CN108048509A - A kind of preprocess method of non-three plain ingredient of efficient removal lignocellulosic - Google Patents

A kind of preprocess method of non-three plain ingredient of efficient removal lignocellulosic Download PDF

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Publication number
CN108048509A
CN108048509A CN201810134844.3A CN201810134844A CN108048509A CN 108048509 A CN108048509 A CN 108048509A CN 201810134844 A CN201810134844 A CN 201810134844A CN 108048509 A CN108048509 A CN 108048509A
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lignocellulosic
plain
solution
efficient removal
preprocess method
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王志敏
宋安东
黄元
王凤芹
张宏森
姜广策
吕东灿
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Henan Agricultural University
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Henan Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

The invention discloses a kind of preprocess methods of non-three plain ingredient of efficient removal lignocellulosic, include the following steps：Lignocellulose-like biomass is added in Fe by S12+In solution, stirring；S2 adds in aqueous hydrogen peroxide solution, passes through Fe2+Oxidation pre-treatment is realized to lignocellulosic with the hydroxy radical of hydroperoxidation generation.Lignocellulosic is pre-processed using the present invention, can utmostly remove non-three plain ingredients in lignocellulosic, while three cellulose contents and basic structure is kept not to be destroyed, realizes lignocellulosic full constituent higher value application.

Description

A kind of preprocess method of non-three plain ingredient of efficient removal lignocellulosic
Technical field
The present invention relates to lignocellulosic processing technology fields, and in particular to a kind of non-three element of efficient removal lignocellulosic The preprocess method of ingredient.
Background technology
Lignocellulosic is rich in cellulose, hemicellulose and lignin, is the most potential energy and biobased products Renewable conversion resource.However, the degradation stubbornly resisting property that plant cell wall is formed in long-term natural evolution, strongly limits wooden The conversion and utilization of the big component of cellulose iii.Traditional biorefinery of lignocellulose is based on the high-value-use of carbohydrate Want target, it is believed that lignin is the principal element for hindering carbohydrate enzymolysis or hydrolysis, and ignores accounting and approach, is even super The non-three plain ingredients for crossing 30% digest influence to carbohydrate.For efficient removal lignin, often do not stint using high temperature, height The harsh condition such as pressure, strong acid, highly basic is pre-processed.This harsh preprocess method can cause the big of carbohydrate Amount loss and structure are destroyed, while the lignin removed, compared with the lignin of script, very big change all has occurred in structure and activity Change, it is difficult to convert and utilize again, be only used for the cheap energy and calorific value material.If mild method maximum journey can be passed through Non- three plain ingredients in degree removing lignocellulosic, and the content of three elements and basic structure is kept not to be destroyed, for wooden fibre The plain full constituent higher value application of dimension will have great importance.
The content of the invention
In view of the deficiencies of the prior art, the present invention is intended to provide a kind of non-three plain ingredient of efficient removal lignocellulosic it is pre- Processing method can utmostly remove non-three plain ingredients in lignocellulosic, while keep three cellulose contents and basic structure not It is destroyed, realize lignocellulosic full constituent higher value application.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of preprocess method of non-three plain ingredient of efficient removal lignocellulosic, includes the following steps：
Lignocellulose-like biomass is added in Fe by S12+In solution, stirring；
S2 adds in aqueous hydrogen peroxide solution, passes through Fe2+Hydroxy radical with hydroperoxidation generation is to lignocellulosic Realize oxidation pre-treatment.
It should be noted that in step S1, the mass concentration of lignocellulose-like biomass is 5-25%, the Fe2+It is molten The concentration of liquid is 0.5-2.0mmol/L.
It should be noted that in step S2, the concentration of the aqueous hydrogen peroxide solution is 0.5-2.5mol/L.
It should be noted that in step S2, Fe2+Time with hydroperoxidation is 48h.
Need further exist for explanation, the Fe2+Solution is solution of ferrous chloride or ferrous sulfate solution.
The beneficial effects of the present invention are：The present invention provides it is a kind of can utmostly remove in lignocellulosic non-three Plain ingredient, while the lignocellulosic green preprocess method that three cellulose contents of holding and basic structure are not destroyed.
The present invention is using ferrous ion and the active hydroxy radical of hydrogen peroxide effect generation come the wooden fibre of oxidation pre-treatment Dimension element, can be with non-the three of efficient removal lignocellulosic plain ingredients, and the content of cellulose, hemicellulose and lignin is seldom damaged It loses.
The present invention can under mild conditions in lignocellulose biomass is pre-processed, be it is a kind of green, temperature The preprocess method of sum.Effective removing of non-three plain ingredients greatly improves the enzyme accessibility of cellulose and hemicellulose, can be with Significantly increase the hydrolysis result of lignocellulosic.What is more important, the efficient removal of non-three plain ingredients, is on the one hand conducive to three Element efficiently separates, while also provides possibility for the depolymerization in situ of lignin.
Specific embodiment
The invention will be further described below, it is necessary to which explanation, following embodiment is using the technical program before It carries, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to the present embodiment.
A kind of preprocess method of non-three plain ingredient of efficient removal lignocellulosic, includes the following steps：
Lignocellulose-like biomass is added in Fe by S12+In solution, stirring；
S2 adds in aqueous hydrogen peroxide solution, passes through Fe2+Hydroxy radical with hydroperoxidation generation is to lignocellulosic Realize oxidation pre-treatment.
It should be noted that in step S1, the mass concentration of the lignocellulose-like biomass is 5-25%, Fe2+It is molten The concentration of liquid is 0.5-2.0mmol/L.
It should be noted that in step S2, the concentration of the aqueous hydrogen peroxide solution is 0.5-2.5mol/L.
It should be noted that in step S2, Fe2+Time with hydroperoxidation is 48h.
Need further exist for explanation, the Fe2+Solution is solution of ferrous chloride or ferrous sulfate solution.
Embodiment 1
Step 1: 10g maize straws are added in into the Fe that 100mL concentration is 1.25mmol/L2+In solution, fully shaking is stirred It mixes, then adds in the aqueous hydrogen peroxide solution that 100mL concentration is 1.5mol/L, sustained oscillation stirring, Fe2+It is anti-with hydrogen peroxide Should, finally obtain mixture.
The Fe2+Mechanism with hydroperoxidation is：
Fe2++H2O2→Fe3++OH-+OH· (1)
Fe3++H2O2→Fe2++2H++O2 (2)
Fe3++O2→Fe2++O2· (3)
Step 2: step 1 mixture obtained by the reaction carries out separation of solid and liquid, isolated solid and liquid, what is obtained consolidates Body fully washs the remaining Fe of removal by deionized water2+、Fe3+With unreacted hydrogen peroxide, 12 are dried in vacuo in 100 DEG C Hour, the maize straw pre-processed.
Step 3: carrying out enzymatic saccharification reaction with cellulase to pretreated maize straw, fermentable sugars is produced.Tool Concrete conditions in the establishment of a specific crime：Solid-liquid mass ratio 1:8,48 DEG C of temperature, pH value 4.8, enzymolysis time 48h.
In step 1, Fe2+With during hydroperoxidation, at interval of 12 it is small when sampling filtering, filtrate is carried out into sorting Survey analysis.
Further the performance and reaction condition of the method for the present invention will be verified below.Table 1 show pretreatment time Influence to maize straw constituent content, biomass and component loss late, table 2 show Fe2+It is pre-processed with hydroperoxidation 48h is to maize straw constituent content, the biomass rate of recovery and the influence for digesting performance.
Table 1
Table 2
Wherein, in Tables 1 and 2, untreated control is untreated maize straw sample.Content (%) refers in sample The content of heterogeneity compared with total weight of solids (dry weight) percentage.Loss late (%) refers to the solid obtained after pretreatment In each ingredient weight (dry weight) compared with the weight (dry weight) of each ingredient in lignocellulose-like biomass before reaction loss Percentage.The solid weight (dry weight) that the biomass rate of recovery then refers to obtain after reaction is compared with solid weight before reaction (dry weight) Percentage.Glucan digestibility be after reaction obtained glucan can be obtained after enzyme hydrolysis glucose (dry weight) compared with The percentage of the glucan (dry weight) obtained after reaction, glucose production rate are then to produce obtained glucose compared with original wood The percentage of the glucan contained in matter cellulose series biomass.
Table 1 illustrates in the present invention, and pretreatment time is to maize straw constituent content, biomass and component loss late It influences.From table 1 it follows that as pretreatment time increases, biomass loss late gradually increases, three element in relict matter Content gradually rises, and during processing time 48h, three element losses are little, and wherein cellulose loss rate is about 5%, hemicellulose loss Rate 13%, lignin loss late are about 10%.At this point, the loss of biomass is mainly caused by the loss of non-three plain ingredients, non-three The removal efficiency of plain ingredient reaches 86.21%.When reaching 72h between when treated, three plain loss lates start to significantly increase, wherein fiber Plain loss late reaches 16.97%, and for hemicellulose loss late up to 28%, lignin loss late reaches 25.32%.When this illustrates reaction Between 48h be the optimal reaction time, not only can be with non-three plain ingredient of efficient removal, but also can utmostly keep the contents of three elements.
Table 2 illustrates in the present invention, Fe2+The specific ingredient of maize straw is contained when pre-processing 48h with hydroperoxidation Amount and the influence of enzymolysis efficiency.From Table 2, it can be seen that the sample compared to untreated control and aqueous solution processing same time Product utilize Fe2+Hydroxy radical is generated with hydroperoxidation, and non-three are greatly improved to lignocellulosic progress oxidation pre-treatment The removal efficiency (ash content and other compositions removal efficiency be respectively 72.42% and 88.78%) of plain ingredient, while utmostly maintain The content of three elements, wherein cellulose loss is about 5%, and xylose and arabinose loss are respectively 13% or so in hemicellulose, second Acyl group loss about 10%；The insoluble lignin loss late about 10% of acid, the molten lignin loss about 16% of acid.At the same time, Portugal gathers Sugared digestibility and glucose yield all significantly improve.This absolutely proves the removing of non-three plain ingredients in lignocellulosic for fiber The enzyme digestion reaction of element and hemicellulose has apparent facilitation, therefore the method for the present invention can effectively realize lignocellulosic Full constituent higher value application.
For those skilled in the art, can be provided various corresponding according to above technical solution and design Change and deform, and all these change and deformation, should be construed as being included within the protection domain of the claims in the present invention.

Claims (5)

1. a kind of preprocess method of non-three plain ingredient of efficient removal lignocellulosic, which is characterized in that include the following steps：
Lignocellulose-like biomass is added in Fe by S12+In solution, stirring；
S2 adds in aqueous hydrogen peroxide solution, passes through Fe2+Lignocellulosic is realized with the hydroxy radical of hydroperoxidation generation Oxidation pre-treatment.
2. the preprocess method of non-three plain ingredient of efficient removal lignocellulosic according to claim 1, which is characterized in that In step S1, the mass concentration of lignocellulose-like biomass is 5-25%, the Fe2+The concentration of solution is 0.5-2.0mmol/ L。
3. the preprocess method of non-three plain ingredient of efficient removal lignocellulosic according to claim 1, which is characterized in that In step S2, the concentration of the aqueous hydrogen peroxide solution is 0.5-2.5mol/L.
4. the preprocess method of non-three plain ingredient of efficient removal lignocellulosic according to claim 1, which is characterized in that In step S2, Fe2+Time with hydroperoxidation is 48h.
5. the preprocess method of non-three plain ingredient of efficient removal lignocellulosic according to claim 1 or 2, feature exist In the Fe2+Solution is solution of ferrous chloride or ferrous sulfate solution.
CN201810134844.3A 2018-02-09 2018-02-09 A kind of preprocess method of non-three plain ingredient of efficient removal lignocellulosic Pending CN108048509A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110283334A (en) * 2019-07-02 2019-09-27 哈尔滨理工大学 A kind of preprocess method improving ash biodegrade effect
CN111116938A (en) * 2020-01-07 2020-05-08 河南农业大学 Method for efficiently extracting lignin from lignocellulose raw material
CN111118087A (en) * 2020-01-07 2020-05-08 河南农业大学 Lignocellulose pretreatment system based on FeOCl and application thereof
CN111118080A (en) * 2020-01-07 2020-05-08 河南农业大学 Lignocellulose pretreatment system based on nano ferroferric oxide and application thereof
CN111116936A (en) * 2020-01-07 2020-05-08 河南农业大学 Lignin separation and extraction method based on FeOCl Fenton reaction
CN111154811A (en) * 2020-01-07 2020-05-15 河南农业大学 Pretreatment system for improving biodegradation efficiency of lignocellulose and application thereof
CN115043676A (en) * 2022-07-01 2022-09-13 东北农业大学 Method for efficiently degrading lignocellulose by biological simulation Fenton-like reaction

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CN107029791A (en) * 2017-04-25 2017-08-11 河南农业大学 A kind of fenton catalyst and preparation method thereof, the application in lignocellulosic pretreatment

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CN107029791A (en) * 2017-04-25 2017-08-11 河南农业大学 A kind of fenton catalyst and preparation method thereof, the application in lignocellulosic pretreatment

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110283334A (en) * 2019-07-02 2019-09-27 哈尔滨理工大学 A kind of preprocess method improving ash biodegrade effect
CN110283334B (en) * 2019-07-02 2021-07-23 哈尔滨理工大学 Pretreatment method for improving biodegradation effect of locust wood
CN111116938B (en) * 2020-01-07 2021-07-16 河南农业大学 Method for efficiently extracting lignin from lignocellulose raw material
CN111118080A (en) * 2020-01-07 2020-05-08 河南农业大学 Lignocellulose pretreatment system based on nano ferroferric oxide and application thereof
CN111116936A (en) * 2020-01-07 2020-05-08 河南农业大学 Lignin separation and extraction method based on FeOCl Fenton reaction
CN111154811A (en) * 2020-01-07 2020-05-15 河南农业大学 Pretreatment system for improving biodegradation efficiency of lignocellulose and application thereof
CN111118087A (en) * 2020-01-07 2020-05-08 河南农业大学 Lignocellulose pretreatment system based on FeOCl and application thereof
CN111116936B (en) * 2020-01-07 2021-07-20 河南农业大学 Lignin separation and extraction method based on FeOCl Fenton reaction
CN111116938A (en) * 2020-01-07 2020-05-08 河南农业大学 Method for efficiently extracting lignin from lignocellulose raw material
CN111154811B (en) * 2020-01-07 2022-11-11 河南农业大学 Pretreatment system for improving biodegradation efficiency of lignocellulose and application thereof
CN111118087B (en) * 2020-01-07 2022-11-15 河南农业大学 Lignocellulose pretreatment system based on FeOCl and application thereof
CN111118080B (en) * 2020-01-07 2022-11-15 河南农业大学 Lignocellulose pretreatment system based on nano ferroferric oxide and application thereof
CN115043676A (en) * 2022-07-01 2022-09-13 东北农业大学 Method for efficiently degrading lignocellulose by biological simulation Fenton-like reaction

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Application publication date: 20180518