CN115772273B - Method for pretreating lignocellulose biomass by using organic solution - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002028 Biomass Substances 0.000 title claims abstract description 23
- 229920005610 lignin Polymers 0.000 claims abstract description 54
- 239000001913 cellulose Substances 0.000 claims abstract description 46
- 229920002678 cellulose Polymers 0.000 claims abstract description 46
- 229940074076 glycerol formal Drugs 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 241000609240 Ambelania acida Species 0.000 claims description 7
- 239000010905 bagasse Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 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 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 241000209046 Pennisetum Species 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical group O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 2
- 238000007865 diluting Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- NTXMCEIJTGBYOK-UHFFFAOYSA-N O.CC1CCC(=O)O1 Chemical compound O.CC1CCC(=O)O1 NTXMCEIJTGBYOK-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a method for pretreating lignocellulose biomass by using an organic solution, which comprises the steps of dismantling and dissolving lignin and hemicellulose serving as raw materials in a glycerol formal system under mild conditions, synchronously blocking and stably dismantling lignin, and recovering lignin and hemicellulose step by step in the solution to further separate and extract each component in the lignocellulose biomass. The filter residue rich in cellulose component obtained by the invention has high cellulose content and is easy to be subjected to enzymolysis, conversion and utilization. The lignin component filter residue obtained by the method has high lignin content and rich beta-O-4 bonds, and is easy to depolymerize, convert and utilize. The invention has wide application range of raw materials, low pressure in the reaction process, and the solvent can be recycled, thereby effectively reducing the cost.
Description
Technical Field
The invention relates to the technical field of biomass energy conversion and utilization, in particular to a method for pretreating lignocellulose biomass by using an organic solution.
Background
Lignocellulosic biomass is a well-known renewable resource that can be converted into fuels, materials, and chemicals by biorefinery. However, the cellulose, hemicellulose and lignin components forming the lignocellulose biomass are mutually connected to form a compact and complex space three-dimensional structure, and each component is difficult to effectively and directly convert and utilize, so that the components are often required to be separated by a pretreatment means so as to be beneficial to the subsequent conversion and utilization of each component, the utilization efficiency of three components of the biomass is improved, and the biorefinery process of the lignocellulose biomass is realized.
In recent years, organic solvent pretreatment has been one of the main methods for achieving separation of components of lignocellulosic biomass. Patent CN106674538 discloses a method for separating and extracting cellulose, hemicellulose degrading sugar and lignin from bamboo, and provides a lignocellulose component separation process with gamma-valerolactone water solution as solvent under the action of acid; patent CN105484083 discloses a green process for separating lignocellulose components, which realizes the separation of lignocellulose components by pretreating biomass by irradiation and coupling tetrahydrofuran or gamma-valerolactone reaction; patent CN103711017 discloses a method for preparing cellulose and lignin by using high-boiling alcohol as a solvent under normal pressure ultrasonic assistance, and the cellulose and lignin in biomass are separated by digestion in a high-boiling alcohol solution at 130-140 ℃; patent CN111154817 discloses a method for efficiently separating lignocellulose by an ionic liquid-high-boiling alcohol composite system and performing enzymolysis, and the component separation efficiency of biomass is further improved by a multi-step composite pretreatment mode.
Although the lignocellulose structure can be effectively broken through by the method for separating the components of the organic solvent to realize the partial or complete separation of the components, the prior art often needs higher reaction temperature (150 ℃), the lignin components are seriously condensed (the reactivity is limited), the multistep pretreatment method brings the defects of solvent circulation, complex component separation process and the like, and the problems of high energy consumption, high environmental pressure and the like are easily generated in the actual application process.
Disclosure of Invention
The invention aims to provide a method for pretreating lignocellulose biomass by using an organic solution, which utilizes glycerol formal to complete the disassembly of hemicellulose and the dissolution of lignin which are biomass raw materials under mild conditions, synchronously end-capped and stably disassemble lignin, efficiently reserve cellulose component filter residues, break a dense structure of lignocellulose and realize the component separation of lignocellulose biomass.
The invention is realized by the following technical scheme:
a method for pretreating lignocellulosic biomass with an organic solution comprising the steps of:
lignocellulose biomass is used as a raw material, and the mass volume ratio of the raw material to the glycerol formal solution is 1g: (8-20) cm 3 Mixing; reacting at 80-140 ℃ for 0.1-3 h, and then separating solid from liquid to obtain the cellulose-rich componentFiltering residues and filtrate dissolved with hemicellulose and lignin; adjusting pH of the filtrate to be acidic, adding water for dilution, then carrying out solid-liquid separation to obtain lignin component filter residues, carrying out reduced pressure distillation on the filtrate, recovering glycerol formal and water, washing residue at the bottom of the kettle with ethanol, and separating to obtain hemicellulose component filter residues.
The glycerol formal solution consists of glycerol formal, water and a catalyst, wherein the volume fraction of the glycerol formal in the solution is (50-100)%, and the concentration of the catalyst in the solution is (0.02-0.2) mol/L; the catalyst is soluble acid, alkali or salt, wherein the acid can be inorganic acid such as sulfuric acid, hydrochloric acid or the like or organic acid such as formic acid, p-toluenesulfonic acid or the like; the alkali can be inorganic alkali such as sodium hydroxide, potassium hydroxide, etc., or organic alkali such as ethylenediamine, acetamide, etc.; the salt may be FeCl 3 、Al 2 (SO 4 ) 3 Cl 3 Iso-strong acid weak alkali salt or Na 3 PO 4 、CH 3 Strong alkali weak acid salts such as COONa.
The granularity of the lignocellulose biomass is 0.5-3 mm.
The pH of the filtrate is preferably 2, and the volume of added water is at least 5 times of the volume of the filtrate.
The lignocellulose biomass is plant or waste containing at least cellulose and lignin, and comprises energy plants such as pennisetum, forestry waste such as wood dust, agricultural waste such as straw, and processing waste of sugar (wine) factories such as bagasse and furfural residue.
The cellulose component filter residue can be used for preparing sugar by enzymolysis of cellulose.
The lignin component filter residue can be used for preparing phenol by depolymerizing lignin.
The beneficial effects of the invention are as follows:
(1) The glycerol formal used in the invention not only has excellent lignin dissolution capability, but also reduces the generation of carbocations in lignin molecules due to the end capping effect of aldehyde, thereby inhibiting the self-condensation reaction of lignin, realizing the pretreatment of lignocellulose biomass under mild conditions, and simultaneously maintaining the reactivity of separating lignin components.
(2) The filter residue rich in cellulose component obtained by the invention has high cellulose content and is easy to be subjected to enzymolysis, conversion and utilization.
(3) The lignin component filter residue obtained by the method has high lignin content and rich beta-O-4 bonds, and is easy to depolymerize, convert and utilize.
(4) The invention has wide application range of raw materials, low pressure in the reaction process, and the glycerol formal with high boiling point can be recycled, thereby effectively reducing the cost.
Detailed Description
The following is a further illustration of the invention and is not a limitation of the invention.
Example 1:
2g of corncob (containing 38.7% of cellulose, 31.4% of hemicellulose and 11.9% of lignin) with granularity of 3.0mm is taken as a raw material, and the mass volume ratio of the raw material to the glycerol formal solution is 1g:8cm 3 Adding a solution with the sulfuric acid concentration of 0.02mol/L and the glycerol formal volume fraction of 50% into a reactor; after 3 hours of reaction at 80 ℃, carrying out solid-liquid separation to obtain 1.07g (cellulose content 66.9%) of cellulose component filter residue; adjusting pH of the filtrate to 2, adding 5 times volume of water, and performing solid-liquid separation to obtain lignin component residue 0.07g (lignin content)>90% >; the filtrate is distilled under reduced pressure, glycerol formal and water are recovered, and residue at the bottom of the kettle is washed and filtered by ethanol to obtain hemicellulose component filter residue of 0.16g.
Example 2:
2g bagasse with granularity of 0.5mm (containing 40.1 percent of cellulose, 24.3 percent of hemicellulose and 18.2 percent of lignin) is taken as a raw material, and the mass volume ratio of the raw material to the glycerol formal solution is 1g:10cm 3 Adding a solution with the sulfuric acid concentration of 0.2mol/L and the glycerol formal volume fraction of 100% into a reactor; after 2 hours of reaction at 100 ℃, carrying out solid-liquid separation to obtain 0.82g (cellulose content 88.6%) of cellulose component filter residue; adjusting pH of the filtrate to 2, adding 5 times volume of water, and performing solid-liquid separation to obtain lignin component residue 0.26g (lignin content)>93% >; the filtrate is distilled under reduced pressure, glycerol formal and water are recovered, and residue at the bottom of the kettle is washed and filtered by ethanol to obtain hemicellulose component filter residue of 0.21g.
Comparative example 1:
reference example 2 was made with the difference that the glycerol formal solution was replaced by a gamma valerolactone solution.
2g bagasse with granularity of 0.5mm (containing 40.1 percent of cellulose, 24.3 percent of hemicellulose and 18.2 percent of lignin) is taken as a raw material, and the mass volume ratio of the raw material to the gamma-valerolactone solution is 1g:10cm 3 Adding a solution with the sulfuric acid concentration of 0.2mol/L and the gamma-valerolactone volume fraction of 100% into a reactor; after 2 hours of reaction at 100 ℃, carrying out solid-liquid separation to obtain 1.12g (cellulose content 66.5%) of cellulose component filter residue; adjusting pH of the filtrate to 2, adding 5 times volume of water, and performing solid-liquid separation to obtain lignin component residue 0.15g (lignin content)>93% >; and (3) distilling the filtrate under reduced pressure, recovering gamma-valerolactone and water, washing and filtering residue at the bottom of the kettle by ethanol, and obtaining hemicellulose component filter residue 0.19g.
Comparative example 2:
reference example 2 was made with the difference that tetrahydrofurfuryl alcohol solution was used instead of glycerol formal solution.
2g bagasse with granularity of 0.5mm (containing 40.1 percent of cellulose, 24.3 percent of hemicellulose and 18.2 percent of lignin) is taken as a raw material, and the mass volume ratio of the raw material to tetrahydrofurfuryl alcohol solution is 1g:10cm 3 Adding 100% tetrahydrofurfuryl alcohol solution with sulfuric acid concentration of 0.2mol/L into the reactor; after 2h of reaction at 100 ℃, carrying out solid-liquid separation to obtain 1.04g (cellulose content of 71.1%) of cellulose component filter residue; adjusting pH of the filtrate to 2, adding 5 times volume of water, and performing solid-liquid separation to obtain lignin component residue 0.19g (lignin content)>93% >; the filtrate is distilled under reduced pressure, tetrahydrofurfuryl alcohol and water are recovered, and residue at the bottom of the kettle is washed and filtered by ethanol to obtain hemicellulose component filter residue of 0.18g.
Example 3:
2g of poplar (containing 46.1% of cellulose, 12.7% of hemicellulose and 24.4% of lignin) with granularity of 0.5mm is taken as a raw material, and the mass volume ratio of the raw material to the glycerol formal solution is 1g:10cm 3 Adding a solution with the sulfuric acid concentration of 0.2mol/L and the glycerol formal volume fraction of 100% into a reactor; after reacting for 2 hours at 120 ℃, carrying out solid-liquid separation to obtain 1.21g (cellulose content of 71.2%) of cellulose component filter residue; adjusting pH of the filtrate to 2, adding 5 times volume of water, and separating solid from liquid to obtain lignin componentFilter residue 0.19g (lignin content)>93% >; the filtrate is distilled under reduced pressure, glycerol formal and water are recovered, and residue at the bottom of the kettle is washed and filtered by ethanol to obtain hemicellulose component filter residue 0.08g.
Example 4:
2g bagasse with granularity of 0.5mm (containing 40.1 percent of cellulose, 24.3 percent of hemicellulose and 18.2 percent of lignin) is taken as a raw material, and the mass volume ratio of the raw material to the glycerol formal solution is 1g:10cm 3 Adding a solution with the aluminum chloride concentration of 0.1mol/L and the glycerol formal volume fraction of 80% into a reactor; after reacting for 0.1h at 140 ℃, carrying out solid-liquid separation to obtain 1.09g (cellulose content 67.6%) of cellulose component filter residue; adjusting pH of the filtrate to 2, adding 5 times volume of water, and performing solid-liquid separation to obtain lignin component residue 0.18g (lignin content)>93% >; and (3) distilling the filtrate under reduced pressure, recovering glycerol formal and water, washing and filtering residues at the bottom of the kettle by ethanol, and obtaining 0.1g of hemicellulose component filter residues.
Example 5:
2g bagasse with granularity of 0.5mm (containing 40.1 percent of cellulose, 24.3 percent of hemicellulose and 18.2 percent of lignin) is taken as a raw material, and the mass volume ratio of the raw material to the glycerol formal solution is 1g:20cm 3 Adding a solution with the concentration of NaOH of 0.2mol/L and the volume fraction of glycerol formal of 60% into a reactor; after reacting for 2 hours at 80 ℃, carrying out solid-liquid separation to obtain 1.36g (cellulose content is 53.2%) of cellulose component filter residue; adjusting pH of the filtrate to 2, adding 5 times volume of water, and performing solid-liquid separation to obtain lignin component residue 0.23g (lignin content)>90% >; and (3) distilling the filtrate under reduced pressure, recovering glycerol formal and water, washing and filtering residues at the bottom of the kettle by ethanol, and obtaining 0.05g of hemicellulose component filter residues.
Example 6:
2g corncob (containing 38.7% of cellulose, 31.4% of hemicellulose and 11.9% of lignin) with granularity of 0.5mm is taken as a raw material, and the mass volume ratio of the raw material to the glycerol formal solution is 1g:20cm 3 Adding a solution with the CH3COONa concentration of 0.2mol/L and the glycerol formal volume fraction of 60% into a reactor; after reacting for 1h at 100 ℃, carrying out solid-liquid separation to obtain 1.40g (cellulose content 50.2%) of cellulose component filter residue; adjusting pH of the filtrate to 2, adding 5 times of bodyThe accumulated water was subjected to solid-liquid separation to obtain 0.14g of lignin component residue (lignin content)>90% >; the filtrate is distilled under reduced pressure, glycerol formal and water are recovered, and residue at the bottom of the kettle is washed and filtered by ethanol to obtain hemicellulose component filter residue of 0.07g.
Example 7:
taking the cellulose component filter residue in the example 2 as a raw material, adding 20FPU/g of cellulose CTec2 enzyme at a substrate concentration of 5%, and carrying out enzymolysis at 50 ℃ for 72 hours at a pH of=4.8, wherein the cellulose enzymolysis rate is 92.3%; the cellulose component filter residue of example 5 was used as a raw material, and 20FPU/g of the CTec2 enzyme of cellulose was added at a substrate concentration of 5%, pH=4.8, and enzymatic hydrolysis was performed at 50℃for 72 hours, with a cellulose enzymatic hydrolysis rate of 90.7%.
Example 8:
taking lignin component filter residues in the example 2 as raw materials, and reacting for 15 hours according to 0.5g of raw materials, 0.2g of ruthenium-carbon (5 wt%) catalyst, 20mL of methanol and 4MPa of hydrogen at 240 ℃, wherein the mass yield of the monophenol product is 31.5% by using gas chromatography combined with mass spectrometer analysis of the product; taking lignin component filter residues of comparative example 1 as raw materials, and reacting for 15 hours at 240 ℃ under the conditions of 0.5g of raw materials, 0.2g of ruthenium-carbon (5 wt%) catalyst, 20mL of methanol and 4MPa of hydrogen, wherein the mass yield of the monophenol product is 7.23% by using gas chromatography combined with mass spectrometer analysis of the product; the lignin component filter residue of comparative example 2 is taken as a raw material, and the quality yield of the monophenol product is 9.55% according to the conditions of 0.5g of raw material, 0.2g of ruthenium-carbon (5 wt%) catalyst, 20mL of methanol and 4MPa of hydrogen for 15 hours, and the product is analyzed by gas chromatography combined with a mass spectrometer.
Claims (9)
1. A method for pretreating lignocellulosic biomass with an organic solution, comprising the steps of:
lignocellulose biomass is used as a raw material, and the mass volume ratio of the raw material to the glycerol formal solution is 1g: (8-20) cm 3 Mixing; after reacting for 0.1-3 h at 80-140 ℃, carrying out solid-liquid separation to obtain filter residues containing cellulose components and filtrate containing hemicellulose and lignin; adjusting pH of the filtrate to acidity, diluting with water, performing solid-liquid separation to obtain lignin component residue, and distilling the filtrate under reduced pressureRecovering glycerol formal and water, washing residue at the bottom of the kettle with ethanol, and separating to obtain hemicellulose component filter residues;
the glycerol formal solution consists of glycerol formal, water and a catalyst, wherein the volume fraction of the glycerol formal in the solution is (50-100)%, and the concentration of the catalyst in the solution is (0.02-0.2) mol/L; the catalyst is soluble acid, alkali or salt.
2. The method for pretreating lignocellulosic biomass with an organic solution of claim 1, wherein the acid is an inorganic or organic acid; the alkali is inorganic alkali or organic alkali; the salt is strong acid weak alkali salt or strong alkali weak acid salt.
3. The method for pretreating lignocellulose biomass with an organic solution according to claim 2, wherein the inorganic acid is sulfuric acid or hydrochloric acid, and the organic acid is formic acid or p-toluenesulfonic acid; the inorganic alkali is sodium hydroxide or potassium hydroxide, and the organic alkali is ethylenediamine or acetamide; the strong acid weak alkali salt is FeCl 3 Or Al 2 (SO 4 ) 3 Cl 3 The strong alkali weak acid salt is Na 3 PO 4 Or CH (CH) 3 COONa。
4. A method of pretreating lignocellulosic biomass with an organic solution according to claim 1, 2 or 3, wherein the filtrate has a pH of 2 and the volume of water added is at least 5 times the volume of the filtrate.
5. A method for pretreating lignocellulosic biomass with an organic solution according to claim 1, 2 or 3, wherein the lignocellulosic biomass has a particle size of 0.5-3 mm.
6. The method for pretreating lignocellulosic biomass by an organic solution of claim 4, wherein the lignocellulosic biomass has a particle size of 0.5-3 mm.
7. A method for pretreating lignocellulosic biomass with an organic solution according to claim 1 or 2 or 3 or 6, wherein the lignocellulosic biomass is a plant or waste comprising at least cellulose and lignin.
8. The method for pretreating a lignocellulosic biomass with an organic solution of claim 4, wherein the lignocellulosic biomass is a plant or waste comprising at least cellulose and lignin.
9. The method for pretreating lignocellulose biomass with an organic solution according to claim 7, wherein the lignocellulose biomass is one or more than two of pennisetum, wood chips, straw, bagasse and furfural residue.
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| CN111630136A (en) * | 2018-04-30 | 2020-09-04 | 绿色技术研究有限公司 | Method for treating bio-based materials and apparatus for treating said bio-based materials |
| CN114085876A (en) * | 2021-11-22 | 2022-02-25 | 浙江理工大学 | Method for comprehensively utilizing lignocellulose by using polyol-based acidic eutectic solvent |
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| CN104164801A (en) * | 2014-08-06 | 2014-11-26 | 复旦大学 | Method for separating and recycling cellulose, semicellulose and lignin in lignocellulosic biomass at one time |
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