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    • 专利摘要:
    Procedure of extraction and functionalization in a single stage of the insoluble lignin present in residual biomass. The present invention relates to a process of extraction and functionalization in a single stage of the insoluble lignin present in the byproducts of the production of bioethanol by fermentation of sugars from biomass. Therefore, the invention could be framed in the field of industrial use of by-products and the valorization of them. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2675810A1
    申请号:ES201730026
    申请日:2017-01-12
    公开日:2018-07-12
    发明作者:Javier MANZANO GÓMEZ；Adrian SOTO PAZ；Mercedes LECEA ROMERA；Miguel VALDIVIA BORRERO；Juan Luis RAMOS MARTÍN
    申请人:Abengoa Research SL；
    IPC主号:
    专利说明:

    The present invention relates to a single stage extraction and functionalization process of the insoluble lignin present in the by-products of obtaining bioethanol by fermentation of sugars from biomass. Therefore, the invention could be framed in the field
    10 of the industrial use of by-products and their recovery.
    STATE OF THE TECHNIQUE
    Lignin is the third most abundant biopolymeric material in the biosphere, only
    15 surpassed by cellulose and xylan. It is defined as a disordered polymer with structural and heterogeneous diversity consisting of units of p-hydroxyphenyls, guayacoles and syringyls joined by different positions (Che n et al. Biotechnol Biofuels (2016) 9:87 "Epoxidation and etherification of alkaline lignin to prepare water-soluble derivatives and its performance in improvement of enzymatic
    20 hydrolysis efficiency ").
    Mainly, lignin is used as a precursor to polymers or carbon fibers when it is functionalized in a controlled manner. The huge number of functionalizable positions that lignin presents makes functionalization in
    25 All these positions are unpredictable, in addition to causing their gelation and thermal instability in ranges close to their glass transition temperature. To avoid such behavior, the modification or controlled functionalization of the hydroxyl positions is carried out.
    30 US2013255216A1 shows different routes for the modification of lignin and its valorization as a precursor of polymers and carbon fibers, where part of the functionalizable groups thereof are masked. The resulting lignin is more thermally stable and less reactive than the starting lignin.
    On the other hand, in the process of obtaining bioethanol by fermentation of sugars from biomass, a by-product with a lignin content is obtained that could be interesting for its recovery. Thus, in the document Chen et al. Biotechnol Biofuels (2016) 9:87 "Epoxidation and etherification of alkaline lignin to prepare water-soluble derivatives and its performance in improvement of enzymatic hydrolysis efficiency", describes a procedure for obtaining lignin derivatives in two steps from the by-products of obtaining ethanol by fermentation of sugars from biomass, obtaining a lignin prepared for industrial use. However, with this procedure a low weight yield of lignin is obtained.
    Therefore, due to the increase in bioethanol production and as a result of obtaining by-products, simple and effective lignin recovery processes would be necessary for later use, valuing these by-products.
    DESCRIPTION OF THE INVENTION
    The present invention provides a method of obtaining functionalized lignin from residual biomass cake, where solubilization of the cake lignin and its chemical modification are carried out in a single step.
    This one-stage extraction and modification process, where solubilization and chemical modification reaction take place simultaneously improves the overall performance of the procedure for obtaining functionalized lignin from a residual biomass cake by more than 26%, compared With the yield that would be obtained by performing the process in two consecutive stages, first the extraction stage and subsequent lignin modification reaction, as described in the prior art.
    These modification reactions give rise to structural changes in the lignin polymer, modifying its properties and thus favoring its solubilization and subsequent recovery, increasing the overall yield of the process and obtaining a functionalized lignin suitable for its subsequent application in the industry.
    Therefore, in a first aspect, the present invention relates to a process
    for obtaining functionalized lignin from residual biomass cake, which comprises the following steps: a) dissolve the biomass cake in an alkaline medium of pH greater than or equal to 10 5 together with a halogenated organic reagent selected from the following,
    • halogenated saturated carbon chain derivative reagent, HC ~ X. .
    3, X being a halogen.
    • halogenated carbon chain derivative reagent with al
    ~ X
    10 minus an H2C unsaturation being X a
    halogen; Y,
    • halogenated epoxy derivative reagent
    or
    ~ X,
    X being a halogen: at a temperature between 80 oC and 120 oC;
    15 b) separating the liquid phase from the solid obtained in step (a); c) add an acid to the liquid obtained in step (b) to a pH less than or equal to 5; and, d) extract the precipitated solid obtained in step (d) and dry.
    In the present invention, the term "residual biomass cake" means the solid obtained from filtering the vinasses resulting from a bioethanol production process by fermentation of sugars from biomass, where that biomass is the organic matter originated in a biological process , spontaneous or provoked, usable as a source of energy and that can be first, second and third
    25 generation as for example, but not limited to corn straw, sugar cane straw and wheat and rice residues among other plant residues.
    In a preferred embodiment, the initial biomass cake for the lignin recovery and modification process present in said cake comes from the process of obtaining bioethanol by fermentation, which comprises the following steps, known to a person skilled in the art:
    (i) The raw material or biomass is received as a bale. The ground and clean materials are sent for pretreatment, which consists of a process that involves hot acid hydrolysis and steam injection with instant decompression of the material to separate the lignin from cellulose and hemicellulose {known as steam explosion (in English "steam explosion")).
    (ii) Below is a conditioning stage, which allows adjusting the temperature, pH and solids content of the pretreated biomass to reach the conditions for the downstream cellulases to function.
    (iii) The conditioned material obtained from the previous stage is then passed to the liquefaction tower, where the viscosity of the material decreases to facilitate the saccharification stage. The saccharification and fermentation take place sequentially to maximize ethanol yield ensuring optimal conditions for each stage.
    (iv) In the fermentation stage, both glucose (C6 sugar) and xylose (C5 sugar) are converted to ethanol simultaneously by means of highly efficient and propagated yeasts.
    Once the material enters the distillation zone, the ethanol is extracted to produce the biofuel under defined market quality specifications. After distillation, the resulting vinasse (liquid solid I separation) is processed to obtain the biomass cake (by filtration) and syrup (by evaporation).
    At that time, cake and syrup is usually introduced into a biomass boiler for energy and steam production (cogeneration). However, in the present invention this cake obtained is used as a starting material for its revaluation, obtaining functionalized lignin in the process of the present invention.
    In a preferred embodiment of the process of the present invention in the step
    (a) the base is selected from NaOH, KOH and LiQH and a combination thereof. More preferably the base is NaOH, even more preferably the base is NaOH with a concentration of between 2% and 4%.
    In another preferred embodiment of the process of the present invention in the step
    (a) the ratio between the cake and the base is 7: 1 to 3: 1, more preferably it is between 7: 1 and 5: 1.
    In another preferred embodiment of the process of the invention the solution of step (a) is heated to a temperature between 90 oC and 100 oC, more preferably for a time between 2 and 4 hours.
    In the present invention, "functionalized Iignin" means that lignin that has substituted, the positions that were originally occupied by hydroxyl groups, by alkyl, allylic chains or chain with epoxides, in the form of ethers in those alcohol groups, after completion of a type 2 nucleophilic substitution reaction in lignin found in a biomass cake.
    The halogenated organic reagents described above are used for this functionalization of lignin.
    In another preferred embodiment of the process of the present invention the halogenated organic reagents are selected from a 1-bromobutane, 1-bromopropane, allyl bromide and epichlorohydrin, more preferably 1-bromopropane.
    In another preferred embodiment of the process of the present invention the separation of step (b) is carried out by filter, press or centrifuge, more preferably filter.
    In another preferred embodiment of the process of the present invention the solid phase of stage (a) which is separated in step (b) is carried to a biomass boiler.
    In the present invention, biomass boiler is understood as "the reactor for obtaining energy and steam from the solid cake with lignin residues.
    In another preferred embodiment of the process of the present invention the liquid phase obtained in step (b) is brought to a cooling stage at a temperature of between 15 oC and 30 oC before performing step (c).
    In another preferred embodiment of the process of the present invention the acid of step (c) is selected from formic acid, sulfuric acid and hydrochloric acid.
    In another preferred embodiment of the process of the present invention the extraction step (d) of the precipitated solid obtained in step (b) is carried out by decantation.
    Throughout the description and claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components
    or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of
    The invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES
    25 Fig. 1. It shows a scheme of the process of extraction and modification in a single stage of the lignin present in the residual biomass cake of the process of obtaining ethanol from lignocellulosic matter.
    30 Fig. 2. Represents the comparison of the overall yields of the extraction and modification processes in one and two stages described in Examples 1 and 2, for different halogenated organic reagents.
    EXAMPLES
    The invention will now be illustrated by tests carried out by the inventors.
    Example 1: Extraction and modification of lignin in one stage (Fig. 1)
    To carry out the extraction and modification of the lignin from the biomass cake, obtained from the filtered vinasses resulting from the process of obtaining ethanol, the following procedure was followed:
    In a reactor, 10 9 of cake was solubilized with 0.06 mmol of 1-bromo propane in a 4% NaOH solution in a solid liquid ratio of 1: 5. The reaction mixture was stirred for 4 hours at 99 ° C, maintaining the pH> 10.
    The following reaction occurred:
    ~ CH,
    pH ::> 10
    Lignin -OH Lignin Lignin
    or
    Scheme 1
    It was then subjected to a solid-liquid separation by vacuum or centrifugal filtration to obtain a liquid and on the other hand a solid composed of sugars remaining from the process, residual lignin and insoluble inorganic compounds.
    The filtrate obtained was subjected to a cooling step at room temperature.
    The liquid obtained rich in lignin was brought to a pH between 5 and 3 by adding 4% hydrochloric acid thus precipitating the functionalized lignin.
    Then, it was again subjected to a solid-liquid separation stage, where in this case the liquid is treated as effluent, and the solid obtained was a functionalized lignin cake with 50% moisture that was
    led to the dryer obtaining between 85 -95% of total solids with a final yield of 50 -60% of functionalized lignin.
    Example 2: Comparative test of lignin extraction and modification in two stages.
    To carry out the extraction and modification of the lignin from the biomass cake, obtained from the filtered vinasses resulting from the process of obtaining ethanol, the following procedure was followed:
    First stage of lignin extraction: 60 9 of cake was subjected to an alkaline medium extraction process using a 4% solution with NaOH, in a 7: 1 weight ratio on a dry basis (this ratio could vary to 3: 1, although it does not cause any change in the development of
    15 process or in the final product), at a temperature of 99 oC, at a residence time of 4 hours and at a pH> 10.
    Then it was subjected to a solid-liquid separation in a filter press obtaining a liquid and on the other hand a solid (sugars remaining from the process, residual and inorganic lignin) that goes to biomass boiler. The lignin-rich liquid is subjected to a cooling stage at room temperature.
    Subsequently, the liquid passes to a 4% sulfuric acid precipitation stage at a pH between 4.5 -3 (never <3).
    It is then subjected to a solid / liquid separation stage where in this case the liquid is treated as effluent and the solid that is a cake (with 50% humidity) is taken to the dryer where it is obtained with an 85-95 % of total solids and 38% yield of lignin extracted.
    Second stage of modification of the extracted lignin: In a reactor 500 mg lignin previously extracted was solubilized with 0.06 mmol of a halogenated 1-bromo propane carbon chain derivative, in a 5% NaOH solution in a solid-liquid ratio of 1:10 . The reaction mixture was stirred for 2 hours at a temperature of 80 ° C.
    It was then subjected to a solid-liquid separation (vacuum filtration or centrifugal) obtaining a liquid and on the other hand a solid (sugars remaining from the process, residual lignin and insoluble inorganic compounds).
    The liquid obtained rich in lignin was brought to pH 3 with 4% hydrochloric acid, thus precipitating the functionalized lignin.
    10 It was again subjected to a solid-liquid separation step and the solid obtained was a lignin cake (with approximately 50% humidity) and dried to 95% of total solids, obtaining a modified lignin. final with a total yield in the two stages of 24 -25%.
    The results obtained in examples 1 and 2 were compared using different halogenated organic reagents (Table 1 and Fig. 2):
    Table 1: Comparison of the overall yields of the extraction processes and modification in one and two stages.
    Reagent Performance One StageTwo Stage PerformancePerformance Increase
    1-Bromobutane 58.8%25.2%33.6%
    1-Bromopropane 50.8%24.8%26%
    Allyl bromide 58.4%24.9%33.5%
    Example 3:Influenceof theweatherinheperformancefinalobtainedfromlignin
    25 functionalized recovered.
    10
    To carry out the extraction and modification of the lignin from the biomass cake, obtained from the filtered vinasses resulting from the process of obtaining ethanol, the following procedure was followed:
    In a reactor, 10 g of cake were solubilized with 0.06 mmol of 1-bromo propane in a 4% NaOH solution in a solid liquid ratio of 1: 5. The reaction mixture was stirred for 2 hours at 90 ° C, maintaining the pH> 10.
    It was then subjected to a solid-liquid separation (vacuum or centrifugal filtration) obtaining a liquid and on the other hand a solid composed of the remaining sugars of the process, residual lignin and insoluble inorganic compounds.
    The filtrate obtained could optionally be subjected to a cooling step at room temperature.
    The liquid obtained rich in lignin was brought to pH 4.5-3 by adding 4% hydrochloric acid thus precipitating the lignin.
    Then it was again subjected to a solid-liquid separation stage, where in this case the liquid is treated as effluent, and the solid obtained was a lignin cake (with 50% humidity) that was taken to the dryer where it took 85 -95% of total solids and obtaining a final yield of 40% of final lignin.
    Example 4:
    In a reactor, 10 g of cake were solubilized with 0.06 mmol of 1-bromo propane in a 4% NaOH solution in a solid / liquid ratio of 1: 5. The reaction mixture was stirred for 2 hours at 70 ° C, maintaining the pH> 10.
    Then, it was subjected to a solid-liquid separation (vacuum or centrifugal filtration) obtaining a liquid and on the other hand a solid composed of the remaining sugars of the process, residual lignin and insoluble inorganic compounds. The filtrate obtained could optionally be subjected to a cooling step at room temperature.
    The liquid obtained rich in lignin was brought to pH 4.5-3 by adding 4-5% hydrochloric acid thus precipitating the lignin.
    Then it was again subjected to a solid-liquid separation stage, where in this case the liquid is treated as effluent, and the solid obtained was a lignin cake (with approximately 50% humidity) which is
    10 led to the dryer with 85 -95% of total solids and obtaining an overall yield of 19.3% of final lignin.
    Taking into account the results obtained in examples 2 to 4, the yields obtained at different temperatures were compared and using 1-bromopropane 15 as a halogenated organic reagent (Table 2):
    Table 2: Comparison of the overall yields of the extraction and modification processes in one and two stages at different temperatures.
    Reagent Performance Two stagesPerformance One stage
    90 ° C 90 oC70 oC
    1-Bromopropane 24.8%50.8%19.3%
    权利要求:
    Claims (11)
    [1]
    1. A method of obtaining functionalized lignin from residual biomass cake comprising the following steps:
    a) dissolve the biomass cake in a base at a pH greater than or equal to 10 together with a halogenated organic compound selected from the following,
    • halogenated saturated carbon chain derivative reagent,
     HC ~ X. .
    3, X being a halogen:
    • halogenated carbon chain derivative reagent with al
    ~ X
    minus an H2C unsaturation being X a
    halogen; or,
    • halogenated epoxy derivative reagent
    or
    ~ x,
    X being a halogen:
    and heat the solution to a temperature between 80 oC and 120 oC,
    b) separating the liquid phase from the solid obtained in step (a);
    c) add an acid to the liquid obtained in step (b) up to a pH
    less than or equal to 5; Y,
    d) extract the precipitated solid obtained in step (c), and dry.
    [2]
    2. The process according to claim 1, wherein the base is selected from NaOH, KOH and LiOH or any combination thereof.
    [3]
    3. The process according to any one of claims 1 or 2, wherein the base is in a concentration of between 2% and 4%.
    [4]
    Four. The method according to any one of claims 1 to 4, wherein the ratio between the cake and the base in step (a) is between 7: 1 to 3: 1.
    [5]
    5. The method according to claim 4, wherein the ratio between the cake and the base in step (a) is between 7: 1 to 5: 1.
    [6]
    6. The method according to any one of claims 1 to 5, wherein the
    Step 5 (a) is carried out at an optimum temperature of between 90 oC and 100 oC for a time of between 2 and 4 hours.
    [7]
    7. The method according to any of claims 1 to 6, wherein the
    Halogenated organic compound is selected from 1-bromobutane, 110 bromopropane, allyl bromide and epichlorohydrin.
    [8]
    8. The method according to any of claims 1 to 7, wherein the separation of step (b) is carried out by filter, press or centrifuge.
    The method according to any one of claims 1 to 8, wherein the solid phase obtained in step (b) is carried to a biomass boiler.
    [10]
    10. The method according to any of claims 1 to 9, wherein the phase
    The liquid obtained in stage (b) is taken to a cooling stage at a temperature between 15 oC and 30 oC before stage (c).
    [11]
    11. The process according to any of claims 1 to 10, wherein the acid of step (c) is selected from formic acid, sulfuric acid and hydrochloric acid.
    [12]
    12. The process according to any of claims 1 to 11, wherein the extraction step (d) of the precipitated solid obtained in step (b) is carried out by decantation.
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    EP3960816A1|2020-08-25|2022-03-02|Indian Oil Corporation Limited|A method to valorize 2g bioethanol waste streams|
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