US20140093918A1 - Methods for converting lignocellulosic materials to useful products - Google Patents

Methods for converting lignocellulosic materials to useful products Download PDF

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US20140093918A1
US20140093918A1 US14/100,510 US201314100510A US2014093918A1 US 20140093918 A1 US20140093918 A1 US 20140093918A1 US 201314100510 A US201314100510 A US 201314100510A US 2014093918 A1 US2014093918 A1 US 2014093918A1
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pretreatment
bagasse
acid
solution
lignocellulosic material
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Zhanying Zhang
Ian Mark O'Hara
William Orlando Sinclair Doherty
Darryn Rackemann
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Syngenta Participations AG
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Queensland University of Technology QUT
Syngenta Participations AG
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Assigned to QUEENSLAND UNIVERSITY OF TECHNOLOGY reassignment QUEENSLAND UNIVERSITY OF TECHNOLOGY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DOHERTY, WILLIAM ORLANDO SINCLAIR, O'HARA, IAN MARK, RACKEMANN, Darryn, ZHANG, Zhanying
Assigned to SYNGENTA PARTICIPATIONS AG reassignment SYNGENTA PARTICIPATIONS AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: QUEENSLAND UNIVERSITY OF TECHNOLOGY
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/02—Pretreatment of the raw materials by chemical or physical means
    • D21B1/021—Pretreatment of the raw materials by chemical or physical means by chemical means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class
    • C13K13/002—Xylose
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention concerns pretreatment solutions for lignocellulosic material and methods for pretreating lignocellulosic material that can be used to produce useful products, such as fermentable sugars.
  • Lignocellulosic material can be used to produce biofuels (e.g., bioethanol) and biochemicals, and thus is an alternative to fossil fuels.
  • biofuels e.g., bioethanol
  • biochemicals e.g., bioethanol
  • the cellulose and/or hemicellulose components of lignocellulosic material need to be converted to monosaccharides (i.e., monosugars) that are capable of being fermented into ethanol or butanol.
  • Prior work in this area has proposed processes for the production of fermentable sugars from lignocellulosic material that involve a chemical and/or physical pretreatment to disrupt the natural structure of the lignocellulosic material, followed by enzymatic hydrolysis of the cellulose and hemicellulose components into monosugars.
  • the monosugars can then be fermented to produce biofuels including ethanol or butanol, and/or other fermentation products such as organic acids and/or other alcohols.
  • these processes currently have not been commercialized due to the high cost, low efficiency, adverse reaction conditions, and other issues associated with the pretreatment process.
  • these processes are not environmentally friendly and in order to achieve effective and efficient hydrolysis, a large addition of enzymes is required, which further increases costs.
  • the present invention addresses previous shortcomings in the art by providing pretreatment solutions for lignocellulosic material and methods for pretreating lignocellulosic material that can be used to produce fermentable sugars.
  • a first aspect of the present invention includes a pretreatment solution for lignocellulosic material comprising about 30% to about 99% by weight alkylene carbonate, about 0.1% to about 5% by weight an acid catalyst, and about 0% to about 20% by weight water.
  • a second aspect of the present invention includes a pretreatment solution for lignocellulosic material comprising about 1% to about 60% by weight polyol, about 30% to about 99% alkylene carbonate, about 0.1% to about 5% acid, and about 0.1% to about 10% water.
  • Another aspect of the present invention includes a method for producing a partially hydrolyzed lignocellulosic material, comprising pretreating a lignocellulosic material with a pretreatment solution comprising about 30% to about 99% by weight alkylene carbonate, about 0.1% to about 5% by weight an acid catalyst, and about 0% to about 20% by weight water, thereby producing a pretreated partially hydrolyzed lignocellulosic material.
  • a further aspect of the present invention includes a method for producing a fermentable sugar, comprising pretreating a lignocellulosic material with a pretreatment solution comprising about 30% to about 99% by weight alkylene carbonate, about 0.1% to about 5% by weight an acid catalyst, and about 0% to about 20% by weight water to produce a pretreated lignocellulosic material, and enzymatically hydrolyzing the pretreated lignocellulosic material, thereby producing a fermentable sugar.
  • Another aspect of the present invention includes a method for producing a partially hydrolyzed lignocellulosic material, comprising pretreating a lignocellulosic material with a pretreatment solution comprising about 1% to about 60% by weight polyol, about 30% to about 99% alkylene carbonate, about 0.1% to about 5% acid, and about 0.1% to about 10% water, thereby producing a pretreated partially hydrolyzed lignocellulosic material.
  • a further aspect of the present invention includes a method for producing a fermentable sugar, comprising pretreating a lignocellulosic material with a pretreatment solution comprising about 1% to about 60% by weight polyol, about 30% to about 99% alkylene carbonate, about 0.1% to about 5% acid, and about 0.1% to about 10% water to produce a pretreated lignocellulosic material, and enzymatically hydrolyzing the pretreated lignocellulosic material, thereby producing a fermentable sugar.
  • FIG. 1 shows FTIR spectra of (a) untreated bagasse, (b) bagasse pretreated with an acid solution, and (c) bagasse pretreated with a glycerol/acid/water solution,
  • FIG. 2 shows SEM images of (a) untreated bagasse, (b) bagasse pretreated with an acid solution, and (c) bagasse pretreated with a glycerol/acid/water solution. Samples were magnified 1000 times.
  • FIG. 3 shows graphs of the kinetics of enzymatic hydrolysis of bagasse pretreated with pretreatment solutions comprising (a) glycerol, (b) ethylene glycol, and (c) 1,2-propanediol.
  • FIG. 4 shows the effect of lignin removal by soda wash on enzymatic hydrolysis of bagasse pretreated with pretreatment solutions comprising (a) ethylene glycol solution and (b) 1,2-propanediol solution.
  • FIG. 5 shows a comparison of dilute acid treatment, caustic soda treatment, and acid-catalyzed aqueous glycerol pretreatment of sugarcane bagasse as well as untreated sugarcane bagasse.
  • FIG. 6 shows a schematic of an acid-catalyzed aqueous glycerol pretreatment biorefinery process.
  • FIG. 7 shows graphs of the kinetics of enzymatic hydrolysis of pretreated sugarcane bagasse carried out at the pilot plant scale.
  • FIG. 8 shows graphs comparing (a) the enzymatic digestibility of different pretreatments, (b) the amount of inhibitors present after different pretreatments, and (c) the temperatures at which different pretreatments are carried out.
  • any feature or combination of features set forth herein can be excluded or omitted.
  • any feature or combination of features set forth herein can be excluded or omitted.
  • the transitional phrase “consisting essentially of” (and grammatical variants) is to be interpreted as encompassing the recited materials or steps “and those that do not materially affect the basic and novel characteristic(s)” of the claimed invention. See, In re Herz, 537 F.2d 549, 551-52, 190 U.S.P.Q. 461, 463 (CCPA 1976) (emphasis in the original); see also MPEP ⁇ 2111.03. Thus, the term “consisting essentially of” as used herein should not be interpreted as equivalent to “comprising.”
  • the present invention relates to pretreatment solutions for lignocellulosic material and methods for hydrolyzing lignocellulosic material that can subsequently be used to produce fermentable sugars.
  • Lignocellulosic or “lignocellulose”, as used herein, refer to material comprising lignin and/or cellulose. Lignocellulosic material can also comprise hemicellulose, xylan, proteins, lipids, carbohydrates, such as starches and/or sugars, or any combination thereof. Lignocellulosic material can be derived from living or previously living plant material (e.g., lignocellulosic biomass). “Biomass,” as used herein, refers to any lignocellulosic material and can be used as an energy source.
  • Lignocellulosic material e.g., lignocellulosic biomass
  • Lignocellulosic material can be derived from a single material or a combination of materials and/or can be non-modified and/or modified.
  • Lignocellulosic material can be transgenic (i.e., genetically modified).
  • Transgenic refers to a plant into which a transgene has been delivered or introduced and the transgene can be expressed in the transgenic plant to produce a product, the presence of which can impart an effect and/or a phenotype in the plant.
  • the term “transgene” as used herein, refers to any nucleic acid sequence used in the transformation of a plant.
  • a transgene can be a coding sequence, a non-coding sequence, a cDNA, a gene or fragment or portion thereof, a genomic sequence, a regulatory element and the like.
  • the lignocellulosic material is a transgenic plant or transgenic plant material that expresses or expressed exogenous enzymes.
  • Lignocellulose is generally found, for example, in the fibers, pulp, stems, leaves, hulls, canes, husks, and/or cobs of plants or fibers, leaves, branches, bark, and/or wood of trees and/or bushes.
  • Exemplary lignocellulosic materials include, but are not limited to, agricultural biomass, e.g., farming and/or forestry material and/or residues, branches, bushes, canes, forests, grains, grasses, short rotation woody crops, herbaceous crops, and/or leaves; energy crops, e.g., corn, millet, and/or soybeans; energy crop residues; paper mill residues; sawmill residues; municipal paper waste; orchard prunings; chaparral; wood waste; logging waste; forest thinning; short-rotation woody crops; bagasse, such as sugar cane bagasse and/or sorghum bagasse, duckweed; wheat straw; oat straw; rice straw; barley straw; rye straw; flax straw; soy hulls; rice hulls; rice straw; tobacco; corn gluten feed; oat hulls; corn kernel; fiber from kernels; corn stover; corn stalks; corn cobs; corn husks; canola; miscanthus;
  • the lignocellulosic material has been processed by a processor selected from the group consisting of a dry grind ethanol production facility, a paper pulping facility, a tree harvesting operation, a sugar cane factory, or any combination thereof.
  • a processor selected from the group consisting of a dry grind ethanol production facility, a paper pulping facility, a tree harvesting operation, a sugar cane factory, or any combination thereof.
  • the lignocellulosic material is bagasse.
  • the methods of the present invention can comprise, consist essentially of, or consist of pretreating the lignocellulosic material (e.g., biomass) with a pretreatment solution of the present invention.
  • pretreatment refers to treating, contacting, soaking, suspending, immersing, saturating, dipping, wetting, rinsing, washing, submerging, and/or any variation and/or combination thereof, the lignocellulosic material with a pretreatment solution of the present invention.
  • the pretreating step can be performed or carried out at a temperature from about 40° C. to about 150° C. or any range therein, such as, but not limited to, about 40° C. to about 90° C., about 50° C. to about 100° C., about 60° C. to about 90° C., about 80° C. to about 150° C., about 90° C. to about 130° C., or about 100° C. to about 130° C.
  • the pretreatment step is carried out at a temperature of about 40° C., 41° C., 42° C., 43° C., 44° C., 45° C., 46° C., 47° C., 48° C., 49° C., 50° C., 51° C., 52° C., 53° C., 54° C., 55° C., 56° C., 57° C., 58° C., 59° C., 60° C., 61° C., 62° C., 63° C., 64° C., 65° C., 66° C., 67° C., 68° C., 69° C., 70° C., 71° C., 72° C., 73° C., 74° C., 75° C., 76° C., 77° C., 78° C., 79° C., 80° C., 81° C., 82° C., 83°
  • the pretreating step can be performed or carried out for a period of time from about 1 minute to about 120 minutes or any range therein, such as, but not limited to, about 5 minutes to about 100 minutes, or about 15 minutes to about 60 minutes.
  • the pretreatment step is carried out for a period of time of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92
  • Lignocellulosic biomass loading i.e. the lignocellulosic material to pretreatment, solution ratio
  • Lignocellulosic biomass loading can be from about 0.1% to about 60% or any range therein, such as, but not limited to, about 5% to about 40%, or about 5% to about 20% by weight of the pretreatment solution.
  • the lignocellulosic biomass loading is about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, or any range therein, by weight of the pretreatment solution.
  • the lignocellulosic biomass loading is about 10% by
  • a pretreatment solution of the present invention can comprise, consist essentially of, or consist of a polyol, an alkylene carbonate, an acid catalyst, water, or any combination thereof.
  • exemplary polyols include, but are not limited to, 1,2-propanediol, 1,3-propanediol, glycerol, 2,3-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanedial, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-methyl-1,3-butanediol, 1,1,1-trimethylolethane, 3-methyl-1,5-pentanediol, 1,1,1-trimethylolpropane
  • a polyol can be present in pure (e.g., refined) or impure (e.g., crude or purified crude) form.
  • a polyol has a purity of about 70% to about 99.9% or any range therein, such as, but not limited to, about 80% to about 99.9%, or about 80% to about 97%.
  • the purity of a′ polyol is about 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or any range therein.
  • Purity forms or grades (e.g., refined, crude, or purified crude) of a polyol can be, but are not limited to, purity grades produced as by-products from biodiesel production processes.
  • a polyol is in pure form (e.g., having, a purity of 99% or more) and in other embodiments a polyol is in crude form (e.g., having a purity of from about 7.0% to about 98%).
  • one or more polyols can be present in the pretreatment solutions of the present invention.
  • 1, 2, 3, 4, 5, or more polyols can be present in the pretreatment solutions of the present invention.
  • a polyol can be present in the pretreatment solution in an amount from about 1% to about 99% by weight of the pretreatment solution or any range therein, such as, but not limited to, about 1% to about 80%, about 10% to about 50%, about 15% to about 35%, about 20% to about 99%, about 40% to about 99%, or about 80% to about 97% by weight of the pretreatment solution.
  • a polyol is present in the pretreatment solution in an amount of about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%05%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 3.6%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 0.50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 70%, 71%, 72%
  • one or more acid catalysts can be present in the pretreatment solutions of the present invention.
  • 1, 2, 3, 4, 5, or more acid catalyst(s) can be present in the pretreatment solutions of the present invention.
  • An acid catalyst can be present in the pretreatment solution in an amount from about 0.1% to about 10.0% or any range therein such as, but not, limited to, about 0.1% to about 5%, about 0.1% to about 1.5%, or about 1% to about 3.0% by weight of the pretreatment solution.
  • an acid catalyst is present in the pretreatment solution in an amount of about 0.1%, 0.2%, 03%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, 2.75%, 3%, 3.25%, 3.5%, 3.75%, 4%, 4.25%, 4.5%, 4.75%, 5%, 5.25%, 5.5%, 5.75%, 6%, 6.25%, 6.5%, 6.75%, 7%, 7.25%, 7.5%, 7.75%, 8%, 8.25%, 8.5%, 8.75%, 9%, 9.25%, 9.5%, 9.75%, 10%, or any range therein, by weight of the pretreatment solution.
  • an acid catalyst is present in an amount of about 0.5% to about 2% by weight of the pretreatment solution.
  • Acid catalyst refers to various water-soluble compounds with a pH of less than 7 that can be reacted with a base to form a salt.
  • Exemplary acid catalysts can be monoprotic or polyprotic and can comprise one, two, three, or more acid functional groups.
  • Exemplary acid catalysts include, but are not limited to, mineral acids, Lewis acids, acidic metal salts, organic acids, solid acids, inorganic acids, or any combination thereof.
  • Specific acid catalysts include, but are not limited to hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, nitric acid, formic acid, acetic acid, methanesulfonic acid, toluene-sulfonic acid, boron trifluoride diethyletherate, scandium (III) trifluoromethanesulfonate, titanium (IV) isopropoxide, tin (IV) chloride, zinc (II) bromide, iron (II) chloride, iron (III) chloride, zinc (II) chloride, copper (I) chloride, copper (I) bromide, copper (II) chloride, copper (II) bromide, aluminum chloride, chromium (II) chloride, chromium (III) chloride, vanadium (III) chloride, molybdenum (III) chloride, palladium (II) chloride, platinum (II) chlor
  • Water can optionally be present in the pretreatment solution in an amount from about 0% to about 80% or any range therein, such as, but not limited to, about 1% to about 60% or about 1% to about 20% by weight of the pretreatment solution.
  • water is present in the pretreatment solution in an amount of about 0%, 1%, 0.2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 6
  • a pretreatment solution of the present invention comprises an alkylene carbonate.
  • alkylene carbonates include, but are not limited to, ethylene carbonate, propylene carbonate, and/or 1,2-butylene carbonate.
  • An alkylene carbonate can be present in a pretreatment solution of the present invention in an amount from about 30% to about 99% by weight of the pretreatment solution or any range therein, such as, but not limited to, about 40% to about 99%, about 55% to about 99%, about 70% to about 99%, about 80% to about 99%, about 90% to about 99%, or about 95% to about 99% by weight of the pretreatment solution.
  • an alkylene carbonate is present in the pretreatment solution in an amount of about 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or any range therein, by weight of the pretreatment solution.
  • an alkylene carbonate is present in the pretreatment solution in an amount
  • a pretreatment solution of the present invention comprises, consists essentially of, or consists of an alkylene carbonate, an acid, and optionally water. In some embodiments, a pretreatment solution of the present invention comprises about 40% to about 99% by weight alkylene carbonate, about 0.1% to about 2% acid, and optionally about 0% to about 5% water.
  • a pretreatment solution of the present invention comprises, consists essentially of, or consists of an alkylene carbonate, a polyol, an acid, and optionally water.
  • an alkylene carbonate and a polyol can be present in a pretreatment solution of the present invention in a ratio from about 0.1:1 to about 10:1 (alkylene carbonate:polyol) or any range therein, such as, but not limited to, from about 0.5:1 to about 5:1, about 1:1 to about 8:1, about 1:5 to about 1:10, or about 1:1 to about 4:1.
  • an alkylene carbonate and a polyol can be present in a pretreatment solution in a ratio of about 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1 (alkylene carbonate:polyol), or any range therein.
  • a pretreatment solution of the present invention can comprise about 1% to about 70% by weight polyol, about 30% to about 99% alkylene carbonate, about 0.1% to about 5% acid, and about 0.1% to about 20% water.
  • a pretreatment solution of the present invention comprises about 40% to about 99% by weight alkylene carbonate, about 10% to about 60% by weight polyol, about 0.1% to about 2% acid, and about 0.1% to about 5% water.
  • a polyol comprises ethylene glycol and an alkylene carbonate comprises ethylene carbonate.
  • the pretreatment step can result in the hydrolysis and/or break down of the lignocellulosic material.
  • Hydrolysis refers to the cleavage or breakage of the chemical bonds that hold the lignocellulosic material together.
  • hydrolysis can include, but is not limited to, the breaking or cleaving of glycosidic bonds that link saccharides (i.e., sugars) together, and is also known as saccharification.
  • Lignocellulosic material in some embodiments, can comprise cellulose and/or hemicellulose. Cellulose is a glucan, which is a polysaccharide.
  • Polysaccharides are polymeric compounds that are made up of repeating units of saccharides monosaccharides or disaccharaides) that are linked together by glycosidic bonds.
  • the repeating units of saccharides can be the same (i.e., homogenous) to result in a homopolysaceharide or cats be different (i.e., heterogeneous) to result in a heteropolysaccharide.
  • Cellulose can undergo hydrolysis to form cellodextrins (i.e., shorter polysaccharide units compared to the polysaccharide units before the hydrolysis reaction) and/or glucose (i.e. a monosaccharide).
  • Hemicellulose is a heteropolysaccharide and can include polysaccharides, including, but not limited to, xylan, glucuronoxylan, arabinoxylan, glucomannan and xyloglucan. Hemicellulose can undergo hydrolysis to form shorter polysaccharide units, and/or monosaccharides, including, but not limited to, pentose sugars, xylose, mannose, glucose, galactose, rhamnose, arabinose, or any combination thereof.
  • the pretreatment step partially hydrolyzes the lignocellulosic material.
  • “Partial hydrolysis” or “partially hydrolyzes” and any grammatical variants thereof, as used herein, refer to the hydrolysis reaction cleaving or breaking less than 100% of the chemical bonds that hold the lignocellulosic material together.
  • the hydrolysis reaction cleaves or breaks less than 100% of the glycosidic bonds of the cellulose and/or hemicellulose present in the lignocellulosic material.
  • the partial hydrolysis reaction can convert less than about 20%, 15%, 10%, or 5% of the cellulose into glucose.
  • the partial hydrolysis reaction can convert less than about 20%, 15%, 10%, or 5% of the hemicellulose into monosaccharides.
  • exemplary monosaccharides include but are not limited to, xylose, glucose, mannose, galactose, rhamnose, and arabinose.
  • the partial hydrolysis reaction can result in the recovery of greater than about 80%, 85%, 90%, or 95% of the glucan present in the pretreated lignocellulosic material compared to the amount of glucan present in the lignocellulosic material before pretreatment.
  • the partial hydrolysis reaction can result in the recovery of less than about 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5% of the xylan in the pretreated lignocellulosic material compared to the amount of xylan present in the lignocellulosic material before pretreatment.
  • the production of undesirable products from lignocellulosic material as a result of the pretreatment step is reduced compared to other processes for the treatment of lignocellulosic material.
  • the terms “reduce,” “reduces,” “reduced,” “reduction” and similar terms refer to a decrease of at least about 5%, 10%, 25%, 35%, 50%, 75%, 80%, 85%, 90%, 95%, 97% or more.
  • Exemplary undesirable products include furfural, acetic acid, 5-hydroxymethylfurfural (HMF), formic acid, and glycerol chlorination products, including, but not limited to, 3-monochloropropane-1,2-diol (3-MCPD), 2-monochloropropane-1,3-diol (2-MCPD), 1,3-dichloropropane-2-ol (1,3-DCP) and 1,2-dichloropropane-3-ol (1,2-DCP).
  • 3-monochloropropane-1,2-diol 3-monochloropropane-1,2-diol (3-MCPD), 2-monochloropropane-1,3-diol (2-MCPD), 1,3-dichloropropane-2-ol (1,3-DCP) and 1,2-dichloropropane-3-ol (1,2-DCP).
  • the undesirable product is at a concentration in the pretreatment solution, filtrate and/or hydrolysate of less than about 20 g/kg, 15 g/kg, 10 g/kg, 5 g/kg, 1 g/kg, 0.5 g/kg, or 0.25 g/kg and is thus reduced compared to other processes for treating lignocellulosic material.
  • the undesirable product is at a concentration in the pretreatment solution, filtrate and/or hydrolysate of less than about 0.25, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 g/kg, or any range therein, and is thus reduced compared to other processes for treating lignocellulosic material.
  • the pretreatment step can break down and/or remove the lignin present in the lignocellulosic material.
  • Lignin in some embodiments, can be removed from the lignocellulosic material by hydrolysis of the chemical bonds that hold the lignocellulosic material together.
  • the pretreatment step can result in the removal of about 80% or less (e.g., about 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, etc.) or any range therein of the lignin in the pretreated lignocellulosic material compared to the amount of lignin present in the lignocellulosic material prior to the pretreating step.
  • about 80% or less e.g., about 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, etc.
  • the pretreatment step can result in the recovery of about 20% or more (e.g., about 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.) or any range therein of the lignin in the pretreated lignocellulosic material compared to the amount of lignin present in the lignocellulosic material prior to the pretreating step.
  • the pretreatment step can affect the structure of the lignocellulosic material.
  • the pretreatment step can result in the dissociation of fibers in the lignocellulosic material, increase the porosity of the lignocellulosic material, increase the specific surface area of the lignocellulosic material, or any combination thereof.
  • the pretreatment step reduces the crystallinity of the cellulose structure by, for example, changing a portion of the cellulose from a crystalline state to an amorphous state.
  • the pretreatment step in some embodiments of this invention, can make the pretreated lignocellulosic material more susceptible to enzymatic digestion compared to lignocellulosic material not subjected to a, pretreatment step described herein.
  • enzymatic digestion of the pretreated lignocellulosic material can be increased by two, three, four, five, six, seven, eight or more times compared to the enzymatic digestion of lignocellulosic material not pretreated with the pretreatment solution as described herein.
  • the lignocellulosic material after treatment of the lignocellulosic material with the pretreatment solution as described herein, can be separated from the pretreatment solution by any means known to those skilled in the art.
  • a method of separating the lignocellulosic material from the pretreatment solution can include, but is not limited to, vacuum filtration, membrane filtration, sieve filtration, partial or coarse separation, or any combination thereof.
  • the separating step can produce a liquid portion (i.e., filtrate or hydrolysate) and a solid residue portion (i.e., the pretreated lignocellulosic material).
  • the pretreated lignocellulosic material can optionally include the pretreatment solution and/or by-products from the pretreatment process, such as, but not limited to, polyol(s), glycerol residue, acid(s), and products produced from the pretreatment process.
  • a post-pretreatment wash solution can comprise a basic solution and/or an organic solvent.
  • a basic solution can have a pH of about pH 8 or greater (e.g., about pH 8, 9, 10, 11, 12, 13, or 14). In particular embodiments, the pH of a basic solution is about pH 10 or greater or about pH 12 or greater.
  • a basic solution can comprise alkaline chemicals, such as, but not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide, and basic salts such as, but not limited to, sodium carbonate and potassium carbonate.
  • the concentration of the alkaline chemical in the basic solution can be from about 0.0002% to about 12% by weight of the basic solution or any range therein, such as, but not limited to from about 0.002 to about 10%, about 0.02 to about 5%, or about 0.01 to about 0.5% by weight of the basic solution. In particular embodiments, the concentration of the alkaline chemical in the basic solution is about 0.2% by weight of the basic solution.
  • a post-pretreatment wash solution comprises an organic solvent.
  • Exemplary organic solvents for a post-pretreatment wash solution include, but are not limited, an alcohol, such as methanol and/or ethanol, acetone, and/or 1,4-dioxane.
  • a post-pretreatment wash can be carried out at a temperature from about 0° C. to about 100° C. or any range therein, such as, but not limited to, from about 0.5° C. to about 80° C., about 5° C. to about 40° C., or about 15° C. to about 35° C.
  • the post-pretreatment wash is carried out at about room temperature (i.e., about 25° C.).
  • a post-pretreatment wash with a post-pretreatment wash solution can be carried out before and/or after the pretreated lignocellulosic material is optionally washed with water.
  • the pretreated lignocellulosic material can be washed with water and/or a post-pretreatment wash solution one or more times, such as 2, 3, 4, or more times.
  • the pretreated lignocellulosic material can be washed with a basic solution after pretreatment.
  • the pretreated lignocellulosic material can be washed with water one or more times after pretreatment, then the pretreated lignocellulosic material is washed with a basic solution one or more times, followed by optionally washing the pretreated lignocellulosic material with water one or more times.
  • the pretreated lignocellulosic material can be washed with an organic solvent one or more times, then washed with water one or more times.
  • the pretreated lignocellulosic material can be separated from the water and/or post-pretreatment wash solution via methods such as, but not limited to, vacuum filtration, membrane filtration, sieve filtration, partial or coarse separation, or any combination thereof.
  • a post-pretreatment wash with a post-pretreatment wash solution removes lignin present in the pretreated lignocellulosic material.
  • a post-pretreatment wash with a post-pretreatment wash solution removes residual lignin present in the pretreated lignocellulosic material.
  • the residual lignin can, in some embodiments, be present in the pretreated lignocellulosic material as a result of lignin condensing on the pretreated lignocellulosic material during and/or after pretreatment with a pretreatment solution of the present invention.
  • the lignin present in the pretreated lignocellulosic material can be dissolved and/or removed by washing the pretreated lignocellulosic material with a post-pretreatment wash solution.
  • the wash with a post-pretreatment wash solution can result in the removal of about 25% or more of lignin as compared to the lignin present in untreated lignocellulosic material (i.e., lignocellulosic material not treated with a pretreatment solution of the present invention and/or not treated with a post-pretreatment wash solution of the present invention).
  • a wash with a post-pretreatment wash solution can result in the removal of about 25%, 30%, 35%, 40%, 45%, 50%, 55%, or more, or any range therein, of lignin compared to the lignin present in untreated lignocellulosic material.
  • a wash with a post-pretreatment wash solution can result in the removal of about 25% to about 50%, or any range therein, of lignin as compared to the lignin present in untreated, lignocellulosic material.
  • the amount of lignin removed from the lignocellulosic material is about 60% or more, such as about 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or more compared to the lignin present in untreated lignocellulosic material.
  • pretreatment with a pretreatment solution of the present invention and post-pretreatment with a post-pretreatment wash solution of the present invention removes about 65% of the lignin present in the lignocellulosic material prior to pretreatment and post-pretreatment.
  • the post-pretreatment wash solution is a basic solution
  • a post-pretreatment wash solution can be collected after washing the pretreated lignocellulosic material.
  • the collected post-pretreatment wash solution is a basic solution that can be used to recover lignin by adjusting the pH of the collected basic solution to an acidic pH (i.e., a pH of less than about 7) with an acid salt or acid, such as, but not limited to, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
  • the pH of the collected basic solution is adjusted to a pH of about 1 to about 7 or any range therein, such as, but not limited to, about 1.5 to about 6.5 or about 2 to about 5.
  • the temperature at which lignin is recovered can be from about 0° C. to about 90° C. or any range therein, such as, but not limited to, about 5° C. to about 70° or about 5° C. to about 40° C.
  • the lignin can be recovered by precipitating the lignin from the collected basic solution and can be collected by filtration, such as, but not limited to, vacuum filtration, membrane filtration, sieve filtration, partial or coarse separation, or any combination thereof.
  • the recovered lignin can be used for the production of a valuable product, such as, but not limited to, a combustion energy product, a phenol substitute in phenolic resins, a polymer additive, a construction material, or any combination thereof.
  • lignin in the pretreated lignocellulosic material negatively affects the enzymatic hydrolysis of cellulose due to non-productive adsorption of the enzymes, such as cellulase, by lignin.
  • Non-productive adsorption of the enzymes by lignin is believed to reduce the actual amount of the enzyme available for enzymatic hydrolysis.
  • by further removal of lignin present in the pretreated lignocellulosic material can improve the rate of enzymatic hydrolysis and reduce the amount of enzyme utilized in the enzymatic hydrolysis.
  • the filtrate or hydrolysate can be collected after and/or during separation for use in pretreating additional lignocellulosic material (i.e., recycling of the filtrate/hydrolysate).
  • the filtrate or hydrolysate can be collected and reused two, three, four, or more times.
  • Additional components can optionally be added to the recycled solution, including but not limited to, additional water, acid catalyst(s), polyol(s), or any combination thereof. In some embodiments of the present invention, water is added to the recycled solution.
  • a pretreated lignocellulosic material can be subject to further processing conditions, such as, but not limited to, steam explosion.
  • the lignocellulosic material is treated with an aqueous acid solution prior to treatment with the pretreatment solution of the present invention (i.e., pre-pretreatment).
  • An aqueous acid solution can comprise, consist essentially of, or consist of mineral acids, Lewis acids, acidic metal salts, organic acids, solid acids, inorganic acids, or any combination thereof.
  • One or more acids e.g., 1, 2, 3, 4, 5, or more acids
  • the acid(s) can be monoprotic or polyprotic and can comprise one, two, three, or more acid functional groups.
  • Exemplary acids include, but are not limited to hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, nitric acid, formic acid, acetic acid, methanesulfonic acid, toluenesulfonic acid, boron trifluoride diethyletherate, scandium (III) trifluoromethanesulfonate, titanium (IV) isopropoxide, tin (IV) chloride, zinc (II) bromide, iron (II) chloride, iron (III) chloride, zinc (II) chloride, copper (I) chloride, copper (I) bromide, copper (II) chloride, copper (H) bromide, aluminum chloride, chromium (II) chloride, chromium (III) chloride, vanadium (III) chloride, molybdenum (III) chloride, palladium (II) chloride, platinum (II) chloride, platinum
  • the acid(s) can be present in the aqueous acid solution in an amount from about 0.1% to about 5.0% or any range therein, such as, but not limited to, about 0.1% to about 2.5% by weight of the acid solution.
  • the acid(s) can be present in the acid solution in an amount of about 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.2%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, 2.75%, 3%, 3.25%, 3.5%, 3.75%, 4%, 4.25%, 4.5%, 4.75%, 5%, or any range therein.
  • a pretreated lignocellulosic material can include the pretreatment solution and/or by-products from the pretreatment process, such as, but not limited to, polyol(s), glycerol residue, acid(s), and products produced from the pretreatment process.
  • a method of the present invention can increase the enzymatic digestibility of a pretreated lignocellulosic material compared to the enzymatic digestibility of untreated lignocellulosic material (i.e., lignocellulosic material not treated as described herein). In some embodiments, a method of the present invention can increase enzymatic digestibility of a pretreated lignocellulosic material by at least about 2 times or 3 times compared to the enzymatic digestibility of untreated lignocellulosic material.
  • An enzyme can be microbially produced and/or plant produced, and can include, but is not limited to, a cellulase, a hemicellulase, a xylanase, a ligninase, a pectinase, a protease, an amylase, a catalase, a cutinase, a glucanase, a glucoamylase, a glucose isomerase, a lipase, a laccase, a phytase, a pullulanase, a xylose isomerase, or any combination thereof.
  • the enzyme compositions can be prepared as a liquid, slurry, solid or gel.
  • the enzyme is/was expressed by the lignocellulosic plant material and retains its functional activity after pretreatment of the lignocellulosic material with the pretreatment solution. Accordingly, in some embodiments of the present invention, no additional enzyme(s) are contacted/added to the pretreated lignocellulosic material for enzymatic hydrolysis.
  • the enzyme is a cellulase and/or xylanase.
  • Cellulase or “cellulases”, as used herein, refer to an enzyme capable of hydrolyzing cellulose to glucose.
  • Non-limiting examples of cellulases include mannan endo-1,4- ⁇ -mannosidase, 1,3- ⁇ -D-glucan glucanohydrolase, 1,3- ⁇ -glucan glucohydrolase, 1,3-1,4- ⁇ -D-glucan glucanohydrolase and 1,6- ⁇ -D-glucan glucanohydrolase.
  • Xylanase or “xylanases”, as used herein, refer to an enzyme capable of at least hydrolyzing xylan to xylobiose and xylotriose.
  • exemplary xylanases can be from a Dictyoglomus sp. including, but not limited to, Dictyoglomus thermophilum Rt46B.1. See, e.g., Gibbs et al. (1995) Appl. Environ. Microbiol. 61:4403-4408.
  • an enzyme can be a high-temperature (i.e., thermostable) and/or low-pH (i.e., acidophilic) tolerant enzyme.
  • thermostable or “thermotolerant” is meant that the enzyme retains at least about 70% activity at about 60° C. for 30 minutes, at least about 65% activity at about 70° C. for 30 minutes, or at least about 60% activity at about 80° C. for 30 minutes.
  • acidophilic as used herein, means that the enzyme retains about 60% to about 90% of its activity at pH 6, retains at least about 65% activity at pH 5.0, or retains at least about 60% activity at pH 4.0.
  • an enzyme can be a dual activity enzyme.
  • a “dual activity enzyme”, as used herein, refers to an enzyme having both xylanase and cellulase activity.
  • the dual activity enzyme can be thermotolerant and/or acidophilic.
  • enzymes include ⁇ -L-arabinofuranosidase, ⁇ -glucuronidase, acetyl mannan esterase, acetyl xylan esterase, ⁇ -galactosidase, ⁇ -glucosidase, exoxylanase, ⁇ -1,4-xylosidase, endo-1,4- ⁇ -xylanase, endo-galactanase, endo- ⁇ -1,4-mannanase, 1,4- ⁇ -D-glucan cellobiohydrolase, endo-1,4- ⁇ -D-glucanase, ⁇ -glucosidase, endo- ⁇ -1,5-arabinanase, exo- ⁇ -1,4-mannosidase, cellobiohydrolases, endoglucanase, exo- ⁇ -1,4-xylosidase, feruloyl esterase, ferulic acid esterase, p
  • An enzyme can be provided as a partially or fully purified full-length enzyme, or active variants or fragments thereof, or can be provided as an enzyme-producing microorganism. Moreover, any of these enzymes can be provided in an amount effective to hydrolyze their substrate (e.g., the pretreated lignocellulosic material, which can optionally include the pretreatment solution and/or by-products from the pretreatment process, such as, but not limited to, polyol(s), glycerol residue, acid(s), and products produced from the pretreatment process), such as in amounts from about 0.001% to about 50%, from about 0.01% to about 50%, from about 0.1% to about 50%, from about 1% to about 50%, from about 10% to about 50%, from about 20% to about 50%, from about 30% to about 50%, from about 40% to about 50% by weight of the substrate, or more.
  • the substrate e.g., the pretreated lignocellulosic material, which can optionally include the pretreatment solution and/or by-products from the pretreatment
  • An enzyme composition also can include agents known to those of skill in the art for use in processing lignocellulosic material (e.g., biomass) including, but not limited to, a chlorine, detergent, hypochlorite, hydrogen peroxide, oxalic acid, peracid, pH-regulating agent, trisodium phosphate, sodium chlorite, sodium nitrate, surfactant, urea, buffer(s), and/or water.
  • detergents include, but are not limited to, anionic, cationic or neutral detergents such as Nonidet (N)P-40, sodium dodecyl sulfate (SDS), sodium lauryl sulfate (SLS), sulfobetaine, n-octylglucoside, deoxycholate, Triton® X-100 (Dow Chemical Co.; Midland, Mich.) and/or Tween® 20 (ICI Americas, Inc.; Bridgewater, N.J.).
  • anionic, cationic or neutral detergents such as Nonidet (N)P-40, sodium dodecyl sulfate (SDS), sodium lauryl sulfate (SLS), sulfobetaine, n-octylglucoside, deoxycholate, Triton® X-100 (Dow Chemical Co.; Midland, Mich.) and/or Tween® 20 (ICI Americas, Inc.; Bridgewater, N.J.).
  • Non-limiting examples of surfactants include a secondary alcohol ethoxylate, a fatty alcohol ethoxylate, a nonylphenol ethoxylate, a phosphate ester of fatty alcohols, a polyoxyethylene ether, a polyethylene glycol, a polyoxyethylenated alkyl phenol, a stearic acid and/or a tridecyl ethoxylate.
  • any of the agents can be provided as partially or fully purified. Moreover, any of these agents can be provided in an amount from about 0.001% to about 50%, from about 0.01% to about 50%, from about 0.1% to about 50%, from about 1% to about 50%, from about 10% to about 50%, from about 20% to about 50%, from about 30% to about 50%, from about 40% to about 50% by weight of the substrate, or more.
  • An enzyme composition of the present invention also can include fungi or other enzyme producing microorganisms, especially ethanologenic and/or lignin-solubilizing microorganisms, that can aid in processing, breaking down, and/or degrading lignocellulosic material.
  • fungi or other enzyme producing microorganisms especially ethanologenic and/or lignin-solubilizing microorganisms, that can aid in processing, breaking down, and/or degrading lignocellulosic material.
  • ethanologenic and/or lignin-solubilizing microorganisms include bacteria and yeast. See generally, Burchhardt & Ingram (1992) Appl. Environ. Microbial. 58:1128-1133; Dien et al. (1998) Enzyme Microb. Tech. 23:366-371; Keating et al. (2004) Enzyme Microb. Tech. 35:242-253; Lawford & Rousseau (1997) Appl.
  • Such microorganisms can produce enzymes that assist in processing lignocellulosic material including, but not limited to, alcohol dehydrogenase, pyruvate decarboxylase, transaldolase, transketolasepyruvate decarboxylase, xylose reductase, xylitol dehydrogenase or xylose isomerase xylulokinase.
  • the ethanologenic and/or lignin-solubilizing microorganisms include, but are not limited to, members of the genera Candida, Erwinia, Escherichia, Klebsiella, Pichia, Saccharomyces, Streptomyces and Zymomonas . See, e.g., Dien (1998), supra; Ingrain & Conway (1988) Appl. Environ. Microbial. 54:397-404; Jarboe et al. (2007) Adv. Biochem. Engin./Biotechnol. 108:237-261; Keating et al. (2004) J. Indust. Microbiol. Biotech.
  • the methods of the present invention can further comprise contacting (e.g., fermenting) the pretreated lignocellulosic material, optionally including the pretreatment solution and/or by-products from the pretreatment process (e.g., polyol(s), glycerol residue, acid(s), and products produced from the pretreatment process), with a microorganism, including, but not limited to, an ethanologenic bacteria, a yeast or a combination thereof.
  • the contacting can be at a pH in a range from about 2 to about 9.
  • the pretreated lignocellulosic material can then be processed for the production of fermentable sugars and/or for biofuel (e.g., ethanol) production.
  • compositions and methods described herein can be used to process lignocellulosic material (e.g., biomass) to many useful organic chemicals, fuels and products.
  • lignocellulosic material e.g., biomass
  • some commodity and specialty chemicals that can be produced from lignocellulosic material include, but are not limited to, acetone, acetate, butanediol, cis-muconic acid, ethanol, ethylene glycol, furfural, glycerol, glycine, lysine, organic acids (e.g., lactic acid), 1,3-propanediol, polyhydroxyalkanoates, and xylose.
  • animal feed and various food/beverages can be produced from lignocellulosic material.
  • compositions and/or methods described herein can be used to produce a pulp, such as a high value pulp.
  • the pulp produced using the compositions and/or methods of the present invention can be used for the production of various materials and/or products, such as, but not limited to, paper, textile, and microcrystalline cellulose.
  • the methods of the present invention comprise enzymatically hydrolyzing the pretreated lignocellulosic material to produce a fermentable sugar.
  • “Fermentable sugar,” as used herein, refers to oligosaccharides and/or monosaccharides that can be used as a carbon source by a microorganism in a fermentation process.
  • Exemplary fermentable sugars include glucose, xylose, arabinose, galactose, mannose, rhamnose, sucrose, fructose, or any combination thereof.
  • the fermentable sugars can be converted to useful value-added fermentation products, non-limiting examples of which include amino acids, such as lysine, methionine, tryptophan, threonine, and aspartic acid; vitamins; pharmaceuticals; animal feed supplements; specialty chemicals; chemical feedstocks; plastics; solvents; fuels or other organic polymers; lactic acid; butanol and/or ethanol, including fuel ethanol and/or fuel butanol; organic acids, including citric acid, succinic acid and maleic acid; and/or industrial enzymes, such as proteases, cellulases, amylases, glucanases, lactases, lipases, lyases, oxidoreductases, transferases and xylanases.
  • amino acids such as lysine, methionine, tryptophan, threonine, and aspartic acid
  • vitamins pharmaceuticals
  • animal feed supplements specialty chemicals
  • chemical feedstocks plastics
  • solvents fuels or other organic
  • the product(s) e.g., a fermentable sugar, ethanol, butanol, etc.
  • the product(s) e.g., a fermentable sugar, ethanol, butanol, etc.
  • Polyol(s) and/or acid(s) can be collected after separation for use in pretreating and/or additional treatment steps (i.e., recycling of the polyol(s) and/or acid(s)).
  • Air-dried depithed bagasse was ground and the material retained between 0.25 mm and 0.50 mm sieve was collected.
  • One gram (moisture content of 5%) of the bagasse was mixed with 10 grams of the pretreatment solution, (e.g., water, acid catalyst, and glycerol).
  • the pretreatment solution e.g., water, acid catalyst, and glycerol
  • the purity grade of the glycerol was analytical grade (i.e., commercial glycerol) with a water content less than 0.5%.
  • the mixture was stirred at 300 rpm and heated at the indicated temperature for a set time as set forth in each example.
  • a filtrate i.e., hydrolysate
  • a solid residue portion i.e., pretreated bagasse
  • a portion of the filtrate i.e., hydrolysate
  • HPLC high performance liquid chromatography
  • RPM monosaccharide column Phenomenex
  • the portion of the hydrolysate that was not neutralized was analyzed for organic acids, 5-hydroxymethylfurfural (HMF), furfural and 3-monochloropropane-1,2-dial (3-MCPD) by HPLC using a Aminex HPX 87H column (Bio-rad).
  • the solid residue i.e., pretreated bagasse
  • the washed solid residue was kept at 2° C.-6° C. prior to enzymatic digestibility analysis.
  • a portion of the solid residue was freeze-dried for composition analysis (e.g., glucan, xylan and lignin) by the Laboratory Analytical Procedure (NREL, 2008).
  • a further portion of the freeze-dried sample was analyzed by Fourier transform infra-red (FUR) spectroscopy and scanning electron microscopy (SEM).
  • FUR Fourier transform infra-red
  • SEM scanning electron microscopy
  • Glucan/xylan/lignin content in pretreated bagasse residue was calculated based on the following formula:
  • Glucan ⁇ / ⁇ xylan ⁇ / ⁇ lignin ⁇ ⁇ content Total ⁇ ⁇ glucan ⁇ / ⁇ xylan ⁇ / ⁇ lignin ⁇ ⁇ in pretreated ⁇ ⁇ bagasse ⁇ ⁇ residue ⁇ 100 ⁇ % Dry ⁇ ⁇ weight ⁇ ⁇ of ⁇ ⁇ pretreated ⁇ ⁇ bagasse ⁇ ⁇ residue
  • Glucan/xylan/lignin recovery was calculated based on the following formula:
  • Glucan ⁇ / ⁇ xylan ⁇ / ⁇ lignin ⁇ ⁇ recovery Total ⁇ ⁇ glucan ⁇ / ⁇ xylan ⁇ / ⁇ lignin ⁇ ⁇ in pretreated ⁇ ⁇ bagasse ⁇ ⁇ residue ⁇ 100 ⁇ % Total ⁇ ⁇ glucan ⁇ / ⁇ xylan ⁇ / ⁇ lignin ⁇ ⁇ in ⁇ ⁇ untreated ⁇ ⁇ bagasse
  • Glucose yield in hydrolysate was calculated based on the following formula:
  • Glucose ⁇ ⁇ yield Total ⁇ ⁇ glucose ⁇ ⁇ measured ⁇ ⁇ in ⁇ ⁇ hydrosylate ⁇ 100 Total ⁇ ⁇ glucan ⁇ ⁇ in ⁇ ⁇ untreated ⁇ ⁇ bagasse ⁇ 1.111
  • Xylose ⁇ ⁇ yield Total ⁇ ⁇ xylose ⁇ ⁇ measured ⁇ ⁇ in ⁇ ⁇ hydrosylate ⁇ 100 ⁇ % Total ⁇ ⁇ xylan ⁇ ⁇ in ⁇ ⁇ intreated ⁇ ⁇ bagasse ⁇ 1.136
  • Furfural yield in hydrolysate was calculated based on the following formula:
  • Furfural ⁇ ⁇ yield Total ⁇ ⁇ furfural ⁇ ⁇ measured ⁇ ⁇ in ⁇ ⁇ hydrosylate ⁇ 100 ⁇ % Total ⁇ ⁇ xylan ⁇ ⁇ in ⁇ ⁇ untreated ⁇ ⁇ bagasse ⁇ 0.727
  • HMF yield in hydrolysate was calculated based on the following formula:
  • H ⁇ ⁇ M ⁇ ⁇ F ⁇ ⁇ yield Total ⁇ ⁇ H ⁇ ⁇ M ⁇ ⁇ F ⁇ ⁇ measured ⁇ ⁇ in ⁇ ⁇ hydrosylate ⁇ 100 ⁇ % Total ⁇ ⁇ glucan ⁇ ⁇ in ⁇ ⁇ untreated ⁇ ⁇ bagasse ⁇ 0.778
  • Enzymatic hydrolysis was conducted in a 20 mL bottle containing 5 mL of enzyme solution. The enzymatic hydrolysis was carried out at 50° C. for 72 hours. The amount of pretreated bagasse used in each assay contained an equivalent of 2% cellulose loading. The enzyme Accellerase® was used for enzymatic hydrolysis of the pretreated bagasse in an amount of 0.5 mL enzyme per gram pretreated bagasse. Accellerase® is an enzyme mixture containing cellulases and xylanases.
  • Enzymatic digestibility was calculated based on the amount of glucose released by enzymatic hydrolysis compared to the total glucan in pretreated bagasse before enzymatic hydrolysis.
  • Digestibility Total ⁇ ⁇ glucan ⁇ ⁇ converted ⁇ ⁇ to ⁇ ⁇ glucose after ⁇ ⁇ enzymatic ⁇ ⁇ hydrolysis ⁇ 100 ⁇ % Total ⁇ ⁇ glucan ⁇ ⁇ in ⁇ ⁇ sample
  • FIG. 1 shows FTIR spectra of untreated bagasse and bagasse pretreated with either an acid solution or a glycerol/acid/water solution.
  • the bagasse samples were either untreated or pretreated with the acid solution or the glycerol/acid/water solution for 60 minutes at 130° C.
  • the acid solution contained 1.2% HCl and 98.8% water.
  • the glycerol/acid/water solution contained 1.2% HCl, 88.8% glycerol, and 10% water.
  • the ester bond signal at 1732 cm ⁇ 1 was weaker in the spectrum of the pretreated samples than that of the untreated sample, suggesting that some ester linkages between lignin and the carbohydrates were cleaved during the pretreatment process (Liu et al., 2009).
  • the peaks at 1515 cm ⁇ 1 and 1605 cm ⁇ 1 which relate to the aromatic skeleton vibrations in lignin (Liu et al., 2009), were present in the pretreated samples, indicating that the pretreatment process did not completely remove lignin.
  • the peaks at 1515 cm ⁇ 1 and 1605 cm ⁇ 1 were sharper for the acid pretreated bagasse than those for the untreated bagasse and the glycerol/acid/water pretreated bagasse, which indicates a higher lignin content in the acid pretreated bagasse. This is consistent with the lignin content shown in Table 1.
  • the peak at 1320 cm ⁇ 1 was sharper for the acid pretreated bagasse than for those of the untreated, bagasse and the glycerol/acid/water pretreated bagasse, possibly due to higher syringyl lignin content in the acid pretreated bagasse.
  • the increase in the peak at around 1200 cm ⁇ 1 for both the acid and glycerol/acid pretreated bagasse suggests an increased contribution from second OH groups (Guo et al., 2008).
  • the peak at 1105 cm ⁇ 1 which refers to the removal of crystalline cellulose, is sharper for the acid pretreated bagasse, and indicates that the acid pretreatment increased the crystallinity of the bagasse (Li et al., 2010).
  • a small sharp band at 898 cm ⁇ 1 is characteristic of ⁇ -glycosidic linkages, and demonstrates the presence of predominant ⁇ -glycosidic linkages between the sugar units in cellulose and hemicellulose (Liu et al., 2009).
  • the peak at 835 cm ⁇ 1 which belongs to a C—H out of plane vibration in lignin, is sharper in the acid pretreated bagasse indicating higher lignin content in the acid pretreated bagasse (Zhao et al., 2008).
  • SEM Scanning electron microscopy analysis was conducted to study changes in bagasse morphology following various pretreatments.
  • the bagasse samples were either untreated or pretreated with an acid solution or a glycerol/acid/water solution for 60 minutes at 130° C.
  • the acid solution contained 1.2% HCl and 98.8% water.
  • the glycerol/acid/water solution contained 1.2% HCl, 88.8% glycerol, and 10% water.
  • the untreated bagasse sample exhibited grid and compact fibrils ( FIG. 2 a ), which hinder the ability of the enzymes to access the cellulosic and hemicellulosic components of the bagasse (i.e., the lignocellulosic material) during saccharification.
  • the morphology of bagasse pretreated with the acid solution did not change significantly compared to untreated bagasse ( FIG. 2 b ), although some pores appeared in the acid pretreated bagasse.
  • pretreatment with the glycerol/acid/water solution destroyed the rigid structure of bagasse ( FIG. 2 c ). Without being bound to a particular theory, this may be attributed to the removal of hemicellulose and some of the lignin from the bagasse, resulting in the dissociation of the fibrils, increased porosity and increased specific surface area of the material.
  • the effect of varying the amount of glycerol in the glycerol/acid/water solution was examined.
  • the amounts of glycerol and water used in the glycerol/acid/water pretreatment solution, which used 1.2% HCl as the acid catalyst, are given in Table 1.
  • Pretreatment of the bagasse samples with a glycerol/acid/water solution was performed at 130° C. for 60 min.
  • Glycerol/acid/water solutions containing more than 78% glycerol produced a solid residue having greater than 60% glucan and less than 8% xylan and an enzyme digestibility of about 88% or more.
  • Bagasse treated with a glycerol/acid/water solution containing 58.8% glycerol showed lower digestibility than bagasse pretreated with pretreatment solutions having higher amounts of glycerol, but greater digestibility than bagasse treated with only 1.2% HCl (Table 1).
  • Table 2 shows the components detected in the hydrolysate after pretreatment.
  • the proportion of glucose in the hydrolysate increased with increasing glycerol content.
  • 5-hydroxymethylfurfural (HMF) a dehydration product of glucose which is usually produced under acidic pretreatment conditions, was not detected in the hydrolysates.
  • 5-HMF is generally considered to be an undesirable product because it is an inhibitor of microorganism growth.
  • Xylose is the hydrolysis product of xylan and can be fermented to biochemicals and ethanol by some microorganisms though currently the fermentation efficiency is not commercially economical.
  • Xylose concentration increased in the hydrolysate with decreasing glycerol content in the pretreatment solution and the furfural values obtained were variable. It was expected that a higher concentration of xylose and furfural would be detected in the hydrolysate from pretreatments with high glycerol concentration because solutions with higher glycerol content have higher acidity, and higher acidity generally produces more xylose and furfural. It is therefore likely that some of the furfural and xylose may have been converted to unidentified products. Furfural is generally considered to be an undesirable product because it is an inhibitor of microorganism growth.
  • the concentration of acetic acid measured in the hydrolysate after pretreatment with the 93.6% glycerol pretreatment solution was less than the amount of acetic acid measured in the hydrolysate after pretreatment with pretreatment solutions containing lower amounts of glycerol.
  • this may be attributable to a side reaction in which acetic acid is consumed by glycerol through an esterification process.
  • acetic acid is generally considered to be an undesirable product because it is an inhibitor of microorganism growth.
  • Glycerol chlorination products include 3-MCPD, 2-monochloropropane-1,2-diol (2-MCPD), 1,3-dichloropropane-2-ol (1,3-DCP) and 1,2-dichloropropane-3-ol (1,2-DCP), with 3-MCPD and 1,3-DCP as the dominant products (Tesser et al., 2007).
  • Table 3 shows the effect of pretreatment temperature on the enzymatic digestibility of pretreated bagasse. Bagasse samples were pretreated with a solution containing 88.8% glycerol, 10.0% water and 1.2% HCl for 60 minutes. A temperature of 130° C. resulted in the highest amount of glucan obtained after pretreatment, as well as rendering the bagasse more amenable to enzyme hydrolysis. Most of the xylan present in bagasse was removed at 130° C.
  • Table 4 shows the effect of HCl concentration in the pretreatment of bagasse and its enzymatic digestibility. Changing the HCl concentration in the pretreatment solution resulted in small changes in the glycerol content, such as from 87.6% to 89.6, since water content in the pretreatment solution was kept at 10%. The small changes in glycerol content did not generate a major impact on the pretreatment process.
  • Each of the bagasse samples were pretreated with a pretreatment solution for 60 minutes at 130° C.
  • the glucan content in the solid residue was about 60% with each of the acid concentrations used in the study.
  • Xylan recovery in the solid residue was about 3.2% and 2.7% using a pretreatment solution with 1.2% and 2.4% HCl, respectively.
  • the digestibility of bagasse pretreated with 1.2% HCl and 2.4% HCl reached 100% in a 72 hour enzymatic hydrolysis assay (Table 4).
  • Bagasse samples were pretreated for about 15, 30, 60, or 90 minutes at 130° C. with a pretreatment solution comprising 88.8% glycerol, 10% water and 1.2% HCl. As shown in Table 5, a higher proportion of xylan was removed from bagasse as pretreatment time increased. The amount of glucan obtained in the solid residue was over 60% even after 15 min of pretreatment.
  • Table 6 shows the glucan and xylan content in the solid residue (%) and total recovery in the solid residue (%) after bagasse pretreatment with a glycerol/acid/water pretreatment solution using H 2 SO 4 as the acid catalyst.
  • the bagasse was treated with the pretreatment solution at 130° C. for 60, 90, or 120 minutes.
  • the amount of glucan in the pretreated bagasse was more than 60% compared to a value of 42.9% for untreated bagasse.
  • the amount of xylan removed from bagasse was more than 80%.
  • Table 7 shows the glucan and xylan content in the solid residue (%) and total recovery in the solid residue (%) after bagasse pretreatment with a pretreatment solution using FeCl 3 as the acid catalyst at 130° C. for 60 min.
  • An increase in the glucan content in the pretreated bagasse was achieved using a pretreatment solution with higher FeCl 3 concentrations.
  • the presence of 10% water in the glycerol/FeCl 3 /water pretreatment solutions resulted in lower glucan content in the solid residue and less digestibility compared to FeCl 3 /glycerol pretreatment solutions containing no water.
  • the effect of glycerol concentration on the enzymatic hydrolysis of acid and soda-pretreated bagasse was investigated.
  • the acid pretreated bagasse was prepared by pretreatment of the bagasse with a 0.73% H 2 SO 4 solution at 170° C. for 15 min in a Parr reactor.
  • the soda pretreated bagasse was prepared by pretreatment of the bagasse with a 18% NaOH solution at 170° C. for 40 min in a Parr reactor.
  • the pretreated bagasse was washed 4 times with 300 mL distilled water. After washing the bagasse, the bagasse was filtrated and air-dried. The air-dried bagasse was milled by a cutting grinder to generate bagasse powder for the enzymatic hydrolysis analysis.
  • glycerol The addition of glycerol from 5% to 30% to the enzymatic hydrolysis solution of pretreated bagasse inhibited cellulase hydrolysis in the first 12 hours.
  • the level of inhibition of cellulase activity increased with increasing glycerol concentration during the first 12 hours.
  • the cellulose digestibility of the pretreated bagasse in the presence of 5% and 10% glycerol surpassed that without glycerol addition after 24 hours and 72 hours.
  • glycerol can be used as an enzyme stabilizer for enzymes during freezing storage and thawing processes.
  • Glycerol has also been used to store some enzymes at temperatures above 0° C. (Costa et al 2002). While not wishing to be bound to any particular theory, the results here indicate that glycerol may stabilize cellulase activity over longer periods of time, even though it inhibits hydrolysis during the initial hydrolysis stage.
  • a bagasse sample was pretreated with a fresh batch of pretreatment solution containing 88.8% glycerol, 10% water, and 1.2% HCl.
  • the pretreatment temperature and time for the initial and subsequent pretreatments were 130° C. and 30 min, respectively.
  • the filtrate/hydrolysate was collected and water was removed by vacuum evaporation at 80° C. to produce a concentrated filtrate. Without adding any additional HCl, the concentrated filtrate was adjusted to a water content of approximately 10% to produce a recycled pretreatment solution.
  • the recycled pretreatment solution was then used to pretreat a fresh bagasse sample.
  • the filtrate was again collected and the same process was followed for recycling the pretreatment solution.
  • the pretreatment solution was recycled a second and third time and each recycled solution was used to pretreat a fresh bagasse sample. After each pretreatment, the pretreated bagasse was collected, washed and filtrated, as describe in Example 1, before enzymatic hydrolysis.
  • the digestibility of bagasse after pretreatment using the first recycled solution was 99%.
  • the first recycled pretreatment solution showed no significant decrease in effectiveness in regards to digestibility compared to the fresh pretreatment solution.
  • the digestibility of bagasse pretreated with the third recycled pretreatment solution remained greater than 92%. While not wishing to be limited by any particular theory, the slight decrease seen in the digestibility of bagasse pretreated with a recycled glycerol solution suggests that the acidity of the pretreatment solution may become weaker after several uses.
  • a two-step pretreatment process for bagasse was utilized to determine the effect on the production of inhibitory components compared to a one-step pretreatment.
  • a dilute acid was used to pretreat bagasse (i.e., pre-pretreatment).
  • the dilute acid pre-pretreatment removes mast of the xylan in bagasse.
  • a glycerol/acid/water pretreatment solution was used to further pretreat the bagasse.
  • Inhibitory components, such as furfural and acetic acid, were significantly reduced in the two-step pretreatment process compared to the one-step pretreatment of the bagasse with the glycerol/acid/water pretreatment solution only.
  • Sugarcane bagasse was used as a model lignocellulosic biomass and was collected from Racecourse sugar mill (Mackay Sugar Limited, Australia) in Mackay, Australia. Sugarcane bagasse was washed in the sugar mill using hot water (90° C.) and the residual sugar attached on bagasse was negligible. The sugarcane bagasse was air-dried, depithed and grinded by a cutter grinder (Retsch® SM100, Retsch GmBH, Germany). The milled bagasse was screened and bagasse having particle sizes of 250-500 ⁇ m was collected and stored for experiment. The moisture of the bagasse powder was 6.9%. Glycerol was purchased from Biolab Scientific Pty Ltd (Australia).
  • Ethylene glycol and 1,2-propanediol were purchased from Sigma-Aldrich company (Australia). All solvents used in this study were analytical grade. AccelleraseTM 1000 (Batch no. 1600877126) was a Danisco product (Genencor Division, Danisco Inc., US) and was purchased through Enzymes Solutions Pty. Ltd (Australia). The filter paper activity of AccelleraseTM 1000 was approximate 40 FPU/mL. All the chemicals used in this study were analytic reagents.
  • Polyol solution which contained a required amount of HCl and water was transferred into a 50 mL glass flask.
  • a magnetic stirrer was placed into the flask.
  • 4.30 g bagasse (4.0 g dry biomass) was transferred into the flask and mixed well.
  • the ratio of liquid to solid was 10:1 (weight to weight).
  • the pretreatment conditions are shown in Table 8.
  • the flask was sealed with a lid avoiding water loss and immersed to a silicone oil bath, which was preheated to the required temperature.
  • the heating element was equipped with a magnetic stirring device (Ika Labortechnik, Germany). The pretreatment was carried out under magnetic stirring (500 rpm) for a required time. After pretreatment, the pretreatment solution was transferred to a beaker and 20 mL water was added.
  • Solvent composition (%) Tempera- Time Condition Polyol HCl water polyol ture (° C.) (min) label glycerol 1.2 10.0 88.8 130 30 Gly-30 1.2 10.0 88.8 130 60 Gly-60 0.0 0.7* 99.3 130 60 Gly-60, no acid ethylene glycol 1.2 10.0 88.8 130 30 EG-30 1.2 10.0 88.8 130 60 EG-60 0.0 0.7* 99.3 130 60 EG-60, no acid 1,2-propanediol 1.2 10.0 88.8 130 30 Diol-30 1.2 10.0 88.8 130 60 Diol-60 0.0 0.7* 99.3 130 60 Diol-60, no acid Water 1.2 98.8 0.0 130 60 Acid in water *The water came from the sugarcane bagasse.
  • Enzymatic hydrolysis was carried out in a 20 mL glass vial containing 5 g solution. The cellulose loading of 2% was used based on cellulose content in bagasse sample.
  • the reaction solution contained 0.05 M citrate buffer to maintain pH at 4.8 and 0.02% sodium azide to prevent the growth of microorganisms.
  • the dosage of Accellerase for enzymatic hydrolysis was 0.5 mL Accellerase/g cellulose (approximate 20 FPU/g cellulose) unless otherwise stated.
  • the reaction was carried out at 50° C. in a rotary incubator (Ratek OM 11 Orbital Mixer, Australia) with shaking speed of 150 rpm.
  • the sampling time was 0 h, 6 h, 0.12 h, 24 h, 48 h and 72 h.
  • the sampling volume was 0.2 mL using a cut-off pipette tip. After sampling, the sample was sealed and incubated for 5 min in a boiling water bath to denature the cellulase. The sample was then centrifuged at 10,000 rpm for 5 min. 0.1 mL supernatant was diluted 10 times by de-ionized water. The diluted sample was filtered through 0.22 ⁇ m disk filter before HPLC analysis. All the enzymatic hydrolysis experiments were conducted in duplicate and the data showed in this study were the means.
  • HPLC HPLC was used to analyze the chemicals generated in this study.
  • a Bio-Rad Aminex HPX-87H column and Waters refractive index detector were used to detect and quantify organic acids (acetic acid, levulinic acid, etc.), 5-hydroxymethylfurfural (HMF) and furfural.
  • the mobile phase was 5 mM H 2 SO 4 at a flow rate of 0.6 nil 1 min.
  • the temperature for the column was 65° C.
  • a Shodex SP 810 carbohydrate column was used to determine the sugars generated in the compositional analysis and enzymatic hydrolysis. The temperature for both columns was 85° C. and the mobile phase was water with a flow rate of 0.5 ml/min.
  • the samples except the enzymatic hydrolysis samples) were neutralized by CaCO 3 before running through the columns.
  • Glucan (xylan) recovery was calculated based on the following equation:
  • Glucan ⁇ ⁇ ( xylan ) ⁇ ⁇ recovery ⁇ ⁇ in ⁇ ⁇ solid ⁇ ⁇ residue Total ⁇ ⁇ glucan ⁇ ⁇ ( xylan ) ⁇ ⁇ in ⁇ ⁇ pretreated ⁇ ⁇ bagasse ⁇ ⁇ residue ⁇ 100 ⁇ % Total ⁇ ⁇ glucan ⁇ ⁇ ( xylan ) ⁇ ⁇ in ⁇ ⁇ untreated ⁇ ⁇ bagasse ( 1 )
  • Glucan digestibility was calculated based on the following equation:
  • Total ⁇ ⁇ glucose ⁇ ⁇ yield Total ⁇ ⁇ glucose ⁇ ⁇ in ⁇ ⁇ enzymatic ⁇ ⁇ hydrolysis ⁇ 0.9 ⁇ 100 ⁇ % Total ⁇ ⁇ glucan ⁇ ⁇ in ⁇ ⁇ untreated ⁇ ⁇ bagasse ( 3 )
  • Glucose ⁇ ⁇ yield Total ⁇ ⁇ glucose ⁇ ⁇ in ⁇ ⁇ pretreatment ⁇ ⁇ hydrosylate ⁇ 0.9 ⁇ 100 ⁇ % Total ⁇ ⁇ glucan ⁇ ⁇ in ⁇ ⁇ untreated ⁇ ⁇ bagasse ( 5 )
  • Xylose ⁇ ⁇ yield Total ⁇ ⁇ xylose ⁇ ⁇ in ⁇ ⁇ pretreatment ⁇ ⁇ hydrosylate ⁇ 0.88 ⁇ 100 ⁇ % Total ⁇ ⁇ xylan ⁇ ⁇ in ⁇ ⁇ untreated ⁇ ⁇ bagasse ⁇ ⁇ weight
  • Furfural ⁇ ⁇ yield Total ⁇ ⁇ furfural ⁇ ⁇ in ⁇ ⁇ pretreatment ⁇ ⁇ hydrosylate ⁇ 1.375 ⁇ 100 ⁇ % Total ⁇ ⁇ xylan ⁇ ⁇ in ⁇ ⁇ untreated ⁇ ⁇ bagasse ⁇ ⁇ weight ( 7 )
  • Pretreatment of sugarcane bagasse was conducted at 130° C. As shown in Table 9, pretreatment polyols without water and acid catalyst only caused slight changes in glucan, xylan and lignin compositions in solid residue compared to treated bagasse. All the pretreatments retained over 90% glucan. Dilute acid pretreatment at 130° C. for 60 min removed 73% xylan and only 18% lignin (corresponding to xylan recovery of 27% and lignin recovery of 82%). Pretreatment of sugarcane bagasse for 30-60 min by aqueous glycerol containing acid catalyst removed 89-96% xylan and 40-44% lignin (corresponding to xylan recovery of 4-11% and lignin recovery of 56-60%). The glucan content in bagasse pretreated by acidic glycerol was between 63-65%.
  • Pretreatment of bagasse by both ethylene glycol and 1,2-propanediol solutions containing acid removed similar amounts of xylan but high amounts of lignin compared to glycerol pretreatment.
  • 1,2-propanediol pretreatment for only 30 min removed up to 77% lignin (corresponding to lignin recovery of 23%) and extension of pretreatment time to 60 min removed further about 5% lignin.
  • Ethylene glycol pretreatment for 30-60 min removed ⁇ 30% lignin, which was 8-13% lower than that by 1,2-propanediol pretreatment.
  • the glucan content in bagasse pretreated by 1,2-propanediol improved to 79% for 30 min pretreatment and 82% for 60 min pretreatment, followed by 76%-78% in bagasse pretreated by ethylene glycol for 30-60 min.
  • the glucan content in bagasse pretreated by both ethylene glycol and 1,2-propanediol was 13-16% higher than that in bagasse pretreated by glycerol.
  • the pretreated bagasse was further enzymatic hydrolyzed with a cellulase loading, of 20 FPU/g glucan.
  • a cellulase loading of 20 FPU/g glucan.
  • pretreatment with all three aqueous polyol solutions containing 1.2% HCl improved glucan digestibility significantly compared to pretreatment with water containing 1.2% HCl and polyols without water and acid catalyst.
  • the digestibility of bagasse pretreated with polyols without water and acid catalyst was very low, 8-10%.
  • Pretreatment with water containing 1.2% HCl only improved glucan digestibility to 38.4%.
  • Pretreatment by acidic glycerol solution for 30 min and 60 min improved glucan digestibility to 92.6% and 97.1%.
  • the 24 h digestibilities were 74% and 84% respectively for bagasse pretreated for 30 min and 60 min.
  • the kinetic curves of enzymatic hydrolysis of bagasse pretreated for 30 min and 60 min by both ethylene glycol and 1,2-propanediol were almost identical ( FIGS. 3 b and 3 c , respectively).
  • the 72 h digestibilities for bagasse pretreated for 30 min and 60 min by both ethylene glycol and 1,2-propanediol solutions were more than 99%.
  • the 24 h digestibilities reached 91% for bagasse pretreated by ethylene glycol and 1,2-propanediol solutions.
  • the 72 h and 24 h total glucose yields (considering the glucan recovery in solid residues) for bagasse pretreated with both ethylene glycol and 1,2-propanediols were 92-94% and 84-86% respectively, which were higher than those for bagasse pretreated with glycerol solutions. All the glucose yields for bagasse pretreated with all the polyols were significantly higher than those for bagasse pretreated with water containing dilute acid and polyol solutions without water and acid catalyst.
  • lignin can form a physical barrier for preventing cellulase access to cellulose and non-productively bind cellulases, which reduce the efficiency of enzymatic hydrolysis (Gilkes et al., 2005). Therefore, removal of lignin could improve enzymatic hydrolysis.
  • 0.2% NaOH solution (pH 12.3) was used to wash bagasse pretreated for 60 min with polyol solutions. As shown in Table 11, dilute soda wash further decreased the lignin content in all pretreated bagasse. The lignin content in bagasse pretreated by both ethylene glycol and 1,2-propanediol solutions was reduced to less than 5% after soda wash. However, the bagasse pretreated by glycerol solution, the lignin content was still significantly high (19.1%) after soda wash. The glucan content in bagasse pretreated by both ethylene glycol and 1,2-propanediol solutions was improved from 78-82% before soda wash to 91-92% after wash.
  • soda wash only improved glucan content in bagasse pretreated by glycerol solution to 72%.
  • the lignin removal by soda wash for sugarcane bagasse pretreated by ethylene glycol and 1,2-propanediol solutions was more readily than pretreated by glycerol solution.
  • the 24 h digestibilities at a cellulase loading of only 6.7 FPU/g glucan for bagasse pretreated with ethylene glycol and 1,2-propanediol solutions with soda wash were 77.6% and 80.0% respectively, 19.2% and 28.0% higher than those for bagasse without soda wash.
  • the 24 h digestibilities at a cellulose loading of 13.3 FPU/g glucan for bagasse with soda wash were comparable to those at a cellulose loading of 20.0 FPU/g glucan for bagasse without soda wash. Therefore, without being bound to any particular theory, lignin removal by soda wash of bagasse pretreated by polyols could improve enzymatic hydrolysis and also reduce the cellulose loading.
  • Samples of sugarcane bagasse were separately treated with a dilute acid, a caustic soda, and an acid-catalyzed aqueous glycerol pretreatment solution and compared as shown in FIG. 5 .
  • the treatment with the dilute acid comprised treating 1.0 kg of bagasse with 0.73% H 2 SO 4 in liquid at 170° C. for 15 minutes in a Parr Reactor.
  • the treatment with caustic soda comprised treating 1.0 kg of bagasse with 3.0% NaOH in liquid (14% Na 2 O on fiber) at 170° C. for 45 minutes in a Parr Reactor.
  • the acid-catalyzed aqueous glycerol pretreatment comprised treating 4 g of bagasse with a pretreatment solution comprising 1.2% HCl, 10% water, and 88.8% glycerol at 130° C. for 60 minutes.
  • FIG. 6 shows a process for converting bagasse into ethanol and other co-products using an acid-catalyzed aqueous glycerol pretreatment process.
  • Raw bagasse e.g., bagasse with 50% moisture
  • a pretreatment solution comprising glycerol in the presence of an acid catalyst (e.g., sulphuric acid or hydrochloric acid).
  • the solid residue obtained after pretreatment is enzymatically hydrolyzed using enzymes, such as microbially produced cellulolytic enzymes, and the material is anaerobically fermented with yeast, such as Saccharomyces cerevisiae , into ethanol. Residual glycerol and unfermented pentoses from the process stream undergo aerobic fermentation to produce a dried animal feed product.
  • the pretreatment liquor (containing principally glycerol, lignin and pentoses) is separated from the solid residue at moderate efficiency and the pretreatment liquor undergoes a purification process to concentrate and purify the glycerol prior to recycling and reuse in pretreatment.
  • Glycerol purification can comprise evaporation (to remove water) followed by vacuum distillation of the glycerol.
  • the liquor residue from the purification stage (containing principally lignin and pentoses) is processed for animal feed production.
  • the ethanol product is distilled and dehydrated to produce fuel grade anhydrous ethanol.
  • the solid residues from distillation (containing principally lignin) can be sold to the sugar factory for combustion for process energy.
  • the liquid residue from distillation and animal feed production (vinasse) can be recycled to farm land where it attracts value as a soil conditioner and fertilizer.
  • Pilot plant experiments were carried out by pretreating sugarcane bagasse with an acid catalyzed aqueous glycerol pretreatment solution using HCl as the acid catalyst.
  • the moisture of the sugarcane bagasse was approximately 50%.
  • a total amount of 20 kg raw sugarcane bagasse (approximately 10 kg dry fibre) was used for each experiment.
  • the general procedure for the pretreatment experiments was as follows:
  • wash stage add the required amount of wash water, heat to the wash temperature with direct injection steam and hold for the wash time. Following the wash, press the material again to separate the wash liquor from the solid residue. The wash liquor drains to the hydrolysate tank and is again sampled. Record the volume or weight of wash liquor collected;
  • Table 13 shows the experimental conditions used in the pilot plant experiments.
  • the glucan digestibility was analyzed using 100 g solution in a 250 mL shaker flask.
  • the solution contained 2% glucan, approximately 20 FPU cellulase/g glucan (Accellerase 1000L, Genencor), and 0.05 M citrate buffer to maintain pH at 4.8.
  • the hydrolysis temperature was maintained at 50° C. and the shaking speed was 150 rpm.
  • Hydrolysate samples were analyzed for organic acid (furfural, 5-HMF, formic acid and levulinic acid) and chlorohythin (3-MCPD) concentrations.
  • organic acid furfural, 5-HMF, formic acid and levulinic acid
  • chlorohythin (3-MCPD) concentrations were low (less than 0.1 g/L) and are not reported.
  • Glucan digestibilities (72 h) of the solid residues from bagasse pretreated by glycerol/acid solutions were higher than those pretreated by water/acid solutions at the same pretreatment temperature and time. Increases in either pretreatment time or pretreatment temperature resulted in improved glucan digestibilities.
  • Pretreatment at 130° C. with glycerol solution containing 0.4% HCl for 15 min resulted in the highest glucan digestibility of non-steam exploded materials of 90.4%, followed by a glucan digestibility (72 h) of 84.6% for the solid residue from pretreatment, at 110° C. for 60 min in a glycerol solution containing the same amount of acid.
  • a glucan digestibility (72 h) of 94.8% was achieved on a sample that had been steam exploded following glycerol pretreatment. This process resulted in an improvement in glucan digestibility of about 10% compared to the pretreatment without steam explosion at the same pre-hydrolysis reaction temperature and time. All of the pretreatments with dilute acid only resulted in glucan digestibilities (72 h) less than 70%.
  • the kinetics of enzymatic hydrolysis of the solid residues from bagasse pretreated by glycerol/acid and water/acid solutions are shown in FIG. 7 .
  • the enzymatic hydrolysis rates were very rapid for the first 6 h. For most samples, after 48 h the increase in glucan digestibility was not significant.
  • HMF 5-hydroxymethylfurfural
  • furfural furfural
  • concentrations and yields of the key sugar degradation components 5-hydroxymethylfurfural (HMF) and furfural in the pretreatment hydrolysate are shown in Table 16.
  • Much lower concentrations of HMF (glucose derivative) and furfural (xylose derivative) were produced with glycerol/HCl pretreatment solutions than with the water/HCl pretreatment solutions.
  • the yields of HMF and furfural compared to the total initial sugarcane bagasse were also very low.
  • the yield of 3-monochloropropane-1,2-diol (3-MCPD, a product from glycerol chlorination) was less than 0.37 g/kg hydrolysate or less than 0.61 g/kg initial glycerol under all conditions. This validated previous results that showed that the presence of water in the pretreatment solution reduced the production of glycerol chlorination products.
  • the solid residue i.e., pretreated bagasse
  • a portion of the washed solid residue was freeze-dried for composition analysis (e.g., glucan, xylan and lignin) by the Laboratory Analytical Procedure (NREL, 2008).
  • the other portion of the washed solid residue was kept at 2° C.-6° C. prior to enzymatic digestibility analysis.
  • bagasse was partially carbonised in the pretreatment with ethylene carbonate solution containing 1.2% H 2 SO 4 as the acid catalyst, the glucan digestibility was only 74.7%, lower than that of bagasse pretreated with ethylene carbonate solution containing 1.2% HCl (80.6%). With lower concentrations of H 2 SO 4 , the glucan digestibility of pretreated bagasse reduced significantly. Pretreatment with acetic acid as the acid catalyst and pretreatment without an acid catalyst led to very poor glucan digestibilities (less than 7%).
  • Table 18 shows the estimated yields of components in the pretreatment hydrolysates from the first series of ethylene carbonate pretreatment experiments. Only minor amounts of HMF (glucan derivative) were generated from the pretreatment process whereas significant amounts of furfural (derivative of C5 sugars) were generated. In addition, significant amounts of ethylene glycol were produced in the reaction, especially in pretreatment solutions with a high acid concentration. Under the same pretreatment conditions, more ethylene glycol was detected when H 2 SO 4 was used as the acid catalyst than when HCl was used.
  • glucan digestibilities (72 h) of the solid residues from bagasse pretreated by ethylene carbonate with 0.4% H 2 SO 4 as the acid catalyst under all conditions were very low, no greater than 11%. Longer pretreatment times and higher pretreatment temperatures resulted in a lower glucan recovery in the solid residues because of partial biomass carbonisation. In contrast, pretreatment with ethylene glycol with 0.4% H 2 SO 4 as the acid catalyst led to much higher 72 h glucan digestibilities although they were still below 81%.
  • Table 20 shows the estimated yields of the major components in the pretreatment hydrolysates from the second series of ethylene carbonate pretreatment experiments.
  • the HMF yields from the pretreatments were very low—no greater than 0.03% of the theoretical yield based on initial glucan content.
  • High furfural yields were observed from pretreatments with acid catalysed ethylene carbonate pretreatment solutions.
  • the furfural yield from acid catalysed ethylene glycol solutions was very low, less than 0.09% of the initial pentose.
  • the furfural yields from pretreatments with acid catalysed ethylene carbonate/ethylene glycol mixtures were higher than those with ethylene glycol solutions but much lower than those with ethylene carbonate only.
  • Table 21 shows the results from pretreatment at 100° C. for 30 min.
  • the pretreatments were conducted in the presence of 0.4% H 2 SO 4 as the acid catalyst with a varying ratio of ethylene carbonate (EC) to ethylene glycol (EG).
  • the initial water content was 0.9%.
  • the glucan digestibility was significantly improved by adding EG into the pretreatment solution compared to a pretreatment solution with EC and no EG.
  • a high glucan digestibility (88-91%) was achieved with the EC/EG ratio range from 2:1 to 9:1.
  • the glucan digestibility of the solid residue after pretreatment with a pretreatment solution comprising EG and no EC was 73.7%.
  • Table 22 shows the results from pretreatment at 80° C. for 30 min.
  • the pretreatments were conducted in the presence of 1.2% H 2 SO 4 as the acid catalyst with a varying ratio of ethylene carbonate (EC) to ethylene glycol (EG).
  • the initial water content was 1.2%.
  • the glucan digestibility was significantly improved by adding EG into the pretreatment solution compared to a pretreatment solution with EC and no EG.
  • a high glucan digestibility (88-91%) was achieved with the EC/EG ratio range from 2:1 to 9:1.
  • the glucan digestibility of the solid residue after pretreatment with a pretreatment solution comprising EG and no EC was only 42.2%.
  • Table 23 shows the results from pretreatment at 60° C. for 30 minutes.
  • the pretreatments were conducted in the presence of 1.2% H 2 SO 4 as the acid catalyst with a varying ratio of ethylene carbonate (EC) to ethylene glycol (EG).
  • the initial water content was 1.2%.
  • the glucan digestibility was significantly improved by adding EG into the pretreatment solution compared to a pretreatment solution with EC and no EG.
  • a high glucan digestibility (41-43%) was achieved with the EC/EG ratio range from 3:1 to 9:1.
  • the glucan digestibility of the solid residue after pretreatment with a pretreatment solution comprising EG and no EC was only 12.0%.
  • Table 24 shows the results from pretreatment with an EC/EG (4:1) pretreatment solution for 30 min at different temperatures.
  • the pretreatment solution contained 1.2% H 2 SO 4 , 1.2% water, 78.1% EC, and 19.5% EG.
  • the temperature had a significant effect on the effectiveness of the pretreatment.
  • the glucan digestibility of the solid residue increased from 41.1% to 97.1% as the pretreatment temperature increased from 60° C. to 90° C.
  • Table 25 shows the results from pretreatment with an EC/EG (4:1) pretreatment solution at different water contents at 90° C. for 30 min.
  • the pretreatments were conducted in the presence of 1.2% H 2 SO 4 as the acid catalyst.
  • the presence of water in the pretreatment solutions had a negative effect on the effectiveness of the pretreatment.
  • the glucan digestibility of the solid residue decreased from 97.1% to 582% as the water content increased from 1.2% to 10%.
  • Pretreatment solutions comprising propylene carbonate and propylene glycol were tested.
  • Table 26 shows the results from pretreatment at 100° C. for 30 min. The pretreatments were conducted in the presence of 0.4% H 2 SO 4 as the acid catalyst with a varying ratio of propylene carbonate (PC) to propylene glycol (PG). The initial water content was 0.9%.
  • PC propylene carbonate
  • PG propylene glycol
  • the glucan digestibility of the solid residue after pretreatment with a pretreatment solution comprising PC and no PG was 3.8%.
  • the glucan digestibility was increased to 49.5% with a PC/PG (9:1) pretreatment solution. Decreasing the PC/PG ratio of the pretreatment solution increased the glucan digestibility of the solid residue.
  • the glucan digestibility was between about 74% and about 80% after pretreatment with a pretreatment solution have a PC/PG ratio from 3:1 to 4:1.
  • the glucan digestibility of the solid residue after pretreatment with a pretreatment solution comprising PG and no PC was 35.3%.
  • FIG. 8A compares pretreatment using a pretreatment solution containing 1.2% H 2 SO 4 , 1.2% water, 78.1% ethylene carbonate (EC), and 19.5% ethylene glycol (EG) at 60° C. and 80° C., pretreatment using a dilute acid solution comprising 0.73% H 2 SO 4 at 170° C. for 15 minutes in a Parr Reactor, and untreated bagasse.
  • FIG. 8B compares the amount of inhibitors present after pretreatment using the dilute acid pretreatment solution and the EC/EG pretreatment solution at 80° C. The temperature at which various pretreatments are carried out at is compared in FIG. 8C .

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