CN115341004A - Method for preparing monosaccharide from biomass raw material - Google Patents
Method for preparing monosaccharide from biomass raw material Download PDFInfo
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- CN115341004A CN115341004A CN202110517368.5A CN202110517368A CN115341004A CN 115341004 A CN115341004 A CN 115341004A CN 202110517368 A CN202110517368 A CN 202110517368A CN 115341004 A CN115341004 A CN 115341004A
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- enzymolysis
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- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000002028 Biomass Substances 0.000 title claims abstract description 60
- 239000002994 raw material Substances 0.000 title claims abstract description 48
- 150000002772 monosaccharides Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 78
- 102000004190 Enzymes Human genes 0.000 claims abstract description 73
- 108090000790 Enzymes Proteins 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 229940088598 enzyme Drugs 0.000 claims description 71
- 230000007071 enzymatic hydrolysis Effects 0.000 claims description 22
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 22
- 239000010902 straw Substances 0.000 claims description 21
- 108010059892 Cellulase Proteins 0.000 claims description 20
- 229940106157 cellulase Drugs 0.000 claims description 20
- 240000008042 Zea mays Species 0.000 claims description 17
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 17
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 17
- 235000005822 corn Nutrition 0.000 claims description 17
- 238000004880 explosion Methods 0.000 claims description 15
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- 239000002245 particle Substances 0.000 claims description 10
- 239000010907 stover Substances 0.000 claims description 10
- 230000001007 puffing effect Effects 0.000 claims description 9
- 108010047754 beta-Glucosidase Proteins 0.000 claims description 8
- 102000006995 beta-Glucosidase Human genes 0.000 claims description 8
- 241000609240 Ambelania acida Species 0.000 claims description 7
- 229920000742 Cotton Polymers 0.000 claims description 7
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- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 235000021307 Triticum Nutrition 0.000 claims description 7
- 239000010905 bagasse Substances 0.000 claims description 7
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- 108010002430 hemicellulase Proteins 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 3
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- 241001520808 Panicum virgatum Species 0.000 claims description 2
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- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 50
- 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 26
- 239000008103 glucose Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 25
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 25
- 239000000758 substrate Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 241000209140 Triticum Species 0.000 description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000002255 enzymatic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- -1 enzyme preparations Chemical compound 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004533 Endonucleases Human genes 0.000 description 1
- 108010042407 Endonucleases Proteins 0.000 description 1
- 108060002716 Exonuclease Proteins 0.000 description 1
- 108010031186 Glycoside Hydrolases Proteins 0.000 description 1
- 102000005744 Glycoside Hydrolases Human genes 0.000 description 1
- POLBLONFVZXVPI-UHFFFAOYSA-N N-methyl-sec-pseudobrucine Natural products O=C1CC2C3C(CC4=O)OCC=C2CN(C)CCC11C3N4C2=C1C=C(OC)C(OC)=C2 POLBLONFVZXVPI-UHFFFAOYSA-N 0.000 description 1
- FLBVMURVUYAZMG-UHFFFAOYSA-N Novacin Natural products CN1CCC23C4C5C(CC(=O)N4c6cc(C)c(C)cc26)OCC=C(C1)C5CC3=O FLBVMURVUYAZMG-UHFFFAOYSA-N 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 102000013165 exonuclease Human genes 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
Classifications
-
- 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
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Emergency Medicine (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention relates to the field of monosaccharide production, and discloses a method for preparing monosaccharide from a biomass raw material, which comprises the following steps: contacting a biomass raw material with a first enzyme preparation in a horizontal reactor, and carrying out first enzymolysis to obtain a liquefied liquid; and (3) in the vertical reactor, contacting the liquefied liquid with an optional second enzyme preparation, and carrying out second enzymolysis to obtain a monosaccharide-containing material. The method of the invention can rapidly liquefy the materials under the condition of high dry matter concentration, accelerate enzymolysis, save the number of hydrolysis tanks, reduce energy consumption, improve production efficiency and reduce operation cost.
Description
Technical Field
The invention relates to the field of monosaccharide production, in particular to a method for preparing monosaccharide from a biomass raw material.
Background
The biomass raw material has wide sources and huge yield, and is one of the renewable raw materials with the most development potential. The main components of biomass include cellulose, hemicellulose and lignin. Wherein, the cellulose is degraded to generate glucose which accounts for more than 30 percent of the biomass raw material and can replace grain raw materials to produce glucose; after degradation, the hemicellulose mainly generates xylose. Glucose and xylose are important food raw materials, and can also be used as raw materials in the fields of medicines, foods, fermentation, printing and dyeing and the like to produce various industrial products, such as ethanol, butanol, organic acids, amino acids, enzyme preparations, xylitol, furfural and the like.
The sugar produced by biomass raw material can be produced by means of hydrolysis, for example, CN101343292A discloses a method for continuous hydrolysis of cellulosic biomass and a device thereof, which directly produces sugar by acid hydrolysis without an enzymolysis process. Since dilute acid can severely corrode equipment, especially at high temperatures (e.g., greater than 140 ℃), the metal corrosion rate can be increased by more than 10 times, greatly reducing the life of the material. Therefore, the requirement for corrosion resistance of the equipment is relatively high, and the corresponding production cost is significantly increased. In addition, in an acidic environment, hemicellulose and part of cellulose can be degraded and generated to finally generate furfural, carboxymethyl furfural and various derivatives, so that raw material loss and waste are caused, and enzymolysis and fermentation are inhibited.
At present, the method adopted is to pretreat the biomass raw material, such as steam explosion, cooking, puffing and the like, so as to destroy the crystal structure of the biomass raw material, and then to carry out enzymolysis by utilizing cellulase to generate monosaccharide. The enzymolysis process of cellulose and hemicellulose is the result of the synergistic action of various enzymes, and usually, under the action of endonuclease, most fibers are degraded to generate soluble glycan, so that an enzymolysis system is in a liquefied state, has better fluidity and obviously reduces viscosity. Then the soluble glycan generates disaccharide under the action of exonuclease, and finally generates glucose or xylose under the action of glycosidase. Thus, the speed and efficiency of enzymatic hydrolysis have a significant impact on sugar yield and production costs.
Factors influencing the enzymolysis speed and efficiency are many, including cellulase activity, enzymolysis substrate concentration, reactor type, stirring effect and the like, wherein the type of the enzymolysis reactor is one of important factors influencing the enzymolysis efficiency. The enzymatic hydrolysis reactor which is commonly used in industry is divided into a vertical type and a horizontal type. The horizontal reactor has more sufficient mixing and good mass transfer effect, and has lower energy consumption than the vertical stirrer under the same stirring condition (Dasari R K, dunaway K, berson R E.A. A screened Surface Bioreactor for Enzymatic purification of Pretreated Corn storage sources. Energy&Fuels,2009, 23. The occupied area of the horizontal reactor is usually larger, and the volume utilization rate is usually smaller, generally about 50 percent; if the diameter is enlarged, the effective volume can be improved, but the power required by the rotation of the stirring paddle is larger, and the control difficulty is high; the volume can be increased by extending the cross shaft, but the cross shaft is too long and is likely to bend downward due to gravity, which makes the manufacturing difficult and costly. These factors limit the size of the horizontal reactor. Wu Ze, etc. studied three horizontal cellulose continuous enzymolysis devices, and the digital analog analysis and comprehensive evaluation of the paddle type and the mixing effect, the results showed that the horizontal reactor has a good enzymolysis effect, but did not solve the problem of industrial scale-up (Wu Ze, etc., mixed conveyor performance study of cellulose continuous enzymolysis devices, cellulose science and technology, 2013, 21 (002): 30-38.). Inbicon of Denmark constructed kiloton grade cellulose ethanol pilot plant, designed 11m 3 The enzymatic hydrolysis reactor of (1), but there has been no report on a larger scale horizontal enzymatic hydrolysis reactor (Larsen J, petersen M O, thirup L, et al, the IBUS process lignocellulosic bioethanol close to a commercial purity [ J].Chem Eng Technol,2008,31:765-772.)。
The vertical reactor can avoid the problems, and the reactor has the advantages of simple operation, easy control, flexible amplification on different scales, small floor area, common equipment for enzymolysis reaction, and maximum scale of 3000m 3 And even larger. However, in the reaction system having a high concentration and a high dry matter content, the vertical reactor is difficult to handle, and requires a large power consumption. After the biomass raw material is pretreated, the structure becomes loose, the water absorption is strong, and when the concentration of the substrate is higher (>10%) with no or little free water, and mixing with agitation is difficult, resulting in difficulty in achieving adequate contact between the cellulase and the substrate, often requiring a long period of time for gradual liquefaction and degradation. In addition, the materials are usually adhered to one position, the wall adhesion is formed quickly after the stirring is started, a cavity is formed at the position where the blades are stirred, the cavity cannot be fully contacted with the materials, the stirring and mixing effects cannot be achieved, the mass transfer effect is poor, the cellulase cannot be fully exerted, and the liquefaction speed is low. If the adding amount of the cellulase is increased, the initial enzymolysis speed can be improved, and the problem is solved to a certain extent, but the use cost of the cellulase is correspondingly increased. Generally, the enzymatic system is usually liquefied for more than 10 hours under the condition of ensuring more economic cellulase addition, especially when the concentration of dry matters is high, such as>30 percent, even more than 30 hours, and then the stirring can be carried out under the lower viscosity to continue the enzymolysis. This also results in a large stirring power required in the earlier stage of the enzymolysis, a long time, a low efficiency and a high energy consumption.
Disclosure of Invention
The invention aims to overcome the problems that a horizontal reactor is difficult to industrialize, and a vertical reactor has large power, long time, high energy consumption, low efficiency and the like when processing a raw material with high dry matter concentration in the prior art, and provides a method for preparing monosaccharide from a biomass raw material.
In order to achieve the above object, the present invention provides a method for preparing monosaccharide from a biomass raw material, comprising: carrying out first enzymolysis on biomass raw materials in a horizontal reactor to obtain liquefied liquid; and carrying out second enzymolysis on the liquefied liquid in the vertical reactor to obtain the monosaccharide-containing material.
By adopting the method, the horizontal reactor and the vertical reactor are used together, the liquefaction speed of the pretreated biomass raw material can be improved under the condition of higher dry matter concentration, the utilization rate of the enzymolysis reactor is improved, the power consumption is reduced, higher enzymolysis efficiency is achieved, and an effective way is explored for the high-value conversion of the biomass raw material.
In addition, the method can also obviously reduce the enzyme dosage for enzymolysis of the biomass raw material.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing monosaccharide from a biomass raw material, which comprises the following steps: contacting a biomass raw material with a first enzyme preparation in a horizontal reactor, and carrying out first enzymolysis to obtain a liquefied liquid; and (3) in the vertical reactor, contacting the liquefied liquid with an optional second enzyme preparation, and carrying out second enzymolysis to obtain a monosaccharide-containing material.
In the present invention, the kind of biomass raw material is a biomass raw material existing in the art as long as it contains biomass, and includes, but is not limited to, at least one of corn stover, corn husks, corn cobs, wheat straw, rice straw, bagasse, bean straw, cotton straw, banana straw, coconut shell, bamboo, switchgrass, giant reed, branches, wood chips, and sawdust. It will be understood that the straw includes the stem and leaves of the plant and optionally the roots.
In the invention, the enzymatic hydrolysis of the biomass raw material is used for preparing monosaccharide containing glucose and xylose.
Preferably, the method further comprises: the method comprises the steps of preprocessing the biomass raw material before first enzymolysis is carried out on the biomass raw material to obtain a preprocessed material.
The pretreatment method of the biomass raw material may be any method conventionally used in the art that can be used for the treatment thereof, and may be adjusted according to the kind of the material.
In the present invention, the method of pretreatment may be a pretreatment method conventionally employed in the art, including but not limited to at least one of steam explosion, cooking and puffing.
In the present invention, the steam explosion method may be a steam explosion method conventional in the art, and preferably includes at least one of neutral steam explosion, dilute acid steam explosion, and alkaline steam explosion.
The steam explosion method preferably comprises mixing the biomass raw material with water or dilute acid or alkaline substance, maintaining the mixture at 150-210 ℃ (for example, at 150, 160, 170, 180, 190, 200, 210 ℃ and any range between any two values) for 1-120min (for example, at 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120min and any range between any two values), and then releasing the mixture under reduced pressure instantly. It should be understood that when the biomass feedstock and water are mixed, there is a neutral steam explosion; when the diluted acid is mixed with the diluted acid, the diluted acid is subjected to steam explosion; when the catalyst is mixed with alkaline substances, alkaline steam explosion is carried out.
In the present invention, the amount of water or dilute acid or base is preferably such that the biomass feedstock content in the mixture of biomass feedstock and water or dilute acid or base is from 30 to 60 wt% (e.g., can be 30, 35, 40, 45, 50, 55, 60 wt% and any range between any two values).
In the present invention, the content of the biomass feedstock is on a dry basis.
In the present invention, the water may be water conventionally used in the art, and may be, for example, tap water, industrial water, and the like.
In the present invention, the dilute acid is a dilute acid conventionally used in the art, such as an acid solution having a concentration of 0.1 to 3 wt% (e.g., any range between any two values and 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.5, 3 wt%) and including, but not limited to, phosphoric acid and sulfuric acid.
In the present invention, the alkaline substance is an alkaline substance conventionally used in the art, such as an alkaline solution having a concentration of 1-20 wt% (such as any range between 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 wt%) and including but not limited to sodium hydroxide, potassium hydroxide, sodium sulfite, potassium sulfite, ammonium sulfite, and ammonia water.
In the present invention, the cooking method may be a cooking method conventional in the art, for example, the biomass raw material and water may be mixed, heated and cooked, and then subjected to solid-liquid separation to obtain a cooked material.
Preferably, the water is used in an amount such that the dry matter content of the biomass feedstock in the material for cooking is between 10 and 30 wt% (e.g., can be 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30 wt% and any range consisting of between any two values).
In a preferred embodiment of the present invention, the material for cooking further contains sulfite and/or bisulfite, such as sodium sulfite, ammonium sulfite, magnesium sulfite, or ammonium bisulfite, etc., and the sulfite or bisulfite content of the material for cooking is 3-20 wt% (e.g., can be 3, 5, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30 wt%, and any range between any two values).
The cooking according to the invention can be carried out by means of a digester, which is a stirred tank reactor or a non-stirred tank reactor (for example, a vertical or horizontal reactor).
Preferably, the cooking is performed under closed conditions.
Preferably, the cooking conditions include: the temperature is 140-200 ℃ (e.g., can be 140, 150, 160, 170, 180, 190, 200 ℃ and any range between any two values), and the time is 5-120min (e.g., can be 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120min and any range between any two values).
In the present invention, the solid-liquid separation method includes, but is not limited to, extrusion, and a centrifugal method may also be used.
It should be understood that the solid-liquid separated material may be subjected to a water washing treatment, for example, water (e.g., 70 to 95 ℃) may be added to the solid-liquid separated material and mixed uniformly, and then the solid-liquid separation may be performed again.
In the present invention, the puffing method may be a puffing method conventional in the art, for example, the biomass raw material and water may be mixed and then puffed to obtain a puffed material.
Preferably, the water is used in an amount such that the biomass feedstock content of the material used for bulking is from 20 to 60 wt% (e.g., can be 20, 25, 30, 35, 40, 45, 50, 55, 60 wt%, and any range of compositions between any two values).
The puffing may be performed in a puffing machine.
Preferably, the conditions of puffing include: the temperature is 120-180 ℃, and the screw rotating speed is 50-80rpm.
In the invention, the pretreated material can be directly used for enzymolysis, or the pretreated material and water are mixed and then adjusted to proper concentration for enzymolysis.
Preferably, the concentration of pretreated material is 10-50 wt% (e.g., can be 10, 15, 20, 25, 30, 35, 40, 45, 50 wt%, and any range between any two values) on a dry matter basis. It will be appreciated that the pretreated material may be used directly when its dry matter concentration is within the aforementioned range, and that the pretreated material may be diluted or concentrated to be within the aforementioned range when its dry matter concentration is outside the aforementioned range.
In general, the biomass material may contain impurities, and may be subjected to a preliminary impurity removal treatment. The method for removing impurities can be a conventional technical means in the field as long as impurities in the biomass raw material can be removed. For example, a dust remover can be used for removing dust impurities, an impurity remover can be used for removing sand and stone impurities, and a magnetic adsorption method can be used for removing iron impurities. The skilled person can combine the aforementioned methods to perform the impurity removal operation as required.
In the present invention, preferably, the method further comprises: before the biomass raw material is pretreated, the biomass raw material is subjected to crushing treatment.
In the present invention, the method of pulverization may be a means conventionally used in the art, for example, a biomass raw material may be pulverized using a pulverizer. Preferably, the crushing treatment is carried out so that the particle size of the particles in the crushed material is 1-3cm. It should be understood that when the pulverized material is in the form of a strand or a thread and the like, the particle size thereof means the length thereof.
It should be understood that the particle size of the particles in the material after the crushing treatment is controlled to be 1-3cm by setting the crushing parameters of the crusher, and does not mean that the particle size of all the particles is 1-3cm, but the particle size of the majority is 1-3cm, for example, 1-3cm is the portion of 90 wt% or more.
The crusher may be a crusher conventional in the art, and may be, for example, a hammer mill, a roll mill, a shear mill, or the like.
In the invention, the pretreated material is subjected to first enzymolysis to obtain liquefied liquid.
The first enzymatic hydrolysis is carried out in a horizontal reactor, which may be a horizontal reactor capable of carrying out enzymatic hydrolysis as it exists in the art. The horizontal reactor may contain a stirring paddle, and may be, for example, a ribbon type, a helical blade type, a plate type, an anchor type, or the like.
Preferably, the first enzyme preparation comprises cellulase, optionally also hemicellulase and/or β -glucosidase.
In the first enzyme preparation, the weight ratio of the cellulase, the hemicellulase and the beta-glucosidase may be 1:0-0.5.
The first enzyme preparation may be obtained in various ways, e.g. commercially available.
In the present invention, the amount of the first enzyme preparation may be selected from a wide range as long as it can degrade the biomass raw material to prepare monosaccharide, and may be added by those skilled in the art as needed. For example, preferably, the first enzyme preparation is used in an amount of 1 to 20 wt%, more preferably 2 to 15 wt% (e.g., may be 2, 4, 6, 8, 10, 12, 14, 15 wt% and any range between any two values) based on the weight of the biomass feedstock dry matter.
The conditions of the first enzymolysis may be that the enzyme can work normally, and preferably, the conditions of the first enzymolysis include: the temperature is 40-60 deg.C, and pH is 4.5-5.5.
In the invention, the time of the first enzymolysis can be selected in a wide range, and the enzymolysis time can also be different according to the different types of materials and the different concentrations of the substrates. Generally, the resulting liquefied liquid can be transported by pumping, i.e. in a pumpable state, preferably the viscosity of the liquefied liquid is 6000mPa · s or less, more preferably 200 to 6000mPa · s.
The viscosity of the enzymolysis system can be measured by NDJ-5S digital display viscometer manufactured by Shunhua constant-average scientific instruments, inc., and the viscosity number can be changed according to the type and rotation speed of the selected rotor. According to different substrate concentrations of an enzymolysis system, a 2# or 3# rotor can be selected, and the rotor is adjusted according to actual conditions in a corresponding measurement range of an instrument, so that the system is finally ensured to be in a pumpable flowing state.
The pump may be a pump conventionally used in the art, and may be, for example, a centrifugal pump, a reciprocating pump, or the like.
Because the time of the second enzymolysis is often several times (for example, more than 5-10 times) of the time of the first enzymolysis, new materials can be added into the horizontal reactor to continue the first enzymolysis, and the liquefied liquid is continuously pumped into the vertical reactor to perform the second enzymolysis, thereby realizing continuous production.
In the invention, the liquefied solution is subjected to second enzymolysis in the vertical reactor to obtain a monosaccharide-containing material. In the enzymolysis, a second enzyme preparation can be added for further accelerating the enzymolysis, or the liquefied solution can be continuously subjected to enzymolysis through the first enzyme preparation without adding an enzyme preparation.
The second enzymatic hydrolysis is carried out in a vertical reactor, which may be one capable of effecting enzymatic hydrolysis as is known in the art. The vertical reactor can contain a stirring paddle, and the stirring paddle can be plate type, anchor type, helical ribbon type, frame type and the like.
Preferably, the second enzyme preparation comprises cellulase, optionally also hemicellulase and/or β -glucosidase. The second enzyme preparation and the first enzyme preparation may be the same or different. Within the preferred range, the time for preparing the monosaccharide can be further shortened, and the yield and productivity of the monosaccharide can be improved.
In a preferred embodiment of the invention, the ratio of the amounts of the first enzyme preparation and the second enzyme preparation is 1:0-0.5, more preferably 1:0.1-0.3, such as 1.
The conditions of the enzymolysis can be only to enable the enzyme to work normally, and preferably, the conditions of the enzymolysis comprise: the temperature is 40-60 deg.C, pH is 4.5-5.5, and enzymolysis time is 48-120h.
Obtaining monosaccharide through enzymolysis, wherein the monosaccharide comprises glucose and xylose. The glucose and xylose content can be determined by HPLC.
In a preferred embodiment of the invention, the method comprises: pretreating a biomass raw material to obtain a pretreated material; contacting the pretreated material with a first enzyme preparation in a horizontal reactor, and carrying out first enzymolysis to obtain a liquefied liquid; and (3) in the vertical reactor, contacting the liquefied liquid with a second enzyme preparation for second enzymolysis to obtain a monosaccharide-containing material. The concentration of the pretreated material is 10-50 wt.% on a dry basis. The first enzyme preparation comprises cellulase, optionally also hemicellulase and/or β -glucosidase. The first enzyme preparation is used in an amount of 2-20 wt% based on the weight of the biomass feedstock dry matter. The viscosity of the liquefied liquid is 200-6000 mPas. The second enzyme preparation comprises cellulase, optionally also hemicellulase and/or β -glucosidase. The dosage ratio of the first enzyme preparation to the second enzyme preparation is 1. Under the preferable conditions, the time for preparing the monosaccharide can be further shortened, and the yield and the productivity of the monosaccharide can be improved.
In the following examples and comparative examples, cellulases are available from novacin under the trade designation CTec2;
xylanase purchased from summer Cheng Gongsi under the brand name FDY-3001;
beta-glucosidase was purchased from summer Cheng Gongsi and sold as SPE-007A.
In the following examples and comparative examples, the biomass feedstock was pulverized into 1-3cm pieces by a hammer mill before pretreatment.
The conditions of the first and second enzymolysis are respectively as follows: the temperature is 50 +/-2 ℃, and the pH is 5 +/-0.5.
In the following examples and comparative examples, the substrate concentration was calculated by taking the weight of the dry matter of the pretreated material as the weight of the substrate.
Glucose yield = amount of glucose produced/amount of glucose that can be produced by total degradation of the feedstock.
Xylose yield = amount of xylose produced/amount of xylose that can be produced by total degradation of the feedstock.
In the following examples and comparative examples, the glucose and xylose contents were determined by HPLC methods under the following conditions:
a chromatographic column: BIO-RAD analytical column HPX-87H;
sample introduction volume: 20 mu L of the solution;
mobile phase: 0.005M sulfuric acid, filtered through a 0.2 μ M filter membrane and degassed;
flow rate: 0.5mL/min;
column temperature: 55-65 ℃;
detector temperature: the temperature is as close as possible to the column temperature;
a detector: a difference detector;
operating time: and (3) 30min.
The viscosity of the enzymolysis system was measured by NDJ-5S digital display viscometer manufactured by Shunhui scientific instruments, inc. in Shanghai, and 3# rotor was used. In the following examples, the viscosity of the product after the first enzymatic hydrolysis was within the range of 200 to 6000 mPas.
The vertical reactor was a custom-made 1L glass jar and plate paddle equipped with an IKA EUROSTAR40 stirrer.
Examples 1 to 1
This example illustrates the preparation of monosaccharides from corn stover.
(1) Carrying out neutral steam explosion pretreatment on the corn straws, wherein the concentration of a substrate is 50 weight percent, the conditions are that the temperature is 180 ℃, and the heat preservation time is 20min.
(2) And (3) putting the pretreated material into a horizontal spiral-ribbon reactor, adding water, adjusting the pH value to be 5.0, and adding an enzyme preparation to perform first enzymolysis, wherein the concentration of the substrate is 15 wt%, and the addition of the enzyme preparation is 5 wt% of the weight of the corn straws. Liquefying the materials after enzymolysis for 3 h. Wherein the enzyme preparation is cellulase.
(3) And (3) transferring the liquefied liquid into a vertical reactor for continuous enzymolysis for 52h, wherein the weight ratio of the addition amount of the enzyme preparation in the step (2) to the addition amount of the enzyme preparation in the step is 1. The results of the glucose yield, xylose yield, glucose concentration and xylose concentration in the monosaccharide-containing material are shown in Table 1.
Examples 1 to 2
This example illustrates the preparation of monosaccharides from corn stover.
The procedure was followed as described in example 1-1, except that the weight ratio of the amount of the enzyme preparation added in step (2) to the amount of the enzyme preparation added in step (3) was 1. As a result, the material was liquefied after 4 hours of the first enzymatic hydrolysis, and then the same procedure as in example 1-1 was repeated.
The results of the conversion of biomass feedstock, glucose concentration and xylose concentration in the resulting monosaccharide-containing material are shown in table 1.
Examples 1 to 3
This example illustrates the preparation of monosaccharides from corn stover.
The procedure was followed as described in example 1-1, with the same total reaction time and total enzyme preparation addition, except that the weight ratio of the amount of enzyme preparation added in step (2) to the amount of enzyme preparation added in step (3) was 1. As a result, the material was liquefied after 5.5 hours of the first enzymatic hydrolysis, and then the same procedure as in example 1-1 was repeated.
The results of the conversion of biomass feedstock, the concentration of glucose and the concentration of xylose in the resulting monosaccharide-containing material are shown in table 1.
Examples 1 to 4
This example illustrates the preparation of monosaccharides from corn stover.
The procedure was followed as described in example 1-1, except that the ratio of the amount of the enzyme preparation added in step (2) to the amount of the enzyme preparation added in step (3) was 1. As a result, the material was liquefied after 7 hours of the first enzymatic hydrolysis, and then the same procedure as in example 1-1 was repeated.
The results of the conversion of biomass feedstock, the concentration of glucose and the concentration of xylose in the resulting monosaccharide-containing material are shown in table 1.
Examples 1 to 5
This example illustrates the preparation of monosaccharides from corn stover.
The procedure was followed as described in example 1-1, except that no enzyme preparation was added in step (3) and the amount of enzyme preparation added in step (2) was 6% by weight of the corn stover. As a result, the material was liquefied after 2 hours of the first enzymatic hydrolysis, and then the same procedure as in example 1-1 was repeated.
The results of the conversion of biomass feedstock, the concentration of glucose and the concentration of xylose in the resulting monosaccharide-containing material are shown in table 1.
Comparative example 1
This comparative example is presented to illustrate the process of making monosaccharides from reference corn stover.
The procedure was as in example 1-1, except that the first enzymatic hydrolysis in the horizontal reactor was not performed, i.e., the pretreated material was added directly to the vertical reactor, water was added, the pH was adjusted to 5.0, and then enzymatic preparation was added for enzymatic hydrolysis, wherein the substrate concentration was 15 wt% and the amount of enzymatic preparation was 6 wt% based on the weight of the corn stover. Liquefying the materials after enzymolysis for 10h, and continuing enzymolysis for 44h.
The results of the conversion of biomass raw material, the concentration of glucose and the concentration of xylose in the resulting enzymatically hydrolyzed material are shown in table 1.
TABLE 1
Example 2
This example is presented to illustrate a method for preparing monosaccharides from wheat straw.
(1) Sodium sulfite was added to wheat straw for cooking, and the concentration of the substrate was 20% by weight and the concentration of sodium sulfite was 5% by weight. Mixing, sealing, heating and steaming at 160 deg.C for 100min. After the cooking is finished, extruding the materials, and carrying out solid-liquid separation.
(2) Adding the pretreated material into a horizontal anchor reactor, adding water, adjusting the pH to 4.8, and adding an enzyme preparation for first enzymolysis, wherein the concentration of a substrate is 20 wt%, and the addition of the enzyme preparation is 10 wt% of the weight of the wheat straws. Liquefying the materials after enzymolysis for 4h. Wherein the enzyme preparation is cellulase.
(3) Placing the liquefied liquid into a vertical reactor for continuous enzymolysis for 60h. Wherein, the results of the concentration of glucose and the concentration of xylose in the material after enzymolysis are shown in Table 2.
Comparative example 2
This comparative example is presented to illustrate a process for making monosaccharides from reference wheat straw.
The operation was performed according to the method described in example 2, except that the horizontal reactor was not used for the enzymatic hydrolysis, the pretreated material was directly added to the vertical reactor, and water and the enzyme preparation were added for the enzymatic hydrolysis, wherein the substrate concentration was 20 wt% and the enzyme preparation was 10 wt% of the weight of the wheat straw. Liquefying the materials after enzymolysis for 15h, and continuing enzymolysis for 49 h. The results of the glucose concentration and the xylose concentration are shown in Table 2.
Example 3
This example illustrates the preparation of monosaccharides from cotton stalks.
(1) Mixing cotton stalk with 2 wt% dilute sulfuric acid, with a substrate concentration of 50 wt%, steam explosion at 165 deg.C, and holding for 15min.
(2) And adding the pretreated material into a horizontal spiral belt type reactor, adding water, adjusting the pH to 5.5, and adding an enzyme preparation for first enzymolysis, wherein the concentration of a substrate is 30 wt%, and the adding amount of the enzyme preparation is 15 wt% of the weight of the cotton stalks. Liquefying the materials after enzymolysis for 16 h. Wherein the enzyme preparation is cellulase.
(3) Placing the liquefied liquid into a vertical reactor for continuous enzymolysis for 84h. Wherein, the results of the concentration of glucose and the concentration of xylose in the material after enzymolysis are shown in Table 2.
Comparative example 3
This comparative example is illustrative of a process for making monosaccharide from a reference cotton stalk.
The operation was carried out according to the method described in example 3, except that, without carrying out the horizontal reactor enzymolysis, the pretreated material was directly added to a vertical reactor, and water and an enzyme preparation were added for the enzymolysis, wherein the substrate concentration was 30 wt% and the enzyme preparation was added in an amount of 15 wt% of the weight of cotton stalks. Liquefying the materials after enzymolysis for 30h, and continuing enzymolysis for 70h. The results of the glucose concentration and the xylose concentration are shown in Table 2.
Example 4
This example illustrates a method for preparing monosaccharide from rice straw.
(1) Mixing rice straw and water, and performing puffing pretreatment, wherein the sleeve temperature is 165 ℃, and the screw rotation speed is 60 r.min -1 The dry matter content was 50% by weight.
(2) And adding the pretreated material into a horizontal plate-type reactor, adding water, adjusting the pH to 4.6, and adding an enzyme preparation for first enzymolysis, wherein the concentration of a substrate is 10 wt%, and the addition of the enzyme preparation is 2 wt% of the weight of the rice straw. Liquefying the materials after enzymolysis for 1 h. Wherein the enzyme preparation is cellulase.
(3) Placing the liquefied liquid into a vertical reactor for continuous enzymolysis for 39h. The results of the glucose concentration and the xylose concentration are shown in Table 2.
Comparative example 4
This comparative example is used to illustrate the process of making monosaccharides from reference rice straw.
The operation was carried out according to the method described in example 4, except that, without carrying out the horizontal reactor enzymolysis, the pretreated material was directly added to the vertical reactor, and water and an enzyme preparation were added for the enzymolysis, wherein the substrate concentration was 10 wt% and the enzyme preparation was added in an amount of 2 wt% of the weight of the rice straw. Liquefying the materials after enzymolysis for 3h, and continuing enzymolysis for 37 h. The results of the glucose concentration and the xylose concentration are shown in Table 2.
Example 5
This example illustrates the preparation of monosaccharides from sugar cane bagasse.
(1) Mixing bagasse with 1.5 wt% dilute sulfuric acid, with a substrate concentration of 50 wt%, steam explosion at 165 deg.C, and holding for 10min.
(2) Adding the pretreated material into a horizontal spiral-ribbon reactor, adding water, adjusting the pH to 5.0, and adding an enzyme preparation for first enzymolysis, wherein the concentration of a substrate is 40 wt%, and the addition amount of a complex enzyme preparation is 20 wt% of the weight of bagasse. The material is liquefied after 28h of the first enzymolysis. Wherein the enzyme preparation is a complex enzyme preparation (cellulase: xylanase =1: 0.3.
(3) Placing the liquefied liquid into a vertical reactor for continuous enzymolysis for 70h. The results of the glucose concentration and the xylose concentration are shown in Table 2.
Comparative example 5
This comparative example serves to illustrate the preparation of monosaccharides from reference bagasse.
The procedure was followed as described in example 5, except that, instead of performing horizontal reactor enzymatic hydrolysis, the pretreated material was directly added to a vertical reactor, water and a complex enzyme preparation were added for enzymatic hydrolysis, wherein the substrate concentration was 40 wt%, the enzyme preparation was added in an amount of 20 wt% of the bagasse, and the enzyme preparation was a complex enzyme preparation (cellulase: xylanase = 1. Liquefying the materials after enzymolysis for 46h, and continuing enzymolysis for 52 h. The results of the glucose concentration and the xylose concentration are shown in Table 2.
TABLE 2
As can be seen from the results in tables 1 and 2, the technical solutions in the examples of the present invention, especially in the case of the preferred enzyme addition method, have the effects of promoting the enzymolysis of the raw materials and significantly improving the yield of sugar.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for preparing monosaccharide from a biomass raw material is characterized by comprising the following steps:
contacting a biomass raw material with a first enzyme preparation in a horizontal reactor, and carrying out first enzymolysis to obtain a liquefied liquid; and (3) in the vertical reactor, contacting the liquefied liquid with an optional second enzyme preparation, and carrying out second enzymolysis to obtain a monosaccharide-containing material.
2. The method of claim 1, wherein the method further comprises: pretreating the biomass raw material to obtain a pretreated material before carrying out first enzymolysis on the biomass raw material;
preferably, the method of pre-treatment comprises at least one of steam explosion, cooking and puffing.
3. A process according to claim 2, wherein the concentration of pretreated material is 10-50% by weight on a dry matter basis.
4. The method of any one of claims 1-3, wherein the conditions of the first enzymatic hydrolysis comprise: the temperature is 40-60 ℃, and the pH is 4.5-5.5;
preferably, the viscosity of the liquefied liquid is 6000mPa · s or less.
5. The method according to any one of claims 1-4, wherein the first enzyme preparation comprises cellulase, optionally also hemicellulase and/or β -glucosidase;
preferably, the first enzyme preparation is used in an amount of 1-20 wt% based on the weight of dry matter of the biomass feedstock.
6. The method of any one of claims 1-5, wherein the conditions of the second enzymatic hydrolysis comprise: the temperature is 40-60 deg.C, pH is 4.5-5.5, and enzymolysis time is 48-120h.
7. The method of claim 6, wherein the second enzyme preparation comprises at least one of cellulase, hemicellulase and β -glucosidase.
8. The method of any one of claims 1-7, wherein the first enzyme preparation and the second enzyme preparation are used in a ratio of 1:0-0.5.
9. The method of any of claims 1-8, wherein the biomass feedstock comprises at least one of corn stover, corn husks, corn cobs, wheat straw, rice straw, bagasse, bean straw, cotton stalk, banana stalk, coconut shell, bamboo, switchgrass, bamboo reed, branches, wood chips, and sawdust.
10. The method of any one of claims 1-9, wherein the method further comprises: before the biomass raw material is pretreated, crushing the biomass raw material;
preferably, the crushing treatment is carried out so that the particle size of the particles in the crushed material is 1-3cm.
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