CN111218490A - Method for pretreating lignocellulose by using ammonia and auxiliary agent - Google Patents
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 23
- 238000000855 fermentation Methods 0.000 claims abstract description 15
- 230000004151 fermentation Effects 0.000 claims abstract description 15
- 240000008042 Zea mays Species 0.000 claims description 33
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 33
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 33
- 235000005822 corn Nutrition 0.000 claims description 33
- 239000010902 straw Substances 0.000 claims description 21
- 108090000790 Enzymes Proteins 0.000 claims description 15
- 102000004190 Enzymes Human genes 0.000 claims description 15
- 229940088598 enzyme Drugs 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 10
- 150000004056 anthraquinones Chemical class 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 6
- 108090000604 Hydrolases Proteins 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000010907 stover Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 241000894006 Bacteria Species 0.000 claims description 2
- 108010059892 Cellulase Proteins 0.000 claims description 2
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 108010059820 Polygalacturonase Proteins 0.000 claims description 2
- 229920001131 Pulp (paper) Polymers 0.000 claims description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 2
- 240000006394 Sorghum bicolor Species 0.000 claims description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 244000098338 Triticum aestivum Species 0.000 claims description 2
- 229940106157 cellulase Drugs 0.000 claims description 2
- 108010093305 exopolygalacturonase Proteins 0.000 claims description 2
- 210000003608 fece Anatomy 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- 229940059442 hemicellulase Drugs 0.000 claims description 2
- 108010002430 hemicellulase Proteins 0.000 claims description 2
- 239000010871 livestock manure Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000011122 softwood Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 238000005422 blasting Methods 0.000 claims 1
- 239000002029 lignocellulosic biomass Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229920005610 lignin Polymers 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- -1 amide compounds Chemical class 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 150000004676 glycans Chemical class 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000000813 microbial effect Effects 0.000 abstract 1
- 229920001282 polysaccharide Polymers 0.000 abstract 1
- 239000005017 polysaccharide Substances 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 15
- 230000007071 enzymatic hydrolysis Effects 0.000 description 14
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 8
- 239000008103 glucose Substances 0.000 description 8
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 6
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 description 2
- 241000322995 Escherichia coli KO11FL Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- 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
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for pretreating lignocellulose by using ammonia and an auxiliary agent, belonging to the field of biorefinery. In the method, a small amount of auxiliary agent is added in the ammonia pretreatment to promote lignin removal and prevent polysaccharide from peeling reaction, so that the conversion efficiency of sugar is effectively improved, meanwhile, the ammonia can convert carboxyl compounds into amide compounds with lower toxicity, the residual ammonia is used as a nitrogen source for microbial fermentation, and the ammonia gas can be recycled. The method reduces the production cost of converting the lignocellulose into the target product, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of biorefinery, and relates to a method for pretreating lignocellulose by using ammonia and an auxiliary agent.
Background
Lignocellulose, which is an important raw material for biofuel, is mainly composed of cellulose, hemicellulose, lignin, and the like. At present, the pretreatment method of lignocellulose mainly comprises ammonia pretreatment, hot water pretreatment, gas explosion pretreatment and ionic liquid pretreatment. Among them, the Ammonia pretreatment is one of the pretreatment methods for converting lignocellulose into products such as ethanol, etc., which can effectively destroy the structure of lignocellulose and increase the internal pores of lignocellulose (Lau mw, Dale B e.g. effective with primary degradation-reaction products from Ammonia Fiber Expansion (AFEX) -treated corn storage on the growth and transfer of Escherichia coli ko11. bioresearch Technology,2010,101(20):7849-7855.), but the Ammonia pretreatment has less effect on lignin and the hydrolysis efficiency is not ideal when high substrate is hydrolyzed by enzyme.
Disclosure of Invention
The invention aims to provide a method for pretreating lignocellulose by using ammonia and an auxiliary agent. The method adds the auxiliary agent into the ammonia pretreatment process, increases the lignin removal rate, improves the lignocellulose conversion rate, reduces the enzyme consumption and reduces the pretreatment cost.
The technical scheme for realizing the purpose of the invention is as follows:
a method for pretreating lignocellulose with ammonia and an auxiliary agent, comprising the steps of:
uniformly mixing a lignocellulose raw material and an auxiliary agent aqueous solution, introducing or adding ammonia until a mixed matrix is alkaline, wherein the mass of the ammonia is 0.5-6.0 of the dry weight of the lignocellulose, and carrying out ammonia method pretreatment at 80-140 ℃, wherein the auxiliary agent is selected from anthraquinone or anthraquinone derivatives, green oxygen, methanol, isopropanol or formaldehyde.
The lignocellulose is conventionally used lignocellulose, and can be wheat straw, corn straw, agricultural and forestry waste, rice straw, sorghum straw, soybean straw, forestry waste, recycled wood pulp fiber, wood chips, softwood, hardwood or animal manure.
The lignocellulose raw material is a conventionally used lignocellulose raw material and can be strip-shaped lignocellulose or granular lignocellulose, the length of the strip-shaped lignocellulose is 0.01 mm-10 cm, and the diameter of the granular lignocellulose is 0.5 mm-10 cm.
Preferably, the mass of the lignocellulose raw material in the pretreatment process is 10-60% of the total mass, and the total mass of the water, the auxiliary agent, the ammonia and the lignocellulose raw material is used as the total mass.
In the auxiliary agent water solution, water accounts for 10-90% of the dry weight of the lignocellulose, and the auxiliary agent accounts for 0.1-2.0% of the dry weight of the lignocellulose.
The ammonia pretreatment is selected from dilute ammonia water pretreatment, ammonia fiber explosion pretreatment (AFEX), extracted ammonia pretreatment (EA), liquid Ammonia Recycle Pretreatment (ARP) or liquid ammonia pretreatment (LAT).
The ammonia is selected from ammonia water solution, liquid ammonia or ammonia gas.
Preferably, the pretreatment time of the ammonia process is 10min to 360min, and the pretreatment time comprises temperature rise time, maintenance time and temperature reduction time.
The invention also provides a fermentation process for improving the conversion rate of cellulose ethanol based on the pretreatment method, which comprises the following steps:
step 1, pretreatment: uniformly mixing a lignocellulose raw material and an auxiliary agent aqueous solution, introducing or adding ammonia until a mixed matrix is alkaline, wherein the mass of the ammonia is 0.5-6.0 of the dry weight of the lignocellulose, and carrying out ammonia method pretreatment at 80-140 ℃, wherein the auxiliary agent is selected from anthraquinone or anthraquinone derivatives, green oxygen, methanol, isopropanol or formaldehyde;
step 3, fermentation: adding fermentation strain, and fermenting to obtain fermented product.
In step 2, the hydrolase is selected from enzymes conventionally used in a lignocellulose fermentation process, and may be cellulase and/or hemicellulase, such as one or a combination of pectinase and xylanase.
In the step 3, the fermentation strain is a strain which is conventionally used in a lignocellulose fermentation process and can be yeast, bacteria, mould and the like.
In step 3, the fermentation product obtained may be bulk chemicals, fine chemicals or animal feed, such as ethanol, butanol, acetone, acetic acid, lactic acid, aliphatic hydrocarbons, fats and oils, proteins, amino acids, etc., depending on the fermentation strain.
Compared with the prior art, the invention has the following advantages:
(1) in the pretreatment process, a trace amount of auxiliary agent is added, so that the lignin removal effect and selectivity are improved, the conversion efficiency of lignocellulose sugar is obviously improved, and the conversion efficiency is improved by over 21 percent.
(2) The ammonia remained in the raw material after the pretreatment can be used as a nitrogen source for the growth of the fermentation strain, so that the cost of additionally adding nutrient substances is reduced.
(3) The pretreated solid does not need operations such as water washing and the like, the operation cost is simplified, the loss of sugar is reduced, the utilization rate of equipment is high, and the method is suitable for industrial production.
Drawings
FIG. 1 is a graph showing the results of the 24-hour enzymatic hydrolysis of sugar concentration of corn stover pretreated with AAQ and AFEX, respectively, in example 1.
FIG. 2 is a graph showing the results of the 24-hour enzymatic hydrolysis of sugar concentration of corn stover pretreated with AAQ and LHW, respectively, in example 2.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
All terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art, unless otherwise defined. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, reagents, starting materials, instruments, equipment and the like used in the present invention are commercially available or prepared by an existing method.
The following abbreviations are used in the examples:
AAQ: ammonia and co-agent pretreatment (amonia andrathhraquinone), AFEX: ammonia burst pretreatment (Ammonia fiber exposure), LHW: hot water pretreatment (Liquid hot water).
Example 1
The comparison of the hydrolysis effects of the corn straw enzyme by adopting AAQ pretreatment and AFEX pretreatment respectively comprises the following steps:
1. preparing raw materials: the corn straws in the farmland are collected, naturally dried and crushed into particles with the particle size of 1-4 mm.
2.1AAQ pretreatment: placing the crushed corn straws into a reaction kettle, wherein the proportion of dry matters to ammonia is 1: 1, water content of 60 percent (based on the dry weight of the corn stalks), anthraquinone content of 0.6 percent (based on the dry weight of the corn stalks), and reaction for 30min at 120 ℃.
2.2AFEX pretreatment: placing the crushed corn straws into a reaction kettle, wherein the proportion of dry matters to ammonia is 1: 1, water content of 60 percent (based on the dry weight of the corn stalks) and reaction for 30min at 120 ℃.
3. Respectively putting the pretreated straws into an enzymatic hydrolysis reactor, adding hydrolase and a citric acid-sodium citrate buffer solution with the mass concentration of 3% into the enzymatic hydrolysis reactor, carrying out enzymatic hydrolysis reaction in a shaking box (250rpm) at 50 ℃, and carrying out enzymatic hydrolysis for 24 hours.
The effect of enzymatic hydrolysis under 3% dry conditions of AAQ pretreatment and AFEX pretreatment is shown in figure 1.Represents the concentration of 3 percent of corn stalk enzyme hydrolysis glucose,represents the concentration of 3% corn stalk enzyme hydrolysis xylose. As can be seen from FIG. 1, the glucose concentration of the corn stalks after the AAQ pretreatment and the 24-hour enzymatic hydrolysis can reach 9.3g/L, while the glucose concentration of the corn stalks after the AFEX pretreatment and the 24-hour enzymatic hydrolysis is only 7.8 g/L. Compared with AFEX, the conversion rate of glucose is increased by 29.5% by AAQ pretreatment corn stalk enzymatic hydrolysis. The xylose concentration of the AAQ pretreated corn straws after 24 hours of enzymatic hydrolysis is 3.4g/L, and the xylose concentration of the AFEX pretreated corn straws is 3.0 g/L.
Example 2
Comparing the hydrolysis effect of AAQ pretreatment and LHW pretreatment corn straw enzyme, comprising the following steps:
1. preparing raw materials: the corn straws in the farmland are collected, naturally dried and crushed into particles with the particle size of 1-4 mm.
2.1AAQ pretreatment: placing the crushed corn straws into a reaction kettle, wherein the proportion of dry matters to ammonia is 1: 1, water content of 60 percent (based on the dry weight of the corn stalks), anthraquinone content of 0.6 percent (based on the dry weight of the corn stalks), and reaction for 45min at 120 ℃.
2.2 LHW pretreatment: placing the crushed corn stalks into a reaction kettle, wherein the dry matter concentration of the corn stalks is 20 percent (based on the total mass) and the reaction is carried out for 5min at 200 ℃.
3. And (2) placing the pretreated straws into an enzyme hydrolysis reactor, adding hydrolase and a citric acid-sodium citrate buffer solution into the enzyme hydrolysis reactor with the substrate mass concentration of 3%, carrying out enzymolysis reaction in an oscillation box (250rpm) at 50 ℃, and carrying out enzyme hydrolysis for 24 hours.
The effect of enzymatic hydrolysis under 3% dry conditions of AAQ pretreatment and AFEX pretreatment is shown in figure 1.Represents the concentration of 3 percent of corn stalk enzyme hydrolysis glucose,represents the concentration of 3% corn stalk enzyme hydrolysis xylose. As can be seen from FIG. 1, the glucose concentration of the corn stalks after AAQ pretreatment and 24 hours of enzymatic hydrolysis can reach 9.9g/L, while the glucose concentration of the corn stalks after LHW pretreatment and 24 hours of enzymatic hydrolysis is only 7.4 g/L. Compared with LHW, the conversion rate of glucose is improved by 33.8% by the enzyme hydrolysis of AAQ pretreated corn stalks. The concentration of xylose in the AAQ pretreated corn straws after 24 hours of enzymatic hydrolysis is 3.8g/L, and the concentration of xylose in the AAQ pretreated corn straws after LHW pretreatment is 3.3 g/L.
Claims (10)
1. A method for pretreating lignocellulose by using ammonia and an auxiliary agent is characterized by comprising the following steps:
uniformly mixing a lignocellulose raw material and an auxiliary agent aqueous solution, introducing or adding ammonia until a mixed matrix is alkaline, wherein the mass of the ammonia is 0.5-6.0 of the dry weight of the lignocellulose, and carrying out ammonia method pretreatment at 80-140 ℃, wherein the auxiliary agent is selected from anthraquinone or anthraquinone derivatives, green oxygen, methanol, isopropanol or formaldehyde.
2. The method of claim 1, wherein the lignocellulosic biomass is selected from the group consisting of wheat straw, corn stover, agricultural and forestry waste, rice straw, sorghum straw, soybean stover, forestry waste, recycled wood pulp fiber, wood chips, softwood, hardwood, and animal manure.
3. The method according to claim 1, wherein the lignocellulosic feedstock is selected from elongated ligno-cellulose having a length of 0.01mm to 10cm or granular ligno-cellulose having a diameter of 0.5mm to 10 cm.
4. The method according to claim 1, wherein the mass of the lignocellulosic feedstock during the pretreatment is between 10% and 60% of the total mass.
5. The method according to claim 1, wherein the water in the aqueous solution of the auxiliary agent is 10-90% of the dry weight of the lignocellulose, and the auxiliary agent is 0.1-2.0% of the dry weight of the lignocellulose.
6. The method of claim 1, wherein the ammonia pretreatment is selected from dilute ammonia pretreatment, ammonia fiber blasting pretreatment, extracted ammonia pretreatment, liquid ammonia recycle pretreatment, or liquid ammonia pretreatment.
7. The method of claim 1, wherein the ammonia is selected from the group consisting of aqueous ammonia solution, liquid ammonia, and ammonia gas.
8. The method of claim 1, wherein the ammonia pretreatment time is 10min to 360 min.
9. Fermentation process according to the method of any one of claims 1 to 8, characterized in that it comprises the following steps:
step 1, pretreatment: uniformly mixing a lignocellulose raw material and an auxiliary agent aqueous solution, introducing or adding ammonia until a mixed matrix is alkaline, wherein the mass of the ammonia is 0.5-6.0 of the dry weight of the lignocellulose, and carrying out ammonia method pretreatment at 80-140 ℃, wherein the auxiliary agent is selected from anthraquinone or anthraquinone derivatives, green oxygen, methanol, isopropanol or formaldehyde;
step 2, hydrolysis: adding water and hydrolase into the pretreated material for hydrolysis;
step 3, fermentation: adding fermentation strain, and fermenting to obtain fermented product.
10. The fermentation process according to claim 9, wherein in step 2, the hydrolytic enzyme is selected from cellulase and/or hemicellulase, and the hydrolytic enzyme is one or a combination of pectinase and xylanase; in step 3, the fermentation strain is selected from yeast, bacteria or mold.
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