CN107936143A - The method that one plant fiber raw material hydrolyzate biological treatment removes lignin - Google Patents

The method that one plant fiber raw material hydrolyzate biological treatment removes lignin Download PDF

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CN107936143A
CN107936143A CN201711193844.2A CN201711193844A CN107936143A CN 107936143 A CN107936143 A CN 107936143A CN 201711193844 A CN201711193844 A CN 201711193844A CN 107936143 A CN107936143 A CN 107936143A
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hydrolyzate
plant fiber
lignin
fiber material
horseradish peroxidase
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CN107936143B (en
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李宗全
王浩伟
邱程龙
高吉杰
刘芹
陈建松
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Qilu University of Technology
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Qilu University of Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0003General processes for their isolation or fractionation, e.g. purification or extraction from biomass

Abstract

The present invention relates to the method that a plant fiber raw material hydrolyzate biological treatment removes lignin, this method is to plant fiber material hydrolyzate first using horseradish peroxidase processing and then cationic polymer flocculation treatment, horseradish peroxidase processing can cause the dissolved lignin of the low molecular weight in hydrolyzate to aggregate into macromolecule lignin, and Precipitation removes a part of lignin;Lignin by horseradish peroxidase after handling, even if without Precipitation partially due to polymerizeing, molecular weight increases, it is also easier to remove during follow-up cation flocculation treatment, then handled using cationic polymer, residual lignin is further removed, horseradish peroxidase of the invention processing combines cationic polymer processing and greatly improves the total removal rate of lignin, while can also substantially reduce loss sugared in cationic polymer processing procedure.

Description

The method that one plant fiber raw material hydrolyzate biological treatment removes lignin
Technical field
The present invention relates to a kind of hydrolyzate component separation method, is specifically related to plant fiber raw material hydrolyzate biology The method that processing removes lignin, belongs to biomass comprehensive and utilizes field.
Background technology
Hemicellulose is one of natural polymer most abundant in nature, and wherein lignocellulose raw material includes timber and non- Timber, as contained substantial amounts of hemicellulose glycan in bagasse, reed and various grasses.The purposes of hemicellulose is very much, The chemicals such as furfural, hydroxymethylfurfural can be produced, high molecular weight hemicellulose can be used for food package film, hydrogel, table The preparation of the biomaterial such as face activating agent and anti-biotic material.In addition, hemicellulose sugar may also pass through fermentative production of ethanol, methanol Deng bio-fuel.Therefore, these hemicellulose glycan how are effectively utilized for biorefinery to have great importance.Will The hemicellulose in lignin fiber raw material is effectively utilized, first has to separate these hemicelluloses from raw material.At present, Hydrolyze method is from the common method of plant fiber material separation hemicellulose, and Hydrolyze method includes sour water solution, certainly hydrolysis and alkaline water Solution, hemicellulose glycan is entered in hydrolyzate after hydrolysis, and in hydrolytic process, except hemicellulose, lignin also can partly drop Solution is entered in hydrolyzate, and the catabolite containing hemicellulose and cellulose and lipophilicity extraction are in addition also possible in hydrolyzate Thing etc..During hydrolyzate fermenting and producing bio-fuel, lignin can also suppress hydrolysis and the fermentation process of enzyme, in addition, lignin And in lignocellulose raw material hydrolyzate color main source.Pure hemicellulose is it is necessary to in hydrolyzate in order to obtain Hemicellulose purified.It is main miscellaneous during impurity is removed from hydrolyzate and obtains concentration and the high sugar juice of purity The removal of matter lignin is relatively difficult.The active charcoal absorption of method, quick lime absorption, macropore of various impurity are removed from hydrolyzate Resin adsorption, cation or non-ionic polymers flocculation and a variety of methods such as membrane filtration are inhaled, concentrate that to remove small molecule miscellaneous using film Film can be blocked during matter, reduces membrane flux and membrane lifetime.
Existing many technologies disclose from lignocellulose raw material hydrolyzate and remove impurity to extract oligosaccharide at present, e.g., China Patent document 200410023875.X discloses a kind of method that xylo-oligosaccharide is extracted from maize cob meal.The invention includes following Sequential steps:(1) maize cob meal is mixed with water, adds weak acid catalyst and cracked, by the xylan dissolution in corncob; (2) it is 5.0~6.0 to adjust xylan pH value of water solution, adds zytase and is digested, high temperature goes out zytase It is living;(3) corncob granulated slag is filtered out, activated carbon and ion exchange resin removal of impurities decoloration are carried out to xylan liquid glucose;(4) macromolecular is cut Stay film to retain macromolecular xylan, filter out low xylan liquid glucose;Sodium filter membrane concentrating and desalinating;(5) by xylo-oligosaccharide liquid glucose vacuum Concentrate and be dried to xylo-oligosaccharide pulvis through excipient or Direct spraying for thick pale yellow shape syrup, xylo-oligosaccharide syrup.But should Method is poor using activated carbon and ion exchange resin removal of impurities decoloration, impurity-eliminating effect, it is impossible to effectively removes lignin, still there is impurity Residual, while easily removed using activated carbon and ion exchange resin removal of impurities together with xylan, cause sugared loss.
Chinese patent literature 201310554290.X, which is disclosed, extracts oligosaccharide in a kind of pre-hydrolyzed solution from plant material Method, step are as follows:(1) polyelectrolyte is added into plant material pre-hydrolyzed solution, the polyelectrolyte is polyaluminium chloride, gathers One of aluminum sulfate, polychloride ferro-aluminum, poly aluminium sulfate iron, poly aluminium iron silicate, poly-iron chloride, polyiron sulfate or combination, polyelectrolyte Addition is 0.01-10g/L, is stirred 5-20 minutes, stands 80-150 minutes, isolated supernatant liquor;(2) with UF membrane Method filters supernatant liquor, obtains oligosaccharide concentrate;(3) evaporative crystallization oligosaccharide concentrate, obtains oligosaccharide after drying.The party The lignin in polyelectrolyte removing hydrolyzate is added in method, impurity-eliminating effect is poor, and efficiency is low.
At present, handled using cationic flocculant is considered as that lignin particularly polymer colloid wood is removed from hydrolyzate The common method of element.The cationic flocculant of use has:Diallyl dimethyl ammoniumchloride (pDADMAC), cation poly- third Acrylamide (CPAM), polyethyleneimine (PEI) and aluminium polychloride (PAC).Chen Xiaoqian and Wang Zhaojiang et al. are by aluminium polychloride (PAC) removal of lignin and in diallyl dimethyl ammoniumchloride (PDADMAC) poplar hydrolyzate, the results showed that PAC and The addition of PDADMAC can remove the part lignin in hydrolyzate, but also result in the loss of part sugar at the same time.Referring to Chen Xiaoqian etc. People, living resources engineering, 2014,152:31-37(Chen Xiaoqian,Wang Zhaojiang,Fu Yingjuan,Li Zongquan, Qin Menghua, Specic lignin precipitation for oligosaccharides Recovery from hot water wood extract, Bioresource Technology, 2014,152:31-37).
Therefore, cationic flocculant processing remove hydrolyzate in lignin when there are problems with:Cationic polymer is wadded a quilt with cotton Solidifying agent dosage is big, low to the dissolved lignin removal efficiency of lower molecular weight, in addition, individually cationic flocculant processing is removing While lignin, sugared loss amount is big.
Problem existing for impurity is removed for existing lignocellulose raw material hydrolyzate:Impurity-eliminating effect is poor, it is impossible to effectively will Lignin removes, and still has impurity residual, sugared loss amount is big, and cationic polymer flocculent dosage is big, it is necessary to a kind of wood of research and development Plain removal rate is high, the low processing method of sugared loss late.
The content of the invention
For in existing plant fiber material hydrolyzate it is sugared isolate and purify during, water is removed using cationic polymer When solving lignin in liquid, and lignin relatively low to low molecular weight dissolved lignin removal efficiency removes poor selectivity, and then causes sugared loss The problem of rate is big, the present invention provide the method that a plant fiber raw material hydrolyzate biological treatment removes lignin.
Summary of the invention:
The method of the present invention first gathers plant fiber material hydrolyzate using horseradish peroxidase processing and then cation Compound flocculation treatment.Horseradish peroxidase processing can cause the dissolved lignin of the low molecular weight in hydrolyzate to aggregate into high score Sub- lignin, Precipitation remove a part of lignin;Lignin by horseradish peroxidase after handling, even if without Precipitation Partially due to polymerize, molecular weight increase, is also easier to remove, then uses during follow-up cation flocculation treatment Cationic polymer processing, further removes residual lignin, therefore can improve wood under relatively low cationic polymer amounts The removal rate of element, while loss sugared in cationic polymer processing procedure can also be substantially reduced.
Term explanation:
From hydrolysis:Plant fiber material only adds water or vapor, and is added without the water that other any chemicals carry out Solution reaction.
Horseradish peroxidase enzyme activity:It is catalyzed pyrogallic acid generation 1.0mg's at 20 DEG C, pH 6.0, in 20 seconds The enzyme amount of purpurogallin is an enzyme-activity unit, enzyme-activity unit:U.
Sugared loss late:Sugared decrement and the percentage of raw sugar in hydrolyzate, are expressed as a percentage in hydrolyzate processing procedure.
Lignin removal rate:The lignin percentage of reduction afterwards before treatment in hydrolyzate.
Detailed description of the invention:
The present invention is achieved by the following technical solutions:
The method that one plant fiber raw material hydrolyzate biological treatment removes lignin, including step:
Horseradish peroxidase is to plant fiber material hydrolyzate enzymatic treatment step;
Hydrolyzate flocculant process step after enzymatic treatment.
Preferable according to the present invention, the horseradish peroxidase is to plant fiber material hydrolyzate enzymatic treatment step It is:Horseradish peroxidase is added into plant fiber material hydrolyzate and hydrogen peroxide carries out enzymatic treatment, horseradish peroxidase Enzyme dosage is 3000-30000U/L hydrolyzates, and hydrogen peroxide use is 2.0-20g/L hydrolyzates, and enzymatic treatment is obtained after removing precipitation Hydrolyzate afterwards.
Preferable according to the present invention, horseradish peroxidase dosage is 5000-20000U/L hydrolyzates, and hydrogen peroxide is used Measure as 4.0-15g/L hydrolyzates.
Preferable according to the present invention, enzymatic treatment temperature is 10 DEG C -60 DEG C, processing time 1h-24h, pH 3.0- 8.0;It is further preferred that enzymatic treatment temperature is 15 DEG C -45 DEG C, and processing time 4h-12h, pH 3.5-6.5.
Preferable according to the present invention, the removing is precipitated as:When mixture standing 2-24 after enzymatic treatment is small, bottom is removed The sediment in portion, supernatant liquor are hydrolyzate after enzymatic treatment;Or the mixture after enzymatic treatment removes precipitation after centrifugation, obtains everywhere Hydrolyzate after reason.
Preferable according to the present invention, the plant fiber material hydrolyzate is to carry out sour water to plant fiber material with water Solution or the hydrolyzate obtained from hydrolysis process.
It is preferable according to the present invention, the plant fiber material be selected from needlebush, leaf wood and bamboo, wheat straw, straw, One kind in bagasse, reed non-wood material.
It is further preferred that the one kind of needlebush in masson pine, larch, Korean pine or dragon spruce, leaf wood is selected from poplar Mixing more than wood, birch, maple or Eucalyptus one or both therein.
It is further preferred that it is 140-200 DEG C, hydrolysis time 15-240min from hydrolysis process temperature, water is fine with plant Dimension raw material mass ratio be:3:1-20:1;
It is further preferred that sour hydrolysis temperature is 120-180 DEG C, hydrolysis time 10-180min, water is former with plant fiber The mass ratio of material is:3:1-20:1, the acid used in sour water solution is hydrochloric acid or sulfuric acid, and sour dosage is 2-30 kilograms of air-dried original per ton Material.
The present invention's can use the prior art to carry out from hydrolysis or sour water solution specific operation process.
The present invention horseradish peroxidase in the presence of hydrogen peroxide can oxylignin phenolic hydroxyl group become benzene oxygen freedom Base, then carries out the transfer of free radical electronics or directly carries out crosslinking generation polymerization, urged Lignin Molecular Weight increase Change lignin polymerization, further, Fe (III) reactions first in hydrogen peroxide and horseradish peroxidase generate high oxidation state Intermediate HRP I;Then the addition of the lignin (reproducibility substrate) of phenolic hydroxy group makes HRP I generate another intermediate HRP II, together When phenolic hydroxy group lignin generation benzene oxygen radical;3rd be phenolic hydroxy group lignin continue HRP II being reduced into it is original peppery Root peroxidase, while produce benzene oxygen radical.The free radical produced in first two steps reaction carries out turning for free radical electronics Move or directly carry out crosslinking and polymerization occurs, increase Lignin Molecular Weight.
The dissolved lignin of a part of low molecular weight is aggregated into insoluble macromolecule by the horseradish peroxidase of the present invention Lignin, a part of lignin is removed by removing to sink to the bottom, even if making without the part lignin of Precipitation in horseradish peroxidase It is polymerize with lower, molecular weight increase, the high lignin of molecular weight is flocculated by follow-up cation further removes residual lignin, point Son amount increase is conducive to the raising of cation flocculation efficiency, therefore the horseradish peroxidase processing of the present invention gathers with reference to cation Compound processing greatly improves the total removal rate of lignin.
Preferable according to the present invention, hydrolyzate flocculant process step is after the enzymatic treatment:Hydrolyzed after to enzymatic treatment Cationic polymer flocculent is added in liquid and carries out flocculation treatment, the hydrolyzate after processing stands or be centrifuged off to obtain after precipitating pure Hydrolyzate after change.
Preferable according to the present invention, the cationic flocculant is low molecular weight, the cationic polymerization of high charge density Thing.
It is further preferred that the cationic flocculant is selected from diallyl dimethyl ammoniumchloride, polyethyleneimine Or mixing more than one or both of polyamine.
It is further preferred that the molecular weight of the diallyl dimethyl ammoniumchloride, polyethyleneimine, polyamine is 8 Ten thousand -30 ten thousand, charge density is more than or equal to 5.0meq/g in pH 7.
Preferable according to the present invention, cationic flocculant dosage is hydrolyzate after 200-800mg/L enzymatic treatments, during processing Between 10-30min, pH 3.0-8.0.
A currently preferred technical solution, a plant fiber raw material hydrolyzate biological treatment remove the side of lignin Method, including step are as follows:
(1) horseradish peroxidase is added into lignocellulosic hydrolysate and carries out enzymatic treatment, horseradish peroxidase dosage For 5000-20000U/L hydrolyzates, hydrogen peroxide use is 4.0-12g/L hydrolyzates, 15 DEG C -45 DEG C of enzymatic treatment temperature, the time 4h-12h, pH 3.5-7.0, remove precipitation, obtain hydrolyzate after enzymatic treatment;
(2) cationic flocculant diallyl dimethyl ammoniumchloride, polyethyleneimine are added to hydrolyzate after enzymatic treatment Handled with one kind in polyamine or the mixture of two of which, the molecular weight of cationic flocculant used is 8 ten thousand to 30 ten thousand; Cationic flocculant dosage is hydrolyzate after 200-800mg/L enzymatic treatments, and processing time 10-30min, pH 3.5-8.0 are quiet Put or be centrifuged off to precipitate obtaining hydrolyzate after purification.
The technical characterstic and excellent results of the present invention is as follows:
The present invention is before plant fiber material hydrolyzate cationic polymer flocculation treatment using at horseradish peroxidase Reason, horseradish peroxidase processing can cause the polymerization of lignin in hydrolyzate, molecular weight increase, so as to cause to be partly dissolved wood Become insoluble lignin after element polymerization so as to Precipitation;Although part lignin is without Precipitation, molecular weight increase, in enzyme It is easier to be flocculated removing when further handling using cationic polymer after processing, therefore after horseradish peroxidase processing, Subsequently under relatively low cationic polymer amounts residual lignin can be made to be flocculated removing.With lower molecular weight and height Under the cationic polymer effect of charge density, sugar in hydrolyzate is reduced while lignin is removed and is flocculated in cationic polymer During loss, improve sugared yield and purity in hydrolyzate.
Embodiment
With reference to embodiment, the present invention is described further, but not limited to this.Adopted in embodiment in check experiment Cationic polymer amounts are preferable dosage.
Embodiment 1
One plant fiber raw material hydrolyzate biologic enzyme treatment method, step are as follows:
(1) hydrolyzate of the poplar from after hydrolyzing, sugared content 10.2g/L, lignin content 4.7g/L, hydrolyzate use horseradish mistake Oxide enzymatic treatment, treatment conditions:Enzyme dosage 10000U/L hydrolyzates, hydrogen peroxide use 8g/L hydrolyzates, 30 DEG C of temperature, when Between 6h, pH 4.0.
(2) hydrolyzate after horseradish peroxidase processing stands 8h, and decantation removes precipitation, and obtained upper strata hydrolyzate is adopted Handled with cationic polymer, cationic polymer is molecular weight 250,000, and positive electricity density is the cationic polymerization of 7.0meq/L Thing polyallyl alkyl dimethyl ammonium chloride, cationic polymer amounts 200mg/L hydrolyzates, treatment temperature room temperature, pH 4.0, time 10 minutes.When standing 8 is small after cationic polymer processing, decantation removes sediment, obtains upper strata hydrolyzate after purification.
The present embodiment is handled again after cationic polymer is handled through horseradish peroxidase, lignin removal rate 71%, Sugared loss late 8.6%.
Reference examples 1:With the method for embodiment 1, difference is, this method is without step (1) horseradish peroxidase Processing, directly carries out step (2) processing, diallyl dimethyl ammoniumchloride dosage is 280mg/ by the hydrolyzate from after hydrolyzing L hydrolyzates, obtained hydrolyzate after purification.After the processing of reference examples 1, lignin removal rate is 45%, and sugar loss in hydrolyzate Rate is 14.2%.
Reference examples:This method directly carries out horseradish peroxidase processing, without flocculation treatment.Lignin removal rate is 55%, and sugared loss late is 4.5% in hydrolyzate.
Embodiment 2
One plant fiber raw material hydrolyzate bioremediation, step are as follows:
(1) hydrolyzate after maple sour water solution, sugared content 18.2g/L, lignin content 8.6g/L, hydrolyzate is first using peppery Root peroxide enzymatic treatment, treatment conditions:Enzyme dosage 15000U/L hydrolyzates, hydrogen peroxide use 10g/L hydrolyzates, temperature 25 DEG C, time 10h, pH4.0.
(2) after horseradish peroxidase processing, the polyethylene that molecular weight is 6.5meq/g for 150,000, positive electricity density is used Imines processing, dosage 150mg/L hydrolyzates, treatment temperature room temperature, pH 4.0,15 minutes time.After cationic polymer processing Centrifugation 15 minutes, removes sediment, obtains the hydrolyzate of upper strata after purification.At horseradish peroxidase-cationic polymer After reason, lignin removal rate 58%, sugared loss late 7.6%.
Reference examples 2:With the method for embodiment 2, difference is, this method is without step (1) horseradish peroxidase Processing, directly carries out step (2) processing, polyethyleneimine dosage is 220mg/L hydrolyzates, is obtained by the hydrolyzate after sour water solution Hydrolyzate after purification.After the processing of reference examples 2, lignin removal rate is 38%, and the loss late of sugar is 13.8%.
Embodiment 3
One plant fiber raw material hydrolyzate bioremediation, step are as follows:
(1) hydrolyzate of the wheat straw from after hydrolyzing, sugared content 8.7g/L, lignin content 3.7g/L, hydrolyzate are adopted first Handled with horseradish peroxidase, treatment conditions:Enzyme dosage 15000U/L hydrolyzates, hydrogen peroxide use 10g/L hydrolyzates, temperature 30 DEG C of degree, time 12h, pH 5.0.
(2) molecular weight is used as 120,000 after horseradish peroxidase processing, positive electricity density is at the polyamine of 6.6meq/g Reason, dosage 160mg/L hydrolyzates, treatment temperature room temperature, pH 5.0,20 minutes time.It is small that 6 are stood after cationic polymer processing When, decantation removes sediment, obtains the hydrolyzate of upper strata after purification.After horseradish peroxidase-cationic polymer processing, Lignin removal rate 67%, sugared loss late 7.1%.
Reference examples 3:With the method for embodiment 3, difference is, this method is without step (1) horseradish peroxidase Processing, directly carries out step (2) processing by the hydrolyzate from after hydrolyzing, and cationic polymerization composition polyamine dosage hydrolyzes for 220mg/L Liquid, obtained hydrolyzate after purification.After the processing of reference examples 3, lignin removal rate is 38%, and the loss late of sugar is 16.0%.
Embodiment 4:
With the plant fiber material hydrolyzate bioremediation described in embodiment 1, except that:
Step (1), horseradish peroxidase treatment temperature are 20 DEG C.
Embodiment 5:
With the plant fiber material hydrolyzate bioremediation described in embodiment 1, except that:
Step (1), the addition of hydrogen peroxide is 6g/L hydrolyzates during enzymatic treatment.
Embodiment 6:
With the plant fiber material hydrolyzate bioremediation described in embodiment 1, except that:
Step (1), hydrolyzate of the reed from after hydrolyzing replace hydrolyzate of the poplar from after hydrolyzing.
Embodiment 7:
With the plant fiber material hydrolyzate bioremediation described in embodiment 1, except that:
Step (1), the hydrolyzate obtained after Eucalyptus sour water solution replace hydrolyzate of the poplar from after hydrolyzing.
Embodiment 8:
With the plant fiber material hydrolyzate bioremediation described in embodiment 1, except that:
The cationic polymer of step (2) is the polydiene propyl group that molecular weight is 120,000, positive electricity density is 7.2meq/g The mixture for the polyethyleneimine that alkyl dimethyl ammonium chloride and molecular weight are 180,000, positive electricity density is 6.8meq/g.
Embodiment 9:
With the plant fiber material hydrolyzate bioremediation described in embodiment 1, except that:
Step (1), the hydrolyzate that bamboo is obtained from after hydrolyzing replace hydrolyzate of the poplar from after hydrolyzing.

Claims (10)

1. the method that a plant fiber raw material hydrolyzate biological treatment removes lignin, including step:
Horseradish peroxidase is to plant fiber material hydrolyzate enzymatic treatment step;
Hydrolyzate flocculant process step after enzymatic treatment.
2. the method that plant fiber material hydrolyzate biological treatment according to claim 1 removes lignin, it is characterised in that The horseradish peroxidase is to plant fiber material hydrolyzate enzymatic treatment step:Add into plant fiber material hydrolyzate Entering horseradish peroxidase and hydrogen peroxide carries out enzymatic treatment, horseradish peroxidase dosage is 3000-30000U/L hydrolyzates, Hydrogen peroxide use is 2.0-20g/L hydrolyzates, and hydrolyzate after enzymatic treatment is obtained after removing precipitation.
3. the method that plant fiber material hydrolyzate biological treatment according to claim 2 removes lignin, it is characterised in that Horseradish peroxidase dosage is 5000-20000U/L hydrolyzates, and hydrogen peroxide use is 4.0-15g/L hydrolyzates.
4. the method that plant fiber material hydrolyzate biological treatment according to claim 2 removes lignin, it is characterised in that Enzymatic treatment temperature is 10 DEG C -60 DEG C, processing time 1h-24h, pH 3.0-8.0;It is further preferred that enzymatic treatment temperature For 15 DEG C -45 DEG C, processing time 4h-12h, pH 3.5-6.5.
5. the method that plant fiber material hydrolyzate biological treatment according to claim 2 removes lignin, it is characterised in that The removing is precipitated as:When mixture standing 2-24 after enzymatic treatment is small, the sediment of bottom is removed, supernatant liquor is at enzyme Hydrolyzate after reason;Or the mixture after enzymatic treatment removes precipitation, hydrolyzate after being handled after centrifugation.
6. the method that plant fiber material hydrolyzate biological treatment according to claim 1 removes lignin, it is characterised in that The plant fiber material hydrolyzate is that sour water solution or the hydrolysis obtained from hydrolysis process are carried out to plant fiber material with water Liquid;The plant fiber material is in needlebush, leaf wood and bamboo, wheat straw, straw, bagasse, reed non-wood material One kind;Preferably, the one kind of needlebush in masson pine, larch, Korean pine or dragon spruce, leaf wood be selected from poplar, birch, Mixing more than maple or Eucalyptus one or both therein;Preferably, it is 140-200 DEG C from hydrolysis process temperature, during hydrolysis Between be 15-240min, the mass ratio of water and plant fiber material is:3:1-20:1;Preferably, sour hydrolysis temperature is 120-180 DEG C, hydrolysis time 10-180min, the mass ratio of water and plant fiber material is:3:1-20:1, the acid used in sour water solution is salt Acid or sulfuric acid, sour dosage are 2-30 kilograms of air-dried raw material per ton.
7. the method that plant fiber material hydrolyzate biological treatment according to claim 1 removes lignin, it is characterised in that Hydrolyzate flocculant process step is after the enzymatic treatment:After to enzymatic treatment cationic polymer flocculent is added in hydrolyzate Flocculation treatment is carried out, the hydrolyzate after processing obtains hydrolyzate after purification after standing or being centrifuged off precipitation.
8. the method that plant fiber material hydrolyzate biological treatment according to claim 7 removes lignin, it is characterised in that The cationic flocculant is low molecular weight, the cationic polymer of high charge density;The cationic flocculant is selected from Mixing more than one or both of diallyl dimethyl ammoniumchloride, polyethyleneimine or polyamine;Preferably, it is described Diallyl dimethyl ammoniumchloride, polyethyleneimine, the molecular weight of polyamine are 80,000-30 ten thousand, and charge density is more than in pH 7 Equal to 5.0meq/g.
9. the method that plant fiber material hydrolyzate biological treatment according to claim 7 removes lignin, it is characterised in that Cationic flocculant dosage be 200-800mg/L enzymatic treatments after hydrolyzate, processing time 10-30min, pH 3.0-8.0.
10. the method that a plant fiber raw material hydrolyzate biological treatment removes lignin, including step are as follows:
(1) horseradish peroxidase is added into lignocellulosic hydrolysate and carries out enzymatic treatment, horseradish peroxidase dosage is 5000-20000U/L hydrolyzates, hydrogen peroxide use are 4.0-12g/L hydrolyzates, 15 DEG C -45 DEG C of enzymatic treatment temperature, the time 4h-12h, pH 3.5-7.0, remove precipitation, obtain hydrolyzate after enzymatic treatment;
(2) cationic flocculant diallyl dimethyl ammoniumchloride, polyethyleneimine are added to hydrolyzate after enzymatic treatment and gathered The mixture of one kind or two of which in amine is handled, and the molecular weight of cationic flocculant used is 8 ten thousand to 30 ten thousand;Sun from Sub- flocculant usage be 200-800mg/L enzymatic treatments after hydrolyzate, processing time 10-30min, pH 3.5-8.0, stand or It is centrifuged off precipitating obtaining hydrolyzate after purification.
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CN114657807A (en) * 2022-04-02 2022-06-24 山东太阳纸业股份有限公司 Method for promoting lignin accumulation in wood pulping prehydrolysis liquid by using biological enzyme

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CN110256608A (en) * 2019-06-24 2019-09-20 齐鲁工业大学 The method that horseradish peroxidase processing removes lignin in plant fiber pre-hydrolyzed solution
CN110280217A (en) * 2019-06-24 2019-09-27 齐鲁工业大学 A kind of lignin adsorbent, preparation method and its application
WO2020258749A1 (en) * 2019-06-24 2020-12-30 齐鲁工业大学 Lignin adsorbent, preparation method therefor and application thereof
CN110256608B (en) * 2019-06-24 2021-04-20 齐鲁工业大学 Method for removing lignin in plant fiber prehydrolysis liquid by horse radish peroxidase treatment
CN114410707A (en) * 2022-01-25 2022-04-29 齐鲁工业大学 Method for purifying sugar in hardwood pulping prehydrolysis liquid
CN114410707B (en) * 2022-01-25 2023-08-15 齐鲁工业大学 Method for purifying sugar in broadleaf wood pulp prehydrolysis liquid
CN114657807A (en) * 2022-04-02 2022-06-24 山东太阳纸业股份有限公司 Method for promoting lignin accumulation in wood pulping prehydrolysis liquid by using biological enzyme

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