CN102392082A - 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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- CN102392082A CN102392082A CN2011103040990A CN201110304099A CN102392082A CN 102392082 A CN102392082 A CN 102392082A CN 2011103040990 A CN2011103040990 A CN 2011103040990A CN 201110304099 A CN201110304099 A CN 201110304099A CN 102392082 A CN102392082 A CN 102392082A
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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 one type of low solubility organic acid catalysis cellulose hydrolysis prepares glucose.
Background technology
The preparation of bio-ethanol is one of main mode of biomass resource trans-utilization, and its committed step is how Mierocrystalline cellulose in the fibrous material or hydrolysis of hemicellulose are become fermentable sugars.Compare cellulase hydrolysis; The acid-catalyzed hydrolysis process has advantages such as cost is low, easily-controlled reaction conditions; But the acid hydrolysis process also exist comprise high to equipment requirements, waste water is hard to manage, hydrolysate is complicated and be difficult for weak point such as purifying. be to solve product complicated problems in the acid hydrolysis process; Have the investigator to propose to use organic acids such as formic acid or toxilic acid to come hydrocellulose and since 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 production of 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; Problems such as product should not separate in the acid hydrolysis process in order to solve, acid recovery difficulty have the investigator to propose to use solid acid catalysis hydrocelluloses such as sulfonation carbon again.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 once more after certain processing, effectively reduced the catalyzer cost.But, using organic acid catalysis method for hydrolysis such as formic acid, principal product glucose and organic acid separation difficulty, and shortcoming such as use solid acid hydrolysis Mierocrystalline cellulose exists hydrolysis time long, and reaction efficiency is low make above-mentioned two kinds of acid in practical application, be restricted.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency that prior art exists, provide one type of 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, under different temperature, has realized heterogeneous and the homogeneous transformation.As DNBA at normal temperatures the solubleness in the water be merely 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 organic acid such as formic acid seemingly, have hydrolysis efficiency height, characteristics that 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 that product separates, and has the easily separated character of solid acid through the simple filtering method.The present invention has combined the effectively hydrolyzing and the segregative advantage of solid acid hydrolysis product of liquid acid, suitability for industrialized continuous production.
The object of the invention is realized through following technical proposals: one type of low solubility organic acid catalysis cellulose hydrolysis prepares the method for glucose, comprises the steps:
(1) cellulosic material is carried out pulverization process, subsequent use;
(2) place reaction kettle to obtain mixed solution in the cellulosic material of 0.5wt%～10wt%, organic acid and the water of 0.5wt%～5wt%;
(3) be 150 ℃～200 ℃ following hydrolysis 0～3h with gained mixed solution in the step (2) in temperature;
(4) carry out filtering separation after hydrolyzed solution is cooled to room temperature, filtrate filtered is a 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 the step (4), repeating step (3), (4) are proceeded hydrolysis and are separated.
After the filter residue make up water in the said step (4), continue repetition (3), (4) step 4～6 times after, hydrocellulose is not the colloidal suspension shape in hydrolyzed solution, available tipping is removed, the deposition residue is an organic acid.This moment must the plain raw material of supplementary fibre.
Said cellulosic material comprises more than one in Microcrystalline Cellulose, sawdust, bagasse, the corn straw.
After the filter residue moisturizing in the said step (4), continue repetition (3), (4) step 8～10 times after, must replenish organic acid.
Said organic acid comprises more than one in phenylformic acid, p-Nitrobenzenecarboxylic acid, 3,5 dinitrobenzoic acids (DNBA) and the 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 the hydrolysate is low, helps follow-up fermentation reaction and prepares ethanol.
(2) the present invention has combined the 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 filtering can realize that product separates.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, and it is short to have shortened hydrolysis time.
(3) the present invention has made full use of organic acid and cellulosic material.Mainly be the organic acid of separating out in unhydrolysed Mierocrystalline cellulose and the process of cooling in the hydrolytic residue, add hydrolysis once more after the entry.Repeatedly after the hydrolysis, add plain raw material of fresh fiber or organic acid, realize hydrolysis once more.
Embodiment
Below in conjunction with embodiment the present invention is done further description, need to prove, case study on implementation does not constitute the qualification that the present invention is required protection domain.
Cellulosic material is a Microcrystalline Cellulose in the present embodiment, and organic acid catalyst is DNBA.
Embodiment 1
Microcrystalline Cellulose and DNBA are added in the water in ratio shown in the table 1, under differing temps, react 2h.Filter rear filtrate and be used for the glucose analysis detection, residue is used to continue hydrolysis.Specifically as shown in table 1.
DNBA compares the hydrolysis effect of Microcrystalline Cellulose under table 1 differing temps
Can know that by table 1 hydrolysis temperature to the influence of glucose yield significantly.When being lower than 190 ℃, the glucose yield raises with the rising of hydrolysis temperature; When being higher than 190 ℃, downward trend appears in the glucose yield.Explanation is under higher temperature, and the product conversion of glucose is by product effect enhancings such as hydroxymethylfurfural, makes the glucose yield reduce on the contrary.
Embodiment 2
Microcrystalline Cellulose and DNBA are added in the water in ratio shown in the table 2,190 ℃ of following hydrolysis different time.Filter rear filtrate and be used for the glucose analysis detection, residue is used to continue hydrolysis.Specifically as shown in table 2.
DNBA compares the hydrolysis effect of Microcrystalline Cellulose under the different hydrolysis times of table 2
Be pointed out that this reaction system need about 40min when room temperature is warming up to target 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.Can know that from table 2 when 190 ℃ of following hydrolysis, the glucose yield reaches peak basically when 1h, the reaction times prolongs again, and the glucose yield increases limited, even glucose generation degraded makes final yield descend.From the consideration that cuts down the consumption of energy, hydrolysis time 1h is enough simultaneously.
Embodiment 3
Microcrystalline Cellulose and DNBA are added in the water in ratio shown in the table 3, at 190 ℃ of following hydrolysis 1h.Filter rear filtrate and be used for the glucose analysis detection, residue is used to continue hydrolysis.Specifically as shown in table 3.
Can know that by 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.Glucose concn is high more in the hydrolyzed solution, helps operation stepss such as concentrating of follow-up fermenting process more.Therefore, the concentration of cellulosic material was controlled at 5～10% o'clock, can be so that all 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 the water in ratio shown in the table 4, at 190 ℃ of following hydrolysis 1h.Filter rear filtrate and be used for the glucose analysis detection, residue is used to continue hydrolysis.Specifically as shown in table 4.
The different DNBA consumptions of table 4 compare the hydrolysis effect of Microcrystalline Cellulose
Can be known that by table 4 Microcrystalline Cellulose can hydrolysis not produce a spot of glucose yet when having catalyzer, 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 the water according to ratio table 5 illustrate, at 190 ℃ of following hydrolysis 0.5h.Filter rear filtrate and be used for the glucose analysis detection, hydrolytic residue is used to continue hydrolysis after adding water.Specifically as shown in table 5.
The hydrolysis effect of the different hydrolysis number of times of table 5 relatively
The a hydrolytic residue through 5 hydrolysis after, Mierocrystalline cellulose is colloidal in water, DNBA still is a solid precipitation.Pour out colloidal Mierocrystalline cellulose mixed solution, add the plain 5g of fresh fiber, carry out the 6th hydrolysis.
B adds DNBA1g in hydrolytic residue, carry out the 9th hydrolysis.
Can cause the cellulose hydrolysis residue to present brown at 190 ℃ of following hydrolysis 1h, show that polyreaction has taken place for hydrolysate etc., generates soil ulmin.For realizing the repetition hydrolysis of Mierocrystalline cellulose residue, the control hydrolysis time is 0.5h.Can be known that by table 5 this repeated experiment has not only utilized the DNBA organic acid, effective degree can reach 6 times, but also has utilized unhydrolysed Mierocrystalline cellulose, makes the total yield of glucose reach 33% (the glucose yield summation that hydrolysis is 1～5 time).
Claims (5)
1. one type of 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, subsequent use;
(2) place reaction kettle to obtain mixed solution in the cellulosic material of 0.5 wt% ~ 10 wt%, organic acid and the water of 0.5 wt% ~ 5 wt%;
(3) with gained mixed solution in the step (2) at 150 ℃ ~ 200 ℃ following hydrolysis 0 ~ 3 h;
(4) hydrolyzed solution is cooled to the room temperature after-filtration, filtrating is that Glucose Liquid, filter residue are unhydrolysed cellulosic material and residual organic acid;
(5) with after the filter residue make up water that obtains in the step (4), repeatedly repeating step (3), (4).
2. one type of 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 the said step (4), and behind the repeating step (3), (4) 4 ~ 6 times, the plain raw material of supplementary fibre.
3. one type of 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 the said step (4), behind the repeating step (3), (4) 8 ~ 10 times, replenishes organic acid.
4. one type of low solubility organic acid catalysis cellulose hydrolysis according to claim 1 prepares the method for glucose, it is characterized in that said cellulosic material comprises more than one in Microcrystalline Cellulose, sawdust, bagasse, the corn straw.
5. one type of low solubility organic acid catalysis cellulose hydrolysis according to claim 1 prepares the method for glucose; It is characterized in that said organic acid comprises more than one in phenylformic acid, p-Nitrobenzenecarboxylic acid, 3,5 dinitrobenzoic acids (DNBA) or the phthalic acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924007A (en) * | 2014-04-18 | 2014-07-16 | 厦门大学 | Method for preparing glucose by using weak-polarity acid to catalyze hydrolysis of cellulose in double liquid phases |
| US9822420B2 (en) | 2013-03-18 | 2017-11-21 | Industrial Technology Research Institute | Method of separating carbohydrate |
| CN110004252A (en) * | 2019-03-27 | 2019-07-12 | 天津大学 | The method for preparing glucose using 2,5- furandicarboxylic acid catalytic cellulose |
Citations (1)
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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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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (4)
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| 何北海等: "木质纤维素化学水解产生可发酵糖研究", 《化学进展》, vol. 19, no. 78, 30 August 2007 (2007-08-30), pages 1141 - 1146 * |
| 孙勇等: "微晶纤维素在甲酸体系中的水解试验研究", 《生物质化学工程》, vol. 42, no. 1, 31 January 2008 (2008-01-31), pages 22 - 26 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9822420B2 (en) | 2013-03-18 | 2017-11-21 | Industrial Technology Research Institute | Method of separating carbohydrate |
| CN103924007A (en) * | 2014-04-18 | 2014-07-16 | 厦门大学 | Method for preparing glucose by using weak-polarity acid to catalyze hydrolysis of cellulose in double liquid phases |
| 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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