METHOD FOR PRODUCING A BIOMASS HYDROLYZE

专利摘要:
The method for producing a biomass hydrolyzate is a process for catalytic deconstruction of biomass using a solvent produced in a bioremediation reaction.
公开号:BR112013016145B1
申请号:R112013016145-0
申请日:2011-12-29
公开日:2019-05-21
发明作者:Randy D. Cortright；Ming Qiao；Elizabeth Woods
申请人:Virent, Inc.；
IPC主号:

专利说明:

METHOD TO PRODUCE A BIOMASS HYDROLYSATE CROSS-REFERENCE TO RELATED APPLICATIONS [001] This application claims the benefit of Provisional Patent Application No. U.S. 61 / 428,461 filed on December 30, 2010.
DECLARATION OF FEDERAL FINANCING [002] This invention was produced with government support under concession No. 70NANB7H7023, requisition No. 4700558 granted by NIST through the ATP program. The government has certain rights in the invention.
FIELD OF TECHNIQUE [003] The present invention is directed to a process in which the liquids produced in a bio-reform process are used in the catalytic deconstruction facilitated by biomass solvent.
BACKGROUND OF THE INVENTION [004] The rising cost of fossil fuel and environmental concerns have stimulated worldwide interest in the development of alternatives to petroleum-based fuels, chemicals and other products. Biomass materials are a possible renewable alternative.
[005] Lignocellulosic biomass includes three main components. Cellulose, a primary sugar source for bioconversion processes, includes high molecular weight polymers formed from tightly bound glucose monomers. Hemicellulose, a secondary sugar source, includes shorter polymers formed from various sugars. Lignin includes chemical portions of phenylpropanoic acid polymerized in a complex three-dimensional structure. The resulting composition of lignocellulosic biomass
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2/55 has approximately 40 to 50% cellulose, 20 to 25% hemicellulose and 25 to 35% lignin in weight percentage.
[006] There is currently a non-compensating process in cost to effectively convert cellulose, hemicellulose and lignin into more suitable components to produce fuels, chemicals and other products. This is generally due to the fact that each of the components of lignin, cellulose and hemicellulose requires different processing conditions, such as temperature, pressure, catalysts, reaction time, etc., in order to effectively break its polymeric structure.
[007] Costly organic solvents such as acetone, 4-methyl-2-pentanone and solvent mixtures can be used to fractionate lignocellulosic biomass in cellulose, hemicellulose and lignin streams (Paszner 1984; Muurinen 2000; and Bozell 1998). Using this process, organic solvents dissolve part of the lignin so that it is possible to separate the dissolved lignin from cellulose and hemicellulose. To the extent that lignin can be separated, it can be burned for energy or it can be converted with a ZSM-5 catalyst into liquid fuel compounds, such as benzene, toluene and xylene (Thring 2000).
[008] After removing lignin from biomass, lignocellulose without lignin can be depolymerized by acid catalytic hydrolysis with the use of acids such as sulfuric acid, phosphoric acid and organic acids. Acid catalytic hydrolysis produces a hydrolyzed product that contains sugars, acid and other components such as polyols, oligosaccharides, organic acids, lignin and proteins. The hydrolysates can be separated using a process of
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3/55 known fractionation. Alternatively, an acid catalytic hydrolysis technology developed by Arkenol, Inc. can be used to convert cellulose and hemicellulose in biomass into sugars with the use of highly concentrated acid and to separate sugars from the acid using a simulated moving bed process ( Farone 1996).
[009] Cellulose and hemicellulose can be used as a raw material for various bioreactor processes, including aqueous phase reform (APR) and hydrodeoxygenation (HDO) - catalytic reform processes that, when integrated with hydrogenation, can convert cellulose and hemicellulose in hydrogen and hydrocarbons, including liquid fuels and other chemicals. APR and HDO methods and techniques are described in U.S. Patent No. 6,699,457; 6,964,757; 6,964,758; and 7,618,612 (all from
Cortright et al. and entitled Low-Temperature Hydrogen Production from Oxygenated Hydrocarbons); U.S. Patent No. 6,953,873 (to Cortright et al. And entitled LowTemperature Hydrocarbon Production from Oxygenated Hydrocarbons); U.S. Patent No. 7,767,867 and 7,989,664 and U.S. Serial Number Application 2011/0306804 (all to Cortright and entitled Methods and Systems for Generating Polyols). Various APR and HDO methods and techniques are described in U.S. Serial Number Patent Application 2008/0216391; 2008/0300434; and 2008/0300435 (all to Cortright and Blommel and entitled Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons); U.S. Patent Application Serial Number 2009/0211942 (to Cortright and entitled Catalysts and Methods for Reforming Oxygenated Compounds); U.S. Serial Number Patent Application 2010/0076233 (Cortright et
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4/55 al. and entitled Synthesis of Liquid Fuels from Biomass); International Patent Application No. PCT / US2008 / 056330 (to Cortright and Blommel and entitled Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons); and Copending Commonly Owned International Patent Application No. PCT / US2006 / 048030 (Cortright et al. and entitled Catalyst and Methods for Reforming Oxygenated Compounds), all of which are hereby incorporated by reference.
[010] Biomass must be deconstructed into less complex oxygenated compounds before use as a raw material for the bio-reform process. There remains a need for cost-effective methods to separate biomass into streams suitable for use in the APR, HDO and other bio-reform processes.
SUMMARY [011] The invention provides methods for producing a biomass hydrolyzate. The method generally involves: (1) reacting water and a water-soluble C2 + O1 + hydrogenated hydrocarbon in a liquid or vapor phase with H2 in the catalytic manner in the presence of a deoxygenation catalyst at a deoxygenation temperature and deoxygenation pressure to producing a biomass processing solvent that comprises a C2 + O1-3 hydrocarbon in a reaction stream; and (2) reacting the biomass processing solvent with a biomass component, hydrogen and a deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to produce a biomass hydrolyzate comprising at least one selected member of the group consisting of in a water-soluble lignocellulose derivative, a water-soluble cellulose derivative, a
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5/55 water-soluble hemicellulose, a carbohydrate, a starch, a monosaccharide, a disaccharide, a polysaccharide, a sugar, a sugar alcohol, an alditol and a polyol.
[012] One aspect of the invention is the composition of the biomass processing solvent. In one embodiment, the biomass processing solvent includes a member selected from the group consisting of an alcohol, ketone, aldehyde, cyclic ether, ester, diol, triol, hydroxycarboxylic acid, carboxylic acid and a mixture thereof.
[013] The biomass processing solvent is produced in the presence of a deconstruction catalyst. In one embodiment, the deconstruction catalyst comprises an acidic resin or a basic resin. The deconstruction catalyst may further comprise a member selected from the group consisting of Fe, Co, Ni, Cu, Ru, Rh, Pd, Pt, Re, Mo, W, alloys thereof and combinations thereof, or a support and a member adhered to the support selected from the group consisting of Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Mo alloys thereof and combinations thereof. In another embodiment, the deconstruction catalyst can comprise,
still, one selected group member which consists of Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, alloys even if combinations From themselves. [014] In one mode, the hydrocarbon oxygenated is selected from the group that It consists in a starch, one
carbohydrate, polysaccharide, disaccharide, monosaccharide, sugar, sugar alcohol, alditol, organic acid, phenol, cresol, ethanediol,
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6/55 ethanedione, acetic acid, propanol, propanediol, propionic acid, glycerol, glyceraldehyde, dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, a butanediol, butanoic acid, an aldotetrose, tartaric acid, an aldopentose, an aldohexose, a ketone , a ketopentose, a ketohexose, a hemicellulose, a cellulosic derivative, a lignocellulosic derivative and a polyol.
[015] The invention also provides a method for producing a biomass hydrolyzate comprising the steps of: (1) reacting in a water catalytic manner and a C2 + O1 + water-soluble oxygenated hydrocarbon in a liquid or vapor phase with H2 in the presence of a deoxygenation catalyst at a deoxygenation temperature and deoxygenation pressure to produce an oxygenate comprising a C2 + O1-3 hydrocarbon in a reaction stream; (2) reacting catalytically in the liquid or vapor phase or oxygenated in the presence of a condensation catalyst at a condensing temperature and condensing pressure to produce a biomass processing solvent comprising one or more C4 + compounds; and (3) reacting the biomass processing solvent with a biomass component, hydrogen and a deconstruction catalyst at a deconstruction temperature and deconstruction pressure to produce a biomass hydrolyzate comprising at least one selected member of the group consisting of in a water-soluble lignocellulose derivative, a water-soluble cellulose derivative, a water-soluble hemicellulose derivative, a carbohydrate, a starch, a monosaccharide, a disaccharide, a polysaccharide, a sugar, a sugar alcohol, an alditol and a polyol.
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7/55 [016] The biomass processing solvent may include a member selected from the group consisting of an alkane, an alkene and an aromatic. In one embodiment, the member is selected from the group consisting of benzene, toluene and xylene.
[017] The deconstruction catalyst can comprise an acidic resin or a basic resin. In one embodiment, the deconstruction catalyst further comprises a member selected from the group consisting of Fe, Co, Ni,
Cu, Ru, Rh, Pd, Pt, Re, Mo, W, alloys thereof and combinations thereof. The deconstruction catalyst may also comprise a support and a member adhered to the support selected from the group consisting of Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Mo, alloys thereof and combinations thereof , or it may also comprise a selected member of the group consisting of Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, alloys thereof and combinations thereof.
[018]In a modality, the hydrocarbon C2 + O1 + is selected of group consisting in a starch, a carbohydrate, one polysaccharide, a disaccharide, a monosaccharide, one sugar, an alcohol from sugar, an alditol,
an organic acid, a phenol, a cresol, ethanediol, ethanedione, acetic acid, propanol, propanediol, propionic acid, glycerol, glyceraldehyde, dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, a butanediol, butanoic acid, an aldotetrose, tartaric acid , an aldopentose, an aldohexose, a ketotetrose, a ketopentose, a ketohexose, a hemicellulose, a cellulosic derivative, a lignocellulosic derivative and a polyol.
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8/55 [019] The condensation catalyst may comprise a member selected from the group consisting of a carbide, a nitride, zirconia, alumina, silica, an aluminosilicate, a phosphate, a zeolite, a titanium oxide, a zinc oxide , a vanadium oxide, a lanthanum oxide, a yttrium oxide, a scandium oxide, a magnesium oxide, a cerium oxide, a barium oxide, a calcium oxide, a hydroxide, a heteropoly acid, an inorganic acid , an acid-modified resin, a base-modified resin and combinations thereof.
[020] The invention also provides a method for deconstructing biomass. The method generally includes reacting a biomass slurry with a biomass processing solvent comprising a C2 + O1-3 hydrocarbon at a deconstruction temperature between about 80 ° C and 350 ° C and a deconstruction pressure between about 0.69 MPa (100 psi) and 13.79 MPa (2,000 psi) to produce a biomass hydrolyzate comprising at least one member selected from the group consisting of a water-soluble lignocellulose derivative, derived from water-soluble cellulose, derived from water-soluble hemicellulose, carbohydrate, starch, monosaccharide, disaccharide, polysaccharide, sugar, sugar alcohol, alditol and polyol, in which the biomass processing solvent is produced by catalytic reaction in the liquid or vapor phase of a solution of aqueous raw material comprising water and water-soluble oxygenated hydrocarbons comprising a C2 + O1 + hydrocarbon with H2 in the presence of a deoxygenation catalyst at a the deoxygenation temperature and deoxygenation pressure.
[021] In one mode, H2 comprises at least
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9/55 minus one of an H2 generated in situ, external H2, or recycled H2. H2 can comprise H2 generated in situ by catalytic reaction in a liquid phase or a vapor phase of a portion of the water and the oxygenated hydrocarbon in the presence of an aqueous phase reform catalyst at a reform temperature and reform pressure.
[022] In one embodiment, the oxygenated hydrocarbon comprises a member selected from the group consisting of a lignocellulose derivative, a cellulose derivative, a hemicellulose derivative, a carbohydrate, a starch, a monosaccharide, a disaccharide, a polysaccharide, a sugar, a sugar alcohol, an alditol and a polyol. The biomass hydrolyzate can be recycled and combined with the biomass slurry.
[023]
One aspect of the invention is the biomass processing solvent which may comprise a member selected from the group consisting of an alcohol, ketone, aldehyde, cyclic ether, ester, diol, triol, hydroxycarboxylic acid, carboxylic acid and a mixture thereof.
In one embodiment, the biomass processing solvent comprises a member selected from the group consisting of ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, pentanol, hexanol, cyclopentanol, cyclohexanol, 2-methylcyclopentanol, a hydroxy ketone, a ketone cyclic, acetone, propanone, butanone, pentanone, hexanone, 2-methyl-cyclopentanone, ethylene glycol, 1,3propanediol, propylene glycol, butanediol, pentanediol, hexanediol, methylglyoxal, butanedione, pentanedione, dicetohexide, acetaldehyde, hydroxyaldehyde, hydroxyaldehyde , hexanal, formic acid, acid
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10/55 acetic, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, lactic acid, glycerol, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol,
-methyltetrahydrofuran,
2,5-dimethyl-tetrahydrofuran,
2-ethyltetrahydrofuran,
2-methyl furan, 2,5-dimethyl furan, 2-ethyl furan, hydroxylmethylfurfural,
3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 5-hydroxymethyl-2 (5H) -furanone, dihydro-5 (hydroxymethyl) -2 (3H) -furanone, tetrahydro-2-furanoic acid, dihydro-5- (hydroxymethyl) - 2 (3H) -furanone, tetrahydrofurfuryl alcohol, 1- (2-furyl) ethanol and hydroxymethyltetrahydrofurfural, isomers thereof and combinations thereof.
[024] The deoxygenation catalyst can deoxygenate water-soluble oxygenated hydrocarbons to produce the biomass processing solvent. In one embodiment, the deoxygenation catalyst comprises a support and a member selected from the group consisting of Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, an alloy of them and a combination of them. The deoxygenation catalyst may further comprise a member selected from the group consisting of Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn , Ge, P, Al, Ga, In, T1, an alloy thereof and a combination thereof. The deoxygenation catalyst can have an active metal function and an acidic function. The support may comprise a member selected from the group consisting of carbon, silica, alumina, zirconia, titania, tungsten, vanadium, heteropoly acid, diatomite, hydroxyapatite, chromia, zeolites and mixtures thereof. The support may be a selected member of the group consisting of zirconia with tungsten, zirconia modified by
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11/55 tungsten, tungsten modified alpha-alumina or tungsten modified alumina theta.
[025] In one embodiment, the aqueous phase reform catalyst comprises a support and a member selected from the group consisting of Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, an alloy thereof and a combination of themselves. The aqueous phase reform catalyst may further comprise a member selected from the group consisting of Cu, B, Mn, Re, Cr, Mo, Bi, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, an alloy thereof and a combination thereof. In another embodiment, the aqueous phase reform catalyst and the deoxygenation catalyst are combined into a single catalyst.
[026] Deoxygenation reactions and aqueous phase reform are conducted at a temperature and pressure at which the thermodynamics are favorable. In one embodiment, the reform temperature is in the range of about 100 ° C to about 450 ° C or about 100 ° C to about 300 ° C and the reform pressure is a pressure at which water and oxygenated hydrocarbons are gaseous. In another embodiment, the reforming temperature is in the range of about 80 ° C to about 400 ° C and the reforming pressure is a pressure in which water and oxygenated hydrocarbon are liquid.
[027] The temperature deoxygenation can to be greater than 120 ° C, or 150 ° C, or 180 ° C, or 200 ° C and smaller what 325 ° C, or 300 ° C, or 280 ° C, or 260 ° C, or 240 ° C, or 220 ° C. The pressure deoxygenation can be greater than 1.38 MPa (200 psig), or 2.52 MPa (365 psig) , or 3.45 MPa (500 psig) or 4.14 MPa (600 psig) and less than 17.24 MPa (2,500 psig), or 15.51 MPa (2,250 psig), or 13.79 MPa (2.00 0 psig), or 12 41
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12/55
MPa (1,800 psig), or 10,34 MPa (1,500 psig), or 8.27 MPa (1,200 psig), or 6,89 MPa (1,000 psig). The deoxygenation temperature can also be in the range of about 120 ° C to 325 ° C and the deoxygenation pressure is at least 10.13 kilopascals (0.1 atmosphere). In other embodiments, the deoxygenation temperature is in the range of about 120 ° C to about 325 ° C or about 200 ° C to 280 ° C and the deoxygenation pressure is between 2.52 MPa (365 psig) and about 17.24 MPa (2,500 psig), or about 4.14 MPa (600 psig) and 12.41 MPa (1,800 psig).
[028] In one embodiment, the APR catalyst and the deoxygenation catalyst are combined into a single catalyst. In this respect, the reform temperature and deoxygenation temperature can be in the range of about 100 ° C to
325 ° C, or about 120 ° C at 300 ° C, or about 200 ° C at 280 ° C and pressure in remodeling and deoxygenation pressure can be in banner in fence in 1.38 MPa (200 psig) at 10.34 MPa (1,500 psig), or fence 1.38 MPa (200 psig) to 8.27 MPa (1,200 psig), or fence in 1.38 MPa (200 psig) at 5 MPa (725 psig). [029] On a aspect, the reaction step an
biomass slurry with a biomass processing solvent is carried out in the same reactor as the catalytic reaction step of the aqueous raw material solution with H2 in the presence of a deoxygenation catalyst. The deconstruction temperature and deoxygenation temperature can be in the range of about 100 ° C to 325 ° C, about 120 ° C to 300 ° C, or about 200 ° C to 280 ° C and the deconstruction pressure and the deoxygenation pressure can be in the range of about 1.38 MPa (200 psig) to 10.34 MPa (1,500 psig), about 1.38 MPa
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13/55 (200 psig) to 8.27 MPa (1,200 psig), or about 4.14 MPa (600 psig) to 12.41 MPa (1,800 psig).
[030] The deconstruction catalyst includes an acid resin and a basic resin and may include a member selected from the group consisting of Fe, Co, Ni, Cu, Ru, Rh, Pd, Pt, Re, Mo, W, and alloys of them or a support and a member selected from the group consisting of Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Mo, their alloys and combinations thereof. The deconstruction catalyst can comprise,
yet, a member selected of the group consisting of Ass , Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag , Au, Sn, Ge, P, Al, Ga , In, Tl, and alloys thereof. [031] Another aspect of the invention includes The stage
dehydration of the biomass hydrolyzate. DESCRIPTION OF THE DRAWINGS
032]
Figure 1 is a flowchart that illustrates a process for catalytic conversion of biomass into liquid fuels using a biomass processing solvent derived from a recycling stream associated with the conversion of biomass hydrolyzate into an APR / HDO process.
[033] Figure 2 is a flow chart that illustrates one process for conversion catalytic in biomass in fuels liquids with the use of one solvent in processing of biomass derivative gives conversion in hydrolyzate of biomass in a APR / HDO process. [034] The figure 3 illustrates the results in deconstruction of organo-catalytic biomass with the use of an biomass processing stream of a process in
bioreformation as an organic solvent.
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14/55 [035] Figure 4 illustrates the results of deconstruction of organo-catalytic biomass with the use of a biomass processing stream from a bio-reform process as an organic solvent and various deconstruction catalysts.
[036] Figure 5 illustrates the results of deconstruction of organo-catalytic biomass with the use of a biomass processing stream from a biorformation process as an organic solvent and a Pd: Ag / W-ZrO2 deconstruction catalyst.
[037] Figure 6 illustrates the selectivity of organic-catalytic biomass deconstruction product with the use of a biomass processing stream from a bio-reform process as an organic solvent and a Pd: Ag / W-ZrO2 deconstruction catalyst.
[038] Figure 7 illustrates the oxygenation level of organo-catalytic biomass deconstruction products with the use of a biomass processing stream from a bioreformation process as an organic solvent and a Pd: Ag / W- deconstruction catalyst New or regenerated ZrO2.
[039] Figure 8 illustrates income from
product deconstruction of organo-catalytic biomass with O use of a current of Processing biomass in one process bioreactor as a solvent organic and one
deconstruction catalyst Pd: Ag / W-ZrO2 new or regenerated.
DETAILED DESCRIPTION OF THE INVENTION [040] The present invention provides methods, reactor systems and catalysts for hydrolyzing or deconstructing biomass with the use of a heterogeneous catalyst and a biomass processing solvent produced in a
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15/55 bioreactor process. The resulting product stream includes a biomass hydrolyzate which can be further processed in a bio-reform process to provide the biomass processing solvent and a product stream for further conversion to the desired compounds. The process of
bioreactor and O process deconstruction can occur separately in many different reactors or together in one single reactor and in general occurrence steady state as part of on one process continuous. [041]According used in this document, the term biomass refers to a, without limitation materials
organics produced by plants (such as leaves, roots, seeds and stems) and microbial and animal metabolic waste. Common biomass sources include: (1) agricultural residues, including corn husks, straw, seed husks, sugarcane remains, bagasse, nut shells, cottonseed residue and livestock manure, poultry and pigs (2) wood materials, including wood or bark, sawdust, piece of wood and grinding debris; (3) municipal solid waste, including recycled paper, used paper and garden clippings; and (4) energy crops, including poplars, willows, yellow millet, miscanthus, sorghum, alfalfa, bluestream prairie, corn, soybeans and the like. The term also refers to the primary building blocks of the previous one, that is, lignin, cellulose, hemicellulose and carbohydrates, such as saccharides, sugars and starches, among others.
[042] As used in this document, the term bioreformation refers to, without limitation, processes for catalytic conversion of biomass and other carbohydrates
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16/55 in lower molecular weight hydrocarbons and oxygenated compounds, such as alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes, diols and other polyols, with the use of aqueous phase reform, hydrogenation, hydrogenolysis, hydrodeoxygenation and / or other conversion processes that involve the use of heterogeneous catalysts. Biorformation also includes the additional catalytic conversion of such lower molecular weight oxygenated compounds to C4 + compounds.
[043] The deconstruction process uses hydrogen, a heterogeneous deconstruction catalyst and a biomass processing solvent or mixture of solvents produced in a bio-reform process. Such a process is illustrated in Figure 1. First, in the deconstruction process, a biomass slurry is combined with a deconstruction catalyst and a biomass processing solvent or mixture of solvents produced in a bio-reform process. The biomass slurry can include any type of biomass that has been cut, shredded, pressed, crushed or processed to a size suitable for conversion. The biomass processing solvent or solvent mixture may contain a wide range of oxygenates, such as ketones, alcohols, cyclic ethers, acids and esters and / or C4 + hydrocarbons, such as C4 + alkanes, C4 + alkenes and aromatic compounds, including benzene, toluene, xylene. In a preferred embodiment, the biomass processing solvent or mixture of solvents is derived from the biomass hydrolyzate or, as illustrated in Figures 1 and 2, from further processing of the biomass hydrolyzate in a bio-reform process.
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17/55 [044] The deconstruction catalyst is a heterologous catalyst that has one or more materials that can catalyze a reaction between hydrogen and lignin, cellulose, hemicellulose and their derivatives to produce the desired oxygenated compounds. The heterologous deconstruction catalyst may include, without limitation, acid-modified resin, base-modified resin and / or one or more of Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Mo, alloys and combinations thereof. The deconstruction catalyst can include these elements alone or combined with one or more Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au , Sn, Ge, P, Al, Ga, In, Tl, Ce and combinations thereof. In one embodiment, the deconstruction catalyst includes Ni, Ru, Ir,
Pt, Pd, Rh, Co or Mo and at least one member selected among W, B, Pt, Sn, Ag, Au, Rh, Co and Mo. [045] Resins will generally include substrates
basic or acidic (for example, supports that have low isoelectric points) that can catalyze biomass deconstruction reactions, followed by hydrogenation reactions in the presence of H2, leading to carbon atoms that are not linked to oxygen atoms.
Heteropoly acids are a class of acids exemplified by such species as solid phase
H3 + xPMo12 -xVxO4 0,
H4SiW12O40, H3PW12O40 and H6P2W18O62. Heteropoly acids also have a well-defined local structure, the most common of which is the tungsten-based Keggin structure. Basic resins include resins that exhibit basic functionality, such as Amberlyst.
[046] The deconstruction catalyst is self-supporting or includes support material. The support
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18/55 may contain any one or more of nitride, carbon, silica, alumina, zirconia, titania, tungsten, vanadium, cerium, zinc oxide, chromia, boron nitride, zirconia with tungsten, heteropoly acids, diatomite, hydroxyapatite and mixtures of themselves. Preferred supports are carbon, m-Zr02, and W-Zr02. In one embodiment, the deconstruction catalyst includes Ni: Mo, Pd: Mo, Rh: Mo, Co: Mo, Pd: Ru, Pt: Re or Pt: Rh on a m-Zr02 support. In another modality, the deconstruction catalyst includes Ru, Ru: Pt, Pd: Ru, Pt: Re, Pt: Rh, Pd: Mo, Pd: Ag or Ru: Pt: Sn on a carbon support or W-ZrO2. In another modality, the deconstruction catalyst includes Fe, Co, Ni, Cu, Ru, Rh, Pd, Pt, Re, Mo or W in a carbon support. The support can also serve as a functional catalyst, as in the case of supports or acidic or basic resins that have acidic or basic functionality.
[047] In one embodiment, the deconstruction catalyst is formed in a honeycomb monolith design so that the biomass slurry, solid phase slurry or the solid / liquid phase slurry can flow through the deconstruction catalyst . In another embodiment, the deconstruction catalyst includes a magnetic element such as Fe or Co so that the deconstruction catalyst can be easily separated from the resulting product mixture.
[048] The product stream resulting from the deconstruction of biomass will generally include water, unreacted or underreacted product, gray and a biomass hydrolyzate which includes lignin and lignocellulosic derivatives, cellulose and cellulosic derivatives, hemicellulose and derivatives
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19/55 hemicellulose, starch carbohydrates, monosaccharides, disaccharides, sugar polysaccharides, sugar alcohols, alditols, polyols and mixtures thereof.
Preferably, the biomass hydrolyzate includes sugar, sugar alcohols, starch saccharides and other polyhydric alcohols. More preferably, the biomass hydrolyzate includes a sugar, such as glucose fructose, sucrose, maltose, lactose, mannose or xylose, or a sugar alcohol, such as arabitol, erythritol, glycerol, isomalt lactitol malitol, mannitol, sorbitol, xylitol, arabitol or glycol. In certain embodiments, the biomass hydrolyzate may also include alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes, diols and other polyols that are useful as the processing solvent. In other embodiments, the biomass hydrolyzate can also include mono-oxygenated hydrocarbons that can be further converted into hydrocarbons
C4 + such as C 4+ alkanes C4 + alkenes and aromatic compounds, including benzene, toluene, xylene, which are useful as liquid fuels and chemicals.
[049]
The resulting biomass hydrolyzate can be collected for further processing in a bioremediation process or, alternatively used as a raw material for other conversion processes, including the production of fuels and chemicals with the use of fermentation or enzymatic technologies.
For example, water-soluble carbohydrates, such as starch, monosaccharides, polysaccharide disaccharides, sugar and sugar alcohols and water-soluble derivatives from lignin, hemicellulose and cellulose are suitable for use in the bio-reform processes. Alternatively, the hydrolyzate of
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The resulting biomass can be recycled and combined into the biomass slurry for further conversion or use as a processing solvent.
[050] In certain applications, the biomass product stream passes through one or more separation steps to separate ashes, unreacted biomass and sub-reacted biomass from the product stream to supply the biomass hydrolyzate. The biomass hydrolyzate may also need additional processing to separate aqueous phase products from organic phase products, such as lignin-based hydrocarbons not suitable for bio-reform processes. The biomass hydrolyzate can also be dehydrated or further purified before being introduced into the bio-reform process. Such dehydration and purification processes are known in the art and may include simulated moving bed technology, distillation, filtration, etc.
BIOMASS PROCESSING SOLVENT [051] The bio-reformation processes convert starches, sugars and other polyols into a wide range of oxygenates, including organic compounds that facilitate the deconstruction of biomass. As used herein, oxygenated generically refers to hydrocarbon compounds that have 2 or more carbon atoms and 1, 2 or 3 oxygen atoms (referred to herein as C2 + O1-3 hydrocarbons), such as alcohols, ketones, aldehydes, cyclic ethers, hydroxycarboxylic acids, carboxylic acids, diols and triols. Preferably, oxygenates have 2 to 6 carbon atoms or 3 to 6 carbon atoms. Alcohols may include, without limitation, primary, secondary, linear, branched or cyclic C2 + alcohols,
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21/55 such as ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol,
-methylcyclopentanonol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and isomers thereof. Ketones can include, without limitation, hydroxy ketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybutan-2-one, pentanone, cyclopentanone, pentane-2,3 -dione, pentane-2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglioxal butanedione, pentanedione, dicetohexane and isomers thereof. Aldehydes can include, without limitation, hydroxyaldehydes, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal octanal, nonal, decanal, undecanal, dodecanal and isomers thereof. Carboxylic acids can include, without limitation, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, isomers and derivatives thereof, including hydroxylated derivatives, such as 2-hydroxybutanoic acid and lactic acid. The diols may include, without limitation, lactones, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol and isomers thereof. Triols may include, without limitation, glycerol, 1,1,1tris (hydroxymethyl) -ethane (trimethylolethane), trimethylolpropane, hexanethiol and isomers thereof. Cyclic ethers include, without limitation, furfural, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol, 2-methylPetition 870190015724, of 02/15/2019, p. 28/74
22/55 tetrahydrofuran,
2,5-dimethyl-tetrahydrofuran,
2methyl furan,
2-ethyl-tetrahydrofuran,
2-ethyl furan, hydroxylmethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro3-furanol, 2,5-dimethyl furan, 5-hydroxymethyl-2 (5H) -furanone, dihydro-5- (hydroxymethyl) -2 (3H) -furanone, tetrahydro acid -2furoico, dihydro-5 (hydroxymethyl) -2 (3H) -furanone tetrahydrofurfuryl alcohol, 1- (2-furyl) ethanol, hydroxymethyltetrahydrofurfural and isomers thereof.
[052]
The oxygenates above can originate from any source, but are preferably derived from oxygenated hydrocarbons resulting from the initial processing of biomass in the biomass slurry. Oxygenated hydrocarbons can be any water-soluble oxygenated hydrocarbon that has two or more carbon atoms and at least one oxygen atom referred to herein as hydrocarbons
C2 + O1 +).
Preferably, the oxygenated hydrocarbon has 12 carbon atoms (C1-12O1-11 hydrocarbon) and more preferably 2 to carbon atoms (C16O1-6 hydrocarbon) and 1, 2, 3,
4, 5 or oxygen atoms. Oxygenated hydrocarbon can also have an oxygen to carbon ratio in the
0.5: 1 to 1.5: 1, including the 0.75: 1.0, 1.0: 1.0,
1.25: 1.0, 1.5: 1.0 and other ratios between them. In one example, oxygenated hydrocarbon has a ratio of oxygen to carbon of 1: 1. Non-limiting examples of water-soluble oxygenated hydrocarbons include starches, monosaccharides, disaccharides, polysaccharides, sugar, sugar alcohols, alditols, ethanediol, ethanedione, acetic acid, propanol, propanediol, propionic acid, glycerol, glyceraldehyde,
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23/55 dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, butanedioles, butanoic acid, aldotetroses, tautaric acid, aldopentoses, aldohexoses, ketotetroses, ketohexoses, alditols, hemicelluloses, cellulosic acids and similar, cellulosic acids. Preferably, the oxygenated hydrocarbon includes starches, sugar, polyhydric alcohols.
sugar alcohols, saccharides and others
More preferably, the oxygenated hydrolyzate includes a sugar, such as glucose, fructose, sucrose, maltose, lactose, mannose or xylose, or a sugar alcohol, such as arabitol, erythritol, glycerol, isomalt, lactitol, malitol, mannitol, sorbitol, xylitol, arabitol or glycol.
[053]
Production of biomass processing solvent [054]
As shown in Table 1 below, the bio-reformation process produces a complex organic mixture.
The mixture of different organics provides good candidate compounds for a high quality biomass deconstruction solvent.
Water phase Organic phase Component % of phase Component % of phase 2-Pentanone 13.75 3-Hexanone 12.98 Butanoic Acid 13.61 2-Hexanone 12.60 2-Butanone 13.08 2-Pentanone 9, 53 Furan, tetrahydro-2,5-dimethyl 10.70 Water 6, 64 Acetone 8, 43 Butanoic Acid 6, 19 Propionic Acid 8, 15 2-Furanomethanol, tetrahydro- 5.68 Acetic Acid 4.82 Furan, tetrahydro-2,5-dimethyl- 5, 29 Pentanoic Acid 4.68 3-Pentanone 4 93
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2-Butanol, (+/-) - 3.77 Pentanoic Acid 4.41 2-Hexanone 3.75 2-Butanone 4.35 3-Hexanone 3.57 2H-Pirana, tetrahydro-2-methyl- 2.78 (R) - (-) - 2-Pentanol 1.82 2-Hexanol 2.22 Isopropyl Alcohol 1.73 Hexanoic Acid 2, 10 Hexanoic Acid 1, 09 Furan, tetrahydro-2-methyl- 1.95 2-Butanone, 3-hydroxy- 1.05 2 (3H) -Furanone, 5ethyldihydro- 1.71 2-Pentanol 1.71 3-Hexanol 1.62 Hexane 1.55 Pentane 1.52 Propionic Acid 1.42
Table 1. Typical Products of a Bioremodal Process [055] Oxygenates are prepared by reacting an aqueous raw material solution containing water and water-soluble oxygenated hydrocarbons with hydrogen over a catalytic material to produce the desired oxygenates. Hydrogen can be generated in situ with the use of aqueous phase reform (H2 generated in situ or H2 APR) or a combination of H2 APR, external H2 or recycled H2, or just simply recycled H2 or H2. The term external H2 refers to hydrogen that does not originate from the raw material solution, but is added to the reactor system from an external source. The term recycled H2 ”refers to unconsumed hydrogen, which is collected and then recycled back to the reactor system for further use. External H2 and recycled H2 can also be referred to collectively or individually as supplementary H2 ”. In general, supplemental H2 can be added for the purpose of supplementing hydrogen APR or to increase the pressure of
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25/55 reaction inside the system or to increase the molar ratio between hydrogen and carbon and / or oxygen in order to enhance the production yield of certain types of reaction product, such as ketones and alcohols.
[056] In processes using H2 APR, the oxygenates are prepared by catalytic reaction of a portion of the aqueous raw material solution containing water and the water-soluble oxygenated hydrocarbons in the presence of an APR catalyst at a reforming temperature and pressure reform to produce H2 APR and catalytic reaction of H2 APR (and recycled H2 and / or external H2) with a portion of the raw material solution in the presence of a deoxygenation catalyst at a deoxygenation temperature and deoxygenation pressure to produce the oxygenated products. In systems using recycled H2 or external H2 as a hydrogen source, oxygenates are simply prepared by catalytic reaction of recycled H2 and / or external H2 with the raw material solution in the presence of the deoxygenation catalyst at the temperatures and deoxygenation pressures . In each of the above, oxygenates can also include recycled oxygenates (recycled C1 + O1-3 hydrocarbons).
[057] The deoxygenation catalyst is preferably a heterologous catalyst that has one or more active materials that can catalyze a reaction between hydrogen and the oxygenated hydrocarbon to remove one or more of the oxygen atoms from the oxygenated hydrocarbon to produce alcohols, ketones, aldehydes, cyclic ethers, carboxylic acids, hydroxycarboxylic acids, diols and triols. In general, the heterologous deoxygenation catalyst will have both an active metal function and an acidic function to achieve the
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Previous 26/55. For example, acidic supports (for example, supports that have low isoelectric points) primarily catalyze the dehydration reactions of oxygenated compounds. The hydrogenation reactions then take place on the metal catalyst in the presence of H2, producing carbon atoms that are not bound to the oxygen atoms.
The bifunctional dehydration / hydrogenation pathway consumes H2 leads to the subsequent formation of various polyols, diols, ketones, aldehydes, alcohols, carboxylic acids, hydroxycarboxylic acids and cyclic ethers, such as furans and pirans.
[058]
Active materials may include, without limitation, Cu, Re, Fe,
Ru, Ir, Co, Rh, Pt,
Pd, Ni, W, Os, Mo,
Ag, Au, alloys thereof and combinations thereof, adhered to may include these a support. The deoxygenation catalyst
elements alone or combined with one or more Mn, Cr, Mo, W, V, Nb, OK, You, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, Ce and combinations thereof. In an modality , O catalyst deoxygenation includes Pt, Pd, Ru, Re, Ni, W or Mo. Already in another modality, the catalyst in
deoxygenation includes Sn, W, Mo, Ag, Fe and / or Re and at least one transition metal selected from Ni, Pd, Pt and Ru. In another embodiment, the catalyst includes Fe, Re and at least Cu or a transition metal from Group VIIIB. In another modality, the deoxygenation catalyst includes Pd in alloy or mixed by adding Cu or Ag and supported by an acid support. In another modality, the deoxygenation catalyst includes Pd in alloy or mixed by adding to a metal of the VIB Group supported by an acidic support. In another modality, the deoxygenation catalyst includes Pd
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27/55 alloyed or mixed by adding a metal from the VIB Group and a metal from the IVA Group on an acidic support. The support can be any of a variety of supports, including a support that has carbon, silica, alumina, zirconia, titania, tungsten, vanadium, chromia, zeolites, heteropoly acid, diatomite, hydroxyapatite and mixtures thereof.
[059] The deoxygenation catalyst can also include an acid support modified or constructed to provide the desired functionality. Heteropoly acids are a class of solid phase acids exemplified by such species as H3 + xPMo12-xVxO4 0, H4SiW12O40, H3PW12O40 and H6P2W18 062.
Heteropoly acids are solid phase acids that have a local structure as well defined, the most common of which is Keggin structure based on tungsten. Another examples may include, without limitations, zirconia with tungsten, modified zirconia by tungsten, modified alpha-alumina
tungsten or tungsten modified alumina theta.
[060] The loading of the first element (ie Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys and combinations thereof) is if in the range of 0.25% by weight to 25% by weight on carbon, with weight percentages of 0.10% and 0.05% of increments between, such as 1.00%, 1.10%,
1.15%, 2.00%, 2.50%, 5.00%, 10.00%, 12.50%, 15.00% and 20.00%.
The preferred atomic ratio of the second element (ie, Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al , Ga, In, Tl, Ce and combinations thereof) is in the range of 0.25 to 1 to 10 to 1, including any ratios between them, such as 0.50, 1.00, 2.50, 5 , 00 and 7.50 for l. If the catalyst is attached to a support, the combination of the catalyst and the support is 0.25% by weight at
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10% by weight of the primary element.
[061] To produce oxygenates, the oxygenated hydrocarbon is combined with water to provide an aqueous raw material solution that has an effective concentration to cause the formation of the desired reaction products. The ratio of water to carbon on a molar basis is preferably from about 0.5: 1 to about 100: 1, including ratios such as 1: 1, 2: 1, 3: 1, 4: 1, 5: 1 , 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 15: 1, 25: 1, 50: 1, 75: 1, 100: 1 and any ratios in between. The raw material solution can also be characterized as a solution that has at least 1.0 weight percent (% by weight) of the total solution as an oxygenated hydrocarbon. For example, the solution may include one or more oxygenated hydrocarbons, with the total concentration of oxygenated hydrocarbons in the solution having at least about 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60 %, 70%, 80% or more by weight, including any percentages between them and depending on the oxygenated hydrocarbons used. In one embodiment, the raw material solution includes at least about 10%, 20%, 30%, 40%, 50% or 60% of a sugar, such as glucose, fructose, sucrose or xylose, or an alcohol of sugar, such as sorbitol, mannitol, glycerol or xylitol, by weight. The ratios between water and carbon and percentages outside the ranges determined above are also included. Preferably, the rest of the raw material solution is water. In some embodiments, the raw material solution consists essentially of water, one or more oxygenated hydrocarbons and, optionally, one or more raw material modifiers described in this document, such as alkali or alkali hydroxides or salts or acids
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29/55 earth alkaline. The raw material solution can also include oxygenated hydrocarbons recycled from the reactor system. The raw material solution can also contain negligible amounts of hydrogen, preferably less than about 1.5 mol of hydrogen per mol of raw material.
[062] The raw material solution is reacted with hydrogen in the presence of the deoxygenation catalyst under the conditions of pressure and deoxygenation temperature and hourly mass space velocity, effective to produce the desired oxygenates. The specific oxygenates produced will depend on several factors, including the raw material solution, reaction temperature, reaction pressure, water concentration, hydrogen concentration, catalyst reactivity and the flow rate of the raw material solution as it affects the spatial velocity (the mass / volume of reagent per unit of catalyst per unit of time), the hourly space velocity of gas (GHSV) and the hourly space velocity of mass (WHSV). For example, an increase in flow rate, and thus a reduction of exposure of raw materials to catalysts over time, will limit the extent of reactions that can occur, thus causing an increased yield for higher level diols and triols, with a reduction in ketone and alcohol yields.
[063] The deoxygenation pressure and temperature are preferably selected to maintain at least a portion of the raw material in the liquid phase at the reactor inlet. It is recognized, however, that temperature and pressure conditions can also be selected to more easily produce the desired products in the phase
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30/55 steam or in a mixed phase that has both a liquid and vapor phase. In general, the reaction should be conducted under process conditions where the proposed reaction thermodynamics is favorable. For example, the minimum pressure required to keep a portion of the raw material in the liquid phase will likely vary with the reaction temperature. As temperatures rise, higher pressures will generally be required to keep the raw material in the liquid phase, if desired. Pressures above those required to keep the raw material in the liquid phase (ie, vapor phase) are also suitable operating conditions.
[064] In general, the deoxygenation temperature should be greater than 120 ° C, or 150 ° C, or 180 ° C, or 200 ° C and less than 325 ° C, or 300 ° C, or 280 ° C, or 260 ° C, or 240 ° C, or 220 ° C. The reaction pressure must be greater than 1.38 MPa (200 psig), or 2.52 MPa (365 psig), or 3.45 MPa (500 psig) or 4.14 MPa (600 psig) and less than 17, 24 MPa (2,500 psig), or 15.51 MPa (2,250 psig), or 13.79 MPa (2,000 psig), or 12.41 MPa (1,800 psig), or 10.34 MPa (1,500 psig), or 8, 27 MPa (1,200 psig), or 6,89 MPa (1,000 psig) or 5 MPa (725 psig). In one embodiment, the deoxygenation temperature is between about 150 ° C and 300 ° C, or between about 200 ° C and
280 ° C, or between about 220 ° C and 260 ° C, or between about 150 ° C and 260 ° C. In another embodiment, the deoxygenation pressure is between about 2.52 MPa (365 psig) and 17.24 MPa (2,500 psig), or between about 3.45 MPa (500 psig) and 13.79 MPa ( 2,000 psig), or between about 4.14 MPa (600 psig) and 12.41 MPa (1,800 psig), or between about 2.52 MPa (365 psig) and 10.34 MPa (1,500 psig).
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31/55 [065] A condensed liquid phase method can also be performed with the use of a modifier that increases the activity and / or stability of the catalyst system. It is preferred that the water and the oxygenated hydrocarbon are reacted at an appropriate pH of about 1.0 to about 10.0, including the pH values in increments of 0.1 and 0.05 between them, and more preferably at a pH of about 4.0 to about 10.0. In general, the modifier is added to the raw material solution in an amount in the range of about 0.1% to about 10% by weight compared to the total weight of the catalyst system used, although the quantities outside that range are included in the present invention.
[066] In general, the reaction should be conducted under conditions where the residence time of the raw material solution on the catalyst is appropriate to generate the desired products. For example, the WHSV for the reaction can be at least about 0.1 gram of oxygenated hydrocarbon per gram of catalyst per hour and most preferably at
WHSV it's about 0.1 to 40 , 0 g / g per hr, including a WHSV of fence of 0.25, 0.5, 0.75 , 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2,3, 2,4, 2,5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4 , 7, 4.8, 4.9, 5 , 0, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40 g / g and the ratios between them (including 0.83, 0, 85, 0, 85, 1.71, 1, 72, 1.73, etc.).
[067] The hydrogen used in deoxygenation action can be H2 generated in situ, external H2 or recycled H2. The amount (moles) of external H2 or recycled H2 introduced in the raw material is between 0 to 100%, 0 to 95%, 0
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32/55 to 90%, 0 to 85%, 0 to 80%, 0 to 75%, 0 to 70%, 0 to 65%, 0 to 60%, 55%, 0 to 50%, 0 to 45% , 0 to 40%, 0 to 35%, 0 to 30%, 0 to 25%, 0 to 20%, 0 to 15%, 0 to 10%, 0 to 5%, 0 to 2%, or 0 to 1 % of the total number of moles of the oxygenated hydrocarbon (s) in the raw material, including all intervals between them. When the raw material solution, or any portion thereof, is reacted with hydrogen APR and external H2 or recycled H2, the molar ratio of hydrogen APR to external H2 (or recycled H2) is at least 1: 100, 1:50 , 1:20; 1:15, 1:10, 1: 5; 1: 3, 1: 2, 1: 1, 2: 1, 3: 1, 5: 1, 10: 1, 15: 1, 20: 1, 50: 1, 100: 1 and ratios between them (including 4: 1, 6: 1, 7: 1, 8: 1, 9: 1,
11: 1, 12: 1, 13: 1, 14: 1, 15: 1, 16: 1, 17: 1, 18: 1 and 19: 1, and vice versa).
HYDROGEN PRODUCTION IN SITU [068] An advantage of the present invention is that it allows the production and use of H2 generated in situ. H2 APR is produced from the raw material under aqueous phase reform conditions with the use of an aqueous phase reform catalyst (APR catalyst). The APR catalyst is preferably a heterologous catalyst that can catalyze the reaction of water and oxygenated hydrocarbons to form H2 under the conditions described below. In one embodiment, the APR catalyst includes a support and at least one Group VIIIB metal, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, alloys and combinations thereof. The APR catalyst can also include at least one additional metal material from Group VIIIB, Group VIIB, Group VIB, Group VB, Group IVB, Group IIB, Group IB, Group IVA or Group VA, such as Cu, B, Mn, Re , Cr, Mo, Bi, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, Ce and alloys and combinations thereof. O
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33/55 Group VIIB's preferred metal includes Re, Mn or combinations thereof. The preferred VIB Group metal includes Cr, Mo, W or a combination thereof. Preferred Group VIIIB metals include Pt, Rh, Ru, Pd, Ni or combinations thereof. The supports can include any of the catalyst supports described below, depending on the desired activity of the catalyst system.
[069] The APR catalyst can also be atomically identical to the deoxygenation catalyst. For example, the APR and deoxygenation catalyst can include Pt in alloy or mixed by adding Ni, Ru, Cu, Fe, Rh, Re, alloys and combinations thereof. The APR and deoxygenation catalyst can also include Ru in alloy or mixed by adding to, Ge, Bi, B, Ni, Sn, Cu, Fe, Rh, Pt, alloys and combinations thereof. The APR catalyst can also include Ni in alloy or mixed by adding Sn, Ge, Bi, B, Cu, Re, Ru, Fe, alloys and combinations thereof.
[070] The preferential loading of the Group VIIIB primary metal is in the range of 0.25% by weight to 25% by weight in carbon, with the weight percentages of 0, 10% and 0.05% of increments between the such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%, 5.00%, 10.00%, 12.50%, 15.00% and 20 , 00%. The preferred atomic ratio of the second material is in the range of 0.25 to 1 to 10 to 1, including ratios between them, such as 0.50, 1.00, 2.50, 5.00 and 7.50 for l.
[071] A preferred catalyst composition is also achieved by the addition of Group IIIB oxides and associated rare earth oxides. In such a case, the preferred components could be lanthanum and cerium oxides. The preferred atomic ratio between compounds in the
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Group IIIB and the primary Group VIIIB metal is in the range of 0.25 to 1 to 10 to 1, including ratios between them, such as 0.50, 1, 00, 2.50, 5, 00 and 7, 50 to l.
[072] Another preferred catalyst composition is one that contains platinum and rhenium. The preferred atomic ratio between Pt and Re is in the range of 0.25 to 1 to 10 to 1, including ratios between them, such as 0.50, 1.00, 2.50, 5.00 and 7.00 to l. The preferred Pt load is in the range of 0.25% by weight to 5.0% by weight, with weight percentages of 0.10% and 0.05% between them, such as .35%,. 45%, .75%, 1.10%, 1.15%, 2.00%,
2.50%, 3.0% and 4.0%.
[073] Preferably, the APR catalyst and the deoxygenation catalyst have the same atomic formulation. The catalysts can also be of different formulations. The catalysts can also be a single catalyst with both the APR and deoxygenation features provided by combining the APR materials described above and deoxygenation materials. In such a case, the preferred atomic ratio between the APR catalyst and the deoxygenation catalyst is in the range of 5: 1 to 1: 5, such as, without limitation, 4.5: 1, 4.0: 1, 3 , 5: 1, 3.0: 1, 2.5: 1, 2.0: 1, 1.5: 1,
1: 1, 1: 1.5, 1: 2.0, 1: 2.5, 1: 3.0, 1: 3.5, 1: 4.0, 1: 4.5 and any amounts between same.
[074] Similar to deoxygenation reactions, pressure and temperature conditions are preferably selected to maintain at least a portion of the raw material in the liquid phase at the reactor inlet. Temperature and pressure conditions can also be selected to produce the desired products in the most favorable stage.
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35/55 of steam or in a mixed phase that has both a liquid and vapor phase. In generation, the APR reaction must be conducted at a temperature at which the thermodynamics are favorable. For example, the minimum pressure required to keep a portion of the raw material in the liquid phase will likely vary with the reaction temperature. As temperatures rise, higher pressures will generally be required to keep the raw material in the liquid phase. Any pressure above that needed to keep the raw material in the liquid phase (ie, vapor phase) is also an appropriate operating condition. For vapor phase reactions, the reaction should be conducted at a reforming temperature where the vapor pressure of the oxygenated hydrocarbon compound is at least about 10.13 kPa (0.1 atm) (and preferably a good deal more high) and the thermodynamics of the reaction is favorable. The temperature will vary depending on the specific oxygenated hydrocarbon compounds used, but is generally in the range of about 100
° C to 450 ° C, or about 100 ° C to 300 ° C, for reactions that occur in steam phase. For reactions in phase net, the temperature of reform can to be of fence in 80 ° C at 400 ° C and the pressure of reform of about 0.5 MPa (72 psig) at 8.96 MPa (1,300 psig) .
[075] In a modality, The temperature in reform is located in between about 100 ° C and 400 ° C, or between about 120 ° C and 300 ° C, or between about in 200 ° C and 280 ° C, or between about 150 ° C and 270 ° C. The pressure for reform it is preferably star about 0.5 MPa (72 psig) and 8.96 MPa (1,300 psig), or in between about 0.5 MPa ( 72 psig) and 8.27 MPa (1,200 psig), or star about 1MPa (145 psig) and 8.27 MPa
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36/55 (1,200 psig), or about 1.38 MPa (200 psig) and 5 MPa (725 psig), or about 2.52 Mpa (365 psig) and 4.86 MPa (700 psig), or about 4.14 MPa (600 psig) and 4.48 MPa (650 psig).
[076] In the modalities where the APR catalyst and the deoxygenation catalyst are combined into a single catalyst, or the reactions are conducted simultaneously in a single reactor, the reform temperature and the deoxygenation temperature can be in the range of about 100 ° C to 325 ° C, or about 120 ° C to 300 ° C, or about 200 ° C to 280 ° C and the reform pressure and deoxygenation pressure can be in the range of about 1.38 MPa ( 200 psig) to 10.34 MPa (1,500 psig), or about 1.38 MPa (200 psig) to 8.27 MPa (1,200 psig), or about 1.38 MPa (200 psig) to 5 MPa (725 psig) ).
[077] A condensed liquid phase method can also be performed using a modifier that increases the activity and / or stability of the APR catalyst system. It is preferred that water and oxygenated hydrocarbon are reacted at an appropriate pH of about 1.0 to 10.0, or a pH of about 4.0 to 10.0, including increments of pH value of 0, 1 and 0.05 between them. In general, the modifier is added to the raw material solution in an amount in the range of about 0.1% to about 10% by weight compared to the total weight of the catalyst system used, although quantities outside this range are included in the present invention.
[078] Alkaline or alkaline earth salts can also be added to the raw material solution to optimize the proportion of hydrogen in the reaction products. Examples of suitable water-soluble salts include one or more
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37/55 most selected from the group consisting of a hydroxide, carbonate, nitrate or alkali metal or alkaline earth chloride salt. For example, adding alkaline (basic) salts to provide a pH of about pH 4.0 to about pH 10.0 to improve the hydrogen selectivity of reform reactions.
[079] The addition of acidic compounds can also provide increased selectivity to the desired reaction products in the hydrogenation reactions described below. It is preferred that the water-soluble acid is selected from the group consisting of nitrate, phosphate, sulfate, chloride salts and mixtures thereof. If an acidic modifier is used, it is preferred that it be present in an amount sufficient to reduce the pH of the aqueous feed stream to a value between about pH 1.0 and about pH 4.0. Reducing the pH of a feed stream in this way can increase the proportion of oxygenates in the final reaction products.
[080] In general, the reaction should be conducted under conditions where the residence time of the raw material solution on the APR catalyst is appropriate to generate an amount of APR hydrogen to react with a second portion of the raw material solution on the deoxygenation catalyst to produce the desired oxygenates. For example, the WHSV for the reaction can be at least about 0.1 gram of oxygenated hydrocarbon per gram of APR catalyst and preferably between about 1.0 to 40.0 grams of oxygenated hydrocarbon per gram of APR catalyst and most preferably between about 0.5 to 8.0 grams of oxygenated hydrocarbon per gram of APR catalyst. In
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38/55 large scale production terms, after the start, the APR reactor system must be process controlled so that the reactions proceed in steady state equilibrium.
BIOMASS PROCESSING SOLVENT WITH COMPOUNDS
C4 + [081] The biomass processing solvent or mixture of solvents may also include C4 + compounds derived from further processing of the oxygenates. In such applications, oxygenates are further converted to C4 + compounds by condensation in the presence of a condensation catalyst. The condensation catalyst will generally be a catalyst that can form longer-chain compounds by bonding two species that contain oxygen through a new carbon-carbon bond and convert the resulting compound into a hydrocarbon, alcohol or ketone, such as a acid catalyst, basic catalyst or a multifunctional catalyst that has both acid and base functionality. The condensation catalyst may include, without limitation, carbides, nitrates, zirconia, alumina, silica, aluminosilicate phosphates, zeolites, titanium oxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides, scandium oxides, oxides magnesium, cerium oxides, barium oxides, calcium oxides, hydroxides, heteropoly acids, inorganic acids, acid-modified resins, base-modified resins and combinations thereof.
The condensation catalyst can include the above alone or in combination with a modifier, such as Ce, La, Y, Sc,
P, B, Bi, Li, Na, K, Rb,
Cs, Mg, Ca,
Sir,
Ba and combinations thereof.
The condensation catalyst can also include a metal, such as Cu, Ag,
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39/55
Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof, to provide functionality of metal.
[082] The condensation catalyst may be self-supporting (that is, the catalyst does not need any other material to serve as a support) or it may need a separate support suitable for suspending the catalyst in the reagent stream. A particularly beneficial support is silica, especially silica which has a large surface area (greater than 100 square meters per gram), obtained by synthesis of sol gel, precipitation or vaporization. In other embodiments, particularly when the condensation catalyst is a powder, the catalyst system can include a binder to assist in forming the catalyst in a desired catalyst format. Applicable forming processes include extrusion, pelletizing, oil dripping or other known processes. Zinc oxide, alumina and a peptizing agent can also be mixed together and extruded to produce a formed material. After drying, this material is calcined at an appropriate temperature for the formation of the active catalytic layer, which usually requires temperatures greater than 450 ° C.
[083] In certain applications, the condensation reaction is carried out using acid catalysts. Acid catalysts may include, without limitation, aluminosilicates (zeolites), silica-alumina phosphates (SAPO), aluminum phosphates (ALPO), amorphous silica alumina, zirconia, sulfonated zirconia, tungsten zirconia, tungsten carbide, molybdenum carbide , titania, acid alumina, phosphate alumina, phosphate silica, carbons
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40/55 sulfonated, phosphate carbons, acid resins, heteropoly acids, inorganic acids and combinations thereof. In one embodiment, a catalyst may also include a modifier, such as Ce,
Y, Sc, La, P, B, Bi, Li, Na
K,
Rb, Cs, Mg,
Ca, Sr, Ba and combinations thereof.
catalyst can also be modified by adding a metal, such as Cu, Ag,
Au
Pt, Ni, Fe,
Co, Ru, Zn,
Cd, Ga,
In, Rh, Pd, Ir, Re,
Mn,
Cr, Mo,
W,
Sn, Os, alloys and combinations thereof, to provide functionality of Ti metal, and / or sulfides and oxide
Zr, V,
Nb, Ta, Mo, Cr, W, Mn,
Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P and combinations thereof. Gallium too if showed particularly useful as a promoter for O gift process. O catalyst acid can to behomogeneous, self-sustaining or stuck at any one From supports
further described below, including supports containing carbon, silica, alumina, zirconia, titania, vanadium, ceria, nitride, boron nitride, heteropoly acids, alloys and mixtures thereof.
[084] Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta and lanthanides can also be exchanged for zeolites to provide an active zeolite catalyst. The term zeolite as used herein refers not only to microporous crystalline aluminosilicate, but also to aluminosilicate structures that contain microporous crystalline metal, such as gallaluminosilicates and galossilicates. Metal functionality can be provided by metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W , Sn, Os, alloys and combinations thereof.
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41/55 [085] Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM and ZSM-48. Zeolite ZSM-5, and the conventional preparation thereof, is described in U.S. Patent No. 3,702,886; Re. 29,948 (highly siliceous ZSM-5); 4,100,262 and 4,139,600, all of which are incorporated herein by reference. The Zeolite
ZSM-11, and the conventional preparation thereof, is described in
U.S. Patent No. U.S. Patent No. 3,709,979, which is hereby incorporated by reference. Zeolite ZSM-12, and its conventional preparation, is described in Patent No. U.S.3.832.449, incorporated herein by reference. Zeolite ZSM-23, and its conventional preparation, is described in Patent No. U.S.4.076.842, incorporated herein by reference. Zeolite ZSM-35, and its conventional preparation, is described in Patent No. U.S.4.016.245, incorporated herein by reference. Another preparation of ZSM-35 is described in Patent No. U.S.4.107.195, the disclosure of which is incorporated herein by reference. The ZSM-48, and conventional of the same,
U.S.4.375.573, incorporated by reference. Other examples described in US Patent No. 5,019,663, the preparation of catalysts and
present is taught by
The Patent n ° The title in in zeolite are Patent No. US
7,022,888, also incorporated by reference in this document.
[086] As described in US Patent No. 7,022,888, the acid catalyst can be a bifunctional pentasil-type zeolite catalyst including at least one metallic element from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru,
Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys
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42/55 and combinations thereof, or a modifier of the group of Ga, In, Zn, Fe, Mo, Au, Ag, Y, Sc, Ni, P, Ta, lanthanides and combinations thereof. The zeolite preferably has a strong acid and dehydrogenation site and can be used with reagent streams that contain an oxygenated hydrocarbon at a temperature below 500 ° C. The bifunctional pentasil-type zeolite may have the crystal structure of the ZSM-5, ZSM-8 or ZSM-11 type consisting of a large number of 5-membered oxygen rings, that is, pentasil rings. Zeolite with a ZSM-5 structure is a particularly preferred catalyst. The bifunctional pentasil zeolite catalyst is preferably ZSM-5 zeolites modified by Ga and / or ln such as H-ZSM-5 impregnated with Ga and / or In, H-ZSM-5 replaced by Ga and / or In , Hgalosilicate of structure of type ZSM-5 and Hgaloaluminosilicate of structure of type ZSM-5. The bifunctional ZSM-5 pentasil type zeolite may contain aluminum and / or gallium in tetrahedron present in the framework or trellis of the framework or zeolite and gallium and indium in octahedron. The octahedron sites are not preferably present in the zeolite framework, but are present in the zeolite channels in close proximity to the zeolitic protonic acid sites, which are attributed to the presence of aluminum and gallium in tetrahedron in the zeolite. Al and / or Ga in tetrahedron or framework is believed to be responsible for the acidic function of zeolite and Ga and / or In in octahedron and non-framework is believed to be responsible for the dehydrogenation function of zeolite.
[087] In one embodiment, the condensation catalyst can be a zeolite H-cockaluminosilicate from
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43/55 bifunctional pentasil type ZSM-5 that has Si / Al of framework (tetrahedron) and the molar ratio of Si / Ga of about 10 to 100 and 15 to 150, respectively and Ga of non-framework (octahedron) of about 0.5 to 5.0 by weight. %. When these pentasil-type H-cockaluminosilicate zeolites are used as a condensation catalyst, the density of strong acid sites can be controlled by the Al / Si molar ratio of the framework: the higher the Al / Si ratio, the greater the density of strong acid sites. The highly dispersed non-framework gallium oxide species can be obtained by removing gallium from the zeolite by its pretreatment with H2 and vaporization. The zeolite that contains strong acid sites with high density and also the highly dispersed non-framework gallium oxide species in proximity to the zeolite acid site is preferred. The catalyst can optionally contain any binder such as alumina, silica or clay material. The catalyst can be used in the form of pellets, extrudates and particles of different shapes and sizes.
[088] Acid catalysts can include one or more zeolite structures that comprise silica-alumina cage-like structures. Zeolites are crystalline microporous materials with a well-defined pore structure. Zeolites contain active sites, usually acidic sites, that can be generated in the zeolite framework. The intensity and concentration of the active sites can be customized for particular applications. Examples of zeolites suitable for condensing secondary alcohols and alkanes may comprise aluminosilicates optionally modified with cations, such as Ga, In, Zn, Mo and mixtures
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44/55 of such cations, as described, for example, in U.S. Patent No. 3,702,886, which is hereby incorporated by reference. As recognized in the art, the structure of the particular zeolite or zeolites can be altered to provide different amounts of various hydrocarbon species in the product mixture. Depending on the structure of the zeolite catalyst, the product mixture may contain various amounts of aromatic and cyclic hydrocarbons.
[089] Alternatively, solid acid catalysts such as phosphate-modified alumina, chloride, silica and other acidic oxides could be used in the practice of the present invention. In addition, either sulfated zirconia or tungsten zirconia can provide the necessary acidity. Re and Pt / Re catalysts are also useful for promoting the condensation of oxygenates into C5 + and / or monooxygenated C5 + hydrocarbons. Re is acidic enough to promote acid-catalyzed condensation. Acidity can also be added to the activated carbon by adding either sulfates or phosphates.
[090] Condensation reactions result in the production of C4 + alkanes, C4 + alkenes, C5 + cycloalkanes, C5 + cycloalkanes, aryls, fused aryls, C4 + alcohols, C4 + ketones and mixtures thereof. The C4 + alkanes and C4 + alkenes have 4 to 30 carbon atoms (C4-30 alkanes and C4-30 alkenes) and can be branched or normal chain alkanes or alkenes. C4 + alkanes and C4 + alkenes may also include fractions of C4-9, C7-14, C12-24 alkanes and alkenes, respectively, with the C4-9 fraction targeting gasoline, the C7-14 fraction targeting jet fuels and the fraction C1224 directed to diesel fuel and other applications
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45/55 industrial. Examples of various C4 + alkanes and C4 + alkenes include, without limitation, butane, butane, pentane, pentene, 2-methylbutane, hexane, hexane, 2-methylpentane, 3-methylpentane,
2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene, octane, octene, 2,2,4, -trimethylpentane, 2,3-dimethylhexane,
2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecane, heptydecdecane , octyldecene, nonildecane, nonildecene, eicosane, eicosene, uneicosane, single sine, doeicosane, doeicosene, trieicosene trieicosene, tetraeicosane, tetraeicosene and isomers thereof.
[091]
C5 + cycloalkanes and C5 + cycloalkanes have 5 to 30 carbon atoms and can be unsubstituted, mono-substituted or multi-substituted. In the case of mono-substituted or multi-substituted compounds, the substituted group may include a branched C3 + alkyl, a normal chain C1 + alkyl, a branched C3 + alkylene, an alkylene
Normal chain C1 +, a normal chain C2 + alkylene, a phenyl or a combination thereof. In one embodiment, at least one of the substituted groups includes an alkyl
Branched C3-12, normal chain C1-12 alkyl, alkylene
Branched C3-12, an alkylene
Normal chain C1-12, a normal chain C2-12 alkylene, a phenyl or a combination thereof. In yet another embodiment, at least one of the substituted groups includes a branched C3-4 alkyl, a normal chain C1-4 alkyl, a branched C3-4 alkylene, a normal chain C1-4 alkylene a chain C2-4 alkylene normal, a phenyl or a combination thereof. The examples
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Desirable 46/55 C5 + cycloalkanes and C5 + cycloalkanes include, without limitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclopentane, methylcyclopentene, ethylcyclopentene, ethylcyclopentene, ethylcyclohexane, ethylcyclohexene and the same iscyclohexene and iso.
BIOMASS DECONSTRUCTION [092] In the deconstruction process, the biomass slurry is combined with the biomass processing solvent described above and reacted with hydrogen over a deconstruction catalyst to form a biomass hydrolyzate. Preferably, the biomass slurry comprises 10 to 50% of the raw material. The biomass slurry can include any type of biomass, including, but not limited to, cut or crushed solids, microcrystalline or cotton cellulose, wood and non-wood lignocelluloses, recycling fibers such as newspaper and cardboard, forest waste and agricultural, including sawdust, bagasse and corn husks, and energy crops, such as miscanthus, yellow millet, sorghum and others. The biomass processing solvent contains a wide range of oxygenates as described above.
[093] The specific products produced will depend on several factors, including the composition of the slurry, reaction temperature, reaction pressure, water concentration, hydrogen concentration, the reactivity of the catalyst and the flow rate of the slurry accordingly. affects space velocity (mass / volume of reagent per unit of catalyst per unit of time), hourly space velocity of gas (GHSV) and hourly space velocity of mass (WHSV). The deconstruction process
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47/55 can be either batch or continuous. In one embodiment, the deconstruction process is a continuous process that uses one or more continuous agitated tank reactors in parallel or in series. In another modality, the deconstruction step and the deoxidation step are conducted in a single reactor.
[094] The deconstruction temperature will, in general, greater than 80 ° C, or 120 ° C, or 150 ° C, or 180 ° C, or 200 ° C, or 250 ° C and less than 350 ° C, or 325 ° C, or 300 ° C, or 280 ° C, or 260 ° C. In one mode, the temperature in deconstruction is between about 80 ° C and 350 ° C, or between about 150 ° C and 350 ° C, or between about 150 ° C e 300 ° C, or between about 200 ° C and 260 ° C or between fence in
250 ° C and 300 ° C.
[095] The deconstruction pressure is generally greater than 0.69 MPa (100 psi), or 1.72 MPa (250 psi), or 2.07 MPa (300 psi), or 4.31 MPa (625 psi), or 6.21 MPa (900 psi), or 6.89 MPa (1,000 psi), or 8.27 MPa (1,200 psi) and less than 13.79 MPa (2,000 psi), or 10.34 MPa ( 1,500 psi), or 8.27 MPa (1,200 psi). In one embodiment, the deconstruction temperature is between about 0.69 MPa (100 psi) and 13.79 MPa (2,000 psi), or between about 2.07 MPa (300 psi) and 10.34 MPa ( 1,500 psi), or between about 6.89 MPa (1,000 psi) and 10.34 MPa (1,500 psi). Preferably, the slurry comes in contact with the deconstruction catalyst for approximately 5 minutes and 2 hours.
[096] In one embodiment, the deconstruction step is carried out in the same reactor as the catalytic reaction step of the aqueous raw material solution with H2 in the presence of a deoxygenation catalyst. In this modality, the deconstruction temperature and the
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48/55 deoxygenation can be in the range of about 100 ° C to 325 ° C, about 120 ° C to 300 ° C, or about 200 ° C to 280 ° C and the deconstruction pressure and deoxygenation pressure can be in the range of about 1.38 MPa
200 psig) at 10.34 MPa
1,500 psi), about 1.38 MPa (200 psig) to 8.27 MPa (1,200 psi), or about
4.14 MPa (600 psig) a
12.47 MPa (1,800 [097]
In general, the reaction should be conducted under conditions where the slurry residence time on the catalyst is appropriate to generate the desired products.
For example, the WHSV for reaction can be at least about 0.1 gram of biomass per gram of catalyst per hour and 0.1 to 40.0 g / g h,
WHSV is more preferably about
including an WHSV in fence of 0, 25, 0.5, 0.75, 1.0, 1.0, 1, 1, 1.2, 1.3 , 1,4, 1, 5, 1.6, 1.7, 1.8 , 1,9, 2.0, 2.1, 2.2, 2, 3, 2.4, 2.5 , 2,6, 2, 7, 2.8, 2.9, 3.0 , 3.1, 3.2, 3.3, 3.4, 3, 5, 3, 6, 3.7 , 3.8, 3, 9, 4.0, 4.1, 4.2 , 4.3, 4.4, 4.5, 4.6, 4, 7, 4.8, 4.9 , 5.0, 6, 7, 8, 9, 10 , 11 , 12, 13, 14 , 15, 20, 25 ^, 30, 3 5, 40 g / g H and reasons between the same ( including 0, 83 0.85 , 0, 85, 1, 71, 1, 72, 1.73, etc. ).
098] can convert from
The present invention effectively utilizes the lower molecular weight oxygenated biomass component in hydrocarbons due to the combination of the processing solvent, the presence of hydrogen in the system and the unique nature of the deconstruction catalyst.
It is believed that both processing solvent and hydrogen facilitate the conversion process by immediate reaction with the various reaction intermediates and the deconstruction catalyst to produce products that are more stable and less subject
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49/55 to degradation.
[099] The hydrogen used in the deconstruction reaction can be H2 of APR or a combination of H2 of APR, external H2 or recycled H2, or just simply external H2 or recycled H2. In general, the amount of H2 recycled in the deconstruction reactor must maintain the reaction pressure inside the system at the desired levels or increase the molar ratio between hydrogen and carbon and / or oxygen in order to increase the production yield of certain types of reaction product.
[0100] The deconstruction process may also include the introduction of supplementary materials to the slurry to assist the deconstruction of biomass or the additional conversion of oxygenated compounds into products more suitable for the bio-reform processes. Supplementary materials may include dopants, such as acetone, glycone acid, acetic acid, H2SO4 and H3PO4.
[0101] The deconstruction process converts lignin, cellulose and hemicellulose in the liquid or solid phase into an organic complex that includes carbohydrates, starches, polysaccharides, disaccharides, monosaccharides, sugars, sugar alcohols, alditols, mono-oxygenates, organic acids , phenols and cresols. In certain applications, the biomass product stream passes through one or more separation steps to separate the catalyst (if any), extracts, unreacted biomass from the biomass hydrolyzate. The biomass hydrolyzate may also need further processing to separate aqueous phase products from organic phase products, such as lignin-based hydrocarbons that are not suitable for bio-reformation processes. O
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50/55 biomass hydrolyzate can also be dehydrated or further purified before being introduced into the bio-reform process. Such dehydration and purification processes are known in the art and may include simulated moving bed technology, distillation, filtration, etc.
[0102] After separating the impurities, the product stream, suitable for use in bio-reform processes, includes carbohydrates, starches, polysaccharides, disaccharides, monosaccharides, sugars, sugar alcohols, alditols, organic acids, phenols, cresols.
The product stream includes minor oxygenates, such as alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes, diols and other polyols, which can be further converted to C4 + hydrocarbons such as C4 + alkanes + C4 + alkenes and aromatic compounds, including benzene , toluene, xylene, with the use of a bio-reformation process.
[0103]
As with unreacted solids, the deconstruction catalyst can be reused in upstream processes.
other extracts can be purged from being recycled to
Lignin, ash and system are used in other processes. For example, lignin can be burned to provide process heat, while protein material can be used for animal feed or as other products.
[0104] Recycling of biomass processing Solvent [0105] As shown above, the biorformation process produces a complex organic mixture of organic compounds. In a modality, as illustrated in Figures and 2, after completing a bioreactor process such as APR
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51/55 and / or HDO, various process streams can be separated and recycled for use as the biomass processing solvent or directed for further processing for conversion to liquid fuels or chemicals.
[0106] In one embodiment, the products of the APR / HDO processes can be separated based on the thermodynamic properties (for example, boiling point) of the oxygenates using standard fractionation techniques. In such an application, the more volatile compounds are separated from a bottom stream that contains less volatile and heavier compounds. This heavy bottom chain includes some of the components listed in Table 1 above. The heavy bottom stream can be divided in such a way that part of the heavy bottom stream is recycled in the bioreformation process for further processing, with the remainder of the recycled heavy bottom stream for mixing with the biomass slurry prior to the process. deconstruction. The organic compounds in the heavy bottom stream help to dissolve and break down the lignin, which improves the removal of lignin from the biomass slurry.
[0107] In another embodiment of the present invention, an effluent stream can be separated from the bio-reform product stream. This effluent stream includes the organic phase components listed in Table 1, as well as some aqueous phase components listed in Table 1. The effluent stream can be recycled for mixing with the biomass slurry prior to the deconstruction process. Residual organic acids in the effluent stream can improve the deconstruction of biomass.
[0108] In certain modalities, the deconstruction of
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52/55 biomass and the bio-reformation process can be conducted simultaneously in a single reactor. In such embodiments, the deconstruction catalyst and the deoxygenation catalyst can be the same catalyst, either combined in a mixture or arranged in a stacked configuration to promote the deconstruction of biomass followed by bio-reformation. An example of a reactor may include a slurry reactor in which the biomass is introduced at a first end with a recycling stream that includes both unreacted and underreacted biomass and biomass processing solvent collected from a heavy bottom stream recent. The combination of the deconstruction catalyst and the biomass processing solvent promotes the deconstruction of biomass, which in turn provides oxygenated hydrocarbons for conversion to oxygenated by the deoxygenation catalyst in the reactor. A portion of the oxygenates, in turn, can either be kept in the reactor, recycled for use as a biomass processing solvent and / or further processed to provide liquid fuels and chemicals.
[0109] The biomass deconstruction process described in this document effectively utilizes the components available in lignocellulosic biomass by hydrolysis of lignin, cellulose and hemicellulose to provide water-soluble oxygenated hydrocarbons for additional use in bio-reform processes. The biomass deconstruction process reduces biomass deconstruction costs by avoiding the need to purchase costly deconstruction solvents and avoiding solvent recovery and cleaning costs by recycling solvent from
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53/55 intermediates produced in bio-reform processes. The biomass deconstruction process also provides a biorethare stream by solubilizing components of lignin, cellulose and hemicellulose in carbohydrates, starches, monosaccharides, disaccharides, polysaccharides, sugars, sugar alcohols, alditols, usable polyols and mixtures thereof.
EXAMPLE 1 [0110] The bagasse deconstruction was carried out with the use of organic phase biohazard products such as the processing solvent, hydrogen and a Ru: Rh / Darco 200 deconstruction catalyst that contains 2.5% ruthenium and 2, 5% rhodium. The solvent was composed of 70% by weight of water-miscible organic bioreactor components and 30% by weight of water. A biomass slurry that has a biomass concentration of 10% by weight of sugar cane bagasse in solvent was reacted for a heating period of 90 minutes and a residence period of 30 minutes at a temperature of
300 ° C and H2 at 8.27 MPa (1,200 psi). A second and a third biomass slurry was reacted without the solvent for the same period at H2 at 8.27 MPa
1,200 psi) and a temperature of 2 60 ° C and 300 ° C, respectively.
0111] results show
A os
Figure 3
experiment s including the yield, aqueous product and a reactor engraving after the process of deconstruction organo- catalytic. O use of the solvent organic improves
significantly the deconstruction of biomass (from 85% to 95%) and the thick gel that exists in the water medium is solubilized. The removal of insoluble material significantly improves the
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54/55 catalyst service life.
EXAMPLE 2 [0112]
The deconstruction of bagasse and lignin was carried out with the use of products from the bioreactor phase as a processing solvent, several catalysts as represented in the organic hydrogen and
Figure 4.
The solvent was composed of 70% by weight of water-miscible organic bioreactor components and 30% by weight of water. Each biomass slurry had a biomass concentration of 10% by weight of biomass (sugarcane bagasse or lignin) in solvent. The biomass slurry was reacted for a heating period of 90 minutes and a residence period of 30 minutes at a temperature of 300 ° C or 260 ° C and H2 at
8.27 MPa (1,200 psi). All catalysts contained metal contents of 2.5% by weight of each metal.
EXAMPLE 3 [0113] The deconstruction of corn straw was conducted with the use of aqueous bioreactor reform products concentrated as a solvent, hydrogen and a Pd: Ag / W-Zr02 deconstruction catalyst containing 2% Pd and Ag. The biomass slurry which has a concentration of 10% by weight of corn straw in solvent was reacted for a heating period of 90 minutes at a temperature of 280 ° C and H2 at 6.89 MPa (1,000 psi) . The product of this reaction was then used as the solvent for two subsequent deconstruction tests that followed the same experimental procedures. Figures 5 to 8 show the conversion results with both new and regenerated catalysts. Figure 5 indicates that the amount of raw material converted was the same when using both a new catalyst and a new one.
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55/55 regenerated. Figures 6 to 8 show increased product concentrations when a regenerated catalyst was used.

权利要求:
Claims (4)
[1]
1/8
CO Ό «5 <Λ ç O (UAND w c O Q> □ o ANDO
FIGURE 1 ο
ε
The gray components
1, characterized in that the condensation catalyst in B2 comprises a member selected from the group consisting of a carbide, a nitride, zirconia, alumina, silica, an aluminosilicate, a phosphate, a zeolite, a titanium oxide, a zinc oxide, a vanadium oxide, a lanthanum oxide, a yttrium oxide, a scandium oxide, a magnesium oxide, a cerium oxide, a barium oxide, a calcium oxide, a hydroxide, a heteropoly acid, an inorganic acid, a acid-modified resin, a base-modified resin and combinations thereof.
5. METHOD, according to claim 1, characterized by:
- the deconstruction catalyst comprises an acidic resin or a basic resin, said deconstruction catalyst preferably further comprises a member selected from the group consisting of Fe, Co, Ni, Cu, Ru, Rh,
Pd, Pt, Re
Mo, W, an alloy thereof and a combination thereof; or
- the deconstruction catalyst comprises a support and a member attached to the support, where the member is selected from the group consisting of Cu, Fe, Ru, Ir, Co, Rh,
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5/9
Pt, Pd, Ni, W, Mo, an alloy thereof and a combination thereof, and wherein said deconstruction catalyst preferably further comprises a selected member of the
group consisting of Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, You, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, an league of them and a combination thereof. 6. METHOD, according the claim 1, characterized by H 2 understand H2 generated in situ per
catalytic reaction in a liquid phase or vapor phase of a portion of the water and the oxygenated hydrocarbon in the presence of an aqueous phase reform catalyst at a reform temperature and reform pressure.
7. METHOD, according to claim 6, characterized by:
- the reform temperature is in the range of 100 ° C to 450 ° C and the reform pressure is a pressure in which water and oxygenated hydrocarbon are gaseous; or
- the reforming temperature is in the range of 100 ° C to 300 ° C, and the reforming pressure is a pressure in which water and oxygenated hydrocarbon are gaseous; or
- the reform temperature is in the range of 80 ° C to 400 ° C, and the reform pressure is a pressure in which water and oxygenated hydrocarbon are liquid.
METHOD, according to claim 6, characterized in that the aqueous phase reforming catalyst comprises a support and a member selected from the group consisting of Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, an alloy of and a combination thereof, and in that said aqueous phase reforming catalyst preferably also comprises a member selected from the group consisting of Cu, B, Mn, Re,
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6/9
Cr, Mo, Bi, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, a league of them and an combination thereof. 9. METHOD, according with the claim 6, featured by the catalyst remodeling aqueous phase it's the catalyst deoxygenation be combined into one
unique catalyst.
10. METHOD, according to the claim 9, featured per: - a retirement temperature and temperature in deoxygenation up to 325 ° C, and the reform pressure and the deoxygenation pressure are in the range of 1.38 MPa
(200 psig) to 2.52 MPa (1,500 psig); or
- the reforming temperature and deoxygenation temperature are 120 ° C to 300 ° C, and the reforming pressure and deoxygenation pressure are in the range of about 1.38 MPa (200 psig) to 8.27 MPa (1,200 psig); or
- the reforming temperature and the deoxygenating temperature are in the range of 200 ° C to 280 ° C, and the reforming pressure and the deoxygenating pressure are in the range of 1.38 MPa (200 psig) at 5 MPa (725 psig).
11. METHOD, according to claim 1, characterized by:
- the deoxygenation temperature is up to 325 ° C, and the deoxygenation pressure is at least 10.13 kPa (0.1 atmosphere); or
- the deoxygenation temperature is up to 325 ° C and the deoxygenation pressure is between 2.52 MPa (365 psig) and about 13.79 MPa (2,000 psig); or
- the deoxygenation temperature is higher than
Petition 870190015724, of 02/15/2019, p. 68/74
7/9
180 ° C, or 200 ° C and less than 325 ° C, or 300 ° C, or 280 ° C, or
260 ° C or 240 ° C or 220 ° C; or
- the deoxygenation pressure be greater than 1.38 MPa (200 psig) , or 2.52 MPa (365 psig) , or 3.45 MPa (500 psig) or 4.14 MPa (600 psig) and lower what 13.79 MPa (2,000 psig), or 12.41 MPa (1. 800 psig), or 10.34 MPa (1,500 psig), or 8 , 27
MPa (1,200 psig), or 6,89 MPa (1,000 psig); or
- the deoxygenation temperature is in the range of 200 ° C to 280 ° C and the deoxygenation pressure is between 4.14 MPa (600 psig) and 12.41 MPa (1,800 psig).
12. METHOD, according to claim 1, characterized by comprising:
- the deoxygenation catalyst further comprises a member selected from the group consisting of Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn , Ge, P, Al, Ga, In, T1, an alloy thereof and a combination thereof; or
- the support comprises a member selected from the group consisting of carbon, silica, alumina, zirconia, titania, vanadium, heteropoly acid, diatomite, hydroxyapatite, chromia, zeolite and mixtures thereof, wherein said support is preferably selected from the group that consists of tungsten zirconia, tungsten modified zirconia, tungsten modified alpha-alumina or tungsten modified alumina theta.
13. METHOD according to claim 1, characterized in that the biomass processing solvent comprises a member selected from the group consisting of ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, pentanol, hexanol, cyclopentanol, cyclohexanol, 2
Petition 870190015724, of 02/15/2019, p. 69/74
8/9 methylcyclopentanol, a hydroxyketone, a cyclic ketone, acetone, propanone, butanone, pentanone, hexanone, 2-methylcyclopentanone, ethylene glycol, 1,3-propanediol, propylene glycol, butanediol, pentanediol, hexanediol, methylamine, butane a hydroxyaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, lactic acid, glycerol, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol, 2-methyl -tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-ethyl-tetrahydrofuran, 2-methyl furan, 2,5-dimethyl furan, 2-ethyl furan, hydroxylmethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro-3furanol, 5-hydroxymethyl-2 (5H) -furanone, dihydro-5 (hydroxymethyl) -2 (3H) -furanone, tetrahydro-2-furoic acid,
dihydro-5- (hydroxymethyl) -2 (3H) -furanone, alcohol tetrahydrofurfuryl, l- (2-furil) ethanol and hydroxymethyltetrahydro furfural, isomers of the same and combinations thereof. 14. METHOD, according to the claim 1, characterized by: - the H2 comp rekind at least one out of one H2
generated in situ, external H2 or recycled H2; or
- the oxygenated hydrocarbon comprises a member selected from the group consisting of a lignocellulose derivative, a cellulose derivative, a hemicellulose derivative, a carbohydrate, a starch, a monosaccharide, a disaccharide, a polysaccharide, a sugar, a sugar alcohol , an alditol and a polyol; or
- the biomass hydrolyzate is recycled and
Petition 870190015724, of 02/15/2019, p. 70/74
9/9 combined with the biomass slurry; or
- the reaction step of a biomass slurry with a biomass processing solvent is carried out in the same reactor as the catalytic reaction step of the aqueous raw material solution with H2 in the presence of a deoxygenation catalyst; or
- the method also includes the step of dehydrating the biomass hydrolyzate.
Petition 870190015724, of 02/15/2019, p. 71/74
1. METHOD TO PRODUCE A BIOMASS HYDROLYSATE, the method comprising either (i) A1 and B1 or (ii) A2, B2 and C2:
TO 1. catalytically react water and an oxygenated hydrocarbon C2 + O1 + soluble in water in a liquid or vapor phase with H2 in the presence of a deoxygenation catalyst at a deoxygenation temperature above 180 ° C and a deoxygenation pressure below 13.79 Mpa (2000 psi) to produce a biomass processing solvent that comprises a C 2+ O1-3 hydrocarbon in a reaction stream; and
B1. reacting the biomass processing solvent with a slurry of biomass, hydrogen and a deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to produce a biomass hydrolyzate comprising water-soluble oxygenated hydrocarbons, said at least one hydrolyzate selected member of the group consisting of a water-soluble lignocellulose derivative, a water-soluble cellulose derivative, a water-soluble hemicellulose derivative, a carbohydrate, a starch, a monosaccharide, a disaccharide, a polysaccharide, a sugar, a sugar alcohol, an alditol and a polyol;
or
A2. catalytically react water and an oxygenated hydrocarbon C2 + O1 + soluble in water in a liquid or vapor phase with H2 in the presence of a deoxygenation catalyst at a deoxygenation temperature above 180 ° C and a deoxygenation pressure below 13.79 Mpa (2000
Petition 870190015724, of 02/15/2019, p. 63/74
[2]
2/8
FIGURE 2 gray components
2. METHOD, according to claim 1, characterized by:
- the biomass processing solvent in A1 and B1 comprises a member selected from the group consisting of an alcohol, ketone, aldehyde, cyclic ether, ester, diol, triol, hydroxycarboxylic acid, carboxylic acid and a mixture thereof; or
- the biomass processing solvent in B2 and C2 comprises a member selected from the group consisting of an alkane, alkene and an aromatic, said biomass processing solvent preferably comprises a member selected from the group consisting of benzene, toluene and xylene .
2/9 psig) to produce an oxygenate comprising C2 + O1-3 hydrocarbon in a reaction stream;
B2. reacting catalytically in the liquid or vapor phase or oxygenated in the presence of a condensation catalyst at a condensing temperature and condensing pressure to produce a biomass processing solvent comprising one or more C4 + compounds; and
C2. reacting the biomass processing solvent with a slurry of biomass, hydrogen and a deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to produce a biomass hydrolyzate comprising water-soluble oxygenated hydrocarbons, said at least one hydrolyzate selected member of the group consisting of a water-soluble lignocellulose derivative, a water-soluble cellulose derivative, a water-soluble hemicellulose derivative, a carbohydrate, a starch, a monosaccharide, a disaccharide, a polysaccharide, a sugar, a sugar alcohol, an alditol and a polyol;
where the method is characterized by comprising (I) or (II):
(I) the steps of (a) producing the biomass processing solvent from water-soluble oxygenated C2 + O1 + hydrocarbon; and (b) reacting the biomass slurry with the biomass processing solvent; occur separately in different reactors; or (II) the steps of (a) producing the biomass processing solvent from water-soluble oxygenated C2 + O1 + hydrocarbon; and (b) reacting the biomass slurry with the biomass processing solvent; occur
Petition 870190015724, of 02/15/2019, p. 64/74
[3]
3/8
FIGURE 3 * 10% bagasse 260C, Ru: RWDarco 200, H2O «10% bagasse 300C. Ru: Rh / Darcco 200. H2O ¢ 10% of bagasse 300C. Ru: Rh / Darco 200, Purging of RAPR mass balance aqueous analytical balance conversion of raw material yield of sugars / polyols
Figure 3: deconstruction of catalytic biomass using a by-product stream from the bioforming process as an organic solvent.
3. METHOD, according to claim 1, characterized in that the C2 + O1 + hydrocarbon is selected from the group consisting of a starch, a carbohydrate, a polysaccharide, a disaccharide, a monosaccharide, a sugar, a sugar alcohol, an alditol, an organic acid,
Petition 870190015724, of 02/15/2019, p. 65/74
4/9 a phenol, a cresol, ethanediol, ethanedione, acetic acid, propanol, propanediol, propionic acid, glycerol, glyceraldehyde, dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, a butanediol, butanoic acid, an aldotetrose, tartaric acid, an aldopentose, an aldohexose, a ketotetrose, a ketopentose, a ketohexose, a hemicellulose, a cellulosic derivative, a lignocellulosic derivative and a polyol.
4. METHOD, according to the claim
3/9 together in a single reactor, in which the raw material for the reactor comprises the said suspension of biomass and said oxygenated hydrocarbon C2 + O1 + soluble in water;
and in which the deoxygenation catalyst comprises a support and a member adhered to the support in which the member is selected from the group consisting of Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os , Mo, Ag, Au, an alloy and a combination thereof; and in which the biomass slurry comprises a biomass component selected from the group consisting of agricultural waste, wood materials, solid urban waste and energy crops.
[4]
4/8
FIGURE 4 s 10% bagasse, 260C, RuRh / OLC +, Purging APR ü * 10% bagasse. 300C, RuRhMl-ZrO2, APR purge € 510% lignin, 300C, RuRh / OLC +, APR purge s 10% bagasse, 260C, PtRe / 206P, APR purge
Bagasse S10%, 300C Ru: Rh / Darcco 200, APR purge

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法律状态:
2016-09-27| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE US61/428,461 DE 30/12/2010 REIVINDICADA NO PCT/US2011/067744, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 167O, ITEM 28 DO ATO NORMATIVO 128/97 E NO ART. 29 DA RESOLUCAO INPI-PR 77/2013. ESTA PERDA SE DEU PELO FATO DE O DEPOSITANTE CONSTANTE DA PETICAO DE REQUERIMENTO DO PEDIDO PCT SER DISTINTO DAQUELE QUE DEPOSITOU A PRIORIDADE REIVINDICADA E NAO APRESENTOU DOCUMENTO COMPROBATORIO DE CESSAO, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 166O, ITEM 27 DO ATO NORMATIVO 128/97 E NO ART. 28 DA RESOLUCAO INPI-PR 77/2013. |

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2017-01-10| B12F| Appeal: other appeals [chapter 12.6 patent gazette]|

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2018-11-21| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-04-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-05-21| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/12/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/12/2011, 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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US201061428461P| true| 2010-12-30|2010-12-30|

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US61/428,461|2010-12-30|

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PCT/US2011/067744|WO2012092436A1|2010-12-30|2011-12-29|Organo-catalytic biomass deconstruction|

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