CN105567880B - A kind of method and its application of lignocellulose degradation - Google Patents
A kind of method and its application of lignocellulose degradation Download PDFInfo
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- CN105567880B CN105567880B CN201410528997.8A CN201410528997A CN105567880B CN 105567880 B CN105567880 B CN 105567880B CN 201410528997 A CN201410528997 A CN 201410528997A CN 105567880 B CN105567880 B CN 105567880B
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Abstract
The present invention relates to technical field of biochemical industry, specifically provide a kind of new method of lignocellulose degradation, it is using halide salt solution as solvent, using inorganic concentrated acid as catalyst, by ligno-cellulosic materials under normal pressure in 100-130 DEG C of reaction 10-120min, after reaction to get arrive ligno-cellulose hydrolysate.The method is hydrolysis of lignocellulose material under high salt concn, and using concentrated acid as catalyst, acid consumption is few, and mild condition, the reaction time is short, and small to reactor corrosion, extent of reaction is easy to control.It is that the halide salt solution of 60%-65% degrades to ligno-cellulosic materials as solvent that the present invention, which selects mass percent, the yield of xylose and glucose is improved significantly in gained ligno-cellulose hydrolysate, it is above 90%, unexpected technical results have been achieved.
Description
Technical field
The present invention relates to technical field of biochemical industry, specifically provide a kind of method of lignocellulose degradation and its answer
With.
Background technique
Lignocellulosic is nature renewable resource abundant, and in universal crops, cellulose accounts for about its dry weight
45% or so.The main chemical compositions of stalk are cellulose, hemicellulose, lignin, the total weight base of above-mentioned three kinds of substances
Originally it is maintained at 70% or so.It at the glucide based on glucose, xylose and converts cellulose and hemicellulose degradation to
Liquid fuel and industrial chemicals are one of the desirable routes for efficiently utilizing stalk.
Cellulose itself be it is heterogeneous, different parts to same chemical reagent or catalyst show it is different can and
Degree, additionally, due between cellulosic molecule and the effect of intramolecular hydrogen bond, heterogeneous reaction is subjected to from outward appearance to inner essence layer-by-layer anti-
Process is answered, cellulose is higher than 250 DEG C in temperature and just starts to thermally decompose, and side chain fracture generates small molecule product in molecular structure,
This is the major reason for causing the disadvantages of cellulose conversion ratio is low, product uniformity is poor；Meanwhile this also cause cellulose need compared with
What high-temperature could thermally decompose.But under homogeneous reaction environment, cellulose is fine under the action of ion liquid system
Dimension element, which dissolves, simultaneously forms homogeneous solution, intermolecular to be broken with intramolecular hydrogen bond or active force is extremely weak, reaction reagent or catalyst
Accessibility improves, under certain condition (such as high temperature, vacuum or high pressure), side chain, hydroxyl etc. in cellulose in glucose unit
Fracture generates the lower product of molecular weight.Therefore, it is necessary to which developing new efficient cellulose turns sugared technology, promote renewable
The effective use of biomass resource.
Summary of the invention
The present invention in order to overcome the deficiencies of the prior art, provides a kind of new method of efficient degradation ligno-cellulosic materials.
The method can significantly improve the transformation efficiency of lignocellulosic, reduce the reaction time.
One aspect of the present invention provides a kind of method of lignocellulose degradation, is using halide salt solution as solvent, with inorganic
Concentrated acid is catalyst, by ligno-cellulosic materials under normal pressure in 100-130 DEG C of reaction 10-120min, after reaction to get
To ligno-cellulose hydrolysate.
The mass percent of the halide salt solution is 60%-65%, the mass body of ligno-cellulosic materials and halide salt solution
Ratio is accumulated as 10-15:1, the mass volume ratio of ligno-cellulosic materials and inorganic acid is 10-20:1.
Wherein, any one of halogen in CaCl2, CaBr2, LiBr；
Any one of inorganic concentrated acid in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid is commercially available concentrated acid；
Any one of ligno-cellulosic materials in xylose residue, corn stalk powder, wood powder.
Further preferred scheme, specifically: the CaBr2 solution for being 60% using mass percent is solvent, with commercially available dense
Hydrochloric acid is catalyst, using corn stalk powder as ligno-cellulosic materials, the wherein quality volume of corn stalk powder and CaBr2 solution
Than for 1:10, the mass volume ratio of corn stalk powder and concentrated hydrochloric acid is 10:1, under normal pressure in 115 DEG C of reaction 15min to get arriving
Wood fibre hydrolysis liquid.
The invention has the following advantages that
Compared with prior art, the method for the invention is hydrolysis of lignocellulose material under high salt concn, and with dense
Acid is catalyst, and acid consumption is few, and mild condition, the reaction time is short, and small to reactor corrosion, extent of reaction is easy to control.This
It is that the halide salt solution of 60%-65% degrades to ligno-cellulosic materials as solvent that mass percent is selected in invention, gained
The yield of xylose and glucose is improved significantly in ligno-cellulose hydrolysate, is above 90%；And with halide salt solution
Concentration is continuously increased, and the yield of xylose is declined slightly, and the yield of glucose slightly improves, but the yield of xylose is consistently lower than
The yield of glucose, unexpected technical results have been achieved.The method of the invention can efficiently utilize lignocellulosic sources,
To solve the problems, such as that making full use of for lignocellulosic opened up a new way for a long time, bioenergy and biology base chemistry are being obtained
Product invention has huge application prospect.
Specific embodiment
The present invention is described in more detail below with reference to specific embodiment.But the present invention is not by the implementation
The limitation of example.There is provided embodiment purpose be in order to keep specification comprehensive and thorough, and it is comprehensive to those skilled in the art
Convey the range of invention.In addition to another definition, all technical and scientific terms used in the present invention are all had as institute of the present invention
Belong to the normally understood same meaning of those of ordinary skill in technical field.
Instrument equipment of the present invention is commonly used equipment in industry, raw materials used and reagent can be selected from it is commercially available any one,
Such as: CaBr2, LiBr, concentrated hydrochloric acid, the concentrated sulfuric acid, concentrated nitric acid etc. are purchased from Chinese medicines group.CaBr2 described in subordinate's embodiment,
The halide salt solutions such as LiBr are to add water to be formulated by halogen.
Embodiment 1
Taking mass percent is 60% CaBr2 solution 5ml, and 0.5g corn stalk powder and the commercially available concentrated hydrochloric acid of 50ul is added,
Under normal pressure in 115 DEG C of reaction 15min；After reaction to get arrive ligno-cellulose hydrolysate.
HPLC measurement result shows that the content of xylose is 0.0969g in above-mentioned ligno-cellulose hydrolysate, and glucose contains
Amount is 0.1923g.
The total content measuring method of xylose and glucose is as follows in ligno-cellulosic materials:
300 ± the 0.1mg of ligno-cellulosic materials for weighing over dry, is placed in weighed seal pipe, marks；Add
72% concentrated sulfuric acid for entering 3ml ± 0.01ml is rotated with poly- fluorine tetraene stick and mixes 1min；Seal pipe places 1h in 30 DEG C of water-baths,
Intermediate agitation 5-10min, the sterile water that 84 ± 0.04ml is added are diluted to 4% diluted acid, mix, pipe is put into safety container frame
On, 121 DEG C.High steam hydrolyzes 1h, takes out, natural cooling.The centrifugation of 2ml liquid is taken out from acidifying solution, measures Portugal with HPLC
The content of grape sugar and xylose calculates the mass percent of glucose and xylose in ligno-cellulosic materials.
The mass percent for measuring xylose in above-mentioned corn stalk powder according to the method described above is 21%, the quality hundred of glucose
Divide than being 41%.It is computed, the total content of xylose is 0.1048g in 0.5g corn stalk powder, and the total content of glucose is
0.2034g。
The calculation shows that utilizes the method for the invention lignocellulose degradation material, xylose and glucose yield difference
It is 92.45%, 94.56%.
In yield=hydrolyzate of xylose in the content of xylose/ligno-cellulosic materials material xylose total content × 100%.
In yield=hydrolyzate of glucose in content/lignocellulosic material of glucose glucose total content ×
100%.
Embodiment 2
Taking mass percent is 62% CaBr2 solution 6ml, 0.5g xylose residue and the commercially available concentrated sulfuric acid of 50ul is added, normal
It depresses in 100 DEG C of reaction 120min；After reaction to get arrive ligno-cellulose hydrolysate.
HPLC measurement result shows that the content of xylose is 0.0114g in above-mentioned ligno-cellulose hydrolysate, and glucose contains
Amount is 0.1509g；And the total content of xylose is 0.0124g in above-mentioned 0.5g xylose residue, the total content of glucose is 0.1627g.
The calculation shows that utilizes the method for the invention lignocellulose degradation material, xylose and glucose yield difference
For 91.93% and 92.73%.
Embodiment 3
Taking mass percent is 65% CaBr2 solution 7.5ml, 0.5g wood powder and 25ul concentrated nitric acid is added, under normal pressure
In 130 DEG C of reaction 10min；After reaction to get arrive ligno-cellulose hydrolysate.
HPLC measurement result shows that the content of xylose is 0.0873g in above-mentioned ligno-cellulose hydrolysate, and glucose contains
Amount is 0.1782g；And the total content of xylose is 0.0925g in above-mentioned 0.5g wood powder, the total content of glucose is 0.1862g.
The calculation shows that utilizes the method for the invention lignocellulose degradation material, xylose and glucose yield difference
For 94.39% and 95.70%.
Embodiment 4
Taking mass percent is 65% LiBr solution 7ml, 0.5g wood powder and the commercially available concentrated nitric acid of 50ul is added, under normal pressure
In 115 DEG C of reaction 10min；After reaction to get arrive ligno-cellulose hydrolysate.
HPLC measurement result shows that the content of xylose is 0.0863g in above-mentioned ligno-cellulose hydrolysate, and glucose contains
Amount is 0.1764g；And the total content of xylose is 0.0925g in above-mentioned 0.5g wood powder, the total content of glucose is 0.1862g.
The calculation shows that utilizes the method for the invention lignocellulose degradation material, xylose and glucose yield difference
For 93.29% and 94.71%.
Embodiment 5
Taking mass percent is 60% LiBr solution 5ml, and 0.5g corn stalk powder and the commercially available concentrated sulfuric acid of 40ul is added,
In 115 DEG C of reaction 15min under normal pressure；After reaction to get arrive ligno-cellulose hydrolysate.
HPLC measurement result shows that the content of xylose is 0.0962g in above-mentioned ligno-cellulose hydrolysate, and glucose contains
Amount is 0.1892g；And the total content of xylose is 0.1048g in above-mentioned 0.5g corn stalk powder, the total content of glucose is
0.2034g。
The calculation shows that utilizes the method for the invention lignocellulose degradation material, xylose and glucose yield difference
For 91.79% and 93.02%.
Embodiment 6
Operating procedure with described in embodiment 1, take respectively mass percent be 30%-75% CaBr2 solution 5ml, respectively plus
Enter 0.5g corn stalk powder and the commercially available concentrated hydrochloric acid of 50ul, under normal pressure in 115 DEG C of reaction 15min；It is wooden to get arriving after reaction
Matter cellulosic hydrolysate.It measures the content of xylose and glucose in ligno-cellulose hydrolysate respectively using HPLC, calculates xylose
With the yield of glucose, concrete outcome is as shown in the table:
From the result in table it is found that when selecting mass percent for the CaBr2 solution of 30%-55% as solvent, with
Being continuously increased for CaBr2 solution concentration, xylose in the resulting ligno-cellulose hydrolysate of the present embodiment degrading maize straws powder
It is also gradually increased with the yield of glucose, but highest yield is no more than 65%, and the yield of xylose is consistently higher than obtaining for glucose
Rate；
When selecting mass percent for the CaBr2 solution of 60%-65% as solvent, gained ligno-cellulose hydrolysate
The yield of middle xylose and glucose is improved significantly, and is above 90%；And being continuously increased with CaBr2 solution concentration,
The yield of xylose is declined slightly, and the yield of glucose slightly improves, but the yield of xylose is consistently lower than the yield of glucose, takes
Obtained unexpected technical effect；
When selecting mass percent for the CaBr2 solution of 70%-75% as solvent, with CaBr2 solution concentration
It is continuously increased, the yield and sharp fall of xylose and glucose in gained ligno-cellulose hydrolysate are below 75%, and wood
The yield of sugar is higher than the yield of glucose again.
To sum up, the new method of lignocellulose degradation material of the present invention is to use mass percent for 60%-65%
Halide salt solution handled as solvent, at this concentration, halogen and lignocellulosic and water phase and lignocellulosic it
Between effect realize optimal proportion, therefore obtain above-mentioned unexpected technical effect.
Claims (2)
1. a kind of method of lignocellulose degradation material, which is characterized in that the method is specific as follows: being with mass percent
60% CaBr2Solution is solvent, using commercially available concentrated hydrochloric acid as catalyst, using corn stalk powder as ligno-cellulosic materials, wherein beautiful
Rice straw powder and CaBr2The mass volume ratio of solution is 1:10, unit g:ml, the quality volume of corn stalk powder and concentrated hydrochloric acid
Than for 10:1, unit g:ml, under normal pressure in 115 DEG C of reaction 15min to get arriving wood fibre hydrolysis liquid.
2. application of the method described in claim 1 in xylose or glucose production.
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| CN1807515A (en) * | 2005-01-20 | 2006-07-26 | 中国科学院过程工程研究所 | Method for preparing degradable material using stalk |
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| CN102154412A (en) * | 2011-01-17 | 2011-08-17 | 同济大学 | Method for increasing sugar yield of cellulase enzymolysis through pretreatment by using ion liquid |
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| CN103849665A (en) * | 2012-11-30 | 2014-06-11 | 中国科学院大连化学物理研究所 | Method for pretreating lignocellulose by using carboxyl functionalized ionic liquid solution |
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|---|---|---|---|---|
| CN1807515A (en) * | 2005-01-20 | 2006-07-26 | 中国科学院过程工程研究所 | Method for preparing degradable material using stalk |
| 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 |
| CN102154412A (en) * | 2011-01-17 | 2011-08-17 | 同济大学 | Method for increasing sugar yield of cellulase enzymolysis through pretreatment by using ion liquid |
| CN102321251A (en) * | 2011-05-27 | 2012-01-18 | 华南理工大学 | Method for separating xylogen from agricultural waste by using compound ion liquid |
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