CN102719569A - Method for preparing glucose by cellulose hydrolysis in water/ionic liquid binary system - Google Patents
Method for preparing glucose by cellulose hydrolysis in water/ionic liquid binary system Download PDFInfo
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- CN102719569A CN102719569A CN2012101889593A CN201210188959A CN102719569A CN 102719569 A CN102719569 A CN 102719569A CN 2012101889593 A CN2012101889593 A CN 2012101889593A CN 201210188959 A CN201210188959 A CN 201210188959A CN 102719569 A CN102719569 A CN 102719569A
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Abstract
The invention relates to a method for preparing reducing sugar by cellulose hydrolysis under environment-friendly conditions and belongs to the technical field of use of reproducible biomass resources. In a water/ionic liquid binary system, cellulose is hydrolyzed under green and mild conditions without acid serving as catalyst, so that a degradation product mainly comprising the glucose is obtained. Ionic liquid-chlorinated imidazole salt which is high in dissolving capability to the cellulose and water form the binary system, and cellulose hydrolysis is accelerated by the aid of the feature of the binary system capable of well promoting the cellulose to be dissolved into mixed liquid. The hydrolysis rate of the microcrystalline cellulose ranges from 60% to 90% and yield of the glucose ranges from 45% to 70% when hydrolysis reaction is carried out with the mass ratio of water to the ionic liquid of 0.1 to 0.4, at the reaction temperature of 120-160 DEG C and with reaction time of 4-8h.
Description
Technical field
The present invention relates to a kind ofly prepare the method for reducing sugar, belong to reproducible technical field of biomass resource utilization with Mierocrystalline cellulose hydrolysis under eco-friendly condition.
Background technology
Water insoluble and the common organic solvents of Mierocrystalline cellulose (cellulose) is the renewable resources that occurring in nature extensively exists.According to estimates, reach 1,000 hundred million ton or more through biosynthetic Mierocrystalline cellulose every year on the earth, and in the Mierocrystalline cellulose of consumption, nearly 1,000,000,000 tons of quilts are used as fuel and building log, and papermaking consumes about 1.0 hundred million tons in addition, and weaving consumes about 0.12 hundred million tons.Under the situation of petrochemical industry resource growing tension, how to make full use of this renewable resources, make its substitute that becomes the petrochemical industry resource become the problem of being badly in need of research.
The macromolecule polysaccharide that Mierocrystalline cellulose mainly is made up of glucose can obtain reducing sugar through hydrolysis, is that alcohol fuel, the treatment process of being paid close attention at present mainly contain acid and alkali hydrolysis, enzymic hydrolysis and ultra (closely) critical hydrolysis thereby be converted into industrial chemicals or ferment.
Acid and alkali hydrolysis not only can bring pollution problem, and can cause big corrodibility to equipment, receives very big restriction in the application.
Enzymic hydrolysis is because enzyme has high selectivity, different enzyme require corresponding conditions, very big for the present difficulty of natural cellulose effectively hydrolyzing of complicacy.
Mierocrystalline cellulose surpasses (closely) critical hydrolysis; Because it just can rapidly and efficiently make cellulose hydrolysis without catalyzer; Has good application prospects as a kind of eco-friendly friendly process process; But owing to carry out extreme high-temperature and high-pressure conditions, the very big difficulty of industrial applications existence at present usually at about 300 ℃ near-critical water or even above in 374 ℃ the supercritical water.And the further reaction easily under HTHP of the reducing sugar of hydrolysis generation, sub product is many, and the separation of reducing sugar is purified all very difficult.
Based on present Research; The present invention sets about with the dispersing and dissolving that augmentor fiber is plain, in water/ionic liquid binary system through adding ionic liquid; Cellulose dissolution is formed in liquid phase on the basis of homogeneous system, under mild conditions, accelerate cellulose hydrolysis and prepare glucose.In addition, the mixed system of ionic liquid and water can increase the dissociation equilibrium constant K w of water, makes H in the system
+And OH
-Ionic concentration improves, and also utilizes cellulosic hydrolysis.
Summary of the invention
The purpose of this invention is to provide a kind of in water/ionic liquid binary system cellulose hydrolysis prepare the method for glucose.
The present invention is the method that cellulose hydrolysis prepares glucose in a kind of water/ionic liquid binary system, it is characterized in that having three steps, is respectively that raw materials pretreatment, hydrolysis and product separate;
raw materials pretreatment: Mierocrystalline cellulose 80 ± 5 ℃ of dryings, be crushed to 20~40 orders;
The b hydrolysis reaction: dried cellulose powder, ionic liquid, water are added in the reaction kettle by corresponding proportion, and design temperature, makes cellulose hydrolysis make glucose at reaction for some time; Used ionic liquid is [Amim] Cl, any among [Bmim] Cl or [Emim] Cl; Cellulose powder and ion liquid mass ratio are 1: (1 ~ 5); The mass ratio of ionic liquid and water is 8: (1 ~ 6); Temperature of reaction is 120 ~ 180 ℃; Reaction times is 3 ~ 10h;
C product separation: with reacted product cooling, add and pour out after a certain amount of ultrapure water dilutes,, obtain containing the liquid product of glucose with the product suction filtration.
The present invention utilizes Mierocrystalline cellulose hydrolysis under water/ionic liquid binary system, has characteristics such as mild condition, productive rate are high, speed of response is fast, environmental protection.
Mierocrystalline cellulose is as a kind of polymkeric substance that forms with glucose polymerisation, and the principal reaction equation that its hydrolysis is converted into glucose is as follows.
Description of drawings
Fig. 1 is solid residue and cellulosic infrared spectrum.
Fig. 2 is HPLC (HPLC) analysis of liquid product and standard glucose sample.
Embodiment
After earlier specific embodiment of the present invention being described in.
Embodiment 1
Mierocrystalline cellulose is placed on 45~65 ℃ of dryings in the baking oven, is crushed to 20~40 orders.Extracting cellulose powder 1g, ionic liquid [Amim] Cl (chlorination-1-allyl group-3-Methylimidazole) 8g, water 3g put into the reaction kettle confined reaction.Temperature of reaction is 150 ℃, time 4h.Reaction finishes, and places cold water to be cooled to room temperature reaction kettle, adds to pour out after a small amount of ultrapure water dilutes, and suction filtration is collected liquid product and solid phase residue respectively.Taking by weighing solid residue, to obtain cellulosic degradation rate be 76.56%.Liquid product confirms that through high pressure liquid chromatographic analysis primary product is a glucose, and yield reaches 62.86%.
Embodiment 2
Mierocrystalline cellulose is placed on 45~65 ℃ of dryings in the baking oven, is crushed to 20~40 orders.Extracting cellulose powder 1g, ionic liquid [Bmim] Cl (chlorination-1-butyl-3-Methylimidazole) 10g, water 1g put into the reaction kettle confined reaction.Temperature of reaction is 140 ℃, reaction times 8h.Reaction finishes, and places cold water to be cooled to room temperature reaction kettle, add pour out after a small amount of ultrapure water dilution, suction filtration.Collect liquid product and solid phase residue respectively.Taking by weighing solid residue, to obtain cellulosic degradation rate be 80.64%.Liquid product confirms that through high pressure liquid chromatographic analysis primary product is a glucose, and yield reaches 63.60%.
Referring to Fig. 1, Fig. 1 is solid residue and cellulosic infrared spectrum, can find that by figure two curves are identical basically, analyzes thus, and solid residue is mainly undegradable Mierocrystalline cellulose.
Referring to Fig. 2, Fig. 2 is the high pressure liquid chromatographic analysis result of liquid product and standard glucose sample, and the chromatographic peak of residence time 3min-3.5min is a glucose on the color atlas of liquid product, explains that the hydrolysis primary product is a glucose.
Claims (1)
1.1 cellulose hydrolysis prepares the method for glucose in water/ionic liquid binary system, it is characterized in that having three steps, is respectively that raw materials pretreatment, hydrolysis and product separate;
raw materials pretreatment: Mierocrystalline cellulose 80 ± 5 ℃ of dryings, be crushed to 20~40 orders;
The b hydrolysis reaction: dried cellulose powder, ionic liquid, water are added in the reaction kettle by corresponding proportion, and design temperature, makes cellulose hydrolysis make glucose at reaction for some time; Used ionic liquid is [Amim] Cl, any among [Bmim] Cl or [Emim] Cl; Cellulose powder and ion liquid mass ratio are 1: (1 ~ 5); The mass ratio of ionic liquid and water is 8: (1 ~ 6); Temperature of reaction is 120 ~ 180 ℃; Reaction times is 3 ~ 10h;
C product separation: with reacted product cooling, add and pour out after a certain amount of ultrapure water dilutes,, obtain containing the liquid product of glucose with the product suction filtration.
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Cited By (3)
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---|---|---|---|---|
CN103740867A (en) * | 2014-01-02 | 2014-04-23 | 上海大学 | Method for preparing glucose by hydrolyzing straw celluloses |
CN113403248A (en) * | 2021-06-10 | 2021-09-17 | 新疆大学 | Two methods for preparing general microbial culture medium by cellulose liquidization based on eutectic system |
CN113480582A (en) * | 2021-06-30 | 2021-10-08 | 广东工业大学 | Green and cyclic comprehensive utilization method for agricultural and forestry solid wastes |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN103740867A (en) * | 2014-01-02 | 2014-04-23 | 上海大学 | Method for preparing glucose by hydrolyzing straw celluloses |
CN113403248A (en) * | 2021-06-10 | 2021-09-17 | 新疆大学 | Two methods for preparing general microbial culture medium by cellulose liquidization based on eutectic system |
CN113480582A (en) * | 2021-06-30 | 2021-10-08 | 广东工业大学 | Green and cyclic comprehensive utilization method for agricultural and forestry solid wastes |
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