CN101333777B - Method for high-efficiency hydrolyzing lignocellulose raw material in ionic liquid - Google Patents
Method for high-efficiency hydrolyzing lignocellulose raw material in ionic liquid Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 33
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 title claims description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010902 straw Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims abstract description 7
- 241000018646 Pinus brutia Species 0.000 claims abstract description 7
- 235000011613 Pinus brutia Nutrition 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
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- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 5
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- 239000001913 cellulose Substances 0.000 claims description 20
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- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- KUXCSJAUFRTLMW-UHFFFAOYSA-N 1-(2-chloroethyl)-3-methyl-2h-imidazole Chemical class CN1CN(CCCl)C=C1 KUXCSJAUFRTLMW-UHFFFAOYSA-N 0.000 claims description 3
- AUUAEUXIHPEPQR-UHFFFAOYSA-N C(C)C1=NC=CC=C1.[Br] Chemical compound C(C)C1=NC=CC=C1.[Br] AUUAEUXIHPEPQR-UHFFFAOYSA-N 0.000 claims description 3
- GQTNINQOCLGIQN-UHFFFAOYSA-N S(=O)(=O)(O)OS(=O)(=O)O.C(CCC)N1CN(C=C1)C Chemical compound S(=O)(=O)(O)OS(=O)(=O)O.C(CCC)N1CN(C=C1)C GQTNINQOCLGIQN-UHFFFAOYSA-N 0.000 claims description 3
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- GEMITLJMEMBDKW-UHFFFAOYSA-N hydrogen sulfate;1h-imidazol-3-ium Chemical compound C1=CNC=N1.OS(O)(=O)=O GEMITLJMEMBDKW-UHFFFAOYSA-N 0.000 claims description 3
- WUNVTWGPFJFCPH-UHFFFAOYSA-N [Cl].C(CCC)N1CN(C=C1)C Chemical compound [Cl].C(CCC)N1CN(C=C1)C WUNVTWGPFJFCPH-UHFFFAOYSA-N 0.000 claims description 2
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- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 4
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- 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 3
- 230000036983 biotransformation Effects 0.000 description 3
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- 239000011976 maleic acid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 150000004676 glycans Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical class CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 101710089042 Demethyl-4-deoxygadusol synthase Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
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- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
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Classifications
-
- 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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- Saccharide Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a method for hydrolyzing lignocellulose materials, in particular to a method for efficiently hydrolyzing the lignocellulosic materials in ionic liquid; and the ionic liquid is taken as a solvent, greater than or equal to 1mol equivalent of water serves as a reactant, and an inorganic acid or an organic acid from catalytic amount to chemometry is taken as a catalyst, the lignocellulose materials such as crop straws, pine powder are reacted under ordinary pressure and at a temperature of not above 100 DEG C for 2 minutes to 34 hours; after the reaction is finished, a hydrolysate is obtained by quenching action with cold water and neutralization with alkali, generating immediately; and the quantitative chemical analysis is conducted to the total reducing sugar in the hydrolysate, indicating that the yield of the reducing sugar can reach 81 percent maximally and the hydrolysis efficiency can reach 58 percent. Compared with the traditional method of hydrolysis, the method has advantaged of non pretreatment process, low acid consumption, mild reaction condition, high hydrolytic activity, fast reaction speed, low corrosion resistance requirements for a reactor, high yield of reducing sugar, and easy tracking of extent of reaction. The method opens a new way for solving the problem of full utilization of lignocellulose existing for a long time.
Description
Technical field
The present invention relates to the hydrolysis of lignocellulose, specifically a kind of in ionic liquid the method for effectively hydrolyzing lignocellulose raw material, be to be solvent with the ionic liquid that cellulose is had the excellent dissolution performance, simultaneously effectively hydrolyzing cellulose and hemicellulose under inorganic acid or organic acid catalysis effect obtain the method for soluble sugar.
Background technology
The lignocellulose resource is present in nature in a large number, is the abundantest on the earth, the most cheap and meets the renewable resource of sustainable development requirement.If the annual cellulosic material that is formed by photosynthesis on the earth is all effectively utilized, the energy that the energy that is produced is consumed considerably beyond the whole world every year.Yet, up to the present human very low to its utilization ratio, the annual living beings total amount about 2.9 * 10 that produces in the whole world
21Joule energy, but utilization rate just nearly 7%.
China's fiber wastes resource is very abundant.According to statistics, annual China produces 700,000,000 tons of agricultural crop straws, more than 400 ten thousand tons of bagasse, more than 1,000 ten thousand tons of forest harvesting processing fiber class residues.This fibrid material mainly is made of cellulose, hemicellulose and lignin three parts.Present above-mentioned fiber wastes is used for the production of products such as furfural, wood sugar, edible fungus except that small part, and major part is rationally utilized.Along with global economy constantly develops, energy shortage will be on the rise.Consider that from the strategy of sustainable development angle rational exploitation and utilization plant cellulose resource has been imperative.
The best approach that the lignocellulose resource is become clean energy resource and environmental friendliness chemical products is to be cellulose and hydrolysis of hemicellulose soluble sugar such as glucose, wood sugar, cellobiose etc. earlier, obtain other high value added product by conversion technology then, as: alcohol fuel, lactic acid, malic acid, biodiesel etc.In whole lignocellulose utilization of resources process, the internationally recognized key technical problem that needs to solve is: overcome the resistance of lignocellulose molecule to bio-transformation, macromolecular polysaccharide is degraded to fermentable sugars; By microbial metabolism engineering and genetic engineering research, carry out bio-transformation by fermentable sugars; Simple and direct, downstream process product isolation technics efficiently.Wherein, macromolecular polysaccharide being hydrolyzed to reducing sugar is maximum at present technology barrier.Because lignin and hemicellulose make lignocellulose form fine and close higher structure to cellulosic protective effect and cellulose self crystal structure closely in the natural plant fibre raw material, cause reagent low to the cellulose accessibility, hydrolysis efficiency is low.
Up to the present, the main approach of lignocellulose hydrolysis has enzyme hydrolysis and classical acid hydrolytic process, and all there are many imperfection parts in they, are difficult to realize large-scale application.As a rule, enzyme hydrolysis can be reacted at normal temperatures, and hydrolysising by-product is few, can be coupled with sweat, belongs to eco-friendly method; But there are problems such as hydrolysing activity is low, speed is slow, cost height.Single dilute acid hydrolysis process needs high temperature, high pressure, and hydrolysis rate is slow, can only the hydrolyzable moiety cellulose, and sugar yield is low.Developed continuous hydrolysis technology afterwards, adopted earlier dilute acid pretreatment technology hydrolyzed hemicellulose, with lime neutralisation treatment is carried out in acid remaining in the hydrolyzate after, collect the resulting liquid glucose of hydrolysis; Solid residue with the phase I hydrolysed residual dehydrates then, carries out concentrated acid again and handles, to reach abundant cellulolytic purpose (Iranmahboob, J.; Nadim, F.; Monemi, S.Biomass Bioenerg.2002,22,401-404.).The method can be handled multiple lignocellulosic material, can react at a lower temperature, has improved the hydrolysis rate and the conversion coefficient of lignocellulose to a certain extent.But also have a series of defectives: loaded down with trivial details, the sour consumption of hydrolysing step is big, seriously polluted.In a word, cellulose and hemicellulose while effectively hydrolyzing are remained the major technique economic obstacle that present lignocellulose resource conversion is utilized, be subjected to World Science circle and industrial circle and continue to show great attention to.
Recently, U.S. Rogers research group (Swatloski, R.P.; Spear, S.K.; Holbrey, J.D.; Et al.J.Am.Chem.Soc.2002,124,4974-4975.) reported that ionic liquid BMImCl is cellulosic good solvent, can dissolve the cellulose of 25wt% at most, form homogeneous phase solution.Since then, the ion liquid dissolving lignocellulosic material has begun to cause people's extensive concern (Zhu, S.D.; Wu, Y.; Chen, Q.; Et al.Green Chem.2006,8,325-327.).But the hydrolysis phenomenon of lignocellulosic material in ionic liquid all do not mentioned in above research.
Summary of the invention
The object of the present invention is to provide a kind of is the method for water-soluble sugar with the lignocellulose raw material effectively hydrolyzing in ionic liquid.The applicant thinks that conventional wooden cellulosic material method for hydrolysis efficient is not high, and main cause is to lack the solvent that raw material fully can be dissolved.Therefore, utilization of the present invention has the ionic liquid of strong solvability to be reaction medium to lignocellulosic material, and raw material is fully disperseed, increase contact area with catalyst, with catalytic amount acid effect, effectively hydrolyzing lignocellulosic obtains soluble sugar under mild operating conditions.
For achieving the above object, the technical solution used in the present invention is:
Ionic liquid with dissolved cellulose and hemicellulose is a solvent, water with 〉=1 molar equivalent is reactant, is catalyst with catalytic amount to stoichiometric inorganic acid or organic acid, and lignocellulose raw material reacted 2 minutes～34 hours in 80 ℃～100 ℃ under normal pressure; After reaction finishes,, promptly get ligno-cellulose hydrolysate with cold water cancellation reaction, with the alkali neutralization.
The use amount of described water is 10～100% of a lignocellulosic material quality; The use amount of acid is 2%～100% of a lignocellulosic material quality; The acid that this patent uses can be organic acids such as inorganic acid such as the commercially available concentrated sulfuric acid, concentrated hydrochloric acid, red fuming nitric acid (RFNA) or SPA or maleic acid.
Described ionic liquid is for there being the ionic liquid 1 of better solvability to cellulose and hemicellulose, 3-dialkylimidazolium or Fixanol, and its substituted alkyl chain length is C
1-C
4Alkyl chain, the anionicsite of salt is chlorine, bromine or bisulfate ion, as: 1-methyl-3-butyl imidazole chlorine (BMImCl), 1-methyl-3-imidazole-butyl bromide (BMImBr), 1-methyl-3-ethyl imidazol(e) bromine (EMImBr), 1-methyl-3-ethyl imidazol(e) chlorine (EMImCl), 1-methyl-3-(2-chloroethyl) imidazoles chlorine (CEMImCl), 1-methyl-3-allyl imidazole chlorine (AMImCl), 1-methyl-3-butyl imidazole disulfate (BMImHSO
4), 1-methyl-3-(4-sulfo group-butyl) imidazole bisulfate (SBMImHSO
4), 1-methyl-3-hexyl imidazoles chlorine (HMImCl), butyl-pyridinium chlorine (BPyCl) or ethylpyridine bromine (BPyBr).
Water-soluble sugar contains monose and cellobiose and other water-soluble oligosaccharides such as glucose, wood sugar, fructose, galactolipin, arabinose through ion chromatography in the hydrolyzate.
Water-soluble sugar in the described hydrolyzate can be separated by ion-exchange with ionic liquid;
Be specially: add hydrolyzate on cation seperation column, with deionized water drip washing, the separation case of thin layer chromatography monitoring glyoxaline cation and liquid glucose is collected water-soluble sugar.In the hydrolyzate water-soluble sugar comprise contain wood sugar, glucose, cellobiose, until oligosaccharides such as other cellulose six sugar.
The present invention has following advantage:
1. compare with traditional enzymatic hydrolysis process, the present invention need not preprocessing process, and the catalyst cost is low, and reaction speed is fast;
2. compare with continuous diluted acid-concentrated acid hydrolysis process, this method acid consumption significantly reduces, the operating condition gentleness, technology is simple, less demanding to the corrosion resistance of reactor, cost is low, environmental friendliness, extent of reaction follows the tracks of easily and control, accessory substance are few;
3. compare with dilute acid hydrolysis, but this method reaction condition gentleness, reaction speed are obviously accelerated the direct hydrolysis cellulose, sugar yield obviously improves;
In a word, compared with prior art, the present invention has plurality of advantages: need not preliminary treatment, technology is easy, reaction speed is fast, less demanding to the corrosion resistance of reactor, hydrolysing activity is high, extent of reaction is followed the tracks of easily and control, solved and under mild operating conditions, utilized catalytic amount acid effect, the technical barrier of effectively hydrolyzing lignocellulosic, for making full use of of lignocellulose opened up new way, has great application prospect aspect bioenergy and the bio-based chemicals obtaining.
The specific embodiment
Ionic liquid preparation: reference literature (Yin, D.H.; Li, C.; Li, B.; Et al.Adv.Synth.Catal.2005,347,137-142.Webb, P.B.; Sellin, M.F.; Kunen, T.E.; Et al.J.Am.Chem.Soc.2003,125,15577-15588.Noda, A.; Watanabe, M.Electrochimica Acta.2000,45,1265-1270.) and patent (WO 00/16902) preparation and purifying 11 kinds cellulose and hemicellulose had the ionic liquid of solvability by force, be used for the enforcement of patent of the present invention.
The lignocellulosic material that this patent embodiment uses has maize straw, straw, bagasse and pine powder, and their cellulose and hemicellulose total content are respectively: 58% (Liu, C.; Wyman, C.E.Bioresour.Technol.2005,96,1978-1985.), 59% (Jin, S.; Chen, H.Process Biochem.2007,42,188-192.), 74% (Matin, C.; Klinke, H.B.; Thomsen, A.B.Enzyme Microb.Technol.2007,40,426-432.) with 62% (vonSivers, M.; Zacchi, G.Bioresour.Technol.1995,51,43.).Above-mentioned data in literature is as the benchmark that calculates reducing sugar yield and hydrolysis efficiency.
The hydrolysis of lignocellulosic material: 4 gram-ion liquid add in 10 milliliters of round-bottomed flasks, are heated to 100 ℃, slowly add the dry lignocellulosic material of 0.20 gram～1.2 grams under the vigorous stirring, are stirred well to DDGS and all dissolve.At this moment, be that the water of 0.03 gram～0.2 gram adds reaction system with quality, be that 2%～90% concentrated acid of lignocellulosic material is a catalyst with the quality, under the normal pressure in 80 ℃～100 ℃ reactions 2 minutes～34 hours.Reaction finishes, and with cold water cancellation reaction, with the NaOH aqueous solution of 0.5mol/L reacting liquid pH value is transferred to 7.0, and hydrolyzate is with 3,5-dinitrosalicylic acid method (DNS method) mensuration total reducing sugars content.Reducing sugar yield and hydrolysis efficiency calculate by following formula respectively:
Wherein theoretical total reducing sugar quality equals that the summation of cellulose and hemicellulose quality multiply by 0.11 value in the raw material.
This method hydrolyzing lignocellulose raw material, the gained reducing sugar yield is up to 76%, and hydrolysis efficiency reaches 58%.
Embodiment 1:
4 gram-ion liquid B MImCl are added in 10 milliliters of round-bottomed flasks, be heated to 100 ℃, slowly add 0.2 gram, 40 purpose maize straws under the vigorous stirring, be stirred to all soluble fractions and all dissolve.At this moment, be that 0.03 water that restrains and 0.04 gram concentrated hydrochloric acid (36wt%) add in the reaction system successively fast with quality, reacted 30 minutes in 100 ℃ under the normal pressure.Reaction finishes, and with cold water cancellation reaction, with the NaOH of 0.5mol/L reacting liquid pH value is transferred to 7.0, and the gained hydrolyzate is with DNS method mensuration content of reducing sugar.Gained reducing sugar yield and hydrolysis efficiency are respectively 66% and 43%.
Embodiment 2～3:
Other process conditions and experimental procedure be with embodiment 1, but use the concentrated hydrochloric acid (36wt%) of different quality to be catalyst, and the cancellation reaction the results are shown in Table 1 under different time.Experimental result shows that the increase of acid amount can make hydrolysis rate accelerate.
Table 1 different quality hydrochloric acid catalysis maize straw hydrolysis result
| Project | Hydrochloric acid quality (g) | Reaction time (min) | Reducing sugar quality (mg) | Reducing sugar yield (%) | Hydrolysis efficiency (%) |
| Embodiment 2 | 0.21 | 10 | 83 | 65 | 42 |
| Embodiment 3 | 0.10 | 15 | 84 | 65 | 42 |
Embodiment 4～5:
Other process conditions and experimental procedure be with embodiment 1, but add water quality be respectively 0.1 gram, 0.2 gram.Stop hydrolysis at different time, the results are shown in Table 2.Experimental result shows that the increase as the water yield of reactant can cause reaction speed significantly to descend, but reducing sugar yield increases.This is because the increase of the water yield causes acid concentration to reduce in the reaction system, the reaction condition milder, thus make the reducing sugar degradation speed slack-off.
Water content is to the rule that influences of results of hydrolysis in table 2 reaction system
| Project | Water consumption (g) | Reaction time (min) | Reducing sugar quality (mg) | Reducing sugar yield (%) | Hydrolysis efficiency (%) |
| Embodiment 4 | 0.1 | 195 | 97 | 75 | 49 |
| Embodiment 5 | 0.2 | 225 | 98 | 76 | 49 |
Embodiment 6:
The maize straw and 0.1 that adds 0.66 gram restrains water as reactant, with 0.04 gram concentrated hydrochloric acid (36wt%) is catalyst, 100 ℃ of reactions 6.5 hours, other process conditions and experimental procedure were with embodiment 1, and gained reducing sugar yield and hydrolysis efficiency are respectively 64% and 41%.
Embodiment 7:
With 0.08 gram concentrated hydrochloric acid (36wt%) is catalyst, the maize straw and 0.2 that in batches adds 1.2 grams restrains water as reactant, 100 ℃ of reactions 8 hours, other process conditions and experimental procedure were with embodiment 1, and gained reducing sugar yield and hydrolysis efficiency are respectively 45% and 31%.
Embodiment 8:
Non-specified otherwise, other process conditions and experimental procedure are with embodiment 1, but the ionic liquid that uses is respectively 1-methyl-3-imidazole-butyl bromide (BMImBr), 1-methyl-3-ethyl imidazol(e) bromine (EMImBr), 1-methyl-3-ethyl imidazol(e) chlorine (EMImCl), 1-methyl-3-(2-chloroethyl) imidazoles chlorine (CEMImCl), 1-methyl-3-allyl imidazole chlorine (AMImCl), 1-methyl-3-butyl imidazole disulfate (BMImHSO
4), 1-methyl-3-(4-sulfo group-butyl) imidazole bisulfate (SBMImHSO
4), butyl-pyridinium chlorine (BPyCl), ethylpyridine bromine (EPyBr) etc. have the ionic liquid of big solvability to fiber.For anionicsite is HSO
4 -Ionic liquid, need not to add hydrochloric acid, ionic liquid is originally held and is done catalyst and solvent.Partial results is listed in table 3.
The maize straw hydrolysis is produced sugared result relatively in table 3 different ionic liquid
| Ionic liquid | Reaction time (min) | Reducing sugar quality (mg) | Reducing sugar yield (%) | Hydrolysis efficiency (%) |
| BMImBr | 60 | 60 | 47 | 30 |
| AMImCl | 30 | 82 | 64 | 41 |
| EPyBr | 6 | 52 | 40 | 26 |
| BMImHSO 4 | 5 | 30 | 23 | 15 |
| SBMImHSO 4 | 2 | 28 | 22 | 14 |
Embodiment 9～11:
Other process conditions and experimental procedure are with embodiment 1, but the lignocellulose raw material of use separate sources (all crossing 40 mesh sieves): straw, pine powder and bagasse.In different time cancellation reaction, results of hydrolysis sees Table 4.
The hydrolysis in hydrochloric acid/ion liquid system of the different lignocellulose raw materials of table 4 is produced sugared result relatively
| Project | The cellulose kind | Reaction time (min) | Reducing sugar quality (mg) | Reducing sugar yield (%) | Hydrolysis efficiency (%) |
| Embodiment 9 | Straw | 45 | 97 | 74 | 49 |
| Embodiment 10 | Pine powder | 50 | 105 | 81 | 53 |
| Embodiment 11 | Bagasse | 60 | 109 | 66 | 55 |
Embodiment 12～15
4 gram-ion liquid B MImCl are added in 10 milliliters of round-bottomed flasks, be heated to 100 ℃, 0.2 gram, 40 purpose maize straws are stirred to all soluble fractions and all dissolve.At this moment, being cooled to 80 ℃, is the water of 0.03 gram and the concentrated sulfuric acid (98wt%) of 0.04 gram with quality, adds fast successively in the reaction system, reacts 6 hours in 80 ℃ under the normal pressure.Reaction finishes, and with cold water cancellation reaction, subsequent processing steps is with embodiment 1 (this is embodiment 12).
Use the 0.1 gram concentrated sulfuric acid (98wt%) to be catalyst among the embodiment 13, reaction temperature is 80 ℃, and all the other process conditions are with embodiment 12.
Use the 0.1 gram concentrated sulfuric acid (98wt%) to be catalyst among the embodiment 14, reaction temperature is 100 ℃, and all the other process conditions are with embodiment 12.
Use the 0.2 gram concentrated sulfuric acid (98wt%) to be catalyst among the embodiment 15, reaction temperature is 100 ℃, and all the other process conditions are with embodiment 12.
Embodiment 12～15 results of hydrolysis see Table 5.
The hydrolysis of sulfuric acid catalysis maize straw is produced sugared result relatively in table 5 ionic liquid
| Project | Concentrated sulfuric acid quality (g) | Reaction temperature (℃) | Reaction time (min) | Reducing sugar yield (%) | Hydrolysis efficiency (%) |
| Embodiment 12 | 0.04 | 80 | 360 | 37 | 24 |
| Embodiment 13 | 0.1 | 80 | 90 | 58 | 37 |
| Embodiment 14 | 0.1 | 100 | 50 | 59 | 38 |
| Embodiment 15 | 0.2 | 100 | 5 | 44 | 28 |
Embodiment 16～18:
Use the lignocellulose raw material (～40 order) of separate sources: straw, pine powder and bagasse.With sulfuric acid is catalyst, and other process conditions and experimental procedure are with embodiment 13, and in different time cancellation reaction, results of hydrolysis sees Table 6.
The hydrolysis in sulfuric acid/ion liquid system of the different lignocellulose raw materials of table 6 is produced sugared result relatively
| Project | The cellulose kind | Reaction time (min) | Reducing sugar quality (mg) | Reducing sugar yield (%) | Hydrolysis efficiency (%) |
| Embodiment 16 | Straw | 15 | 94 | 72 | 47 |
| Embodiment 17 | Pine powder | 35 | 101 | 64 | 51 |
| Embodiment 18 | Bagasse | 60 | 116 | 70 | 58 |
Embodiment 19～21:
Be catalyst with 0.1 gram red fuming nitric acid (RFNA), SPA or maleic acid respectively, other condition is with embodiment 12, and the reaction different time the results are shown in Table 7.As seen, common inorganic acid and organic acid all have obvious catalysis to the lignocellulose raw material hydrolysis in ionic liquid.
The hydrolysis of different acid catalysis maize straw is produced sugared result relatively in table 7 ionic liquid
| Project | Catalyst | Reaction time | Reducing sugar quality (mg) | Reducing sugar yield (%) | Hydrolysis efficiency (%) |
| Embodiment 19 | Nitric acid (65-68wt%) | 40min | 93 | 73 | 47 |
| Embodiment 20 | Phosphoric acid (85wt%) | 34h | 57 | 44 | 29 |
| Embodiment 21 | Maleic acid (99%) | 23h | 76 | 59 | 38 |
Embodiment 22
Ionic liquid is as follows with the separation method of sugar:
Get 100 milliliters of cationic ion-exchange resins, earlier with the saturated NaCl solution soaking resin of 2 times of volumes 24 hours, as seen supernatant liquid flavescence was with the abundant rinsing of clear water.With 10 times of volume NaOH aqueous solution (5w/v%) drip washing, then extremely neutral with water wash, again with 10 times of volume hydrochloric acid solutions (5w/v%) drip washing.Totally three circulations so.At last with 10 times of volume NH
4The Cl aqueous solution (5w/v%) is washed pouring, is washed to the cation seperation column (NH that neutrality obtains activating again
4 +Type).
Cation seperation column (the NH that activation is good
4 +Type) contain 55 milligrams of ion liquid hydrolyzates of BMImCl after the adding neutralization, with deionized water drip washing, the separation case of thin layer chromatography monitoring glyoxaline cation and liquid glucose.The liquid glucose that separation is obtained merges, and concentrates, and measures content of reducing sugar with the DNS method.The reducing sugar separation yield is 92%.The separation method of sugar is similar with it in other ionic liquid lignocellulose raw material hydrolyzates.
By above embodiment as can be seen: the present invention for a kind of be solvent with the ionic liquid, be catalyst with inorganic acid or organic acid, the brand-new approach of effectively hydrolyzing lignocellulose raw material.Compared with prior art, it has significant advantage: lignocellulose raw material need not that preliminary treatment, technology are easy, mild condition, reaction speed are fast, the acid consumption less, to less demanding, the sugared yield height of the corrosion resistance of reactor.The present invention directly is converted into soluble sugar with lignocellulose raw material, has overcome the resistance of lignocellulose compound to bio-transformation, helps to solve the major technique obstacle of lignocellulose resource higher value application.The present invention is efficiently utilizing the lignocellulose resource, obtains bioenergy and the bio-based field of chemicals has broad application prospects.
Claims (4)
1. the method for a hydrolyzing lignocellulose raw material in ionic liquid, it is characterized in that: be solvent with the ionic liquid, with water is reactant, is catalyst with inorganic acid or organic acid, and lignocellulose raw material reacted 2 minutes～34 hours in 80 ℃～100 ℃ under normal pressure; After reaction finishes,, promptly get ligno-cellulose hydrolysate with cold water cancellation reaction, with the alkali neutralization;
The use amount of described water is 15%～300% of a lignocellulose raw material quality; The use amount of acid is 2%～100% of a lignocellulose raw material quality; Lignocellulose raw material and ion liquid mass ratio are 0.05～0.30.
2. it is characterized in that in accordance with the method for claim 1: described lignocellulose raw material is maize straw, wheat straw, straw, bagasse, pine powder and/or bamboo bits.
3. in accordance with the method for claim 1, it is characterized in that: described ionic liquid is the ionic liquid 1 that fiber is have better solvability, 3-dialkylimidazolium or Fixanol, and its substituted alkyl chain length is C
1-C
4Alkyl chain, the anionicsite of salt is chlorine, bromine or bisulfate ion.
4. it is characterized in that in accordance with the method for claim 1: described ionic liquid is 1-methyl-3-butyl imidazole chlorine, 1-methyl-3-imidazole-butyl bromide, 1-methyl-3-ethyl imidazol(e) bromine, 1-methyl-3-ethyl imidazol(e) chlorine, 1-methyl-3-(2-chloroethyl) imidazoles chlorine, 1-methyl-3-allyl imidazole chlorine, 1-methyl-3-butyl imidazole disulfate, 1-methyl-3-(4-sulfo group-butyl) imidazole bisulfate, butyl-pyridinium chlorine or ethylpyridine bromine.
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| CN102071266A (en) * | 2010-12-03 | 2011-05-25 | 江南大学 | Application of ionic liquid to preparation of reducing sugar by cellulose hydrolysis |
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| CN105039424B (en) * | 2015-07-07 | 2018-08-21 | 河南科技大学 | A method of producing ethyl alcohol using the biomass containing cellulose |
| CN106622285B (en) * | 2015-11-02 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of load type carbon based solid acid catalyst, preparation method and application |
| GB201520453D0 (en) * | 2015-11-20 | 2016-01-06 | Imp Innovations Ltd | Process |
| KR102246046B1 (en) * | 2019-08-16 | 2021-04-28 | 한국세라믹기술원 | Manufacturing method of mesoporous silica from biomass |
| CN110609004B (en) * | 2019-09-26 | 2022-08-02 | 武汉海关技术中心 | Analysis and detection method for chromium metal element in solid food sample |
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