CN117587649A - Application method of eutectic solvent in biorefinery - Google Patents
Application method of eutectic solvent in biorefinery Download PDFInfo
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- CN117587649A CN117587649A CN202311427561.5A CN202311427561A CN117587649A CN 117587649 A CN117587649 A CN 117587649A CN 202311427561 A CN202311427561 A CN 202311427561A CN 117587649 A CN117587649 A CN 117587649A
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- 239000002904 solvent Substances 0.000 title claims abstract description 92
- 230000005496 eutectics Effects 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 31
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229920005610 lignin Polymers 0.000 claims abstract description 68
- 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 claims abstract description 43
- 239000008103 glucose Substances 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims description 143
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 239000008367 deionised water Substances 0.000 claims description 57
- 229910021641 deionized water Inorganic materials 0.000 claims description 57
- 239000007787 solid Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 238000006555 catalytic reaction Methods 0.000 claims description 44
- 238000005406 washing Methods 0.000 claims description 43
- 239000004744 fabric Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 30
- 238000005119 centrifugation Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 23
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 14
- 238000002390 rotary evaporation Methods 0.000 claims description 14
- 241000219000 Populus Species 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 8
- 241000018646 Pinus brutia Species 0.000 claims description 8
- 235000011613 Pinus brutia Nutrition 0.000 claims description 8
- 150000001721 carbon Chemical class 0.000 claims description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 8
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 244000302661 Phyllostachys pubescens Species 0.000 claims description 5
- 235000003570 Phyllostachys pubescens Nutrition 0.000 claims description 5
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 5
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 108010059892 Cellulase Proteins 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229940106157 cellulase Drugs 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 3
- 229960003237 betaine Drugs 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 2
- 235000019743 Choline chloride Nutrition 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- 102000004190 Enzymes Human genes 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 2
- 229960003178 choline chloride Drugs 0.000 claims description 2
- 229940088598 enzyme Drugs 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 abstract description 15
- 229920002678 cellulose Polymers 0.000 abstract description 15
- 229920002488 Hemicellulose Polymers 0.000 abstract description 13
- 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 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 description 13
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 13
- 238000011049 filling Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000007789 sealing Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002292 Radical scavenging effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- VVLAIYIMMFWRFW-UHFFFAOYSA-N 2-hydroxyethylazanium;acetate Chemical compound CC(O)=O.NCCO VVLAIYIMMFWRFW-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- OBVDZJAOUJTMDJ-UHFFFAOYSA-N diaminomethylideneazanium chloride trihydrochloride Chemical compound Cl.Cl.Cl.Cl.NC(N)=N OBVDZJAOUJTMDJ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
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- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- 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
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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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
-
- 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
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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
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Wood Science & Technology (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention provides an application method of a eutectic solvent in biorefinery, and a multi-site novel eutectic solvent is prepared through design, has the advantages of environment friendliness, low cost, easiness in preparation and the like, and can be used for separating cellulose, lignin and hemicellulose by a mild, clean and efficient one-step method and converting the cellulose, lignin and hemicellulose into glucose, furfural and nano lignin with oxidation resistance.
Description
Technical Field
The invention belongs to the technical field of lignocellulose refining, and particularly relates to a method for mildly, cleanly and efficiently separating cellulose, lignin and hemicellulose from lignocellulose, converting the cellulose, lignin and hemicellulose into glucose, furfural and preparing nano lignin with oxidation resistance.
Background
In recent years, with the increasing demand for non-renewable resources such as petroleum and natural gas, the world is faced with a serious resource crisis. How to convert lignocellulose into a high value-added product is a key to solving the energy crisis as a renewable resource with abundant reserves on earth, however, the effective conversion of lignocellulose is hindered by the existence of a degradation-resistant barrier of lignocellulose; lignocellulosic biomass mainly comprises cellulose, hemicellulose and lignin, the key to converting which is how to clean and efficiently separate these three components;
the main separation methods at present are dilute acid method, alkaline method, organic solvent method, ionic liquid method and the like. However, these conventional methods corrode equipment, require severe conditions such as high temperature and high pressure, or pollute the environment with volatile toxic chemical agents, and have high product costs due to the volatility and non-recyclability of solvents. As a novel solvent, the eutectic solvent has the advantages of environmental protection, low cost, easy preparation and the like. More importantly, the eutectic solvent can effectively remove lignin and hemicellulose, better preserve cellulose, and provide a precondition for clean and efficient separation of the three main elements;
chinese patent No. 110258157A discloses a method for pretreating lignocellulose by using betaine eutectic solvent, wherein the mass ratio of lignocellulose to pretreatment solvent is 1:30, the lignocellulose raw material and the pretreatment solvent are uniformly mixed, and the mixture is stirred at 100 ℃ for 48 h to obtain pretreated solid-phase cellulose residues, and the glucose yield reaches 90%;
chinese patent No. 112899313A discloses an acid eutectic solvent, a preparation method and application thereof in pretreatment of straw to improve enzymolysis efficiency, extraction of lignin and enzymolysis saccharification of straw residues are carried out, the lignin removal rate of the straw reaches 84%, the cellulose retention rate reaches 90%, and the enzymolysis efficiency of the straw residues reaches 89%;
chinese patent No. CN113603889a discloses a method for pretreating lignocellulose by using lewis base to assist neutral eutectic solvent, the solid-liquid mixture is subjected to heating pretreatment, the mixed liquid is subjected to vacuum filtration, the washing liquid is washed to obtain solid residue and liquid residue, and the enzymolysis saccharification rate is 94.5%;
however, the prior art represented by the above patents all have the following disadvantages: the process conditions are severe, the temperature of the conditions is too high or the flow time is longer; in addition, the prior art for preparing lignocellulose can only separate and convert a single component, and cannot realize the efficient separation or conversion application of the lignocellulose main component.
Disclosure of Invention
Aiming at the problems that the lignocellulose main component cannot be efficiently separated and converted in the prior art, and only a single component can be separated; therefore, the invention provides an application method of the eutectic solvent in biorefinery, which uses a mild and clean eutectic solvent to efficiently separate cellulose, lignin and hemicellulose, and converts the separated cellulose, lignin and hemicellulose into glucose, furfural and nano lignin with oxidation resistance.
In order to achieve the above purpose, the technical scheme adopted in the application is as follows:
a method for applying a eutectic solvent in biorefinery, comprising the steps of:
step one: pulverizing one or more of moso bamboo, poplar, pine and xylose residues into particles with the size of 20-80 meshes by using a pulverizer; loading the crushed particles into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting 9 h by using a mixed solution of toluene and ethanol to obtain lignocellulose;
step two: mixing lignocellulose and eutectic solvent, putting the mixture into a reaction bottle, adding a rotor into the reaction bottle, and then moving the reaction bottle onto a reaction kettle for heating and stirring reaction; after the reaction is finished, a mixture after the reaction is obtained;
step three: centrifuging the mixture after reaction by using a centrifuge, and centrifuging the mixture for 5 min at 9000 rpm to separate solid from liquid, thereby obtaining centrifuged liquid and centrifuged solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, and adding a proper amount of deionized water; centrifuging the centrifuged liquid and deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding a catalyst into the pretreatment liquid to perform catalytic reaction, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; drying the washed solid in an oven at 60 ℃ for 24 h, and then carrying out 48 h enzymolysis at 50 ℃ and 150 rpm to obtain glucose;
the eutectic solvent is prepared by the following method:
mixing a hydrogen bond acceptor and a hydrogen bond donor; reacting at the temperature of 30-60 ℃ and the stirring speed of 300 r-600 r/min until a uniform transparent liquid is formed, namely the eutectic solvent; cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:2-10;
the hydrogen bond acceptor is one or more of choline chloride, guanidine hydrochloride, betaine, tetramethyl ammonium chloride and tetramethyl ammonium bromide; the hydrogen bond donor is one or more of formic acid, oxalic acid, lactic acid, malic acid, glycolic acid and ethylene glycol;
the preparation reaction time of the eutectic solvent is 0.3 h-2.0 h.
Preferably, in the first step, the volume ratio of toluene to ethanol in the mixed solution is 2:1.
Preferably, in the second step, the volume ratio of lignocellulose to the eutectic solvent in the reaction bottle is 1:5-15; the heating reaction condition in the reaction kettle is that the temperature is raised to 80-120 ℃, the stirring rotation speed is 400 r-600 r/min, and the reaction time is 0.5-3.0 h.
Preferably, in the third step, when the furfural is prepared, the catalyst for catalytic reaction is sulfonated carbon-based, sulfuric acid or sulfated titanium oxide; the catalytic reaction condition is that the temperature is 90-130 ℃ for 15-60 min; the addition amount of the catalyst is 2% of the mass of the pretreatment liquid.
Preferably, in the third step, when glucose is prepared, the enzyme of the enzymolysis reaction is cellulase, and the activity of the cellulase is 15 FPU/g.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention provides an application method of a eutectic solvent in biorefinery, which is characterized in that the novel multi-site eutectic solvent is prepared by design, and the solvent has the advantages of environmental protection, low cost, easy preparation and the like; the method can separate cellulose, lignin and hemicellulose in a mild, clean and efficient one-step method in biorefinery application, and convert the cellulose, lignin and hemicellulose into glucose, furfural and nano lignin with oxidation resistance;
2. experiments show that the yield of the enzymatic hydrolysis cellulose glucose in the method of the invention can approach 100% at 48 h, and the RSI value (free Radical Scavenging Index (RSI) is defined as IC 50 Can more visually represent the antioxidation result, and a higher RSI value represents a higher antioxidation activity) is up to 18%, and the yield of the catalytic conversion of hemicellulose into furfural is up to 80%.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort to a person skilled in the art.
Fig. 1 is a flow chart of the present application.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be rendered by reference to the appended drawings and examples. It should be noted that, in the case of no conflict, the embodiments of the present application and the features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the present invention is not limited to the specific embodiments of the disclosure that follow.
As shown in fig. 1, example 1, preparation of eutectic solvent: mixing hydrogen bond acceptor guanidine hydrochloride 95.53 g and hydrogen bond donor ethylene glycol 186.20 g in a beaker; sealing, heating, stirring and reacting at 60 ℃ at a stirring rate of 500 r/min until a uniform and transparent liquid is formed, namely the environment-friendly eutectic solvent (DES); cooling the environment-friendly eutectic solvent to room temperature and placing the environment-friendly eutectic solvent into a drying vessel for standby;
the application of the eutectic solvent in biorefinery comprises the following specific steps:
step one: pulverizing pine wood to 40-60 meshes by a pulverizer; filling the crushed pine into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting 9 h by using a mixed solution of toluene and ethanol in a volume ratio of 2:1;
step two: extracting 3.0. 3.0 g, adding pine into a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml eutectic solvent, heating to 120 ℃ for reaction 1 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfonated carbon base accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Example 2 preparation of eutectic solvent: mixing hydrogen bond acceptor guanidine hydrochloride 47.77 g and hydrogen bond donor ethylene glycol 186.20 g in a beaker; sealing, heating and stirring at 60 ℃ at a stirring rate of 500 r/min until a uniform transparent liquid is formed, namely the eutectic solvent (DES); cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the application of the eutectic solvent in biorefinery comprises the following specific steps:
step one: pulverizing pine wood to 40-60 meshes by a pulverizer; filling the crushed pine into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting 9 h by using a mixed solution of toluene and ethanol in a volume ratio of 2:1;
step two: extracting 3.0. 3.0 g, adding pine into a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml eutectic solvent, heating to 120 ℃ for reaction 1 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfonated carbon base accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Example 3 preparation of eutectic solvent: mixing hydrogen bond acceptor tetramethyl ammonium bromide 77.03 g and hydrogen bond donor formic acid 115.08 g in a beaker; sealing, heating and stirring at 60 ℃ at a stirring rate of 500 r/min until a uniform transparent liquid is formed, namely the eutectic solvent (DES); cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the application of the eutectic solvent in biorefinery comprises the following specific steps:
step one: crushing poplar to 40-60 meshes by a crusher; filling crushed poplar into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain a mixture of 9: 9 h;
step two: extracting poplar 3.0. 3.0 g, adding the poplar into a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml eutectic solvent, heating to 100 ℃ to react 1.5 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfated titanium oxide accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Example 4 preparation of eutectic solvent: mixing hydrogen bond acceptor tetramethyl ammonium bromide 77.03 g and hydrogen bond donor lactic acid 225.20 g in a beaker; sealing, heating and stirring at 60 ℃ at a stirring rate of 500 r/min until a uniform transparent liquid is formed, namely the eutectic solvent (DES); cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the application of the eutectic solvent in biorefinery comprises the following specific steps:
step one: crushing poplar to 40-60 meshes by a crusher; filling crushed poplar into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain a mixture of 9: 9 h;
step two: extracting poplar 3.0. 3.0 g, adding the poplar into a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml eutectic solvent, heating to 100 ℃ to react 1.5 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfated titanium oxide accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Example 5 preparation of eutectic solvent: mixing hydrogen bond acceptor tetramethyl ammonium bromide 77.03 g and hydrogen bond donor lactic acid 270.24 g in a beaker; sealing, heating and stirring at 60 ℃ at a stirring rate of 500 r/min until a uniform transparent liquid is formed, namely the eutectic solvent (DES); cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the application of the eutectic solvent in biorefinery comprises the following specific steps:
step one: crushing the xylose residues to 40-60 meshes by a crusher; filling the crushed xylose residue into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain 9 h;
step two: taking 3.0 g extracted xylose residues to a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml eutectic solvent, heating to 110 ℃ to react 1 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfonated carbon base accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Example 6 preparation of eutectic solvent: mixing hydrogen bond acceptor tetramethyl ammonium bromide 77.03 g and hydrogen bond donor lactic acid 270.24 g in a beaker; sealing, heating and stirring at 60 ℃ at a stirring rate of 500 r/min until a uniform transparent liquid is formed, namely the eutectic solvent (DES); cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the application of the eutectic solvent in biorefinery comprises the following specific steps:
step one: crushing the xylose residues to 40-60 meshes by a crusher; filling the crushed xylose residue into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain 9 h;
step two: taking 3.0 g extracted xylose residues to a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml eutectic solvent, heating to 110 ℃ to react 1.5 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfonated carbon base accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Example 7 preparation of eutectic solvent: mixing hydrogen bond acceptor tetramethyl ammonium bromide 77.03 g and hydrogen bond donor lactic acid 270.24 g in a beaker; sealing, heating and stirring at 60 ℃ at a stirring rate of 500 r/min until a uniform transparent liquid is formed, namely the eutectic solvent (DES); cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the application of the eutectic solvent in biorefinery comprises the following specific steps:
step one: crushing the xylose residues to 40-60 meshes by a crusher; filling the crushed xylose residue into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain 9 h;
step two: taking 3.0 g extracted xylose residues to a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml eutectic solvent, heating to 110 ℃ to react 2 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfonated carbon base accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Example 8 preparation of eutectic solvent: mixing hydrogen bond acceptor guanidine hydrochloride 95.53 g and hydrogen bond donor formic acid 276.18 g in a beaker; sealing, heating and stirring at 60 ℃ at a stirring rate of 500 r/min until a uniform transparent liquid is formed, namely the eutectic solvent (DES); cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the application of the eutectic solvent in biorefinery comprises the following specific steps:
step one: crushing the xylose residues to 40-60 meshes by a crusher; filling the crushed xylose residue into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain 9 h;
step two: taking 3.0 g extracted xylose residues to a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml eutectic solvent, heating to 100 ℃ to react 2 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfonated carbon base accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Example 9 preparation of eutectic solvent: mixing hydrogen bond acceptor guanidine tetrahydrochloride 95.53 g and hydrogen bond donor formic acid 276.18 g in a beaker; sealing, heating and stirring at 60 ℃ at a stirring rate of 500 r/min until a uniform transparent liquid is formed, namely the eutectic solvent (DES); cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the application of the eutectic solvent in biorefinery comprises the following specific steps:
step one: crushing the xylose residues to 40-60 meshes by a crusher; filling the crushed xylose residue into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain 9 h;
step two: taking 3.0 g extracted xylose residues to a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml eutectic solvent, heating to 120 ℃ to react 2 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfated titanium oxide accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Comparative example 1, lignin, furfural and glucose were prepared by the ionic liquid method, which comprises the following specific steps:
step one: crushing the xylose residues to 40-60 meshes by a crusher; filling the crushed xylose residue into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain 9 h;
step two: taking 3.0 g extracted xylose residues to a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml ethanolamine acetate solution, heating to 120 ℃ to react 2 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfated titanium oxide accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Comparative example 2, a dilute acid hydrolysis process for the preparation of lignin, furfural and glucose, comprises the following specific steps:
step one: pulverizing moso bamboo to 40-60 meshes by a pulverizer; filling crushed phyllostachys pubescens into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain 9 h;
step two: extracting Phyllostachys Pubescens 3.0. 3.0 g, adding into high temperature pressure bottle, adding rotor, and adding 45 ml 1.5% H 2 SO 4 Heating to 120 ℃ to react 2 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfated titanium oxide accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
Comparative example 3, lignin, furfural and glucose were prepared by the organic solvent method, which comprises the following specific steps:
step one: crushing poplar to 40-60 meshes by a crusher; filling crushed poplar into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting the cloth bag with a mixed solution of toluene and ethanol in a volume ratio of 2:1 to obtain a mixture of 9: 9 h;
step two: extracting poplar 3.0. 3.0 g, adding into a high-temperature pressure-resistant bottle, adding a rotor, then adding 45 ml of organic solvent, wherein the organic solvent comprises deionized water, acetone, formic acid and ethanol, heating to 120 ℃ to react 2 h, and stirring at a speed of 500 r/min; after the reaction is finished, cooling to room temperature to obtain a mixture after the reaction;
step three: transferring the mixture after reaction into a 50 ml centrifuge tube, and centrifuging for 5 min at 9000 rpm to separate solid from liquid after centrifugation and solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding sulfated titanium oxide accounting for 2% of the mass of the pretreatment liquid into the pretreatment liquid as a catalyst to perform catalytic reaction, wherein the catalytic reaction temperature is 120 ℃, the reaction time is 30 min, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; the washed solid was dried in an oven at 60℃for 24 h, followed by 48-h enzymatic hydrolysis at 50℃and 150 rpm to yield glucose.
DPPH antioxidant test was performed on the purified DES lignin of examples 1 to 9 and comparative examples 1 to 3, the antioxidant capacity of lignin samples was quantitatively evaluated by using 2, 2-biphenyl-1-picrylhydrazyl (DPPH) radical scavenging method, and the RSI value (radical scavenging index (RSI) was defined as IC 50 Can more visually represent the antioxidant result, and a higher RSI value represents a higher antioxidant activity); high performance liquid chromatography is used to detect examples 1-9 and comparative examples 1-pairsCalculating the furfural yield according to the concentration of the furfural in the proportion of 3; determining glucose yields after enzymolysis of examples 1-9 and comparative examples 1-3; the RSI values, furfural yields and glucose yields of examples 1-9 and comparative examples 1-3 are shown in Table 1,
TABLE 1 RSI values, furfural yields, and glucose yield results for examples 1-9 and comparative examples 1-3
As can be seen from comparative examples 1 to 9 and comparative examples 1 to 3, the application method of the eutectic solvent in biorefinery is that the antioxidant capacity RSI value, the furfural yield and the glucose yield of lignin are far higher than those of lignin of comparative examples 1 to 3; in addition, the application method of the eutectic solvent in biorefinery has the advantages of being environment-friendly, low in cost, easy to prepare and the like, and can mildly, cleanly and efficiently separate cellulose, lignin and hemicellulose and convert the cellulose, lignin and hemicellulose into glucose, furfural and nano lignin with oxidation resistance.
The present invention is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present invention will still fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. A method of using a eutectic solvent in biorefinery, comprising the steps of:
step one: pulverizing one or more of moso bamboo, poplar, pine and xylose residues into particles with the size of 20-80 meshes by using a pulverizer; loading the crushed particles into a cloth bag, placing the cloth bag into a Soxhlet extractor, and extracting 9 h by using a mixed solution of toluene and ethanol to obtain lignocellulose;
step two: mixing lignocellulose and eutectic solvent, putting the mixture into a reaction bottle, adding a rotor into the reaction bottle, and then moving the reaction bottle onto a reaction kettle for heating and stirring reaction; after the reaction is finished, a mixture after the reaction is obtained;
step three: centrifuging the mixture after reaction by using a centrifuge, and centrifuging the mixture for 5 min at 9000 rpm to separate solid from liquid, thereby obtaining centrifuged liquid and centrifuged solid after centrifugation;
preparing lignin: pouring the centrifuged liquid into a clean beaker, adding a proper amount of deionized water, centrifuging the centrifuged liquid and the deionized water by using a centrifuge, and centrifuging the centrifuge for 5 min under the condition of 9000 rpm to obtain centrifuged lignin and pretreatment liquid; freeze-drying 48 to h to obtain purified DES lignin;
preparing furfural: performing vacuum rotary evaporation on the pretreatment liquid at 60 ℃ to remove deionized water, adding a catalyst into the pretreatment liquid to perform catalytic reaction, and obtaining furfural after the catalytic reaction is finished;
glucose preparation: washing the centrifuged solid with deionized water until the washing liquid is clear and transparent and the pH value of the washing liquid reaches neutrality; drying the washed solid in an oven at 60 ℃ for 24 h, and then carrying out 48 h enzymolysis at 50 ℃ and 150 rpm to obtain glucose;
the eutectic solvent is prepared by the following method:
mixing a hydrogen bond acceptor and a hydrogen bond donor; reacting at the temperature of 30-60 ℃ and the stirring speed of 300 r-600 r/min until a uniform transparent liquid is formed, namely the eutectic solvent; cooling the eutectic solvent to room temperature and putting the eutectic solvent into a drying dish for standby;
the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:2-10;
the hydrogen bond acceptor is one or more of choline chloride, guanidine hydrochloride, betaine, tetramethyl ammonium chloride and tetramethyl ammonium bromide; the hydrogen bond donor is one or more of formic acid, oxalic acid, lactic acid, malic acid, glycolic acid and ethylene glycol;
the preparation reaction time of the eutectic solvent is 0.3 h-2.0 h.
2. The method of claim 1, wherein in the first step, the volume ratio of toluene to ethanol in the mixed solution is 2:1.
3. The method for applying the eutectic solvent to biorefinery according to claim 1, wherein in the second step, the volume ratio of lignocellulose to the eutectic solvent in the reaction bottle is 1:5-15; the heating reaction condition in the reaction kettle is that the temperature is raised to 80-120 ℃, the stirring rotation speed is 400 r-600 r/min, and the reaction time is 0.5-3.0 h.
4. The method for applying the eutectic solvent to biorefinery according to claim 1, wherein in the third step, when furfural is prepared, a catalyst for catalytic reaction is sulfonated carbon-based, sulfuric acid or sulfated titanium oxide; the catalytic reaction condition is that the temperature is 90-130 ℃ for 15-60 min; the addition amount of the catalyst is 2% of the mass of the pretreatment liquid.
5. The method of claim 1, wherein in the third step, the enzyme of the enzymolysis reaction is cellulase and the cellulase activity is 15 FPU/g.
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