CN102071266A - Application of ionic liquid to preparation of reducing sugar by cellulose hydrolysis - Google Patents
Application of ionic liquid to preparation of reducing sugar by cellulose hydrolysis Download PDFInfo
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- CN102071266A CN102071266A CN 201010571207 CN201010571207A CN102071266A CN 102071266 A CN102071266 A CN 102071266A CN 201010571207 CN201010571207 CN 201010571207 CN 201010571207 A CN201010571207 A CN 201010571207A CN 102071266 A CN102071266 A CN 102071266A
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- ionic liquid
- reducing sugar
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- cellulose hydrolysis
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Abstract
The invention relates to dissolution of straws and hydrolysis of celluloses, in particular to a method for preparing reducing sugar by dissolving the straws and hydrolyzing the celluloses in ionic liquid. The method comprises the following steps of: adding 1-ethyl-3-methylimidazole acetate serving as a straw solvent into Fe3+-containing aqueous solution and reacting in the presence of acidic ionic liquid serving as a catalyst under normal pressure at the temperature of between 110 and 140 DEG C for 0.5 to 5 hours; quenching with cold water; neutralizing with alkali liquor to prepare cellulose hydrolyzate; and measuring reducing sugar content by a 3,5-dinitrosalicylic acid method, wherein the reducing sugar in the hydrolyzate and the ionic liquid can be separated by an ion exchange method and the ionic liquid can be repeatedly used. Experiment results show that the reducing sugar yield is up to 93 percent to the maximum extent. Compared with the conventional straw cellulose hydrolysis method, the method has the advantages of solving the problems of complicated pretreatment, low hydrolysis activity, high corrosion to equipment, high cellulose solvent viscosity, inconvenience of operation and the like and providing a new approach for full utilization of the straws.
Description
Technical field
The present invention relates to the dissolving and the cellulosic hydrolysis of stalk, is solvent with the ionic liquid that stalk is had the excellent dissolution ability specifically, adds to contain Fe
3+The aqueous solution, hydrocellulose under presence of acidic ionic liquid catalyst obtains the method for reducing sugar.
Background technology
Because a large amount of, the immoderate use of fossil oil has caused problems such as energy dilemma and environmental degradation, make human dual-pressure in the face of energy and environment, therefore, the human renewable energy source of being badly in need of seeking a kind of environmental protection.The agricultural crop straw output of China is about 700,000,000 tons/year, occupies first place in the world.The main component of stalk is Mierocrystalline cellulose, hemicellulose and xylogen, is a kind of renewable resources of preciousness.At present, China's stalk main application is papermaking, feed, the also field and the use that acts as a fuel, and is in the situation of high flow rate, high pollution, low output fully.The straw utilization rate is about 33%, and wherein major part does not add processing, only accounts for 2.6% through what utilize after the technical finesse.Therefore, the comprehensive utilization agricultural crop straw is for economizing on resources, protect environment, increasing farmers' income, promote the Sustainable development of agricultural all to have important practical significance.
Mierocrystalline cellulose is to pass through β-1,4 glycosidic link macromolecular compound that couple together, that have linear structure with D-glucopyranose base, its complex structure, and inside exists a large amount of crystalline regions, non-crystalline region structure and hydrogen bond, makes solvent low to cellulosic accessibility.Common solvent is difficult to dissolving cellulos, has caused the obstacle of cellulose resource utilization.Developing effective cellosolve system is the key that solves this difficult problem.For cellulose hydrolysis, traditional method is to use cellulase hydrolysis or mineral acid hydrolysis.Enzymic hydrolysis can at room temperature be carried out, and hydrolysising by-product is few, but the hydrolysis efficiency of this method is low, speed is slow, and cellulase costs an arm and a leg and can't reclaim to use and cause cost higher.Use mineral acid hydrolysis to use sulphuric acid hydrolysis usually, sulfuric acid is serious to equipment corrosion, and is higher to equipment requirements, and degraded product is many, the trouble of aftertreatment simultaneously, and environmental pollution is serious.
Ionic liquid is green solvent and catalyzer, and it is used as the focus of studying.Discovery 1-ethyl-3-Methylimidazole acetate such as the chemistry Zhang Jun of institute of the Chinese Academy of Sciences were cellulosic fine solvents in 2005, can dissolve the Mierocrystalline cellulose of 25wt% at most, formed homogeneous phase solution.Recently, the researchist points out that 1-ethyl-3-Methylimidazole acetate also has good dissolving ability to xylogen, (Fu, D.; Mazza, G.; Tamaki, Y., Lignin Extraction from Straw by Ionic Liquids and Enzymatic Hydrolysis of the Cellulosic Residues.J.Agric.Food Chem 2010,58 (5), 2915-2922.); The Jiang Feng of the Chemistry and Physics Institute of university of the Chinese Academy of Sciences etc. as solvent, have realized cellulosic green homogeneous hydrolysis with acidic ion liquid as catalyzer with [bmim] Cl ionic liquid.But [bmim] Cl viscosity is too big, and inconvenient operation when industrial production has also increased cost though added cosolvent reduction viscosity.Therefore, the objective of the invention is to use viscosity ionic liquid very low, that Mierocrystalline cellulose and xylogen are had the excellent dissolution ability simultaneously, add and contain Fe as the stalk solvent
3+The aqueous solution, acidic ion liquid is a catalyzer, makes the green homogeneous hydrolysis of Mierocrystalline cellulose, reaches higher hydrolysis efficiency.
Summary of the invention
The method that the purpose of this invention is to provide the application of a kind of ionic liquid in cellulose hydrolysis.
For achieving the above object, the technical scheme taked of the present invention is:
With 1-ethyl-3-Methylimidazole acetate is the stalk solvent, adds to contain Fe
3+The aqueous solution, acidic ion liquid is a catalyzer, under normal pressure, react 0.5～5h in 110 ℃～140 ℃, promptly get cellulosic hydrolysate with cold water cancellation reaction, alkali lye neutralization, use 3,5-dinitrosalicylic acid method is surveyed reducing sugar content, and the reducing sugar in the hydrolyzed solution can be separated by ion exchange method with ionic liquid, and ionic liquid can be reused.
The described Fe that contains
3+The amount of the aqueous solution be 2～4 times of corresponding glucose molar equivalent; Contain Fe
3+The concentration of the aqueous solution be C (
Fe 3+)=0.025～0.1mol/L; The quality of catalyzer is that 100～400% stalks of stalk quality and the mass ratio of solvent are 0.04～0.25.
Wherein, the stalk solvent is 1-ethyl-3-Methylimidazole acetate, and catalyzer is 1-methyl-3-(4-sulfonic group butyl) imidazole bisulfate, 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate, 1-methyl-3-(4-sulfonic group butyl) imidazoles villaumite, 1-methyl-3-(3-sulfonic group propyl group) imidazoles villaumite.
Described method, wherein, the oil bath reacting by heating.
Described method, wherein, ionic liquid reclaims and uses.
The present invention has following advantage:
1. the viscosity of stalk solvent is very low, need not to add cosolvent, and is easy to operate, is convenient to industrial production;
2.Fe3+ cellulosic acid hydrolysis is had promoting catalysis, can improve the productive rate of reducing sugar;
3. ionic liquid stable performance can be reclaimed use, and the aftertreatment cost is low, environmental friendliness;
4. the catalytic performance of ionic-liquid catalyst is good, and speed of response is fast, reaction conditions gentleness, hydrolysis productive rate height.
Embodiment
According to the synthetic method of relevant ions liquid, the preparation and purifying ionic liquid, simultaneously stalk is carried out mechanical disintegration, drying, be used for the enforcement of patent of the present invention.
Utilize the ionic liquid of preparation to carry out stalk dissolving and cellulose hydrolysis, lifting down, its ultimate principle of example explanation is: 1-ethyl-3-Methylimidazole acetate is added in the round-bottomed flask, and the oil bath heating slowly adds stalk under the vigorous stirring, be stirred to the stalk dissolving, will contain Fe
3+The aqueous solution and catalyzer add reaction system, get a certain amount of reaction solution at set intervals, with cold water cancellation reaction, supernatant liquor is got in the alkali lye neutralization after the centrifugation, with 3,5-dinitrosalicylic acid method (DNS method) mensuration total reducing sugars content.Present method records reducing sugar yield and reaches as high as 93%.Reducing sugar sugar in the hydrolyzed solution can be separated by ion exchange method with ionic liquid, and ionic liquid can be reused.
The present invention will be further described below in conjunction with embodiment, is not limitation of the invention.
Embodiment 1:
15 gram 1-ethyl-3-Methylimidazole acetate being added in the round-bottomed flask, be heated to 140 ℃, slowly add 0.6 gram stalk under the vigorous stirring, be stirred to the stalk dissolving, is the Fe that contains of 0.11 gram with quality
3+The aqueous solution (C
(Fe3+)=0.025mol/L) and 0.6 gram 1-methyl-3-(4-sulfonic group butyl) imidazole bisulfate add reaction system, get a certain amount of reaction solution at set intervals, react with the cold water cancellation, with the NaOH of 0.5mol/L the pH of reaction solution is transferred to 7.0, get supernatant liquor after the centrifugation, measure total reducing sugars content with the DNS method.Method records reaction 4h thus, and reducing sugar yield is 85%.
Embodiment 2～4:
Other processing condition and experimental procedure are 150% of corresponding stalk quality with embodiment 1 but use the stalk and the catalyst quality of different mass, survey reducing sugar in the different time sampling, and results of hydrolysis sees Table 2.Proof is guaranteeing stalk fully under the dissolved situation, and its meltage does not have to influence to results of hydrolysis substantially.
The meltage of table 1 stalk in ionic liquid is to the influence of results of hydrolysis
| Project | Stalk quality (g) | Hydrolysis time (h) | Reducing sugar yield (%) |
| Embodiment 2 | ?1.5? | ?3.5? | 84? |
| Embodiment 3 | ?2.25? | ?3.5? | 82? |
| Embodiment 4 | ?3.75? | ?3.5? | 80? |
Embodiment 5:
15 gram 1-ethyl-3-Methylimidazole acetate being added in the round-bottomed flask, be heated to 140 ℃, slowly add 0.6 gram stalk under the vigorous stirring, be stirred to the stalk dissolving, is the Fe that contains of 0.11 gram with quality
3+The aqueous solution (C
(Fe3+)=0.025mol/L) and 1.2 gram 1-methyl-3-(4-sulfonic group butyl) imidazole bisulfates add reaction systems, get a certain amount of reaction solution at set intervals, react with the cold water cancellation, with the NaOH of 0.5mol/L the pH of reaction solution is transferred to 7.0, get supernatant liquor after the centrifugation, measure total reducing sugars content with the DNS method.Method records reaction 3h thus, and reducing sugar yield is 89%.
Embodiment 6:
15 gram 1-ethyl-3-Methylimidazole acetate being added in the round-bottomed flask, be heated to 140 ℃, slowly add 0.6 gram stalk under the vigorous stirring, be stirred to the stalk dissolving, is the Fe that contains of 0.22 gram with quality
3+The aqueous solution (C
(Fe3+)=0.0375mol/L) and 1.2 gram 1-methyl-3-(4-sulfonic group butyl) imidazole bisulfates add reaction systems, get a certain amount of reaction solution at set intervals, react with the cold water cancellation, with the NaOH of 0.5mol/L the pH of reaction solution is transferred to 7.0, get supernatant liquor after the centrifugation, measure total reducing sugars content with the DNS method.Method records reaction 3h thus, and reducing sugar yield is 93%.
Claims (6)
1. ionic liquid prepares application in the reducing sugar at cellulose hydrolysis, and it is characterized in that: with the ionic liquid that can dissolve stalk is solvent, adds to contain Fe
3+The aqueous solution, acidic ion liquid is a catalyzer, in 110 ℃～140 ℃ reaction 0.5～5h, promptly get cellulosic hydrolysate with cold water cancellation reaction, alkali lye neutralization under normal pressure, uses 3,5-dinitrosalicylic acid method (DNS method) survey reducing sugar content.
2. ionic liquid according to claim 1 prepares application in the reducing sugar at cellulose hydrolysis, it is characterized in that: the described Fe of containing
3+The amount of the aqueous solution be 2～4 times of corresponding glucose molar equivalent; Contain Fe
3+The concentration of the aqueous solution be C (
Fe 3+)=0.025～0.1mol/L; The quality of catalyzer is 100～400% of a stalk quality; The mass ratio of stalk and solvent is 0.04～0.25.
3. ionic liquid according to claim 1 prepares application in the reducing sugar at cellulose hydrolysis, it is characterized in that: solvent is for there being the ionic liquid 1-ethyl-3-Methylimidazole acetate ([emim] Ac) of excellent dissolution ability to stalk, its structural formula is as follows.
4. ionic liquid according to claim 1 prepares application in the reducing sugar at cellulose hydrolysis, and it is characterized in that: acidic ionic liquid catalysts is 1-methyl-3-(4-sulfonic group butyl) imidazole bisulfate, 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate, 1-methyl-3-(4-sulfonic group butyl) imidazoles villaumite, 1-methyl-3-(3-sulfonic group propyl group) imidazoles villaumite.
5. ionic liquid according to claim 1 prepares application in the reducing sugar at cellulose hydrolysis, and it is characterized in that: the reducing sugar in the hydrolyzed solution can be separated by ion exchange method with ionic liquid, and ionic liquid can be reused.
6. ionic liquid according to claim 1 prepares application in the reducing sugar at cellulose hydrolysis, it is characterized in that: use the oil bath heating.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102288596A (en) * | 2011-07-06 | 2011-12-21 | 四川理工学院 | Method for measuring reducing sugar concentration with flow chemical analyzer |
| CN102660881A (en) * | 2012-05-09 | 2012-09-12 | 北京林业大学 | Method for efficiently separating lignin |
| CN102675264A (en) * | 2012-05-22 | 2012-09-19 | 江南大学 | Method for preparing 5-hydroxymethylfurfural (HMF) by hydrolyzing cellulose by using binuclear ionic liquid as catalyst |
| CN102719569A (en) * | 2012-06-11 | 2012-10-10 | 上海大学 | Method for preparing glucose by cellulose hydrolysis in water/ionic liquid binary system |
| CN102989513A (en) * | 2012-11-28 | 2013-03-27 | 华中农业大学 | Acidic ionic liquid catalyst, synthesis method thereof, and method for catalyzing microcrystalline cellulose hydrolysis |
| CN103409566A (en) * | 2013-08-26 | 2013-11-27 | 重庆大学 | Method for degrading lignocellulose to generate reducing sugar |
| CN103549304A (en) * | 2013-11-04 | 2014-02-05 | 西南大学 | Method for increasing content of water-soluble dietary fiber in bean dregs by virtue of ionic liquid |
| CN104450983A (en) * | 2014-12-24 | 2015-03-25 | 江南大学 | Method for producing reducing sugar by cellulose |
| CN105039424A (en) * | 2015-07-07 | 2015-11-11 | 河南科技大学 | Method for producing ethanol from biomass containing cellulose |
| CN109627347A (en) * | 2018-12-12 | 2019-04-16 | 怀化学院 | The preprocess method of cellulose |
| CN109932362A (en) * | 2019-04-01 | 2019-06-25 | 中国科学院过程工程研究所 | The test method of content of reducing sugar in a kind of ion liquid system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333777A (en) * | 2007-06-27 | 2008-12-31 | 中国科学院大连化学物理研究所 | Method for high-efficiency hydrolyzing lignocellulose raw material in ionic liquid |
| CN101514375A (en) * | 2008-02-20 | 2009-08-26 | 青岛生物能源与过程研究所 | Method for preparing reducing sugar by catalyzing hydrocellulose |
| CN101597654A (en) * | 2009-06-23 | 2009-12-09 | 云天化集团有限责任公司 | A kind of method of utilizing protoplasm material to prepare reducing sugar |
-
2010
- 2010-12-03 CN CN 201010571207 patent/CN102071266A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333777A (en) * | 2007-06-27 | 2008-12-31 | 中国科学院大连化学物理研究所 | Method for high-efficiency hydrolyzing lignocellulose raw material in ionic liquid |
| CN101514375A (en) * | 2008-02-20 | 2009-08-26 | 青岛生物能源与过程研究所 | Method for preparing reducing sugar by catalyzing hydrocellulose |
| CN101597654A (en) * | 2009-06-23 | 2009-12-09 | 云天化集团有限责任公司 | A kind of method of utilizing protoplasm material to prepare reducing sugar |
Non-Patent Citations (1)
| Title |
|---|
| 《催化学报》 20090415 姜锋等 酸性离子液中纤维素的水解 279-283 1-6 第30卷, 第04期 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102288596A (en) * | 2011-07-06 | 2011-12-21 | 四川理工学院 | Method for measuring reducing sugar concentration with flow chemical analyzer |
| CN102660881B (en) * | 2012-05-09 | 2015-04-01 | 北京林业大学 | Method for efficiently separating lignin |
| CN102660881A (en) * | 2012-05-09 | 2012-09-12 | 北京林业大学 | Method for efficiently separating lignin |
| CN102675264A (en) * | 2012-05-22 | 2012-09-19 | 江南大学 | Method for preparing 5-hydroxymethylfurfural (HMF) by hydrolyzing cellulose by using binuclear ionic liquid as catalyst |
| CN102719569A (en) * | 2012-06-11 | 2012-10-10 | 上海大学 | Method for preparing glucose by cellulose hydrolysis in water/ionic liquid binary system |
| CN102989513B (en) * | 2012-11-28 | 2015-02-04 | 华中农业大学 | Acidic ionic liquid catalyst, synthesis method thereof, and method for catalyzing microcrystalline cellulose hydrolysis |
| CN102989513A (en) * | 2012-11-28 | 2013-03-27 | 华中农业大学 | Acidic ionic liquid catalyst, synthesis method thereof, and method for catalyzing microcrystalline cellulose hydrolysis |
| CN103409566A (en) * | 2013-08-26 | 2013-11-27 | 重庆大学 | Method for degrading lignocellulose to generate reducing sugar |
| CN103549304A (en) * | 2013-11-04 | 2014-02-05 | 西南大学 | Method for increasing content of water-soluble dietary fiber in bean dregs by virtue of ionic liquid |
| CN103549304B (en) * | 2013-11-04 | 2015-08-12 | 西南大学 | Ionic liquid is utilized to improve the method for water-soluble dietary fibers in bean dregs content |
| CN104450983A (en) * | 2014-12-24 | 2015-03-25 | 江南大学 | Method for producing reducing sugar by cellulose |
| CN105039424A (en) * | 2015-07-07 | 2015-11-11 | 河南科技大学 | Method for producing ethanol from biomass containing cellulose |
| CN109627347A (en) * | 2018-12-12 | 2019-04-16 | 怀化学院 | The preprocess method of cellulose |
| CN109627347B (en) * | 2018-12-12 | 2021-04-09 | 怀化学院 | Pretreatment method of cellulose |
| CN109932362A (en) * | 2019-04-01 | 2019-06-25 | 中国科学院过程工程研究所 | The test method of content of reducing sugar in a kind of ion liquid system |
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Application publication date: 20110525 |