CN103882158B - A kind of method synthesizing monosaccharide for cellulose hydrolysis - Google Patents
A kind of method synthesizing monosaccharide for cellulose hydrolysis Download PDFInfo
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- CN103882158B CN103882158B CN201210563876.8A CN201210563876A CN103882158B CN 103882158 B CN103882158 B CN 103882158B CN 201210563876 A CN201210563876 A CN 201210563876A CN 103882158 B CN103882158 B CN 103882158B
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Abstract
A kind of method synthesizing monosaccharide for cellulose hydrolysis, this method adopts the method for liquid phase oxidation pretreatment, makes the methylol in cellulosic structure be converted into carboxyl, and then the cellulose of oxidation pre-treatment and water react generation monosaccharide.
Description
Technical field
The present invention provides a kind of new method for cellulose hydrolysis to monosaccharide and oligosaccharide, specifically, adopts pretreatment oxidized cellulose part functional group to generate carboxyl, and the hydrolysis under the acidic catalyst effect of the carboxyl generated of the cellulose of oxidation processes generates monosaccharide.
Background technology
Hydrocellulose; via glucose; bio-fuel and multi-chemical can be obtained, not only will not as with starch, grease for raw material prepare bio-fuel cause crisis in food, and the energy and environmental problem solving facing mankind is had very profound significance. Adopt mineral acid (such as sulphuric acid, hydrochloric acid etc.) catalyzing cellulose hydrolysis traditionally, not only product and catalyst separation difficulty, and equipment requirements is high, environmental pollution is serious. Enzyme hydrolysis has reaction condition gentleness, feed stock conversion height and advantages of environment protection, but owing to the activity of cellulase is not high, recycling rate of waterused is low and causes that process and use cost are too high. Solid acid catalysis cellulose hydrolysis, has the advantage that catalyst is prone to recycle, but such catalyst activity is relatively low at present, have impact on its application.
Summary of the invention
The present invention provides a kind of new method for cellulose hydrolysis to monosaccharide, the method namely adopting oxidation pre-treatment, the functional group's (such as methylol) making cellulosic sections is converted into carboxyl, and then the cellulose of oxidation pre-treatment and water react generation monosaccharide.
The method utilizes the carboxyl that the functional group conversions of cellulosic sections generates, the carrying out of direct catalyzing cellulose hydrolysis reaction, it is to avoid extra addition catalyst.
For achieving the above object, the technical solution used in the present invention is:
Adopt hydrogen peroxide, NaClO, KMnO4、K2Cr2O7、HNO3For oxidant, with water for solvent, cellulose is carried out oxidation pre-treatment. Cellulose after process, with water for reaction medium, under inert atmosphere exists, hydrolysis obtains monosaccharide and polysaccharide, and cellulose hydrolysis reacts, and the mass ratio of cellulose and water is at 0.01-0.25.
The concentration of oxidant is 0.1%-30%, and addition (counts) 0.5%-20% for cellulose glucose unit molal quantity with oxidation equivalent; Described cellulose is the 3%-25% of reaction medium weight.
According to method provided by the invention, under these conditions, the reaction temperature that cellulose oxidation processes is 40-120 DEG C, 0.5-3 hour response time. Cellulose hydrolysis reacts at 100-220 DEG C, reacts 0.5-10 hour and carries out.
This method is mainly characterized in that: and utilizes the functional group conversions that oxidant liquid phase oxidation makes cellulose surface is carboxyl, and then under the catalytic action of carboxyl, cellulose hydrolysis is monosaccharide. This method avoid and additionally add catalyst, solve cellulose and not readily dissolve, it is difficult to the difficult point contacted with the active center of catalyst, there is reaction condition gentleness, it is easy to the advantage of operation.
Accompanying drawing explanation
The infrared spectrum of the cellulose sample after Fig. 1: NaClO oxidation.
Detailed description of the invention
Embodiment 1:
Take 5 grams of alpha-celluloses (0.031mol glucose unit), join in the aqueous solution of NaClO of 30 milliliters of 1mol/L, under agitation, 100 DEG C, react 2 hours, be then filtered off solid, washing, drying. Infrared spectrum measurement proves there is carbonyl (as shown in Figure 1) in sample. Sample is through acid base titration, and carboxyl-content is 0.25mmol/g.
Cellulose hydrolysis reaction carries out in pressure vessel, takes the cellulose of 2 grams of oxidation processes, adds 15 milliliters of water as reactant and solvent, and in nitrogen displacement container, atmosphere 3 times, is warming up to 150 DEG C, reacts 6 hours. Cellulosic conversion ratio is measured by weight method, and the mensuration of hydrolyzate total reducing sugars adopts DNS method to measure. The method that DNS method measures total reducing sugars is as follows: utilize 3,5-dinitrosalicylic acids (DNS) reagent as developer, adopts fixed wave length 511nm to carry out colorimetric analysis on ultraviolet-visible spectrophotometer. Glucose yield adopts glucose analyser to measure.
According to analysis method above, cellulosic conversion ratio is 45%, and the yield of reducing sugar is 23%, and glucose yield is 17%.
Embodiment 2:
Except the H adopting same volume and concentration2O2Replacing outside the NaClO aqueous solution in embodiment 1, other condition is identical with embodiment 1. Cellulosic conversion ratio is 36%, and the yield of reducing sugar is 22%, and glucose yield is 18%.
Embodiment 3:
Except the HNO adopting same volume and concentration3Replacing outside the NaClO aqueous solution in embodiment 1, other condition is identical with embodiment 1. Cellulosic conversion ratio is 30%, and the yield of reducing sugar is 18%, and glucose yield is 12%.
Embodiment 4:
Except the KMnO adopting same volume, 0.5mol/L4Replacing outside the NaClO in embodiment 1, other condition is identical with embodiment 1. Cellulosic conversion ratio is 20%, and the yield of reducing sugar is 13%, and glucose yield is 8%.
Embodiment 5:
Except the K adopting same volume, 0.25mol/L2Cr2O7Replacing outside the NaClO in embodiment 1, other condition is identical with embodiment 1. Cellulosic conversion ratio is 28%, and the yield of reducing sugar is 16%, and glucose yield is 11%.
Embodiment 6:
Being except oxidant except adopting 30 milliliters of 0.5mol/LNaClO, other condition is identical with embodiment 1. Cellulosic conversion ratio is 12%, and the yield of reducing sugar is 7%, and glucose yield is 4%.
Embodiment 7:
Being except oxidant except adopting 30 milliliters of 4mol/LNaClO, other condition is identical with embodiment 1. Cellulosic conversion ratio is 55%, and the yield of reducing sugar is 29%, and glucose yield is 18%.
Embodiment 8:
Being oxidant except adopting 20 milliliters of 1mol/LNaClO, other condition is identical with embodiment 1. Cellulosic conversion ratio is 26%, and the yield of reducing sugar is 17%, and glucose yield is 12%.
Embodiment 9:
Being oxidant except adopting 60 milliliters of 1mol/LNaClO, other condition is identical with embodiment 1. Cellulosic conversion ratio is 42%, and the yield of reducing sugar is 28%, and glucose yield is 21%.
Embodiment 10:
Except the cellulosic temperature of oxidation processes is 50 DEG C, other condition is identical with embodiment 1. Cellulosic conversion ratio is 22%, and the yield of reducing sugar is 15%, and glucose yield is 12%.
Embodiment 11:
Except the cellulosic temperature of oxidation processes is 110 DEG C, other condition is identical with embodiment 1.Cellulosic conversion ratio is 50%, and the yield of reducing sugar is 31%, and glucose yield is 20%.
Embodiment 12:
Except the oxidation processes cellulosic time is 0.5 hour, other condition is identical with embodiment 1. Cellulosic conversion ratio is 18%, and the yield of reducing sugar is 13%, and glucose yield is 7%.
Embodiment 13:
Except the oxidation processes cellulosic time is 3 hours, other condition is identical with embodiment 1. Cellulosic conversion ratio is 48%, and the yield of reducing sugar is 29%, and glucose yield is 19%.
Embodiment 14:
Except amount cellulosic in hydrolysis changes into 0.5 gram, other condition is identical with embodiment 1. Cellulosic conversion ratio is 50%, and the yield of reducing sugar is 28%, and glucose yield is 17%.
Embodiment 15:
Except amount cellulosic in hydrolysis changes into 3.5 grams, other condition is identical with embodiment 1. Cellulosic conversion ratio is 40%, and the yield of reducing sugar is 24%, and glucose yield is 16%.
Embodiment 16:
Except amount cellulosic in hydrolysis changes into 8.0 grams, other condition is identical with embodiment 1. Cellulosic conversion ratio is 45%, and the yield of reducing sugar is 28%, and glucose yield is 18%.
Claims (3)
1. the method for cellulose hydrolysis synthesis monosaccharide, it is characterised in that: adopting oxidizing cellulose to produce carboxyl under liquid-phase condition, the cellulose after oxidation reacts with water under carboxyl catalytic action, and hydrolysis generates glucose; In oxidation equivalent, the 0.5%-20% making consumption be cellulose glucose unit molal quantity of oxidant;
Described oxidant is hydrogen peroxide, NaClO, KMnO4、K2Cr2O7、HNO3In one or two or more kinds;
In liquid phase, the mass concentration of oxidant is 0.1%-30%;
Described oxidation reaction carries out in aqueous phase, and reaction temperature is 40-120 DEG C, 0.5-3 hour response time;
Cellulose after oxidation, with water for reaction medium, inert atmosphere 100-220 DEG C of hydrolysis, reacts 0.5-10 hour, obtains monosaccharide under existing;
Cellulose hydrolysis reacts, and the mass ratio of cellulose and water is at 0.01-0.25.
2. in accordance with the method for claim 1, it is characterised in that: described cellulose is the 3%-25% of reaction medium weight.
3. in accordance with the method for claim 1, it is characterised in that: after the cellulose after oxidation is separated by filtration washing, dry, for hydrolysis.
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| CN101289817A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Process for effectively hydrolyzing cellulose in ion liquid |
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| CN102639706A (en) * | 2009-04-30 | 2012-08-15 | 安尼基有限责任公司 | Method for preparing sugars from lignocellulose-containing biomass, comprising the step of alcohol-alkali delignification in the presence of H2O2 |
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| CN101932715A (en) * | 2007-02-26 | 2010-12-29 | 韩国生产技术研究院 | Method of producing biofuel using sea algae |
| CN101289817A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Process for effectively hydrolyzing cellulose in ion liquid |
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