignocellulosic biomass materials containing hemicellulose, cellulose and lignin polymers.
BACKGROUND OF THE INVENTION
Lignocellulosic biomass materials are renewable sources for the production of amino acids for feed and food supplements, monomers and polymers for the plastics industry, and renewable sources for different types of fuels, sugar substitutes for polyol (xylitol, sorbitol, mannitol and others similar), and numerous other chemicals that can be synthesized from C5 and C6 sugars. However, efficient and economical processes to extract C5 and C6 sugars from biomass are still a challenge. Lignocellulosic biomass materials are composite materials which contain, in addition to the lignocellulosic polymers, a large variety of small amounts of lipophilic or amphiphilic compounds, for example fatty acids, abietic acids, phytosteroids, as well as proteins and elements of ash. During the hydrolysis of the hemicellulose polymers, the esters linkages in the sugar molecules can also be hydrolyzed, releasing unsubstituted sugar molecule together with a significant amount of methanol and acetic acid. Additional organic acids such as lactic acid, glucuronic acid, galacturonic acid, formic acid and levulinic acid are also typically found in the In addition to these, the lignin polymer tends to release, under moderate hydrolysis conditions, some soluble short chain lignin molecules. Water. Accordingly, the typical hydrolyzate is a highly complex multi-component solution. This poses a substantial challenge in the separation and refining of sugars to obtain useful grades of the extracted sugars.
SUMMARY OF THE INVENTION
The invention provides methods of refining a sugar stream. The method comprises (i) contacting the sugar stream with an amine extractant to form a blend; and (ii) separating from the blend a first stream comprising the amine extractant and an acid or impurity; and a second stream comprising one or more sugars. Optionally, the first stream is an organic stream and the second stream is an aqueous stream. Optionally, the first stream comprises less than 0.5% w / w sugars. Optionally, the second stream comprises less than 0.5% w / w acid. Optionally, the second stream comprises less than 0.5% w / w amine. Optionally, the second stream comprises less than 0.5% w / w of impurities. Optionally, the impurities are extracted from the sugar stream in the amine extractant. In some embodiments, the method further comprises, prior to step (i), contacting the sugar stream with a strong acid cation exchanger to remove residual cations. Optionally, the amine extractant comprises an amine and a diluent. Optionally, the ratio of the amine to the diluent is 3: 7. Optionally, the ratio of the amine to the diluent is 5.5: 4.55. Optionally, the ratio of the amine to the diluent is between 3: 7 and 6: 4. Optionally, the diluent comprises an alcohol. Optionally, the diluent comprises a C 6, C 8, C 10, C 12, Cl 2, Cl 4, Cl 6 or kerosene alcohol. Optionally, the diluent comprises hexanol. Optionally, the amine is an amine comprising at least 20 carbon atoms. Optionally, the amine is tri-laurylamine. In some embodiments, the method further comprises removing the diluent from the second stream using a filled distillation column. Optionally, at least 95% of the diluent in the second stream is removed. In some embodiments, the method further comprises contacting the sugar stream with a strong acid cation exchanger to remove residual amines, thereby forming a hydrolyzate in which the amine has been removed. In some embodiments, the method further comprises contacting the hydrolyzate wherein the amine has been removed with a weak base anion exchanger to form a neutralized hydrolyzate. In some embodiments, the method further comprises evaporating the hydrolyzate to form a concentrated hydrolyzate. In some embodiments, the method further comprises fractionating the hydrolyzate in a monomeric sugar stream and an oligomeric sugar stream. In some embodiments, the method further comprises purifying or concentrating the monomeric sugar stream. In some embodiments, the method further comprises, prior to contact between the sugar stream and an amine extractant, forming a first mixture, allowing the residual acid in the sugar stream to hydrolyze at least some oligomeric sugars in the sugar stream into monomeric sugars . Optionally, the method further comprises, before allowing, to dilute the sugar stream into a lower sugar concentration. Optionally, the method further comprises, prior to allowing, increasing the acid concentration in the sugar stream. Optionally, the acid concentration is increased to remain above 0.5%. In some embodiments, the method further comprises combining the oligomeric sugar stream with the sugar stream before the sugar stream comes into contact with the amine extract; wherein the residual acid in the sugar stream hydrolyses at least part of the oligomeric sugars into the oligomeric sugar stream into monomeric sugars. Optionally, the method further comprises contacting the first stream with a basic solution to form a neutralized amine extractant. Optionally, the contact is performed at 70 ° C. Optionally, the method further involves, before contacting the first stream with a basic solution, further washing the first stream with an aqueous stream to remove the sugar from the first stream. Optionally, the first washed stream comprises less than 0.1% w / w sugar. Optionally. the method further comprises washing at least a portion of the neutralized amine extractant with water, and recycling the washed amine extractant. Optionally, the method further comprises treating part of the stream of the neutralized amine extract washed by heating with 10% lime. Optionally, the contact is performed at 80 to 90 ° C.
The invention further provides methods for removing acid from an acidic sugar chain of hemicellulose. The method comprises (i) contacting an acidic sugar stream of hemicellulose comprising an acid and one or more sugars of hemicellulose with an amine extractant to form an amine mixture; and (ii) separating from the amine mixture a first stream comprising the acid and the amine extractant. and a second stream comprising the sugar chain of the hemicellulose. In some embodiments, the method further comprises prior to step (i) contacting a lignocellulosic feedstock with an acidic aqueous solution; and separating the acidic aqueous solution from the lignocellulosic feedstock thereby forming a lignocellulosic stream and the sugar acid stream from the hemicellulose. Optionally. the first stream is an organic stream and the second stream is an aqueous stream. Optionally, the first stream comprises less than 0.5% w / w and sugars from the hemicellulose. Optionally, the second stream comprises less than 0.5% w / w acid. Optionally, the second stream comprises less than 0.5% w / w amine. Optionally, the second stream comprises less than 0.5% w / w of impurities. Optionally, the impurities are extracted from the sugar acid stream of the hemicellulose in the amine extractant. Optionally, the amine extractant comprises an amine and a diluent. Optionally, the ratio of the amine to the diluent is 3: 7. Optionally, the ratio of the amine to the diluent is 5.5: 4.55. Optionally. the ratio of the amine to the diluent is between 3: 7 and 6: 4. Optionally. the diluent comprises an alcohol. Optionally, the diluent comprises a C6, C8, C10, C10, C14, O6 or kerosene alcohol. Optionally, the diluent comprises hexanol. Optionally, the amine is an amine comprising at least 20 carbon atoms. Optionally, the amine is tri-laurylamine. Optionally, the aqueous acid solution comprises 0.1 to 2% acid. Optionally, the acid comprises H 2 SO 4 and / or SO 2 and / or H 2 SO 3, and / or HCl. In some embodiments, the method further comprises removing the diluent from the second stream using a filled distillation column. Optionally, at least 95% of the diluent in the second stream is removed. In some embodiments, the method further comprises contacting the second stream with a strong acid cation exchanger to remove residual amines thereby forming a sugar stream wherein the amine has been removed. In some embodiments, the method further comprises contacting the sugar stream wherein the amine has been removed with a weak base anion exchanger to form a sugar stream neutralized. In some embodiments, the method further comprises evaporating the sugar stream thereby forming a concentrated sugar solution. In some embodiments, the method further comprises fractionating the sugar stream into a stream enriched with xylose and a mixed sugar stream. Optionally. the sugars are fractionated using an ion exchange resin. Optionally. the ion exchange column is an anion exchange resin. Optionally, the anion exchange resin has a particle size in the range of 200 to 400 Âμm. Optionally, the anion exchange resin has a particle size in the range of 280 to 320 Âμm. Optionally, fractionation is performed in a simulated moving bed mode. Optionally, fractionation is performed in a simulated sequential moving bed mode. Optionally. the simulated sequential mobile bed chromatography system comprises steps 1 to 3; a feed stream is passed into an adsorbent and a first stream of the raffinate is washed from the adsorbent during step 1; a second reboiler stream is washed from the adsorbent with a desorbent stream during step 2; and the desorbent is recycled back to the adsorbent during step 3; wherein the xylose-enriched stream is extracted in both step 1 and step 2. Optionally, the desorbent flow rate of the chromatography system is equal to the sum of the extract flow rate and the rate of flow of the extract. In some embodiments, the method further comprises xylose of the xylose-enriched stream. In some embodiments, the method further comprises contacting the first stream with a basic solution to form a neutralized extractant. In some embodiments, the method further involves, prior to contacting the first stream with a basic solution, further washing the first stream with an aqueous stream to remove the sugar from the hemicellulose of the first stream. Optionally, the first washed stream comprises less than 0.1% w / w sugar. In some embodiments, the method further comprises washing the neutralized extractant with water, and recycling the washed amine extractant. In some embodiments, the method further comprises treating part of the neutralized washed extract by heating it with 10% lime. Optionally, the lignocellulosic current is used to produce bioenergetic pellets.
The invention further provides methods for fractionating a liquid sample comprising a mixture of a first fraction and a second fraction. The method comprises (i) fractionating the liquid sample with a sequential simulated moving bed chromatography system; wherein the simulated sequential mobile bed chromatography system comprises steps 1 to 3; a feed stream is passed into an adsorbent and a first stream of the raffinate is washed from the adsorbent during step 1; a second reboiler stream is washed from the adsorbent with a desorbent stream during step 2; and the desorbent is recycled back to the adsorbent during step 3; (ii) recovering one or more of the product from the chromatography system; wherein the product stream is extracted in both step 1 and step 2. Optionally, the liquid sample further comprises a third fraction. Optionally, the desorbent flow rate of the chromatography system is equal to the sum of the extract flow rate and the rate of the raffinate. Optionally, the chromatography system comprises an ion exchange resin. Optionally, the ion exchange resin is an anion exchange resin. Optionally, the ion exchange resin has a particle size in the range of 200 to 400 μηι. Optionally. the ion exchange resin has a particle size in the range of 280 to 320 Âμm.
The invention further provides a mixture of hemicellulose sugar. The mixture comprises one or more, two or more, three or more, four or more, five or more, or six or seven or eight or more of the following characteristics: (i) monosaccharides in a ratio to the total dissolved sugars> 0 , 50 wt / wt; (ii) glucose in a ratio to the total monosaccharides <0.25 w / w; (iii) xylose at a ratio to total monosaccharides> 0.18 wt / wt; (iv) fructose in a ratio to the total monosaccharides <0.10 w / w; (v) fructose in a ratio to the total monosaccharides> 0.01 w / w; (vi) furfural in the amount of up to 0.01% w / w; and (vii) one or more phenols in the amount of up to 500 ppm; and (viii) hexanol in the amount of up to 0.1% w / w. Optionally, the ratio of monosaccharides to total dry solids is> 0.70 w / w. Optionally, the ratio of monosaccharides to total dry solids is> 0.90 wt.%. Optionally, the ratio of glucose to total monosaccharides is <0.15 w / w. Optionally, the ratio of glucose to total monosaccharides is <0.13 w / w. Optionally, the ratio of glucose to total monosaccharides is <0.06 w / w. Optionally, the ratio of xylose to total monosaccharides is> 0.20 wt.%. Optionally, the ratio of xylose to total monosaccharides is> 0.50 w / w. Optionally, the ratio of xylose to total monosaccharides is> 0.70 wt.%. Optionally, the ratio of fructose to total monosaccharides is> 0.02 w / w. Optionally, the ratio of fructose to total monosaccharides is <0.08 w / w. Optionally, the blend contains furfural in the amount of up to 0.005% w / w. Optionally, the blend contains furfural in the amount of up to 0.001% w / w. Optionally, the blend contains phenols in the amount of up to 400 ppm. Optionally, the blend contains phenols in the amount of up to 300 ppm.
The invention further provides a mixture of hemicellulose sugar of the xylose-enriched stream. The mixture comprises one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, or ten or more of the following characteristics: oligosaccharides in a ratio to the total dissolved sugars <0.10 w / w; (ii) xylose at a ratio to the total dissolved sugars> 0.50 w / w; (iii) arabinose in a ratio to the total dissolved sugars <0.10 w / w; (iv) galactose in a ratio to the total dissolved sugars <0.05 w / w; (v) the sum of glucose and fructose in a ratio to the total dissolved sugars <0.10 w / w; (vi) mannose at a ratio to the total dissolved sugars <0.02 w / w; (vii) fructose in a ratio to the total dissolved sugars <0.05 w / w; (viii) furfural in the amount of up to 0.01% w / w; (ix) phenols in the amount of up to 500 ppm; and (x) hexanol in the amount of up to 0.1% w / w. Optionally, the ratio of oligosaccharides to total dissolved sugars is <0.07. Optionally, the ratio of oligosaccharides to total dissolved sugars is <0.05. Optionally, the ratio of xylose to total dissolved sugars is> 0.40 w / w. Optionally, the ratio of xylose to total dissolved sugars is> 0.70 wt.%. Optionally, the ratio of xylose to total dissolved sugars is> 0.80 w / w. Optionally, the ratio between the sum of glucose and fructose and the total dissolved sugars is <0.09. Optionally, the ratio between the sum of glucose and fructose and the total dissolved sugars is <0.05. Optionally, the blend contains furfural in the amount of up to 0.005% w / w. Optionally, the blend contains furfural in the amount of up to 0.001% w / w. Optionally, the blend contains phenols in the amount of up to 60 ppm. Optionally, the blend contains phenols in the amount of up to 0.05 ppm.
The invention further provides a mixture of hemicellulose sugar in which xylose has been removed. The mixture comprises one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, or ten or more of the following characteristics: oligosaccharides in a ratio to the total dissolved sugars> 0.15 w / w; (ii) the sum of glucose and fructose in a ratio to the total dissolved sugars> 0.20 w / w; (iii) arabinose at a ratio to the total dissolved sugars> 0.02 w / w; (iv) galactose in a ratio to the total dissolved sugars> 0.02 w / w; (v) xylose in a ratio to the total dissolved sugars <0.20; (vi) mannose at a ratio of total dissolved sugars> 0.01; (vii) fructose in a ratio to the total dissolved sugars <0.05; (viii) furfural in the amount of up to 0.01% w / w; (ix) phenols in the amount of up to 500 ppm; and (x) hexanol in the amount of up to 0.1% w / w. Optionally, the ratio of oligosaccharides to total dissolved sugars is> 0.20 w / w. Optionally, the ratio of oligosaccharides to total dissolved sugars is> 0.23 w / w. Optionally, the ratio of oligosaccharides to total dissolved sugars is> 0.25 weight / weight. Optionally, the ratio between the sum of glucose and fructose and the total dissolved sugars is> 0.10 w / w. Optionally. the ratio between the sum of glucose and fructose and the total dissolved sugars is> 0.25 weight / weight. Optionally, the ratio between the sum of glucose and fructose and the total dissolved sugars is> 0.35 w / w. Optionally, the blend contains furfural in the amount of up to 0.005% w / w. Optionally, the blend contains furfural in the amount of up to 0.001% w / w. Optionally, the blend contains phenols in the amount of up to 60 ppm. Optionally, the blend contains phenols in the amount of up to 0.05 ppm. Optionally, the ratio of xylose to total dissolved sugars is <0.30 w / w. Optionally, the ratio of xylose to total dissolved sugars is <0.15 w / w. Optionally, the ratio of xylose to total dissolved sugars is <0.10 w / w.
The invention further provides a mixture of the hemicellulose sugar of the mother liquor. The mixture comprises one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, or ten or more of the following characteristics: oligosaccharides in a ratio to the total dissolved sugars <0.15 w / w; (ii) xylose at a ratio to the total dissolved sugars> 0.40 w / w; (iii) arabinose in a ratio to the total dissolved sugars <0.15 w / w; (iv) galactose in a ratio to the total dissolved sugars <0.06 w / w; (v) the sum of glucose and fructose in a ratio to the total dissolved sugars <0.20 w / w; (vi) mannose at a ratio to the total dissolved sugars <0.03; (vii) fructose in a ratio to the total dissolved sugars <0.04; (viii) furfural in the amount of up to 0.01% w / w; (ix) phenols in the amount of up to 500 ppm; and (x) hexanol in the amount of up to 0.1% w / w. Optionally, the ratio of oligosaccharides to total dissolved sugars is <0.12. Optionally, the ratio of oligosaccharides to total dissolved sugars is <0.10. Optionally, the ratio of oligosaccharides to total dissolved sugars is <0.20. Optionally, the ratio of xylose to total dissolved sugars is> 0.50 w / w. Optionally, the ratio of xylose to total dissolved sugars is> 0.60 wt.%. Optionally, the ratio of xylose to total dissolved sugars is> 0.70 wt.%. Optionally, the ratio between the sum of glucose and fructose and the total dissolved sugars is <0.30. Optionally, the ratio between the sum of glucose and fructose and the total dissolved sugars is <0.20. Optionally, the ratio between the sum of glucose and fructose and the total dissolved sugars is <0.10. Optionally, the blend contains furfural in the amount of up to 0.005% w / w. Optionally, the blend contains furfural in the amount of up to 0.001% w / w. Optionally, the blend contains phenols in the amount of up to 60 ppm. Optionally, the blend contains phenols in the amount of up to 0.05 ppm.
The invention further provides a method of producing a sugar stream of cellulose. The method comprises (i) moving a lignocellulosic stream and a countercurrent acid stream through a plurality of stirred tank reactors to produce a stream of acid hydrolyzate and an acidic lignin stream; and (ii) separating the acid hydrolyzate stream from the acid lignin stream: wherein the plurality of stirred tank reactors comprises a first reactor, a last reactor, and one or more intermediate reactors; in which the lignocellulosic current enters the first reactor, the acid stream enters the last reactor, the acid hydrolyzate stream exits the first reactor, and the lignin stream exits the last reactor. In some embodiments, the method further comprises, prior to step (i), contacting a lignocellulosic feedstock with an acidic aqueous solution; and separating the acidic aqueous solution from the lignocellulosic feedstock, thereby forming an acidic sugar stream from the hemicellulose and the lignocellulosic stream. In some embodiments, the method further comprises, prior to step (i), reducing the particle size in the lignocellulosic stream to 400 to 5000 microns. Optionally, the acid hydrolyzate stream comprises one or more sugars from the cellulose. Optionally, the acid hydrolyzate stream further comprises one or more sugars from the hemicellulose. In some embodiments, the method further comprises (iii) contacting the acid hydrolyzate stream comprising an acid and one or more sugars of the cellulose with an extractant of the solvent S1 to form a first blend; and (iv) separating from the first blend a first stream comprising the acid and solvent extractant S1 and a second stream comprising one or more sugars from the cellulose; wherein the acid is extracted from the acid hydrolyzate stream into the solvent extractant Sl. Optionally, the contact is performed at 50 ° C. In some embodiments, the method further comprises (v) evaporating the second stream comprising one or more sugars from the cellulose to form a second concentrated stream; and (vi) repeating step (iii) and (iv) above to form a stream comprising the acid and extractant of solvent S1 and a stream comprising one or more sugars of the cellulose. Optionally. the acid hydrolyzate stream is evaporated before the acid hydrolyzate stream contacts the solvent extractant Sl, thereby reducing the acid concentration in the acid hydrolyzate stream to azeotrope. Optionally. the first stream is an organic stream and the second stream is an aqueous stream. In some embodiments, the method further comprises (v) contacting the second stream with an amine extractant to form a second blend; and (vi) separating from the second blend a third stream comprising the acid and the amine extractant and a fourth stream comprising one or more sugars from the cellulose. In some embodiments, the method further comprises prior to contacting the second stream with an amine extractant to form a second blend, allowing the residual acid in the second stream to hydrolyze at least some of the oligomeric sugars in the sugar stream into monomeric sugars. thus forming a sugar chain of cellulose. In some embodiments, the method further comprises, prior to allowing, diluting the second stream to a lower sugar concentration. Optionally, an oligomeric sugar stream is added to the second stream before the second stream contacts the amine extract; wherein the residual acid in the second stream hydrolyses at least some oligomeric sugars in the mixture of the oligomeric sugar stream and the second stream into monomeric sugars. Optionally, the third stream is an organic stream and the fourth stream is an aqueous stream. Optionally, the acid hydrolyzate stream is separated from the lignin stream using a filter, membrane, or hydrocyclone. Optionally, the acid stream comprises at least 40% w / w acid. Optionally, solvent extractant Sl comprises an alcohol. Optionally, solvent extractant Sl comprises a C6, C8, C10, C10, Cl4, 06 alcohol or kerosene or a mixture of the aforementioned. Optionally, solvent extractant Sl comprises hexanol. Optionally, the amine extractant comprises an amine and a diluent. Optionally. the ratio of the amine to the diluent is 3: 7. Optionally, the ratio of the amine to the diluent is 5.5: 4.55. Optionally, the ratio of the amine to the diluent is between 3: 7 and 6: 4. Optionally, the diluent comprises an alcohol. Optionally, the diluent comprises a C6, C8, C10, C10, C14, O6 or kerosene alcohol. Optionally, the diluent comprises hexanol. Optionally, the amine is an amine comprising at least 20 carbon atoms. Optionally, the amine is tri-laurylamine. Optionally, the lignocellulosic feedstock mainly comprises cellulose and lignin. Optionally, at least a portion of the acid hydrolyzate stream leaving one or more intermediate tanks is added to the lignocellulosic stream before the lignocellulosic stream enters the first reactor. Optionally, the lignocellulosic stream is heated. Optionally, the acid hydrolyzate stream contains 22 to 33% weight / weight acid. In some embodiments, the method further comprises removing the diluent from the fourth stream using a filled distillation column. Optionally, at least 95% of the diluent in the fourth stream is removed. In some embodiments, the method further comprises contacting the fourth stream with a strong acid cation exchanger to remove residual amines, thereby forming a hydrolyzate in which the amine has been removed. In some embodiments, the method further comprises contacting the hydrolyzate wherein the amine has been removed with a weak base anion exchanger to form a neutralized hydrolyzate. In some embodiments, the method further comprises evaporating the hydrolyzate to form a concentrated hydrolyzate. In some embodiments, the method further comprises fractionating the hydrolyzate in a monomeric sugar stream and an oligomeric sugar stream. In some embodiments, the method further comprises purifying or concentrating the monomeric sugar stream. In some embodiments, the method further comprises combining the oligomeric sugar stream with the second stream before the second stream comes into contact with the amine extract; wherein the residual acid in the second stream hydrolyses at least some oligomeric sugars in the oligomeric sugar stream into monomeric sugars. In some embodiments, the method further comprises contacting the first stream comprising the acid and solvent extractant S1 with an aqueous solution to form a deacidified extractant and an aqueous re-extract; wherein the acid is extracted from the first stream into the aqueous re-extract. Optionally, the contact is performed at 50 ° C. In some embodiments, the method further comprises contacting the first stream with an azeotropic or higher acidic solution prior to contacting the first stream with an aqueous solution to form a deacidified extractant and aqueous re-extractant to recover the sugars from the first stream. Optionally, the aqueous reextract comprises 15 to 20% acid and is used in a downstream process. In some embodiments, the method further comprises evaporating the aqueous re-extract at a first pressure, thereby generating a superazeotropic acid solution having a higher acid concentration than that of the aqueous re-extract prior to evaporation. In some embodiments, the method further comprises evaporating the superazeotropic acid solution at a second pressure to generate a superazeotropic gaseous acid, wherein the second pressure is greater than the first pressure. In some embodiments, the method further comprises absorbing the superazeotropic gaseous acid in an aqueous solution to produce a concentrated acidic solution. In some embodiments, the method further comprises contacting the third stream with a basic solution to form a neutralized amine extractant. Optionally, the contact is performed at 70 ° C. In some embodiments, the method further comprises prior to contacting the third stream with a basic solution, further washing the third stream with an aqueous stream to remove sugar cellulose from the third stream. Optionally, the washed third stream comprises less than 0.1 w / w sugar content of the cellulose. In some embodiments, the method further comprises washing at least a portion of the neutralized amine extractant with water, and recycling the washed amine extractant. In some embodiments, the method further comprises treating part of the stream of the neutralized amine extractant and washing it by warming it with 10% lime. Optionally, the contact is performed at 80 to 90 ° C.
The invention further provides a method of hydrolyzing oligomeric sugars. The method comprises (i) contacting a stream of acid hydrolyzate comprising an acid and one or more sugars of the cellulose with an extractant of the solvent Sl to form a first mixture; (ii) separating from the first blend a first stream comprising the acid and solvent extractant S1 and a second stream comprising one or more sugars from the cellulose; wherein the acid is extracted from the acid hydrolyzate stream into the solvent extractant Sl; (iii) allowing the residual acid in the second stream to hydrolyze at least some oligomeric sugars in the sugar stream into monomeric sugars. thereby forming a stream of cellulose sugar; and (iv) fractionating the sugar chain of the cellulose into a stream of monomeric sugar and an oligomeric sugar stream. In some embodiments, the method further comprises, prior to fractionating, adding an oligomeric sugar stream into the second stream, wherein the residual acid in the second stream hydrolyses at least some oligomeric sugars into the blend of the second stream and the stream of oligomeric sugar into sugars thus forming a chain of cellulose sugar. In some embodiments, the method further comprises, prior to allowing, diluting the second stream at a lower sugar concentration. In some embodiments, the method further comprises, prior to allowing, increasing the acid concentration in the second stream. Optionally, the acid concentration is increased to remain above 0.5%. Optionally, the acid hydrolyzate stream is evaporated before the inlet stream contacts the solvent extractant S1, thereby reducing the acid concentration in the acid hydrolyzate stream in azeotrope. In some embodiments, the method further comprises contacting the sugar chain of the cellulose with an anion exchanger to remove the acid from the stream. Optionally, the hydrolysis is catalyzed by HCl at the maximum concentration of 1.2% w / w. Optionally, the hydrolysis is catalyzed by HCl at the maximum concentration of 0.7% w / w. Optionally, the hydrolysis is carried out at a temperature between 60 ° C and 150 ° C. Optionally, the secondary hydrolyzate contains at least 70% of monomeric sugars for total sugars in the weight / weight ratio. Optionally, the total sugar content of said secondary hydrolyzate is at least 90% w / w of the sugar content of said low acid aqueous mixture.
The invention further provides a mixture of C 6 sugar in high concentration. The mixture comprises one or more, two or more, three or more, or four or more, five or more, or six or more of the following characteristics: (i) monosaccharides in a ratio to the total dissolved sugars> /Weight; (ii) glucose in a ratio to the total dissolved sugars in the range of 0.40 to 0.70 weight / weight; (iii) 1 to 200 ppm chlorine; (iv) furfural in the amount of up to 0.01% w / w; (v) phenols in the amount of up to 500 ppm; and (vi) hexanol in the amount of up to 0.1% w / w. Optionally, the ratio of monosaccharides to total dissolved sugars is> 0.90 weight / weight. Optionally, the ratio of monosaccharides to total dissolved sugars is> 0.95 weight / weight. Optionally, the ratio of glucose to total dissolved sugars is in the range of 0.40 to 0.60 w / w. Optionally, the ratio of glucose to total dissolved sugars is in the range of 0.50 to 0.60 w / w. Optionally, the chlorine concentration is in the range of 10 to 100 ppm. Optionally, the chlorine concentration is in the range of 10 to 50 ppm. Optionally, the blend contains furfural in the amount of up to 0.005% w / w. Optionally, the blend contains furfural in the amount of up to 0.001% w / w. Optionally, the blend contains phenols in the amount of up to 400 ppm. Optionally, the blend contains phenols in the amount of up to 100 ppm. Optionally, the ratio of xylose to total dissolved sugars is in the range of 0.03 to 0.12 w / w. Optionally, the ratio of xylose to total dissolved sugars is in the range of 0.05 to 0.10 w / w. Optionally, the ratio of arabinose to total dissolved sugars is in the range of 0.005 to 0.015 w / w. Optionally, the ratio of galactose to total dissolved sugars is in the range of 0.025 to 0.035 w / w. Optionally, the ratio of mannose to total dissolved sugars is in the range of 0.14 to 0.18 w / w.
The invention further provides a method of producing a high purity lignin. The method comprises (i) adjusting the pH of an aqueous solution comprising lignin to an acidic pH; (ii) contacting the aqueous acid lignin solution with a lignin extraction solution comprising a solvent of limited solubility, thereby forming a first stream comprising the lignin and the lignin extracting solution, and a second stream comprising soluble impurities in water; (iii) contacting the first stream with a strong acid cation exchanger to remove residual cations, thereby obtaining a first purified stream; and (iv) separating the solvent of limited solubility from the lignin, thereby obtaining a high purity lignin composition. Optionally, the separation step comprises precipitating the lignin by contacting the first purified stream with water. Optionally, the first purified stream is brought into contact with hot water and thus evaporate (flash evaporation) the solvent of limited solubility Optionally, the separation step comprises evaporating the solvent of limited solubility of the lignin Optionally, the evaporation comprises dry spray The aqueous solution comprising lignin is generated by the dissolution of a lignin material in an alkaline solution, optionally the aqueous solution comprising lignin is generated by a process selected from pulping, milling, biorrefying, kraft pulping, sulphite pulping, caustic pulping, hydromechanical pulping, moderate acid hydrolysis of the lignocellulose feedstock, concentrated acid hydrolysis of the lignocellulose feedstock, supercritical water hydrolysis or sub water -supercritical of the raw material of the lignoce lulose, ammonia extraction from the raw material of lignocellulose. Optionally, the lignin material is a deacidified lignin; the method further comprises, prior to step (i), contacting an acid lignin with a hydrocarbon solvent to form a blend; heating the hydrocarbon solvent to remove the acid from the mixture, thereby obtaining a deacidified lignin. Optionally, the pH of the aqueous lignin solution is adjusted to 3.5 to 4. Optionally, the first stream is an organic stream and the second stream is an aqueous stream. Optionally, the lignin material is an acid lignin obtained by extracting the sugar from hemicellulose from a lignocellulosic feedstock followed by hydrolysis of cellulose with the use of an acid. Optionally, the lignin material is a deacidified lignin. Optionally, the aqueous solution is water. Optionally. the aqueous solution is an acidulant.
The invention further provides a method of producing a deacidified lignin. The method comprises contacting an acid lignin with a hydrocarbon solvent; and heating the hydrocarbon solvent to remove an acid from the acid lignin, thereby obtaining a deacidified lignin. Optionally, acid lignin is obtained by removal of the cellulosic and hemicellulosic material from a lignocellulosic feedstock. Optionally, the hydrocarbon is 1SOPARK. Optionally, the solvent of limited solubility is methyl ethyl ketone. Optionally, the acid lignin is washed with an aqueous wash solution to remove the residual sugars and acid before the acid lignin is contacted with the hydrocarbon solvent. Optionally, the aqueous wash solution is an aqueous reextract according to certain embodiments of the present invention. Optionally, the lignin material is washed with the aqueous solution countercurrently. Optionally, the lignin material is washed in multiple stages. Optionally, the high purity lignin is characterized by at least one. two. three, four, five, six, seven, eight, nine, ten, eleven, twelve or thirteen characteristics selected from the group consisting of: (i) aliphatic hydroxyl group of lignin in the amount of up to 2 mmol / g; (ii) at least 2.5 mmol / g of the phenolic hydroxyl group of the lignin: (iii) at least 0.4 mmol / g of the carboxylic hydroxyl group of the lignin: (iv) sulfur in an amount up to 1% w / w; (v) nitrogen in the amount of up to 0.05% w / w; (vi) chlorine in the amount of up to 0.1% w / w; (vii) 5% degradation temperature greater than 250 ° C; (viii) degradation temperature 10% greater than 300 ° C; (ix) low ash content; (x) a CaHbOc formula; wherein a is 9, b is less than 10 and c is less than 3; (xi) a minimum degree of condensation of 0.9; (xii) a methoxyl content of less than 1.0; and (xiii) an O / C weight ratio below 0.4.
The invention further provides a lignin composition characterized by at least one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or thirteen characteristics selected from the group consisting of: ) aliphatic hydroxyl group of lignin in the amount of up to 2 mmol / g; (ii) at least 2.5 mmol / g of the phenolic hydroxyl group of the lignin; (iii) at least 0.4 mmol / g of the carboxylic hydroxyl group of the lignin; (iv) sulfur in the amount of up to 1% w / w; (v) nitrogen in the amount of up to 0.05% w / w; (vi) chlorine in the amount of up to 0.1% w / w; (vii) 5% degradation temperature greater than 250 ° C; (viii) degradation temperature 10% greater than 300 ° C; (ix) low ash content; (x) a CaHbOc formula; wherein a is 9, b is less than 10 and c is less than 3; (xi) a minimum degree of condensation of 0.9; (xii) a methoxyl content of less than 1.0; and (xiii) an O / C weight ratio below 0.4. Optionally, the lignin composition comprises the aliphatic hydroxyl group of lignin in the amount of up to 1 mmol / g. Optionally, the lignin composition comprises the aliphatic hydroxyl group of lignin in the amount of up to 0.5 mmol / g. Optionally, the lignin composition comprises at least 2.7 mmol / g of the phenolic hydroxyl group of the lignin. Optionally, the lignin composition comprises at least 3.0 mmole / g of the phenolic hydroxyl group of the lignin. Optionally, the lignin composition comprises at least 0.4 mmol / g of the carboxylic hydroxyl group of the lignin. Optionally, the lignin composition comprises at least 0.9 mmol / g of the carboxylic hydroxyl group of the lignin.
The invention further provides a lignin composition characterized by at least one. two, three or four characteristics selected from the group consisting of: (i) at least 97% lignin based on dry matter; (ii) an ash content in the amount of up to 0.1% w / w; (iii) a total carbohydrate content in the amount of up to 0.05% w / w; and (iv) a volatile content in the amount of up to 5% w / w at 200 ° C. Optionally, the blend has a non-molten particulate content in the amount of up to 0.05% w / w.
The invention further provides a method of producing high purity lignin from a biomass. The method comprises (i) removing sugars from hemicellulose from the biomass. thereby obtaining a lignin-containing residue; wherein the lignin-containing residue comprises lignin and cellulose; (ii) contacting the lignin containing residue with a lignin extraction solution to produce a lignin extract and a cellulosic residue; wherein the lignin extraction solution comprises a solvent of limited solubility, an organic acid, and water, wherein the solvent of limited solubility and water form an organic phase and an aqueous phase; and (iii) separating the lignin extract from the cellulosic residue; wherein the lignin extract comprises the lignin dissolved in the solvent of limited solubility. Optionally, the removal of sugars from the hemicellulose does not remove a substantial amount of the cellulosic sugars. Optionally, the solvent of limited solubility and water in the lignin extraction solution is in an approximate ratio of 1: 1. In some embodiments, the method further comprises purifying the cellulosic residue to obtain cellulose pulp. Optionally, the cellulose pulp comprises lignin in the amount of up to 10% w / w. Optionally, the cellulose pulp comprises lignin in the amount of up to 7% w / w. In some embodiments, the method further comprises contacting the lignin extract with a strong acid cation exchanger to remove residual cations, thereby obtaining a purified lignin extract. In some embodiments, the method further comprises separating the solvent of limited solubility from the lignin extract thereby obtaining a high purity lignin. In some embodiments, the method further comprises evaporating the solvent of limited solubility of the lignin. Optionally, the evaporation comprises dry spray. In some embodiments, the method further comprises washing the cellulose residue with the solvent of limited solubility and with water, thereby obtaining cellulose pulp. In some embodiments, the method further comprises contacting the cellulose pulp with an acid to produce an acid hydrolyzate stream comprising cellulose sugars. In some embodiments, the method further comprises (i) contacting the acid hydrolyzate stream comprising an acid and one or more sugars of the cellulose with an extractant of the solvent Sl to form a first mixture; and (ii) separating from the first blend a first stream comprising the acid and solvent extractant S1 and a second stream comprising one or more sugars from the cellulose; wherein the acid is extracted from the acid hydrolyzate stream into the solvent extractant Sl. In some embodiments, the method further comprises (iii) evaporating the second stream comprising one or more sugars from the cellulose to form a second concentrated stream; and (vi) repeating step (iii) and (iv) above to form a stream comprising the acid and extractant of solvent S1 and a stream comprising one or more sugars of the cellulose. In some embodiments, the method further comprises (v) contacting the second stream with an amine extractant to form a second blend; and (vi) separating from the second blend a third stream comprising the acid and the amine extractant and a fourth stream comprising one or more sugars from the cellulose. In some embodiments, the method further comprises hydrolyzing the cellulose pulp in an aqueous suspension comprising hydrolytic enzymes. In some embodiments, the method further comprises (i) shaking or stirring the slurry comprising cellulose pulp, hydrolytic enzymes and an acidulating agent in a temperature controlled tank; (ii) separating from the slurry a first stream comprising cellulose pulp and a second stream comprising the sugars from hydrolyzed cellulose; (iii) returning the first stream to the controlled temperature tank for further hydrolysis. Optionally, the separation is performed using a separation device selected from a filter, a membrane, a centrifuge, a hydrocyclone. Optionally, the concentration of the dissolved glucose in the aqueous suspension is controlled below the level of inhibition of the hydrolytic enzymes. In some embodiments, the method further comprises (i) contacting the second stream with an amine extractant to form a first mixture; and (ii) separating from the first blend a third stream comprising the acid and the amine extractant and a fourth stream comprising one or more sugars from the cellulose. In some embodiments, the method further comprises allowing the residual acid in the fourth stream to hydrolyze at least some oligomeric sugars in the sugar stream into monomeric sugars, thereby forming a stream of the sugar from the cellulose. In some embodiments, the method further comprises, prior to allowing, diluting the second stream to a lower sugar concentration. In some embodiments, the method further comprises, prior to allowing, increasing the acid concentration in the second stream. Optionally, the acid concentration is increased to remain above 0.5%. In some embodiments, the method further comprises contacting the fourth stream with a strong acid cation exchanger to remove the residual amines, thereby forming a hydrolyzate in which the amine has been removed. In some embodiments, the method further comprises contacting the hydrolyzate wherein the amine has been removed with a weak base anion exchanger to form a neutralized hydrolyzate. In some embodiments, the method further comprises evaporating the hydrolyzate to form a concentrated hydrolyzate. In some embodiments, the method further comprises fractionating the hydrolyzate in a monomeric sugar stream and an oligomeric sugar stream. In some embodiments, the method further comprises purifying or concentrating the monomeric sugar stream. In some embodiments, the method further comprises (iv) contacting the first stream with an alkaline solution and thereby dissolving the residual solid lignin in the cellulose pulp; (v) separating the cellulose pulp residue from the dissolved lignin, thereby forming an aqueous solution comprising lignin; (vi) adjusting the pH of an aqueous solution comprising lignin to an acidic pH; (vii) contacting the aqueous acid lignin solution with a lignin extraction solution comprising a solvent of limited solubility, thereby forming a third stream comprising the lignin and the lignin extracting solution, and a fourth stream comprising soluble impurities in water; (viii) contacting the third stream with a strong acid cation exchanger to remove residual cations, thereby obtaining a purified third stream; and (ix) separating the solvent from the limited solubility of the lignin. thereby obtaining a high purity lignin composition. Optionally, the separation is performed by filtration. Optionally, the separation step comprises precipitating the lignin by contacting the first purified stream with water. Optionally, the third purified stream is brought into contact with hot water, thus evaporating (flash evaporation) the solvent of limited solubility. Optionally, the separation step comprises evaporating the solvent of limited solubility of the lignin. Optionally, evaporation comprises dry spray.
The invention further provides a method of producing a conversion product. The method comprises (i) providing a fermenter; and (ii) fermenting a medium comprising at least one member selected from the group consisting of a mixture of hemicellulose sugar according to certain embodiments of the invention; a mixture of xylose-enriched stream hemicellulose sugar according to certain embodiments of the invention; a xylose stream according to certain embodiments of the invention (for example, a stream of crystallized xylose or a redissolved xylose stream); a mixture of hemicellulose sugar in which xylose has been removed according to certain embodiments of the invention; a mixture of the hemicellulose sugar of the mother liquor according to certain embodiments of the invention; a C 6 sugar blend in high concentration according to certain embodiments of the present invention, in the fermenter to produce a conversion product. The invention further provides a method of producing a conversion product (i) providing at least one member selected from the group consisting of a mixture of hemicellulose sugar according to certain embodiments of the invention; a mixture of xylose-enriched stream hemicellulose sugar according to certain embodiments of the invention; a xylose stream according to certain embodiments of the invention (for example, a stream of crystallized xylose or a redissolved xylose stream); a mixture of hemicellulose sugar in which xylose has been removed according to certain embodiments of the invention; a mixture of the hemicellulose sugar of the mother liquor according to certain embodiments of the invention; a mixture of C 6 sugar in high concentration according to certain embodiments of the invention; and (ii) converting the sugars into at least one member into a conversion product using a chemical process. In some embodiments, the methods further comprise processing the conversion product to produce a consumer product selected from the group consisting of detergent, polyethylene based products, polypropylene based products, polyolefin based products, polylactic acid (polylactide), polyhydroxyalkanoate based products and polyacrylic based products. Optionally, the conversion product includes at least one member selected from the group consisting of alcohols, carboxylic acids, amino acids, monomers for the polymer and protein industry. Optionally, the detergent comprises a sugar based surfactant, a fatty acid surfactant, a fatty alcohol surfactant, or an enzyme derived from cell culture. Optionally, the polyacrylic-based products are selected from the group consisting of plastics, floor waxes, carpets, paints, coatings, adhesives, dispersions, flocculants. elastomers, acrylic glass, absorbent articles, incontinence diapers, sanitary napkins, feminine hygiene products and diapers. Optionally, the polyolefin products are selected from the group consisting of milk containers, detergent bottles, margarine jars, refuse containers, water pipes, absorbent articles, diapers, nonwoven, HDPE toys and HDPE detergent packs . Optionally, the polypropylene-based products are selected from the group consisting of absorbent, diaper, and non-woven articles. Optionally, the products based on polylactic acid are selected from the group consisting of agricultural products and dairy products, plastic bottles, biodegradable and disposable products. Optionally, polyhydroxyalkanoate based products are selected from the group consisting of agricultural packaging, plastic bottles, coated paper, extruded or molded article, feminine hygiene products, tampon applicators, absorbent articles, disposable non-woven products, wipes, clothing for medical surgery, adhesives, elastomers, films, coatings, aqueous dispersants. fibers, pharmaceutical intermediates and binders. Optionally, the conversion product includes at least one member selected from the group consisting of ethanol, butanol, isobutanol, a fatty acid, a fatty acid ester, a fatty alcohol and biodiesel. In some embodiments, the methods further comprise processing the conversion product to produce at least one product selected from the group consisting of a condensation product of isobutene, aviation fuel, gasoline, and gasool. diesel fuel, drop-in fuel, diesel fuel additive and precursor to those mentioned. Optionally, gasool is gasoline enriched with ethanol or gasoline enriched with butanol. Optionally, the product is selected from the group consisting of diesel fuel, gasoline, aviation fuel and drop-in fuels.
The invention further provides a consumer product, a precursor of a consumer product, or an ingredient of a consumer product produced from the product of the conversion according to the methods for producing a product of the conversion described herein. The invention further provides a consumer product, a precursor of a consumer product, or an ingredient of a consumer product comprising at least one conversion product produced by the methods for producing a conversion product described herein in that the conversion product is selected from the group consisting of fatty acids and carboxylic acids, dicarboxylic acids. hydroxycarboxylic acids, hydroxyl dicarboxylic acids, hydroxylic fatty acids, methylglyoxal, mono, di or polyalcohols, alkanes, alkenes, aromatic substances, aldehydes, ketones, esters, biopolymers, proteins, peptides. amino acids. vitamins, antibiotics and pharmaceuticals. Optionally, the product is gasoline, aviation fuel, or biodiesel enriched with ethanol. Optionally, the product for the consumer has a ratio between carbon 14 and carbon 12 equal to or greater than 2.0 χ 10'13. Optionally, the consumer product comprises an ingredient according to certain embodiments of the present invention and an additional ingredient produced from a raw material, except lignocellulosic material. Optionally, the ingredient and the additional ingredient produced from a feedstock, other than the lignocellulosic material, have essentially the same chemical composition. Optionally, the consumer product, the precursor of a consumer product, or the ingredient of a consumer product further comprises a marker molecule in the concentration of at least 100 ppb. Optionally, the marker molecule is selected from the group consisting of furfural, hydroxymethylfurfural, condensation products of furfural or hydroxymethylfurfural, color compounds derived from sugar caramelization, levulinic acid, acetic acid, methanol, galacturonic acid and glycerol.
The invention further provides a method of converting lignin into a conversion product. The method comprises (i) providing a composition according to certain embodiments of the present invention, and (ii) converting at least a portion of the lignin into the composition into a conversion product. Optionally, the conversion comprises treatment with hydrogen. In some embodiments, the method further comprises producing hydrogen from the lignin. Optionally, the conversion product comprises at least one item selected from the group consisting of bio-oil, fatty and carboxylic acids, dicarboxylic acids, hydroxyl carboxylic acids, hydroxyl dicarboxylic acids and hydroxyl fatty acids, methylglyoxal, mono, di or polyalcohols , alkanes. alkenes, aromatic substances, aldehydes, ketones, esters, phenols, toluenes. and xylenes. Optionally, the conversion product comprises a fuel or a fuel ingredient. Optionally, the conversion product comprises para-xylene. Optionally, a consumer product produced from the conversion product or a consumer product containing the conversion product as an ingredient or component. Optionally, the product contains at least one chemical selected from the group consisting of lignosulfonates. bio-oil, fatty and carboxylic acids, dicarboxylic acids, hydroxyl dicarboxylic acids and hydroxyl fatty acids, methylglyoxal, mono, di or polyalcohols, alkanes, alkenes, aromatic substances, aldehydes. ketones, esters, biopolymers, proteins, peptides, amino acids, vitamins, antibiotics, para-xylene and pharmaceuticals. Optionally, the product contains para-xylene. Optionally, the product is selected from the group consisting of dispersants, emulsifiers, complexing agents. flocculants, binders. pelletizing additives, resins, carbon fibers, active carbon, antioxidants, flame retardant, liquid fuel, aromatic chemicals, vanillin, adhesives, binders. absorbents, toxin binders, foams, coatings, films, rubbers and elastomers, sequestrants, fuels, and expanders. Optionally, the product is used in a selected area of the group consisting of food, feed, materials, agriculture, transportation and construction. Optionally, the product has a ratio of carbon 14 to carbon 12 equal to or greater than 2.0 x 10 13.
Optionally, the product contains an ingredient according to certain embodiments of the present invention and an ingredient produced from a raw material, except lignocellulosic material. Optionally, the ingredient according to certain embodiments of the present invention and the ingredient produced from a feedstock. except lignocellulosic material have essentially the same chemical composition. Optionally, the product contains a marker molecule in the concentration of at least 100 ppb. Optionally, the marker molecule is selected from the group consisting of furfural and hydroxymethyl furfural, condensation products, colored compounds, acetic acid, methanol, galacturonic acid, glycerol, fatty acids and resin acids.
DESCRIPTION OF THE DRAWINGS
Figures 1 to 6 are simplified flow schemes of methods for the treatment of lignocellulosic material according to some embodiments of the invention.
Figure 7 depicts a chromatographic fractionation of a refined sugar blend to obtain a fraction enriched with xylose and a mixed sugar solution containing glucose, arabinose and a variety of DP2 + components.
Figure 8A is a simplified schematic of a countercurrent stirred reactor system for hydrolysis of cellulose in an aqueous solution containing HCl. Figure 8B synthesizes the results collected during a eucalyptus hydrolysis campaign using the system described in Figure 8A which includes 4 tanks for 30 days of continuous operation. The black lines indicate the target values for acid and dissolved sugar; the gray lines indicate the acid and sugar levels of each stage (tank).
Figure 9A shows the acid level in the aqueous phase stream leaving the hydrolysis system (gray lines), the level after solvent A extraction (black lines) and the level after solvent B (solvent lines in light gray color). Figure 9B shows the level of sugars in the solvent after extraction of the acid into the solvent (gray lines) and the level of sugars in the solvent after exfoliation of the sugars into an acidic solution (black lines). Figure 9C shows the acid level in the charged solvent stream (light gray lines), the acid level in the solvent after re-extraction (black lines) and the resulting level in the aqueous phase (gray lines).
Figure 10 represents the% of mono / total sugars in the aqueous solution after extraction of the solvent (gray lines) and after the second hydrolysis (black lines). DPI represents the monosaccharide.
Figure 11A: the level of residual hydrochloric acid in the aqueous stream after the second hydrolysis. B: percentage of acidity removal from the aqueous phase to the amine solvent phase.
Figure 12: Analysis of impurities of solvent Sl after purification with lime. Note only the accumulation of hexyl acetate, while all other major impurities are kept at a very low level, indicating that the purification process should be slightly stronger so that the acetate is removed more effectively.
Figure 13 depicts the production of the superazeotropic HCl solution of> 41% obtained by directing a flow of the HCI gas which is distilled from the aqueous solutions to a lower concentration HCl solution. Figure 14A is a simplified scheme of a lignin washing system. Figure 14B shows the average concentration of acid and sugar in the lignin lavage system per stage: black lines - acid concentration; gray line - sugar concentration. The sugar concentration is reduced from more than 30% to less than 3%, although the acid concentration is reduced from more than 33% to less than 5%.
Figure 15 (A) 3 P NMR spectrum of high purity lignin; (B) 13 C NMR spectrum of lignin.
Figure 16 is a simplified flowchart of an example of cellulosic fractionation of sugar according to some embodiments of the present invention.
Figure 17 is a schematic representation of an exemplary treatment method of the lignocellulosic biomass material according to some embodiments of the present invention.
Figure 18 is a schematic representation of an exemplary method of extracting and purifying the sugar from hemicellulose according to some embodiments of the present invention. GAC stands for granular activated carbon. MB stands for mixed bed (for example, mixed bed cation / anion resin).
Figure 19 is a schematic representation of an exemplary method of hydrolysis of cellulose and the major refining of sugar according to some embodiments of the present invention.
Figure 20 is a schematic representation of an exemplary lignin processing method according to some embodiments of the present invention.
Figure 21 is a schematic representation of an exemplary lignin refining method according to some embodiments of the present invention.
Figure 22 depicts an exemplary method of cellulose hydrolysis of cellulose according to some embodiments of the present invention.
Figure 23 is a simplified flow scheme according to some alternative embodiments of the invention for the processing of lignocellulosic biomass and acid recovery.
Figure 24 is a simplified flow scheme according to some alternative embodiments of the invention for the processing of lignocellulosic biomass and acid recovery.
Figure 25 is a schematic overview of an exemplary hydrolysis system that produces a lignin stream that acts as the inlet stream in several exemplary embodiments of the invention.
Figure 26a is a schematic overview of a deacidification system according to some exemplary embodiments of the invention for the refining of the cellulose sugar.
Figure 26b is a schematic view of an optional solvent and / or water withdrawal system according to some exemplary embodiments of the invention for the refining of the cellulose sugar.
Figure 26c is a schematic view of an optional pre-evaporation module according to some exemplary embodiments of the invention for the refining of the cellulose sugar.
Figure 26d is a schematic view of a deacidification system similar to that of Figure 26a depicting optional additional or alternative components.
Figure 27 is a simplified flowchart of a method according to alternative embodiments of the invention for the refining of the cellulose sugar.
Figure 28 is a simplified flowchart of a method according to alternative embodiments of the invention for the refining of the cellulose sugar.
Figure 29 is a simplified flowchart of a method according to alternative embodiments of the invention for the refining of the cellulose sugar.
Figure 30 is a schematic representation of a system similar to that of Figure 26b indicating flow control components.
Figure 31a is a simplified flowchart of a method according to alternative embodiments of chemical conversions and monosaccharide fermentation.
Figure 31b is a simplified flowchart of a method according to alternative embodiments of chemical conversions and monosaccharide fermentation.
Figure 32 is a simplified flowchart of a method according to alternative embodiments of the invention for the refining of the cellulose sugar.
Figure 33 is a simplified flowchart of a method according to alternative embodiments of the invention for the refining of the cellulose sugar.
Figure 34 is a simplified flowchart of a method according to alternative embodiments of the invention for processing lignin.
Figure 35 is a simplified flowchart of a method according to alternative embodiments of the invention for processing lignin.
Figure 36 is a simplified flowchart of a method according to alternative embodiments of the invention for processing lignin.
37 is a representation of thermogravimetric analysis (TGA) data indicating the percentage by weight as a function of temperature for samples of high purity lignin according to exemplary embodiments of the invention incubated in N2.
Figure 38 is a graph of thermogravimetric analysis (TGA) data indicating percent by weight as a function of temperature for lignin samples as in Figure 37 incubated in air.
39 is a simplified flowchart of a method according to some exemplary embodiments of the invention for lignin processing.
Figure 40 is a simplified flow scheme of a method according to alternative embodiments of the invention for the solubilization of lignin. PPTTP stands for "predetermined pressure-temperature-time profile." Figure 41 is a simplified flow scheme of a method according to some exemplary lignin conversion processes.
Figure 42A is a simplified flow scheme of a method of treatment of the cellulose pulp and the residual lignin according to some embodiments of the invention; Figure 42B shows the concentration of glucose in the solution at different initial cellulose pulp fillers in the reactor (10 to 20% by weight of dry solid); Figure 42C illustrates the comparative saccharification of cellulose pulp obtained by extracting hemicelluloses followed by extraction of acid / solvent lignin (E-HDLM), and a commercial cotton liner Sigmacell.
Figure 43 is a simplified flow scheme of a method according to alternative embodiments of the invention for the solubilization of lignin.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to the processing and refining of lignocellulosic biomass for the production of hemicellulose sugars, cellulose sugars, lignin, cellulose and other high-value products.
An overview of the processing and refining of the lignocellulosic biomass according to the embodiments disclosed herein is provided in Figure 17. In general, the processing and refining processes of the lignocellulosic biomass include: (1) pretreatment 1770; (2) extracting sugar from hemicellulose 1700 and purification 1710; (3) hydrolysis of cellulose 1720 and refining of sugar of cellulose 1730; (4) processing lignin 1740 and refining 1750; and (5) direct extraction of 1760 lignin.
Various products can be manufactured from this process. For example, extraction of the sugar from hemicellulose 1700 and purification 1710 produces a mixture of sugar from hemicellulose. xylose, and a mixture of hemicellulose sugar in which xylose was removed, as well as bioenergetic pellets. Hydrolysis of cellulose 1720 and the sugar refining process of cellulose 1730 produce a blend of the cellulose sugar. The processing of lignin 1740 and the refining process 1750 produce high purity lignin and high purity cellulose. The process of direct extraction of 1760 lignin produces high purity lignin.
Processing and refining of the lignocellulosic biomass begins with the pretreatment 1770, during which the lignocellulosic biomass, for example, can be peeled, cut, chopped, dried, or ground into particles.
During the extraction of the sugar from hemicellulose 1700, the sugars from the hemicellulose are extracted from the lignocellulosic biomass, forming an acidic sugar stream from the hemicellulose 1700A and a stream of the 1700B lignocellulosic residue. The 1700B lignocellulosic residue stream consists basically of cellulose and lignin. As an unexpected fact, it has been discovered in the present invention that sugars from hemicellulose can be effectively extracted and converted into monomeric sugars (e.g.> 90% of the total sugar) by treatment of the biomass under moderate conditions, for example with an acid in low concentrations, heat and optionally pressure.
The sugar acid stream of hemicellulose 1700-A is purified in the purification of the sugar from hemicellulose 1710, the acids and impurities extracted together with the sugars from the hemicellulose can be easily removed from the sugar stream of the hemicellulose by solvent extraction (see Figure 18 for details, for example, extraction of the amine 1831 in Figure 18). Once the acids and impurities have been removed from the hemicellulose sugar stream, the stream is neutralized and optionally evaporated to a higher concentration. A mixture of the 1710-P1 high purity hemicellulose sugar is obtained, which can be fractionated to obtain the xylose and the hemicellulose sugar mixture in which xylose 1710-P3 has been removed. The xylose is then crystallized to obtain xylose 1710-P2.
Lignocellulosic residue 1700-B mainly contains cellulose and lignin. In some methods, the lignocellulosic residue 1700-B can be processed to make 1700-P bioenergetic pellets which can be burned as fuel.
In some methods, the lignocellulosic residue 1700-B can be directly processed to extract lignin. This process produces 1760-P1 high purity lignin and 1760-P2 high purity cellulose. The novel lignin purification process of the invention utilizes a solvent of limited solubility, and can produce lignin having a purity of greater than 99%.
In some methods, the lignocellulosic residue 1700-B can then be subjected to the hydrolysis of the cellulose 1720 to obtain the sugar mixture of the 1730-P cellulose containing mainly C6 sugars. The unusual hydrolysis process of the cellulose described herein allows the hydrolysis of the cellulose of different lignocellulosic materials using the same group of equipment. Hydrolysis of cellulose 1720 from lignocellulosic residue 1700-B results in an acid hydrolyzate stream 1720-A and an acid lignin stream 1720-B.
The acid hydrolyzate stream 1720-A is then subjected to the sugar refining of cellulose 1730 (see Figure 19 for details, for example, sugar refining of cellulose 1920 in Figure 19). The acids in the acid hydrolyzate stream 1720-A can be removed using an unusual solvent extraction system. The deacidified main sugar stream is fractionated later for the removal of the oligosaccharides from the monosaccharides. The acid can be recovered and the solvents can be purified and recycled. The resulting cellulose sugar blend 1730-P has unusually high monomeric sugar contents, in particular a high glucose content.
The acid stream of lignin 1720-B is then subjected to 1740 lignin processing and 1750 lignin refining to obtain 1750-P high purity lignin (see Figures 20-21 for details). The crude lignin stream 1720-B is first processed to remove any acids and the residual sugar during processing of lignin 1740. The deacidified lignin 1740-A is purified to obtain the high purity lignin (1750 lignin refining). The novel lignin purification process of the invention utilizes a solvent of limited solubility, and can produce a lignin having a purity of greater than 99%.
Sections I-VIII below illustrates the processing and refining of the lignocellulosic biomass according to some embodiments disclosed herein. Section I discusses pretreatment 1770. Sections II and III discuss the extraction of sugar from hemicellulose 1700 and purification 1710. Sections IV and V discuss the hydrolysis of cellulose 1720 and the refining of sugar from cellulose 1730. Sections VI and VII discuss the processing of lignin 1740 and lignin 1750. Section VIII discusses the direct extraction of lignin 1760. I. Pretreatment Prior to the extraction of sugar from hemicellulose 1700, lignocellulosic biomass may be by choice , previously treated. Pretreatment refers to the reduction of biomass size (eg, cracking or evaporation), which does not substantially affect the biomass lignin, cellulose and hemicellulose compositions. Pretreatment facilitates more efficient and more economical processing of a downstream process (eg, extraction of sugar from hemicellulose). Preferably, the lignocellulosic biomass is peeled, cut, chopped and / or dried to obtain the pretreated lignocellulosic biomass. Pretreatment may also use, for example, ultrasonic energy or hydrothermal treatments which include water. heat, steam or pressurized steam. Pretreatment may occur or may be applied to various types of containers, reactors, tubes, flow through cells and the like. In some methods, it is preferred that lignocellulosic biomass be treated prior to the extraction of the sugar from hemicellulose 1700. In some methods, pretreatment is unnecessary, i.e., lignocellulosic biomass can be used directly in the extraction of sugar from hemicellulose 1700.
Optionally, the lignocellulosic biomass may be milled or ground to reduce particle size. In some embodiments, the lignocellulosic biomass is comminuted so that the average particle size is in the range of 100 to 10,000 microns, preferably 400 to 5,000, for example, 100 to 400, 400 to 1,000, 1,000 to 3,000, 3,000 to 5,000, or 5,000 to 10,000 microns. In some embodiments, the lignocellulosic biomass is comminuted so that the average particle size is less than 10,000,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 1,000, or 400. II. Sugar Extraction of Hemicellulose The present invention provides an advantageous method of extracting sugars from hemicellulose from lignocellulosic biomass (extraction of sugar from hemicellulose 1700). Preferably, an acidic aqueous solution is used to extract the lignocellulosic biomass. The acidic aqueous solution may contain any acids, inorganic or organic. Preferably, an inorganic acid is used. For example, the solution may be an acidic aqueous solution containing an inorganic or organic acid such as H 2 SO 4, H 2 SO 3 (which may be introduced as dissolved acid or SO 2 gas), HCl. and acetic acid. The acidic aqueous solution may contain an acid in the amount of 0 to 2% acid or more, for example 0 to 0.2%, 0.2 to 0.4%, 0.4 to 0.6% 6 to 0.8%, 0.8 to 1.0%, 1.0 to 1.2%, 1.2 to 1.4%, 1.4 to 1.6%, 1.6 to 1.8 %, 1.8 to 2.0% or more by weight / weight. Preferably, the aqueous solution for extraction includes 0.2 to 0.7% H 2 SO 4 and 0 to 3,000 ppm SO 2. The pH of the acidic aqueous solution may be, for example, in the range of 1 to 5, preferably 1 to 3.5.
In some embodiments, the raising of temperature or pressure in the extraction is preferred. For example, a temperature in the range of 100 to 200Â ° C, or greater than 50Â ° C, 60Â ° C, 70Â ° C, 80Â ° C, 90Â ° C, 100Â ° C, 110Â ° C, 120Â ° C, 130Â ° C ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 190 ° C or 200 ° C can be used. Preferably, the temperature is in the range of 110 to 160øC, or 120 to 150øC. The pressure may be in the range of 1 to 10 mPa, preferably 1 to 5 mPa. The solution can be heated for 0.5 to 5 hours, preferably 0.5 to 3 hours, 0.5 to 1 hour, 1 to 2 hours or 2 to 3 hours, optionally with a cooling period of one hour.
Impurities such as ash, acid-soluble lignin, fatty acids, organic acids, such as acetic acid and formic acid, methanol, proteins and / or amino acids. glycerol, sterols, abietic acid and waxy materials may be extracted together with the hemicellulose sugars under the same conditions. These impurities can be separated from the aqueous phase by extraction of the solvent (for example, using an amine-containing solvent and alcohol).
After extraction of the sugar from hemicellulose 1700, the stream of the lignocellulosic residue 1700-B can be separated from the sugar vapor of the hemicellulose 1700-A sugar by any relevant means, including filtration, centrifugation or sedimentation to form a liquid stream and a solid current. The acidic sugar vapor of hemicellulose 1700-A contains hemicellulose sugars and impurities. The 1700-B lignocellulosic residue stream contains predominantly cellulose and lignin.
The stream of lignocellulosic residue 1700-B can be washed further to recover additional hemicellulose sugars and the acid catalyst trapped in the biomass pores. The recovered solution can be recycled back to the acidic sugar stream of hemicellulose 1700-A. or recycled back into the sugar extraction reactor of hemicellulose 1700. The remainder of the stream of the lignocellulosic residue 1700-B may be mechanically compressed to increase the solids content (e.g., dry solid content at 40 to 60%). The filtrate from the compression stage may be recycled back into the sugar acid stream of hemicellulose 1700-A, or recycled back into the sugar extraction reactor of hemicellulose 1700. Optionally, the remainder of the lignocellulosic residue 1700-B is triturated to reduce the size of the particles. Optionally, the compressed lignocellulosic residue is then dried to lower the moisture content, for example, below 15%. The dry matter can be further processed for extraction of lignin and cellulose sugars (process 1720 and 1760 in Figure 17). Alternatively, the dry matter can be pelleted. forming 1700-P pellets capable of being burned as a source of energy for the production of heat and electricity or for use as a feedstock for conversion to bio-oil.
Alternatively, the stream of the lignocellulosic residue 1700-B can be further processed to extract lignin (process 1760 in Figure 17). Prior to the extraction of the lignin, the stream of the lignocellulosic residue 1700-B can be separated, washed, and compressed as described above.
It has been unusually noted that extraction of the sugar from hemicellulose 1700 can produce, in a single extraction process, a hemicellulose sugar stream containing at least 80 to 95% monomeric sugars. For example, the sugar chain of hemicellulose may contain more than 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% sugars monomeric. In addition, the present method produces minimal amounts of lignocellulose degradation products, such as furfural, levulinic acid, and formic acid. In addition, a yield of xylose greater than 93% of the theoretical value can be obtained. In general, 18 to 27% of total sugars and at least 70%, 75% or 80% or more of the sugars of the hemicellulose can be extracted using the present method.
The sugar acid stream of hemicellulose 1700-A is then subjected to purification of hemicellulose sugar 1710. Various sugar products of hemicellulose can be obtained from the purification. Exemplary purified products include the sugar blend of hemicellulose 1710-P1, xylose 1710-P2, and the sugar blend of hemicellulose in which xylose 1710-P3 was removed. III. Purification of hemicellulose sugar Before purification of hemicellulose sugar 1710, the sugar acid stream of hemicellulose 1700-A from the extraction of sugar from hemicellulose 1700 may optionally be filtered, centrifuged or concentrated by evaporation. For example, the sugar chain of the hemicellulose may be contacted with a strong acid cation exchanger (e.g., in the H + form) to convert all salts into their respective acids.
Sugar purification of hemicellulose is illustrated in more detail according to an exemplary embodiment of the present invention as shown in Figure 18. As shown in Figure 18, the sugar acid stream of hemicellulose 1800-A is first subjected to a strong cation exchange resin and then extraction of the amine 1831, during which acids and impurities are extracted from the sugar stream from the hemicellulose into the amine extractant. The hemicellulose sugar stream into which the acids were excluded 1831-A is then purified by ion exchange 1832, including a strong acid cation exchanger 1833 and optionally followed by a weak base anion exchanger 1834. neutralized hemicellulose wherein the amine was removed is 1832-A is optionally evaporated 1835 to form a sugar blend of hemicellulose 1836. Optionally. the sugar stream from the neutralized hemicellulose and wherein the amine has been removed 1832-A can also be refined by contacting the granulated activated carbon prior to evaporation 1835.
The sugar blend of the hemicellulose 1836 may optionally be fractionated (process 1837 in Figure 18) to obtain high purity C5 sugars, such as xylose. Fractionation can be accomplished by any means, preferably using a simulated moving bed (SMB) or sequential simulated moving bed (SSMB). Examples of the simulated moving bed process are disclosed, for example, in U.S. Patent No. 6,379,554, U.S. Patent No. 5,102,553, U.S. Patent No. 6,093,326, and U.S. Patent No. No. 6,187,204, examples of the simulated sequential moving bed process can be found in GB 2 240 053 and U.S. Patent No. 4,332,623, as well as U.S. Patent Nos. 4,379,751 and 4,970,002 , their individual contents being incorporated into the present by means of this citation. In an exemplary SMB or SSMB configuration, the resin bed is divided into a series of separate containers each having a sequence through a series of 4 zones (feed, separation, feed / separation / raffinate and safety) and connected by a recirculation circuit. A tube system connects the containers and directs, in the appropriate sequence to (or from) each container, each of the four media accommodated by the process. Such media are generally referred to as feed, eluent, extract and raffinate. For example, a feed may be the sugar blend of hemicellulose 1836, the eluent may be water, the extract is an xylose enriched solution, and the raffinate is an aqueous solution containing high molecular weight sugars and other monomeric sugars, arabinose, galactose and glucose. Optionally, the eluent may be an aqueous solution comprising low concentration of the hydroxide ion to maintain the resin in the hydroxyl form, or the eluent may be an aqueous solution comprising low acid concentration to maintain the resin in the protonated form. For example, a feed comprising the 30% sugar blend, where the xylose corresponds to about 65 to 70% of the blend, may be fractionated with the use of an SSMB to obtain an extract comprising about 16 to 20% where the xylose corresponds to 82% or more, and a raffinate comprising the 5 to 7% sugar blend with only 15 to 18% xylose.
When an SSMB is used for fractionation, xylose exits the extract stream and longer chain sugars, as well as glucose, galactose and arabinose, exit the raffinate stream. The xylose stream 1837-A can optionally be refined by contacting the activated carbon granulated and refined with the mixed bed prior to evaporation to the highest concentration (process 1838 in Figure 18). Then, the 1839-A refined xylose stream, as an option, can be evaporated once again and crystallized (see, for example, the process shown in Figure 18 by 1841). The products are the xylose crystal 1842 and the hemicellulose sugar blend in which xylose 1843 was removed.
The stream of the 1831-A amine extractant can be re-extracted with an aqueous solution containing a base (for example, sodium hydroxide, sodium carbonate, and magnesium hydroxide) (see, for example, the process shown in Figure 18 by 1850). A portion of the solvent may be further purified with the use of a lime solution (e.g., calcium oxide, calcium hydroxide, calcium carbonate, or a combination of those listed) (see, for example, the process shown in Figure 18 1860) and the purified solvent can be recycled again for the extraction of amine 1831.
Specific Methods for Purification of Hemicellulose Sugar (Figures 1 to 7) Several preferred modes of purification of hemicellulose sugar are shown in Figures 1 to 7. In Figure 1, during the extraction of sugar from hemicellulose 101, at least one portion of the hemicellulose and the impurities are extracted from the lignocellulosic biomass by liquid extraction (for example using an acidic aqueous solution) to produce an acid sugar chain of the hemicellulose and a stream of the lignocellulosic residue. In some embodiments, the extraction of the sugar from hemicellulose 101 employs pressurized cooking (for example, 120 to 150 ° C, 1 to 5 mPa). The sugar acid stream of the hemicellulose is subjected to extraction of the amine 102 using an amine extractant having an amine of at least 20 carbon atoms, resulting in a sugar stream from the hemicellulose wherein the acid has been excluded and an extractant stream of amine. In one example, the stream of the amine extractant is subjected to a wash with water and then to reextraction 103 with a base. At least a portion of the amine extractant stream is then subjected to purification and filtration 104 before being recycled again for the extraction of the amine 102. The other part of the stream can be returned directly for reuse in the extraction of the amine 102.
In Figure 2, at least a portion of the hemicellulose and the impurities are extracted in the extraction of the sugar from the hemicellulose 201 by liquid extraction (for example using an acidic aqueous solution). In some embodiments, the extraction of the sugar from the hemicellulose 201 produces an acid sugar chain of the hemicellulose and a stream of the lignocellulosic residue. In some embodiments, the extraction of sugar from hemicellulose 201 employs pressurized cooking. In some embodiments, the sugar acid stream of the hemicellulose is subjected to extraction of the amine 202 using an amine extractant having an amine having at least 20 carbon atoms, resulting in a sugar stream from the hemicellulose wherein the acid has been excluded and a stream of the amine extractant. The stream of the amine extractant is subjected to a wash with water and then to a reextraction 203 with a base. At least a portion of the amine extractant stream is then subjected to purification and filtration 204 before being recycled for reuse in the extraction of the amine 202. The other part of the stream can be returned directly for reuse in the extraction of the amine 202. The aqueous stream resulting from reextraction 203 is subjected to a cation exchange 205 and then to distillation 206. In some embodiments, the distillation 206 produces acids.
In Figure 3, at least a portion of hemicellulose and impurities are extracted in the extraction of sugar from hemicellulose 301 by liquid extraction (for example using an acidic aqueous solution) to produce an acidic sugar stream of hemicellulose and a stream of the lignocellulosic residue. In some embodiments, the extraction of sugar from hemicellulose 301 employs pressurized cooking. In some embodiments, the sugar acid stream of the hemicellulose is subjected to the extraction of the amine 302 using an amine extractant having an amine having at least 20 carbon atoms, resulting in a sugar stream from the hemicellulose wherein the acid has been excluded and a stream of the amine extractant. In some embodiments, the amine extractant stream is washed with water and then reextracted 303 with a base. At least a portion of the stream of the amine extractant is then subjected to purification and filtration before reuse in the extraction of the amine 302. The other part of the stream can be returned directly for reuse in the extraction of the amine 302. The stream of the lignocellulose residue is dried, ground. if necessary, and pelletized to produce lignocellulose pellets (Process 310 in Figure 3).
In Figure 4, at least a portion of hemicellulose and impurities are extracted in the extraction of sugar from hemicellulose 401 by liquid extraction (for example using an acidic aqueous solution) to produce an acidic sugar stream of hemicellulose and a stream of the lignocellulosic residue. In some embodiments, the extraction of sugar from hemicellulose 401 employs pressurized cooking. In some examples, the sugar acid stream of the hemicellulose is subjected to the extraction of the amine 402 using an amine extractant having an amine having at least 20 carbon atoms, resulting in a sugar stream from the hemicellulose wherein the acid has been excluded and a stream of the amine extractant. In some embodiments, the amine extractant stream is washed with water and then reextracted 403 with a base. At least a portion of the amine extractant stream is then subjected to purification and filtration prior to reuse in the extraction of the amine 402. The other part of the stream can be returned directly for reuse in the extraction of the amine 402. The sugar stream of the hemicellulose in which the acid was excluded is then subjected to refining 407. In the example shown the refined sugar stream is then concentrated in the evaporator 410 followed by fractionation at 40 ° to produce a high concentration xylose containing stream and a sugar stream of the hemicellulose in which xylose was excluded. The high concentration xylose containing stream is then crystallized 408 to produce the crystal sugar product. The resulting mother liquor is recycled to the evaporator 410.
In Figure 5, at least a portion of hemicellulose and impurities are extracted in the extraction of sugar from hemicellulose 501 by liquid extraction (for example using an acidic aqueous solution) to produce an acidic sugar stream of hemicellulose and a stream of the lignocellulosic residue. In some embodiments, the extraction of sugar from hemicellulose 501 employs pressurized cooking. In some embodiments, the sugar acid stream of the hemicellulose is subjected to extraction of the amine 502 using an amine extractant having an amine of at least 20 carbon atoms, resulting in a sugar stream from the hemicellulose wherein the acid has been excluded and a stream of the amine extractant. In some embodiments, the amine extractant stream is washed with water and then reextracted 503 with a base. At least a portion of the stream of the amine extractant is then subjected to purification and filtration prior to reuse in the extraction of the amine 502. The other part of the stream can be returned directly for reuse in the extraction of the amine 502. The sugar stream of the hemicellulose in which the acid was excluded is then subjected to refining 507. In the example shown, the refined sugar stream is then concentrated in the evaporator 510, followed by fractionation at 50 ° to produce a high concentration xylose containing stream and a sugar stream of hemicellulose in which xylose was excluded. The high concentration xylose containing stream is crystallized (process 508) to produce the crystal sugar product. The resulting mother liquor is recycled to evaporator 510.
In Figure 6, at least a portion of hemicellulose and impurities are extracted in the extraction of the sugar from hemicellulose 601 by liquid extraction (for example using an acidic aqueous solution) to produce an acidic sugar stream of hemicellulose and a stream of the lignocellulosic residue. In some embodiments, the extraction of sugar from hemicellulose 601 employs pressurized cooking. In some embodiments, the sugar acid stream of the hemicellulose is subjected to extraction of the amine 602 using an amine extractant having an amine having at least 20 carbon atoms, resulting in a sugar stream from the hemicellulose wherein the acid has been excluded and a stream of the amine extractant. In some embodiments, the stream of the amine extractant is subjected to a wash with water and then to reextraction 603 with a base. At least a portion of the amine builder stream is then subjected to purification and filtration prior to reuse in the extraction of amine 602. The stream of the lignocellulosic residue is milled and pelletized (process 610) to produce lignocelluloses pellets. The sugar stream of the hemicellulose to which the acid was excluded is then subjected to refining 607. In the example shown, the stream of refined sugar is concentrated in the evaporator 610, followed by fractionation at 60 ° to produce a high concentration xylose containing stream and a hemicellulose sugar chain in which xylose was excluded. The high concentration xylose containing stream is crystallized 608 to produce the crystal sugar product. The resulting mother liquor is recycled to evaporator 610.
Figure 7 depicts a chromatographic fractionation of a refined sugar blend to obtain a fraction enriched with xylose and a mixed sugar solution containing glucose, arabinose and a variety of DP2 + components.
A more detailed description of these exemplary embodiments of hemicellulose sugar purification is provided below. 1. Amine Extraction As discussed above, the sugar stream of hemicellulose 1800-A can be extracted with an amine extractant containing an amine base and a diluent, to remove mineral acid (s), organic acids , furfural. (see, for example, the process shown in Figures 1 to 6 by the number X02, where X is 1, 2, 3, 4, 5 or 6 depending on the figures; The extraction can be performed by any method suitable for extracting acids. Preferably, the sugar stream of hemicellulose 1800-A is extracted with an amine extractant countercurrently, for example, the sugar stream of hemicellulose 1800-A flows in the direction opposite to the flow of the amine extractant. The countercurrent extraction can be performed in any suitable device, for example a mixing-decanter device, tanks for grinding. columns, or any other equipment appropriate for this extraction mode. Preferably the extraction of the amine is carried out in a mixer-settler designed to minimize emulsion formation and reduce phase separation time. A mixer-settler has a first stage which mixes the phases together, followed by a quiescent settling stage which allows the phases to evaporate by gravity. Various mixer-decanters known in the art may be used. In some methods, the phase separation can be enhanced by the incorporation of a suitable centrifuge into the mixer-settler.
Typically, the great majority of sugars remain in the hemicellulose sugar stream where the acid has been excluded 1831-B, while most of the organic or inorganic acids (eg acids used in extracting sugar from hemicellulose) and of the impurities are extracted into the amine extractant stream 1831-A. The amine extractant stream 1831-A may be contacted with a countercurrent aqueous stream to recover any residual sugars absorbed in the stream of the amine extractant. In some embodiments, the amine extractant stream 1831-A contains less than 5, 4, 3, 2, 1, 0.8, 0.6, 0.5, 0.4, 0.2, 0.1% w / w sugars from hemicellulose. In some embodiments, the sugar chain of the hemicellulose wherein the acid has been excluded 1831-B contains less than 5, 4, 3, 2, 1, 0.8, 0.6, 0.5, 2, 0.1% w / w acid. In some embodiments, the sugar chain of the hemicellulose wherein the acid has been excluded 1831-B contains less than 5, 4, 3, 2, 1, 0.8, 0.6, 0.5, 2, 0.1% w / w amine. In some embodiments, the sugar chain of the hemicellulose wherein the acid has been excluded 1831-B contains less than 5.4, 3, 2, 1, 0.8, 0.6, 0.5, 0.4, 2, 0.1% w / w of impurities.
The amine extractant may contain 10 to 90% or preferably 20 to 60% w / w of one or a plurality of amines having at least 20 carbon atoms. Such amine (s) may be primary, secondary, and tertiary amine (s). Examples of tertiary amines include tri-laurylamine (TLA, for example, COGNIS ALAMINE 304 from Cognis Corporation, Tucson AZ, USA), tri-octylamine, triisococtylamine, tri-caprylylamine and tri-decylamine.
Diluents suitable for use in the extraction of the amine include an alcohol, such as butanol, isobutanol, hexanol, octanol, decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetracosanol and triacontanol. Preferably, the diluent is a long chain alcohol (e.g., C6, C8, C10, C10, Cl2, Cl4, Cl6 alcohol) or kerosene. The diluent may have additional components. More preferably, the diluent comprises n-hexanol or 2-ethylhexanol. With maximum preference, the diluent comprises n-hexanol. In some embodiments, the diluent essentially consists of, or consists of, n-hexanol.
Optionally, the diluent contains one or more additional components. In some methods, the diluent contains one or more ketones, one or more aldehydes having at least 5 carbon atoms, or other alcohol.
Preferably, the amine is tri-lauryl amine and the diluent is hexanol. The ratio of the amine to the diluent may be, for example, between 3: 7 and 6: 4 w / w. In some methods, the amine extraction solution contains tri-laurylamine and hexanol in a ratio of 1: 7, 2: 7, 3: 7, 6: 4, 5.5: 4.55, 4: 7, 5: 7, 7: 7, 5: 4, 3: 4, 2: 4 or 1: 4 weight / weight. Preferably, the amine extraction solution contains tri-laurylamine and hexanol in a ratio of 3: 7 w / w.
Extraction of the amine may be carried out at any temperature at which the amine is soluble, preferably at 50 to 70 ° C. Alternatively, more than one extraction step (for example, 2, 3 or 4 steps) may be employed. The ratio of the amine extractant stream (organic phase) to the sugar stream of hemicellulose 1800-A (aqueous phase) may be from 0.5 to 5: 1, 1 to 2.5: 1, or preferably 1 , 5 to 3.0: 1 w / w. 2. Re-extraction The amine extractant stream 1831-A contains mineral and organic acid as well as impurities extracted from the products of sugar and biomass degradation. The acids may be extracted from the stream of the 1831-A amine extractant in a reextraction step (see, for example, the process shown in Figures 1 to 6 for the number X03, wherein X is 1, 2, 3, 4, 5 or 6, respectively, process 1850 in Figure 18).
Optionally, prior to re-extraction 1850, the amine extractant stream 1831-A can be washed with an aqueous solution to recover any sugars in the stream. Typically, after washing, the amine extractant stream 1831-A has less than 5%, 2%. 1%. 0.5%, 0.2%, 0.1%, 0.05% sugars.
The reextraction medium is an aqueous solution containing a base. For example, the extraction medium may be a solution containing NaOH. Na 2 CO 3, Mg (OH) 2, MgO or NH 4 OH. The concentration of the base may be from 1 to 20% w / w, preferably 4 to 10% w / w. Preferably, the base of choice produces a soluble salt when reacted with the acids in the acid-charged organic stream. Preferably, the amount of the base in the reextraction medium is 2 to 10% more than the stoichiometric equivalent of the acids in the organic stream.
Retreatment 1850 may be performed in any device, for example a mixing-decanter device, tanks for grinding. columns, or any other suitable equipment for this mode of reextraction. Preferably, the re-extraction is carried out in a mixer-settler designed to minimize emulsion formation and reduce phase separation time, for example, a mixer-settler equipped with low emulsification mixers for high rate separation, or in line with a centrifuge to increase the separation. The re-extraction may result in the removal of at least 93% of the mineral acid and at least 85% of the organic acid from the organic phase.
The withdrawal 1850 can be performed in multiple reactors. In one example, the 1850 reextraction is carried out in 4 reactors. In the first reactor, the amount of base is equivalent to the carboxylic acid and only the carboxylic acids are re-extracted to produce a solution of its salt (s) (e.g., sodium salt). In the second reactor, the mineral acid is reextracted. The currents leaving each reactor are treated separately to allow recovery of the organic acids. Optionally, the aqueous streams leaving the reextraction steps may be combined. Typically, the combined stream contains at least 3% of the mineral acid anion (eg, sulfate ion, sulfuric and / or sulfuric acids, when used in the extraction of sugar from hemicellulose 1700), and 0.2 to 3% acid acetic acid, as well as lower concentrations of other organic acids. The aqueous stream may contain low concentration of the organic phase diluent, typically less than 0.5%, depending on the solubility of the diluent used in the water. Preferably, the aqueous stream exiting the reextraction is maintained to allow segregation of the chemicals present in these streams. In one example, Ca2 + and SO42 ', which are detrimental to anaerobic digestion, are referred separately for aerobic treatment.
The organic phase diluent can be removed from the aqueous phase by distillation, where in many cases these diluents may form a heterogeneous azeotrope with water having a boiling point lower than the solvent of the separate diluent , therefore, the energy required to remove the diluent by distillation is significantly reduced because of the large excess of water in the diluent. The distilled solvent can be recovered and recycled back to the solvent reservoir for further use. The stripped aqueous phase of the diluent can be delivered to the plant waste treatment plant. 3. Purification of the solvent The stream of the amine extractant, now neutralized after removal of the acid, can be washed with water to remove the remaining salts from the re-extraction. It is particularly preferred that certain mixed extracts may be partially saturated with water (as with certain alcohols, for example). The washing stream may be combined with the aqueous re-extracting stream. A fraction of the washed amine extractant, typically 5 to 15% of the total weight of the amine extractant stream, may be diverted to the purification and filtration step indicated as X04 in Figures 1 to 6 (see, moreover, process 1860 in Figure 18). The remaining amine extractant is recycled for the amine extraction indicated as X02 in Figures 1 to 6.
The fraction diverted to the purification step (X04 in Figures 1 to 6, process 1860 in Figure 18) may be treated with a slurry of lime (e.g., a solution of lithium 5%, 10%, 15% , 20%, 25% w / w). The ratio of solvent to lime suspension may be in the range of 4 to 10.4 to 5, 5 to 6, 6 to 7, 7 to 8, 8 to 9, or 9 to 10. Treatment may be conducted in any suitable device, for example a thermostatic mixing tank. The solution can be heated for at least 1 hour at 80 to 90 ° C. Lime reacts with residual organic acids and esters of organic acids and effectively adsorbs the organic impurities present in the organic phase, such as acid soluble lignin and furfural, as visualized by changing from dark to light color. Impurities and contaminated lime may be filtered or centrifuged to recover the purified organic phase, which is washed with water and recycled back to the amine extraction step (X02 in Figures 1 to 6; process 1831 in Figure 18). The aqueous stream may be diverted to other streams of aqueous waste. Any solid cake that can be formed by the lime reaction can be used in the waste water treatment plant as the neutralizing salt for residual acids from the ion exchange regenerations, for example.
The aqueous reextraction stream contains salts of organic acids. This stream can be contacted with a cation exchanger to convert all salts into their respective organic acids (see, for example, the process shown in Figures 2, 5 and 6 by the number X05 where X is 2, 5 or 6, respectively). Alternatively, the organic acids can be converted to the acid form by acidifying the solution with a strong mineral acid. The acidified stream may be distilled to collect formic acid and acetic acid (see, for example, the process shown in Figures 2, 5 and 6 by the number X06 where X is 2, 5 or 6, respectively). The remaining aqueous streams are diverted to scrap. 4. Sugar Purification The sugar chain of the hemicellulose in which the acid has been excluded may be further purified (see, for example, Figures 4 to 6). For example, the diluent in the sugar chain of the hemicellulose in which the acid has been removed may be removed using a filled distillation column. The distillation can remove at least 70%, 80%, 90% or 95% of the diluent in the sugar stream from the hemicellulose where the acid has been excluded. With or without the diluent distillation step, the sugar stream from the hemicellulose to which the acid has been removed may also be brought into contact with a strong acid cation exchanger (SAC) to remove any metal cation residues and any residues from amines. Preferably the sugar chain of the hemicellulose in which the acid was excluded is purified using a filled distillation column followed by a strong acid cation exchanger.
Preferably the sugar chain of the hemicellulose into which the acid has been removed may then be contacted with a weak base anion (WBA) exchanger to remove excess protons. The sugar stream of the neutralized hemicellulose in which the amine has been removed may have its pH adjusted and be evaporated to 25 to 65%, and preferably. 30 to 40% w / w of sugars dissolved in any conventional evaporator, for example a multi-effect evaporator or a mechanical vapor recompression evaporator (MVR).
Any solvent residue present in the hemicellulose sugar stream can also be removed by evaporation. For example, the solvent which forms a heterogeneous azeotrope with water may be separated and returned to the solvent cycle. Optionally, the concentrated sugar solution may be brought into contact with activated carbon to remove residual organic impurities. The concentrated sugar solution may also be brought into contact with mixed bed resin system to remove any residual ions or colored bodies. Optionally, the now refined sugar solution can be further concentrated by conventional evaporator or MVR.
The resulting stream is a mixture of the highly purified hemicellulose sugar (for example, 1836 in Figure 18) which comprises, for example, 85 to 95% w / w of monosaccharides in relation to the total dissolved sugars. The composition of sugars depends on the composition of the initial biomass. A mixture of the hemicellulose sugar produced from the wood biomass of coniferous trees may have 65 to 75% (w / w) of C6 saccharides in the sugar solution relative to the total sugars. On the other hand, a mixture of hemicellulose sugar produced from wood biomass of hardwoods may contain 80 to 85% w / w of C6 sugars in relation to total sugars. The purity of the stream, in any case, may be sufficient for fermentation processes and / or catalytic process using such sugars.
The sugar blend of the highly purified hemicellulose 1836 is characterized by one or more, two or more, three or more, four or more, five or more, six or more features which include (i) monosaccharides in a ratio to total dissolved sugars> 0.50 w / w; (ii) glucose in a ratio to the total monosaccharides <0.25 w / w; (iii) xylose at a ratio to total monosaccharides> 0.18 wt / wt; (iv) fructose in a ratio to the total monosaccharides <0.10 w / w; (v) fructose in a ratio to the total monosaccharides> 0.01 w / w; (vi) furfural in the amount of up to 0.01% w / w; (vii) phenols in amounts up to 500 ppm; and (viii) a trace amount of hexanol. For example, the sugar blend may be a mixture with a high ratio of monosaccharides to total dissolved sugars, low glucose, and high xylose content. In some embodiments, the sugar blend is a mixture with a high ratio of monosaccharides to total dissolved sugars, low glucose, high xylose content, and low impurities (e.g., low furfural and phenolic contents). In some embodiments, the mixture is characterized by a high ratio of monosaccharides to total dissolved sugars, low glucose content, high xylose content, low impurities (e.g., low furfural and phenolic contents), and a trace amount of hexanol.
In some embodiments, the resulting stream is a sugar mixture having a high monomeric ratio. In some sugar blends, the ratio of monosaccharides to total dissolved sugars is greater than 0.50, 0.60, 0.70, 0.75, 0.80, 0.85, 0.90, or 0.95 weight /Weight. In some embodiments, the resulting stream is a mixture of low sugar glucose. In some sugar blends, the ratio of glucose to total monosaccharides is below 0.25, 0.20, 0.15, 0.13, 0.10, 0.06, 0.05, 0.03, or 0 , Weight / weight. In some embodiments, the resulting stream is a sugar mixture with high xylose content. In some sugar blends, the ratio of xylose to total monosaccharides is above 0.10, 0.15, 0.18, 0.20, 0.30, 0.40, 0.50, 70, 0.80 or 0.85 w / w.
In some 1836 sugar blends, the ratio of fructose to total dissolved sugars is below 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0 , 09, 0.10, 0.15, 0.20, 0.25 or 0.30 w / w. In some 1836 sugar blends, the ratio of fructose to total dissolved sugars is greater than 0.001, 0.002, 0.005, 0.006, 0.007, 0.008, 0.009,0.01, 0.02, 0.03, 0.04, 05.0.06.0.07, 0.08, or 0.09 w / w.
The sugar blend of the above hemicellulose includes very low impurities (for example, furfural and phenol). In part of the resulting stream, the sugar blend has furfural in the amount of up to 0.1%, 0.05%, 0.04%, 0.03%, 0.04%, 0.01%, 0.075%, 0.005 %, 0.004%, 0.002% or 0.001% w / w. In part of the resulting stream, the sugar blend has phenols in the amount of up to 500 ppm. 400 ppm. 300 ppm, 200 ppm. 100 ppm. 60 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm. 5 ppm. 1 ppm, 0.1 ppm, 0.05 ppm, 0.02 ppm or 0.01 ppm. The hemicellulose sugar mixture is further characterized by a trace amount of hexanol, for example 0.01 to 0.02%. 0.02 to 0.05%, 0.05 to 0.1%, 0.1% to 0.2%, 0.2 to 0.5%, 0.5 to 1%, or less than 1.0 , 5, 0.2, 0.1, 0.05, 0.02, 0.01, 0.005, 0.002, 0.001%, weight / weight of hexanol.
This high purity sugar solution may be used in the manufacture of industrial products and consumer products as described in PCT / IL2011 / 00509 (for all purposes, such document is hereby incorporated by reference). In addition, the coniferous tree sugar product containing 65 to 75 wt% C6 sugars can be used as fermentation feed for species uniquely capable of using C6 sugars, and the resulting mixture of C5 and product can be separated, the C5 may then be refined to obtain a C5 product as described in PCT / US2011 / 50435 (for all purposes, such document is incorporated herein by reference).
The fermentation product includes at least one member selected from the group consisting of alcohols, carboxylic acids, amino acids, monomers for the polymer and protein industry, and wherein the method further comprises processing said fermentation product to produce a product selected from the group consisting of detergent, polyethylene based products, polypropylene based products, polyolefin based products, polylactic acid based products (polylactide), polyhydroxyalkanoate based products and polyacrylic based products.
These fermentation products can be used in separate or with other components as food or feed, pharmaceuticals, nutraceuticals, plastic parts or components for the production of various consumer products, fuel, gasoline, chemical additive or surfactant.
The high purity sugar solution products are suitable for chemical catalytic conversions since the catalysts are usually sensitive to the impurities associated with the products of sugar and biomass degradation. Typically, the purity is greater than 95, 96, 97, 98%, preferably greater than 99, 99.5 or 99.9%. This product contains small amounts of marker molecules, including, for example, residual diluent, for example hexanol, 1-ethyl hexanol, kerosene or any other diluents used, as well as furfural, hydroxymethylfurfural, condensation products of furfural or hydroxymethylfurfural compounds colored derivatives derived from sugar caramelization, levulinic acid, acetic acid, methanol, galacturonic acid or glycerol. 5. Sugar fractionation [00129] Some biomass materials contain high concentration of a single sugar as part of their hemicellulosic sugar composition. For example, eucalyptus and bagasse contain high concentration of xylose. A simple sugar like xylose has specific application and much higher industrial value than a sugar mixture. Therefore, it is highly beneficial to fractionate the sugar stream to obtain a high concentration of the simple sugar to facilitate the crystallization of the sugar and the production of the high purity simple sugar product.
The sugar mixture of the hemicellulose 1836 may optionally be concentrated by evaporation, and fractionated 1837 (for example by chromatographic separation) to yield a stream enriched with xylose 1837-A having greater than 75, 78, 80, 82, 84 , 85, 86, 88, 90% xylose, and a sugar mixture of hemicellulose in which xylose 1837-B was removed. The hemicellulose sugar blend in which xylose 1837-B has been removed may be used as a substrate for fermentation processes capable of fermenting C5 / C6 sugar blends as substrate for chemical conversion or as substrate for anaerobic digestion in order to produce energy.
Chromatographic fractionation to obtain xylose concentration enrichment can be carried out with ion exchange resins (for example, a cation exchange resin and an anion exchange resin) as the column filling material. Cation exchange resins include strong acid cation exchange resins and weak acid cation exchange resins. The strong acid cation exchange resins may be in the form of monovalent or multivalent metal cations, for example in the form H +, Mg 2+, Ca 2+ or Zn 2+ form. Preferably, the resins are in Na + form. Strong acid cation exchange resins typically have a styrene backbone, which is preferably crosslinked with 3 to 8%, preferably 5 to 6.5% divinylbenzene. The weak acid cation exchange resins may be in the form of monovalent or multivalent metal cations, for example in the form H +, Mg 2+ or Ca 2+, preferably in Na + form.
Chromatographic fractionation may be performed in a batch mode or a simulated moving bed mode (SMB) or sequential simulated moving bed mode (SSMB). The temperature of the chromatographic fractionation typically is in the range of 20 to 90øC, preferably 40 to 65øC. The pH of the solution to be fractionated may be acidic or adjusted to a range of 2.5 to 7, preferably 3.5 to 6.5 and most preferably 4 to 5.5. Typically, fractionation can be performed at a linear flow rate of about 1 m / h to 10 m / h on the separation column.
[00133] Anion exchange resins have often been used in the past for the demineralization of solutions, i.e., for ion exchange, or for discoloration, that is. for adsorption. In some embodiments of the invention, there may be little or no liquid ion exchange or adsorption between the resin and the solution. In this case, an ion exchange resin of the anion type is used for its properties as a chromatographic substrate, instead of the column basically destined to the exchange of liquid ions.
Chromatographic separation differs from other column separations (eg, ion exchange or adsorption) in that the main component in the feed mixture is so strongly retained by the sorbent that it requires additional reagents to be routinely used between cycles to regenerate the column by removing the strongly retained components before the next separation cycle. In general, a chromatographic column can be reused for multiple cycles prior to regeneration without the columns needing some degree of periodic cleaning or regeneration. The function of an ion exchange column or adsorption is to bind the components together, necessitating frequent regeneration so that the resin is reused. In contrast, the function of a chromatographic column is to impart differential mobility so that the components move through the column in order to effect separation, but not to bind them so strongly to the main components. Regeneration of a chromatographic column may be necessary from time to time due to the incidental attachment of minor components or impurities to the resin. The minimum amount of reactants required for resin regeneration is a major advantage of chromatographic separations over ion exchange separations. The operational cost of chromatographic separations is primarily due to the energy required to evaporate the water (or other solvent) from the diluted products, and to a lesser extent, the regeneration or infrequent replacement of the resin.
A preferred method for large-scale chromatographic separations is the simulated sequential moving bed (SSMB) or, alternatively, the simulated moving bed (SMB). Both methods use several columns packed with a suitable sorbent and connected in series. These are power and solvent access ports (including recycled solvent), and exit ports for two or more products (or other separate fractions). The injection of the solution of the mixture to be separated is periodically alternated between the columns along the flow direction of the liquid, thus simulating the continuous movement of the sorbent relative to the ports and the liquid. SMB is a continuous countercurrent type operation. SSMB is a more advanced method, requiring sequential operation. Its advantages over SMB and older methods include: the need for fewer columns in the SSMB method than in the SMB method, therefore, less need for resin and the associated installation cost is significantly reduced in the large system; the pressure profile is better controlled, facilitating the use of more sensitive resins; recoverability / purity is greater than that achieved with SMB systems.
Fractionation of xylose from refined mixed sugar solution X09 (X indicates 4, 5 or 6 in Figures 4 to 6; process 1837 in Figure 18) may preferably be obtained using a base anion exchanger (SBA) having a particle size of -280 to 320 Âμm. The largest particle size is advantageous over the much smaller particle sizes used in US6451123. The larger particle size reduces the return pressure of the column to an industrially viable range. Suitable commercial SBA resins may be purchased from Finex (AS 510 GC Type 1, Strong Base Anion, gel form), similar grades may be purchased from other manufacturers, including Lanxess AG, Purolite, Dow Chemicals Ltd. or Rohm & Haas. The SBA resin may be in the form of sulfate or chlorine, preferably in the form of sulfate. SBA is partially impregnated with hydroxyl groups by low NaOH concentration, the base to sulphate variation is from 3 to 12% to 97 to 88%, respectively. To maintain this level of OH groups in the resin, a low NaOH level, sufficient to replace the hydroxyl removed by the sugar adsorption, may be included in the desorption pulse, causing the xylose to be retained longer than the other sugars in this resin. The fractionation may be conducted in the SSMB mode at about 40 to 50 ° C, resulting in a xylose rich stream containing at least 79%, at least 80%, at least 83%, preferably at least 85% xylose relative to total sugars, and a mixed sugar stream, at a recovery of at least 80%, at least 85% xylose.
In some methods, the SSMB sequence includes three steps. In the first step, a stream of the product is extracted by exposing and washing the adsorbent with a desorbent stream ("extract-desorbent" step). Simultaneously, a feed stream is passed through the adsorbent and a stream of the raffinate is washed from the adsorbent ("feed for raffinate" step). In the second step, a raffinate stream is extracted by exposing and washing the adsorbent with a desorbent stream ("desorbent to raffinate" step). In the third step, the desorbent is recycled back to the adsorbent ("recycling" step).
Typically, the product is extracted so that the raffinate flow equals the flow of the desorbent, but results in high desorbent consumption to achieve recovery of the desired product. Preferably, in some SSMB sequences, the product is extracted in more than one step (for example, not only in step 1, but also in step 2). In some methods, the product stream is not extracted only in the first step, but also in the second step (i.e., the "desorbent to raffinate" step). When the product is extracted in more than one step, the desorbent flow rate is equal to the sum of the extract flow rate and the raffinate flow rate. In some embodiments, the desorbent flow rate is practically equal to the sum of the extract flow rate and the rate of flow of the extract. In some embodiments, the desorbent flow rate is in the range of 50 to 150%, 60 to 140%, 70 to 130%, 80 to 120%, 90 to 110%, 95 to 105%, 96 to 104%, 97 to 103%, 98 to 102%, 99 to 101%, or 99.5 to 100.5%, of the sum of the extract flow rate and the rate of flow of the extract. This change in the SSMB sequence decreases the required desorbent, resulting in recovery of the desired product with much less desorbent volume, while maintaining the SSMB chromatographic profiles in the four (4) zones and six (6) columns and their purity .
Following fractionation X09, the sugar chains may optionally be contacted with a weak acid cation exchange resin (WAC) in the H + form to neutralize the sugar stream. This acidification allows the evaporation of the sugar chain and maintains the stability of the sugar. The WAC resin can be regenerated by a mineral acid or preferably by contacting the acid scavenger stream of the SAC resin used in the sugar refining step X07 (X indicates 4, 5 or 6 in Figures 4 to 6). After the WAC neutralization step, the mixed sugar stream may optionally be directed to the evaporator XI0 (X indicates 4, 5 or 6 in Figures 4 to 6), while the xylose-rich stream is directed to the sugar crystallizer X08 (X indicates 4, 5 or 6 in Figures 4 to 6).
The chain enriched with xylose 1837-A is characterized by one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, ten or more characteristics which include (i) oligosaccharides in a ratio to the total dissolved sugars <0.10 w / w; (ii) xylose at a ratio to the total dissolved sugars> 0.50 w / w; (iii) arabinose in a ratio to the total dissolved sugars <0.10 w / w; (iv) galactose in a ratio to the total dissolved sugars <0.05 w / w; (v) the sum of glucose and fructose in a ratio to the total dissolved sugars <0.10 w / w; (vi) mannose at a ratio to the total dissolved sugars <0.02 w / w; (vii) fructose in a ratio to the total dissolved sugars <0.05 w / w; (viii) furfural in the amount of up to 0.01% w / w; (ix) phenols in the amount of up to 500 ppm; and (x) a trace amount of hexanol. For example, the sugar mixture 1837-A is a mixture characterized by a low ratio of oligosaccharides to dissolved total sugars and a high ratio of xylose to total dissolved sugars. In some embodiments, the 1837-A sugar blend is a mixture characterized by a low ratio of oligosaccharides to dissolved total sugars, a high ratio of xylose to total dissolved sugars, and low impurities (e.g., low furfural and phenols). In some embodiments, the 1837-A sugar blend is a mixture characterized by a low ratio of oligosaccharides to dissolved total sugars, a high ratio of xylose to total dissolved sugars, low impurities (e.g., low levels of furfural and phenols ), and a trace amount of hexanol. In some embodiments, the 1837-A sugar mixture is a mixture characterized by a low ratio of oligosaccharides to total dissolved sugars, a high ratio of xylose to total dissolved sugars, a low ratio of the sum of glucose to fructose and total dissolved sugars, low impurities (eg, low furfural and phenolic contents), and a trace amount of hexanol.
In some embodiments, the xylose enriched stream 1837-A is a sugar blend characterized by a high ratio of xylose to total dissolved sugars. In some sugar blends, the ratio of xylose to total dissolved sugars is greater than 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0 , 80, 0.85 or 0.90 w / w. In some embodiments, the xylose enriched stream 1837-A is a sugar blend characterized by a low ratio of oligosaccharides to dissolved total sugars. In some sugar blends, the ratio of oligosaccharides to total dissolved sugars is less than 0.002, 0.005, 0.007, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0 , 0.09, 0.10, 0.20 or 0.30 w / w. In some embodiments, the xylose-enriched 1837-A stream is a low sugar / fructose sugar blend. In some sugar blends, the ratio of the sum of glucose and fructose to total dissolved sugars is less than 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 07, 0.08, 0.09, 0.10, 0.20, 0.25 or 0.30 w / w. In some embodiments, the 1837-A xylose-enriched stream is a sugar mixture having a high ratio of xylose to total sugars, a low ratio of oligosaccharides to total dissolved sugars, and low glucose and fructose contents.
In some 1837-A sugar blends, the ratio of arabinose to total dissolved sugars is less than 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02, 0.03, 0.04, 0 , 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20 or 0.30 w / w. In some 1837-A sugar blends, the ratio of galactose to total dissolved sugars is less than 0.0005, 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.10 w / w. In some 1837-A sugar blends, the ratio of mannose to total dissolved sugars is less than 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02. 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20 or 0.30 weight / weight. In some 1837-A sugar blends, the ratio of fructose to total dissolved sugars is less than 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20 or 0.30 w / w.
The 1837-A sugar blend includes a very low concentration of impurities (e.g., furfural and phenol). In some 1837-A sugar blends, the sugar blend has furfural in the amount of up to 0.1%, 0.05%, 0.04%, 0.03%, 0.04%, 0.01%, 0.075% %, 0.005%, 0.004%, 0.002% or 0.001% w / w. In some 1837-A sugar blends, the sugar blend has phenols in the amount of up to 500 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm, 60 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm, 5 ppm, 1 ppm, 0.1 ppm, 0.05 ppm. 0.02 ppm or 0.01 ppm. The sugar mixture is further characterized by a trace amount of hexanol, for example, 0.01 to 0.02%, 0.02 to 0.05%, 0.05 to 0.1%, 0.1% to 0.2%, 0.2 to 0.5%, 0.5 to 1%, or less than 1, 0.5, 0.2, 0.1, 0.05, 0.02. 0.01, 0.005, 0.002, 0.001% w / w hexanol.
The hemicellulose sugar mixture in which xylose 1837-B is removed is characterized by one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, ten or more features including (i) oligosaccharides in a ratio to the total dissolved sugars> 0.15 w / w; (ii) the sum of glucose and fructose in a ratio to the total dissolved sugars> 0.10 w / w; (iii) arabinose at a ratio to the total dissolved sugars> 0.02 w / w; (iv) galactose in a ratio to the total dissolved sugars> 0.02 w / w; (v) xylose in a ratio to the total dissolved sugars <0.20; (vi) mannose at a ratio of total dissolved sugars> 0.01; (vii) fructose in a ratio to the total dissolved sugars <0.05; (viii) furfural in the amount of up to 0.01% w / w; (ix) phenols in the amount of up to 500 ppm; and (x) a trace amount of hexanol. For example, the sugar blend may be a mixture characterized by a high ratio of oligosaccharides to dissolved total sugars, and a high ratio of glucose / fructose to total dissolved sugars. In some embodiments, the 1837-B sugar mixture is a mixture characterized by a high ratio of oligosaccharides to dissolved total sugars, a high ratio of glucose to fructose to total dissolved sugars, and low impurities (e.g. furfural and phenols). In some embodiments, the sugar blend is a blend characterized by a high ratio of oligosaccharides to total dissolved sugars, a high ratio of glucose to fructose to total dissolved sugars, low impurities (e.g., low levels of furfural and phenols) , and a trace amount of hexanol. In some embodiments, the sugar blend is a blend characterized by a high concentration of xylose, a high ratio of oligosaccharides to total dissolved sugars, a high ratio of the sum of glucose to fructose and total dissolved sugars, and low impurities (eg low levels of furfural and phenols).
In some embodiments, the hemicellulose sugar blend in which xylose 1837-B was removed is a sugar blend characterized by a high ratio of oligosaccharides to dissolved total sugars. In some sugar blends, the ratio of oligosaccharides to total dissolved sugars is greater than 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0 , 55 or 0.65 wt.%. In some embodiments, the hemicellulose sugar blend in which xylose 1837-B was removed is a high sugar / fructose sugar blend. In some sugar blends, the ratio of the sum of glucose and fructose to total dissolved sugars is greater than 0.05, 0.10, 0.13, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50 or 0.55 w / w. In some embodiments, the xylose broth is a sugar mixture having a high ratio of oligosaccharides to total dissolved sugars, and high glucose and fructose contents.
In some 1837-B sugar blends, the ratio of arabinose to total dissolved sugars is greater than 0.02, 0.03, 0.04, 0.05, 0.06, 0.08, 0.10 , 0.12, 0.20 or 0.30 w / w. In some 1837-B sugar blends, the ratio of galactose to total dissolved sugars is greater than 0.02, 0.03, 0.04, 0.05, 0.06, 0.08, 0.10, 12, 0.20 or 0.30 w / w. In some 1837-B sugar blends, the ratio of xylose to total dissolved sugars is less than 0.30, 0.20, 0.18, 0.17, 0.16, 0.15, 0.12, 10 or 0.05 w / w. In some 1837-B sugar blends, the ratio of mannose to total dissolved sugars is greater than 0.005, 0.006, 0.007, 0.008, 0.010, 0.015 or 0.020 weight / weight. In some 1837-B sugar blends, the ratio of fructose to total dissolved sugars is less than 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10 or 0.20 w / w.
The 1837-B sugar blend includes a very low concentration of impurities (e.g., furfural and phenols). In part of the resulting stream, the sugar blend has furfural in the amount of up to 0.1%, 0.05%, 0.04%, 0.03%, 0.04%, 0.01%, 0.075%, 0.005 %, 0.004%, 0.002% or 0.001% w / w. In 1837-B sugar blends, the sugar blend has phenols in the amount of up to 500 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm. 60 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm. 5 ppm, 1 ppm, 0.1 ppm. 0.05 ppm, 0.02 ppm or 0.01 ppm. The sugar mixture is further characterized by a trace amount of hexanol, for example, 0.01 to 0.02%, 0.02 to 0.05%, 0.05 to 0.1%, 0.1% to 0.2%, 0.2 to 0.5%, 0.5 to 1%, or less than 1, 0.5, 0.2, 0.1, 0.05, 0.02, 0.01, 0.005, 0.002, 0.001%, weight / weight of hexanol. 6. Crystallization of sugar [00148] This exemplary description relates to the process shown in Figures 4, 5 and 6 by the number X08, where X is 4, 5 or 6 respectively (process 1841 in Figure 18). Pure xylose is known to crystallize from supersaturated mixed sugar solutions. To this end, the stream of the sugar solution resulting from the X07 sugar refining is concentrated by X10 evaporation, and fractionated by chromatographic separation at X09 to produce a xylose-enriched stream (corresponding to 1837-A in Figure 18) of greater than 75 , 78, 80, 82, 84, 85, 86, 88, 90% xylose, and a sugar mixture of hemicellulose in which xylose (corresponding to 1837-B in Figure 18) was removed. The xylose-enriched stream (corresponding to 1837-A in Figure 18) from the X09 fractionation is fed into a X08 crystallization module (process 1841 in Figure 18) to produce xylose crystals.
In some methods, the xylose-enriched stream 1837-A is optionally evaporated before being fed into a crystallization module 1841 to produce xylose crystals. The crystals can be collected from the mother liquor using any convenient means, for example, centrifugation. Depending on the crystallization technique, the crystals may be washed with the appropriate solution, for example, an aqueous solution or solvent. The crystals can either be dried or redissolved in water to produce the xylose syrup. Typically, a yield of 45 to 60% of the potential xylose can be crystallized in a cycle of 20 to 35 hours, preferably 24 to 28 hours.
After crystallization, the hemicellulose sugar mixture of the mother liquor 1843 may be recycled back to the fractionation step because it contains fairly high xylose content, for example> 57% xylose,> 65% and more typically > 75% xylose. Alternatively, the sugar mixture from the hemicellulose of the mother liquor 1843 can be sent for anaerobic digestion to obtain the energy achievable with this fraction.
In some embodiments, the hemicellulose sugar mixture of the mother liquor 1843 is a sugar blend characterized by the high concentration of xylose. In some sugar blends, the sugar blend has more than 65, 67, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80 or 85% w / w xylose.
The sugar solution stream originating from part of the wood of specific hardwoods and grasses, such as bagasse, may contain at least 60% xylose and more typically 60 to 80% or 66 to 73% w / w xylose . Xylose can be used as a raw material for the bacterial and chemical production of furfural and tetrahydrofuran. Xylose can also be used as a starting material for the preparation of xylitol, an alternative low calorie sweetener with beneficial properties for dental care and diabetes control, and has been shown to contribute to atrial cleansing and respiratory tract infections higher. Due to these beneficial properties, xylitol is incorporated into foods and beverages, toothpastes and mouthwashes, chewing gums and confectionery. The world market for xylitol is limited because of its high price when compared to other non-reducing polyol sugars (ca. sorbitol, mannitol). The method of the present invention provides an economical method for the production of xylose and xylitol.
The hemicellulose sugar mixture of the mother liquor 1843 is characterized by one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, ten or more features including (i) oligosaccharides in a ratio to the total dissolved sugars <0.15 w / w; (ii) xylose at a ratio to the total dissolved sugars> 0.40 w / w; (iii) arabinose in a ratio to the total dissolved sugars <0.15 w / w; (iv) galactose in a ratio to the total dissolved sugars <0.06 w / w; (v) the sum of glucose and fructose in a ratio to the total dissolved sugars <0.20 w / w; (vi) mannose at a ratio to the total dissolved sugars <0.03; (vii) fructose in a ratio to the total dissolved sugars <0.04; (viii) furfural in the amount of up to 0.01% w / w; (ix) phenols in the amount of up to 500 ppm; and (x) a trace amount of hexanol. For example, the 1843 sugar blend is a mixture characterized by a low ratio of oligosaccharides to total dissolved sugars and a high ratio of xylose to total dissolved sugars. In some embodiments, the 1843 sugar blend is a mixture characterized by a low ratio of oligosaccharides to total dissolved sugars, a high ratio of xylose to total dissolved sugars, and low impurities (e.g., low levels of furfural and phenol) . In some embodiments, the sugar mixture 1843 is a mixture characterized by a low ratio of oligosaccharides to total dissolved sugars, a high ratio of xylose to total dissolved sugars, low impurities (e.g., low furfural and phenolic contents), and a trace amount of hexanol. In some embodiments, the sugar mixture 1843 is a mixture characterized by a low ratio of oligosaccharides to total dissolved sugars, a high ratio of xylose to total dissolved sugars, a low ratio of the sum of glucose to fructose and total sugars low impurities (for example, low levels of furfural and phenols), and a trace amount of hexanol.
In some embodiments, the hemicellulose sugar mixture of the mother liquor 1843 is a sugar blend characterized by a high ratio of xylose to total dissolved sugars. In some sugar blends, the ratio of xylose to total dissolved sugars is greater than 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75 , 0.80 or 0.85 w / w. In some embodiments, the hemicellulose sugar blend of the 1843 mother liquor is a sugar blend characterized by a low ratio of oligosaccharides to dissolved total sugars. In some sugar blends, the ratio of oligosaccharides to total dissolved sugars is less than 0.005, 0.007, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0 , 0.09, 0.10, 0.20, 0.30 or 0.35 w / w. In some embodiments, the 1843 mother liquor hemicellulose sugar blend is a low sugar / fructose sugar blend. In some sugar blends, the ratio of the sum of glucose and fructose to total dissolved sugars is less than 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, 0.25, 0.30 or 0.35 w / w. In some embodiments, the sugar mixture of hemicellulose from the mother liquor 1843 is a sugar mixture having a high ratio of xylose to total sugars, a low ratio of oligosaccharides to dissolved total sugars, and low glucose and fructose contents.
In some 1843 sugar blends, the ratio of arabinose to total dissolved sugars is less than 0.002, 0.003, 0.004, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0 , 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30 or 0.35 w / w. In some 1843 sugar blends, the ratio of galactose to total dissolved sugars is less than 0.001, 0.002, 0.003, 0.004, 0.005, 0.010, 0.015, 0.020, 0.025, 0.030, 0.035, 0.040, 0.05, 0.05, 0.06, 0.065, 0.07, 0.08, 0.09 or 0.10 w / w. In some 1843 sugar blends, the ratio of mannose to total dissolved sugars is less than 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 06, 0.07, 0.08, 0.09, 0.10, 0.20 or 0.30 weight / weight. In some 1843 sugar blends, the ratio of fructose to total dissolved sugars is less than 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 06.0.07, 0.08, 0.09, 0.10, 0.20 or 0.30 w / w.
The sugar blend 1843 includes a very low concentration of impurities (e.g., furfural and phenols). In some 1843 sugar blends, the sugar blend has furfural in the amount of up to 0.1%, 0.05%, 0.04%, 0.03%, 0.04%. 0.01%, 0.075%, 0.005%, 0.004%, 0.002% or 0.001% w / w. In some 1843 sugar blends, the sugar blend has phenols in the amount of up to 500 ppm, 400 ppm, 300 ppm, 200 ppm. 100 ppm, 60 ppm, 50 ppm. 40 ppm, 30 ppm, 20 ppm. 10 ppm, 5 ppm, 1 ppm, 0.1 ppm, 0.05 ppm. 0.02 ppm or 0.01 ppm. The sugar mixture is further characterized by a trace amount of hexanol, for example, 0.01 to 0.02%, 0.02 to 0.05%, 0.05 to 0.1%, 0.1% to 0.2%, 0.2 to 0.5%, 0.5 to 1%, or less than 1, 0.5, 0.2, 0.1, 0.05, 0.02, 0.01, 0.005, 0.002, 0.001%, weight / weight of hexanol. 7. Hemicellulose Sugar Product [00157] This section refers to the use of mixed sugar chains produced in the sugar refining step X07, or fractionated from the xylose-enriched stream in step X09, wherein X is 4, 5 or 6 in Figures 4, 5, and 6, respectively. This high purity mixed sugar product may be used in a fermentation process. This fermentation process may employ a genetically modified microorganism or microorganism (GMO) of the genera Clostridium, Escherichia (for example, Escherichia coli), Salmonella, Zymomonas, Rhodococcus, Pseudomonas, Bacillus, Enterococcus, Alcaligenes, Lactobacillus, Klebsiella, Paenibacillus, Corynebacterium, Brevibacterium, Pichia, Candida, Hansenula and Saccharomyces. Host hosts that may be of particular interest include Oligotropha carboxidovorans, Escherichia coli, Bacillus licheniformis, Paenibacillus macerans, Rhodococcus erythropolis, Pseudomonas putida, Lactobacillus plantar um, Enterococcus faecium, Cupriavidus necator, Enterococcus gallinarium, Enterococcus faecalis, Bacillus suhtilis and Saccharomyces cerevisiae. In addition, any known strains of the above species may be used as the starting microorganism. Optionally, the microorganism may be an actinomycete selected from Streptomyces coelicolor, Streptomyces lividans, Slreptomyces hygroscopicus or Saccharopolispora erytraea. In various exemplary embodiments, the microorganism may be a eubacterial selected from Pseudomonas fluorescens, Pseudomonas aeruginosa, Bacillus suhtilis or Bacillus cereus. In some examples, the genetically modified microorganism or microorganism is a gram negative bacterium.
The conversion product performed by the fermentation may be, for example, an alcohol, carboxylic acid, amino acid, monomer for the polymer or protein industry. A particular example is lactic acid, which is the building monomer of polylactic acid, multi-use polymer.
The conversion product may be processed to produce a consumer product selected from the group consisting of a detergent, a polyethylene based product, a polypropylene based product, a polyolefin based product. a polylactic acid (polylactide) based product, a polyhydroxyalkanoate based product and a polyacrylic based product. The detergent may include a sugar based surfactant, a fatty acid surfactant, a fatty alcohol surfactant or an enzyme derived from cell culture.
The polyacrylic-based product may be a plastic, a floor wax, a carpet, an ink, a coating, an adhesive, a dispersion, a flocculant, an elastomer, an acrylic glass, an absorbent article, a diaper for incontinence, a feminine absorbent, a feminine hygiene product and a diaper. The polyolefin-based products may be a milk container, a detergent bottle, a margarine jar, a garbage container, a tubing pipe, an absorbent article, a diaper, a nonwoven, an HDPE toy or a carton of HDPE detergent. The polypropylene-based product may be an absorbent article, a diaper or a nonwoven. The polylactic acid-based product may be a packaging of an agricultural product or a dairy product, a plastic bottle, a biodegradable product or a disposable product. The polyhydroxyalkanoate based products may be packaging of an agricultural product, a plastic bottle, a coated paper, a molded or extruded article, a feminine hygiene product, a tampon applicator, an absorbent article, a disposable non-woven product or handkerchief , a medical surgical garment, an adhesive, an elastomer, a film, a coating, an aqueous dispersant, a fiber, an intermediate of a pharmaceutical substance or a binder. The conversion product may be ethanol, butanol, isobutanol, a fatty acid, a fatty acid ester, a fatty alcohol or biodiesel.
Xylose can be reacted with chlorambucil to obtain the benzenobutanoic acid, 4- [bis (2-chloroethyl) amino] -2,2-p-xylopyranosylhydrazide, an analog of the chlorosuccinyl glycosylated having utility as antitumor agent and / or antimetastatic. The xylose can be reacted with phenethyl bromide and 1-bromo-3,3-dimethoxypropane to give (2S, 3S, 4S) -2H-pyrrole, 3,4-dihydro-3,4-bis (phenylmethoxy) 2 - [(phenylmethoxy) methyl] -, 1-oxide, used as an α-glycosidase inhibitor to prevent and / or treat diabetes mellitus, hyperlipidemia, neoplasm, and viral infection.
The product of the sugar mixture can be converted into combustible products, for example, a condensation product of isobutene, aviation fuel, gasoline, gasool. diesel fuel, drop-in fuel, diesel fuel additive or a precursor to those cited. This conversion may be carried out by catalytic fermentation or chemical conversion. The gasool may be gasoline enriched with ethanol and / or butanol enriched gasoline.
[00163] Consumer products, precursor of a consumer product, or ingredient of a consumer product may be produced with the conversion product or include at least one conversion product such as a carboxylic acid or fatty acid , a carboxylic diacid, a hydroxycarboxylic acid, a dihydroxycarboxylic acid, a hydroxy fatty acid, methylglyoxal, mono, di or polyalcohol, an alkane, an alkene, an aromatic substance, an aldehyde, a ketone, an ester, a biopolymer, a protein, a peptide, an amino acid, a vitamin, an antibiotic and a pharmaceutical substance. For example, the product may be gasoline enriched with ethanol, aviation fuel or biodiesel.
[00164] The consumer product may have a ratio of carbon 14 to carbon 12 equal to or greater than 2.0 χ 10'13. The consumer product may include an ingredient of a consumer product as described above and an additional ingredient produced from a raw material, except lignocellulosic material. In some cases, the ingredient and the additional ingredient produced from the raw material, except for lignocellulosic material, have essentially the same chemical composition. The consumer product may include a marker molecule in the concentration of at least 100 ppb. The label molecule may be, for example, hexanol, 1-ethyl hexanol, furfural or hydroxymethylfurfural. condensation products of furfural or hydroxymethylfurfural, colored compounds derived from the caramelization of sugar, levulinic acid, acetic acid, methanol, galacturonic acid or glycerol. IV. Once the sugars are extracted from the hemicellulose, the stream of the lignocellulosic residue 1700-B can then be subjected to the hydrolysis of the cellulose 1720 to obtain a stream of acid hydrolyzate 1720-A and the acid lignin stream 1720-B (see Figure 17). Preferably, prior to the hydrolysis of the cellulose, the biomass is milled or ground to reduce particle size (see, for example, Figures 3 and 6, numbers 310 and 610). After extracting the sugar from the hemicellulose, it is much easier to grind or grind lignocellulosic residue. Therefore, it is preferable to grind or grind the biomass at this stage because it consumes less energy.
In comparison to the non-crushed particles, for example flakes, the crushed particles may be suspended in the liquid of the hydrolysis, and may be circulated from container to container. The crushed particles of different lignocellulosic biomass materials can be processed by the same group of equipment using similar or equal operational parameters. The reduced particle size greatly accelerates the downstream cellulose hydrolysis process. Preferably, the lignocellulosic biomass is comminuted so that the average particle size is in the range of 100 to 10,000 microns, preferably 400 to 5,000, for example, 100 to 400, 400 to 1,000, 1,000 to 3,000, 3,000 to 5,000 or 5,000 to 10,000 microns. Preferably, the lignocellulosic biomass is comminuted such that the average particle size is less than 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 1,000, or 400.
Any hydrolysis methods and systems may be used for cellulose hydrolysis, including enzymatic means and chemical methods. For example, simulated moving bed systems may be used for the hydrolysis of cellulose as disclosed in WO2012061085 (for all purposes, such document is incorporated herein by reference). In one embodiment, the present invention contemplates a method of extracting sugars from the cellulose using the stirred tank hydrolysis system (see Figure 8A). This countercurrent system is advantageous for acidic hydrolysis of cellulose sugars. When multiple tanks are used, the system allows separate temperature control for each individual tank. The system can be adapted for various lignocellulosic biomass materials.
As exemplified in Figure 8A, the stream of the 1700-B lignocellulosic residue having a moisture content of 5 to 85% w / w is milled or ground to a particle size of 400 to 5,000 microns (preferably -1,400 microns) using any industrial mill, including hammer mill and pin mill. If the moisture content is greater than 15%, the crushed lignocellulosic residue is dried to <15% moisture. The hydrolysis system includes a number of n tilt tanks (e.g., n = 1 to 9, preferably 4) serially connected as shown in Figure 8A. The aqueous liquid in the tank, containing acid, dissolved sugar and suspended biomass, is recycled by a high pressure pump with a high flow rate that promotes the stirring of the solution in each tank. The flow line is also adapted with a solid / liquid separation device (e.g., a filter, a membrane or a hydrocyclone) enabling at least part of the liquid and the dissolved molecules, i.e. acid and sugars, to be permeated, producing then a permeate (or filtered) stream. At least part of the feed liquid is retained by the solid / liquid separation device to produce retentate stream, thereby causing the liquid to stir in the reactor. The superazeotropic HCl solution with a minimum acid concentration of 41% is fed to tank n. The permeate from the tank separation unit n is fed into the reactor n-1, while at least part of the retentate is recycled back into the tank η. The permeate from tank n-1 is fed into tank n-2, while the retentate is recycled back into tank n-1 and so on. The permeate exiting the tank 1 of the series is the acid hydrolyzate stream 1720-A. The solids concentration in each stirred tank reactor may be maintained between 3 to 15%, 3 to 5%, 5 to 10% or 10 to 15% w / w. In general, the biomass is retained in the system for 10 to 48 hours. The temperature of each reactor is controlled separately in the range of 5 to 40 ° C.
In some embodiments, the stream of crushed lignocellulosic residue 1700-B is added to the first stage of a series of stirred tank reactors (e.g., 1 to 9 reactors, preferably 4 reactors). The slurry is mixed by stirring or recirculating the broth inside the reactors. At least part of the retentate from the tank 1 is fed into the tank 2; at least part of the retentate from the tank 2 is fed into the tank 3 and so on. Lastly. the acid lignin stream 1720-B exits the tank n into the lignin washing system.
Concentrated hydrochloric acid (> 35%, 36%, 37%, 38%, 39%, 40%, 41%, or preferably 42%) is added in the last reactor in the series, and hydrochloric acid less concentrated (~ 25%, 26%, 27%, 28%, 29%, 30%, or preferably 31%) leaves the first reactor in the series.
In some embodiments, the hydrolyzed sugars leave the first reactor in the series. The 1720-A acid hydrolyzate stream containing the sugar and cellulose sugars is transferred from the last reactor to the second and to the last reactor and so on until the hydrolyzate leaves the first reactor for further purification. In an exemplary reactor system, the hydrolyzate leaving the first reactor has between 8 and 16% of sugars and hydrochloric acid. In some embodiments, the acid hydrolyzate stream 1720-A may contain more than 8%, 9%, 10%, 11%, 12%. 13%, 14%, of dissolved sugars. In some embodiments, the acid hydrolyzate stream 1720-A may contain more than 22%, 24%, 26%, 28%, 30%, 32%, 34%, or 36% HCl. In some embodiments, the acid hydrolyzate stream 1720-A may contain less than 32%, 30%, 28%, 26%, 24%, 22% or 20% HCl.
The temperature in all reactors is maintained in the range of 5 to 80øC, for example, 15 to 60øC, preferably 10 to 40øC. The total retention time of the biomass in all reactors may range from 1 to 5 days, for example 1 to 3 days, preferably 10 to 48 hours.
Preferably, when multiple stirred tank reactors are used, at least a portion of the aqueous and acidic stream of the hydrolyzate leaving an intermediate reactor (e.g., reactor 2 or 3) is mixed with the stream of lignocellulosic residue 1700- B before the 1700-B current is fed into the first reactor. The 1700-B stream is previously hydrolyzed by the aqueous and acidic stream of the hydrolyzate from the intermediate reactor before being brought into contact with the strong acid in the first reactor. Preferably, the prehydrolysis mixture is heated at 15 to 60øC, preferably 25 to 40øC, preferably at most 40øC for 5 minutes to 1 day. preferably 15 to 20 minutes. In one example, the eucalyptus is hydrolyzed using stirred tank reactors. After the initial introduction of eucalyptus wood into the acid, viscosity initially increases as a result of the rapid dissolution of the oligomers into cellulosic sugars, high viscosity impedes the ability to pump and recirculate the aqueous solution through the system; the brief stirring of the stream of the crushed lignocellulosic residue 1700-B with the hydrolyzate of the intermediate reactor at high temperature further accelerates the hydrolysis of the monomer-dissolved oligomers along with the reduction of the viscosity. In another example, the eucalyptus is first contacted with the acid solution exiting stage 2 (i.e., ~33% concentration) at 35 to 50 ° C for 15 to 20 minutes. The previously hydrolyzed eucalyptus can be fed into the system much more rapidly and is further hydrolyzed into the stirred tank reactors.
[00174] Agitated tank reactors can be used for various materials, including hardwood trees. wood from coniferous trees, and bagasse. Exemplary results with the use of a stirred tank system with 4 reactors are given in Figure 8B.
After the hydrolysis of the cellulose, residues remaining in the lignocellulosic biomass form the acid lignin stream 1720-B. The acid lignin stream 1720-B can be further processed and refined to produce unusual lignin compositions as described in more detail herein. The acid hydrolyzate stream 1720-A produced by the hydrolysis of the cellulose is further refined as described below. V. Cellulose Sugar Refining The present invention provides a method for the refining of sugars. Specifically, the present method efficiently refines the sugars from the acid hydrolyzate stream 1720-A which contains a mineral acid (e.g., HCl or H2 SO4). An output cellulose sugar composition according to the embodiments disclosed herein has a high monomeric sugar content.
An exemplary method of refining the sugar of cellulose according to some embodiments of the present invention is provided in Figure 19 (process 1900). The acid hydrolyzate stream 1720-A can then be subjected to solvent extraction Sl 1921, during which the acid hydrolyzate stream 1720-A is contacted with an extractant of the solvent S1, and the acids are extracted from the stream 1720- A to solvent extractant Sl. The resulting mixture is separated into a first stream 1921-A (organic stream) containing the acid and solvent extractant Sl and a second stream 1921-B (aqueous stream) containing sugars from the cellulose.
Optionally, the extraction of the Sl 1921 solvent can be carried out in multiple steps, for example two or more steps. Preferably, extraction of the Sl 1921 solvent is performed in two steps: 1921-1 and 1921-11. In some methods, during extraction 1921-1, the acid concentration in the acid hydrolyzate stream 1720-A is reduced to less than 15%, less than 14% less than 13%, less than 12%, or even lower values, resulting in a partially deacidified hydrolyzate. In some methods, the partially deacidified hydrolyzate is evaporated to remove water, resulting in increased concentration of sugar and acids (e.g., an acid concentration between 13% and 14% w / w). Preferably, the partially deacidified concentrated hydrolyzate is extracted with solvent SI again during extraction 1921-11, resulting in a sugar stream containing less than 5% less than 4% less than 3%, preferably between 2 and 3% acid or values even smaller ones.
In some methods, the 1921-A stream is washed to recover the sugars by extraction with a current of 20 to 25% HCI. In some methods, extraction 1921-A, extraction 1921-B, contact with the first stream 1921-A and re-extraction 1950 are conducted at 40 to 60 ° C, at 45 to 55 ° C, preferably at 50 ° C .
In some methods, the second stream 1921-B is diluted with oligomeric sugars 1931 from the fractionation process downstream 1930 and optionally with additional aqueous streams. When oligomeric sugars 1931 are combined with the second stream 1921-B, the oligomeric sugars are hydrolyzed by the residual acids in the second stream 1921-B (the "secondary hydrolysis" process 1929 in Figure 19).
The second stream 1921-B may optionally be contacted with a strong acid cation exchanger 1922 to convert the salts into their respective acids. The sugar stream is then extracted with an amine extractant to remove mineral acid (s), organic, furfural acids, acid soluble lignin (process 1923 in Figure 19), and in that time the sugar stream is placed in contact with an amine extractant comprising amine and a diluent. The resulting mixture is separated into a third stream 1923-A (organic stream) containing the acid and the amine extractant and a fourth stream 1923-B (aqueous stream) containing sugars from the cellulose. In some methods, contacting the amine extractant is carried out at 50 to 80 ° C, at 55 to 70 ° C, preferably at 70 ° C.
The fourth stream 1923-B is then purified by evaporation to remove the residual diluent which is dissolved in the aqueous phase followed by the ion exchange medium 1924, including a strong acid cation exchanger 1925 to remove amines and optionally followed by a the weak base anion exchanger 1926. The neutralized hydrolyzate in which the amine 1924-A has been removed may be optionally evaporated (process 1927 in Figure 19) to form a sugar stream from the 1928 cellulose, which may be further fractionated to obtain C6 sugars chain monomeric ones, such as glucose (process 1930 in Figure 19). The fractionation separates a stream of monomeric sugars 1932 from a stream of oligomeric sugar 1931.
The monomeric sugar stream 1932 may optionally be evaporated to a higher concentration (process 1933) followed by neutralization with an ion exchanger (process 1934). The stream of neutralized monomeric sugar is optionally evaporated again (process 1935 in Figure 19) to yield a sugar blend of 1936 cellulose.
The acids in the stream in which the 1921-A sugar was excluded can be recovered (process 1940 in Figure 19). At least a portion of the solvent can be purified and recycled again for solvent extraction Sl 1921. A portion of the solvent Sl can be further purified with the use of a solution of lime (e.g., calcium oxide, calcium hydroxide, calcium, or a combination of the aforementioned) and the purified solvent can be recycled again for solvent extraction S1 1921.
The third stream 1923-A can be reextracted with an aqueous solution containing a base (process 1950 in Figure 19). The reextracted amine may be recycled again for extraction of the amine 1923. At least a portion of the solvent may be purified using a solution of lime ((for example, calcium oxide, calcium hydroxide, calcium carbonate, or a combination of the aforesaid) ) (process 1960 in Figure 19) and the purified solvent can be recycled again for extraction of amine 1923.
A more detailed description of these exemplary embodiments of the cellulose sugar refining is provided below. After pre-evaporation After hydrolysis of the cellulose and prior to solvent extraction Sl 1921, the acid hydrolyzate stream 1720-A can optionally be evaporated (process 1910 in Figure 19) to concentrate the sugars and remove the mineral acid (e.g., HCl). For example, the concentration of HCI in the stream (e.g., -33%) is above its azeotrope (-22%), the sugar stream may be first evaporated to remove the acid gas for the azeotrope. The 1720-A stream is then evaporated to the sugar concentration target on the azeotrope, allowing concentration of multiple effects. An evaporated sugar solution having about 30% dry solids content can be obtained by this process.
The evaporated sugar stream (for example, having azeotrope HCI) may be extracted with an extractant (Process 1921 in Figure 19) as described below. Alternatively, the acid hydrolyzate stream 1720-A (for example, having superazeotropic HCI, for example 22 to 33% or more of HCI) can be directly extracted with an extractant without the evaporation step. 2. Extraction The preferred extractant is an extractant containing a solvent S1 (process 1921 in Figure 19). The solvent Sl suitable for use in the extraction is a solvent having a boiling point at 0.1 MPa (1 atm) between 100 ° C and 200 ° C and which forms a heterogeneous azeotrope with water. In some solvents S1, the heterogeneous azeotrope has a boiling point at 0.1 MPa (1 atm) below 100 ° C. For example, the solvent Sl may be a solvent containing an alcohol or kerosene. Examples of alcohols suitable for the production of a S 1 solvent include butanol, isobutanol, hexanol, octanol, decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetracosanol. and triacontanol. Preferably, the solvent Sl is a long chain alcohol (e.g., C6, C8, C10, C10, C14, C16 alcohol) or kerosene. More preferably, the solvent S 1 comprises n-hexanol or 2-ethylhexanol or mixtures of those mentioned. With the maximum preference, the solvent Sl comprises n-hexanol. In some embodiments, the solvent Sl consists essentially of, or consists of, n-hexanol.
Optionally, the solvent S1 comprises one or more additional components. In some methods, the solvent SI comprises one or more ketones, one or more aldehydes having at least 5 carbon atoms, or other alcohol.
[00191] Extraction can be performed in a countercurrent system. Optionally, the extraction can be performed on multiple extraction columns, for example two extraction columns. In the first column, the acid is extracted into the extractant, leaving the acid concentration in the sugar stream below the azeotrope. The extractant leaving column 1 can optionally be washed with azeotropic acid water solution to recover any sugars absorbed in the extractant back into the water solution, which can be recycled in the hydrolysis. The sugar stream, now below the concentration of azeotropic acid, is distilled. The sugar solution is reconcentrated, again obtaining a higher concentration of the acid. The concentrated sugar solution can be extracted with the extractant to remove the residual acid. In general, acid recovery may exceed 97.5%.
The (e.g., 5 to 20, 10 to 15%) portion of the extractant washed with azeotropic acid water solution can be purified using various acid-removal methods, esters. soluble impurities such as furfural and phenols. For example, the extractant can be purified by liming, as disclosed in WO2012018740 (for all purposes, such document is incorporated herein by reference). Preferably, the extractant is treated with lime at 10% concentration. Preferably, the purification is performed using a lime / solvent ratio of 5 to 10: 1. The mixture is heated, for example, for 1 hour at 85 ° C. The residual salts in the mixture may be removed by separation as filtration or centrifugation. The purified extractant is recycled back into the washed extractant. 3. Recovery of acid The first 1921-A stream (extract from the acid-loaded S1 solvent) can be re-extracted with water to recover the acids (process 1940 in Figure 19). After recovery of the acid, an acid free extractant (for example, with less than 0.3 to 0.5% acid content) is returned for extraction. An aqueous solution containing about 15 to 20% of acids is recovered, which can be used in downstream processes, for example, for lignin washing.
Optionally, prior to 1940 acid recovery, the first 1921-A stream can be washed with an aqueous solution (preferably an aqueous acidic solution) to recover any sugars in the stream. In some methods, the first 1921-A stream is washed with a solution of azeotrope acid. Typically, after washing, the amine extractant stream 1923-A has less than 5%, 2%, 1%, 0.5%, 0.2%. 0.1%, 0.05% sugar.
Recovery of the acid can be accomplished by any suitable methods. Preferably, the recovery of the acid is carried out by treating at least a fraction of the re-extract in an evaporation module with at least one low pressure evaporator and with at least one high pressure evaporator.
In some methods, the evaporation module may generate an aqueous solution of superazeotropic HCl and an aqueous solution of subazeotropic HCl. For example, the low pressure evaporator generates the aqueous solution of superazeotropic HCl and the high pressure evaporator generates the aqueous solution of subazeotropic HCl. In some embodiments, "high pressure" indicates superatmospheric pressure, and "low pressure" indicates subatmospheric pressure. "Superazeotropic" and "subazeotropic" indicates a concentration of HCl relative to the azeotropic HCl concentration of a water / HCl mixture at ambient temperature and pressure. "Subazeotropic" [00197] In some methods, the evaporation module generates a subazeotropic acid condensate, and superazeotropic gas HCI. Optionally, the low pressure evaporator generates a subazeotropic acid condensate containing, for example, up to 2%, 1%, 0.1% or 0.01% HCl as it is. Optionally, the high pressure evaporator generates superazeotropic HCI gas. Preferably, the low pressure evaporator generates a subazeotropic acid condensate and the high pressure evaporator generates superazotropic gas HCI.
The recycled HCI stream includes the gaseous HCI from the high pressure evaporator (for example, after absorption in an aqueous solution in an absorber). The gaseous HCI can be mixed with the azeotropic stream to produce 42% acid for hydrolysis in a two stage downwelling film absorber system.
The first stream 1921-A can be further treated with a slurry of lime (e.g., 5%, 10%, 15%, 20%, 25% w / w lime solution). The ratio of the solvent to the lime suspension may be in the range of 4 to 10, 4 to 5, 5 to 6, 6 to 7, 7 to 8, 8 to 9, or 9 to 10. Treatment may be conducted in any suitable device, for example a thermostatic mixing tank. The solution can be heated for at least 1 hour at 80 to 90 ° C. Lime reacts with residual organic acids and esters of organic acids and effectively adsorbs the organic impurities present in the organic phase, such as acid soluble lignin and furfural. as viewed by changing the color from dark to light. Impurities and contaminated lime can be filtered or centrifuged to recover the purified organic phase, which is washed with water and recycled again for solvent extraction Sl 1921. The aqueous stream can be diverted to other aqueous waste streams. Any solid cake capable of being formed by the lime reaction can be used in the wastewater treatment plant as a neutralizing salt for residual acids from the ion exchange regenerations, for example. Secondary hydrolysis Second stream 1921-B (sugar stream where the acid was removed) still contains a residual amount of oligomeric acids and sugars, typically 2-3%. The present method optionally provides a secondary hydrolysis step 1929 wherein the residual acid in the sugar stream catalyzes the conversion of oligomeric sugars into monomeric sugars.
Optionally, second stream 1921-B is combined with a recovered oligomeric sugar stream 1931 from the downstream fractionation step and optionally with additional aqueous streams.
Secondary hydrolysis may be carried out at a temperature above 60 ° C, for example at 70 ° C to 130 ° C, 80 ° C to 120 ° C or 90 ° C to 110 ° C. Preferably, the reaction is carried out at 120 ° C. The secondary hydrolysis may be carried out for at least 10 minutes, between 20 minutes and 6 hours, between 30 minutes and 4 hours or between 45 minutes and 3 hours. Preferably, the reaction is carried out for about one hour.
Typically, secondary hydrolysis under these conditions increases the yield of monomeric sugars with minimal or no degradation of the sugars. Prior to secondary hydrolysis, the sugar stream typically contains 30 to 50% of oligomeric sugars.
After secondary hydrolysis, the sugar chain monomeric sugar content as a fraction of total sugars may be above 70%, 75, 80%, 85% or 90%. Preferably, the sugar stream after the secondary hydrolysis contains 86 to 89% or even more than 90% of monomeric sugars as a fraction of total sugars. Typically, the degradation of the monomeric sugars during the hydrolysis may be below 1%, below 0.2%, below 0.1% or below 0.05%.
The second hydrolysis method may be applied more generally to hydrolyse any oligomeric sugar stream. Preferably, the oligomeric sugar stream (e.g., the second stream 1921-B, the recovered oligomeric sugar stream 1931, or a mixture of the second stream 1921-B and the recovered oligomeric sugar stream 1931) is diluted prior to the second hydrolysis (for example, to a sugar concentration below 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% , 18%, 19%, 20% w / w). In some second hydrolysis methods, the concentration of the acid in the sugar stream can be increased by the addition of an acid in the sugar stream. In some methods, the concentration of the acid to effect the secondary hydrolysis is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%. 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 2.0% or 5.0%. Preferably, the sugar stream contains 0.6 to 0.7% acid and 11% sugar. 5. Extraction of the amine Preferably, the sugar stream from the secondary extraction and / or hydrolysis 1929 is deacidified to exclude the acids in the stream. Optionally, the stream may be first brought into contact with a strong acid cation exchanger 1922 to convert the salts into their respective acids. The sugar stream may then be extracted (for example, countercurrently) with an extractant containing an amine base and a diluent to remove mineral acid (s), organic acids, furfural, acid-soluble lignin (process 1921 in Figure 19). The extraction of the amine can be carried out under the same or similar conditions as described above for the purification of hemicellulose sugar.
The amine extractant may contain 10 to 90% or preferably 20 to 60% w / w of one or a plurality of amines having at least 20 carbon atoms. Such amine (s) may be primary, secondary, and tertiary amine (s). Examples of tertiary amines include tri-laurylamine (TLA, for example, COGNIS ALAMINE 304 from Cognis Corporation, Tucson AZ, USA), tri-octylamine. tri-isooctylamine. tri-caprylylamine and tri-decylamine.
Diluents suitable for use in the extraction of the amine include an alcohol such as butanol. isobutanol, hexanol, octanol, decanol, dodecanol. tetradecanol, pentadecanol, hexadecanol, octadecanol. eicosanol, docosanol, tetracosanol, and triacontanol. Preferably, the diluent is a long chain alcohol (e.g., C6, C8, C10, C10, Cl2, Cl4, Cl6 alcohol) or kerosene. The diluent may have additional components. More preferably, the diluent comprises n-hexanol or 2-ethylhexanol. With maximum preference, the diluent comprises n-hexanol. In some embodiments, the diluent essentially consists of, or consists of, n-hexanol.
Optionally, the diluent contains one or more additional components. In some methods, the diluent contains one or more ketones, one or more aldehydes having at least 5 carbon atoms, or other alcohol.
Preferably, the amine is tri-laurylamine and the diluent is hexanol. Preferably, the amine extraction solution contains tri-laurylamine and hexanol in the ratio of 3: 7.
Extraction of the amine may be carried out at any temperature where the amine is soluble, preferably at 50 to 70 ° C. Optionally, more than one extraction step (for example, 2, 3 or 4 steps) can be used. The ratio between the amine extractant stream (organic phase) and the sugar stream of hemicellulose 1800-A (aqueous phase) may be 0.5 to 5: 1, 1 to 2.5: 1, or preferably 1: 5 to 3.0: 1.
A method of extracting the amine can be applied more generally for the refining or purification of any sugar stream (for example, hemicellulose sugar stream, cellulose sugar stream, a mixed sugar stream), particularly a stream of moderately acidic sugar (for example, containing 1 to 5%, 0.1 to 1%, 1 to 2%, 2 to 3%, 3 to 4%, 5 to 6% weight / weight of acid). The method of extracting the amine according to some embodiments of the invention is particularly useful for the refining or purification of a sugar stream containing impurities. Typical impurities in a sugar stream include ash, acid-soluble lignin, fatty acids, organic acids such as acetic acid and formic acid, methanol, proteins and / or amino acids, glycerol, sterols, abietic acid and waxy materials. Typically, with the use of the amine extraction method, a sugar stream can be purified to have less than 1%, 0.8%, 0.6%, 0.5%, 0.4%, 0.2% weight / weight or less impurities. In some methods, a sugar stream can be purified to have less than 1%. 0.8%, 0.6%, 0.5%, 0.4%, 0.2% weight / weight or less of acids. 8. Reextraction The third stream 1923-A (acid-charged amine extractant) contains mineral and organic acid, as well as impurities extracted from the products of sugar and biomass degradation. The acids may be extracted from the third stream 1923-A in a reextraction step 1950. The reextraction may be carried out under the same or similar conditions as described above with respect to the purification of the sugar from the hemicellulose.
Optionally, prior to 1950 recrystallization, the amine extractant stream 1923-A can be washed with an aqueous solution to recover any sugars in the stream. Typically, after washing, the amine extractant stream 1923-A has less than 5%, 2%. 1%, 0.5%, 0.2%, 0.1%, 0.05% sugars. 9. Purification of the solvent The amine extractant stream. now neutralized upon removal of the acid, can be washed with water to remove the remaining salts from the reextraction (Process 1960 in Figure 19). It is particularly preferred that certain mixed extracts may be partially saturated with water (as with certain alcohols, for example). The washing stream may be combined with the aqueous re-extracting stream. Purification of solvent 1960 may be carried out under the same or similar conditions as described above with respect to the purification of hemicellulose sugar.
The fraction diverted to the purification step (process 1960 in Figure 19) can be treated with a slurry of lime (e.g., 5%, 10%, 15%, 20%, 25% w / w solution of lime). The ratio of solvent to lime suspension may be in the range of 4 to 10.4 to 5, 5 to 6, 6 to 7, 7 to 8, 8 to 9, or 9 to 10. Treatment may be conducted in any suitable device, for example a thermostatic mixing tank. The solution can be heated for at least 1 hour at 80 to 90 ° C. Lime reacts with residual organic acids and esters of organic acids and effectively adsorbs the organic impurities present in the organic phase, such as acid soluble lignin and furfural, as visualized by changing from dark to light color. Impurities and contaminated lime can be filtered or centrifuged to recover the purified organic phase, which is washed with water and recycled back to the amine extraction step (Process 1923 in Figure 19). The aqueous stream may be diverted to other streams of aqueous waste. Any solid cake that can be formed by the lime reaction can be used in the waste water treatment plant as the neutralizing salt for the residual acids from the ion exchange regenerations, for example. 10. Purification of sugar The sugars in the fourth stream 1923-B (deacidified aqueous stream) may be further purified. Purification of the sugar may be carried out under the same or similar conditions as described above with respect to the purification of the sugar from the hemicellulose.
For example, the fourth stream 1923-B may be contacted with a strong acid cation exchanger (SAC) 1925 to remove any residues of metal cations and any residual amines, preferably followed by a base anion exchanger (WBA) 1926 to remove excess protons. The neutralized hydrolyzate in which the 1924-A amine has been removed may have its pH adjusted and evaporated to 25 to 65% and preferably 30 to 40% w / w of sugars dissolved in any conventional evaporator, for example a multi-effect evaporator or a mechanical vapor recompression evaporator (MVR) (process 1927 in Figure 19). Any solvent residue present in the aqueous phase can also be removed by evaporation. For example, the solvent forms a heterogeneous azeotrope with water and can be separated and returned to the solvent cycle. The concentrated sugar solution may be brought into contact with the mixed bed resin system to remove any residual ions or colored bodies. If desired, the now refined sugar solution may be further concentrated by the conventional evaporator or MVR.
The resulting stream of cellulose sugar 1928 is a highly purified sugar solution having a high monomeric ratio, for example about 85 to 95% monosaccharides in relation to the total dissolved sugars. The composition of sugars depends on the composition of the initial biomass. The purity of the stream, in either case, may be sufficient for fermentation and / or catalytic processes using such sugars. 11. Sugar Fractionation The sugar stream of the 1928 cellulose can be fractionated into a 1932 monomeric sugar stream and a 1931 oligomeric sugar stream (process 1930 in Figure 19). The sugar stream of 1928 cellulose is a highly concentrated sugar stream. In some embodiments, the sugar stream of the 1928 cellulose may comprise at least 40%, 45%, 50%, 51%, 52%, 53%, 54%, 55%, 56% or 58% or intermediate or higher concentrations of total sugars. Optionally, stream 1928 includes 40 to 75%, 45 to 60% or 48 to 68% of total weight / weight sugars.
Figure 16 is a simplified flowchart of a sugar fractionation method of cellulose according to an exemplary embodiment of the invention. As shown in process 1610 of Figure 16, in some embodiments, the sugar stream from cellulose 1928 is contacted with an anion exchanger prior to feeding the stream into a chromatographic resin at 1610. The anion exchanger may be an anion exchanger of weak base resin (WBA) or an anion an amine having at least 20 carbon atoms.
The sugar stream of cellulose 1928 (the blend of monomeric and oligomeric cellulosic sugars) is then fed into a chromatographic resin. Optionally, the sugars from the secondary hydrolysis may be incorporated into the sugar stream of the weakly acidic cellulose (e.g., less than 0.5, 0.4, 0.3, 0.2 or 0.1% HCl) 1928.
The chromatographic resin is next fed with an aqueous solution (optionally water) to produce an oligomer rich oligomer 1622 fragment (as compared to total sugars) relative to the 1610 fed mixture and a 1624 monomer fragment rich in monomeric sugars (as compared to total sugars) compared to the 1610 feed (process 1620 in Figure 16). In some embodiments, monomer fragment 1624 may have at least 80, 82, 84, 86, 88, 90, 92, 94, 96 or 98% of monomeric sugars relative to the total (by weight) sugars. The aqueous solution fed to the chromatographic resin in process 1620 may be water from a previous evaporation step, or a sugar stream from the hemicellulose from a pressurized lavage, as described in copending application PCT / US2012 / 064541 (for all purposes , such document is hereby incorporated by reference). In some embodiments, oligomer fragment 1622 includes at least 5, 10, 20, 30, 40, 50% or intermediate or greater percentages of total sugars recovered from the resin fed to 1610.
In some embodiments, the oligomer fragment 1622 may be further processed. For example, the oligomer fragment 1622 may be concentrated or evaporated. In some embodiments, the oligomeric sugars in the oligomer fragment 1622 are hydrolyzed (process 1630), thereby increasing the ratio of monomers and oligomers in oligomer fragment 1622. In some embodiments, hydrolysis 1630 is catalyzed by HCl at the maximum concentration of 1, 5, 1.0, 0.8, 0.7, 0.6 or 0.5%. In some embodiments, hydrolysis 1630 is catalyzed by HCl at the maximum concentration of 1.5, 1.2, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5% by weight. In some embodiments, hydrolysis 1630 is catalyzed by HCl in the concentration of 0.3 to 1.5%; 0.4 to 1.2% or 0.45 to 0.9% w / w. In some embodiments, the hydrolysis 430 is carried out at a temperature between 60 and 150 ° C; between 70 and 140 ° C or between 80 and 130 ° C. A secondary hydrolyzate 1632 enriched with monomeric sugars (in relation to total sugars) may be produced by hydrolysis 1630 of at least a portion of the oligomeric sugars in the oligomer fragment 1622. In some embodiments, the sugars of the secondary hydrolyzate 1632 are used as a portion of the sugar blend fed in 1610.
In some embodiments, the secondary hydrolyzate 1632 contains at least 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90 or 95% monomeric sugars relative to the total sugar content. In some embodiments, the total sugar content of the secondary hydrolyzate 1632 is at least 86, 88, 90, 92, 94, 96, 98, 99, 99.5 or 99.9% by weight of the sugar content.
The monomer fragment 1624 forms a monomeric sugar stream 1932. The monomeric sugar stream 1932 may optionally be evaporated to a higher concentration (process 1933 in Figure 19) before being neutralized using an ion exchanger 1934. neutralized monomeric sugar, as an option, can be evaporated again (process 1935 in Figure 19). The final product is a blend of cellulose sugar in high concentration 1936.
The resulting high concentration cellulose sugar blend 1936 is characterized by one or more, two or more, three or more, four or more, five or more, six or more features which include (i) monosaccharides in a ratio in relation to total dissolved sugars> 0,85; (ii) glucose in a ratio to the total dissolved sugars in the range of 0.40 to 0.70; (iii) 1 to 200 ppm chlorine; (iv) furfural in the amount of up to 0.01% w / w; (v) phenols in the amount of up to 500 ppm; and (vi) a trace amount of hexanol. For example, the sugar blend may be a mixture characterized by a high ratio of monosaccharides (particularly glucose) to dissolved total sugars. In some embodiments, the sugar blend is characterized by a high ratio of monosaccharides to total dissolved sugars, a high ratio of glucose to total dissolved sugars, and 1 to 200 ppm of chlorine. In some embodiments, the sugar blend is characterized by a high ratio of monosaccharides to total dissolved sugars, a high ratio of glucose to total dissolved sugars, and low impurities (e.g., low furfural and phenolic contents). In some embodiments, the sugar blend is characterized by a high ratio of monosaccharides to total dissolved sugars, a high ratio of glucose to total dissolved sugars, low impurities (e.g., low furfural and phenolic contents), and a -hexanol stripping. In some embodiments, the sugar blend is characterized by a high ratio of monosaccharides to total dissolved sugars, a high ratio of glucose to total dissolved sugars, low impurities (e.g., low furfural and phenolic contents) hexanol trace, and 1 to 200 ppm chlorine.
The blend of C 6 sugar in high concentration has high monosaccharide content. In some embodiments, the monomeric sugar stream contains a sugar blend having a ratio of monosaccharides to dissolved total sugars greater than 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0 , 90, 0.95 or 0.99. In some embodiments, the monomeric sugar stream contains a sugar mixture having a ratio of glucose to total dissolved sugars in the range of from 0.40 to 0.70, 0.40 to 0 , 50, 0.50 to 0.60, 0.60 to 0.70, or 0.40 to 0.60. In some embodiments, the monomeric sugar stream contains a sugar blend with a high monosaccharide content and a ratio of glucose to total dissolved sugars in the range of from 0.40 to 0.70.
In some embodiments, the monomeric sugar stream contains a sugar blend having a ratio of xylose to total dissolved sugars in the range of 0.03 to 0.12, 0.05 to 0.10, 0.03 to 0 , 0.05 to 0.075, 0.075 to 0.10, 0.12 to 0.12, 0.12 to 0.15, or 0.15 to 0.20. In some embodiments, the monomeric sugar stream contains a sugar blend having a ratio of arabinose to total dissolved sugars in the range of 0.005 to 0.015, 0.025 to 0.035.0.005 to 0.010, 0.010 to 0.015, 0.015 to 0.020, 0.020 to 0.025, 0.025 to 0.030, 0.030 to 0.035, 0.035 to 0.040, 0.040 to 0.045, or 0.045 to 0.050. In some embodiments, the monomeric sugar stream contains a sugar mixture having a mannose to total dissolved sugar ratio in the range of 0.14 to 0.18, 0.05 to 0.10, 0.10 to 0.15, 0.15 to 0.20, 0.20 to 0.25, 0.25 to 0.30, or 0.30 to 0.40.
The sugar blend has a very low concentration of impurities, such as furfural and phenol. In part of the resulting stream, the sugar blend has furfural in the amount of up to 0.1%, 0.05%, 0.04%, 0.03%, 0.04%, 0.01%, 0.075%, 0.005 %, 0.004%, 0.002% or 0.001% w / w. In part of the resulting stream, the sugar blend has phenols in the amount of up to 500 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm, 60 ppm. 50 ppm. 40 ppm, 30 ppm, 20 ppm, 10 ppm, 5 ppm. 1 ppm, 0.1 ppm. 0.05 ppm, 0.02 ppm or 0.01 ppm. The sugar blend is further characterized by a trace amount of hexanol, for example, 0.01 to 0.02%, 0.02 to 0.05%. 0.05 to 0.1%, 0.1% to 0.2%, 0.2 to 0.5%, 0.5 to 1%, or less than 1, 0.5, 0.2, 0.1, 0.05, 0.02, 0.01, 0.005, 0.002, 0.001%, weight / weight of hexanol. In addition, the sugar mixture is characterized by a trace amount of chlorine, for example, 1 to 10, 10 to 20, 20 to 30, 30 to 40, 40 to 50, 50 to 100, 100 to 150, 150 to 200, 10 to 100, or 10 to 50 ppm chlorine. SAW. Processing of the lignin After the hydrolysis of the cellulose, residues remaining in the lignocellulosic biomass are mainly lignins. The present invention provides methods for producing unusual lignin compositions using a unique refining and processing system. An exemplary method of processing lignin according to some embodiments of the present invention is provided in Figure 20 (Process 2000). 1. Lignin washing The 2020 lignin washing process is designed to remove free sugars and hydrochloric acid remaining in the acid lignin stream 1720-B exiting the last reactor of stirred tank reactors. Optionally, wet milling of the lignin prior to washing is performed. Wet grinding 2010 contributes to increased washing efficiency.
The lignin washing process 2020 may utilize various numbers of washing stages (e.g., two-stage washing). In one method, 2 to 9 or 3 to 10 washing stages are used. Each washing stage may consist of a separator (e.g., a hydrocyclone, screen, filter, membranes) where the mixture of acid, sugar, and lignin solids is separated with the liquid stream moving to the previous stage and with the stream of concentrated lignin solids which moves to the next wash stage. The temperature of each washing stage may be the same or different. For example, the latter stage may be carried out at a slightly higher temperature than in the previous reactors, for example 25 ° C to 40 ° C versus 10 ° C to 20 ° C. Preferably, the method utilizes a 7-stage countercurrent system.
In some methods, each washing stage is performed on a hydrocyclone. The pressure in the hydrocyclones may be from 405 to 90 psig (275.8 to 620.5 kPa). In some methods, two washing streams serve more than two hydrocyclones. For example, the first wash stream has 40 to 43% HCI and the second wash stream has 32 to 36% HCI. The first washing stream may enter the first hydrocyclone and the second wash stream enters the last hydrocyclone. Optionally. the washing temperature increases as the HCl concentration decreases in the wash.
Preferably, the lavage system is countercurrent with a solution of azeotropic acid added to the last wash stage. Lignin containing free sugars and concentrated acid enters the first wash stage. The use of the azeotropic concentration is advantageous because it does not dilute the solution with water, which later necessitates the reconcentration of the acid solution in greater cost.
Optionally, the lavage system is countercurrent with a weak acid lavage (5 to 20% HCl concentration) added to the last wash stage. Lignin containing free sugars and concentrated acid enters the first wash stage.
The multi-stage washing process can remove up to 99% of the free sugars and 90% of the excess acid that enters the washing process along with the lignin. The washed lignin leaves at the last stage for further processing.
As discussed in terms of acid recovery during the sugar refining process, the acid-charged extractant can be re-extracted with water to recover the acids. The recovered acid stream contains about 15 to 23% acid at the temperature of about 50 ° C. Preferably, this recovered acid stream is used for lignin washing.
The acid stream leaving the lignin wash may contain up to 38 to 42% acid, which may be recycled in the hydrolysis.
The lignin leaving the lignin wash may contain 0.5 to 1.5% sugars. The lignin can be compressed to remove excess liquid. The compressed lignin may contain up to 35 to 50% solids, and preferably less than 1% residual sugars and 13 to 20% HCl. 2. Deacidification The washed (and optionally compressed) lignin 2020A is then deacidified by the contact with a hydrocarbon solvent 2040-A (process 2040 in Figure 20). Optionally, wet milling 2030 is performed prior to contact. Moist grinding contributes to increased deacidification efficiency. This increased efficiency translates into reduced contact time and / or reduced ratio between the wash current and the feed stream.
Various hydrocarbon solvents may be used. Preferably, the hydrocarbon has a boiling point at atmospheric pressure between 100 to 250 ° C, 120 to 230 ° C, or 140 to 210 ° C. Examples of hydrocarbons suitable for the present invention include dodecane and various isoparaffinic fluids (for example, ISOPAR G, H, J, K, L, or M of ExxonMobil Chemical, USA). In some methods, the selected isoparaffinic fluid is substantially insoluble in water.
In some deacidification processes, the hydrocarbon solvent is mixed with the lignin to produce a slurry. For example, the hydrocarbon solvent is mixed with hydrocarbon lignin (e.g., Isopar K.) for dry lignin of about 7/1; 9/1; 11/1; 15/1; 30/1; 40/1 or 45/1 w / w (or intermediate or higher ratios). Preferably, 9 parts of the hydrocarbon (eg, Isopar K.) are contacted with 1 part of the washed lignin stream (for example, about 20% of the solid lignin as it is found).
The mixture is then evaporated to remove the acid from the slurry. The acid evaporates together with the hydrocarbon solvent. The evaporated acid can be recovered and recycled in the hydrolysis process.
The deacidified lignin stream may include less than 2%, 1.5%, 1.0%, 0.5%, 0.3%, 0.2% or 0.1% of HCl. Deacidified lignin chain may contain at least 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98% or 99% solid lignin.
[00246] Optionally. the deacidified lignin is dried to remove the hydrocarbon solvent. Preferably, the deacidified and dried lignin has less than 5% solvent and less than 0.5% acid. VII. Lignin Refining [00247] The deacidified and dry lignin may be pelleted to produce fuel pellets, or may be further processed to produce unusual lignin compositions as described below. An exemplary method of refining lignin according to some embodiments of the present invention is provided in Figure 21 (process 2100). 1. Alkaline Solubilization [00248] According to some exemplary embodiments of the present invention, lignin (for example, deacidified lignin) is solubilized to generate an aqueous lignin solution. For example, lignin can be solubilized by a pulping, grinding process. biorrefine selected from kraft pulping, sulphite pulping, caustic pulping, hydromechanical pulping, moderate acid hydrolysis of lignocellulose feedstock, concentrated acid hydrolysis of the lignocellulose feedstock, supercritical or sub-supercritical water hydrolysis of the lignocellulose feedstock , extraction of ammonia from the raw material of lignocellulose. Preferably, the lignin is solubilized using an alkaline solution. In an exemplary embodiment as shown in Figure 19, the deacidified 2040-B lignin or the deacidified and dry lignin 2050-A is dissolved in an alkaline solution to form an alkaline lignin 2110-A solution. The alkaline solubilization 2110 may be performed at a temperature above 100 ° C, 110 ° C, 120 ° C or 130 ° C, or below 200 ° C, 190 ° C, 180 ° C, 170 ° C, 160 ° C C or 150 ° C. Preferably, the alkaline solubilization 2110 is carried out at 160 to 220 ° C, 170 to 210 ° C, 180 to 200 ° C, or 182 to 190 ° C. The reaction may be carried out for a duration of at least 10, 20, 30, 40, 50, 60, 70, 80, 90 or 120 minutes, or less than 10, 9, 8, 7, 6, 5, 5, 5 , 4.5, 4 or 3.5 hours. Preferably, the alkaline solubilization 2110 is carried out for about 6 hours (e.g., 182 ° C). An increase in cooking time and / or cooking temperature contributes to an increase in lignin fragmentation and / or degradation.
[00249] An alkaline concentration of at least 5%, 6%; 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or intermediate or greater percentages (when expressed as 100X base / (base + water) be used for alkaline solubilization. Optionally, the alkaline solution includes ammonia and / or sodium hydroxide and / or sodium carbonate.
After alkaline solubilization, the residual hydrocarbon (eg, IsoPar K or dodecane) from the deacidification is easily separated into a separate organic phase which is decanted and recycled. 2. Purification of the Solvent of Limited Solubility The aqueous lignin solution (for example the lignin alkaline solution) may be processed to prepare the high purity lignin unused material using a solvent of limited solubility (process 2120 in Figure 21). It has surprisingly been found that lignin can be dissolved in a solvent of limited solubility 2120-B (e.g., methyl ethyl ketone), and that lignin purified with the use of a solvent of limited solubility has unexpectedly superior properties. In some embodiments, the solvent of limited solubility is a solvent organic with solubility in water at 20øC below about 30% by weight of the solvent in water.
For example, the alkaline solution may be contacted with a 2120-A acidulant (e.g., HCI) and simultaneously or thereafter may be mixed with a 2120-B limited solubility solvent to form a biphasic system containing lignin acid. Various acidulants known in the art may be used to adjust the pH of the alkaline solution to below 7.0, 6.0, 5.0, 4.0, 3.0, 2.0 or 1.0. Preferably, the pH is about 4.0, for example ~ 3.5 to 4.0. The 2120-A acidulant converts the basic lignin into acid lignin. The lignin is dissolved to form the solvent phase while the water-soluble impurities and the salts remain in the aqueous phase. The lignin in the solvent phase can be washed with water and optionally purified using a strong acid cation exchanger to remove the residual cations.
The solvent of limited solubility must have low solubility in water, the solubility at room temperature must be below 35% by weight, less than 28% by weight, less than 10% by weight. The solvent should form two phases with water, and the solubility of the water in it should be up to 20%, up to 15%. of up to 10%, up to 5% at room temperature. Preferably the solvent should be stable under acidic conditions at the maximum temperature of 100 ° C. Preferably, the solvent should form a heterogeneous azeotrope with water, with a boiling point below 100øC when the azeotrope composition contains at least 50% of the solvent, at least 60% of the solvent relative to the total azeotrope. The solvent should have at least one hydrophilic functional group selected from ketone, alcohol and ether or other polar functional group. Preferably said solvent should be commercially available at low cost.
Examples of suitable solvents for the present invention include methyl ethyl ketone, methyl isobutyl ketone. diethyl ketone. methyl isopropyl ketone, methylpropyl ketone, mesityl oxide, diacetyl, 2,3-pentanedione, 2,4-pentanedione, 2,5-dimethylfuran, 2-methylfuran, 2-ethylfuran, 1-chloro-2-butanone, methyl tert-butyl ether, diisopropyl ether, anisole, ethyl acetate, methyl acetate, ethyl formate. isopropyl acetate, propyl acetate, propyl formate. isopropyl ether, 2-phenylethanol, toluene, 1-phenylethanol, phenol, m-cresol, 2-phenylethyl chlorine, 2-methyl-2H-furan-3-one, γ-butyrolactone. acetal, methyl ethyl acetal, dimethyl acetal. Optionally. the solvent of limited solubility includes one or more esters, ethers and ketones having 4 to 8 carbon atoms.
To obtain high purity solid lignin, the solvent of limited solubility is separated from the lignin (process 2140 in Figure 21). For example, the solvent of limited solubility can be evaporated. Preferably, the solvent of limited solubility can be separated from the lignin by mixing the solvent solution containing acid lignin with water at an elevated temperature (e.g., 75øC, 85øC, 90øC). The precipitated lignin can be recovered, for example, by filtration or centrifugation. The solid lignin can be dissolved in any suitable solvents (for example, phenyl ethyl alcohol) to produce lignin solutions.
Alternatively, the solution of the limited solubility solvent containing acid lignin may be mixed with another solvent (for example, toluene). The solvent of limited solubility can be evaporated while the substitution solvent (for example, toluene) remains in the solution. A solution of lignin in a desired solvent can be prepared. 3. High purity lignin [00257] High purity lignin obtained using the solubility limited solvent purification method has unexpected and superior properties over natural lignins. It has been found that high purity lignin has lower aliphatic hydroxyl group and higher phenolic hydroxyl group, indicating drift or condensation along the side chain and condensation between phenolic fractions. The high purity lignin of the invention is more condensed than the natural lignins or other industrial lignins. The content of methoxy and aliphatic chains is lower and the degree of methylation is very high.
In some embodiments, high purity lignin is characterized by one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more , ten or more, eleven or more, twelve or more, thirteen or more, fourteen or more, fifteen or more, sixteen or more, seventeen or more, eighteen or more, characteristics which include (a) aliphatic hydroxyl group of lignin in the quantity of up to 2 mmol / g; (b) at least 2.5 mmol / g of the phenolic hydroxyl group of the lignin; (c) at least 0.35 mmol / g of the carboxylic hydroxyl group of the lignin; (d) sulfur in the amount of up to 1% w / w; (e) nitrogen in the amount of up to 0.05% w / w; (f) chlorine in the amount of up to 0.1% w / w; (g) 5% degradation temperature greater than 250 ° C; (h) 10% degradation temperature greater than 300 ° C; (i) low ash content; (j) a CaHbOc formula; wherein a is 9, b is less than 10 and c is less than 3; (k) minimum degree of condensation of 0.9; (1) methoxy content less than 1.0; (m) an O / C weight ratio of less than 0.4, (n) at least 97% lignin based on the dry matter; (o) ash content in the amount of up to 0.1% w / w; (p) total carbohydrate content in the amount of up to 0.05% w / w; (q) volatile content in the amount of up to 5% w / w at 200 ° C; and (r) non-molten particulate content in the amount of up to 0.05% w / w.
In some embodiments, high purity lignin is characterized by one or more, two or more, three or more, four or more, five or more, features which include (a) at least 97% lignin based on matter dry; (b) an ash content in the amount of up to 0.1% w / w; (c) total carbohydrate content in the amount of up to 0.05% w / w; (d) volatile content in the amount of up to 5% w / w at 200 ° C; and (e) non-molten particulate content in the amount of up to 0.05% w / w. For example, high purity lignin may be a lignin characterized by (a) at least 97% lignin based on dry matter; (b) ash content in the amount of up to 0.1% w / w; (c) total carbohydrate content in the amount of up to 0.05% w / w; and (d) volatile content in the amount of up to 5% w / w at 200 ° C.
In some embodiments, the high purity lignin of the invention is of high purity. In some cases, high purity lignin is more than 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99, 99, or 99.9% pure. In some embodiments, the high purity lignin of the invention has low ash content. In some cases, high purity lignin has ash content in the amount of up to 5, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0 , 2, 0.1, 0.05, 0.02, 0.01% w / w. In some embodiments, the high purity lignin of the invention has low carbohydrate content. In some cases, high purity lignin has a total carbohydrate content in the amount of up to 0.005, 0.0075, 0.01, 0.015, 0.020, 0.025, 0.030, 0.035, 0.04, 0.045, 0.05, 06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.5, 1.0, 2.0, 5.0% w / w. In some cases, high purity lignin has a volatile substance content at 200 ° C in the amount of up to 0.1, 0.2, 0.5, 1, 2, 3,4, 5, 6, 7, 9.10% w / w.
In some embodiments, the high purity lignin of the invention has low, non-molten particulate content. In some cases, high purity lignin has unmelted particulate content in the amount of up to 0.005, 0.0075, 0.01, 0.015, 0.020, 0.025, 0.030, 0.035, 0.04, 0.045, 0.05, 0 , 0.07, 0.08, 0.09, 0.1, 0.2, 0.5, 1.0, 2.0, 5.0% w / w.
In some embodiments, high purity lignin is characterized by one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more. , ten or more, eleven or more, twelve or more, thirteen or more, features including (a) aliphatic hydroxyl group of lignin in the amount of up to 2 mmol / g; (b) at least 2.5 mmol / g of the phenolic hydroxyl group of the lignin; (c) at least 0.35 mmol / g of the carboxylic hydroxyl group of the lignin; (d) sulfur in the amount of up to 1% w / w; (e) nitrogen in the amount of up to 0.05% w / w; (f) chlorine in the amount of up to 0.1% w / w; (g) 5% degradation temperature greater than 250 ° C; (h) 10% degradation temperature greater than 300 ° C; (i) low ash content; (j) a CaHbOc formula; wherein a is 9, b is less than 10 and c is less than 3; (k) a minimum degree of condensation of 0.9; (1) methoxy content less than 1.0; and (m) an O / C weight ratio of below 0.4. For example, high purity lignin may be a lignin characterized by (a) aliphatic hydroxyl group of lignin in the amount of up to 2 mmol / g; (b) at least 2.5 mmol / g of the phenolic hydroxyl group of the lignin; and (c) at least 0.35 mmol / g of the carboxylic hydroxyl group of the lignin. In some embodiments, high purity lignin is characterized by (a) aliphatic hydroxyl group of lignin in the amount of up to 2 mmol / g; (b) at least 2.5 mmol / g of the phenolic hydroxyl group of the lignin; (c) at least 0.35 mmol / g of the carboxylic hydroxyl group of the lignin, (d) sulfur in the amount of up to 1% w / w, (e) and nitrogen in the amount of up to 0.05% w / w. In some embodiments, high purity lignin is characterized by (a) less than 2 mmol / g of the aliphatic hydroxyl group of lignin; (b) at least 2.5 mmol / g of the phenolic hydroxyl group of the lignin; (c) at least 0.35 mmol / g of the carboxylic hydroxyl group of the lignin. (d) sulfur in the amount of up to 1% w / w, (e) nitrogen in the amount of up to 0.05 w / w% and (f) chlorine in the amount of up to 0.1 w / w%. In some embodiments, high purity lignin is characterized by its thermal degradation properties, for example, a degradation temperature 5% above 250 ° C; a degradation temperature 10% above 300 ° C. In some embodiments, high purity lignin is characterized by a CaHbOc formula; wherein a is 9, b is less than 10 and c is less than 3, a minimum degree of condensation of 0.9, a methoxyl content of less than 1.0, and an O / C weight ratio below 0.4 . In other embodiments, high purity lignin is characterized by an O / C weight ratio below 0.40, 0.39, 0.38, 0.37, 0.36, 0.35, 0.34, 0 , 33, 0.32, 0.31, 0.30, 0.29, 0.28, 0.27, 0.26, 0.25, 0.24, 0.23, 0.22, 0.21 , 0.20, or 0.20 to 0.22, 0.22 to 0.24, 0.24 to 0.26, 0.26 to 0.28, 0.28 to 0.30, 0.32 to 0.34, 0.34 to 0.36, 0.36 to 0.38, or 0.38 to 0.40.
In some embodiments, the high purity lignin of the invention has low content of the aliphatic hydroxyl group. In some cases, high purity lignin has the aliphatic hydroxyl group of lignin in the amount of up to 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 8, 0.9, 1.0, 1.2, 1.4, 1.6, 1.8, 1.9 or 2.0 mmol / g. In some embodiments, the high purity lignin of the invention has a high content of the phenolic hydroxyl group of the lignin. In some cases, high purity lignin has more than 2.0, 2.2, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 or 4.0 mmol / g of the phenolic hydroxyl group of the lignin. In some embodiments, the high purity lignin of the invention has a high content of the carboxylic hydroxyl group of the lignin. In some cases, high purity lignin has greater than 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.60, 0.70, 80, 0.90, 1.0 mmol / g of the carboxylic hydroxyl group of the lignin. In some embodiments, the high purity lignin of the invention has low aliphatic hydroxyl group content, high lignin phenolic hydroxyl group content, and high lignin carboxylic hydroxyl group content. In some cases, the high purity lignin of the invention has an aliphatic hydroxyl group of lignin in the amount of up to 2 mmol / g, at least 2.5 mmol / g of the phenolic hydroxyl group of the lignin, and at least 0.35 mmol / g of the carboxylic hydroxyl group of lignin. In some cases, the high purity lignin of the invention has an aliphatic hydroxyl group of lignin in the amount of up to 1 mmol / g. at least 2.7 mmol / g of the phenolic hydroxyl group of the lignin, and at least 0.4 mmol / g of the carboxylic hydroxyl group of the lignin. In some cases, the high purity lignin of the invention has an aliphatic hydroxyl group of lignin in the amount of up to 0.5 mmol / g, at least 3.0 mmol / g of the phenolic hydroxyl group of the lignin. and at least 0.9 mmol / g of the carboxylic hydroxyl group of the lignin.
In some embodiments, the high purity lignin of the invention has low sulfur content. In some cases, high purity lignin has sulfur in the amount of up to 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 , 1.0, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5.0, 10.0% w / w. In some embodiments, the high purity lignin of the invention has low nitrogen content. In some cases, high purity lignin has nitrogen in the amount of up to 0.005, 0.0075, 0.01, 0.015, 0.020, 0.025, 0.030, 0.035, 0.04, 0.045, 0.05, 0.06, 0 , 0.08, 0.09, 0.1, 0.2, 0.5, 1.0, 2.0, 5.0% w / w. In some embodiments, the high purity lignin of the invention has low chlorine content. In some cases, high purity lignin has chlorine in the amount of up to 0.01, 0.02. 0.05, 0.10, 0.15, 0.20, 0.25, 0.5, 0.75, 1.0, 2.0% weight / chlorine. In some embodiments, the high purity lignin of the invention has low ash content.
The high purity lignin of the invention also has superior thermal properties, such as thermal stability. In some embodiments, the high purity lignin of the invention has a degradation temperature of 5% above 100, 150, 200, 210, 220, 230, 240, 250, 260, 270, 280, 280, 290 or 300 ° C. In some embodiments, the high purity lignin of the invention has a degradation temperature of 10% above 200, 250, 275, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390 or 400 ° C.
In some embodiments, the high purity lignin of the invention may be characterized by a CaHbOc formula; wherein a is 9, b is less than 10 and c is less than 3. In some cases, b is less than 9.5, 9.0, 8.5, 8.0, 7.5 or 7.0. In some cases, c is less than 2.9, 2.7, 2.6 or 2.5. In other embodiments, high purity lignin is characterized by an O / C weight ratio below 0.40, 0.39, 0.38, 0.37, 0.36, 0.35, 0.34, 0.33 , 0.32, 0.31, 0.30, 0.29, 0.28, 0.27, 0.26, 0.25, 0.24, 0.23, 0.22, 0.21, 0 , 20, or 0.20 to 0.22, 0.22 to 0.24, 0.24 to 0.26, 0.26 to 0.28, 0.28 to 0.30, 34, 0.34 to 0.36, 0.36 to 0.38, or 0.38 to 0.40.
In some embodiments, the high purity lignin of the invention has a high degree of condensation. In some cases, the high purity lignin of the invention has a minimum degree of condensation of 0.7, 0.8, 0.9, 0.95, 1.0, 1.1, 1.2, 1.3, 1.4 or 1.5. In some embodiments, the high purity lignin of the invention is characterized with a low methoxyl content. In some cases, the high purity lignin of the invention has a methoxyl content of less than 1.0, 0.9, 0.8, 0.7, 0.6 or 0.5. 4. Downstream process Exemplary anti-solvent process: In some embodiments, an antisolvent is used for desolventization. For example, methyl ethyl ketone (MEK) has solubility of 27.5 grams in 100 grams of aqueous solution (acid lignin dissolved in a solvent of limited solubility, which is MEK in this embodiment). In some embodiments, spraying the lignin dissolved in MEK in the water (e.g. at room temperature) dissolves the MEK in the water. The solubility of lignin in the mixture of water and MEK (at the appropriate ratio water: MEK) is low, so that the lignin precipitates. In some embodiments, the MEK is separated from the mixture by the distillation of its azeotrope (73.5øC, 89% MEK).
[00269] Each solvent / solvent combination represents a further embodiment of the invention. Exemplary solvent / anti-solvent combinations include MEK-water; MEK-decanol and MEK-decane.
In some embodiments, the solvent of limited solubility (eg, MEK; boiling point = 79.6 ° C) is distilled and separated from the lignin dissolved therein. In some embodiments, the distillation includes contacting the solvent of limited solubility with the lignin dissolved therein with a hot gas (e.g., dry spray). Optionally, contact with a hot gas is performed after pre-evaporation, which increases the concentration of lignin in the solvent of limited solubility. In some embodiments, the distillation includes contacting the solvent of limited solubility with the lignin dissolved therein with a hot liquid. In some embodiments, the contacting includes spraying the solvent of limited solubility with the lignin dissolved therein in a hot liquid (optionally, after certain preconcentration). In some embodiments, the hot liquid includes water and / or oil and / or Isopar K. In some embodiments, the hot liquid includes an antisolvent. In some embodiments, the distillation includes contacting the solvent of limited solubility with the lignin dissolved therein with a surface of the hot solid.
In some embodiments, a hot liquid is contacted with the solvent of limited solubility with the lignin dissolved therein. The hydrophilic / hydrophobic properties of the hot liquid affect the surface properties of the separated solid lignin. In some embodiments, in such distillation modalities employing the contacting of the solvent of limited solubility with the lignin dissolved therein with a hot liquid, the chemical nature of the lignin solvent affects the surface properties of the separated solid lignin. In some embodiments, hot liquid influences the nature and availability of the reactive functions in the separated solid lignin. In some embodiments, the nature and availability of the reactive functions in the separated solid lignin contribute to the efficiency of the compounds, for example with other polymers. In some embodiments, the temperature of the hot liquid influences the molecular weight of the separated solid lignin.
Exemplary spinning process: In some embodiments, spraying the lignin dissolved in the solvent of limited solubility by forming a hot liquid and / or contacting with an antisolvent produces lignin in the outside suitable for wet spinning. These processes can be adapted to produce lignin in the form suitable for wet spinning by adjusting various parameters. such as, for example, absolute and / or relative temperatures of the two liquids and / or the concentration of lignin dissolved in the solvent of limited solubility. In some embodiments, the concentration of lignin dissolved in the solvent of limited solubility contributes to the viscosity of the lignin / solvent solution.
Exemplary modifying reagents: In some embodiments, the hot liquid with which the lignin dissolved in the solvent of limited solubility is contacted includes a modifying reagent. Optionally, the hot liquid is the modifying reagent. In some embodiments, upon contact with the hot liquid, the lignin reacts with and / or is coated by the modifying reagent.
Exemplary coating process: Some exemplary embodiments in which the distillation is carried out by contacting the dissolved lignin in the solvent of limited solubility with a surface of the hot solid results in coating the surface of the solid with a lignin layer. According to some embodiments, such a coating serves to encapsulate the surface of the solid. Encapsulation of this type is useful, for example, in the slow release fertilizer formulation and / or the provision of a moisture barrier. In some embodiments, the solid to be coated is supplied as fibers. The resulting coated fibers are useful, for example, in the manufacture of composite materials. In some embodiments, the lignin is dissolved in a volatile solvent (e.g., MEK). The use of a volatile solvent of limited solubility contributes to the coating ability of thermally sensitive solids. In some embodiments, a plasticizer is added to the lignin dissolved in the solvent of limited solubility. Optionally, the plasticizer contributes to improve the resulting coating.
In some embodiments, the lignin dissolved in the solvent of limited solubility is sprayed together with a second polymer having a linear arrangement that causes the formation of mast-like lignin molecules to form. The resulting high aspect ratio copolymer arrangements are useful in structural applications (for example, carbon fibers). VIII. Direct extraction of lignin from lignocellulosic biomass [00276] As already discussed with respect to the extraction of sugars from hemicellulose, the present invention, in one aspect, provides an unusual method of lignin extraction directly from lignocellulosic biomass after extraction of sugars from hemicellulose . The method uses a solvent of limited solubility, and works satisfactorily with biomass particles of varying sizes. Therefore, it is not necessary to grind the particles before the lignin is extracted.
The extraction of the sugars from the hemicellulose of the biomass results in a residue containing lignin. In some methods, the extraction of the sugars from the hemicellulose does not remove a substantial amount of the cellulosic sugars. For example, extraction of sugars from the hemicellulose does not remove more than 1.2, 5, 10, 15, 20, 30, 40, 50, 60% w / w of the cellulose. In some methods, the lignin-containing residue contains lignin and cellulose. In some methods, the lignin-containing residue contains less than 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1% hemicellulose. In some embodiments, the lignin can be directly extracted from the lignocellulosic biomass without the removal of sugars from the hemicellulose.
The lignin extraction solution contains a solvent of limited solubility, an acid, and water. Examples of solvents of limited solubility suitable for the present invention include methyl ethyl ketone. diethyl ketone. methyl isopropyl ketone, methyl propyl ketone, mesityl oxide, diacetyl, 2,3-pentanedione, 2,4-pentanedione, 2,5-dimethylfuran, 2-methylfuran, 2-ethylfuran, 1-chloro-2-butanone. methyl tert-butyl ether, diisopropyl ether, anisole, ethyl ethyl acetate, methyl acetate, ethyl formate, isopropyl acetate, propyl acetate, propyl formate, isopropyl formate, 2-phenylethanol, toluene, 1-phenylethanol, phenol, m 2-phenylethyl chloride, 2-methyl-2H-furan-3-one, γ-butyrolactone, acetal, methyl ethyl acetal, dimethyl acetal, morpholine, pyrrole, 2-picoline, 2,5-dimethylpyridine. Optionally, the solvent of limited solubility includes one or more esters, ethers and ketones having 4 to 8 carbon atoms. For example, the solvent of limited solubility may include ethyl acetate. Optionally, the limited solubility solvent consists essentially of, or consists of, ethyl acetate.
The ratio of the limited solubility solvent to the water suitable for performing the lignin extraction may vary depending on the biomass material and the particular limited solubility solvent used. In general, the ratio of solvent to water is in the range of 100: 1 to 1: 100, for example 50: 1 to 1:50, 20: 1 to 1:20, and preferably 1: 1.
[00280] Various inorganic and organic acids can be used for the extraction of lignin. For example, the solution may contain an inorganic or organic acid such as H2 SO4, HCl, acetic acid and formic acid. The acidic aqueous solution may contain 0 to 10% acid or more, for example 0 to 0.4%, 0.4 to 0.6%, 0.6 to 1.0%, 1.0 to 2.0 %, 2.0 to 3.0%, 3.0 to 4.0%, 4.0 to 5.0% or above these values. Preferably, the aqueous solution for extraction and hydrolysis comprises 0.6 to 5%, preferably 1.2 to 1.5% of acetic acid. The pH of the acidic aqueous solution may be, for example, in the range of 0 to 6.5.
[00281] High temperatures and / or pressures are preferred in lignin extraction. For example, the extraction temperature of the lignin may be in the range of 50 to 300øC, preferably 160 to 200øC, for example 175 to 185øC. The pressure may be in the range of 1 to 10 mPa, preferably 1 to 5 mPa. The solution may be heated for 0.5 to 24 hours, preferably for 1 to 3 hours.
Lignin is extracted in the solvent of limited solubility (organic phase), the remaining solid mostly contains cellulose. After the solid phase is washed to remove the residual lignin, the cellulose can be used to produce pulp, or as the starting material for hydrolysis (acidic or enzymatic). An exemplary method of cellulose hydrolysis of cellulose according to some embodiments of the present invention is shown in Figure 22. In some exemplary embodiments, the hydrolysis of cellulose and the refining of the cellulose sugar may be carried out under the same or similar conditions as described above in Sections IV and V. Residual lignin can be processed and refined using the procedures described above in sections VI and VII.
Optionally, the pH of the solvent is adjusted to 3.0 to 4.5 (e.g., 3.5 to 3.8). In this pH range, the lignin is protonated and easily extracted into the organic phase. The organic phase comprising solvent and lignin is brought into contact with the strong acid cation exchanger to remove residual metal cations. To obtain high purity solid lignin, the solvent of limited solubility is separated from the lignin, for example, evaporated. Preferably, the solvent of limited solubility can be separated from the lignin by mixing the solvent solution containing acid lignin with water at an elevated temperature (e.g., 80 ° C). The precipitated lignin can be recovered, for example, by filtration or centrifugation. The solid lignin can be dissolved in any suitable solvents (for example, phenyl ethyl alcohol) to produce the lignin solutions.
Alternatively, the solution of the limited solubility solvent containing acid lignin may be mixed with another solvent (for example, toluene). The solvent of limited solubility can be evaporated while the substitution solvent (for example, toluene) remains in the solution. A solution of lignin in a desired solvent can be prepared.
Figure 43 is a schematic description of a process for solvent-acid extraction of the lignin from the lignocellulose material in which the hemicellulose has been excluded and for the refining of the lignin soluble in the solvent according to certain embodiments of the invention. This process results in the stream 200, which comprises the solvent and the dissolved lignin, wherein the residual ash is below 1000 ppm, preferably below 500 ppm, wherein the polyvalent cations are below 500 ppm, preferably below 200 ppm relative to lignin (dry basis) and residual carbohydrate is below 500 ppm relative to lignin (dry basis). The solution is free of particulate matter. IX. Treatment of scrap water In order to utilize the energy stored in organic solutes and to comply with environmental requirements, aqueous waste streams containing organic matter can be treated in anaerobic digesters to produce methane, which can be burned. However, anaerobic digesters are known to be contaminated with high levels of sulfate ions at a given level of chemical oxygen demand (COD), and are also limited so that the incoming stream has less than 400 ppm of calcium ions to prevent accumulation of calcium carbonate in the digester. Aqueous waste streams produced at various stages of the inventive stream as described above satisfy such requirements. In addition, as previously disclosed, the reextraction can be performed in several steps that allow better control of the inorganic ion level as opposed to organic matter. X. Lignin Applications The high purity lignin composition according to the embodiments disclosed herein has low ash content, low sulfur and / or phosphorus concentration. Such a high purity lignin composition is particularly suitable for use in catalytic reactions because it contributes to the reduction in fouling and / or contamination of the catalyst. A low sulfur lignin composition is especially desired for use as fuel additives, for example, in gasoline or diesel fuel.
[00288] Some other potential applications for high purity lignin include carbon fiber production, asphalt production, and as a component in biopolymers. Such uses include, for example, additives for drilling oil wells, concrete additives, colorants, dispersants, agricultural chemicals, animal feed, industrial binders, special polymers for the paper industry, auxiliary agents for the recovery of precious metals, wood preservation, non-sulfur lignin products, automotive brakes, wood panel products, bio-dispersants, polyurethane foams, epoxy resins, printed circuit boards, emulsifiers, sequestrants, water treatment formulations, building board strength additive , adhesives, raw material for vanillin, xylitol, and as a source for alcohol paracoumaril, coniferil, sinapil.
Additional embodiments of the invention are disclosed in Sections XI to XIV. XI. Alternative Modes of Lignocellulosic Biomass Processing and Acid Recovery The embodiments disclosed in this section generally relate to the processing of a lignocellulosic substrate for the production of sugars and / or lignin and the recovery of the acid (for example, recovery of HCI).
For example, some embodiments disclosed herein may be used to produce an HCl solution having a concentration above 37% by reextracting the HCl from a solvent-based extractor Sl to generate a solution of subazeotropic HCl followed by distillation above atmospheric pressure to generate the HCI gas. The HCl gas is then absorbed by the subazeotropic HCl solution to produce a HCl solution with concentration above 37%.
First exemplifying method Figure 23 is a simplified flow scheme of a method according to some embodiments. In Figure 23, dashed lines indicate a flow of solvent and the solid lines indicate a flow of HCI (gas or aqueous solution) and / or sugars and / or lignin.
The exemplary method depicted includes hydrolyzing a lignocellulosic material (not shown) with a stream of recycled HCI (e.g., 130 and / or 160) to form an aqueous hydrolyzate (advancing downward from 110 in the drawing) and a solid lignin stream (i.e. a stream that includes solid lignin that advances to the right from 110 in the drawing). Optionally, the solid lignin stream is subjected to grinding (for example after 110 and before 160). In some embodiments, the hydrolyzate includes a sugar and HCl mixture above 20%. 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35% w / w HCl / [HCl and water] and / or the lignin stream includes HCl above 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35% w / w HCl / [HCl and water].
The exemplary method shown also includes extracting (120A and / or 120B) the hydrolyzate with a recycle extractant which includes a solvent S1. The extraction involves at least two extraction steps (120A and 120B). In some embodiments, the 120A extract includes more than 20%, more than 25%, more than 30%, more than 35% or 40% w / w or more of HCl / [HCl and water]. Due to the nature of the solvents S1, acid and water are preferably extracted, to the detriment of the sugars.
Optionally, the method includes increasing a ratio of the monomeric sugar to the oligomeric sugar in the sugar mixture (for example by secondary hydrolysis 124) and polishing (for example by chromatography 128) the blend to produce a polished blend ( 129) containing at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% weight / weight of monomeric sugars in relation to total sugars and less than 1% 0.7%, less than 0.5%, less than 0.3, less than 0.1% or less than 0.01% w / w HCl as it is. In some embodiments, increasing the ratio of the monomeric sugar to the oligomeric sugar in the sugar blend includes the chromatographic separation 128 to separate a monomer fragment from an oligomer fragment. In some embodiments, the monomer fragment is collected as polished sugars 129 and the oligomer fragment is recycled to the secondary hydrolysis 124 as indicated by the upward arrow 128 to 124.
Treatment of the sugar mixture from the hydrolysis 110 by the extractions 120A and 120B together with the secondary hydrolysis 124 and chromatography 128 is described in PCT / US2012 / 024033 (for all purposes, such a document is incorporated herein by reference ).
The exemplary method depicted also includes the (e.g., 130 and / or 132) reextraction of the extract with an aqueous solution to form a deacidified extractant and an aqueous reextraction. The aqueous solution may be water. The aqueous solution may also include one or more solutes.
The exemplary method shown also includes incorporation of the deacidified extractant into the recycle extractant (dashed line 132 to 120B). In some embodiments, at least a portion of the extractant is diverted to the purification 135. Exemplary methods for purification are set forth in PCT / US2011 / 046153 (for all purposes, such document is incorporated herein by reference).
The exemplary embodiment shown includes evaporating a water and HCl mixture from the hydrolyzate prior to extraction (120A and / or 120B). In some embodiments, the evaporated mixture proceeds to the absorber 150. In some embodiments, at least a portion of the evaporated mixture is condensed and routed to the high pressure evaporator 142 (See Figure 24). Optionally, routing the evaporated mixture to the absorber 150 contributes to reducing energy consumption in the evaporation module 145. In some embodiments, the reduction in the volume of liquid or the reduction in the HCl concentration of the stream from 120A to 130 contributes to reducing the energy consumption at 145. In some embodiments, at least a portion of the water and HCl mixture from evaporation 111 (after passage through the absorber 150) washes the solid lignin stream (e.g. at 162 and / or 160).
In some embodiments, the aqueous reextraction produced at 130 is incorporated into the stream of recycled HCI which arrives at the hydrolysis 110. In some embodiments, the reextraction of 130 resumes for the extraction 120A (see Figure 24).
In some embodiments, the increase includes at least one between the chromatographic separation 128 and the (secondary) acid catalyzed hydrolysis 124 of oligomeric sugars. Optionally, the increase includes both the chromatographic separation 128 and the acid catalyzed hydrolysis 124 of the oligomeric sugars.
In some embodiments, the oligomeric sugars are hydrolyzed into monomeric sugars (124) between a pair of at least two extraction steps (e.g., 120A and 120B). In other embodiments, the method includes the hydrolysis of the oligomeric sugars into monomeric sugars (124) after the extraction step (s) or before the extraction step (s) (not shown). In some embodiments, the hydrolysis 124 is catalyzed by the acid remaining in the aqueous stream leaving the extraction 120A. Optionally. the acid is further diluted by an aqueous stream from the chromatography 128 which is transmitted to the hydrolysis 124.
In some embodiments, the increase includes the chromatographic separation 128 performed on the blend after extraction 120A and 120B. In some embodiments, polishing includes the chromatographic separation 128 performed in the blend after extraction 120A and 120B. In some embodiments, the increase and the polish include the chromatographic separation 128 performed on the blend after the extraction 120A and 120B. Optionally, the chromatographic separation 128 generates a sugar fragment and an oligomer fragment. In some embodiments, the sugar fragment acts as a polished blend 129 and the oligomer fragment is rich in oligomeric sugars. In some embodiments, the oligomer fragment is rich in HCl. In some embodiments, the chromatographic separation 128 contributes to the increase and to the polishing. In some embodiments, the increase includes acid catalyzed hydrolysis of the oligomeric sugars and the oligomer fragment is recycled to acid catalyzed hydrolysis 124 (see arrow 128).
[00304] In some embodiments the lignin stream contains sugars. The solid lignin stream is washed with at least a fraction of the reextract or at least a fraction of the diluted reextract. A stream of washed lignin and a wash water are generated. The wash water is included as at least a portion of the recycled HCI stream. In Figure 23, this occurs as the reextractor flows from 132 through the absorber 150 to the second wash of the lignin 162. The solid lignin advances from the second lignin wash 162 to the deacidification 164 and the wash water retreats back to the hydrolysis 110 by the first washing of the lignin 160. In some embodiments, the wash water includes 70%, 75%, 80%, 85%, 90% or 95% w / w, or intermediate or greater percentages of the sugars originally present in the lignin stream (before washing). In some embodiments, the solid lignin stream is washed with at least a portion of the water and HCl mixture of evaporation 111 (e.g., 162 and / or 160). In some embodiments, the at least a portion of the water and HCl mixture passes through the absorber 150 prior to washing the lignin. Exemplary methods for washing a lignin stream with a stream of recycled HCI are described in more detail in PCT / IL2011 / 000424 (for all purposes, such document is incorporated herein by reference). The deacidified lignin 165 contains less than 0.5%, less than 0.3% or less than 0.2% w / w HCL
In some embodiments, at least a reextraction fraction of 132 is treated in an evaporation module 145. The exemplary evaporation module 145 shown includes at least one low pressure evaporator 140 and at least one high pressure evaporator 142. In some embodiments, the evaporation module 145 generates a subazeotropic acid condensate, and superazeotropic gas HCI, and the recycled HCI stream includes the gaseous HCI. Optionally, the low pressure evaporator 140 generates a subazeotropic acid condensate. Optionally, the high pressure evaporator 142 generates superazotropic gas HCI. In some embodiments, the subazeotropic acid condensate contains HCl in the amount of up to 2%, 1%, 0.1% or 0.01% w / w as is. In some embodiments, the recycled HCI stream includes the gaseous HCI of 142 (e.g., after uptake into an aqueous solution in the absorber 150).
In some embodiments, the solid lignin stream is washed with another fraction of the reextract to generate a washed lignin stream and a wash water. In some embodiments, this other fraction includes gaseous HCI of 142 which binds to the reextraction of 132 in the absorber 150 and proceeds to the second washing of lignin 162. In some embodiments, this other fraction comprises at least a portion of the water and HCl mixture of the evaporation 111 which binds to the reextraction of 132 in the absorber 150 and proceeds to the second washing of the lignin 162.
In some embodiments, the evaporation module 145 generates an aqueous solution of superazeotropic HCl and an aqueous solution of subazeotropic HCl. In some embodiments, the at least one low pressure evaporator 140 generates the aqueous solution of superazeotropic HCl and the at least one high pressure evaporator 142 generates the aqueous solution of subazeotropic HCl.
In some embodiments, the lignin stream is deacidified 164 to form deacidified lignin and a deacidification HCI stream, and the incorporation of the deacidification HCI stream into the recycled HCI stream. In Figure 23, the deacidification HCI stream proceeds via low pressure distillation 140 to high pressure distillation 142. In some embodiments, the gaseous HCI of 142 is recycled for hydrolysis 110 by means of the absorbers 150 and / or an aqueous flow of the diluted liquid HCl is recycled to the hydrolysis 110 by reextraction 130. In some embodiments, the deacidification 164 is performed in the presence of an azeotropic HCl solution and / or a superazeotropic HCl solution formed as the bottom of the low pressure distillation 140 and / or a subazeotropic HCl solution formed as the bottom of the high pressure distillation 142. In some embodiments, the deacidification HCI stream of 164 is treated in the evaporation module 145 which contains a high pressure distillation to form a solution of subazeotropic HCl and HCI and incorporate the HCI gas stream into the recycled HCI stream. In some embodiments, the high pressure distillation unit 142 forms the subazeotropic HCl solution and the gaseous HCI stream.
In some embodiments, the retanning 130 and / or 132 is performed with water and / or a diluted (subazeotropic) acidic solution (for example, formed as a condensate from the low pressure distillation 140) and / or a solution of HCl (for example, formed as the bottom of the high pressure distillation 142). In some embodiments, the reextraction is performed in two stages (130 and 132), one diluted stage and one concentrated stage. Optionally, the diluted stage is performed with at least one of water and a dilute acidic solution (for example, formed as a low pressure evaporation condensate 140). In some embodiments, the concentrated stage is performed with at least one solution between an azeotropic HCl solution, a superazeotropic HCl solution (for example, formed as the bottom of the low pressure evaporation 140) and a solution of subazeotropic HCl (for example, formed as the bottom of high pressure evaporation 142).
In some embodiments, the extract of 120A first passes through a reextraction in the concentrated stage 130 forming a concentrated reextraction and then a reextraction in the diluted stage 132 forming a dilute reextraction. In some embodiments, the extract includes sugars and the concentrated reextract comprises at least 70% of such sugars. Optionally. the method includes incorporating the concentrated reextract into the recycled HCI stream (arrow from 130 to 110 in Figure 23). In other exemplary embodiments of the invention, concentrated reextraction is incorporated into the extraction 120A where it optionally contributes to sugar recovery (see Figure 24). Optionally, the incorporation of the concentrated reextracts into the recycled HCI stream contributes to the sugar recovery.
When reextraction is performed in two stages (130 and 132), reducing the concentration of HCI in the reextractor in the second stage (132) contributes to increasing the extraction efficiency of the HCI in that second stage.
In some embodiments, a fraction of the diluted reextracts is treated in the evaporation module 145 containing at least one low pressure evaporator 140 and at least one high pressure evaporator 142 to generate a condensate of subazeotropic acid and gaseous (superazeotropic) HCI, and the method includes incorporating the gaseous HCI into the recycled HCI stream. Optionally, the low pressure evaporator 140 generates the subazeotropic diluted acid condensate. Optionally, the high pressure evaporator 142 generates the gaseous HCI.
In some embodiments, the lignin stream is washed with a dilute re-fraction fraction of 132 (after passage through the absorber 150; Figure 23) and / or with a fraction of the blend of 111 (Figure 24) to generate a stream washed lignin and a wash water containing sugars. In some embodiments, the washed lignin stream proceeds to deacidification 164 and the wash water retreats to be incorporated into the stream of recycled HCI that arrives at the hydrolysis 110.
In some embodiments, the solid lignin stream includes sugars, and the solid lignin stream is washed with a fraction of the diluted reextraction of 132. Optionally, the method includes the uptake of HCl in the fraction of the diluted reextracts of 132 before wash. In some embodiments, the method comprises absorbing the HCI (150) in at least a portion of the 111 mixture prior to washing (see Figure 24).
In some embodiments, the method includes contacting the superazeotropic HCl with a concentrated HCl stream to generate a HCl solution of intermediate concentration and / or the method includes contacting the subazeotropic HCl with a concentrated HCl stream to generate a concentration of HCI solution. In some embodiments, the concentrated HCI stream is a gaseous stream (e.g., 142 and / or 111) and the contact includes absorption in a gas-liquid absorber (e.g. at 150). In some embodiments, the method includes contacting the evaporated water and HCl mixture of said hydrolyzate produced at 111 with at least one other HCl stream. In some embodiments, the method includes washing the solid lignin stream with the HCI solution of intermediate concentration (for example, 150). Additional exemplary method Referring to Figure 23, some embodiments relate to a method which comprises hydrolyzing a lignocellulosic material with a recycled HCI stream containing wash water (optionally a lignin wash water). In some embodiments, the hydrolysis 110 forms an aqueous hydrolyzate and a solid lignin stream. Optionally, the hydrolyzate includes a mixture of sugar and HCl above 20%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35% weight of HCI / [HCl and water] and / or the lignin stream contains HCl above 25%, 26%, 27%, 28%. 29%, 30%. 31%, 32%, 33%, 34% or 35% w / w HCl / [HCl and water] and sugars.
In some embodiments, the method comprises extracting (120A and / or 120B) the hydrolyzate with a recycled (optionally deacidified) extractant which includes a solvent S1. In some embodiments, the extraction involves at least two extraction steps (120A and 120B are shown) to form an extract containing more than 20% or more of 25% w / w HCl / [HCl and water]. In some embodiments, the extraction is performed in a single extraction step.
Optionally, the method includes increasing a ratio of the monomeric sugar to the oligomeric sugar in the sugar blend and polishing the sugar blend to produce a polished blend containing at least 70% monomeric sugars relative to the total sugars and less than 1% w / w HCl (for example, by secondary hydrolysis 124 and / or by chromatography 128).
In some embodiments, the method comprises (130 and / or 132) reextraction of the extract with an aqueous solution to form a deacidified extractant. In some embodiments, the reextraction involves at least two reextraction stages (130 and 132). Optionally. one of these re-extractions is a concentrated stage (130) forming a concentrated reextract and an extract wherein the HCI has been excluded and the other is a dilute stage (132) forming a dilute reextract and a deacidifying extractant.
In some embodiments, the method includes washing the solid lignin stream with a lignin wash stream containing at least a fraction of the reextraction of 132 to produce a washed lignin stream and a wash water. In some embodiments, the lavage stream passes through the absorber 150 where the concentration of HCI is increased by contact with the gaseous HCI.
In some embodiments, the method includes deacidifying the washed lignin stream to form deacidified washed lignin 165 and a deacidifying HCI stream (arrow from 164 to 140).
In some embodiments, the method includes evaporating an aqueous LP-HCl solution (i.e., feeding to 140 from 132) in at least one low pressure evaporator 140 to generate a subazeotropic diluted acid condensate and a solution aqueous solution of superazeotrope HCl and evaporate an aqueous solution of HP-HCl (i.e., feed to 142 from 140) in at least one high pressure evaporator 142 to generate the gaseous HCl and the aqueous solution of subazeotropic HCl. In some embodiments, the aqueous solution of LP-HC1 includes the solution of subazeotropic HCl and / or dilute reextrate and / or the deacidification HCl stream. In some embodiments, the aqueous LP-HC1 solution includes the superazeotropic HCl solution and / or the deacidification HCI stream or the diluted reextract. In some embodiments, the concentrated reextraction stage 130 employs the superazeotropic solution of the low pressure evaporation 140 or the subazeotropic solution of the high pressure evaporation 142 as re-extracting. In some embodiments, the subazeotropic acid condensate from the low pressure evaporation 140 acts as a reextractor in the diluted stage 132 of the reextraction.
In some embodiments, the method includes pre-evaporating a mixture of water and HCl from the hydrolyzate prior to extraction (120A and / or 120B). Various possible uses of this mixture and / or its effects on energy consumption in the evaporation module 145 are set forth above. In some embodiments, at least a portion of the water and HCl mixture from evaporation 111 washes the solid lignin (e.g., 162 and / or 160). In some embodiments, such washing occurs after at least a portion of the mixture passes through the absorber 150.
In some embodiments, the lignin wash stream includes a fraction of the diluted reextraction of 132 and a fraction of said gaseous HCI generated in the high pressure evaporation 142 (arrow from 150 to 162).
In some embodiments, the method includes contacting the superazeotropic HCl with a concentrated HCl stream to generate an intermediate concentration HCl solution. In some embodiments, the method includes contacting the subazeotropic HCI with a concentrated HCI stream to generate an intermediate concentration HCI solution. In some embodiments, the concentrated HCI stream is a gaseous stream (e.g., 142) and the contact includes absorption in a gas-liquid absorber (e.g., 150). In some embodiments, the method comprises contacting the evaporated mixture of water and HCI from the hydrolyzate (arrow 111 to 150, Figure 23 and / or to 142, Figure 24) with at least one other HCI stream. In some embodiments, the washing of the solid lignin stream (e.g. at 162) employs the intermediate concentration HCI solution (e.g., 150).
Exemplary Additional Flow Paths Referring to Figure 24, in some embodiments, the HCl / water streams are transmitted by the low pressure evaporation unit 140 for reextraction 130 and / or deacidification of the lignin 164. In some embodiments, an HCl / water stream is transmitted by the low pressure evaporation unit 140 to the absorber 150 (for example, by mixing with the stream 111 as shown).
Exemplary System [00327] Turning to Figure 23, some embodiments of the present invention provide a system that includes an absorber 150 adapted to receive a gaseous HCI flow from an evaporation module 145, optionally from the high pressure evaporation unit 142 and absorbs the gaseous HCI in an aqueous solution to produce a concentrated solution of HCl. In some embodiments, the absorber 150 absorbs a mixture of HCI and water from the pre-evaporation module 111.
In some embodiments, the system includes a lignin deacidification module (160 + 162 + 164) adapted to contact the concentrated solution of HCI (from 150) with an acid lignin stream in a countercurrent flow. In some embodiments, the system includes a reextraction module (132 and / or 130) adapted to provide the aqueous solution by re-extracting a solvent extract Sl from a hydrolyzed acid of the lignocellulosic material. In some embodiments, the system includes an extraction module (120A and / or 120B) adapted to provide solvent extract Sl to the reextraction module (132 and / or 130). In some embodiments, the system includes a hydrolysis vessel 110 adapted to receive a lignocellulosic material and to release a stream of acid lignin and a hydrolyzate containing sugars and HCl. In some embodiments, the system includes a solvent recycling circuit (see dotted arrow 132 to 120B, with or without purification 135). In some embodiments, the system includes an evaporation module 145 which includes at least one evaporation unit low pressure 140 and at least one high pressure evaporation unit 142. In some embodiments, the system includes a pre-evaporation module 111 configured to evaporate a mixture of water and HCl from the hydrolyzate and transmit at least a portion of the mixture to the absorber 150. In some embodiments, the low pressure evaporation unit 140 is adapted to produce a subazeotropic acid condensate and a superazeotropic HCl solution from a re-extrusion provided by the reextraction module 132. In some embodiments, the high pressure evaporation unit 142 is adapted to produce the gaseous HCl and a solution of subazeotropic HCl.
Exemplary Evaporation Considerations In some embodiments, low pressure evaporation 140 is performed at about 50øC and about 10 kPa (100 millibar) (bottom). In some embodiments, the high pressure evaporation 142 is performed at about 135øC and at about 400 kPa (4 bar) (bottom). XII. Alternative Modes of Cellulose Sugar Refining [00330] Figure 26a is a schematic representation of an exemplary embodiment of a sugar refining module generally indicated as 202. This specification relates to HCI as an exemplifying acid, although other acids can be employed. HCI is specifically mentioned by way of example in this section. Other acids (for example, sulfuric acid) may be used.
Module 202 is a system which includes a secondary hydrolysis unit 240 adapted to receive an inlet stream 131a which includes a sugar blend in an aqueous solution of superazeotropic HCl. And increasing the ratio of monomeric sugars to oligomeric sugars in an output stream 131b and a chromatography component 270 adapted to separate said output stream to produce a monomeric sugar rich monomer fragment 230 and a rich oligomeric fragment 280 oligomeric sugars. In some embodiments, the stream 131a comprises at least 20% w / w sugar in an aqueous solution of HCl. In some embodiments, the oligomer fragment 280 is recycled to the secondary hydrolysis unit 240. Optionally, this recycling contributes to reducing the concentration of acid and / or sugar during the hydrolysis.
In some embodiments, the separation of monomers from oligomers is not absolute. In some embodiments, the monomer fragment 230 includes at least 65%, 70%, 75%, 80%, 85%, 90%, 95%, 97,5% or 99% w / w (or intermediate or greater percentages) of monomeric sugars as a percentage of total sugars. In other embodiments, the oligomer fragment 280 includes at least 65%, 70%, 75%, 80%, 85%, 90%, 95%, 97,5% or 99% w / w (or intermediate or greater percentages) of oligomeric sugars as a percentage of total sugars. In some embodiments, the oligomer fragment 280 includes residual acid.
In some embodiments, the system includes an acid extractor (two extractors 210a and 210b are shown) adapted to contact at least one current between the input current 130 and the output current 131b or 131c with an extractant containing a solvent S 155. In some embodiments, removal of the acid by extraction contributes to reduce re-oligomerization of the monomers and / or to reduce resin damage and / or recycleability of the acid to the main hydrolysis reactor 110 (Figure 25). In some embodiments, the acid extractor comprises at least two acid extractors 210a and 210b arranged in series. In some exemplary embodiments, the arrangement obeys the scheme in the figure, so that the secondary hydrolysis reactor 240 is disposed between any pair of at least two acid extractors (210a and 210b).
In some embodiments, the system includes a filtration unit 250 positioned to filter the outlet stream 131b of the secondary hydrolysis unit 240. In some embodiments, the system includes an ion exchange component 251 adapted to remove the residual acid 156 of the outlet stream 131c or 133. In some embodiments, the delivery of the acid extractor 210b contributes to reducing the amount of residual acid in 156. In some embodiments, the system includes an evaporation unit 260 disposed between the secondary hydrolysis unit 240 and the chromatography component 270. The evaporation unit 260 increases the total sugar concentration in the stream 13le entering the chromatography unit 270. Optionally, the higher concentration of sugars contributes to the monomer separation efficiency of the oligomers at 270. In some embodiments, the system includes an evaporation unit (290; Figure 26c) and said secondary hydrolysis reactor. Unit 290 is described in more depth in the context of Figure 26c.
The module 202 may also be described as a system which includes an acid extractor 210 (two extractors 210a and 210b are shown in the drawing) and a chromatography component 270. In some embodiments, the chromatography component 270 employs technology simulated moving bed (SMB) and / or sequential simulated moving bed (SSMB). In some embodiments, 12 columns are used operating in the SSMB mode. In other exemplary embodiments of the invention, larger or smaller numbers of columns are used. In some embodiments, the chromatography component acts to separate an oligomer rich oligomeric fragment 280 from a monomeric fragment rich in monomeric sugars (enrichment, in this case, in relation to total sugars).
The exemplary exemplary acid extractors 210a and 210b shown are adapted to extract acid from an inlet stream 130, wherein an inlet stream contains a sugar blend in an aqueous solution of superazeotropic HCl. In some embodiments, the sugar blend comprises at least 20%; at least 22%; at least 24%; at least 26% or at least 28% w / w sugar in an aqueous solution of superazeotropic HCl. In some embodiments, the aqueous solution of superazeotropic HCl includes 22, 23, 24, 25, 26, 27, 28, 29, 30% w / w or intermediate or greater percentages of HCl / [HCl and water]. According to further exemplary embodiments of the invention the aqueous solution of superazeotropic HCl includes less than 40%, 38%, 36%, 34% or less of 32% w / w HCl / [HCl and water]. In some embodiments, the adaptation includes regulation of relative flow rates and / or extractant composition and / or temperature conditions. In some embodiments, the extraction is with an extractant which includes an S1 solvent (as defined above) to produce a sugar output stream 131a. In some embodiments, the solvent S1 includes at least one of n-hexanol and 2-ethylhexanol. In some embodiments, the solvent S1 is hexanol and the extraction is carried out at the temperature of 45-55 ° C, optionally at about 50 ° C. In Figure 26a the extractant is shown as solvent 155 for the sake of clarity. In ordinary practice, materials other than the solvent S1 may be present in the extractant. In some embodiments, these additional materials result from the recycling of the extractant.
The chromatography component 270 is adapted to separate the sugars from the outlet stream 131a to produce an oligomeric sugar rich oligomer 280 fragment and a monomeric sugar rich monomer fragment 230. (relative to the inlet stream for the chromatography component 270). In some embodiments, the chromatography component 270 includes an ion exchange resin. Exemplary adaptations include resin choice, flow rate, and elution conditions.
In some embodiments, the acid extractor (210 + 210b) produces a countercurrent flow between the inlet stream 130 and the extractant which includes the solvent 155. At some point during the extraction, the HCI 140 (dashed arrows) is separated from stream 130 and begins to flow along with solvent 155 (solid arrows) in the extractant. In some embodiments, the resulting liquid phase S1 / HC1 contains more than 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38% or 40% w / [HCl / (HCl and water)]. Optionally, the resulting liquid phase S1 / HC1 contains less than 50%, less than 48%, less than 46%, less than 44% or less than 42% w / w [HCl / (HCl and water)].
In some embodiments, countercurrent flow is created by delivering the solvent-containing extractant 155 through the recovery module 150 at one end of the acid extractor bottom 210b while the inlet stream 130 is delivered to one end of the extractor acid 210a. In some embodiments, one or more pumps (not shown) delivers the solvent-containing extractant 155 and / or the inlet stream 130 to the extractor (s) 210. In some embodiments, the acid extractor 210 includes at least one column. Optionally. The pulsed column is a pulsed column of Bateman (Bateman Litwin, The Netherlands).
Bateman's pulsed column includes a wide diameter vertical tube stuffed with upstanding disk & threaded dampers that ensure contact between the downstream 130 and the upstream extractor 155 as they pass through the column. The solvent in the extractant 155 removes at least 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or at least 92% weight or intermediate or greater percentages of acid 140 of stream 130.
In some embodiments, the sugars leave the extractor (s) 210 in a stream wherein the acid has been deleted 131a and access the secondary hydrolysis module 240.
The various exemplary embodiments of the invention relate to the refining of sugar, and considerations regarding the recycling of HCl and / or solvent. In order to avoid confusion, the description below will accompany the sugar stream 130 as it proceeds through the modulus 202 to emerge as the monomer fragment 230. In some embodiments, the monomer fragment 230 is substantially free of acid (e.g. less than 0.1 or less than 0.05% as is.). In other embodiments, the monomer fragment 230 includes less than 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2 % or even less than 0.1% w / w HCl in the state in which it is present.
Resuming at this time for the sequential description of the sugar inlet stream 130 as it moves through the module 202: the stream 130 flows through the extractor 210 (here shown as 210a and 210b) and is extracted with a extracting agent which includes a solvent S1155 and HCl 140. In some embodiments. Stream 130 comprises at least 20% total sugars and a superazeotropic concentration of HCl in an aqueous solution prior to extraction at 210a. These total sugars may include up to 30, 40, 50, 60 or even 70% (by weight) of oligosaccharides or intermediate or greater percentages.
In some embodiments, the sugars emerge from the extractors 210a and 210b as a stream having a reduced acid content 131a. Optionally, the extraction at 210 removes water and / or HCl so that the sugar concentration at 131a is greater than at 130. The ratio of monomeric sugars to oligomeric sugars remains substantially unchanged at this stage. The HCl concentration was reduced by extraction at 210. HCI 140 and solvent Sl 155 exited from the extractor 210a to the recovery module 150. In some embodiments, the HCl 140 and the solvent S 155 are subjected to distillation. The recovery module 150 recycles the separated HCI (dashed arrow) into the hydrolysis reactor 110 and sends the separate solvent 155 to the extractor 210b. In some embodiments, the recovery module 150 employs re-extraction as described in section XI.
In some embodiments, the reduced acid stream 131a flows into the secondary hydrolysis reactor 240 where it is optionally mixed with an oligomer fragment 280 (finely dashed arrow) of the chromatography unit 270. In some embodiments, the hydrolysis 240 is disposed between the acid extractor (s) 210 and the chromatography component 270.
As the oligomer fragment 280 is further diluted relative to total sugars and to HCl than to stream 131a, this blend acts to reduce the sugar concentration (and the HCl concentration) in the secondary hydrolysis 240. Optionally, streams additional aqueous solutions are added at this stage to further reduce the total sugar concentration and / or to reduce acid concentration and / or increase the proportion of oligomeric sugars. Optionally, reduction of the sugar concentration contributes to a lower equilibrium concentration of the oligomers.
For example, the oligomer fragment 280 has additional sugars, primarily oligomeric sugars. The effect of this mixture is that the HCl concentration is reduced to 1.0%. 0.9%, 0.8%, 0.7%, 0.65, 0.5% w / w or less as is. Optionally, the concentration of HCl is reduced to the range of from 0.3% to 1.5%, from 0.4% to 1.2% or from 0.45% to 0.9% w / w. In some embodiments, the total sugar concentration in 240 is reduced to less than 25%, to less than 22%, to less than 19%, to less than 16%, to less than 13% or even to less than 10%. % weight / weight. In some embodiments, the oligomer fragment 280 acts as a return loop of the oligomeric sugar.
After this mixing, the resulting sugar solution in the diluted HCl is then subjected to a secondary hydrolysis reaction in module 240. In some embodiments, this secondary hydrolysis continues for at least 1, at least 2 or at least 3 hours or intermediate or longer periods. Optionally, the duration of this secondary hydrolysis is from 1 to 3 hours, optionally, by about 2 hours. In some embodiments, the temperature is maintained below 150, 140, 130, 120, 110, 100 or below 90øC or intermediate or lower temperatures. In some embodiments, the temperature is maintained between 60 ° C and 150 ° C, between 70 ° C and 140 ° C or between 80 ° C and 130 ° C. In some embodiments, the secondary hydrolysis performed on the 240 module results in the proportion of monomeric sugars of 80 to 90%, optionally 85 to 88%, optionally. about 86% of the total sugars In some embodiments, the secondary hydrolysis carried out in module 240 results in the proportion of monomeric sugars of at least 72%. 74%, 76%, 78%, 80%, 82%. 84%, 86%, 88% or even at least 90% w / w of the total sugars. In some embodiments, the resulting secondary hydrolyzate 131b contains at least 20%, 22, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44% 46%, 48% or 50% w / w of total sugars.
Although a single secondary hydrolysis reactor 240 is represented between the acid extractor (210a and 210b) and the chromatography component 270 for simplification purposes, one or more hydrolysis reactors 240 may be provided.
In some embodiments, the hydrolysis reactor (s) 240 operates at 95, 100, 105, 110, 115, 120 or 125 ° C or intermediate or lower temperatures. In some embodiments, the hydrolysis reactor (s) 240 operates at a pressure of 180, 190, 200, 210 or 220 kPa (1,8, 1,9, 2,0, 2,1 or 2.2 bar). In some embodiments, the hydrolysis reaction continues for 1 to 3 hours, 1.5 to 2.5 hours or 1.7 to 2 hours. In some embodiments, the hydrolysis reaction at 240 is performed at 95 ° C for about 2 hours at atmospheric pressure. In other exemplary embodiments of the invention, the hydrolysis reaction at 240 is carried out at 125 ° C for about 1.7 hour to about 200 kPa (2 bar).
In some embodiments, the resulting secondary hydrolyzate 131b exits the module 240 and proceeds to the filtration unit 250. In some embodiments, the filtration unit 250 is positioned to filter a stream exiting the secondary hydrolysis reactor 240. In some embodiments, the filtration unit 250 removes fine particles from the secondary hydrolyzate 131b. In some embodiments, these particles are periodically washed from the filter and sent back to the extractor (s) 210, optionally using a mixture of acid (e.g., HCI), solvent S1 and water. In some embodiments, the filtration unit 250 includes microfiltration components. In some embodiments, the filtered secondary hydrolyzate 131c proceeds to the anion exchanger 251 disposed between the secondary hydrolysis reactor 240 and the chromatography component 270.
In some embodiments, the anion exchanger 251 includes a weak base anion exchange resin (WBA) and / or an amine including at least 20 carbon atoms. In some embodiments, the anion exchanger 251 separates the residual acid (e.g., HCI) 156 from the stream 131c. The stream 156 contains, according to alternative embodiments, the acid, its salt or a combination of the aforementioned. In some embodiments, the anion exchanger at 251 is an amine and the salt at 156 includes amine chloride. In some embodiments, the use of an amine as an anion exchanger in 251 contributes to the removal of the color from the sugars and / or contributes to reducing downstream sugar polish.
In some embodiments, the regeneration of the anion exchanger is accomplished by treating the HCL-charged anion exchanger with a base. In some embodiments, the base is selected from alkali metal and ammonium hydroxides, bicarbonates and carbonates. In some embodiments, the regeneration forms a chlorine salt of alkali metals or ammonia and the salt is treated to reform the HCl and base. In some embodiments, the base is an ammonium base and the ammonium chlorine is formed and used, at least partially, as a fertilizer.
Optionally, residual HCI or salt 156 is discarded as residue. In some embodiments, more than 80, 82, 84, 86, 88, 90, 92, 94, 96 or more than 98% w / w HCl entering the anion exchanger 251 exits the stream 156. In some embodiments, the concentration of HCl in stream 132 is less than 2.5%, 2%, 1.5%, 1.0%, 0.5%, 0.3%, 0.2%, 0.1%, less than 0.05% or less than 0.01% by weight / weight as is.
In some embodiments, the anion exchanger 251 includes an amine and operates the temperature (s) from 40 to 60øC, optionally about 50øC. In some embodiments, the stream 132 exiting the anion exchanger 251 proceeds to a cation exchanger module 253. In some embodiments, the cation exchanger module 253 separates the divalent cations (e.g., Mg ++ and / or Ca ++) from the stream of sugar. In some embodiments, the sugars 13ld are separately eluted from a divalent cation stream 157. In some embodiments, the anion exchanger 251 and / or cation exchanger module 253 dilutes the total sugars concentration in the stream 13ld leaving the modulus cation exchanger 253. In some embodiments, the concentrated sugar stream 131 per evaporation unit 260. In some embodiments, the evaporation unit 260 is positioned between the anion exchanger 251 and the chromatography component 270. In some embodiments, the evaporation unit 260 operates at a temperature of 60, 70, 80 or 90øC or intermediate or higher temperatures. In some embodiments, the evaporation unit 260 operates at a pressure of 150, 250, 350, 450, 550, 650, 750, 850, or 950 mbar) or intermediate or higher pressures. In some embodiments, the temperature and / or pressure conditions vary in a controlled manner in the evaporation unit 260 during evaporation. Optionally, the contents of the unit 260 are divided into portions and each portion is evaporated under different conditions. In some embodiments, the heat from an anterior portion evaporates a next portion.
[00356] The evaporation unit 260 removes water 142 from the stream 13Id. Optionally, at least a portion of water 142 of the evaporation unit 260 serves as an eluant for the chromatography component 270 and / or as a diluent in the secondary hydrolysis module 240. Evaporation of the water causes the sugar concentration to increase. This increase in sugar concentration may contribute to the oligomerization (re-oligomerization) of sugars, especially if HCl is present. In some embodiments, the removal of 140 and / or 156 HCI contributes to a reduction in reoligomerization. Exemplary modes for reducing such re-oligomerization are discussed in the "Exemplary equilibrium considerations" section.
The concentrated filtered secondary hydrolyzate 13le leaves the evaporation unit 260 with at least 32%, optionally. at least 35% by weight / weight of sugars. In some embodiments, 13ld leaves the evaporation unit 260 between 40% and 75%, between 45% and 60% or between 48% and 68% weight / weight of sugars. In some embodiments, an increase in the sugar concentration contributes to an increase in the chromatographic separation efficiency.
In some embodiments, concentrated filtered secondary hydrolyzate 131 leaves the evaporation unit 260 with at least 30, 40, 50 or 60% w / w or higher percentages of total sugars. The concentrated filtrate secondary hydrolyzate 131 is continued to the chromatography component 270, which optionally includes an ion exchange resin. The concentrated filtrate secondary hydrolyzate 13le includes a lower acid concentration than hydrolyzate 131c due to the removal of the HCl 156 at 251. In some embodiments, the concentrated filtrate hydrolyzate 131e comprises less than 1%, less than 0.9%, less than 0 , 8%, 0.7%, 0.6%, 0.5%. 0.4%, 0.3%, 0.2%, 0.1% or 0.05% w / w HCl as is. The "Exemplary equilibrium considerations" are described in this section.
The stream 131e is fed onto the chromatography resin and eluted using an aqueous solution. In some embodiments, the aqueous solution 142 which is applied from the evaporator 260 may serve as an elution stream. This elution produces a cut of oligomer 280 (fine dashed arrows for the secondary hydrolysis module 240) and a cut of monomer 230.
The chromatographic separation 270 includes contacting the sugar mixture and the elution stream. The elution stream is water or an aqueous solution. In some embodiments, the aqueous solution is formed at another stage of the process. In some embodiments, an aqueous stream of hemicellulose sugars is used. Optionally, the aqueous sugar hemicellulose stream is a byproduct of hot water lignocellulosic material. Methods for pretreating lignocellulosic material with hot water are described in PCT / US2012 / 064541 (incorporated herein by reference for all purposes).
In some embodiments, a cation exchange resin is employed for the chromatographic separation 270. According to some embodiments, the resin is at least partially charged with alkali metal or ammonium cations.
In some embodiments, the cut of monomer 230 contains 80%, 85%, 90%, 95% or 97.5% w / w or intermediate or greater percentages of the sugars that were originally present in the blend 130. In embodiments, such sugars are about 80 to 98%, optionally about 89 to 90% monomeric sugars and about 2 to 20%, optionally, about 10 to 11% w / w of oligomeric sugars. In some embodiments, such sugars are at least 80%, at least 82, at least 84%, at least 86%, at least 88%, at least 90%, at least 92%, at least 94%, at least 96% , at least 98% w / w or intermediate or higher percentages of monomeric sugars out of the total sugars. In some embodiments, the cut of monomer 230 contains at least 20%, at least 22, at least 24%, at least 26%, at least 28%, at least 30%, at least 32%, at least 34% at least at least 36%, at least 38%, at least 40%, at least 42%, at least 44%, at least 46%, at least 48% or at least 50% weight / weight of total sugars. Any sugars that remain in the oligomer cut can be recovered to a large extent in subsequent rounds of recycling. In some embodiments, the sugars remaining in the oligomer cut may be converted from an oligomer-rich blend to a mixture which is primarily monomeric sugars.
Although the refining process has been described with a linear progression for the sake of clarity, in practice it may be partially continuous and / or cyclic.
Optional Additional Refining Components Figure 26b represents additional optional components of module 200 generally depicted as module 204. Optional module 204 further refines output 230 of module 202. Exemplarily shown module 204 includes a desolventiser 272 adapted to remove any remaining residual solvent 155 from the cut of monomer 230. Such a solvent can be recovered by sending the same to the recovery module 150 or to the extraction unit 210 (210a is indicated in the drawing). Sugars continue to purify medium 274 adapted to remove impurities prone to adversely affect downstream fermentation. In some embodiments, the purification medium 274 includes granular carbon optionally provided in a column. Optionally, the granular carbon removes impurities which include color bodies, color precursors, hydroxymethylfurfural, nitrogen compounds, furfural and proteinaceous materials. Each of these materials has the potential to inhibit fermentation.
In some embodiments, the purification medium 274 includes an ion exchange resin. In some embodiments, the ion exchange resin removes any anions and / or cations. In some embodiments, such anions and / or cations include amino acids, organic acids and mineral acids. Optionally, the ion exchange resin includes a combination of strong acid cation resin and weak base anion resins.
In some embodiments, the purification medium 274 polyols the sugars with a mixed bed system using a combination of strong base cation resin and strong base anion resin. In some embodiments, the sugar concentration at this stage is about 34 to 36%. In some embodiments, a concentrator 276 adapted to increase a solids content of the cut of monomer 230 is employed. Concentrator 276 optionally evaporates water. In some embodiments, the resulting refined sugar output 230 'is a solution of 77 to 80% sugar with 70% or more, 80% or more, 90% or 95% w / w or more of the sugars present as monomers.
In some embodiments, a resulting product (e.g., resulting from 230) includes at least 50%, 60%, 65%, 70% or 75% w / w sugar. In some embodiments, the resulting product includes at least 92%, 94%, 96%, 97% or 98% w / w of monomeric sugars relative to the total sugars. In some embodiments, the resulting product includes less than 0.3%, 0.2%, 0.1% or 0.05% w / w HCl as is. Exemplary optional pre-evaporation module Figure 26c represents optional additional components of module 200 generally depicted as module 205. In such embodiments which include the same, optional module 205 is positioned upstream of extractor 210a (Figure 26a) . In some embodiments, the inlet stream 130 (as described above) enters pre-evaporation module 290. Pre-evaporation optionally includes distillation and / or application of vacuum pressure. Pre-evaporation in module 290 produces a gaseous mixture of HCl and water and a modified inlet stream of 13æg. In some embodiments, the modified inlet stream 13lg has a higher sugar concentration and a lower concentration of HCl than the inlet stream 130. For example, in some embodiments, the modulus 290 increases the sugar concentration in the stream of 25 % to 30% w / w. In some embodiments, the 290 module decreases the HCI concentration from 33% to 27% w / w [HCl / (HCl and water)].
In some embodiments, the module 290 operates at a temperature of 50 to 70 ° C, optionally at about 55 to 60 ° C. In some embodiments, the module 290 operates at a pressure of 10 to 20 kPa (100 to 200 mbar), optionally 12 to 18 kPa (120 to 180 mbar), optionally, about 15 kPa (150 mbar). In some embodiments, the evaporation at 290 produces a vapor phase with a higher HCl concentration than in the feed stream 130. According to these embodiments, the pre-evaporation at 290 decreases the HCl concentration by at least 2%, 4%, 6%, 8%, 10%, 12%, 14% or 16% w / w in relation to their concentration at 130 ° C. In some embodiments, preevaporation at 290 increases the total sugar concentration in at least 2%, 4%, 6%, 8%, 10%, 12%, 14% or 16% w / w in relation to their concentration at 130 ° C.
In some embodiments, the vapor phase HCI concentration of 290 is greater than 30, 35, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58 or 60% w / w or intermediate or greater percentages [HCl / (HCl and water)].
According to those embodiments of the invention which include the pre-evaporation module 290, the stream 13lg replaces 130 as an inlet stream for the extractor 210a in Figure 26a.
Exemplary considerations in the use of an amine extractant as an anion exchanger Figure 26d depicts a deacidification system similar to that of Figure 26a with optional or alternative additional components generally indicated as 206. The numbers in Figure 26d which are also used in Figure 26a indicate similar components or chains. Some items depicted in Figure 26a and previously explained herein are not represented in Figure 26d for the sake of clarity. The exemplary embodiment shown is suitable for the embodiments of the invention employing an amine extractant in the anion exchanger 251.
In some embodiments, the filtered secondary hydrolyzate 131c contains 6 to 16%, 7 to 15%, 8 to 14%, 9 to 13% or 10 to 12% w / w of sugars. In some embodiments, the filtered secondary hydrolyzate 131c contains less than 1.2%, 1.1%, 1.0%, 0.9%, 0.8%, or 0.7% w / w HCl in a state in which it is. In some embodiments, the filtered secondary hydrolyzate 131c contains more than 0.2%, 0.3%, 0.4%, or 0.5% w / w HCl in a state in which it is present.
In some embodiments, the amine in 251 is provided as part of an extractant. For example, in some embodiments, the extractant comprises 40 to 70%, 45 to 65%, 48 to 60% or 50 to 55% amine by weight and also includes a diluent. Suitable amines for use in the 251 extract include trilaurylamine (TLA, for example, COGNIS ALAMINE 304, available from Cognis Corporation, Tucson AZ, USA), trioctylamine, tricaprylylamine and tridecylamine. All these are tertiary amines. In other exemplary embodiments of the invention, primary and secondary amines with at least 20 carbon atoms are employed. Diluents suitable for use in the extractant at 251 include long chain alcohols (e.g., hexanol and / or dodecanol). In some embodiments, the diluent contains additional components.
In some embodiments, an organic: aqueous phase ratio of the amine extractant (relative to aqueous phase 131c) in 251 is between 1: 1 and 1: 4; between 1: 1.2 and 1: 3.5; between 1: 1.4 and 1: 3.0, optionally, about 1: 2. In some embodiments, extraction with an amine at 251 occurs in 4 or less, 3 or less, 2 or less or 1 stage (s). In some embodiments, each stage occurs in a mixer-settler. In some embodiments, mixing at a given stage continues for less than 10 minutes, 8 minutes, 6 minutes, 4 minutes or 2 minutes, or intermediate or shorter times. In some embodiments, deposition at a given stage continues for less than 10 minutes, 8 minutes, 6 minutes, 4 minutes, 2 minutes or 1 minute, or intermediate or shorter times. In some embodiments, the extraction with an amine at 251 occurs at 40 ° C to 80 ° C; 45 ° C to 75 ° C; 50 ° C to 70 ° C or about 60 ° C.
In some embodiments, a stream of sugar 132 (e.g., 132a in Figure 26d) leaving 251 contains less than 1,000 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm. less than 300 ppm. less than 200 ppm or less than 100 ppm HCl or intermediate or lower amounts of HCl. In some embodiments, the sugar stream 132 (e.g., 132a in Figure 26d) leaving 251 contains more than 20 ppm, more than 40 ppm, more than 60 ppm or more than 80 ppm, or intermediate or higher amounts of HCl.
In some embodiments, the extract 156 contains amine chloride. In some embodiments, the extract 156 includes residual sugars. Optionally, such sugars are recovered by washing with water.
In some embodiments, the (refined) sugar stream 132a exiting the amine extraction 251 contains only small amounts of amine because of the low amine solubility (e.g., TLA) in aqueous solution. Optionally. the refined 132a is concentrated at about 40% to 80% (or saturation); about 45% to 75% (or saturation) or about 50% to 70%, optionally about 60% w / w sugars (evaporator 260) and / or treated on a 253 cation exchanger prior to chromatographic separation 270. In some embodiments, the cation exchanger 253 removes the amine (e.g., TLA) from refining 132b in stream 157.
In some embodiments, an optional stripping unit 252 evaporates residual hexanol 133 (used as a diluent at 251) from refining 132a. In some embodiments, the recovered hexanol 133 is used in the extraction 210b, as shown. In other exemplary embodiments of the invention, the recovered hexanol 133 is used as part of the diluent in the extractant at 251 (not shown). The hexanol depletion refining 132b proceeds to cation exchanger 253 and / or evaporation 260. Evaporation 260 increases the concentration of sugars to about 60% of sugars and / or removes any remaining hexanol.
Exemplary amine recovery by re-extraction Referring to Figure 26d, amine extraction at 251 yields an extract 156 including an amine chloride salt. In some embodiments, the reextraction 255 produces the regenerated amine 258 and the salts 256. Reextraction 255 employs a base 257 (e.g., NajCCh, NH 3 or NaOH). In some ways. Na2 CO3 serves as the base 257 and CO2 249 is produced. In other exemplary embodiments of the invention, NaOH serves as the base 257 and NaOH is regenerated by electrodialysis by decomposition of the water of salts 256 (NaCl). Contact of an aqueous basic solution (base 257 diluted with salts of recycled portions 256) (indicated as 256r) with extract 156 transforms the amine chloride into regenerated amine 258 and a chloride salt (e.g., NaCl; 256). If Na2 CO3 serves as the base, CO2 249 is also produced. Since the amine (e.g., TLA) is immiscible with water, the regenerated amine 258 separates from the aqueous phase at reextraction 255 and can be easily returned to the anion exchanger 251 for another round of amine extraction. Excess salts 256 are removed as a 256p product stream.
In some embodiments, salts 256 are recovered from reextraction 255 as a NaCl solution of 10%, 12%, 14%, 16%, 18% or 20% w / w or intermediate or greater percentages. In some embodiments, the reextraction 255 puts the extract 156 in contact with a 20% recycled NaCl solution (256 as indicated by the dashed arrow) in which the base 257 (e.g., Na2 CO3) is added. Reextraction 255 produces regenerated amine 258 and salts 256. In some embodiments, a portion of salts 256 is recycled at reextraction 255. The remaining salts 256 are optionally removed as a stream of product. In some embodiments, the ratio of organic phase: aqueous phase at 255 is between 7: 1 and 1: 1; between 6: 1 and 2: 1; between 5: 1 and 3: 1 or between 4.5: 1 and 3.5: 1. In some embodiments, reextraction 255 is conducted in a single step.
In some embodiments, the organic phase including regenerated amine 258 includes <0.3%; <0.25%; <0.2%; <0.15%; <0.1% or <0.05% w / w HCl as is.
In some embodiments, the amount of base 257 (e.g., Na 2 CO 3) is stoichiometric or 10%, 15%, 20%, 25% or 30% weight / weight above stoichiometric or intermediate or lower percentages above stoichiometric relative to HCI at 156 For example, if stream 156 also includes extracted carboxylic acids, the base used should be in an amount sufficient to transfer both the chloride ions and the carboxylic acids to their salt form. In some embodiments, this results in amine regeneration. In some embodiments, the reextraction 255 is conducted at 60 to 100 ° C; 65 to 95 ° C; 70 to 90 ° C or 75 to 85 ° C.
In some embodiments, the organic phase including regenerated amine 258 is washed with an aqueous solution to remove residual salts (e.g., NaCl, and / or organic acid salts) before returning to 251 (not shown).
Exemplary diluent considerations [00385] In some embodiments, stream 131c entering the extraction of amine 251 (to be extracted by the amine) contains residual hexanol 155 from the extraction 210a and / or 210b. For example, the amount of residual hexanol is 0.05%; 0.1%; 0.2%; 0.3%; 0.4% or 0.5% or intermediate amounts in several exemplary embodiments of the invention. As described above, the extraction of amine at 251 employs an extractant which includes amine and diluent. In some embodiments, the diluent component of the extractant includes hexanol. In some embodiments, the concentration of hexanol (as part of the 251 extractant diluent) is 35%, 40%, 45%, 50%, 55% or 60% or intermediate or lower percentages relative to the total extractant at 251. Accordingly with such embodiments, both the refined 132a from the amine extraction 251 and the extract 156 (and the salt product 256) contain small amounts of hexanol. For example, the refining 132a contains 0.3%, 0.4%, 0.5% or 0.6% hexanol in several exemplary embodiments of the invention.
In some embodiments, the salts 256 contain 0.10%, 0.14%. 0.18%, 0.22%, 0.26%, 0.38% in several exemplary embodiments of the invention. In the exemplary embodiments, both the refined 132a and the salts 256 are concentrated and the hexanol 133 in the refined 132a is distilled in the remover 252.
In some embodiments, the hexanol concentration in the extractant is maintained at a desired level (e.g., 44%) by providing the "replacement" hexanol prior to a next amine extraction cycle at 251. The amount of hexanol is, for example, about 1.5% relative to the desired level of hexanol in the extractant. In some embodiments, the replacement hexanol is provided by the distillation of hexanol 133 from the refined 132a and the application of hexanol 133 for extraction of amine 251. In some embodiments, the organic phase including the regenerated amine 258 is washed with an aqueous solution which includes condensed hexanol 133 to combine washing of residual salts and the reintroduction of hexanol.
In other exemplary embodiments of the invention, the amine extractant diluent (for example, TLA) includes kerosene and / or an alcohol of a chain length greater than 10, for example, Cl 2, 4, or 6 as a component primary. According to these embodiments, the hexanol of stream 131c accumulates in the amine extractant. In some embodiments, the hexanol accumulated in the amine extractant is removed by distillation.
Exemplary Carboxylic Acid Considerations [00389] In some embodiments, the sugar stream 131c contains carboxylic acid anions that result from hydrolysis 110 (Figure 25). For example, such carboxylic acids include acetic acid and / or formic acid in various embodiments of the invention.
In some embodiments, a number of proton equivalents in the sugar solution 131c is less than the number of anion equivalents (including chloride). In some embodiments, the solution 131c is treated in a cation exchanger 253 'in the acid form prior to the extraction of amine 251. In some embodiments, the cation exchanger 253' converts the anions into the solution 131c in its acid form. In some embodiments, the cation exchanger 253 'removes organic impurities and / or contributes an enhancement in phase contact and / or phase separation in the extraction of amine 251.
In some embodiments, extraction of amine 251 removes HCI and / or organic acids from sugars in stream 131c. In some embodiments, such removal contributes to a decrease in load on the downstream polishing components. In some embodiments, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% w / w or intermediate or larger percentages of organic acids are removed by extraction of amine 251.
In some embodiments, the reextraction based on (e.g., Na2 CO3) is divided into two stages. In the first stage, the amount of NajCO.i is equivalent to that of the carboxylic acid and only the carboxylic acids are reextracted to produce a solution of its (for example, sodium) salt (s). In the second stage, HCI is reextracted. In this case, the first stage is performed with a base, but not with a recycled NaCl solution. The second stage uses the recycled NaCl as described above herein.
Such carboxylic acid considerations also apply to the removal of HCl when a weak base anion exchange resin is employed at 251. Such weak base anion exchange resin also adsorbs carboxylic acids after treatment with 253 cation exchanger '.
First exemplifying method Figure 27 is a simplified flowchart of a method, according to an exemplary embodiment of the invention, generally represented as 300. Method 300 comprises extracting a sugar blend 310 in an aqueous solution of superazeotropic HCl with an extractant which includes a solvent S1. In some embodiments, the superazeotrope HCI solution includes aqueous solution of 22, 23, 24, 25, 26, 27, 28, 29, 30% w / w or intermediate or greater percentages of HCl / [HCl and water] . In some embodiments, the superazeotrope HCI solution comprises 40, 38, 36, 34 or 32% w / w or intermediate or lower percentages of HCl / [HCl and water].
In some embodiments, the method 300 includes separating a 321 S1 / HC1 liquid phase containing more than 20, 22, 24, 26, 28, 30, 32, 34, 36, 38 or 40% w / w HCl / [HCl and water] and / or less than 50, 48, 46, 44 or 42% w / w HCl / [HCl and water] of the sugar mixture. Optionally, the method 300 includes separating the S1 from the HCl, for example by distillation and / or re-extraction. In some embodiments, such separation is concurrently conducted with the lignin wash 120 (Figure 25) as described in section XI above and copending application WO / 2011/151823 (incorporated herein by reference for all purposes).
In some embodiments, the sugar blend 310 includes the hydrolyzate 130 (Figure 25 or 26a) and / or an acid stream received from the lavage of the extractant Sl from the extract. Optionally, washing the extractor Sl from the extract includes re-extraction.
In some embodiments, the method includes placing a resulting aqueous phase in contact with an anion exchanger and separating an anion exchanger charged with HCI 334 from the sugar blend.
The exemplary method shown 300 includes increasing a ratio of monomeric sugar to oligomeric sugar (of the sugar in the blend) to produce a blend enriched with monomeric sugar 342 containing at least 70, 75, 80, 85, 90, 95, 96 , 97.5 or still 99% w / w or intermediate or higher percentages of monomeric sugars (in relation to total sugars) by weight. In some embodiments, such increase can be achieved by secondary hydrolysis (see 240 in Figure 26a) and / or chromatographic separation (see 270 in Figure 26a). In some embodiments, a combination of these techniques is employed. Thereby, the increase 340 may occur after the separation 322 and / or after the separation 332, as shown.
In some embodiments, the increase 340 includes performing the chromatographic separation (see 270 in Figure 26a). In some embodiments, a feed for the chromatographic separation 270 includes less than 1.0, 0.9, 0.7, 0.5, 0.3 or 0.1% w / w or intermediate or lower percentages of HCl with based on HCl / (HCl and water). In some embodiments, the chromatographic separation 270 includes employing a cation exchange resin for separation. In some embodiments, the cation exchange resin is at least partially charged with alkali metal (e.g., sodium or potassium) and / or ammonium cations. In some embodiments, chromatographic separation 270 includes placing the resin in contact with the sugar blend and with an elution stream. In some embodiments, the elution stream is water or an aqueous solution. In some embodiments, the aqueous solution is formed at another stage of the process. In some embodiments, the aqueous stream includes hemicellulose sugars. Optionally, a stream containing hemicellulose sugars results from the substrate pretreatment 112 (Figure 25) with hot water. Exemplary hot water treatments of substrate 112 are disclosed in copending application No. PCT / US2012 / 064541 (incorporated herein by reference for all purposes). In such embodiments employing a cation exchange resin, the elution includes contacting with an aqueous solution which includes hemicellulose sugars in some cases.
In such embodiments of the invention wherein the increase 340 includes the chromatographic separation (see 270 in Figure 26a) the ratio of monomeric sugar to oligomeric sugar is increased by 80, 82, 84, 84, 86, 88, 90, 92, 94, 96 or 98% w / w or intermediate or greater percentages.
In some embodiments, the hydrolysis occurs between the extraction 320 and the contact 330 (see 240 in Figure 26a). In some embodiments, the 340 increase by hydrolysis 240 increases the ratio of the monomeric sugar to the oligomeric sugar to 72, 74, 76, 78, 80, 82, 88 or 90% w / w or intermediate or greater percentages.
In some embodiments, the chromatographic separation (see 270 in Figure 26a) produces a cut of oligomer (280; Figure 26a) enriched with oligomeric sugars relative to the sugar blend 310 and a monomer cut (230; Figure 26a) enriched with monomeric sugars relative to the sugar blend 310 on a weight basis. In such embodiments of the invention which do not include the contact 330 with an anion exchanger the blend enriched with monomeric sugar may include residual HCI.
In such exemplary embodiments of the invention wherein the rise 340 includes both the secondary hydrolysis 240 and the chromatographic separation 270, the ratio of monomeric sugars and oligomeric sugars in the mixture enriched with monomeric sugar 342 (e.g., cut of monomer 230 in Figure 26a) is 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96 or 98% w / w or intermediate or larger percentages.
In some embodiments, the extraction 320 of the sugar blend 310 concludes before a rise 340 a ratio between the monomeric sugar and the oligomeric sugar in the blend, as shown in Figure 27. In many embodiments of the invention the extraction 320 is less than 100% efficient, so that the blend still contains HCI after extraction 320 is complete. In further exemplary embodiments of the invention, the increase 340 includes hydrolyzing (for example, 240 in Figure 26a) the oligomeric sugars in monomeric sugars before beginning to extract 320 the sugar blend 310 (not shown in Figure 27). This option is represented in Figure 26a if the stream 130 continues directly up to 240.
In some embodiments, the hydrolysis occurs between the separation 322 and the contact 330 (see 240 in Figure 26a). In some embodiments, the chromatographic separation (see 270 in Figure 26a) produces a cut of oligomer (280; Figure 26a) enriched with oligomeric sugars relative to the sugar blend 310 and a cut of sugar-enriched monomer (230; Figure 26a) monomeric with respect to the 310 sugar blend in one on a weight basis.
The exemplary method shown 300 includes separating a liquid phase of S1 / HCl 324 from mixture 310 (for example, by extraction 320). In some embodiments, the liquid phase S1 / HC1 324 includes more than 20, 25, 30, 35 or even more than 40% HCl / [HCl and water]. In some embodiments, S1 / HC1 liquid phase 324 includes less than 50, 48, 46.44 or 42% w / w HCl / [HCl and water].
In some embodiments, the solvent S1 includes n-hexanol or 2-ethylhexanol. Optionally, one of these two solvents is combined with another solvent S1. In some embodiments, the solvent Sl consists essentially of n-hexanol. In some embodiments, the solvent Sl consists essentially of 2-ethylhexanol. Optionally, solvent Sl includes another alcohol and / or one or more ketones and / or one or more aldehydes having at least 5 carbon atoms. In some embodiments, the solvent Sl has a boiling point at 0.1 MPa (1 atm) between 100 ° C and 200 ° C and forms a heterogeneous azeotrope with water, the azeotrope of which has a boiling point at 0.1 MPa ( 1 atm) of less than 100 ° C.
In some embodiments, the extraction 320 includes countercurrent extraction. In some embodiments, the extraction 320 serves to reduce the concentration of HCI to less than 10%. 5%, 2.5% or 1% w / w or intermediate or lower percentages. In some embodiments, the monomer sugar enriched blend 342 contains at least 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48 or 50% w / w or intermediate or higher percentages of total sugars. In some embodiments, such concentration is higher than in the 310 mixture.
In some embodiments, the monomer sugar enriched blend 342 includes less than 25, 20, 15 or 10% or 5%, 3% w / w or less oligomeric sugars (i.e., higher dimers or oligomers) outside of total sugars. In some embodiments, the contact anion exchanger 330 is a weak base resin (WBA). Optionally, the WBA regeneration 335 is in contact with a base. In some embodiments, the base includes a hydroxide and / or a bicarbonate and / or a carbonate of one or more alkali metal and / or ammonia. In some embodiments, regeneration 335 forms an alkali metal chloride and / or ammonium salt and the salt is treated to reform the HCl and base. In some embodiments, the base is an ammonium base and the ammonium chloride is formed as the salt. Optionally, the formation of ammonium chloride adds value to the process because ammonium chloride is useful as a fertilizer.
In some embodiments, the contact 330 occurs after said extraction 320, as shown. In some embodiments, the contact 330 occurs after the secondary hydrolysis 240 (Figure 26a) conducted in the sugar blend 130 (131a). In some embodiments, the contact 330 occurs prior to the chromatographic separation 270 (Figure 26a). In some embodiments, the contact 330 occurs with a stream having acid concentration similar to that of the secondary hydrolysis 240. In some embodiments, the contact 330 reduces the concentration of HCl to less than 1.0, 0.9, 0.7, 0.5 , 0.3 or 0.1% w / w or intermediate or lower concentrations of HCl based on HCl / (HCl and water). In some embodiments, the post-contacting blend 330 is concentrated prior to the chromatographic separation (see 260 and 270 in Figure 26a). Optionally, the absence of acid at this stage contributes to a reduction in the re-oligomerization and / or degradation of sugars to an insignificant level.
In some embodiments, the contacting anion exchanger 330 is an amine comprising at least 20 carbon atoms. In some embodiments, the amine is a tertiary amine, for example, trioctylamine, tricaprylylamine, tridecylamine or trilaurylamine.
In some embodiments, the method 300 includes decreasing a concentration of HCl in the aqueous superabsorbent HCl solution to prepare the sugar blend 310 prior to the extraction 320. In some embodiments, said decrease is a relative decrease of 2,4,6 , 8, 10, 12, 14 or 16% w / w or intermediate or greater relative percentages. Optionally, evaporation at 290 (Figure 27c) contributes to this reduction.
In some embodiments, the method 300 includes increasing a sugar concentration in the sugar blend 310 prior to the extraction 320. In some embodiments, such increase is a relative increase of 2, 4, 6, 8, 10, 12, 14 or 16% w / w or intermediate or greater relative percentages. Optionally, evaporation at 290 (Figure 26c) contributes to this increase.
Product by Exemplary Process Some embodiments relate to a composition produced by a method 300. In some embodiments, the composition comprises at least 50% sugars by weight in a state in which at least 90% of monomeric sugars in relation to total sugars and less than 0,3% of HCl as it is. In some embodiments, the relative monomer concentration in the composition is 92, 94, 96, 97 or 98% w / w or intermediate or greater percentages relative to the total sugars. In some embodiments, the composition includes at least 55, 60, 65, 70 or 75% w / w of total sugars by weight. In some embodiments, the composition includes less than 0.2, 0.1 or 0.05 HCl as it is.
Second exemplary method Figure 28 is a simplified flowchart of a sugar refining method according to another exemplary embodiment of the invention, generally represented as 400. Method 400 includes feeding a resin in a chromatographic mode with a mixture of aqueous low acid sugar which includes monomeric and cellulose oligomeric sugars. In some embodiments, the method includes incorporating the sugars from the secondary hydrolysis (for example, 240 in Figure 26a) into the low aqueous sugar sugar blend. The term &quot; low acid &quot; as used herein and in the corresponding claims indicates less than 0.5, 0.4, 0.3, 0.2 or 0.1% w / w HCl in a state in which . In some embodiments, the sugar blend is provided as an aqueous solution. Optionally, the mixture includes residual solvent Sl. Suitable resins are described in the "Exemplary Chromatography Resins" of that section. Optionally, a strong acid cationic resin is employed.
In some embodiments, the sugar blend comprises at least 40%, 45%, 50%, 51%, 52%, 53%, 54%, 55%, 56% or 58% by weight / wt. Or intermediate concentrations or higher total sugars. Optionally, the sugar blend comprises 40-75% w / w of total sugars by weight, in some embodiments, about 45-60%, in some embodiments, about 48-68% w / w.
The exemplary method shown 400 includes feeding the resin with an aqueous solution (optionally water) to produce a cut of oligomer 422 enriched with oligomeric sugars (as compared to total sugars) with respect to the feed fed into 410 and a cut of monomer 424 enriched with monomeric sugars (in relation to total sugars) relative to the blend fed into 410. In some embodiments, the monomer cut 424 is at least 80, 82, 84, 86, 88, 90, 92, 94 , 96 or 98%, or intermediate or higher percentages of monomeric sugars out of total sugars (by weight).
In some embodiments, the aqueous solution fed to 420 includes water from a previous evaporation step (e.g., 142 in Figure 26a). In some embodiments, the aqueous solution fed to 420 includes a stream of hemicellulose sugars from a pressure wash, as described in copending application PCT / US2012 / 064541 (incorporated herein by reference for all purposes).
Optionally, the cut of oligomer 422 includes at least 5, at least 10, optionally 20, optionally 30, optionally 40, optionally 50% w / w or intermediate or greater percentages of the total sugars recovered from the feed resin in 410.
In some embodiments, the cut of oligomer 422 is subjected to adjustment. In some embodiments, the fit includes hydrolyzing 430 the oligomeric sugars in oligomer cut 422. Other adjustment strategies (not shown) include the concentration and / or evaporation of water. In some embodiments, the adjustment increases the ratio of monomers to oligomers. In some embodiments, hydrolysis 430 is catalyzed by HCl at a concentration of not more than 1.5%; 1.0%; 0.8%. 0.7%, 0.6% or 0.5% w / w or intermediate or lower percentages as is.
In such exemplary embodiments of the invention wherein the adjustment includes hydrolysis 430, a secondary hydrolyzate 432 enriched with monomeric sugars (in relation to total sugars) is produced by the hydrolysis of at least a portion of the oligomeric sugars in the cut of oligomer 422 is produced . Optionally, hydrolysis 430 is conducted in conjunction with hydrolysis 240 (Figure 26a) in a mixture of 131a (Figure 26a) and oligomer cut 422. Optionally, oligomer cut 422 dilutes sugars at 131a and this dilution enhances kinetics of hydrolysis.
In some embodiments, the sugars from the secondary hydrolyzate 432 are used as a portion of the sugar blend fed to 410 as indicated by the up arrow.
In some embodiments, hydrolysis 430 is catalyzed by HCl at a concentration of not more than 1.5%, 1.2%, 1%, 0.9%, 0.8%; 0.7%; 0.6% or 0.5% w / w or intermediate or lower values on a weight basis. In some embodiments, hydrolysis 430 is catalyzed by HCl at a concentration of 0.3 to 1.5%; 0.4 to 1.2% or 0.45 to 0.9% w / w. In some embodiments, the hydrolysis 430 is carried out at a temperature between 60 and 150 ° C; between 70 and 140 ° C or between 80 and 130 ° C.
In some embodiments, the secondary hydrolyzate 432 contains at least 70%; at least 72%; 74%; 76%; 78%; 80%; 82%; 84%; 86%; 88% or 90% w / w; (or intermediate or higher percentages) monomeric sugars in relation to the total sugar content. In some embodiments, the total sugar content of the secondary hydrolyzate 432 is at least 86, 88, 90, 92, 94, 96, 98, 99 or 99.5% w / w or intermediate or greater percentages by weight of the sugar content of the blend fed to 410.
In some embodiments, method 400 includes the 409 sugar blend treatment which includes monomeric and cellulosic oligomeric sugars with an anion exchanger. According to these embodiments, the treated mixture from 409 proceeds to 410, as shown. In some embodiments, the anion exchanger includes a weak base resin (WBA) anion exchanger and / or an anion or an amine having at least 20 carbon atoms.
Third exemplary method Figure 29 is a simplified flowchart of a sugar refining method according to another exemplary embodiment of the invention, generally represented as 500. Method 500 includes hydrolyzing a 530 mixture of oligomeric and monomeric sugars. Specifically, method 500 includes providing a blend of oligomeric and monomeric sugars in a total concentration of at least 20, 22, 24, 26, 28, 30, 32, 34, 36 or 40% by weight / weight or intermediate percentages or greater in an aqueous solution of at least 1.5% HCl and / or less than 38% w / w HCl.
In some embodiments, the blend provided at 510 is 20-38%, 22-36%, 24-30%, or 26-32% w / w HCl. In other exemplary embodiments of the invention, the blend provided at 510 has 1.7 to 6%, 1.9 to 5.5%, 2.1 to 5%, 2.3 to 4.5% w / w HCl In the state it is.
In some embodiments, the blend provided in 510 has 30% total sugars and / or 27% HCl (for example, if pre-evaporation 290 is present, however, extraction 210a is absent). In other exemplary embodiments of the invention, the blend provided at 510 has 25% total sugars and / or 33% HCl (for example, if both pre-evaporation 290 and extraction 210a are absent). In some embodiments, the blend provided in 510 includes at least 4% HCl; at least 6% HCl or at least 8% HCl (by weight). In some embodiments, the blend provided in 510 includes less than 10% HCl; less than 8% HCl; less than 6% HCl or less than 4% HCl (by weight). In some embodiments, the method 500 includes reducing the sugar concentration in the blend to below 5% by 5%; below 22%; below 20%; below 18% or below 16% (by weight). In some embodiments, the HCl concentration remains above 4.6, 8 or 10 after reducing 520.
The exemplary method shown 500 includes the hydrolysis 530. The hydrolysis 530 produces a secondary hydrolyzate 532 enriched with monomeric sugars (in relation to the total sugars).
In some embodiments, the method 500 includes placing the secondary hydrolyzate 532 in contact with an anion exchanger 540. In some embodiments, the 540 contact facilitates separation of 550 of the in-hydrolyzed sugars 532a from the reaction catalyst (e.g., HCl).
In some embodiments, separation 550 includes recovering an aqueous deacidified hydrolyzate 552 from the anion exchanger charged with HCI 554. In some embodiments, the HCI 140 is washed from the charged anion exchanger 554 to regenerate the anions. In some embodiments, such regeneration occurs by washing with a salt forming base such that it includes a chloride salt and not HCI per se.
In some embodiments, the anion exchanger at 540 includes a weak base resin (WBA) anion exchanger and / or an amine having at least 20 carbon atoms.
In some embodiments, the hydrolysis 530 employs a mineral acid, such as, HCl as a catalyst. Optionally, enrichment results from the hydrolysis of at least a portion of the oligomeric sugars in the blend. Optionally, hydrolyzate 532 contains at least 72%, at least 78%, at least 82%, at least 88%, at least 90% or at least 93% w / w of monomeric sugars or intermediate or higher percentages relative to to the total quantity of sugars in it.
In some embodiments, the concentration of HCl in the blend at 510 may be in the range of 2 to 3%, for example 2.5 or 2.6% by weight. In some embodiments, the hydrolysis 530 is catalyzed by 0.5; 0.6; 0.7; 0.8; 0.9; 1.0; 1.1; 1,2; 1,3; 1.4 or 1.5% HCl. 0.3 to 1.5%; 0.4 to 1.2% or 0.45 to 0.9% by weight as is. In some embodiments, hydrolysis 530 is catalyzed by HCl at a concentration of not more than 1.2%.
In some embodiments, the percentage of HCl is reduced by diluting the mixture prior to hydrolysis 530. In some embodiments, the dilution occurs with cut of oligomer 280 (see Figure 26a). In some embodiments, the hydrolysis 530 is carried out at a temperature in the range of 60 ° C to 150 ° C; 70 ° C and 140 ° C or 80 ° and 130 ° C. Optionally. less than 1% non-hydrolytic sugar degradation occurs during hydrolysis 530. In some embodiments, the (sub) total hydrolyzate sugar content 532 is at least 90; 95; 97.5 or 99% (or intermediate or greater percentages) by weight of the sugar content of the blend supplied in 510. In some embodiments, the hydrolyzate 532 enriched with monomeric sugars contains at least 70, at least 75, at least 80, by at least 85 or at least 90% (or intermediate or higher percentages) by weight of monomeric sugars out of the total sugars.
In some embodiments, the method 500 includes evaporating the water 260 (see Figure 26a) from the hydrolyzate 532. Optionally, at least part of such evaporation occurs at a temperature below 70øC or below 80øC. Optionally, at least 63%, optionally at least 70% of the total sugars are monomers after evaporation 260. In some embodiments, less than 10, 5, 2.5 or even less than 1% or intermediate or lower percentages of monomeric sugars in the hydrolyzate 532 oligomerize during evaporation 260 (see Figure 26a).
In some embodiments, the contact 540 is prior to evaporation (see 251 and 260 in Figure 26a) and an aqueous deacid hydrolyzate 132 (Figure 26a) is formed.
In some embodiments, the method 500 includes removing 558 divalent cations from the aqueous deacidified hydrolyzate 552 (optionally, prior to evaporation) with a cation exchanger. Optionally, removal 558 reduces the sugar concentration, since some water is added to wash the sugars from the cation exchanger.
The exemplary method shown 500 includes feeding a resin into a chromatographic mode (see 270 in Figure 26a) with the hydrolyzate 552 (optionally after removal 558) and feeding the resin with an aqueous solution to produce a cut of oligomer 572 enriched with oligomeric sugars (in proportion to total sugars) relative to hydrolyzate 552 and a cut of monomer 574 enriched with monomeric sugars (in proportion to total sugars) relative to hydrolyzate 552. Optionally, feed an aqueous solution which serves to release the sugars from the resin. In some embodiments, the resin is an ion exchange resin.
Referring again to Figure 26a, the feed 13le in the chromatographic separation 270 is enriched with monomeric sugars relative to the feed 131a in the secondary hydrolysis 240, while the monomer cut 230 of the chromatographic treatment 270 is enriched with monomeric sugars in comparison to the feed stream 131 e.
Optionally, the cut of oligomer 572 is recycled (up arrow), so that the blend supplied at 510 includes sugars from an anterior oligomer cut 572.
In some embodiments, the method 500 includes separating an anion exchanger loaded with HCI 554 from the hydrolyzate 532 to form the aqueous deacidified hydrolyzate (i.e., low acid) 552. Optionally, the contact 540 occurs prior to a evaporation procedure (see 260 in Figure 26a) and aqueous deacid hydrolyzate 552 is formed.
Fourth Example Method [00442] Figure 32 is a simplified flowchart of a method for increasing the ratio of monomeric sugars to total sugars in an inlet sugar stream generally indicated as method 1000. In some embodiments, the method 1000 includes hydrolyzing 1010 oligomeric sugars in an inlet sugar stream 1008 to produce an outlet stream 1012 which includes monomeric sugars. In some embodiments, the inlet stream 1008 is a mixture of monomeric and oligomeric sugars. In some embodiments, the stream 1008 includes 30, 40, 50, 60, 70 or 80% by weight of oligomeric sugars (or intermediate or greater percentages) relative to total sugars. In some embodiments, the stream 1008 has a total sugar concentration of 20%, 25%, 30%, 35% or 40% or intermediate or greater concentrations. In some embodiments, the stream 1008 has a concentration of HCl / [HCl and water] of 20%, 25%, 30% or 35% by weight or intermediate or greater concentrations.
In some embodiments, the method 1000 comprises enriching 1020 monomeric sugars from the outlet stream 1012 to produce a monomer cut 1030 by chromatography. In some embodiments, monomer cut 1030 includes 80%, 85%, 90% %, 95%, 97.5% or 99% by weight or more monomers as a percentage of total sugars.
In some embodiments, the method 1000 includes at least two of the following optional actions: (i) evaporating 1009 HCI (and / or water) 1007 from the input sugar stream 1008;
(1011 and / or 1014) the inlet sugar stream 1008 and / or the outlet stream 1012 with an extractant (1013 and / or 1016) which includes a solvent S1; and (iii) contacting the outlet stream 1012 with an anion exchanger 1019 adapted to remove acid from the stream.
[00448] Some modalities include only actions (i) and (ii). Other exemplary embodiments of the invention include only actions (i) and (iii). Still other exemplary embodiments of the invention include only actions (ii) and (iii). Still other exemplary embodiments of the invention include all three actions (i), (ii) and (iii). Among those embodiments of the invention which include action (i), the liquids 1007 optionally include HCl and / or water. Optionally, evaporation 1009 serves to reduce the concentration of HCl and / or to increase the total sugar concentration in stream 1008. Among those embodiments which include action (ii), some embodiments only include contacting the inlet sugar stream 1008 with extractant 1013, which includes a solvent Sl; other embodiments include only contacting 1014 the outlet stream 1012 with the extractor 1016 which includes a solvent Sl; further embodiments include both contacting 1011 the input sugar stream 1008 and contacting 1014 the output stream 1012 with the extractant 1016 containing a solvent S1. As shown in Figure 26a, in some embodiments, the 1016 extractant is reused as 1013 extractant (See 210a and 210b of Figure 26a and the accompanying explanation).
In some embodiments, the method 1000 includes contacting the extractant 1013 and at least one of the evaporation 1009 and the contact 1014 with the anion exchanger 1019.
Fifth Exemplary Method Figure 33 is a simplified flowchart of a sugar refining method according to another exemplary embodiment of the invention represented generally as 1100. Method 1100 includes deacidifying a 1108 sugar mixture in an aqueous solution of HCl superazeotrope. In some embodiments, the aqueous solution of superazeotrope HCI has a concentration of HCl, as previously described herein. Deacidification 1109 includes extracting 1110 with a extractant. which includes a solvent Sl, and then contacting 1112 with an anion exchanger and separating by means of chromatography 1120 a cut of oligomer 1122 enriched in oligomeric sugars relative to the sugar blend 1108 and a cut of 1124 enriched monomer with respect to the sugar blend 1108 based on weight. In some embodiments, the anion exchanger 1112 includes a weak base resin (WBA) and / or an amine comprising at least 20 carbon atoms.
In some embodiments, method 1100 includes hydrolyzing 1130 sugars from oligomer cut 1122 to form monomeric sugars 1132.
Again with reference to Figure 26a, the method 1100 routes the stream 131a to the anion exchanger 251 and forwards the stream 132 to the chromatography component 270 (optionally through the cation exchanger 253 and / or the evaporator 260 as shown) . Exemplary Hybrid Method [00453] Again with reference to Figure 26a, in some embodiments, a portion of stream 131a is routed to the anion exchanger 251 without secondary hydrolysis at 240, while a second portion of stream 131a proceeds through secondary hydrolysis 240 to the anion exchanger 251. Both parties eventually achieve a chromatographic component 270 (the same or different) and the resulting oligomer cut (s) 280 is taken up for the secondary hydrolysis at 240.
Exemplary Solvent Selection Considerations In some embodiments, the extraction 320 (Figure 27) of the sugar mixture with the extractant containing SI results in a selective transfer or selective extraction of HCI from the sugar blend to the extractant to form a SI / HCI liquid phase (324) and a sugar mixture with HCI depletion (e.g., 131a in Figure 26a).
The selectivity of the extraction of HCI over water (Sa / w) can be determined by equilibrating the hydrolyzate with the extractant and analyzing the acid and water concentrations in the equilibrated phases. In this case, the selectivity is: Sa / w = (Ca / Cw) org / (Ca / Cw) aq where (Ca / Cw) aq is the ratio of acid concentration to water concentration in phase (Ca / Cw) org is the ratio of acid concentration to water concentration in the organic phase.
Sa / w may depend on various parameters, such as temperature and the presence of other solutes in the aqueous phase, for example carbohydrates. Selective extraction of acid over water means Sa / w> 1. In some embodiments, extraction 320 of HCI from the sugar blend 310 provides, under at least some conditions, a Sa / w of at least about 1.1, optionally at least about 1.3 and optionally at least about 1.5.
Similarly, the acid selectivity on a carbohydrate (Sa / c) can be determined by equilibrating the hydrolyzate with said extractant and analyzing the molar concentrations of the acid and the carbohydrate in the equilibrated phases. In this case, the selectivity is: Sa / c = (CA / Cc) org / (CA / Cc) aq.
(Ca / Cc) aq is the ratio of acid concentration to carbohydrate (or carbohydrate) concentration in the aqueous phase and (Ca / Cc) org is the ratio of acid concentration to concentration of carbohydrate (or carbohydrate) in the organic phase.
Sa / c may depend on various parameters, such as temperature and the presence of other solutes in the aqueous phase, for example, HCl. The selective extraction of acid on carbohydrate means Sa / c> 1. In some embodiments, the extraction 320 of HCI from the sugar mixture 310 by the extractant has, under at least some conditions, a Sa / c of at least about 2, optionally at least about 5 and optionally at least about 10.
[00463] N-hexanol has a relatively high Sa / w and a relatively low Sa / c. 2-ethyl-1-hexanol has a relatively low Sa / w and a relatively low Sa / c.
These characteristics of the two hexanols caused previous efforts to utilize them in the context of separating sugars from HCI to concentrate on the combination of two among them, or in the use of one of the same in combination with a solvent (see, for example, the document under US 4,237,110 by Forster et al.).
In some embodiments, n-hexanol or 2-ethyl-1-hexanol is employed as the sole solvent S1 in the extraction 320.
Exemplary primary hydrolysis efficiency In some embodiments, at least 70 wt% (optionally, greater than 80, 90, 95 wt%) of polysaccharides in the lignocellulosic substrate 112 hydrolyze to soluble carbohydrates in the hydrolysis reactor 110. In In some embodiments, the concentration of soluble carbohydrates in the hydrolysis medium increases with the progress of the hydrolysis reaction.
Exemplary extractant considerations [00467] Optionally, the extractant comprises a mixture of an alcohol and the corresponding alkyl chloride. Optionally, the extractant includes hexanol and hexyl chloride. In some embodiments, the extractant includes 2-ethyl-1-hexanol and 2-ethyl-1-hexyl chloride. Optionally, the extractant includes hexanol, 2-ethyl-1-hexanol, hexyl chloride and 2-ethyl-1-hexyl chloride. Optionally, the alcohol / alkyl chloride weight ratio is greater than about 10, optionally greater than about 15, optionally greater than about 20, and optionally greater than about 30. In some embodiments, the extractant also includes water. In some embodiments, a different carbohydrate impurity is selectively extracted in the extractant, causing purification of the carbohydrate in extract 131a (Figure 26a). Optionally, the degree of selective extraction varies so that 30%, optionally 40%, optionally 50%, optionally 60%, optionally 70%; optionally 80%; optionally 90% or intermediate or greater percentages are achieved.
Exemplary selective transfer parameters Optionally, extraction 320 selectively transfers HCI from the sugar mixture 310 to the extractant to form the liquid phase 131 and I / HCI 324 extract. In some embodiments, at least 85% of the HCl at least 88%, at least 92% or at least 95% (by weight) are transferred to the extractant from the sugar mixture. In some embodiments, the extract 131a contains residual HCI. Optionally, residual HCI is equivalent to about 0.1 to about 10% of the HCl in the sugar mixture 310, optionally, about 0.5 to about 8% and optionally about 2 to about 7% by weight .
Exemplary weight ratios In some embodiments, a total soluble cut-off carbohydrate concentration of oligomer 280 or 422 ranges from 1% to 30%, optionally from 2% to 20%, and optionally from 3% to 10% by weight. In some embodiments, the cut-off HCI concentration of oligomer 422 is less than 0.2%. less than 0.1% or less than 0.05% by weight.
Exemplary secondary hydrolysis conditions In some embodiments, hydrolysis 430 (Figure 28) and / or 340 (Figure 27) of oligomer cut oligomer 422 (Figure 28) is conducted at a temperature greater than 60 ° C, optionally between 70 ° C and 130 ° C, optionally between 80 ° C and 120 ° C and optionally between 90 ° C and 110 ° C. In some embodiments, the hydrolysis 430 and / or 340 proceeds for at least 10 minutes, optionally between 20 minutes and 6 hours, optionally between 30 minutes and 4 hours and optionally between 45 minutes and 3 hours.
In some embodiments, the secondary hydrolysis under these conditions increases the yield of monomeric sugars with little or no sugar degradation. In some embodiments, the monomers as a fraction of total sugars are greater than 70%, optionally greater than 80%, optionally greater than 85% and optionally greater than 90% by weight following the hydrolysis 340 and / or 430. In some embodiments, the degradation of monomeric sugars during the hydrolysis is less than 1%, optionally less than 0.2%, optionally less than 0.1% and optionally less than 0.05% by weight.
Exemplary chromatographic resins main types are available commercially. In some embodiments, the resins of one or more of these four types are employed.
In some embodiments, the resin employed in 410 (Figure 28) and / or 270 (Figure 26b) is a strong acid cation exchange resin in which sodium, potassium or ammonium replaces, at least partially, hydrogen ions in the resin.
Strong acid cation resins include Purolite® resins, such as PUROL1TE PCR 642H + and / or 642K resin (The Purolite Company, Bala Cynwood, PA, USA).
In some embodiments, the purification medium 274 (Figure 26b) includes a resin. Optionally, this resin is a mixed bed system with the use of a combination of strong cation resin and strong base anion resin. Mixed bed resins suitable for use in this context are also available from Purolite Company (Bala Cynwood, PA, USA).
Exemplary Anion Exchangers [00478] A wide variety of weak base resins (WBA) is available commercially. Many of these are suitable for use in the context of various embodiments of the invention (for example, at 251 in Figure 26a). Suitable resins include DOWEX 66 (Dow Chemical Co., USA) and A100 and / or A103S and / or [00472] Some embodiments employ an ion exchange resin (IE) (e.g., 410 and / or 270).
There are four main types of ion exchange resins which differ in their functional groups: strongly acidic (for example, with the use of sulfonic acid groups, such as sodium polystyrene sulfonate or polyAMPS), strongly basic (e.g., with the use of quaternary amine groups, for example, trimethylammonium, for example, polyAPTAC), weakly acidic (eg with the use of carboxylic acid groups) and weakly basic groups (for example, with the use of primary, secondary, and / or schedule, such as polyethylene amine).
The resins belonging to each of these four A105 and / or A109 and / or Al11 and / or A120S and / or 133S and / or A830 and / or A847 (The Purolite Co., USA).
In some embodiments, a wide variety of amine extracts of less than 20 carbon atoms are available. Exemplary amine extracts for use in the embodiments of the invention include tertiary amines, for example tri-octylamine, tri-caprylylamine, tri-decylamine or tri-laurylamine. Exemplary IX [00480] A wide variety of ion exchangers (IX) is commercially available. Many of these are suitable for use in the context of various embodiments of the invention (for example, at 253 in Figure 26a). Suitable resins include strong acid cation exchange resins such as DOWEX 88 (Dow Chemical Co., USA) or Cl00 and / or C100E and / or C120E and / or Cl00X10 and / or SGC650 and / or Cl50 and / or Cl60 (The Purolite Co., USA).
Exemplary equilibrium considerations [00481] HCI catalyzes both the hydrolysis of oligomeric sugars and the oligomerization of monomeric sugars. For a suitable period of time, a balance would be established. The direction of the reaction is influenced by the concentration of sugar and the ratio of monomersoligomers. The kinetics of the reaction can be influenced by the temperature and / or concentration of HCl.
[00482] Again with reference to Figure 26a and secondary hydrolysis unit 240: in some embodiments, the inlet sugar concentration has an excess of oligomers with respect to the equilibrium conditions. Dilution with the cut of oligomer returning from the chromatography unit 270 displaces the balance of monomer: oligomer for even further from the equilibrium conditions. Under these conditions, HCI drives the reaction towards the hydrolysis.
The sugar composition exiting the hydrolysis unit 240 is much closer to the equilibrium conditions, since the oligomers have been hydrolyzed. However, evaporation 260 could shift the balance to monomeric excess. If this occurs, HCI would tend to catalyze the re-oligomerization of monomers. The chromatographic separation 270 is operated according to a modality at a significantly higher sugar concentration than that of the secondary hydrolysis 240. In order to avoid re-oligomerization during the concentration of the sugars, the acid 156 is removed by contacting a anion exchanger 251, in some embodiments of the invention.
At the equilibrium of the secondary hydrolysis reaction, the ratio of the monomeric sugars to the oligomeric sugars is a function of the total sugar concentration. The reaction kinetics are adjusted by the HCL temperature and concentration. The choice of HCl temperature and concentration is a matter of optimization, taking into account operating and capital costs. In any case, the balance can be achieved. Altematively, the reaction can be stopped before reaching equilibrium. This is a matter of optimization of several factors, such as degradation of monomeric sugars and capital and operating costs. In some embodiments, the secondary hydrolysis is halted when it reaches at least 70, 75, 80, 85 or 90% by weight of the equilibrium ratio or intermediate or greater percentages.
Exemplary Flow Control Considerations [00485] In some embodiments, liquids with varying degrees of viscosity need to be transported from one module or component to another. In some embodiments, the sugar concentration and / or solvent concentration and / or HCl concentration contribute to the viscosity of a solution. In some embodiments, such transport depends, at least in part, on gravity. In some embodiments, pumps may be employed to carry liquids. In some embodiments, liquids move in different directions and / or different rates. Optionally, some liquids are lied in reservoirs for later use. In some embodiments, a controller serves to regulate one or more liquid streams.
Figure 30 is a schematic representation indicating the flow control components of a sugar refining module similar to that of Figure 26a generally indicated as 800. In the context of the system 100, the module 800 is analogous to the module 200. Numbers beginning with the numeral "1" refer to solutions or chains described earlier in this document. Many of those numbers starting with the numeral "8" refer to similar numbers beginning with the numeral "2" in Figure 26a and are described only in terms of their relationship to the flow control components here.
In some embodiments, the pump 811a provides an SI-based extractant stream 155 through acid extractors 810a and 810b. The flow charges HCI 140 along with it. The extractors are arranged in series and the flow is pumped through 810b to 810a. In some embodiments, a single 810 puller is used.
The pump 812a provides a flow of sugar blend 130 to the acid extractor (s) 810a. In some embodiments, the controller 890 regulates the flow rates of the pumps 812a and 81a to ensure efficient extraction of acid from the extractant. Optionally, a correct relative flow rate contributes to this efficiency. In some embodiments, pumps 812a and 811a are provided as part of a Bateman pulsed column. as described earlier in this document. In some embodiments, the flow rates in the pumps 812a and / or 811a are varied to adapt the acid extractor 810a to provide a desired degree of extraction efficiency.
In some embodiments, the acid reducing stream 131a emerges from the extractor 810a and is withdrawn through the secondary hydrolysis module 840 by the pump 842. Again, the controller 890 regulates a flow rate through the module 840 to ensure that a degree of hydrolysis is achieved. Optionally, an additional pump 832 moves the stream 131a to the secondary hydrolysis module 840 as shown. The resulting secondary hydrolyzate 131b is pumped to the filtration unit 850. Optionally, the filtration pump 852 removes the hydrolyzate 131b through filters in the unit and / or pumps the secondary hydrolyzate 131c filtered to the anion exchanger 851. In some embodiments, a separate pump 848 periodically provides a rinse flow (arrow pointing right) to the filtration unit 850 to wash accumulated debris from the filters. In some embodiments, the controller 890 coordinates the operation of the pumps 848 with 842 and / or 852 to ensure proper operation of the filter unit 850.
In some embodiments, the filtered stream 131c is pumped through the anion exchanger 851 by the pump 854 to produce a deacidified hydrolyzate 132. In some embodiments, a separate pump 849 releases a lavage stream to the anion exchanger 851 to produce a dilute HCI stream 156. In some embodiments, the controller 890 coordinates the operation of the pumps 854 with 849 and / or 856 to ensure proper operation of the anion exchanger 851.
In some embodiments, the pump 856 withdraws the deacidified hydrolyzate 132 through the cation exchanger module 853. The output stream 13ld is reduced in cation content. In some embodiments, a separate pump 852 releases a lavage stream into the module 853 to produce a stream of eluted cations 157. In some embodiments, the controller 890 coordinates the operation of the pumps 852 with 856 and / or 862 to ensure proper operation of module 853.
In some embodiments, the outlet stream 131d is withdrawn in the evaporation unit 860 by the pump 862 which increases the sugar concentration by evaporation of water. The resulting concentrated filtrate secondary hydrolyzate 131e is pumped to the chromatography component 870 by the pump 872.
In some embodiments, the water 142 produced by the evaporator 860 is pumped by the collection mechanism 864 to the chromatography unit 870 for use as an elution fluid. Since the chromatography unit 870 cyclically alternates between elution and sample feed, in some embodiments, the collection mechanism 864 optionally includes a water reservoir, as well as a pump.
In some embodiments, the controller 890 coordinates the action of the collection mechanism 864 and pump 872 to cyclically feed the resin in the chromatography unit 870 with a sample stream and an elution stream. Such elution and cyclic feed produce a cut of oligomer 280 which is recycled to the hydrolysis unit 840 by the pump 872 and a cut of the monomer 230 which is optionally pumped by the pump 872 to the module 204 (Figure 26b).
Optionally, the controller 890 responds to feedback from sensors (not shown) positioned at the inputs and / or outputs of various modules and / or units. In some embodiments, such sensors include flow sensors and controller 890 regulates relative flow rates. In some embodiments, a split between the oligomer cut and the monomer cut is made based on historical resin performance data in the 870 chromatography unit in terms of effluent bed volumes after sample feed.
[00496] In some embodiments, the sensors include parametric detectors. Optionally, the parametric detectors monitor the sugar concentration and / or acid concentration. In some embodiments, the sugar concentration is measured by analyzing the refractive index and / or viscosity. Optionally, the acid concentration is monitored by pH measurement. In some embodiments, a partition between the oligomer cut and the monomer cut is made based on the actual resin performance data in the 870 chromatography unit in terms of specific sugar concentration, as judged by the refractive index and / or concentration of acid as estimated from the pH.
Exemplary Monomer Concentrations [00497] Again with reference to Figure 26a, in several exemplary embodiments of the invention, monomer sugar enriched mixture 131b produced by secondary hydrolysis 240 includes 72, 74, 76, 78, 80, 82, 84, 86, 88 or 90% by weight or intermediate or higher percentages of monomeric sugars by weight relative to the total sugars. In some embodiments, in a number of exemplary embodiments of the invention, the monomer cut 230 from the chromatography 270 includes 80, 82, 84, 86, 88, 90, 94, 96, 98, 99 or 99.5% by weight or percentages intermediate or higher amounts of monomeric sugars by weight in relation to total sugars.
Exemplary Operations Orders [00498] Again with reference to Figure 26a, many exemplary embodiments of the invention include the secondary hydrolysis unit 240 and the chromatography component 270 and various combinations of other components and / or units.
In some embodiments, the sugars from stream 130 proceed directly to the secondary hydrolysis unit 240 and the secondary hydrolyzate 131b proceeds (optionally through the filtration unit 250) to the acid extractor 210b, to the anion exchanger 251 and then (optionally through the cation exchanger module 253) and then to the evaporation unit 260 and then to the chromatography unit 270.
In some embodiments, the sugars from stream 130 proceed directly to the secondary hydrolysis unit 240 and the secondary hydrolyzate 131b proceeds (optionally through the filtration unit 250) to the acid extractor 210b and then to the evaporation unit 260 and then to the chromatography unit 270.
In some embodiments, the stream 130 is pre-evaporated at 290 (Figure 26c), and then the sugars from stream 130 proceed to the secondary hydrolysis unit 240 and the secondary hydrolysate 131b proceeds (optionally through the unit of filtration 250) to the acid extractor 210b, to the anion exchanger 251 and then (optionally through the cation exchanger module 253) and then to the evaporation unit 260 and then to the evaporation unit 260. Chromatography 270.
In some embodiments, the stream 130 is pre-evaporated at 290 (Figure 26c), and then the sugars from stream 130 proceed to the secondary hydrolysis unit 240 and the secondary hydrolysate 131b proceeds (optionally through the unit of filtration 250) to the acid extractor 210b and then to the evaporation unit 260 and then to the chromatography unit 270.
In some embodiments, the stream 130 is drawn into the acid extractor 210a and then the sugars from stream 130 proceed to the secondary hydrolysis unit 240 and the secondary hydrolyzate 131b proceeds (optionally through the filtration unit 250) to the acid extractor 210b, to the anion exchanger 251 and then (optionally through the cation exchanger module 253) and then to the evaporation unit 260 and then to the chromatography unit 270.
In some embodiments, the stream 130 is pre-evaporated at 290 (Figure 26c), drawn into the acid extractor 210a, and then the sugars from stream 130 proceed to the secondary hydrolysis unit 240 and the hydrolyzate (optionally via the filter unit 250) to the acid extractor 210b, to the anion exchanger 251 and then (optionally through the cation exchanger module 253) and then to the evaporation unit 260 and then to the chromatography unit 270.
In some embodiments, stream 130 is pre-evaporated at 290 (Figure 26c), drawn into the acid extractor 210a, and then the sugars from stream 130 proceed to the secondary hydrolysis unit 240 and the secondary hydrolyzate 131b is continued (optionally through the filtration unit 250) to the acid extractor 210b, to the evaporation unit 260 and then to the chromatography unit 270.
In some embodiments, stream 130 is pre-evaporated at 290 (Figure 26c), drawn into the acid extractor 210a, and then the sugars from stream 130 proceed to the secondary hydrolysis unit 240 and the secondary hydrolyzate 131b is continued (optionally through the filtration unit 250) to the evaporation unit 260 and then to the chromatography unit 270.
In some embodiments, the stream 130 is extracted into the acid extractor 210a and then the sugars from stream 130 proceed to the secondary hydrolysis unit 240 and the secondary hydrolyzate 131b proceeds (optionally through the filtration unit 250 ) to the evaporation unit 260 and then to the chromatography unit 270. Additional exemplary methods and related products Figure 31a is a simplified flowchart of a method according to another exemplary embodiment of the invention generally represented as 900 The method 900 includes providing a fermentor 910 and fermenting a 920 medium including monomeric sugars to produce a conversion product 930. In some cases, the processes shown in Figures 25 and 26a and / or 26b and / or 26c are conducted in a single plant or system together with fermentation 920.
Figure 31b is a simplified flowchart of a method according to another exemplary embodiment of the invention represented generally as 901. Method 901 includes providing a 911 solution containing monomeric sugar and converting the sugars into the solution into a 931 conversion product with the use of a chemical process 921.
In some embodiments, the monomeric sugars, or solution containing monomeric sugar, may be provided as a blend enriched with monomeric sugar (e.g., 342 or 1032) and / or as a cut of monomer (e.g., 230 or 574) and / or as a hydrolyzate containing monomeric sugars (e.g., 510, 532 or 552).
In some embodiments, fermentation 920 and / or chemical process 921 are as described in the documents under nos. US 7,629,010; US 6,833,149; US 6,610,867; US 6,452,051; US 6,229,046; US 6,207,209; US 5,959,128; US 5,859,270; US 5,847,238; US 5,602,286; and US 5,357,035, the contents of which are incorporated herein by reference. In various embodiments, the processes described in the above US patents are combined with one or more methods, as described herein, for example with secondary hydrolysis and / or chromatography, as described herein.
In some embodiments, the fermentation 920 may employ a genetically modified organism (GMO). A wide range of GMOs is potentially compatible with the sugars produced by the methods described herein. GMOs may include members of the genera Clostridium, Escherichia, Salmonella, Zymomonas, Rhodococcus, Pseudomonas, Bacillus, Enterococcus, Alcaligenes, Lactobacillus, Klebsiella, Paenibacillus, Corynebacterium, Brevibacterium, Pichia, Candida. Hansenula and Saccharomyces. Hosts that may be of particular interest include Oligotropha carboxidovorans, Escherichia coli, Bacillus licheniformis, Paenibacillus macerans, Rhodococcus erythropolis, Pseudomonas putida. Lactobacillus plantarum. Enterococcus faecium, Enterococcus gallinarium, Enterococcus faecalis, Bacillus subtilis and Saccharomyces cerevisiae. In addition, any of the known strains of these species can be used as a starting microorganism. In several exemplary embodiments, the microorganism is an actinomycete selected from Streptomyces coelicolor, Streptomyces lividans. Streptomyces hygroscopicus or Saccharopolyspora erytraea. In various exemplary embodiments, the microorganism is an eubacteria selected from Escherichia coli, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas aeruginosa, Bacillus subtilis or Bacillus cereus.
In some exemplary embodiments, GMO is a gram-negative bacterium. In some exemplary embodiments, the recombinant microorganism is selected from the genera Zymomonas, Escherichia, Alcaligenes and Klebsiella. In some exemplary embodiments, the recombinant microorganism is selected from the species Escherichia coli, Cupriavidus necator and Oligotropha carboxidovorans. In some exemplary embodiments, the recombinant microorganism is an E. coli strain.
In some embodiments, fermentation 920 produces lactic acid as conversion product 930. The potential of lactic acid as a utility chemical, for example, for use in the production of various industrial polymers, is known. This has been described, for example, in patents n25. U.S. 5,142,023; 5,247,058; 5,258,488; 5,357,035; 5,338,822; 5,446,123; 5,539,081; 5,525,706; 5,475,080; 5,359,026; 5,484,881; 5,585,191; 5,536,807; 5,247,059; 5,274,073; 5,510,526; and 5,594,095. (The full disclosures of these seventeen patents, which are owned by Cargill, Inc. of Minneapolis, Minn., Are incorporated herein by reference.) There is general interest in the development of improved techniques for the generation and isolation of lactic. Furthermore, because of their potential commercial value, there is a great interest in the isolation of the other valuable related lactate products, such as lactide, amides and lactate esters, and oligomers; see, for example, the same 17 patents.
In general, large amounts of lactic acid can readily be generated by conducting large-scale industrial microbial fermentation processes, particularly with the use of sugars produced by the exemplary methods as described herein, such as dextrose, in the medium, along with appropriate amino acid and mineral based nutrients. Typically, such productions occur at broth temperatures of at least 45øC, usually around 48øC.
Problematic issues regarding the generation of lactic acid include, inter alia, adequate pH control within the fermentation system to ensure the proper environment for the microbial action, separation and isolation of either or both of the lactic acid such as lactate salts from the fermentation process and the downstream insulation and production involving the isolated lactic acid or lactic acid derived product.
In some embodiments, the sugars produced by the exemplary methods described herein are incorporated into a fermentation product, as described in the following patents US, the contents of which are each incorporated herein by reference: US 7,678,768; US 7,534,597; US 7,186,856; US 7,144,977; US 7,019,170; US 6,693,188; US 6,534,679; US 6,452,051; US 6,361,990; US 6,320,077; US 6,229,046; US 6,187,951; US 6,160,173; US 6,087,532; US 5,892,109; US 5,780,678; and 5,510,526.
In some embodiments, the conversion product (930 or 931) may be, for example, an alcohol, carboxylic acid, amino acid, monomer for the polymer or protein industry. In some embodiments, the conversion product (930 or 931) is processed to produce a consumer product selected from the group consisting of a detergent, a polyethylene based product, a polypropylene based product, a polypropylene based product. polyolefin base. a polylactide acid based product (polylactide), a polyhydroxyalkanoate based product and a polyacrylic based product. Optionally, the detergent includes a sugar based surfactant, a fatty acid surfactant, a fatty alcohol surfactant or a cell culture derived enzyme. Optionally, the polyacrylic-based product is a plastic, a floor polisher, a carpet, an ink, a coating, an adhesive, a dispersion, a flocculant, an elastomer, an acrylic glass, an absorbent article, an incontinence pad , a sanitary napkin, a feminine hygiene product and a diaper. Optionally, the polyolefin products are a milk jug, a detergent bottle, a margarine tub, a garbage container, a plumbing, an absorbent article, a diaper, a nonwoven, a HDPE toy or a carton for HDPE detergent. Optionally, the polypropylene-based product is an absorbent article, a diaper or a nonwoven. Optionally, the product based on polylactic acid is a packaging of an agricultural product or a dairy product, a plastic bottle, a biodegradable product or a disposable. Optionally, the polyhydroxyalkanoate based products are a package of an agricultural product, a plastic bottle, a coated paper, an extruded or molded article, a feminine hygiene product, an inner absorbent applicator, an absorbent article, a towel or non-disposable tissue, medical surgical dress, adhesive, elastomer, film, coating, aqueous dispersant, fiber, pharmaceutical intermediate or binder. Optionally, the conversion product 930 or 931 is ethanol, butanol, isobutanol, a fatty acid, a fatty acid ester, a fatty alcohol or biodiesel.
In some embodiments, the 900 or 901 method includes processing the conversion product 930 or 931 to produce at least one product, such as, for example, a condensation product of isobutene, jet fuel, gasoline, gasool, diesel fuel, drop-in fuels, diesel fuel additives or a precursor thereof.
Optionally, the gasool is gasoline enriched with ethanol and / or butanol enriched gasoline.
In some embodiments, the product produced from the 930 or 931 conversion product is diesel fuel, gasoline, jet fuel or a drop-in fuel.
A number of exemplary embodiments of the invention include consumer products, consumer product precursors and consumer product ingredients produced from the conversion product 930 or 931.
Optionally, the product intended for the consumer, precursor of a product intended for the consumer or ingredient of a product intended for the consumer, comprises at least one conversion product 930 or 931, such as, for example, a carboxylic acid or fatty acid, a dicarboxylic acid, a hydroxyl carboxylic acid, a hydroxyl dicarboxylic acid, a hydroxyl fatty acid, methylglyoxal, mono, di, or polyalcohol, an alkane, an alkene, an aromatic, an aldehyde, a ketone, an ester, a biopolymer, a protein, a peptide, an amino acid, a vitamin, an antibiotic and a pharmaceutical.
For example, the product may be gasoline enriched with ethanol, jet fuel or biodiesel.
Optionally, the product intended for the consumer has a carbon-14 to carbon-12 ratio of about 2.0 x 10 -13 or greater. Optionally, the product intended for the consumer includes an ingredient of a consumer product as described above, and an additional ingredient produced from a raw material other than the lignocellulosic material. In some embodiments, the ingredient and the additional ingredient produced from a raw material other than the lignocellulosic material are essentially of the same chemical composition. Optionally, the product intended for the consumer includes a marker molecule in a concentration of at least 100 ppb.
In some embodiments, the marker molecule may be, for example, furfural, hydroxymethylfurfural. products of furfural or hydroxymethylfurfural condensation, color compounds derived from the caramelization of sugar, levulinic acid, acetic acid, methanol, galacturonic acid or glycerol. ΧΠΙ. Alternative Modes of Lignin Processing Figure 25 is a schematic representation of an exemplary hydrolysis system which produces a lignin stream which serves as an inlet stream, generally indicated as 100. The system 100 includes a hydrolysis vessel 110 which captures lignocellulosic substrate 112 and produces two output streams. The first outflow stream is an acid hydrolyzate 130 which contains an aqueous solution of HCl with dissolved sugars. The second outlet stream 120 is a lignin stream. Processing the lignin stream 120 to remove HCI and water is a goal of this application. Recycling of HCI removed is an additional goal of this application. The forms for performing such recycling without diluting HCI are an important feature of some exemplary embodiments described herein. In some embodiments, the lignin stream 120 contains less than 5%, less than 3.5%, less than 2% or less than 1% by weight of cellulose relative to lignin on a dry matter basis.
In some embodiments, the hydrolysis vessel 110 is of the type described in co-pending international application No. 2. PCT / US2011 / 057552 (incorporated herein by reference for all purposes). In some embodiments, the hydrolysis vessel may include hydrolysis reactors of one or more types. In some embodiments, the substrate 112 contains pine wood. The hydrolyzed stream processing 130 occurs in the sugar refining module 201 and produces refined sugars 230 that are substantially free of residual HCI. For the purposes of the system overview 100, it is sufficient to note that the module 201 produces a recycled HCI stream 140 that is directed to the hydrolysis vessel 110. In some embodiments, the HCI 140 is recovered from the hydrolyzate 130 by extraction with a solvent-based extractant 155. Optionally, such extraction occurs in the refining module 201. In some embodiments, the extractant 155 is separated from the HCI 140 in the solvent recovery module 150. In some embodiments, the lignin stream 120 includes significant amounts of HCl and dissolved sugars. Exemplary Method Figure 34 is a simplified flowchart of a method for processing a lignin stream indicated generally as 200. The feed stream 208 corresponds to the lignin stream 120 of Figure 25.
Method 200 includes washing (210a and / or 210b) a feed stream 208. Feed stream 208 includes one or more sugars dissolved in a solution of aqueous superazeotropic HCl and solid lignin. In many cases, the solid lignin in stream 208 is moistened by or impregnated with the solution. In some embodiments, the lavage (210a and / or 210b) serves to remove sugars from the lignin. In some embodiments, washing (210a and / or 210b) is performed with a wash HCI solution (207a and / or 207b) which includes at least 5% by weight of HCl to form a solution of washed sugars (212a and / or 212b) and a washed lignin stream 214. In some embodiments, the washed lignin stream 214 includes solid lignin, water, and HCl.
Method 200 also includes contacting 220 washed lignin stream 214 with recycled hydrocarbon 218 to form a deaerated lignin 222 stream and a vapor phase 224 containing HCl and water. In some embodiments, the contact 220 of the recycled hydrocarbon 218 with the washed lignin stream 222 occurs at 65, 70, 75, 80, 85 or 90øC or higher or intermediate temperatures. Optionally, the contact 220 is conducted at a temperature at which the hydrocarbon 218 boils. In some embodiments, the vapor phase 224 also contains hydrocarbon 218 (not shown). In some embodiments, the deacidified lignin stream 222 includes solid lignin and less than 2% HCI by weight.
In some embodiments, the method 200 includes condensing the vapor phase 224 to form a solution of condensed aqueous HCI 232. In some embodiments, the method 200 includes using the condensed aqueous HCI solution 232 in the lavage 210a and / or 210b. In some embodiments, method 200 includes using 236 the aqueous condensed HCl solution 232 in the hydrolysis 110 of a lignocellulosic material 112 (see Figure 25). In some embodiments, condensation 230 produces additional recovered hydrocarbon 231 (not shown). In some embodiments, the recovered hydrocarbon 231 is recycled 233 from the deacidified lignin 222 to 218. In some embodiments, the recycle 233 includes one or more of the centrifugation, vapor condensation, evaporation, and distillation.
Exemplary washing considerations In some embodiments, a concentration of lignin at the feed rate at 208 is between 5% and 50%, 15% and 45%, 20% and 40% or 25% and 35% by weight, such as as it is. In some embodiments, a concentration of HCI in the feed stream is between 35 and 45%, 37% and 44%, 38% and 43% or 39% and 42.5% by weight of HCl / [HCl and water]. In some embodiments, a sugar concentration in stream 208 is between 5% and 35%, 10% and 30%, 12% and 27%, 15% and 25% by weight, as is.
In some embodiments, the glucose contains at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of the total sugars in the feed stream 208. In some embodiments, the glucose contains 50% to 80%, 50% to 85%, 50% to 90%, 50% to 95%, 50% to 99%, 60% to 80%, 60% to 85%, 60% to 90% 60% to 95% or 60% to 99% by weight of the total sugar in the feed stream 208. In some embodiments, stream 208 contains one or more C5 sugars and C5 sugars are less than 50, less than 40, less than 30, less than 20, less than 10 or less than 5% of total sugars in stream 208.
In some embodiments, the lavage 210a and / or 210b of the feed stream 208 includes at least one countercurrent contact. In some embodiments, a concentration of HCI in the solution 207a and / or 207b is at least 20, at least 25, at least 30, at least 35 or at least 40% by weight.
In some embodiments, the feed stream washer 208 includes a first countercurrent contact 210a with a first solution 207a containing at least 5% by weight of HCl to form a first washed sugar solution 212a and a second contact of countercurrent solution 210b with a second solution 207b containing at least 5% by weight of HCl to form a second solution of washed sugars 212b. In some embodiments, a concentration of HCl in the first solution 207a is at least 35, at least 37, at least 39, at least 41 or at least 42% by weight. In some embodiments, a concentration of HCl in the second solution 207b is at least 20, at least 25, at least 28, at least 30 or at least 32% by weight. In some embodiments, a sugar concentration in the washed lignin stream 214 is less than 5%, 4%, 3%, 2% or 1%, as found.
[00537] In some embodiments, the number of washing stages varies. In Figure 34, two washing stages are shown (210a and 210b). In other exemplary embodiments of the invention, a greater number of washing stages is implanted. For example, three to ten washing stages are implanted in some embodiments of the invention. In some embodiments, a washing temperature changes between the stages. For example, in some embodiments, the latter stage or stages are conducted at a slightly elevated temperature compared to the early stages, for example, 25øC to 40øC, as compared to 10øC at 20øC. In some embodiments, each washing stage is performed on a hydrocyclone. Optionally, the pressure on the hydrocyclones is 275.8 to 620.5 kPa (40 to 90 psig). In some embodiments, two washing streams (207a and 207b) serve more than two hydrocyclones. In some embodiments, lavage stream 207a has a HCl concentration of 40 to 43% and lavage stream 207b has a HCl concentration of 32 to 36%. In some embodiments, stream 207a enters the first hydrocyclone (from the feed stream 208) and stream 207b enters the last hydrocyclone (from the feed stream 208). Optionally, the wash temperature increases as the HCl concentration decreases in the wash.
[00538] In some embodiments, the wet milling of the feed stream 208 prior to the washing 210 (210a and / or 210b) is conducted.
Optionally, wet milling contributes to an increase in wash efficiency. In some embodiments, the wet milling of the stream 214 prior to the contact 220 is conducted. Optionally, wet milling contributes to an increase in deacidification efficiency. This increased efficiency is in terms of a reduced time for contact 220 and / or a reduction in the ratio between the washing stream 210a and / or 210b and the feed stream 208.
Exemplary Contact Considerations In some embodiments, the hydrocarbon employed in contact 220 has a boiling point at atmospheric pressure between 100 ° C and 250 ° C, 120 ° C and 230 ° C or 140 ° C and 210 ° C. Suitable hydrocarbons include isoparaffinic fluids (for example, ISOPAR G, H, J, K, L or M available from ExxonMobil Chemical, USA). In some embodiments, the isoparaffinic fluid is substantially insoluble in water. In some embodiments, dodecane is employed as a hydrocarbon 218 at contact 220.
In some embodiments, 9 parts of Isopar K. as hydrocarbon 218 are placed in contact 220 with 1 part of washed lignin stream 214 (e.g., about 20% solid lignin as found). According to these embodiments, a ratio of Isopar K. to dry lignin is about 7/1; 9/1; 11/1; 15/1; 30/1; 40/1 or 45/1 by weight (or intermediate or greater ratios) is contacted at 220.
In some embodiments, the lavage 210a and / or 210b is at a pressure between 275.8 and 620.5 kPa (40 and 90 psig). In some embodiments, the contact 220 is conducted at atmospheric pressure. In some embodiments, the deacidified lignin stream 222 includes less than 2%, less than 1.5%, less than 1.0%, less than 0.5%. less than 0.3%, less than, 0.2% or less than 0.1% HCl by weight, as it is found. In some embodiments, the deacidified lignin stream 222 contains at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% by weight of solid lignin, as found.
Exemplary condensation considerations In some embodiments, a concentration of HCl in condensed aqueous HCl solution 232 is greater than 20%, greater than 22%, greater than 24%, greater than 26% or greater than 28% by weight as HCl / (HCl and water).
Additional exemplary recycling cycles [00543] In some embodiments, the method 200 includes the use of washed sugar solution 212a or 212b in the hydrolysis of a lignocellulosic material (for example, at 110 in Figure 25). In some embodiments, the method 200 includes the use of the first washed sugar solution 212a in the hydrolysis of a lignocellulosic material. In some embodiments, method 200 includes the use of the second washed sugar solution 212b in the hydrolysis of a lignocellulosic material.
Exemplary hydrolysis considerations In some embodiments, the lignocellulosic material 112 (Figure 25) includes softwood (e.g., pine). In some embodiments, the lignocellulosic material 112 includes hardwood (e.g., eucalyptus or oak). In some embodiments, a hydrolysis temperature at 110 (Figure 25) is less than 25, less than 23, less than 21, less than 19, less than 17 or less than 15 ° C.
Second exemplary method Figure 35 is a simplified flowchart of a method for processing a lignin stream indicated generally as 300 according to some embodiments. In some embodiments, the feed stream 308 corresponds to the lignin stream 120 of Figure 25.
The method 300 includes deacidifying a feed stream 308 containing solid lignin, an aqueous superazeotropic HCl solution and at least one sugar to form a deacidified lignin stream 312. In some embodiments, stream 312 includes solid lignin and less than 2%, less than 0.3%, less than 0.2% or less than 0.1% of HCl by weight / weight in the state in which it is. In some embodiments, stream 312 includes lignin that is at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% w / w solid (or intermediate percentages or larger).
The method depicted also includes cooking the solid lignin 312 in an alkali solution 318 to form an alkaline solution 322 including dissolved lignin. In some embodiments, the yield of lignin dissolved in alkaline solution 322 is at least 85%, 90%, 92.5%, 95%, 97.5%, 99%, 99.5% or substantially 100% w / w of the amount of lignin in stream 312. In some embodiments, the lignin concentration dissolved in 322 is at least 5%, 7%, 8%, 10%, 15%, 20% or 25% w / w or intermediate or (expressed as dissolved solids). In some embodiments, the baking 320 is conducted at a temperature greater than 100øC, greater than 110øC, greater than 120øC or greater than 130øC. In some embodiments, the baking 320 is conducted at a temperature of less than 200 ° C, less than 190 ° C, less than 180 ° C, less than 170 ° C, less than 160 ° C or less than 150 ° C. In some embodiments, the baking 320 is conducted at a temperature between 160 ° C and 220 ° C, 170 ° C and 210 ° C, 180 ° C and 200 ° C, or 182 ° C and 190 ° C. In some embodiments, the cooking 320 has a duration of at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 120 minutes. In some embodiments, the cooking 320 has a duration of less than 10, less than 9, less than 8, less than 7, less than 6, less than 5.5, less than 5, less than 4.5, less than 4 or less than 3.5 hours. In some embodiments, the cooking time is about 6 hours (e.g., 182 ° C). In some embodiments, an increase in cooking time and / or cooking temperature contributes to an increase in lignin fragmentation and / or degradation. In some embodiments, the baking 320 is baking in an alkali solution containing less than 20%, less than 15%, less than 10%, less than 5% or less than 2% solvent. Optionally, the baking 320 is baking in an alkali solution which is substantially free of solvent. The baking 320 is conducted in a composition which is substantially cellulose-free so that it is very different from the pulp of wood.
In some embodiments, an alkaline concentration of alkaline solution 318 is adjusted so that the alkaline concentration at 320 is at least 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12% , 13%, 14%, 15% w / w or intermediate or greater percentages when expressed as 100X base / (base and water) on a weight basis. The table below illustrates exemplary amounts and ratios of cooking components 320 of laboratory scale experiments.
Exemplary conditions of laboratory scale experiments The lab scale conditions of line 3 of Table 1 were increased to a semi-industrial procedure as follows: 13.61 kilograms (30 pounds) of 50% Lignin in hydration / volatiles (15 pounds) dry lignin solids) 4.76 kilograms (10.5 pounds) dry NaOH solids supplied as a 50% caustic solution 68.04 kilograms (150 pounds) of water (includes (10.5 pounds) of water in 50% caustic solution) 6.6 kilograms (15 pounds) of IsoPar K (in the wet lignin; residual solvent at 222 in Figure 34) [00550] In the semi- the lignin / NaOH ratio was 1.42 and the alkaline concentration was 6.5% (comparison to line 3 in the above table).
In some embodiments, the lignin stream 312 contains deacidification residual hydrocarbon (e.g., dodecane) 310. By cooking 320, the lignin in stream 312 dissolves in the aqueous alkali phase, so that the residual hydrocarbon separates Easily in a separate organic phase which is decanted and recycled. In some embodiments, the alkali solution 318 includes ammonia and / or sodium hydroxide and / or sodium carbonate.
Method 300 includes purifying the dissolved lignin 330 to form purified lignin precipitate 333. In some embodiments, purification 330 includes contacting 331 the alkaline solution 332 containing lignin dissolved with a water soluble solvent 334 to form a precipitate of solid lignin 333 and an alkaline solution 336 which includes the water-soluble solvent. In some embodiments, the water soluble solvent 334 includes methanol and / or ethanol and / or acetone.
In some embodiments, the precipitate 333 contains basic lignin. In some embodiments, separation 337 facilitates recycling 338 of water soluble solvent 334 and / or recycling 339 of alkali solution 318. Separation 337 optionally includes evaporation (e.g., distillation) and / or cooling and / or adjustment of pH.
Exemplary lignin states [00554] In some embodiments, the lignin carries acid phenol function (s) in protonated form - ROH - and / or in dissolved form - RO (-). In some embodiments, the lignin carries carboxylic function (s), in the protonated form -RCOOH- and / or in the dissolved form -RCOO (-). The "acid functions" referred to herein are a combination of phenol and a carboxylic function which are either in protonated or dissociated form. In some embodiments, acid lignin is a lignin wherein more than half of the acid functions are in the protonated form and the basic lignin is a lignin wherein more than half of the acid functions are in the dissociative form.
Third exemplary method Figure 36 is a simplified flowchart of a method for processing a indicated lignin stream to generate as 400. In some embodiments, feed stream 308 corresponds to the lignin stream 120 of Figure 25. Method 400 is similar to method 300 in Figure 35 in most respects. The major difference between method 400 and method 300 is in the form that purification 330 is performed. This difference in purification 330 results in different forms of lignin (i.e., 333 to 432).
In some embodiments of method 400, solid lignin at 312 is acidic. In some embodiments, the cooking 320 in the alkaline solution 318 produces an alkaline solution 322 which contains dissolved basic lignin. In some embodiments of the depicted method 400, the basic lignin purification 330 of the solution 322 includes contacting the alkali solution 322 with an acidifier 428 to produce purified acid lignin 432. In some embodiments, a solution of HCI serves as the acidifier 428. In some embodiments, the acidifier 428 is added until the pH decreases to 3.7, up to 3.6, up to 3.5 or up to 3.4.
In some embodiments, in purified acid lignin 432 at least 50%, at least 60%, at least 70%, at least 80%, at least 90% or at least 95% of the acid functions are in the protonated form. In some embodiments, in the basic lignin at least 50%, at least 60%, at least 70%, at least 80%. at least 90% or at least 95% of the acid functions are in the dissociated form. In some embodiments, the purified acid lignin 432 is dissolved in solvent 334. In some embodiments, the deacidified lignin stream 312 contains less than 2%, less than 1.5%, less than 1.0%, less than 0.5 %, less than 0.3%, less than 0.2 or less than 0.1% HCl by weight / weight as is.
Referring now to both Figure 35 and Figure 36: In some embodiments, purification 330 includes contacting 331 the alkaline solution 322 with a water-soluble solvent 334 to form a precipitate of basic solid lignin 333 and an alkaline solution 336 containing said water soluble solvent, separating precipitate 333 and contacting 431 (Figure 36) the separated basic solid lignin precipitate 333 (Figure 35) with acidulant 428. In some embodiments, the purification 330 includes contacting 431 the alkaline solution 322 with the acidulant 428 to form a solid acid lignin precipitate 432. In some cases, the addition of alkaline solution 322 is in an amount that is only sufficient to solubilize the lignin (i.e., stoichiometry). In some embodiments, the purification 330 includes contacting the alkaline solution 322 with the acidifier 428 and with a solvent of limited solubility (e.g., MEK, not shown) in contact 431 to form a solvent solution containing acid lignin 432 dissolved therein . Optionally, the solvent is separated (e.g., by evaporation) to form a solid purified acid lignin and a solvent stream to be recycled (not shown). In some embodiments, the deacidification residual hydrocarbon (e.g., ISOPAR K) 310 forms a separate phase at the top of the alkaline solution 322 and is removed prior to contact with the solvent of limited solubility. For example, in some embodiments, the lignin is decanted from the bottom of the cooking vessel (320) before the solvent of limited solubility is added. In some embodiments, the purification 330 includes contacting said separate basic (solid) lignin precipitate 333 with an acidifier 428 and with a solvent of limited (not shown) solubility to form a solvent solution containing dissolved acid lignin 432. Optionally, the solvent of limited solubility is separated (e.g., by evaporation) to form a solid purified acid lignin and a solvent stream to be recycled (not shown).
Exemplifying deacidification options In some embodiments of method 300 (Figure 35) and method 400 (Figure 36), deacidification 310 includes contacting lignin in hydrocarbon feedstock 308 (optionally recycled hydrocarbon) to form a deacidified lignin stream 312 containing solid, optionally acidic, lignin. In some embodiments, stream 312 includes solid lignin and less than 2%, less than 1.5%, less than 1%, less than 0.5%, less than 0.3%. less than 0.2% or less than 0.1% w / w HCl as it stands and a vapor phase 224 containing HCl and water and optionally hydrocarbon. This option is described above herein in the context of Figure 34.
Exemplary Washing Options In some embodiments of Method 300 and Method 400, the lignin in stream 308 is washed with a wash HCI solution, including at least 5% by weight of HCl as it is to form a solution of washed sugars and a washed lignin stream containing solid (optionally acidic) lignin, water and HCl. This option is described in the context of Figure 34. Optionally, washing is conducted prior to deacidification.
Exemplary Purification Variations In some embodiments, the contact 431 of the separated basic solid lignin precipitate 428 includes lavage with an acidulant solution 428. Optionally, such lavage is conducted at two or more contact stages / 431 and / or countercurrent mode. In some embodiments, the contact 431 of the basic lignin precipitate with the acidifier 428 converts the basic lignin precipitate to the acidic solid lignin 432. In some embodiments, the contact 431 of the alkaline solution 322 with the acidulant 428 includes contact with CO 2 under a pressure superatmospheric. In some embodiments, the superatmospheric pressure is 0.1, 0.19, 0.29, or 8.3 kPa (2.4, 6, 8 or 10 bar) or intermediate or greater pressures.
In some embodiments, the contact 431 of the alkaline solution 322 includes contact with acidulant 428 and with a solvent of limited solubility concomitantly. In other embodiments, contacting the alkaline solution 322 with the acidulant 428 is conducted prior to contact with a solvent of limited solubility. In other exemplary embodiments of the invention, contacting the alkaline solution 322 with the acidulant 428 is conducted upon contact with a solvent of limited solubility. In some embodiments, the solvent of limited solubility has a boiling point of less than 150, less than 140, less than 130, less than 120 or less than 110 ° C at atmospheric pressure.
Exemplary Removal of Cation Referring now to Figure 36, Method 400 includes the removal of cations from purified acid lignin 432 (dissolved in solvent of limited solubility). In some embodiments, the ion exchange 440 removes cations 443 from the purified acid lignin 432 in the solvent of limited solubility (e.g. MEK) to produce low cation lignin 442. In some embodiments, the ion exchange 440 employs a resin (e.g., PUROLITE Cl50 in H + form; Purolite, Bala Cynwyd, PA, USA). The anion exchange can be seen as part of preparation 710 (Figure 39).
The table below summarizes cation concentrations remaining in the low cation 442 lignin of two 432 lignin batches subjected to ion exchange with PUROLITE Cl50 440. Lot II, which has a lower total cation concentration, employed more resin per lignin amount and slower feed rate.
[00566] Cations associated with lignin after SAC treatment
Exemplary Concentrations of Sugar In some embodiments, a concentration of decaurized lignin 312 sugar in sugar is less than 5%, less than 4%, less than 3%, less than 2% or less than 1% w / w In the state it is. In some embodiments, a concentration of sugar in alkaline solution 322 is less than 3%, less than 2%, less than 1%. less than 0.5% or less than 0.3% by weight / weight as is.
Exemplary solvents [00568] Some embodiments employ solvent of limited solubility. Optionally, the solvent of limited solubility includes one or more of esters. ethers and ketones having 4 to 8 carbon atoms. In some embodiments, the solvent of limited solubility includes ethyl acetate. Optionally, the limited solubility solvent essentially consists of, or consists of. ethyl acetate. Some embodiments employ a water-soluble solvent. Optionally, the water-soluble solvent includes one or more of methanol, ethanol and acetone.
Exemplary Acidulants In some embodiments, the acidulant 428 includes one or more mineral acids and / or one or more organic acids. In some embodiments, acidulant 428 includes acetic acid and / or formic acid and / or SCb and / or CCS. Additional exemplary method Figure 39 is a simplified flowchart of a method for preparing solid lignin indicated generally as 700 according to some embodiments. The method 700 includes dissolving 720 acid lignin 722 in a solvent of limited solubility (e.g., MEK) and desolventisation 730 to produce solid lignin 732. In some embodiments, the acid lignin 722 is formed by cellulose hydrolysis 710 on a lignocellulosic substrate 708 (corresponds to 112 in Figure 25) with an acid. In some embodiments, acid lignin 722 is derived from lignin stream 120 (Figure 25) and includes lignin remaining after substantially all of the cellulose on substrate 112 has been hydrolyzed at 110 ° C.
In some embodiments, the preparation 710 includes precipitating the acid lignin (e.g., 432 of Figure 36) from an alkaline solution and dissolving the acid lignin in the solvent of limited solubility (e.g., methyl ethyl ketone; MEK). In some embodiments, the preparation 710 includes precipitating basic lignin from an alkaline solution (for example, by contacting 331 with water-soluble solvent 334 to form ppt 333; and acidifying the basic lignin 333 to form acid lignin 432 and dissolving the acid lignin 432 in the solvent of limited solubility. In some embodiments, the preparation 710 includes contacting an alkaline solution which includes dissolved basic lignin (e.g., 322 of Figure 35) with an acidulant (e.g., 428 of Figure 36) and with a solvent of limited solubility to form a solvent solution containing dissolved acid lignin. In some embodiments, the ratio of limited solubility solvent to alkaline solution 322 is between 1: 3 and 10: 1. In some embodiments, the ratio of limited solubility solvent to alkaline solution 322 is about 3: 1. Under these conditions, the counting produces two phases.
In some embodiments, acidulant 428 (e.g., HCI) is added to obtain a pH of 3.7, at 3.6, at 3.5, at 3.4, at 3.3 or at 3, 2 or intermediate pH. In some embodiments, by contacting 431 with a sufficient amount of acidifier 428, the organic phase separates from the aqueous phase and the lignin precipitates and partially dissolves in the solvent of limited solubility (e.g., MEK). In some embodiments, the inorganic contaminants (e.g., ash and / or salts) dissolve in the aqueous phase.
In some embodiments, desolvventisation 720 includes contacting the acid lignin dissolved in a solvent of limited solubility prepared in 710 with an antisolvent (e.g., water and / or hydrocarbon (s)). In some embodiments, the solvent of limited solubility includes ethyl acetate. (for example, the antisolvent is water and the evaporation includes azeotropic distillation of MEK).
In some embodiments, desolventization 720 includes evaporation of the solvent of limited solubility. In some embodiments, the evaporation of the solvent of limited solubility includes spray drying and / or contact with a hot liquid and / or contact with a hot solid surface. In some embodiments, contact with a solid surface produces a solid lignin coating on the hot solid surface.
In some embodiments, the hot liquid has a boiling point higher than that of the solvent of limited solubility by at least 10 ° C. Examples of such liquids include water, hydrocarbons and aromatic compounds.
In some embodiments, the method 700 includes wet spinning of the lignin during desolventisation 720. In some embodiments, the method 700 includes contacting the lignin with a modifying reagent. In some embodiments, the modifying reagent is added to the solvent of limited solubility. In some embodiments, the modifying reagent is added to an antisolvent used for desolventization. In either case, the lignin contacts the modifying reagent when the solvent of limited solubility comes into contact with the antisolvent. In some embodiments, the addition of the modifying reagent occurs prior to or during desolventization.
For example, a plasticizer (i.e., modifying reagent) is added to the solvent of limited solubility in some embodiments of the invention. In some embodiments, the modifying reagent includes a surfactant. In some embodiments, the modifying reagent has a physical and / or chemical interaction with lignin.
In some embodiments, method 700 includes coating a solid surface with solid lignin 722 (for example, during desolvvenation 720). In some embodiments of the method 700 which employ spray drying for desolventisation 720, the method includes coagulating the lignin with a second polymer having a linear arrangement. In some embodiments, this co-sparing contributes to the formation of a resultant solid lignin rod-like assembly 722.
Exemplary Compositions Some embodiments relate to a lignin composition prepared by a method as described hereinbefore. Such a composition has at least 97% w / w lignin on a dry matter basis (i.e., less than 3% w / w non-lignin material). In some embodiments, such a composition has an ash content of less than 0.1% w / w and / or a total carbohydrate content of less than 0.05% w / w and / or a volatile content of less than 5% w / w at 200 ° C. In some embodiments, the composition has a non-molten particulate content (diameter> 1 micron; 150øC) of less than 0.05 w / w%. In some embodiments, the composition includes lignin at a concentration of 97% to 99%, 97% to 99.5%, 97% to 99.9%, or 98% to 99% w / w on a dry matter basis . In some embodiments, the lignin concentration is about 97.5%, about 98%, about 98.5%, about 99%, or about 99.5% weight / weight. In some embodiments, the ash content is 0.001% to 0.1%, 0.01% to 0.1%, 0.05% to 0.1% or 0.001% to 0.05% w / w. In some embodiments, the ash content is about 0.1%, about 0.05%, about 0.02%, about 0.01%, or about 0.005% weight / weight. In some embodiments, the volatile content is from 0.01% to 5%, 0.05% to 5%. 0.3% to 5%, 0.4% to 5%. 0.5% to 5%. 1 to 5%, 0.1% to 1%, 0.1% to 2%, or 0.1% to 1% w / w. In some embodiments, the volatile content is about 0.01%, about 0.02%. about 0.03%, about 0.04%, about 0.05%, about 0.06%, about 0.06%, about 0.07%, about 0.08%, about 0.09%, about 0.1%, about 0.12%, about 0.15%, about 0.2%, about 0.3%, about 0.4%, about 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1.0%, about 1.5%, about 2.0%, about 2.5% %, about 3.0%, about 4.0% or about 5.0% w / w. In some embodiments, the lignin composition has a chloride content of less than 500 ppm. less than 200 ppm. less than 100 ppm, less than 50 ppm. less than 20 ppm. less than 10 ppm or less than 5 ppm. In some embodiments, the chloride content is about 200 ppm, about 100 ppm, about 50 ppm, about 20 ppm. about 10 ppm, about 5 ppm or about 1 ppm. In some embodiments, the chloride content is 0.1 to 10 ppm, 1 to 20 ppm. 1 to 50 ppm, or 1 to 100 ppm.
The present invention provides a lignin composition comprising: (i.e. less than 3% non-lignin material); an ash content of less than 0.1% w / w; a total carbohydrate content of less than 0.05% w / w; a volatile content of less than 5% at 200 ° C; and at least 1 ppm hydrocarbon having a boiling point greater than 140Â ° C, 150Â ° C, 160Â ° C, 170Â ° C or 180Â ° C. In some embodiments, the hydrocarbon concentration is 1 to 10 ppm, 1 to 20 ppm, 1 to 30 ppm, 1 to 40 ppm, 1 to 50 ppm, 1 to 100 ppm, 1 to 1,000 ppm, 10 to 100 ppm, 20 at 100 ppm, 50-200 ppm. 50 to 500 ppm. In some embodiments, the hydrocarbon concentration is about 1 ppm. 5 ppm. 10 ppm. 15 ppm, 20 ppm. 25 ppm, 30 ppm, 35 ppm, 40 ppm or 50 ppm. Optionally, the composition has a non-molten particulate content (diameter of> 1 micron; at 150 ° C) of less than 0.05%. In some embodiments, the unfused particulate content is 0.0001 to 0.05%, 0.001 to 0.05% or 0.01 to 0.05% w / w. In some embodiments, the concentration of the non-molten particulate is about 0.001%, about 0.005%, about 0.01%, about 0.02%, about 0.03%, about 0.04%, about of 0.05% w / w.
Exemplary thermogravimetric profiles [00581] Figures 37 and 38 show thermogravimetric profiles for lignin according to the exemplary modalities of the invention over similar profiles for commercially available Lignin Kraft (Sigma-Aldrich, St. Louis, Mo, USA). Figure 37 is a plot of thermogravimetric analysis (TGA) data indicating percent by weight as a temperature function for lignin samples according to the exemplary embodiments of the invention and conventional Kraft lignin incubated in N2. Analysis of the TGA data derivative indicated that the lignin according to the exemplary embodiments tested of the invention is stable at about 420øC while Kraft lignin is significantly degraded at 310øC.
Figure 38 is a plot of thermogravimetric analysis (TGA) data indicating percent by weight as a function of temperature for lignin samples as in Figure 37 incubated in air. Analysis of the TGA data derivative indicated that the lignin according to the exemplary embodiments tested of the invention is completely oxidized to about 420 ° C while the Kraft lignin carbonizes at that temperature. XIV. Alternative Modes of Lignin Solubilization Figure 40 is a flowchart depicting a lignocellulose processing method generally indicated as method 100. The depicted method 100 includes extracting 130 ashes, one or more lipophilic materials. and one or more hemicellulose sugars from a lignocellulose substrate 110 to form at least one extract stream 132 and an extracted substrate 135 containing cellulose and lignin. The ash extraction 130, one or more lipophilic materials. lignin and one or more hemicellulose sugars may occur in any order. For example, extraction may occur sequentially or concomitantly. In some embodiments, one or more extracted solutes are separated from the substrate separately from one or more other extracted solutes. Optionally, this includes two or more extractions. According to the exemplary method depicted, the extract stream 132 is separated from the extracted substrate 135.
The method 100 also includes solubilizing 140 lignin in extracted substrate 135 to produce a solid cellulose composition 150 which contains at least 60% dry cellulose and a lignin stream 142. In some embodiments, the solid cellulose composition 150 includes 70%, 80%, 90%, or even 95% or more of cellulose. In some embodiments, the solubilization 140 includes contacting an alkaline solution (e.g., pH> 9.0) and / or an organic solvent and / or a base and / or a supercritical solvent and / or a sulfonating agent and / or a people of rust.
The method 100 also includes hydrolyzing 160 solid cellulose composition 150 with an acid to form a hydrolyzate 162 which includes soluble sugars and acid and deacidifying the hydrolyzate 162 to form a deacidified sugar solution 172. In some embodiments, the hydrolysis 160 is carried out in a vessel and at least 90% of available sugars in solid cellulose composition 150 have a pot residence time of <16 hours.
In some embodiments, a chemical reaction that increases the extratibildity of one or more solutes in the substrate is conducted prior to, or concurrent with, extraction. For example, the lignin may be reacted with a sulfonating agent or an oxidizing agent to solubilize it and render it more extractable. In some embodiments, the extraction conditions may be adjusted to increase the solubility of one or more potential solutes in the substrate. Extraction conditions that can be altered to increase the solubility of a potential solute include temperature, degree of oxidation, and pH. In some embodiments, the substrate is mechanically treated (for example by grinding or grinding) to increase the transfer rate of one or more potential solutes in an applied solvent (extraction liquid). In some embodiments, the substrate is chemically modified to take one or more more soluble substrate components under extraction conditions.
In some embodiments, extraction includes the removal of monomeric and oligomeric subunits released from polymers as solutes. For example, hemicellulose consists primarily of water insoluble polymeric sugars having a solubility of 1% or less in water at 100 ° C. However, under suitable conditions, depolymerisation liberates sugars with a solubility of more than 1% in water at 100 ° C (e.g., monomers such as xylose, mannose, or arabinoses; oligomers containing one or more of such monomers). The lipophilic material includes water insoluble fatty compounds, for example, pine resin resins, tar and resins, terpenes. and other volatile organic compounds.
In some embodiments, extraction 130 extracts one or more protein materials. In some embodiments, extraction 130 removes pectin or galactatonic acid oligomers from the substrate. In some embodiments, the extraction includes a single extraction 130 which produces a single extraction stream 132. In other embodiments, the extraction includes two or more extractions 130 which produce two or more extract streams 132. In some embodiments, a single extraction is conducted in multiple stages. In some embodiments, the hydrolysis 160 employs HCI as a catalyst. Optionally, the hydrolysis 160 includes contacting the solid cellulose composition 150 with a solution of HCl wherein HCl / (HCl + H 2 O) is at least 25, 30%, 35%, 37%, 39% or at least 41% w / w. In some embodiments, the lignin content of hydrolyzate 162 is in an amount up to 5%, 4%, 3%, 2% or 1% w / w. Optionally, the hydrolyzate 162 is essentially lignin-free. In some embodiments, the solids content of hydrolyzate 162 is in an amount up to 5%, 4%, 3%, 2% or 1%. Optionally, the hydrolyzate 162 is essentially free of solids. In some embodiments, deacidification 170 includes contact with a solvent S1. Optionally, the solvent S includes hexanol and / or 2-ethyl hexanol.
In some embodiments, the method 100 includes applying a predetermined pressure-temperature-time-profile (PPTTP) profile 108 to the lignocellulosic substrate 110. In some embodiments, the PPTTP 108 is characterized by a severity factor of at least 3, 3.2, 3.4, 3.6, 3.8 or 4.0. In some embodiments, the PPTTP 108 is characterized by a severity factor of less than 5, 4.8, 4.6, 4.4 or 4.2. Optionally, PPTTP 108 is characterized by a severity factor of 3.4 to 4.2, optionally 3.6 to 4.0, optionally 3.8 to 24.
Exemplary Extraction Conditions In some embodiments, the extraction 130 includes hydrolyzing polysaccharides (not to be confused with the hydrolysis 160) in the substrate 110 and removing the water-soluble polysaccharides formed. Optionally, the removal includes washing and / or pressing. In some embodiments, a hydration content of the substrate 110 is at least 40%. at least 50% or at least 60% during both such hydrolysis and removal.
In some embodiments, during both hydrolysis and removal, a substrate temperature is at least 50 ° C, at least 60 ° C, at least 70 ° C, at least 80 ° C, or at least 90 ° C.
In some embodiments, such hydrolysis is conducted at a temperature greater than 100 ° C and the removal is conducted at a temperature of less than 100 ° C. In some embodiments, such hydrolysis is conducted at superatmospheric pressure and removal is conducted at atmospheric pressure. Optionally, removal includes washing with a solution of an acid. In some embodiments, the acid includes sulfuric and / or sulfurous acid. In such embodiments employing sulfuric acid, the concentration is optionally 5% or less.
In some embodiments, extraction 130 includes contacting an extractant containing a water-soluble organic solvent. Examples of suitable water-soluble organic solvents include alcohols and ketones. In some embodiments, the solvent includes acetone. Optionally, the solvent includes a weak acid, such as sulfurous acid, acetic acid or phosphorous acid. In some embodiments, the extraction 130 includes contacting an alkaline solution (pH> 9.0) and / or an organic solvent and / or a base and / or a supercritical solvent and / or a sulfonating agent and / or a oxidation. In some embodiments, the extraction 130 involves contacting the substrate 110 with a solvent at an elevated temperature. In some embodiments, the extraction 130 involves contacting an alkali or alkaline solution at an elevated temperature. In some embodiments, the extraction 130 involves oxidation and / or sulfonation and / or contact with a reactive fluid. Several methods for extraction 130 are described in Carvalheiro et al. (2008; Journal of Scientific & Industrial Research 67: 849-864); E. Muurinen (Dissertation entitled "Organosolv pulping: A review and distillation study related to peroxyacid pulping" (2000) Department of Process Engineering, Oulu University, Finland) and Bizzari et al. (CEH Marketing research report: Lignosulfonates (2009) pages 14 to 16).
Exemplary Characteristics of Extracted Substrate In some embodiments, a ratio of cellulose to lignin in the extracted substrate 135 is greater than 0.6, greater than 0.7 or even greater than 0.8. In some embodiments, the extracted substrate 135 includes <0.5% ash. In some embodiments, the extracted substrate 135 includes <70 ppm of sulfur. In some embodiments, the extracted substrate 135 includes <5% soluble carbohydrate. In some embodiments, the extracted substrate 135 includes <0.5% pine resin.
Exemplary Characteristics of Solid Cellulose Composition In some embodiments, the solid cellulose composition 150 includes at least 80%, 85%, 90%, 95% or 98% cellulose based on dry matter. In some embodiments, the cellulose in the solid cellulose composition 150 is at least 40%, 50%, 60%, 70% or 80% crystalline. In some embodiments, less than 50%. 40%, 30% or 20% of the cellulose in solid cellulose composition 150 is crystalline cellulose.
In some embodiments, the solid cellulose composition 150 includes at least 85%, 90%, 95% or 98% of the cellulose on lignocellulose substrate 110. In some embodiments, the solid cellulose composition 150 includes less than 50% , less than 60%, less than 70% or less than 80% of the ashes on lignocellulose substrate 110. In some embodiments, the solid cellulose composition 150 includes less than 50%, less than 60%, less than 70% or less than 80% of the calcium ions in the lignocellulose substrate 110. In some embodiments, the solid cellulose composition 150 includes less than 30%, 20%, 10% or even less than 5% by weight / weight of the lipophilic materials in the substrate of lignocellulose 110. In some embodiments, the solid cellulose composition 150 comprises in a quantity of up to 30% 20%, 10% or 5% w / w weight of the lignin on lignocellulose substrate 110. In some embodiments, the solid cellulose composition 150 includes water-soluble carbohydrates in a concentrated less than 10% by weight. 8% by weight, 6% by weight, 4% by weight, 2% by weight or 1% by weight. In some embodiments, the solid cellulose composition 150 includes acetic acid in an amount of <50%, <40%, <30 or even <20% w / w of the acetate function in 110.
In some embodiments, the lignocellulose substrate 110 includes pectin. Optionally, the solid cellulose composition 150 includes less than 50%, 40%, 30% or 20% by weight / weight of the pectin in the substrate 110. In some embodiments, the lignocellulose substrate 110 includes bivalent cations. Optionally, the solid cellulose composition 150 includes less than 50%. 40%, 30% or 20% w / w bivalent cations present in the substrate 110.
Exemplary Parameters of Acid Hydrolysis In some embodiments, acid hydrolysis 160 is carried out in a vessel and <99% of the solid cellulose composition 150 is removed from the vessel as hydrolyzed 162 while> 1% of the solid cellulose composition 150 is removed as residual solids. Exemplary vessel configurations suitable for use in such embodiments are described in copending PCT application US 2011/57552 (incorporated herein by reference for all purposes). In some embodiments, the vessel employs a drip bed. Optionally, there is essentially no removal of solids from the bottom of the vessel. In some embodiments, the vessel has no drain.
In some embodiments, at least 90% of available sugars in the solid cellulose composition 150 have a pot residence time of <16 hours; <14; <12; <10 <15 or even <2 hours.
Exemplary flow characteristics of hemicellulose In some embodiments, the extraction 130 produces a hemicellulose sugar stream (depicted as extract stream 132) characterized by a purity of at least 90%, at least 92%, at least 94% , at least 96% or at least 97% w / w based on dry matter.
In some embodiments, the hemicellulose sugar stream has a w / w ratio between sugars and hydroxymethylfurfural greater than 10: 1, greater than 15: 1 or greater than 20: 1. In some embodiments, the hemicellulose sugar stream has a hydroxymethylfurfural content of less than 100 PPM, 75 PPM, 50 PPMH or even less than 25 PPM.
Optionally, the hemicellulose sugar stream includes soluble fibers.
In some embodiments, the hemicellulose sugar stream includes acetic acid in an amount equivalent to at least 50%, at least 60%, at least 70% or at least 80% w / w of the acetate function at the substrate 110.
In some embodiments, the substrate 110 includes pectin and the hemicellulose sugar stream includes methanol in an amount equivalent to at least 50%, at least 60%, at least 70% or at least 80% weight / weight of the substrate. methanol in pectin.
In some embodiments, the hemicellulose sugar stream includes bivalent cations in an amount equivalent to at least 50%, at least 60%, at least 70%, at least or even at least 80% w / w of its content of 110.
Exemplary Sugar Conversion In some embodiments, Method 100 (Figure 40) includes fermenting the deacidified sugar solution 172 to produce a conversion product 182. In other embodiments, the method 100 (Figure 40) includes subjecting the solution of deacidified sugar 172 to a non-biological process 181 to produce a conversion product 182. Non-biological exemplary processes include pyrolysis, gasification and "bio-forming" or "aqueous phase reforming (APR)" as described by Blommel and Cartwright in a report entitled "Production of Conventional Liquid Fuels from Sugars" (2008) as well as in US 6,699,457, US 6,953,873, US 6,964,757, US 6,964,758, US 7,618,612 and PCT / US2006 / 048030; the present as a reference for all purposes).
In some embodiments, method 100 includes processing 190 the conversion product 182 to produce a consumer product selected from the group consisting of detergent, polyethylene based products, polypropylene based products, polypropylene based products. polyolefin, polylactic acid (polylactide) based products, polyhydroxyalkanoate based products and polyacrylic based products.
In some embodiments, the detergent contains a sugar based surfactant, a fatty acid surfactant, a fatty alcohol surfactant, or an enzyme derived from cell culture. In some embodiments, a polyacrylic-based product is selected from among plastics, floor polishes, carpets, paints, coatings, adhesives, dispersions, flocculants, elastomers. acrylic glass, absorbent articles, incontinence pads. absorbents, feminine hygiene products and diapers. In some embodiments, the polyolefin products are selected from milk jugs, detergent bottles, margarine tubes, waste containers, water pipes, absorbent articles, diapers, nonwoven, HDPE toys and HDPE detergent pack. In some embodiments, the polypropylene-based products are selected from absorbent articles, diapers and nonwoven articles. In some embodiments, the products based on polylactic acid are selected from the packaging of agricultural products and dairy products, plastic bottles, biodegradable and disposable products. In some embodiments, the polyhydroxyalkanoate based products are selected from among agricultural packaging, plastic bottles, coated papers, molded or extruded articles, feminine hygiene products, tampon applicators, absorbent articles, disposable tissues and tissues, medical surgical suits , adhesives, elastomers, films, coatings, aqueous dispersants, fibers, pharmaceutical intermediates and binders. In other exemplary embodiments of the invention, the conversion product 182 includes at least one member of the group consisting of ethanol, butanol, isobutanol, a fatty acid, a fatty acid ester, a fatty alcohol and biodiesel.
According to these embodiments, the method 100 may include processing 190 of the conversion product 182 to produce at least one consumer product selected from the group consisting of a condensation product of isobutene, jet fuel, gasoline , gasool, diesel fuel. drop-in fuel, diesel fuel additive and a precursor thereof. In some embodiments, gasool is gasoline enriched with ethanol or gasoline enriched with butanol. In some embodiments, the consumer product 192 is selected from the group consisting of diesel fuel, gasoline, alcohol fuel, and drop-in fuels.
The invention also provides a consumer product 192, a precursor of a consumer product 192, or an ingredient of a consumer product 192 produced from the conversion product 182 Examples of such products intended for the consumer 192, precursor of a consumer product 192, and ingredients of a consumer product 192 include at least one conversion product 182 selected from carboxylic acids and fatty acids. dicarboxylic acids, hydroxyl carboxylic acids. hydroxyl dicarboxylic acids, hydroxyl fatty acids, methylglyoxal, mono, di or polyalcohols, alkanes. alkenes, aromatics, aldehydes. ketones, esters, biopolymers, proteins, peptides, amino acids, vitamins, antibiotics and pharmaceuticals.
In some embodiments, the product intended for the consumer 192 is gasoline enriched with ethanol, jet fuel or biodiesel. Optionally, the consumer product 192, or precursor thereof, precursor of a consumer product, or an ingredient thereof has a carbon to carbon 12 ratio of about 2.0 χ 10 13 or more. In some embodiments, the consumer product 192 includes an ingredient as described above and an additional ingredient produced from a raw material other than lignocellulosic material. In some embodiments, the ingredient and the additional ingredient produced from a raw material other than lignocellulosic material are essentially of the same chemical composition. In some embodiments, the consumer product includes a marker molecule in a concentration of at least 100 ppb. In some embodiments, the marker molecule is selected from the group consisting of furfural, hydroxymethylfurfural, furfural or hydroxymethylfurfural condensation products, color compounds derived from sugar caramelization, levulinic acid, acetic acid, methanol, galacturonic acid and glycerol.
In some embodiments, the solubilization 140 produces a lignin stream 142.
Exemplary Characteristics of the Lignin Stream Figure 41 is a simplified flow chart of a method for processing a lignin stream indicated generally as the method 200. In embodiment 200, the lignin stream 208 corresponds to the lignin stream 142 of the lignin stream. Figure 40.
In some embodiments, the lignin stream 208 is characterized by a purity of at least 90-92%, 94%, 96% or 97% w / w or more. The purity of the lignin stream 208 is measured on a solvent-free basis. In some embodiments, the solvent includes water and / or an organic solvent. The concentrations of impurities in the lignin stream 208 are in the state in which they are present. In some embodiments, the lignin stream 208 includes a chloride (Cl) content in an amount of up to 0.5%, 0.4%, 0.3%, 0.2%, 0.1 or 0.05% in weight / weight. In some embodiments, the lignin stream 208 includes an ash content in an amount up to 0.5%, 0.4%, 0.3%, 0.2% or 0.1% weight / weight. In some embodiments, the lignin stream 208 includes phosphorus at a concentration of less than 100 ppm, less than 50 ppm, less than 25 ppm, less than 10 ppm, less than 1 ppm. less than 0.1 ppm or less than 0.01 ppm. In some embodiments, the lignin stream 208 includes a soluble carbohydrate content in an amount up to 5%, 3%, 2% or 1% w / w. In some embodiments, the lignin stream 208 includes one or more furfural at a total concentration of at least 10 ppm, at least 25 ppm, at least 50 ppm, or at least 100 ppm. In some embodiments, the lignin stream 208 includes <0.3%, <0.2% or <0.1% w / w bivalent cations. In some embodiments, the lignin stream 208 includes <0.07%, <0.05% or <0.03% w / w sulfur. In some embodiments, the lignin stream 208 includes lignin in solution and / or a suspension of solid lignin in a liquid. In some embodiments, the liquid includes water and / or an organic solvent. Alternatively, the lignin stream 208 may be provided as a wet solid or a dry solid. In such embodiments which include lignin in solution, the lignin concentration may be greater than 10%, 20%, 30% or greater than 40% w / w. Exemplary lignin conversion method [00615] Again with reference to Figure 41, in some embodiments, the method 200 includes converting at least a portion of lignin into lignin stream 208 into a conversion product 212. In some embodiments, converting 210 employs depolymerization, oxidation, reduction, precipitation (through neutralization of the solution and / or solvent removal), pyrolysis, hydrogenolysis, gasification or sulfonation. In some embodiments, the conversion 210 is optionally conducted in the lignin while in solution or after precipitation. In some embodiments, converting 210 includes treating lignin with hydrogen. In some embodiments, converting 210 includes producing hydrogen from the lignin.
In some embodiments, the conversion product 212 includes at least one item selected from the group consisting of bio oil, carboxylic and fatty acids, dicarboxylic acids, hydroxy dicarboxylic acids, hydroxyl carboxylics and hydroxyl fatty acids, methylglyoxal, monoalcohols , di-alcohols or poly-alcohols, alkanes, alkenes, aromatics, aldehydes. ketones, esters, phenols, toluenes and xylenes. In some embodiments, the conversion product includes a fuel or a fuel ingredient. Optionally, the conversion product includes para-xylene.
In some embodiments, converting 210 includes aqueous phase reforming. In some embodiments, converting 210 includes at least one bioformation reaction. Exemplary types of bio-reaction include catalytic hydrotreating and catalytic condensation, zeolite (for example ZSM-5) acid condensation, base catalyzed condensation, hydrogenation, dehydration, alkene oligomerization, and alkylation (alkene saturation). In some embodiments, the conversion takes place in at least two stages (e.g. 210 and 220) which produces conversion products 212 and 222, respectively. Optionally, a first stage (210) includes reforming the aqueous phase. In some embodiments, the second stage 220 includes at least one of catalytic hydrotreatment and catalytic condensation.
Optionally, the method 200 is characterized by a hydrogen consumption of less than 0.07 tons per ton of product 212 and / or 222.
Exemplary Lignin Products [00619] The present invention also provides a consumer product, a precursor of a consumer product or an ingredient of a consumer product produced from a lignin stream 208. In some embodiments , the product intended for the consumer is characterized by an ash content of less than 0,5% by weight and / or a carbohydrate content of less than 0,5% by weight and / or a sulfur content of less than 0% , 1% by weight and / or extractive content of less than 0,5% by weight. In some embodiments, the consumer product produced from the lignin stream 208 includes one or more of bio-oil, carboxylic acids and fatty acids, dicarboxylic acids, hydroxy dicarboxylic acids, hydroxyl carboxylic acids and hydroxyl fatty acids, methylglyoxal, monoalcohols, di-alcohols or poly-alcohols, alkanes, alkenes, aromatics, aldehydes, ketones, esters, biopolymers. proteins, peptides, amino acids, vitamins, antibiotics and pharmaceuticals. In some embodiments, the consumer product includes one or more of the dispersants, emulsifiers, complexing agents, flocculants, binders, pelletizing additives, resins, carbon fibers, active carbon, antioxidants. liquid fuel, aromatic chemicals, vanillin, adhesives, binders, absorbents, toxin binders, foams, coatings, films, rubbers and elastomers. sequestrants, fuels and expanders. In some embodiments, the product is used in an area selected from the group consisting of food, feed, materials, agriculture, transportation, and construction. Optionally, the product intended for the consumer has a carbon-14 to carbon-12 ratio of about 2.0 x 10 -13 or greater.
Some embodiments relate to a consumer product containing an ingredient as described above and an ingredient made from a raw material in addition to lignocellulosic material. In some embodiments, the ingredient and ingredient produced from a raw material other than the lignocellulosic material are essentially the same chemical composition.
In some embodiments, the consumer product includes a marker molecule at a concentration of at least 100 ppb. In some embodiments, the marker molecule is selected from the group consisting of furfural and hydroxymethylfurfural, condensation products, color compounds, acetic acid, methanol, galacturonic acid, glycerol, fatty acids and resin acids.
In some embodiments, the product is selected from the group consisting of dispersants, emulsifiers, complexing agents, flocculants. binders, pelletizing additives, resins, carbon fibers, active carbon, antioxidants. liquid fuel, aromatic chemicals, vanillin, adhesives, binders. absorbents, toxin binders, foams, coatings, films, rubbers and elastomers, sequestrants, fuels and expanders.
EXAMPLES
It is to be understood that the examples and embodiments described herein are for the purposes of illustration only and are not intended to limit the scope of the claimed invention. It is also to be understood that various modifications or changes in light of the examples and embodiments described herein will be suggested to those skilled in the art and should be included within the spirit and scope of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.
Example 1 - Small scale hemicellulose sugar extraction Table 1 provides a summary of the chemical analysis of the liquor resulting from the extraction of hemicellulose sugar from various types of biomass. The% monomeric sugar is expressed as%, by weight of the total weight of sugars. All other results are expressed as% by weight relative to the dry biomass.
All the treatments were run in a 0.5 1 pressure reactor equipped with a heating and cooling system and stirrer. The reactor was charged with biomass and liquid in determined quantities on the table. The reactor was heated to the temperature indicated in the table, the time count was started when the reactor reached 5 ° C below the designated temperature. Once the time elapsed, the reactor was cooled. The solid and liquid were separated and the content of the obtained liquor was analyzed, all data were recalculated with respect to the weight of dry biomass. HPLC methods were applied to evaluate the% of Total Sugars in the liquor,% of monomeric sugars and% of Acetic Acid. The% Degradation Product is the sum of% Furfurais (analysis by HPLC or GC),% Formic Acid (HPLC) and% Levulinic Acid (HPLC). Acid-Soluble Lignin was analyzed according to the NREL method TP-510-42627.
Table 1: Treatment conditions and chemical analysis of the resulting liquor 1% Total Sugars (% TS) as measured by HPLC in the liquor 2 DB - Dry Biomass 3% Monomers out of total dissolved sugars measured by HPLC in 4% of Acetic Acid as measured by HPLC in the liquor 5% Degradation Products =% Furfural +% Formic Acid +% Levulinic Acid. % Furfural measured by GC or HPLC,% Formic acid and% Levulinic acid as measured by HPLC 6 0.5% H 2 SO 4 + 0.2% SO 2 7 0.7% H 2 SO 4 + 0.03% Acetic acid Example 2 - Large-scale chemical analysis of lignocellulose matter after extraction of hemicellulose sugar Table 2 provides a summary of the chemical analysis of various types of biomass after extracting hemicellulose sugar.
Pine (A1202102-5): Fresh Lobelloly (Pinus Teada) pine chips (145.9 lb dry wood) were fed to a Rapid Cycle Digester (RDC, Andritz, Springfield , Ohio). An acidic aqueous solution (500 lb) was prepared by adding 0.3% H2 SO4 and 0.2% SO2 to the water in a separate tank. The solution was heated to 135øC and then added to the digester to cover the wood. The solution was circulated through the wood for 40 minutes while maintaining the temperature. After 60 minutes, the resulting liquor was drained to a liquor tank and with the use of water vapor. the wood was blown into a cyclone to collect the wood (128.3 lb of dry wood) and ventilate the steam. The extracted wood was analyzed for sugar content, carbohydrate composition, ashes, elements (through 1CP) and extractives of DCM. The analysis of the semidefinished lignocellulose material shows the extraction of 42.4% of Arabinane, 10.5% of Galactan, 9.6% of Xylan, 14.3% of Mannan and 11.8% of Glucan, indicating that, in most cases, the hemicellulose is extracted. The analyzes also show 11.6% of "others", including ASL, extractives and ash. The overall carbohydrate fraction in the remaining solid is no different, in the margin of measurement error, from that of the initial biomass due to such removal of "others". However, it is easily seen that the extracted wood chips are darker in color and are more brittle than fresh biomass.
Pine (A1204131 -14 (K1)): Fresh Loblloly (Pinus Teada) pine chips (145.9 lb dry wood) were fed to a Rapid Cycle Digester (RDC, Andritz, Springfield, Ohio). An acidic aqueous solution (500 lb) was prepared by adding 0.3% H2 SO4 and 0.2% SCb to the water in a separate tank. The solution was heated to 135øC and then added to the digester to cover the wood. The solution was circulated through the wood for 180 minutes while maintaining the temperature. After 180 minutes, the resulting liquor was drained to a liquor tank and using water vapor. the wood was blown into a cyclone to collect the wood (121.6 lbs. of dry wood) and ventilate the steam. The material was analyzed as described above. Analyzes of semidefined lignocellulose material show the extraction of 83.9% Arabinane, 84.3% Galactan, 50.1% Xylan, 59.8% Mannan and no extraction of glucan, which indicates the effective extraction of hemicellulose. The analyzes also show the extraction of 21.8% of "others", including lignin, extractives and ash.
Eucalyptus (Eucalyptus Globulus) (79.1 kg dry wood) was fed into a Rapid Cycle Digester (RDC, Andritz Springfield, Ohio). An aqueous acid solution was prepared by adding 0.5% H2 SO4 and 0.2% SO2 to the water in a separate tank. The solution was heated to 145 ° C and then added to the digester to cover the wood. The solution was circulated through the wood for 60 minutes while maintaining the temperature, then heating was stopped while the circulation continued for another 60 minutes, allowing the solution to cool. After 120 minutes, the resulting liquor was drained to a liquor tank and with the use of water vapor. the wood was blown into a cyclone to collect the wood (58.8 kg dry wood) and ventilate the steam. The material was analyzed as described above. The analyzes showed that 20.1% of the carbohydrates were extracted from wood xylose (dry wood base) containing 70% of such sugars, and 91% of the sugars in the liquor are present as monomers. Under such conditions, the concentration of acetic acid in the liquor was 3.6% (dry wood base) showing the maximum removal of acetate groups from hemicellulose sugars; 4.2% (dry wood base) of acid-soluble lignin. Such results indicate the effective extraction of hemicellulose and, specifically, xylose, along with the hydrolysis of the acetate groups of the substituted xylosanes. At the same time, a significant amount of lignin soluble in extractives, acids and ash is also extracted into the liquor.
Table 2: Chemical analysis of lignocellulose matter after hemicellulose sugar extraction Hemicellulose sugar extraction: 135 ° C for 60 minutes, 0.3% H2SO4, 0.2% SO2. 2 Hemicellulose sugar extraction: 135Â ° C for 180 minutes, 0.3% H2 SO4.0.2% SO2. 3 Hemicellulose sugar extraction: 145 ° C for 60 minutes + 60 minutes cooling, 0.3% H2 SO4, 0.2% SO2.
Example 3 - Aqueous and Organic Currents Resulting from Amine Extraction with Hardwood.
The acidic hemicellulose sugar stream resulting from the extraction of hemicellulose sugar from Eucalyptus flakes (as exemplified in Example 2) was used in this small scale experiment. The aqueous stream before extraction was prepared by extracting the eucalyptus in a solution containing 0.5% H2 SO4 and 0.2% SO2, separating the liquid from the solid and contacting the liquid with a resin of strong cation exchange. The results provided were obtained in a batch experiment in which the ratio of the organic phase (amine extract, tri-laurylamine: hexanol ratio 3: 7) to the aqueous phase (hemicellulose sugar stream) was 4: 1, the contact time of 15 minutes at 60 ° C. A highly effective extraction of sulfuric acid and acetic acid is observed along with a good extraction of acid soluble lignin (75%) and minimal loss of sugars (2%) into the organic phase.
Table 3 provides the chemical analysis of the aqueous stream before and after the extraction of amine, expressed as%, by weight of the aqueous solution.
Table 3: Chemical composition of the aqueous stream before and after the extraction of amine __________________________________________________________________ Example 4 - Re-extraction of the acid from the amine extractant.
The amine extractant from Example 3 was contacted with 1% sodium carbonate solution at a ratio of 1: 1 for 15 minutes at 60 ° C. It is observed that 84% of acetic acid and 89% of sulfuric acid were reextracted from the organic phase of the amine extractant. Organic acids can be recovered from re-extraction. Alternatively, the re-extraction may be diverted to residue treatment. Table 4 summarizes the acid concentrations in the amine extractant before and after reextraction.
Table 4: Concentration of mineral acid and acetic acid in the organic stream before and after reextraction Example 5 - Eucalyptus sugar composition [00633] Eucalyptus sugar composition (DH2C001): The Eucalyptus Globulus flakes were extracted by treating about (dry basis) with an aqueous solution containing 0.5% H 2 SO 4 and 0.2% SO 2, at a ratio of 2.66 of liquid to solid in a temperature controlled tank and stirred at the temperature average of 130 to 135 ° C for 3 hours. The collected liquor was collected, the flakes were washed with water, the wash water was then used to prepare the acid solution from the next batch by adding acids as needed. The hemicellulose-depleted chips were then crushed at ~ 1,400 microns and dried at ~ 15% moisture.
The acidic hemicellulose sugar stream ran through a SAC column. The sugar stream was then batchwise extracted twice with an extractant having tri-laurylamine: hexanol at a ratio of 30:70. The ratio of extractant to sugar stream 2: 1. The resulting aqueous phase was further purified with the use of a SAC column, a WBA resin and a mixed bed resin. The pH of the resulting stream was adjusted to 4.5 with 0.5% HCl and the sugar solution was evaporated to the final concentration of -70% DS.
The resulting hemicellulose sugar mixture was evaporated to a total sugar concentration of 70-80% to make it osmotically stable. Table 5A provides a chemical analysis of the resulting hemicellulose sugar blend.
Table 5A: Chemical analysis of a mixture of hemicellulose sugar produced by extracting sugar from hemicellulose and purifying eucalyptus flakes. [00636] Bagasse sugar composition (DB4D01): The bagasse was fragmented in a wood shredder. In a temperature controlled tank, 60 lb. bagasse (dry basis) was then treated with an aqueous solution containing 0.5% H2 SO4, at a net to solid ratio of 14.2. The average temperature of the temperature controlled tank was maintained at 130 to 135 ° C for 3 hours. The solution was circulated through pumping. The resulting liquor was collected and the solids were washed with water. The wash water was then used to prepare the acid solution for the next batch by adding acids as needed. The lignocellulose matter with hemicellulose depletion was collected and dried.
The acidic hemicellulose sugar stream ran through a SAC column. The sugar stream was then continuously extracted from a number of mixer-decanters (2 stages) with an extractant having tri-laurylamine: hexanol at a ratio of 30:70. The ratio of in the range of to sugar chain was maintained in the range of 2: 1 to 1.5: 1. The resulting aqueous phase was further purified with the use of a SAC resin, a WBA resin, granular active carbon and a mixed bed resin. The pH of the resulting stream was adjusted to 4.5 with 0.5% HCl and the sugar solution was evaporated to a ~ 30% concentration of DS. The resulting sugar stream contains about 7% arabinose, 2.5% galactose, 6.5% glucose, 65% xylose, 1.5% mannose, 4% fructose and 14% oligosaccharides (all as%, total weight / sugars). Such a sugar solution was further processed through fractionation in a SSMB system, resulting in a xylose rich fraction and a xylose depletion fraction. Each fraction was concentrated by evaporation. Table 5B provides a chemical analysis of the resulting xylose-rich sugar solution.
Table 5B: Chemical analysis of a mixture of hemicellulose sugar produced by extraction of hemicellulose sugar and purification of bagasse Example 6 - Fractionation of xylose from the hemicellulose sugar mixture Xylose was fractionated from the mixture of hemicellulose sugar containing 17% w / w glucose, 71% w / w xylose, 7% w / w arabinose. 0.3% w / w galactose, 0.2% w / w mannose and 5% w / w of mixed dimeric saccharides. The composition of such a mixture is representative for hemicellulose sugar compositions from flakes of wood (for example, Eucalyptus flakes) and some herbs (eg bagasse).
A pulse test was conducted using 250 ml of Finex AS 510 GC, styrene divinylbenzene Type I copolymer, SBA gel, trimethylamine functional group. Specific gravity 1.1 to 1.4g / cm3, medium size of microsphere of 280 millimicrons. The gel was in the form of sulphate. It was preconditioned with 1.5 volume bed (BV) of 60 mM OH ', adjusting the resin to 8 to 12% OH and leaving the remainder as the sulfate. A 5 ml sample was injected, followed by elution of water at 3 ml / min. Effective fractionation of xylose from the blend was observed, with the sugars mixed with peak at 0.61 and 0.65 BV and xylose with peak at 0.7 BV. The results of the pulse test are described in Figure 7.
In a pulse test, a column was charged with a sample and washed with an eluent. The elution fractions were collected and analyzed. For different sugars, the elution resulted in different interaction with the column materials, which led to different elution profiles. Based on the elution profile, it can be determined whether the elution conditions can be applied to a continuous method (for example, SSMB) to fractionate the sugars. An exemplifying elution profile is provided in Figure 7.
A pulse test chromatogram demonstrates that xylose is eluted last and all other monomeric sugars and oligomers are eluted first. The separation shown is sufficient to support the increasing scale change from such chromatographic fractionation to a simulated moving bed (SMB) or sequential simulated moving bed (SSMB) continuous system.
Example 7 - Hydrolysis of lignocellulosic materials with hemicellulose depletion in a continuous countercurrent hydrolysis system The eucalyptus wood chips were subjected to extraction of hemicellulose sugar as described in Examples 1 and 2. The remaining lignocellulose material with hemicellulose depletion was used in this Example.
The stirred tank hydrolysis reactor system is depicted in Figure 8A. An automatically controlled and monitored 4-tank system was used. The lignocellulose material with depleted hemicellulose (e.g., particles of an average size of ~ 1,400 microns) is suspended in an aqueous solution containing approximately 33% HCl and 8% sugar. The suspension is about 5% solids. The suspension is fed to tank 1 at a rate of 5 gph. Simultaneously, a solution of 42% HCI at approximately 2 gph is fed to tank 4. The solution in each tank is circulated through a pump at a rate of 50 gpm to suitably hold the solution in the mixed tank and allow good flow in cross-section through a separation membrane which is a part of the flow cycle. The membrane permeate from tank 1 is diverted to the hydrolyzate collection tank for deacidification and refinement. The retentate from tank 1 is returned to the tank for additional hydrolysis and a portion of the flow is transferred to tank 2 to maintain a constant level in tank 1. All series tanks are configured with the same permeate and control flow parameters of level. Typical concentrations of acid and sugar are shown in Figure 8B. The temperature of each tank is typically retained at 15.55 ° C (60 ° F), 12.77 ° C (55 ° F), 10 ° C (50 ° F), 10 ° C (50 ° F) for the tanks 1 to 4, respectively. The retentate for tank 4 is transferred to the lignin washing process based on the same level control.
The results of 30 day continuous hydrolysis of hemicellulose depleted eucalyptus are shown in Figure 8B. The black lines show the target value for the% HCI in reactor 1 to 4 and the hydrolyzate collection tank which transfers the same to the wash (deacification) and% sugar values (which corresponds to the total dissolved sugars in the solution) for tanks 1 to 4 and the collection tank, while the gray lines show the average value collected over 30 days for the same points. The countercurrent nature of the system is visualized: the acid enters the system in reactor 4 and proceeds toward 3, 2, and 1. The sugars have been continuously dissolved so that the sugar level has increased in the same direction. The mass of solid entered reactor 1, proceeding and decreasing through 2, 3 and 4.
When an additional reactor ("reactor 0") is used before the hemicellulose-depleted lignocellulose material enters reactor 1, the hydrolysis of highly oligomeric soluble sugars can be accelerated. In reactor 0, the hemicellulose-depleted lignocellulose material contacts the acid for 15 to 20 minutes at elevated temperature (35 to 45 ° C). Once such oligomers continue to hydrolyze to the smaller units, the viscosity falls sharply. It is observed that when reactor 0 was used, the average sugar% at all stages increased. Typically, such a hydrolysis system yields more than 97% of the cellulosic polymers and residues of the hemicellulosic polymers to dissolve in the hydrolyzate as oligomeric and monomeric sugars. The hydrolysis leaving solid essentially comprises lignin and less than 5%, usually less than 3% bound cellulose.
Example 8 - Recovery of acid, extraction and re-extraction of hexanol The hydrolyzate produced in the hydrolysis system flows into the extraction system to remove the acid from the aqueous phase and recover it for further use. HCI is extracted in a countercurrent extraction system that includes 2 extraction columns (extraction A and extraction B) using hexanol as the extractant. All extraction and re-extraction processes are performed at 50 ° C. Figure 9A shows the data collected over 30 days of the HCI level in the hydrolyzate that is drawn into the extraction system (upper line), the level is ~ 30%; the acid level after extraction A moves into extraction B (dark squares), the level is ~ 8%; the level of residual acid after extraction B (gray triangles) the level is less than 5%, typically 2 to 3%. The water is coextracted with the acid, consequently the aqueous phase becomes more concentrated, the typical sugar level is 16-20%.
The aqueous phase is then directed to the further treatment. The charged organic phase is first washed to recover the sugars from the solvent and the sugars, then, for re-extraction to recover the acid for recycling. Solvent washing is conducted in a column similar to that used for extraction with 20 to 25 w / w% HCl solution. Figure 9B depicts the level of sugars in the solvent phase after extraction B enters the lavage column (top line) which is typically 0.2 to 0.4% and the level of sugars in the washed solvent phase (bottom line ), typically less than 0.05%. Thereafter, the solvent is reextracted in another countercurrent extraction column compared to an aqueous phase containing less than 1% HCl. Figure 9C shows data accumulated over a 30 day cycle, where the level of HCI in the solvent entering reextraction is ~ 8% (gray triangles), the level of HCl in the solvent after reextraction is less than 0.5% (bottom line) and the acid level in the aqueous phase leaving the reextraction is ~ 18.5%.
Example 9 - Secondary hydrolysis The sugar solution exiting the extraction typically contains about 2.5% HCl and 16 to 20% sugars, however, typically only about 60 to 70% of such sugars are present as monomers. The sugar solution was diluted to have less than 13% sugar and about 0.6% residual acid. The solution was heated in a stirred tank at 120øC for about 45 minutes, the resulting composition comprising more than 90% monomers. It was then cooled to less than 60 ° C to prevent recondensation of the monomers. The data collected over 30 days are represented in Figure 10, showing the% of monomeric sugars (of the total sugars) before the secondary hydrolysis (bottom line) and after the secondary hydrolysis.
Example 10 - Amine Purification The sugar solution after the secondary hydrolysis was sent to the amine extraction process in which the solution came in contact with an extractant containing tri-laurylamine and hexanol in a ratio of 45:55 . The extractant ratio for sugar (O / W) of 1.8: 1 weight: weight was used and the extraction is controlled at a temperature of 50 to 60 ° C. The extraction is performed in a mixer-settler. The residual acid was extracted into the organic phase, the residual organic acids, furfural and phenolic molecules (related to lignin) were also extracted into that phase. Figure 11A shows the pH measured in the aqueous phase which is subjected to amine purification. Figure 11B shows the calculated efficiency of the acid extraction for the amine / hexanol phase as measured by titration of the organic phase. The loaded extractant is sent to another mixer-decanter where the solvent has been re-extracted with a base (typically Mg (OH) 2 or NaOH). Finally, the solvent was sent to a third mixer-settler where the solvent was washed with water. Once washed, the solvent was recycled back to the first extraction stage.
Example 11 - Purification of hexanol from the main solvent extraction step The solvent from the main extraction process extracts along with the acid and water many of the impurities present in the hydrolyzate. In addition, the organic acids react under the acidic conditions to form the esters with the alcoholic solvent (for example, hexyl acetate, hexyl formate). A fraction (e.g. ~ 10%) of the re-extracted solvent from the previous extraction process was separated and treated with lime (for example, with an aqueous phase containing 10% lime slurry). In doing so, the impurities were removed. The addition of lime was set at. about 1.5% by weight of the hexanol charged to the reactor. The 2-phase system was stirred at 80 ° C for 3 hours. The solution was then cooled to <50 ° C, the phases were separated in a blender-settler and the solvent phase was washed with water before resuming to the extraction solvent feed.
[00651] The level of impurities in the treated hexanol, including furfural. hexyl formate, hexyl acetate, hexyl chloride and hydroxymethylfurfural, was detected by gas chromatography. The data collected during the 30-day operation are shown in Figure 12. The only impurity accumulated was hexyl acetate. The kinetics of hexyl acetate hydrolysis is the slowest among such impurities, which can be solved by increasing the fraction or treatment conditions.
Example 12 - Acid Recovery: production of 42% acid in an HCl absorber
The HCI gas recycled from the evaporative process floated through a commercial downlink film (SGL) absorber. Two absorbents were used to ensure complete absorption of HCL gas. Absorbents were maintained at 5 to 10 ° C (for example, with the use of a cooler). HCl gas was absorbed through an HCl solution in the absorbent to increase the concentration of HCl at high concentration (e.g., greater than 41%). Data collected over a 30-day operating period are shown in Figure 13, which shows that the target concentration is generally achieved.
Example 13 - Lignin Wash An exemplary lignin wash system is shown in Figure 14A. The lignin of the hydrolysis system inserted into the lignin washing system in which it was washed is a countercurrent system with a 5 to 20% HCl solution. A 7-stage lavage system was used. The concentration of acid and sugars at each stage (mean result over 30 days of data collection) is shown in Figure 14B. In stage 1 the suspension of lignin had about 4% of sugars and about 34% of HCI. The concentration of sugars and acid decreases over the 7 stages. The suspension leaving stage 7 typically comprises less than 2.0% sugars and slightly more than 27% HCI.
Example 14 - Characterization of high purity lignin chemical structure obtained from solvent purification of limited solubility Lignin solids were washed according to Example 13. The washed lignin was heated in Isopar K at 100 ° C to deacidify the lignin. The deacidified lignin was then separated from the liquid phase. The deacidified lignin solid (-20 lb) was heated with a solution of NaOH (28 lb NaOH and 197 lb water) in a stirred reactor at 360 ° F (182.22 ° C) for 6 hours. The dissolved lignin solution can be cooled. The organic and aqueous phase of Isopar K were separated. The aqueous lignin solution came in contact with methyl ethyl ketone (MEK) at a ratio of ~1: 2 volume / volume. The pH of the aqueous solution is adjusted to 3.3 to 3.5 with HCl. The MEK phase was collected and placed in contact with a strong acid cation exchanger. The refined lignin solution was partially evaporated by dripping it into a hot water bath (~ 85 ° C). The precipitated lignin was filtered and washed with water on a filter press.
High purity lignin element analysis and commercial lignin are provided in the table below: Inductively coupled plasma (ICP) analysis of high purity pine lignin is given below: [00656] thermal properties of pine lignin are given in the table below.
NMR results indicated that high purity lignin has a low aliphatic hydroxyl group and high phenolic hydroxyl group, as shown in the tables below and in Figure 15. The values for the natural lignin are the values reported in the literature.
High purity hydroxyl group content and natural ignites Characterization by 13C NMR of lignin * Effects of two-stage dilute acid pretreatment on the structure and composition of lignin and cellulose in loblolly pine. Ragauskas AJ, Bioenerg. Rés 2008; 1 (3 to 4): 205 to 214.
[00660] # "Lignin structural changes resulting from ethanol organosolv treatment of loblolly pine". Ragauskas AJ, Energ Fuel 2010; 24 (1): 683-689.
[00661] A "Quantitative characterization of a hardwood milled wood lignin by nuclear magnetic resonance spectroscopy". Kadla JF. J Agr Food. Chem. 2005; 53 (25): 9,639 to 9,649.
Example 15 - Direct Lignin Extraction After the hemicellulose sugars were extracted from the eucalyptus flakes, the remainder was mainly cellulose and lignin. The remainder was delignified with the use of an aqueous organic solution containing acetic acid according to the procedure described below.
Eucalyptus wood chips (20.0 g) were mixed with a 50/50 v / v solution of methyl ethyl ketone (MEK) and water containing 1.2% acetic acid w / w solution to a 1:10 (100 ml of water, 100 ml of MEK and 2.2 g of acetic acid). The mixture was treated at 175 ° C for 4 hours in a stirred reactor. Then the system can cool down to 30 ° C before the reactor is opened. The slurry was decanted and the solid collected for further analysis.
After the reaction, there were 127 g of free liquid, of which 47.2 g are organic and 79.8 g are aqueous. The organic phase contained 1.1 g of acetic acid, 10.4 g of water and 5.5 g of dissolved solids (0.1 g of sugars and 5.4 g of others, which are mainly lignin). The aqueous phase contains 1.4 g of acetic acid, 2.1 g of dissolved solids (1.5 g of sugars and 0.6 g of others).
After decanting the liquid, the black slurry and white precipitate were in the bottom of the bottle. Such material was vacuum filtered and thoroughly taken with 50/50 v / v MEK / water (119.3 g MEK 148.4 g water) at room temperature until the color of the liquid turned very pale yellow. Three phases were collected; 19.7 g of organic, 215 g of water and 7 g of dry white solid. The organic phase contained 0.08 g of acetic acid and 0.37 g of solids dissolved. The aqueous phase contained 0.56 g of acetic acid and 0.6 g of solids dissolved.
[00666] All organic phases were consolidated. The pH of the foot solution adjusted to pH 3.8. The solution can then be separated into an aqueous phase (containing salts) and an organic phase (containing lignin). The organic phase containing lignin was recovered and purified using a strong acid cation column. The organic solution was then added dropwise in a 80 ° C water bath to precipitate the lignin.
13C Solid State NMR analysis of the white precipitate indicates that it comprises, for the most part, cellulose (pulp). The amount of lignin is not detectable. The reaction is successful in the delignification of the eucalyptus wood chips.
Example 16 - Sugar Analysis of Hydrolyzed Pine Wood Cellulose The pine wood chips were subjected to the extraction of hemicellulose sugar as described in Examples 1 and 2. Cellulose hydrolysis was performed using a system of simulated moving bed hydrolysis as described in PCT / US2011 / 057552 (now incorporated by reference for all purposes). Purification of cellulose sugar was conducted as described in Examples 8 and 9. A strong base anion exchanger was used instead of the extraction of amine for the sugar purification similar to example 10 (all are the same except that the amine is in a solid phase, which is the SBA resin). The compositions of the cellulose sugars were described in the table below.
Analysis of pineapple hydrolyzate cellulose sugars is given below: Example 17 - Sugar analysis of pine wood hemicellulose Pine wood chips were extracted with hemicellulose sugar as described in US Pat. Examples 1 and 2. The hemicellulose sugar was purified as described in Examples 3 and 5 except that a solid-base amine-containing solid-base anion exchanger was used. The resulting sugar solution was concentrated. The compositions of hemicellulose sugars have been described in the table below.
The analysis of pine wood hemicellulose sugars is given below: Example 18 - Eucalyptus hemicellulose sugar analysis [00672] The eucalyptus wood chips were subjected to extracting hemicellulose sugar as described in Examples 1 and 2. The hemicellulose sugar was purified as described in Examples 3 and 5. The hemicellulose sugar compositions were described in the table below.
The sugar analysis of Eucalyptus hemicellulose is given below: Example 19 - Sugar stream analysis Bagasse was subjected to the extraction of hemicellulose sugar as described in Examples 1 and 2. Hemicellulose sugar is purified as described in Examples 3 and 5. The resulting sugar solution is concentrated and fractionated as described in Example 6 to obtain a xylose rich solution containing more than 80% xylose and a second stream containing oligomeric and monomeric sugars. The composition of the sugar blend is determined in the table below. Example 20 - Cellulose hydrolysis by cellulase Cellulose pulp (eucalyptus pulp) was obtained as the remainder after the extraction of lignin and hemicellulose. The slurry of cellulose pulp having 10 to 20% solids in 0.05M acetate buffer, pH 4.55, 5% / cellulose, cellulase: 1: 1 cellobiase was prepared. The suspension was stirred at 55 ° C. The samples of the liquor were taken periodically for analysis of the dissolved sugars. The dissolved sugars were mostly glucose, however, some residual hemicellulose sugars remaining in the pulp may also be included. Dissolved sugar contains 7.78% lignin and 94.22% holocellulose, (89.66% glucose). As the% solids increase, the overall yield decreases (contact that enzyme loading is the same). However, the yield was higher compared to a hydrolyzed reference sample under the same conditions with Sigmacell (Sigma # S5504 cotton type 50, 50 μm), as viewed in Figure 42B. The cellulose pulp is well saccharified by the cellulase blending enzyme (although it still contains residual lignin). The E-HDLM reaction rate is higher than the reference material.
Example 21 - Enhancement of the SSMB Sequence for Superior Product Recovery The xylose separation of the hemicellulose sugar blend was conducted on a SSMB ProSep SSMB Operation model 12-column carousel design SSMB system constructed for such purpose , (hereinafter ProSep SSMB 2.0 Operation). The enhanced sequence contains 6 stages, each of which has two columns. The columns were packed with Finex AS 510 GC, styrene divinylbenzene copolymer in gel form, SBA Type I, trimethylamine functional group, specific gravity 1.1 to 1.4 g / cm 3, median microsphere size of 280 millimicrons. The gel was in the form of sulphate. It was preconditioned with 1.5 volume bed (BV) of 60 mM OH ', adjusting the resin to 8 to 12% OH and leaving the remainder as the sulfate. The table below compares the common pulse sequence of Operation ProSep SSMB 1.0 (original model) with the improved sequence of Operation ProSep SSMB 2.0. _____________________________ [00677] Xylose was separated according to the improved sequence of Operation ProSep SSMB 2.0. A feed solution containing about 30% w / w sugars was provided. The feed solution contains about 65% w / w xylose of the total sugars. The product stream containing about 16.4% of sugars was extracted. The product stream contained more than 80% w / w (e.g., in some cases, more than 82%, 84%, 85% w / w) xylose of the total sugars. Recovery was greater than 80% w / w. The raffinate containing about 5% w / w of total sugars was obtained. The raffinate contains only about 16.5% w / w of the total sugars.

权利要求:
Claims (16)
[1]
A method of producing high purity lignin from a biomass CHARACTERIZED in that it comprises: (i) removing the hemicellulose sugars from the biomass, thereby obtaining a residue containing lignin; wherein the lignin containing residue comprises lignin and cellulose; (ii) placing the lignin-containing residue in contact with a lignin-extracting solution for 0.5 to 24 hours to produce a lignin extract and a cellulosic residue; wherein the lignin extraction solution comprises a solvent of limited solubility, an organic acid and water, wherein the solvent of limited solubility and water form an organic phase and an aqueous phase; and (iii) separating the lignin extract from the cellulosic residue; wherein the lignin extract comprises lignin dissolved in the solvent of limited solubility; and wherein the solvent of limited solubility is an organic solvent having a solubility in water at 20 ° C less than about 30% by weight of the solvent in water.
[2]
A method according to claim 1, CHARACTERIZED by the fact that the removal of hemicellulose sugars does not remove more than 20% by weight of the cellulosic sugars.
[3]
A method according to claim 1, characterized in that the solvent of limited solubility and water in the lignin extraction solution is in a ratio of about 1: 1 v / v.
[4]
A method according to claim 1, characterized in that it further comprises purifying the cellulosic residue to obtain cellulose pulp.
[5]
A method according to claim 4, characterized in that the cellulose pulp comprises lignin in an amount of up to 10% by weight.
[6]
A method according to claim 1, CHARACTERIZED in that it further comprises placing the lignin extract in contact with a strongly acid cation exchanger to remove the residual cations, thereby obtaining a purified lignin extract.
[7]
A method according to claim 1 or 6, characterized in that it further comprises separating the solvent of limited solubility from the lignin extract thereby obtaining high purity lignin.
[8]
A method according to claim 7, characterized in that the separation comprises the evaporation of the solvent of limited solubility of the lignin extract.
[9]
A method according to claim 8, characterized in that the evaporation comprises spray-drying.
[10]
A method according to claim 1, characterized in that it further comprises washing the cellulose residue with the solvent of limited solubility and with fresh water thereby obtaining cellulose pulp.
[11]
A method according to claim 10, characterized in that it further comprises placing the cellulose pulp in contact with an acid for from 5 minutes to 1 day to produce a stream of acid hydrolyzate comprising the cellulose sugars.
[12]
A method according to claim 11, characterized in that it further comprises contacting the acid hydrolyzate stream comprising an acid and one or more cellulose sugars with a solvent extractor S1 to form a first mixture; and separating from the first mixture an organic stream comprising the acid and the solvent extractor S1 and an aqueous stream comprising the one or more cellulose sugars.
[13]
A method according to claim 12, characterized in that it further comprises evaporating the aqueous stream comprising the one or more cellulose sugars to form a concentrated aqueous stream; contacting the concentrated aqueous stream with the solvent extractor SI to form a second blend; and separating from the second blend a second organic stream comprising the acid and the solvent extractor S1 and a second aqueous stream comprising the one or more cellulose sugars.
[14]
A method according to claim 12, characterized in that it comprises placing the aqueous stream in contact with an amine extractor to form an amine mixture; and separating from the amine mixture an amine extraction stream comprising the acid and the extraction of amine and a stream of sugars comprising the one or more cellulose sugars.
[15]
A method according to claim 1, characterized in that the solvent of limited solubility is selected from methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl isopropyl ketone, methyl propyl ketone, mesityl, diacetyl, 2,3-pentanedione, 4-pentanedione, 2,5-dimethylfuran, 2-methylfuran, 2-ethylfuran, 1-chloro-2-butanone, methyl tert-butyl ether, diisopropyl ether, anisole, ethyl acetate, methyl acetate, ethyl formate, acetate isopropyl ether, propyl acetate, propyl formate, isopropyl formate, 2-phenylethanol, toluene, 1-phenylethanol, phenol, m-cresol, 2-phenylethyl chlorine, 2-methyl-2H-furan-3-one, γ-butyrolactone, acetal , methyl ethyl acetal, dimethyl acetal.
[16]
A method according to claim 1, CHARACTERIZED by the fact that the solvent of limited solubility is methyl ethyl ketone.

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法律状态:
2018-05-02| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-05-08| B25A| Requested transfer of rights approved|Owner name: VIRDIA, INC. (US) |

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2018-05-22| B25G| Requested change of headquarter approved|Owner name: VIRDIA, INC. (US) |

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2018-12-04| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-01-02| B15K| Others concerning applications: alteration of classification|Free format text: A CLASSIFICACAO ANTERIOR ERA: C07H 1/08 Ipc: C07H 1/08 (1974.07), C13K 1/02 (1968.09), C08H 8/0 |

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2019-04-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-06-25| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/05/2013, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/05/2013, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

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申请号 | 申请日 | 专利标题

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US201261642338P| true| 2012-05-03|2012-05-03|

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US61/642,338|2012-05-03|

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US201261662830P| true| 2012-06-21|2012-06-21|

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US201261672719P| true| 2012-07-17|2012-07-17|

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US201261680661P| true| 2012-08-07|2012-08-07|

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US201261681299P| true| 2012-08-09|2012-08-09|

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US201261693637P| true| 2012-08-27|2012-08-27|

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US201261715703P| true| 2012-10-18|2012-10-18|

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