CN102392082B - Method for preparing glucose by catalyzing hydrolysis of cellulose by low-solubility organic acid - Google Patents
Method for preparing glucose by catalyzing hydrolysis of cellulose by low-solubility organic acid Download PDFInfo
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- CN102392082B CN102392082B CN 201110304099 CN201110304099A CN102392082B CN 102392082 B CN102392082 B CN 102392082B CN 201110304099 CN201110304099 CN 201110304099 CN 201110304099 A CN201110304099 A CN 201110304099A CN 102392082 B CN102392082 B CN 102392082B
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Abstract
The invention discloses a method for preparing glucose by catalyzing the hydrolysis of cellulose by low-solubility organic acid. The method comprises the following main steps of: adding 0.5 to 10 weight percent of crushed cellulose raw materials, 0.5 to 5 weight percent of organic acid and water into a reaction kettle to obtain a mixed solution; hydrolyzing the mixed solution at the temperature of between 150 and 200 DEG C for 0 to 3 hours; after reaction is finished, cooling to room temperature; and filtering and separating hydrolyzate to obtain filtrate serving as sugar liquid, wherein filter residues contain cellulose raw materials which are not hydrolyzed and residual organic acid, and after water is replenished, the residues can be hydrolyzed again; and after the residues are hydrolyzed for multiple times, the fresh cellulose raw materials or organic acid is added, so that the residues can be hydrolyzed again. The method has the advantages of a few hydrolytic byproducts of the water-soluble organic acid and simple separation of hydrolytic products of solid acid, and the hydrolysis can be performed continuously by utilizing the organic acid and the cellulose raw materials fully to prepare the glucose, so the method is suitable for industrial continuous production.
Description
Technical field
The invention belongs to the Wood Adhesives from Biomass field, be specifically related to the method that a class low solubility organic acid catalysis cellulose hydrolysis prepares glucose.
Background technology
The preparation of bio-ethanol is one of biomass resource trans-utilization major way, and its committed step is how the Mierocrystalline cellulose in fibrous material or hydrolysis of hemicellulose are become fermentable sugars.compare cellulase hydrolysis, it is low that the acid-catalyzed hydrolysis process has a cost, the advantages such as easily-controlled reaction conditions, but the acid hydrolysis process also exist comprise equipment requirements high, waste water is difficult, hydrolysate is complicated and be difficult for the weak point such as purifying. and be the problem that solves product complexity in the acid hydrolysis process, there is the investigator to propose to come hydrocellulose with organic acids such as formic acid or toxilic acids, due to organic acid acidity than mineral acids such as sulfuric acid or hydrochloric acid a little less than, the hydrolysis reaction selectivity is high, thereby effectively reduce the generation of the by products such as 5 hydroxymethyl furfural, the liquid glucose that hydrolysis obtains is more suitable for the production in follow-up alcohol prepared by fermenting, the problems such as in the acid hydrolysis process, product should not separate in order to solve, acid recovery difficulty have again the investigator to propose to use the solid acid catalysis hydrocelluloses such as sulfonation carbon.On the one hand, solid acid catalyst is simple with separating of glucose, and on the other hand, such solid acid can be used for hydrolysis reaction again after certain processing, effectively reduce the catalyzer cost.But, use the organic acid catalysis method for hydrolysis such as formic acid, principal product glucose and organic acid separation difficulty, and use the solid acid hydrolysis Mierocrystalline cellulose to exist hydrolysis time long, the shortcoming such as reaction efficiency is low makes above-mentioned two kinds of acid be restricted in practical application.
Summary of the invention
The object of the invention is to overcome the prior art above shortcomings, provide a class organic acid catalysis cellulose hydrolysis to prepare the method for glucose.The phenylformic acid series organic acid that the present invention uses has special dissolving properties, has realized heterogeneous at different temperature and transformation homogeneous phase.As DNBA at normal temperatures the solubleness in water be only 0.135g, and the solubleness in boiling water is greater than 5g, solubleness improves more than 30 times.Therefore under hydrolysis temperature, such organic acid hydrolysis reaction is the homogeneous acid catalyzed reaction, with the organic acid such as formic acid seemingly, have the advantages that hydrolysis efficiency is high, byproduct of reaction is few.After reaction finished, system was cooled to room temperature, and the organic acid of the overwhelming majority is separated out from aqueous phase, can realize product separation by simple filter method, has the easily separated character of solid acid.The present invention combines effectively hydrolyzing and the segregative advantage of solid acid hydrolysis product of liquid acid, and suitability for industrialized is produced continuously.
Purpose of the present invention realizes by following technical proposals: a class low solubility organic acid catalysis cellulose hydrolysis prepares the method for glucose, comprises the steps:
(1) cellulosic material is carried out pulverization process, standby;
(2) organic acid of the cellulosic material of 0.5wt%～10wt%, 0.5wt%～5wt% and water are placed in reactor and obtain mixed solution;
(3) be to be hydrolyzed 0～3h under 150 ℃～200 ℃ with gained mixed solution in step (2) in temperature;
(4) carry out filtering separation after hydrolyzed solution being cooled to room temperature, the filtrate after filtration is Glucose Liquid, and filter residue is unhydrolysed cellulosic material and residual organic acid;
(5) with after the filter residue make up water that obtains in step (4), repeating step (3), (4) are proceeded hydrolysis and are separated.
After filter residue make up water in described step (4), after continue repeating (3), (4) step 4～6 times, hydrocellulose is not the colloidal suspension shape in hydrolyzed solution, and available tipping is removed, and the precipitation residue is organic acid.This moment must supplementary fibre element raw material.
Described cellulosic material comprises more than one in Microcrystalline Cellulose, sawdust, bagasse, maize straw.
After filter residue moisturizing in described step (4), after continue repeating (3), (4) step 8～10 times, must replenish organic acid.
Described organic acid comprises more than one in phenylformic acid, p-nitrobenzoic acid, 3,5 dinitrobenzoic acids (DNBA) and phthalic acid.
Compared with prior art, the present invention has the following advantages:
(1) acid of the present invention's use is the low solubility organic acid, and reaction conditions is gentle, energy consumption is low; Than mineral acids such as sulfuric acid, the by-products content in hydrolysate is low, is conducive to follow-up fermentation reaction and prepares ethanol.
(2) the present invention combines effectively hydrolyzing and the segregative advantage of solid acid hydrolysis product of liquid acid.Than water-soluble organic acids such as formic acid, toxilic acids, reaction system is in process of cooling, and most organic acid is separated out from water, and simple filtration can realize product separation.Than solid acid hydrolysis processes such as sulfonation carbon, this organic acid is homogeneous reaction under temperature of reaction, thereby the efficient of hydrolysis reaction improves greatly, has shortened hydrolysis time short.
(3) the present invention takes full advantage of organic acid and cellulosic material.Be mainly the organic acid of separating out in unhydrolysed Mierocrystalline cellulose and process of cooling in hydrolytic residue, can again be hydrolyzed after adding entry.Repeatedly after the hydrolysis, add fresh fiber element raw material or organic acid, realize hydrolysis again.
Embodiment
The invention will be further described below in conjunction with embodiment, need to prove, case study on implementation does not consist of the restriction to the claimed scope of the present invention.
In the present embodiment, cellulosic material is Microcrystalline Cellulose, and organic acid catalyst is DNBA.
Embodiment 1
Microcrystalline Cellulose and DNBA are added in water in ratio shown in table 1, react 2h under differing temps.After filtering, filtrate is used for the glucose analysis detection, and residue is used for continuing hydrolysis.Specifically as shown in table 1.
Under table 1 differing temps, DNBA compares the hydrolysis effect of Microcrystalline Cellulose
As shown in Table 1, hydrolysis temperature on the impact of glucose yield significantly.During lower than 190 ℃, the glucose yield raises with the rising of hydrolysis temperature; During higher than 190 ℃, downward trend appears in the glucose yield.Explanation is at higher temperature, and the product conversion of glucose is the by product effect enhancings such as hydroxymethylfurfural, makes the glucose yield reduce on the contrary.
Embodiment 2
Microcrystalline Cellulose and DNBA are added in water the different time of hydrolysis under 190 ℃ in ratio shown in table 2.After filtering, filtrate is used for the glucose analysis detection, and residue is used for continuing hydrolysis.Specifically as shown in table 2.
Under the different hydrolysis times of table 2, DNBA compares the hydrolysis effect of Microcrystalline Cellulose
Be pointed out that, need approximately 40min when this reaction system is warming up to target temperature from room temperature, this temperature-rise period is not counted in hydrolysis time, and therefore, when hydrolysis time was 0h, the glucose yield was greater than zero.As known from Table 2, when being hydrolyzed under 190 ℃, the glucose yield reaches maximum value substantially when 1h, and the reaction times extends again, and the glucose yield increases limited, and even glucose occurs to degrade and makes final yield descend.For the consideration that reduces energy consumption, hydrolysis time 1h is enough simultaneously.
Embodiment 3
Microcrystalline Cellulose and DNBA are added in water in ratio shown in table 3, are hydrolyzed 1h under 190 ℃.After filtering, filtrate is used for the glucose analysis detection, and residue is used for continuing hydrolysis.Specifically as shown in table 3.
As shown in Table 3, along with the increase of Mierocrystalline cellulose consumption, the glucose yield is on a declining curve, and glucose concn is fast rise trend.In hydrolyzed solution, glucose concn is higher, more is conducive to the operation stepss such as concentrating of follow-up fermenting process.Therefore, when the concentration of cellulosic material is controlled at 5～10%, can be so that the equal higher level of glucose yield and glucose concn.
Table 3DNBA compares the hydrolysis effect of different concns Microcrystalline Cellulose
Embodiment 4
Microcrystalline Cellulose and DNBA are added in water in ratio shown in table 4, are hydrolyzed 1h under 190 ℃.After filtering, filtrate is used for the glucose analysis detection, and residue is used for continuing hydrolysis.Specifically as shown in table 4.
The different DNBA consumptions of table 4 compare the hydrolysis effect of Microcrystalline Cellulose
As shown in Table 4, Microcrystalline Cellulose also can be hydrolyzed when there is no catalyzer and produce a small amount of glucose, and when adding a small amount of organic acid, the glucose yield increases sharply.But when the organic acid consumption surpassed 1wt%, the glucose yield increased limited, even also slightly descended.Possible cause is that the speed of side reaction also increases sharply when the high consumption of organic acid, makes final glucose yield descend on the contrary.Therefore, when DNBA was used for cellulose hydrolysis, consumption should be controlled in 1%.
Embodiment 5
Microcrystalline Cellulose and DNBA are added in water according to ratio table 5 illustrate, are hydrolyzed 0.5h under 190 ℃.After filtering, filtrate is used for the glucose analysis detection, and hydrolytic residue is used for continuing hydrolysis after adding water.Specifically as shown in table 5.
The hydrolysis effect of the different hydrolysis of table 5 number of times relatively
After a hydrolytic residue was hydrolyzed through 5 times, Mierocrystalline cellulose was colloidal in water, and DNBA is still solid precipitation.Pour out colloidal Mierocrystalline cellulose mixed solution, add fresh fiber element 5g, carry out the 6th hydrolysis.
B adds DNBA1g in hydrolytic residue, carry out the 9th hydrolysis.
Hydrolysis 1h can cause the cellulose hydrolysis residue to present brown under 190 ℃, shows that polyreaction has occured for hydrolysate etc., generates soil ulmin.For realizing the hydrolysis that repeats of Mierocrystalline cellulose residue, the controlled hydrolysis time is 0.5h.As shown in Table 5, this repeated experiment has not only utilized the DNBA organic acid, and effective degree can reach 6 times, but also has utilized unhydrolysed Mierocrystalline cellulose, makes the total yield of glucose reach 33% (being hydrolyzed the glucose yield summation of 1～5 time).
Claims (4)
1. a class low solubility organic acid catalysis cellulose hydrolysis prepares the method for glucose, it is characterized in that comprising the steps:
(1) cellulosic material is carried out pulverization process, standby;
(2) 3,5 dinitrobenzoic acids of the cellulosic material of 0.5wt%～10wt%, 0.5wt%～5wt% and water are placed in reactor and obtain mixed solution;
(3) gained mixed solution in step (2) is hydrolyzed 0～3h under 150 ℃～200 ℃;
(4) filter after hydrolyzed solution is cooled to room temperature, filtrate is Glucose Liquid, and filter residue is unhydrolysed cellulosic material and residual organic acid;
(5) with after the filter residue make up water that obtains in step (4), repeatedly repeating step (3), (4).
2. a class low solubility organic acid catalysis cellulose hydrolysis according to claim 1 prepares the method for glucose, after the filter residue make up water that it is characterized in that obtaining in described step (4), and after repeating step (3), (4) 4～6 times, supplementary fibre element raw material.
3. a class low solubility organic acid catalysis cellulose hydrolysis according to claim 1 prepares the method for glucose, after the filter residue make up water that it is characterized in that obtaining in described step (4), after repeating step (3), (4) 8～10 times, replenishes organic acid.
4. a class low solubility organic acid catalysis cellulose hydrolysis according to claim 1 prepares the method for glucose, it is characterized in that described cellulosic material comprises more than one in Microcrystalline Cellulose, sawdust, bagasse, maize straw.
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| TWI476203B (en) | 2013-03-18 | 2015-03-11 | Ind Tech Res Inst | Method of separating carbohydrate |
| CN103924007B (en) * | 2014-04-18 | 2015-10-14 | 厦门大学 | One class low-pole acid Two Liquid Phases catalyzing cellulose hydrolysis prepares the method for glucose |
| CN110004252A (en) * | 2019-03-27 | 2019-07-12 | 天津大学 | The method for preparing glucose using 2,5- furandicarboxylic acid catalytic cellulose |
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| CN101381754A (en) * | 2008-10-21 | 2009-03-11 | 华南理工大学 | Method for producing fermentable sugars by hydrolysis of cellulosic component sulphonation separation couple enzyme |
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| CN101381754A (en) * | 2008-10-21 | 2009-03-11 | 华南理工大学 | Method for producing fermentable sugars by hydrolysis of cellulosic component sulphonation separation couple enzyme |
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