CN105779531B - A kind of method of improved high temperature liquid water preprocessing lignocellulose biolobic material - Google Patents

A kind of method of improved high temperature liquid water preprocessing lignocellulose biolobic material Download PDF

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CN105779531B
CN105779531B CN201610326905.7A CN201610326905A CN105779531B CN 105779531 B CN105779531 B CN 105779531B CN 201610326905 A CN201610326905 A CN 201610326905A CN 105779531 B CN105779531 B CN 105779531B
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high temperature
solute
temperature liquid
lignin
polar non
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CN105779531A (en
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袁振宏
余强
庄新姝
卞士祥
王琼
王闻
亓伟
谭雪松
周桂雄
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Guangzhou Institute of Energy Conversion of CAS
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Abstract

The invention discloses a kind of methods of improved high temperature liquid water preprocessing lignocellulose biolobic material, this method in hydrolytic process by adding biology base polar non-solute, part water is substituted with biology base polar non-solute, not only increase system Mass and heat transfer effect, lignin from biomass and surface class lignin are also dissolved simultaneously, to realize the effectively hydrolyzing of hemicellulose, the efficient removal of lignin, and reduce water consumption, solvent can recycle;The inherently biomass hydrolysate such as biology base polar non-solute such as tetrahydrofuran, furfural, substitution part water is conducive to raising system mass transfer characteristic and lignin dissolution, solving hemicellulose in the method for high temperature liquid water preprocessing lignocellulose biolobic material can not further hydrolyze, the removal efficiency of lignin is low, the problem of releasing of subsequent fiber element enzyme and cellulose hydrolyzes is hindered, also solves the problems, such as that highly water intensive, cellulase dosage is high.

Description

A kind of method of improved high temperature liquid water preprocessing lignocellulose biolobic material
Technical field:
The present invention relates to the technical fields that biomass is converted to new energy, and in particular to a kind of improved high temperature liquid water is pre- The method for handling lignocellulose-like biomass.
Background technique:
The biorefinery production energy and high valuable chemicals are carried out using lignocellulose-like biomass, for ensureing state Family's energy and economic security have positive effect, and have for slowing down the environmental pollution got worse also highly important existing Sincere justice.By in lignocellulose-like biomass glycosyl high molecular polymer-hemicellulose and cellulose be hydrolyzed to and can ferment Property sugar, be production cellulosic ethanol, butanol, the derived energy chemical products such as biogasoline, and then realize the indispensability basis of biorefinery. But the close space three-dimensional structure of cellulose-hemicellulose-lignin constitutes the natural anti-rotation screen of wood fiber biomass Barrier removes lignin/hemicellulose steric hindrance by preconditioning technique, increases surface of material aperture and surface area, reduction cellulose Crystallinity and the degree of polymerization, and then broken biological matter converts barrier, for improving the more of cellulase hydrolysis rate and subsequent microorganism Sugar utilization is most important.
High-temperature liquid state water pretreatment (Liquid Hot Water) refers to using temperature between 150 DEG C -350 DEG C, pressure Compressed liquid water higher than its saturated vapor pressure is the method for reaction medium.Because itself H+ and OH- concentration is higher by about than normal water 101.5 times and itself has the function of acid-base catalysis.Compared with the chemical pretreatments such as traditional soda acid, ammonia fiber explosion, this method without Chemical reagent addition, and catabolite is few, thus have become the research hotspot of preprocessing technical field.However document [Bioresource Technology144 (2013) 210-215] in the shortcomings that mentioning high-temperature liquid state water pretreatment there are highly water intensive, highly energy-consumings, it is such as sweet Bagasse handles 20min under 160 DEG C, 5% concentration, and residue cellulase hydrolysis rate is 76.3%, when further decreasing water consumption, Residue enzymatic hydrolyzation is only 22.1% under 20% concentration;The reduction of water reduces the Mass and heat transfer efficiency of reaction system, in biology Matter and high temperature liquid water contact interface, hemicellulose is hydrolyzed to xylan, but xylan can not be diffused into water phase further Hydrolysis, be trapped in biological surface xylan can further polymerization reaction generate class lignin product, on the one hand inhibit partly The hydrolysis of cellulose, the releasing on the other hand hindering subsequent fiber element enzyme and cellulose hydrolyze.In addition, high concentration of substrate is located in advance Hemicellulose conversion coefficient is lower during reason, is respectively 74.2% and 28.1% under 5% and 20% concentration.If in preprocessing process Most of hemicellulose cannot be removed, subsequent residue enzymatic hydrolysis certainly will be will lead to, pentose/hexose common fermentation difficulty increases. At the same time, low delignification rate makes enzyme dosage during residue cellulase hydrolysis high, these limit this Popularization and application of the green preconditioning technique in lignocellulose-like biomass diastatic fermentation field.
Summary of the invention:
The object of the present invention is to provide a kind of method of improved high temperature liquid water preprocessing lignocellulose biolobic material, By adding biology base polar non-solute in hydrolytic process, the mass transfer characteristic of system is not only improved, also while dissolving life Lignin and surface class lignin, to realize the efficient removal of the effectively hydrolyzing of hemicellulose, lignin, and drop in substance Low water usage amount.The inherently biomass hydrolysate such as biology base polar non-solute such as tetrahydrofuran, furfural substitutes part Water is conducive to raising system mass transfer characteristic and lignin dissolution, solves high temperature liquid water preprocessing lignocellulose class biology Hemicellulose can not be hydrolyzed further in the method for matter, and the removal efficiency of lignin is low, hinder subsequent fiber element enzyme and cellulose Releasing hydrolysis the problem of, also solve the problems, such as that highly water intensive, cellulase dosage is high.
The present invention is achieved by the following technical programs:
A kind of method of improved high temperature liquid water preprocessing lignocellulose biolobic material, this method includes following step It is rapid:
It is that 100-200 mesh lignocellulose-like biomass is added in hydrolysis reactor by granularity, volumetric concentration, which is added, is Biology base polar non-solute/water mixed liquid of 1%-70%, substrate mass concentration are 10%~20%, are stirred evenly, 5-60min is hydrolyzed at 160-200 DEG C, product is separated by solid-liquid separation after reaction, and most of cellulose and part wood are retained in solid phase Quality, obtained liquid phase carry out organic phase/aqueous phase separation again, and hemicellulose derived carbohydrate rich in, has in obtained water phase Machine mutually recycles to obtain biology base polar non-solute;Solid phase residue pH4.8 carries out cellulose hydrolyzation 48h, and every gram of substrate adds Add 5~15FPU of cellulase, obtains the liquid phase rich in glucose and the solid residue rich in lignin.
The biology base polar non-solute includes tetrahydrofuran, furfural etc..
Preferably, according to the property of different lignocellulose-like biomass, be passed through in the reactor ammonia, carbon dioxide, One of sulfur dioxide, oxygen, air, nitrogen pressurize, so that reaction environment is alkalinity or acidity or oxidation or inertia Environment.
Preferably, the biology base polar non-solute of recycling is recycled as the reaction solution of next round hydrolysis.
The lignocellulose-like biomass is selected from sweet sorghum slag, bagasse, poplar bits, corncob, corn stover, wheat straw Stalk, straw, switchgrass, energy grass etc..
The features of the present invention and it is a technical advantage that:
(1) it by adding biology base polar non-solute in hydrolytic process, is replaced with biology base polar non-solute For part water, system Mass and heat transfer effect is not only increased, also while dissolving lignin from biomass and surface class lignin, from And realize the efficient removal of the effectively hydrolyzing of hemicellulose, lignin, and reduce water consumption, solvent, which can recycle circulation, to be made With;
(2) this method combines the dissolution characteristics of high temperature liquid water self-catalysis and polar non-solute, realizes half fiber Dimension element is molten altogether with lignin, reduces the dosage of subsequent fiber element enzyme;
(3) compared with conventional high-temperature liquid water law, not only delignification rate increases, but also obtained hemicellulose is derivative Sugared concentration is high, is conducive to subsequent transformation and utilizes;
(4) compared with conventional organic solvents method, during hemicellulose derived carbohydrate is soluble in the aqueous phase, lignin is dissolved in organic phase, Product separation process is simpler, and the inherently biomass by hydrolyzation such as biology base polar non-solute such as tetrahydrofuran, furfural Product, process are more green.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1: high temperature liquid water/Tetrahydrofuran System
Using switchgrass as raw material, it is crushed to 100-200 mesh, is launched in intermittent stirring reaction under high pressure narrow-necked earthen jar, is pressed It is tetrahydrofuran/water mixed liquid that 10% addition volumetric concentration is 1% according to substrate mass concentration, closed reaction system is heated to 165~175 DEG C of speeds of agitator are 500rpm, and being passed through carbon dioxide and keeping reaction pressure is that 3Mpa hydrolyzes 40min, and reaction terminates Afterwards, collect reactant be separated by solid-liquid separation, solid-phase component analysis it is found that cellulose retention rate be 90.1%, delignification rate It is 74.5%, liquid phase is directly distilled to recover tetrahydrofuran and is recycled as next reaction solution, and remaining water phase is through high performance liquid chromatography Analysis is about not added with 3 times of tetrahydrofuran situation it is found that total xylose (including xylose and xylo-oligosaccharide) rate of recovery is 81.8% (high temperature liquid water treatment conditions are identical).Solid phase residue is added cellulolytic enzyme and is hydrolyzed, and substrate mass concentration is 10%, After hydrolyzing 48h under the conditions of enzyme concentration 5FPU/g, pH4.8,50 DEG C, 150rpm, cellulase hydrolysis rate is 82.5%, is about not added with Tetrahydrofuran handles 4 times of residue enzymatic hydrolyzation.
Embodiment 2: high temperature liquid water/Tetrahydrofuran System
Using straw as raw material, it is crushed to 100-200 mesh, is launched in intermittent stirring reaction under high pressure narrow-necked earthen jar, according to Substrate mass concentration is tetrahydrofuran/water mixed liquid that 15% addition volumetric concentration is 70%, and closed reaction system is heated to 175~185 DEG C of speeds of agitator are 500rpm, and being passed through nitrogen and keeping reaction pressure is that 4Mpa hydrolyzes 30min, after reaction, are received Collection reactant is separated by solid-liquid separation, it is found that cellulose retention rate is 94.4%, delignification rate is for solid-phase component analysis 82.3%, liquid phase is directly distilled to recover tetrahydrofuran and is recycled as next reaction solution, and remaining water phase is through high performance liquid chromatography point Analysis is about not added with 4 times of tetrahydrofuran situation it is found that total xylose (including xylose and xylo-oligosaccharide) rate of recovery is 89.2% (high temperature liquid water treatment conditions are identical).Solid phase residue is added cellulolytic enzyme and is hydrolyzed, and substrate mass concentration is 10%, After hydrolyzing 48h under the conditions of enzyme concentration 10FPU/g, pH4.8,50 DEG C, 150rpm, cellulase hydrolysis rate is 88.2%, is not added about Add 5 times of tetrahydrofuran processing residue enzymatic hydrolyzation.
Embodiment 3: high temperature liquid water/furfural system
Using poplar bits as raw material, it is crushed to 100-200 mesh, is launched in reaction under high pressure narrow-necked earthen jar, according to substrate matter Amount concentration is furfural/water mixed liquid that 20% addition volumetric concentration is 50%, and closed reaction system is heated to 185~195 DEG C, Speed of agitator is 500rpm, and being passed through sulfur dioxide and keeping reaction pressure is that 5Mpa hydrolyzes 50min, after reaction, is directly carried out It is separated by solid-liquid separation, water layer is mainly sugared product, and furfural layer is mainly sugared catabolite and lignin degradation products, and water phase is through efficient liquid Analysis of hplc is about not added with the 5 of furfural situation it is found that total xylose (including xylose and xylo-oligosaccharide) rate of recovery is 75.7% Again (high temperature liquid water treatment conditions are identical).The furfural extraction in furfural layer and solid residue is arrived with low boiling point solvents such as acetone In acetone, extract liquor carries out acetone and furfural separation by distillation, and obtained furfural circulation is for processing next time.Solid residue at It is found that cellulose retention rate is 89.9%, cellulolytic enzyme is added in delignification rate 91.1%, solid phase residue for analysis It is hydrolyzed, substrate mass concentration 10%, enzyme concentration 15FPU/g, pH4.8,50 DEG C, after hydrolyzing 48h under the conditions of 150rpm, fiber Plain enzymatic hydrolyzation is 89.6%, is about not added with 7 times of furfural processing residue enzymatic hydrolyzation.
Above embodiments prove, substitute high temperature liquid water, Ke Yishi using biology base polar non-solute part The high-efficiency pretreatment of existing wood fiber biomass, it is bad to compensate for low delignification rate in conventional high-temperature liquid water preprocessing process Gesture reduces cellulase dosage, balances the contradictory relation of water consumption and pretreating effect, it is seen that the improved high-temperature liquid state The economy of water pretreatment process is greatly improved.

Claims (4)

1. a kind of method of improved high temperature liquid water preprocessing lignocellulose biolobic material, which is characterized in that this method packet It includes following steps: being that 100-200 mesh lignocellulose-like biomass is added in hydrolysis reactor by granularity, volumetric concentration, which is added, is Biology base polar non-solute/water mixed liquid of 1%-70%, the biology base polar non-solute be selected from tetrahydrofuran, Furfural;Substrate mass concentration is 10%~20%, stirs evenly, 5-60min is hydrolyzed at 160-200 DEG C, and product carries out after reaction It is separated by solid-liquid separation, most of cellulose is retained in solid phase and partial lignin, obtained liquid phase carry out organic phase/aqueous phase separation again, Hemicellulose derived carbohydrate rich in obtained water phase, organic phase recycle to obtain biology base polar non-solute;It will consolidate Phase residue pH4.8 carries out cellulose hydrolyzation 48h, and every gram of substrate adds 5~15FPU of cellulase.
2. the method for high temperature liquid water preprocessing lignocellulose biolobic material according to claim 1, which is characterized in that One of ammonia, carbon dioxide, sulfur dioxide, oxygen, air, nitrogen is passed through in the reactor to pressurize.
3. the method for high temperature liquid water preprocessing lignocellulose biolobic material according to claim 1, which is characterized in that Recycle the reaction solution that obtained biology base polar non-solute is recycled as next round hydrolysis.
4. the method for high temperature liquid water preprocessing lignocellulose biolobic material according to claim 1, which is characterized in that The lignocellulose-like biomass be selected from sweet sorghum slag, bagasse, poplar bits, corncob, corn stover, Wheat Straw, straw, One of switchgrass, energy grass.
CN201610326905.7A 2016-05-16 2016-05-16 A kind of method of improved high temperature liquid water preprocessing lignocellulose biolobic material Expired - Fee Related CN105779531B (en)

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CN106520846A (en) * 2016-11-08 2017-03-22 奥为(天津)环保科技有限公司 Improved lignocellulose biomass hydrothermal pretreatment method
CN107385119A (en) * 2017-08-28 2017-11-24 华南理工大学 A kind of method that corncob rapidly and efficiently prepares xylose hydrolysis fluid
CN109874928B (en) * 2019-01-16 2022-10-04 中国科学院广州能源研究所 Hydrothermal depolymerization method for improving quality of silage raw materials

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CN101586136A (en) * 2009-07-03 2009-11-25 中国科学院广州能源研究所 Method of high-efficiency pretreatment on biomass
CN102660882A (en) * 2012-05-17 2012-09-12 刘德江 Method for producing cellulose and fuel ethanol by dissolving plant straw with solvent

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