CN102153763A - Lignocellulose acid/alkali coupling pretreatment method - Google Patents

Lignocellulose acid/alkali coupling pretreatment method Download PDF

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CN102153763A
CN102153763A CN2011100074872A CN201110007487A CN102153763A CN 102153763 A CN102153763 A CN 102153763A CN 2011100074872 A CN2011100074872 A CN 2011100074872A CN 201110007487 A CN201110007487 A CN 201110007487A CN 102153763 A CN102153763 A CN 102153763A
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lignocellulose
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齐崴
黄仁亮
苏荣欣
何志敏
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Tianjin University
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Abstract

The invention relates to a lignocellulose acid/alkali coupling pretreatment method. Lignocellulose is separated into cellulose, hemicellulose and lignin by acid/alkali coupling pretreatment; and simultaneously, lignocellulose components are separated and subjected to high-efficiency enzymolysis and saccharification. The method comprises the steps of lignocellulose pretreatment, component separation, cellulose enzymolysis, solvent recovery and the like. The lignocellulose material is pretreated by formic acid or dilute sulphuric acid and is then subjected to solid-liquid separation, wherein the liquid component is used for recovering hemicellulose hydrolyzed sugar and part of lignin; and the solid component is further treated by ammonia water or a sodium hydroxide solution and is then subjected to solid-liquid separation, the liquid component is used for recovering lignin, and the solid component (cellulose) is subjected to enzymolysis and saccharification. By converting the lignocellulose into cellulose hydrolyzed sugar (glucose), hemicellulose hydrolyzed sugar (xylose and xylooligosaccharide) and lignin, the invention provides a basis for full-biomass utilization and develops a green process route for recovering the pretreatment solvent.

Description

A kind of lignocellulose soda acid coupling pretreatment process
Technical field
The invention belongs to biomass resource trans-utilization technical field, particularly relate to a kind of lignocellulose soda acid coupling pretreatment process, particularly, utilize soda acid coupling pre-treatment to separate lignocellulose and be Mierocrystalline cellulose, hemicellulose and xylogen, realize that simultaneously the lignocellulose component is separated and efficient enzymatic saccharification.
Background technology
From lignocellulose resource preparation biomass energy and bio-based chemical, progressively set up the biorefining economic model, can alleviate the dependence of petroleum industry and reduce pollution environment.In the conversion process of lignocellulose, based on the conversion technology of sugared platform because reaction conditions gentleness, advantages of environment protection enjoy favor.Yet how complicated polysaccharide is still restricting the development of lignocellulose biorefining in the effectively hydrolyzing lignocellulosic.
Lignocellulose mainly is made up of Mierocrystalline cellulose, hemicellulose and xylogen.Wherein, Mierocrystalline cellulose is by β-1 by D-glucose, 4 glycosidic links connect the long chain molecule that forms, long chain molecule further forms a kind of supramolecule rock steady structure with highly crystalline district, closely inlaying hemicellulose and xylogen around it simultaneously, this complicated stable structure makes Mierocrystalline cellulose be difficult to directly by enzymic hydrolysis.For improving cellulase hydrolysis efficient, must carry out pre-treatment to lignocellulosic material.
Change the lignocellulose physicochemical characteristic by pre-treatment and can effectively improve cellulase hydrolysis efficient.At present, lignocellulose pretreatment method is broadly divided into physics method, chemical method, physico-chemical processes and biological process.The physics method mainly improves cellulase hydrolysis efficient by means such as mechanical disintegration, microwave, steam explosions, and weak point is that the process power consumption is high, and equipment is had high input.Chemical method utilizes chemical reagent (as acid, alkali) hydrolyzed hemicellulose or remove xylogen, also can cause the variation of its physical property when changing the lignocellulose chemical constitution, as degree of crystallinity, can reach internal surface area etc.Chemical method is owing to advantages such as process operation is simple, power consumption is low, effect is obvious are expected to be used widely in the industrial production from now on.Biological rule mainly adopts the xylogen in the lignocellulose degradation raw materials such as white-rot fungi or lignin-degrading enzymes, thereby improves cellulosic enzymolysis efficiency.Biological process is in the experimental phase, remains further to be studied.At present, most pretreatment processs are difficult to realize simultaneously that the total composition of lignocellulose separates and efficient enzymolysis.In addition, traditional pre-treatment thinking also often is confined to obtain to be converted into the alcoholic acid Mierocrystalline cellulose, and the processing of hemicellulose, xylogen is fully paid attention to.Therefore, in order to reduce production costs, preprocessing process should separate this three big component when realizing the Mierocrystalline cellulose efficiently saccharifying, purifying, and then is converted into useful products separately.
Summary of the invention
The object of the present invention is to provide a kind of new lignocellulose soda acid coupling pretreatment process, can overcome the defective of prior art.It is the soda acid coupling pretreatment process of separation of lignocellulose component and efficient enzymolysis, can realize lignocellulose three big components separation and the efficient enzymatic saccharifications of Mierocrystalline cellulose simultaneously, and the recovery of realization solvent is used again.
Lignocellulose soda acid of the present invention coupling pretreatment process relates generally to lignocellulose pre-treatment, component separation, cellulase hydrolysis, solvent recuperation and operation such as uses again, comprises the steps:
(1) air-dry lignocellulose (maize straw, corn cob, straw or wood chip etc.) is carried out mechanical disintegration and handle, particle diameter is between 100 orders~1cm.
(2) lignocellulose after the pulverizing utilizes formic acid or dilution heat of sulfuric acid to handle.
A. formic acid is handled: adding concentration down at 40~100 ℃ is formic acid solution stir process 1~10h of 70~95wt%, the solid-to-liquid ratio of lignocellulose and formic acid solution (w/v) is 1: 50~1: 5, the hydrochloric acid addition is 0~1/25 of a formic acid volume, and mixing speed is 20~300rpm.
B. dilute sulphuric acid is handled: adding concentration down at 80~150 ℃ is dilution heat of sulfuric acid stir process 5min~2h of 0.5~10wt%, and the solid-to-liquid ratio of lignocellulose and dilution heat of sulfuric acid (w/v) is 1: 50~1: 5, and mixing speed is 20~300rpm.
(3) reaction paste after the acid treatment carries out solid-liquid separation through centrifugal, suction filtration of eddy current or Plate Filtration, liquid material and solid substances.
(4) liquid material that step (3) is obtained carries out solvent recuperation
A. formic acid is handled: reclaim by the formic acid in underpressure distillation, extracting rectifying or the azeotropic distillation method liquid towards material, after formic acid solution reclaimed, xylogen and hydrolysis of hemicellulose sugar precipitated.The soluble sugar that is dissolved in water, the water-insoluble xylogen is collected through solid-liquid separating method; The main component of liquid material is hydrolysis of hemicellulose sugar such as wood sugar, wood oligose.
B. dilute sulphuric acid is handled: liquid material carries out acid-base neutralisation to be handled, and adds the 10wt% sodium hydroxide solution, is 6.5~7.5 up to system pH.
(5) solid substances that step (3) is obtained carries out the processing of ammoniacal liquor or sodium hydroxide solution again.
A. ammonia treatment: adding concentration down at 40~80 ℃ is ammonia soln stir process 2~24h of 10~25wt%, and the solid-to-liquid ratio of solid substances and ammonia soln (w/v) is 1: 20~1: 2, and mixing speed is 20~300rpm.
B. sodium-hydroxide treatment: adding concentration down at 60~120 ℃ is sodium hydroxide solution stir process 1~12h of 0.5~10wt%, and the solid-to-liquid ratio of solid substances and sodium hydroxide solution (w/v) is 1: 50~1: 5, and mixing speed is 20~300rpm.
(6) feed liquid after the alkaline purification is carried out solid-liquid separation, liquid material and solid substances, described solid-liquid separating method is that eddy current is centrifugal, suction filtration or Plate Filtration.
(7) liquid material that step (6) is obtained carries out solvent recuperation
A. ammonia treatment: carry out ammoniacal liquor and reclaim (underpressure distillation, extracting rectifying, azeotropic distillation), collect the xylogen precipitation that produces; Or carry out neutralizing treatment with the dilution heat of sulfuric acid of step (4b), and collect the xylogen precipitation after the solid-liquid separation, liquid material is hydrolysis of hemicellulose sugar such as wood sugar, wood oligose.
B. sodium-hydroxide treatment: add the 98wt% concentrated sulfuric acid solution and carry out neutralizing treatment, collect the xylogen precipitation after the solid-liquid separation; Or carry out neutralizing treatment with the dilution heat of sulfuric acid of step (4b), and collect the xylogen precipitation after the solid-liquid separation, liquid material is hydrolysis of hemicellulose sugar such as wood sugar, wood oligose.
(8) solid substances that obtains of step (6) is usefulness cellulase and beta-glucoside enzymic hydrolysis 2~72h in 4.8 the citrate buffer solution through washing, dry back at pH, the enzyme heap(ed) capacity of every gram dextran is respectively 5~60FPU cellulase and 0~60CBU beta-glucosidase, the solid-to-liquid ratio of solid substances and citrate buffer solution (w/v) is 1: 100~1: 10, temperature of reaction is 50 ℃, and rotating speed is 20~300rpm.
(9) enzyme digestion reaction finishes the back material is carried out solid-liquid separation, and the liquid material main component is cellulose hydrolysis sugar such as glucose, and a spot of solid substances is hard-degraded substances such as xylogen.
Lignocellulose soda acid coupling pretreatment process provided by the invention compared with prior art has the following advantages.
(1) realizes that simultaneously the lignocellulose total composition separates and the efficient enzymatic saccharification of Mierocrystalline cellulose, for full biomass utilization provides the basis.
(2) the cellulosic component purity height of gained is beneficial to and realizes follow-up high solid-liquid ratio enzymatic saccharification or simultaneous saccharification and fermentation, thereby obtains products such as high concentration glucose, ethanol.
(3) temperature operation in the normal pressure, mild condition is easily controlled, and saves power consumption, and facility investment is little.
(4) the pre-treatment solvent cheaply is easy to get, and recyclable usefulness again, is economically viable friendly process.
Description of drawings
The formic acid ammoniacal liquor combined treatment of utilizing Fig. 1 realizes that the lignocellulose component is separated and the process flow sheet of efficient enzymatic saccharification.
Fig. 2 adopts the present invention to handle the high-efficient liquid phase chromatogram of (formic acid) maize straw gained hydrolysis of hemicellulose sugar.
Fig. 3 adopts the present invention to handle the high-efficient liquid phase chromatogram of (combination of formic acid ammoniacal liquor) corn cob gained cellulase hydrolysis products.
Fig. 4 adopts the present invention to handle (combination of formic acid ammoniacal liquor) cellulosic enzymolysis curve of corn cob gained.
Embodiment
Embodiment 1
Taking by weighing particle diameter is 20~80 present maize straw 1000g, adds 15L formic acid (88wt%) and 150mL hydrochloric acid (37wt%) and places treatment tank.In 65 ℃, 150rpm water bath with thermostatic control behind the reaction 3h with the reacting slurry solid-liquid separation.(1) liquid ingredient reclaims formic acid and hydrochloric acid through underpressure distillation, and the formic acid rate of recovery reaches 92%.Add water 500mL dissolving hydrolysis of hemicellulose sugar at normal temperatures and pressures, and utilize high performance liquid chromatography (HPLC) analyzing and testing (result as shown in Figure 2), the hydrolysis of hemicellulose rate reaches 90%; The water-insoluble xylogen is through centrifugal or filtered and recycled.(2) solid ingredient is carried out ammonia treatment again, treatment condition are: ammonia concn 15wt%, solid-to-liquid ratio 1: 8,60 ℃ of treatment temps and reaction times 16h.With the material solid-liquid separation, wherein, liquid ingredient reclaimed ammoniacal liquor (rate of recovery reaches 90%) through underpressure distillation after reaction finished, and collected the xylogen precipitation that generates, and the xylogen yield reaches 84%; Solid ingredient is washed with distilled water to pH6~7, and the oven dry back is quantitative, and the Mierocrystalline cellulose retention rate is 89%.
Maize straw solid ingredient after handling is carried out enzymolysis, enzymatic hydrolysis condition: solid-to-liquid ratio is that 1: 50, temperature are that 50 ℃, rotating speed are that 150rpm, pH4.8 citrate buffer solution, enzyme heap(ed) capacity are every gram Dextran 60 FPU cellulase and 60CBU beta-glucosidase.After enzymolysis finishes reacting slurry is taken out, carry out suction filtration behind the enzyme 10min that in boiling water bath, goes out.Liquid ingredient utilizes the HPLC analyzing and testing, and cellulase hydrolysis transformation efficiency (24h) is 81%.
Embodiment 2
Taking by weighing the 1000g particle diameter is that 20~80 purpose maize straws add in the treatment tank, adds the 2wt% dilution heat of sulfuric acid at 1: 15 by solid-to-liquid ratio.In 120 ℃ of pressure kettle the reaction 45min after with the reacting slurry solid-liquid separation.Liquid ingredient is used for follow-up neutralizing treatment; Solid ingredient is carried out the sodium hydroxide solution processing again, and treatment condition are: naoh concentration 2wt%, solid-to-liquid ratio 1: 10,80 ℃ of treatment temps and reaction times 8h.After reaction finishes with the material solid-liquid separation.(1) liquid material after liquid ingredient and dilute sulphuric acid are handled neutralizes, and the water-insoluble xylogen of generation is through centrifugal or filtered and recycled, and the xylogen yield reaches 87%; Liquid ingredient utilizes the HPLC analyzing and testing, and the hydrolysis of hemicellulose rate reaches 89%.(2) solid ingredient is washed with distilled water to pH6~7, and the oven dry back is quantitative, and the Mierocrystalline cellulose retention rate is 93%.
Maize straw solid ingredient after handling is carried out enzymolysis, enzymatic hydrolysis condition: solid-to-liquid ratio is that 1: 50, temperature are that 50 ℃, rotating speed are that 150rpm, pH4.8 citrate buffer solution, enzyme heap(ed) capacity are every gram Dextran 60 FPU cellulase and 60CBU beta-glucosidase.After enzymolysis finishes reacting slurry is taken out, carry out suction filtration behind the enzyme 10min that in boiling water bath, goes out.The filtrate of collecting is utilized the HPLC analyzing and testing, and cellulase hydrolysis transformation efficiency (24h) is 83%.
Embodiment 3
Taking by weighing particle diameter is 20~80 purpose corn cob 1000g, adds 10L formic acid (88wt%) and 100mL hydrochloric acid (37wt%) and places treatment tank.In 60 ℃, 150rpm water bath with thermostatic control behind the reaction 3h with the reacting slurry solid-liquid separation.(1) liquid ingredient reclaims formic acid and hydrochloric acid through underpressure distillation, and the formic acid rate of recovery reaches 92%.The hydrolysis of hemicellulose sugar that is dissolved in water utilizes the HPLC analyzing and testing, and the hydrolysis of hemicellulose rate reaches 91%; The water-insoluble xylogen is through centrifugal or filtered and recycled.(2) solid ingredient is carried out ammonia treatment again, treatment condition are: ammonia concn 15wt%, solid-to-liquid ratio 1: 6,60 ℃ of treatment temps and reaction times 12h.With the material solid-liquid separation, liquid ingredient reclaimed ammoniacal liquor (rate of recovery reaches 90%) through underpressure distillation after reaction finished, and collected the xylogen precipitation that generates, and the xylogen yield can reach 83%; Solid ingredient is washed with distilled water to pH6~7, and the oven dry back is quantitative, and the Mierocrystalline cellulose retention rate is 87%.
Corn cob solid ingredient after handling is carried out enzymolysis, enzymatic hydrolysis condition: solid-to-liquid ratio is that 1: 20, temperature are that 50 ℃, rotating speed are that 150rpm, pH4.8 citrate buffer solution, enzyme heap(ed) capacity are every gram dextran 30FPU cellulase and 60CBU beta-glucosidase.After enzymolysis finishes reacting slurry is taken out, carry out solid-liquid separation behind the enzyme 10min that in boiling water bath, goes out.Liquid ingredient utilizes HPLC analyzing and testing (result as shown in Figure 3), and the cellulase hydrolysis transformation efficiency is 85% behind the hydrolysis 24h, and hydrolysis 48h can reach 91% (Fig. 4).
Embodiment 4
Taking by weighing the 1000g particle diameter is that 20~80 purpose corn cobs add in the treatment tank, adds the 2wt% dilution heat of sulfuric acid at 1: 10 by solid-to-liquid ratio.In 120 ℃ of pressure kettle the reaction 45min after with the reacting slurry solid-liquid separation.Liquid ingredient is used for follow-up neutralizing treatment; Solid ingredient is carried out the sodium hydroxide solution processing again, and treatment condition are: naoh concentration 2wt%, solid-to-liquid ratio 1: 10,80 ℃ of treatment temps and reaction times 8h.Reaction is carried out solid-liquid separation with material after finishing: the liquid material after (1) liquid ingredient and dilute sulphuric acid are handled neutralizes.The water-insoluble xylogen that produces is through centrifugal or filtered and recycled, and the xylogen yield reaches 86%; Supernatant liquor utilizes high performance liquid chromatography (HPLC) analyzing and testing, and the hydrolysis of hemicellulose rate reaches 89%.(2) solid ingredient is washed with distilled water to pH6~7, and the oven dry back is quantitative, and the Mierocrystalline cellulose retention rate is 90%.
Corn cob solid ingredient after handling is carried out enzymolysis, enzymatic hydrolysis condition: solid-to-liquid ratio is that 1: 20, temperature are that 50 ℃, rotating speed are that 150rpm, pH4.8 citrate buffer solution, enzyme heap(ed) capacity are every gram dextran 30FPU cellulase and 60CBU beta-glucosidase.After enzymolysis finishes reacting slurry is taken out, carry out solid-liquid separation behind the enzyme 10min that in boiling water bath, goes out.Liquid ingredient utilizes the HPLC analyzing and testing, and cellulase hydrolysis transformation efficiency (24h) is 86%.

Claims (10)

1. a lignocellulose soda acid coupling pretreatment process is characterized in that it comprises the steps:
(1) air-dry lignocellulose is carried out mechanical disintegration and handle, particle diameter is between 100 orders~1cm;
(2) adding of the lignocellulose after pulverizing acid solution is handled, and acid solution is formic acid solution or the dilution heat of sulfuric acid that contains small amount of hydrochloric acid;
(3) reaction paste after the acid treatment carries out solid-liquid separation, gets liquid material and solid substances;
(4) liquid material that step (3) is obtained carries out solvent recuperation
A. formic acid is handled: reclaim by the formic acid in underpressure distillation, extracting rectifying or the azeotropic distillation method liquid towards material, after formic acid solution reclaimed, xylogen and hydrolysis of hemicellulose sugar precipitated.The soluble sugar that is dissolved in water, the water-insoluble xylogen is collected through solid-liquid separating method;
B. dilute sulphuric acid is handled: liquid material carries out acid-base neutralisation to be handled, and adds sodium hydroxide solution, is 6.5~7.5 up to system pH.
(5) solid substances that step (3) is obtained carries out alkaline purification again, and alkaline solution is ammonia soln or sodium hydroxide solution;
(6) feed liquid after the alkaline purification is carried out solid-liquid separation, gets liquid material and solid substances;
(7) liquid material that step (6) is obtained carries out solvent recuperation
A. ammonia treatment: carry out ammoniacal liquor and reclaim, collect the xylogen precipitation that produces, or carry out neutralizing treatment with the dilution heat of sulfuric acid of step (4b), collect xylogen after the solid-liquid separation and precipitate, liquid material is hydrolysis of hemicellulose sugar such as wood sugar, wood oligose;
B. sodium-hydroxide treatment: add the 98wt% concentrated sulfuric acid solution and carry out neutralizing treatment, collect the xylogen precipitation after the solid-liquid separation, or carry out neutralizing treatment with the dilution heat of sulfuric acid of step (4b), and collect the xylogen precipitation after the solid-liquid separation, liquid material is hydrolysis of hemicellulose sugar such as wood sugar, wood oligose;
(8) solid substances that obtains of step (6) is hydrolyzed with cellulase and beta-glucosidase in pH is 4.8 citrate buffer solution through washing, after dry;
(9) enzyme digestion reaction finishes the back material and carries out solid-liquid separation, and the liquid material main component is cellulose hydrolysis sugar such as glucose, and a spot of solid substances is hard-degraded substances such as xylogen.
2. method according to claim 1 is characterized in that described formic acid solution concentration is 70~95wt%, and dilution heat of sulfuric acid concentration is 0.5~10wt%, and ammonia soln concentration is 10~25wt%, and concentration of sodium hydroxide solution is 0.5~10wt%.
3. method according to claim 1, the solid-to-liquid ratio (w/v) that it is characterized in that described lignocellulose of step (2) and formic acid solution is 1: 50~1: 5, the hydrochloric acid addition is 0~1/25 of a formic acid volume, treatment temp is 40~100 ℃, reaction times is 1~10h, and rotating speed is 20~300rpm.
4. method according to claim 1 is characterized in that the solid-to-liquid ratio (w/v) of described lignocellulose of step (2) and dilution heat of sulfuric acid is 1: 50~1: 5, and treatment temp is 80~150 ℃, and the reaction times is 5min~2h, and rotating speed is 20~300rpm.
5. method according to claim 1 is characterized in that the solid-to-liquid ratio (w/v) of described solid substances of step (5) and ammonia soln is 1: 20~1: 2, and treatment temp is 40~80 ℃, and the reaction times is 2~24h, and rotating speed is 20~300rpm.
6. method according to claim 1 is characterized in that the solid-to-liquid ratio (w/v) of described solid substances of step (5) and sodium hydroxide solution is 1: 50~1: 5, and treatment temp is 60~120 ℃, and the reaction times is 1~12h, and rotating speed is 20~300rpm.
7. method according to claim 1 is characterized in that step (3), step (4a), step (6), step (7) and the described solid-liquid separating method of step (9) are that eddy current is centrifugal, suction filtration or Plate Filtration.
8. method according to claim 1 is characterized in that the enzyme heap(ed) capacity of the described every gram dextran of step (8) is respectively 5~60FPU cellulase and 0~60CBU beta-glucosidase.
9. method according to claim 1 is characterized in that the solid-to-liquid ratio (w/v) of described solid substances of step (8) and citrate buffer solution is 1: 100~1: 10, and temperature of reaction is 50 ℃, and the reaction times is 2~72h, and rotating speed is 20~300rpm.
10. a lignocellulose soda acid coupling pretreatment process is characterized in that it comprises the steps:
(1) air-dry lignocellulose is carried out mechanical disintegration and handle, particle diameter is between 100 orders~1cm;
(2) lignocellulose after the pulverizing utilizes formic acid or dilution heat of sulfuric acid to handle.
A. formic acid is handled: adding concentration down at 40~100 ℃ is formic acid solution stir process 1~10h of 70~95wt%, the solid-to-liquid ratio of lignocellulose and formic acid solution (w/v) is 1: 50~1: 5, the hydrochloric acid addition is 0~1/25 of a formic acid volume, and mixing speed is 20~300rpm; Or
B. dilute sulphuric acid is handled: adding concentration down at 80~150 ℃ is dilution heat of sulfuric acid stir process 5min~2h of 0.5~10wt%, and the solid-to-liquid ratio of lignocellulose and dilution heat of sulfuric acid (w/v) is 1: 50~1: 5, and mixing speed is 20~300rpm;
(3) reaction paste after the acid treatment carries out solid-liquid separation through centrifugal, suction filtration of eddy current or Plate Filtration, liquid material and solid substances;
(4) liquid material that step (3) is obtained carries out solvent recuperation
A. formic acid is handled: reclaim by the formic acid in underpressure distillation, extracting rectifying or the azeotropic distillation method liquid towards material, after formic acid solution reclaimed, xylogen and hydrolysis of hemicellulose sugar precipitated; The soluble sugar that is dissolved in water, the water-insoluble xylogen is collected through solid-liquid separating method; The main component of liquid material is hydrolysis of hemicellulose sugar such as wood sugar, wood oligose;
B. dilute sulphuric acid is handled: liquid material carries out acid-base neutralisation to be handled, and adds the 10wt% sodium hydroxide solution, is 6.5~7.5 up to system pH;
(5) solid substances that step (3) is obtained carries out the processing of ammoniacal liquor or sodium hydroxide solution again;
A. ammonia treatment: adding concentration down at 40~80 ℃ is ammonia soln stir process 2~24h of 10~25wt%, and the solid-to-liquid ratio of solid substances and ammonia soln (w/v) is 1: 20~1: 2, and mixing speed is 20~300rpm;
B. sodium-hydroxide treatment: adding concentration down at 60~120 ℃ is sodium hydroxide solution stir process 1~12h of 0.5~10wt%, and the solid-to-liquid ratio of solid substances and sodium hydroxide solution (w/v) is 1: 50~1: 5, and mixing speed is 20~300rpm;
(6) feed liquid after the alkaline purification is carried out solid-liquid separation, liquid material and solid substances, described solid-liquid separating method is that eddy current is centrifugal, suction filtration or Plate Filtration;
(7) liquid material that step is obtained carries out solvent recuperation
A. ammonia treatment: with underpressure distillation, extracting rectifying or azeotropic distillation ammoniacal liquor is reclaimed, collect the xylogen precipitation that produces; Or carry out neutralizing treatment with the dilution heat of sulfuric acid of step (4b), and collect the xylogen precipitation after the solid-liquid separation, liquid material is hydrolysis of hemicellulose sugar such as wood sugar, wood oligose;
B. sodium-hydroxide treatment: add the 98wt% concentrated sulfuric acid solution and carry out neutralizing treatment, collect the xylogen precipitation after the solid-liquid separation; Or carry out neutralizing treatment with the dilution heat of sulfuric acid of step (4b), and collect the xylogen precipitation after the solid-liquid separation, liquid material is hydrolysis of hemicellulose sugar such as wood sugar, wood oligose;
(8) solid substances that obtains of step (6) is usefulness cellulase and beta-glucoside enzymic hydrolysis 2~72h in 4.8 the citric acid-sodium citrate damping fluid through washing, dry back at pH, the enzyme heap(ed) capacity of every gram dextran is respectively 5~60FPU cellulase and 0~60CBU beta-glucosidase, the solid-to-liquid ratio of solid substances and citrate buffer solution (w/v) is 1: 100~1: 10, temperature of reaction is 50 ℃, and rotating speed is 20~300rpm;
(9) enzyme digestion reaction finishes the back material is carried out solid-liquid separation, and the liquid material main component is cellulose hydrolysis sugar such as glucose, and a spot of solid substances is hard-degraded substances such as xylogen.
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