CN106086084A - The preprocess method of a kind of Ethanol Production Process with Straw and application - Google Patents

The preprocess method of a kind of Ethanol Production Process with Straw and application Download PDF

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Publication number
CN106086084A
CN106086084A CN201610427735.1A CN201610427735A CN106086084A CN 106086084 A CN106086084 A CN 106086084A CN 201610427735 A CN201610427735 A CN 201610427735A CN 106086084 A CN106086084 A CN 106086084A
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China
Prior art keywords
straw
corn straw
preprocess method
production process
fenton reagent
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Pending
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CN201610427735.1A
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Chinese (zh)
Inventor
陈富于
刘庆玉
孙清
李阳
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Shenyang Agricultural University
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Shenyang Agricultural University
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Priority to CN201610427735.1A priority Critical patent/CN106086084A/en
Publication of CN106086084A publication Critical patent/CN106086084A/en
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/02Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06Ethanol, i.e. non-beverage
    • C12P7/08Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2201/00Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Abstract

The present invention relates to the technical field of lignocellulose raw material production ethanol, the preprocess method of a kind of Ethanol Production Process with Straw and application.The method comprises the following steps: (1), by after corn straw smashing, is crossed 40# sieve, is placed in exsiccator standby;(2) corn straw and Fenton reagent are placed in triangular flask, react 24~72h under normal temperature condition, after reaction terminates, corn straw is carried out successively vacuum filtration, cleans and dry, obtain the corn straw of pretreatment.Using the present invention pretreated straw enzymolysis glucose yield to improve 57%, it is simple to operate, it is not necessary to high-temperature high-pressure apparatus, low for equipment requirements, and energy consumption is low, is suitable for industrialized production.

Description

The preprocess method of a kind of Ethanol Production Process with Straw and application
Technical field
The present invention relates to the technical field of lignocellulose raw material production ethanol, a kind of Ethanol Production Process with Straw Preprocess method and application.
Background technology
Biomass are a kind of important Renewable resources, and utilizing biomass to produce alcohol fuel is a kind of new utilization of energy Form, environmental pollution is little, is current study hotspot.China's biomass material enriches, and wherein corn straw annual production is up to 700,000,000 Many tons, account for the 35% of biomass material.If biomass resource can be converted into available liquid or gaseous fuel, will be strong The series of problems such as crisis of resource, energy shortage and the environmental pollution that the alleviation mankind are faced, possess good application prospect.
Being mainly of stalk raw materials is formed network structure by cellulose, hemicellulose and lignin by covalent bond, Causing cellulose follow-up saccharification efficiency low, alcohol yied is low.It is therefore desirable to by pretreatment, destroy lignin to fiber Element and the parcel of hemicellulose, reduce the degree of crystallinity of cellulose, improves follow-up saccharification efficiency, and then improves biomass economy rate.
At present, the preprocess method of corn straw mainly has Physical, chemical method and bioanalysis.Physical mainly includes machine Tool pulverizing, Micro-wave pretreatment, steam explosion pretreatment and pyrolysis pretreatment etc..Such method primary disadvantage is that energy consumption Greatly, the energy consumption of mechanical activation comminution accounts for the 50%~60% of total energy consumption, and treatment effeciency is low.Steam explosion method for pretreating is that use is more extensively General, preferably a kind of method for the treatment of effect, the advantage of this method for pretreating is to add any chemical substance.But utilize this method When carrying out pretreatment, part lignocellulosic materials can be degraded under the high temperature conditions, produces follow-up enzymolysis and fermentation Process has the poisonous and harmful substance of inhibitory action.Chemical Pretreatment method mainly has mineral acid, inorganic base and organic solvent pretreatment Etc. method, its mechanism mainly makes lignocellulose generation imbibition, destroys the crystalline texture of cellulose, makes cellulose, half fiber Element and lignin occur to dissolve and degrade.The energy consumption of bioanalysis pretreatment is low, easy and simple to handle, the most free from environmental pollution, but it processes Efficiency is low, long processing period.
Summary of the invention
In order to solve the problems referred to above, it is an object of the invention to propose the preprocess method of a kind of Ethanol Production Process with Straw and answer With, overcome the deficiency of existing lignocellulose raw material production alcohol pre-treatment technology, use the inventive method effectively to carry High enzymolysis glucose yield, reacts without high-temperature high-pressure apparatus, requires low to consersion unit.
In order to achieve the above object, the technical scheme is that
The preprocess method of a kind of Ethanol Production Process with Straw, comprises the following steps:
(1) by after corn straw smashing, cross 40# sieve, be placed in exsiccator standby;
(2) corn straw and Fenton reagent are placed in triangular flask, the molar concentration scope of ferrous chloride in Fenton reagent For: 0.1~10mmol/L, in Fenton reagent, the concentration range of hydrogen peroxide is: 0.05~5wt%, reacts 24 under normal temperature condition ~72h, after reaction terminates, corn straw is carried out successively vacuum filtration, cleans and dry, obtain the corn straw of pretreatment.
The quality volume of the preprocess method of described Ethanol Production Process with Straw, the dry in corn straw and Fenton reagent Ratio is 1g:(10~50) mL.
The preprocess method of described Ethanol Production Process with Straw, drying temperature is 50~110 DEG C.
The preprocess method of described Ethanol Production Process with Straw, answering in biomass fuel ethanol or biomass ferment engineering With.
Advantages of the present invention and providing the benefit that:
1, present invention pretreatment corn straw at normal temperatures and pressures, it is to avoid it is dangerous that high energy consumption and High Temperature High Pressure are brought Factor, pretreated straw enzymolysis glucose yield improves 57%.
2, apparatus structure involved in the present invention is simple, easy to operate, is not related to high-temperature high-pressure apparatus and the technique of complexity, Energy consumption is low, it is easy to Industry Promotion, is suitable for industrialized production.
3, Fenton reagent involved in the present invention is low concentration ferrous ion and hydrogen peroxide, the ferrous ion of high concentration and Hydrogen peroxide treatment can cause cellulose degradation and free radical to reduce, and hinders the reaction of ferrous ion and more hydroxyl radical free radicals Formed.
Detailed description of the invention
In specific implementation process, corn straw of the present invention produces the preprocess method of ethanol, and corn straw tries with Fenton The dominant response process of agent is as follows:
The oxidisability of hydrogen peroxide own is very strong, but when low concentration, oxidability is limited, Fe2+Raw with hydroperoxidation Becoming OH free radical, increase the oxidability of hydrogen peroxide, reaction equation is as follows:
Fe2++H2O2→Fe3++OH-+·OH
Fe3++H2O2→Fe2++H++·OOH
Highly active OH and the hydroxyl reaction on glucopyranosyl ring in cellulose chain, destruction cellulosic molecule is interior and divides Hydrogen bond between son, unformed area and the partially crystallizable district of cellulose are oxidized, and hydroxyl is oxidized to aldehyde radical and carboxyl, generate activity Organic substance free radical, causes cellulose depolymerization, changes fiber surface pattern.React as follows:
The present invention is expanded on further, it should be appreciated that detailed description of the invention described herein below in conjunction with embodiment It is merely to illustrate and explains the present invention, being not limited to the present invention.
Embodiment 1
In the present embodiment, corn straw produces the preprocess method of ethanol, comprises the following steps:
1, by after corn straw smashing, cross 40# sieve, be placed in exsiccator standby.
2, in the Fenton reagent of preparation 300mL: FeCl2Concentration be 1mmol, H2O2Concentration be 3wt%.
3, being placed in above-mentioned solution by the corn straw after size-reduced for 10g sieving, react 24h under normal temperature condition, vacuum is taken out Filter, clean rear 105 DEG C of drying, obtain the corn straw of pretreatment.
Embodiment 2
In the present embodiment, corn straw produces the preprocess method of ethanol, comprises the following steps:
1, by after corn straw smashing, cross 40# sieve, be placed in exsiccator standby.
2, in the Fenton reagent of preparation 300mL: FeCl2Concentration be 2mmol, H2O2Concentration be 2wt%.
3, being placed in above-mentioned solution by the corn straw after size-reduced for 10g sieving, react 24h under normal temperature condition, vacuum is taken out Filter, clean rear 50 DEG C of drying, obtain the corn straw of pretreatment.
Embodiment 3
In the present embodiment, corn straw produces the preprocess method of ethanol, comprises the following steps:
1, by after corn straw smashing, cross 40# sieve, be placed in exsiccator standby.
2, in the Fenton reagent of preparation 300mL: FeCl2Concentration be 3mmol, H2O2Concentration be 1wt%.
3, being placed in above-mentioned solution by the corn straw after size-reduced for 10g sieving, react 48h under normal temperature condition, vacuum is taken out Filter, clean rear 80 DEG C of drying, obtain the corn straw of pretreatment.
Embodiment 4
In the present embodiment, corn straw produces the preprocess method of ethanol, comprises the following steps:
1, by after corn straw smashing, cross 40# sieve, be placed in exsiccator standby.
2, in the Fenton reagent of preparation 200mL: FeCl2Concentration be 3mmol, H2O2Concentration be 0.5wt%.
3, being placed in above-mentioned solution by the corn straw after size-reduced for 10g sieving, react 48h under normal temperature condition, vacuum is taken out Filter, clean rear 105 DEG C of drying, obtain the corn straw of pretreatment.
Embodiment 5
In the present embodiment, corn straw produces the preprocess method of ethanol, comprises the following steps:
1, by after corn straw smashing, cross 40# sieve, be placed in exsiccator standby.
2, in the Fenton reagent of preparation 200mL: FeCl2Concentration be 5mmol, H2O2Concentration be 3wt%.
3, being placed in above-mentioned solution by the corn straw after size-reduced for 5g sieving, react 72h under normal temperature condition, vacuum is taken out Filter, clean rear 105 DEG C of drying, obtain the corn straw of pretreatment.
Application examples
By the corn straw of pretreatment in embodiment 1 to 5, apply in biomass fuel ethanol or biomass ferment engineering In, experimental data and technique effect are as follows:
Relevant with enzymolysis time by low concentration Fenton reagent pretreatment corn straw glucose yield, enzymolysis time 48h Portugal Grape candy output is higher than 24h.Improving through Fenton reagent pretreated straw enzymolysis glucose yield, enzymolysis 24h, glucose produces Amount can improve 47%;Enzymolysis 48h, glucose yield can improve 57%.Enzymolysis before and after different ratio Fenton reagent pretreated straw Glucose yield is shown in Table 1.
Enzymolysis glucose yield change before and after table 1 different ratio Fenton reagent pretreated straw
Sample number into spectrum Enzymolysis 24h glucose yield/mg Enzymolysis 48h glucose yield/mg
1 79.16783 106.7439
2 86.84725 106.7439
3 88.24351 117.914
4 81.61128 116.8668
5 97.66825 127.3387
Blank straw 66.60151 81.26222
Embodiment and application examples result show, the preprocess method of corn straw of the present invention, it is possible to fully make Fenton reagent Mix with straw, utilize Fe2+With H2O2Reaction produces the strong oxidizing property of hydroxyl radical free radical (OH), to a certain degree destroys lignin Parcel to cellulose, reduces the degree of crystallinity of fibrousness, and after making pretreatment, the enzymolysis glucose yield of corn straw improves.This Bright simple to operate, it is not necessary to high-temperature high-pressure apparatus, energy consumption is low, it is adaptable in biomass fuel ethanol and biomass ferment engineering.

Claims (4)

1. the preprocess method of an Ethanol Production Process with Straw, it is characterised in that comprise the following steps:
(1) by after corn straw smashing, cross 40# sieve, be placed in exsiccator standby;
(2) corn straw and Fenton reagent being placed in triangular flask, in Fenton reagent, the molar concentration scope of ferrous chloride is: 0.1~10mmol/L, in Fenton reagent, the concentration range of hydrogen peroxide is: 0.05~5wt%, under normal temperature condition react 24~ 72h, after reaction terminates, carries out corn straw vacuum filtration successively, cleans and dry, obtain the corn straw of pretreatment.
The preprocess method of Ethanol Production Process with Straw the most according to claim 1, it is characterised in that: the dry in corn straw Matter is 1g:(10~50 with the mass volume ratio of Fenton reagent) mL.
The preprocess method of Ethanol Production Process with Straw the most according to claim 1, it is characterised in that: dry temperature be 50~ 110℃。
4. the preprocess method of the Ethanol Production Process with Straw described in a claim 1, it is characterised in that: at biomass fuel ethanol Or the application in biomass ferment engineering.
CN201610427735.1A 2016-06-16 2016-06-16 The preprocess method of a kind of Ethanol Production Process with Straw and application Pending CN106086084A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107119094A (en) * 2017-06-16 2017-09-01 中南大学 A kind of method of utilization lignin-degrading bacteria reinforcing abandoned biomass Fenton reaction pretreatments
CN109320985A (en) * 2018-08-15 2019-02-12 江苏福瑞森塑木科技股份有限公司 Colorful wood plastic composite board modelled after an antique and preparation method thereof
CN110283334A (en) * 2019-07-02 2019-09-27 哈尔滨理工大学 A kind of preprocess method improving ash biodegrade effect
CN113583879A (en) * 2021-08-02 2021-11-02 中国农业科学院农产品加工研究所 Straw enzymolysis composition and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DAWN M.KATO,等: "Pretreatment of lignocellulosic biomass using Fenton chemistry", 《BIORESOURCE TECHNOLOGY》 *
PRATEEK JAIN,等: "Effect of Fenton’s pretreatment on cotton cellulosic substrates to enhance its enzymatic hydrolysis response", 《BIORESOURCE TECHNOLOGY》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107119094A (en) * 2017-06-16 2017-09-01 中南大学 A kind of method of utilization lignin-degrading bacteria reinforcing abandoned biomass Fenton reaction pretreatments
CN107119094B (en) * 2017-06-16 2020-11-17 中南大学 Method for strengthening Fenton reaction pretreatment of waste biomass by using lignin-degrading bacteria
CN109320985A (en) * 2018-08-15 2019-02-12 江苏福瑞森塑木科技股份有限公司 Colorful wood plastic composite board modelled after an antique and preparation method thereof
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
CN113583879A (en) * 2021-08-02 2021-11-02 中国农业科学院农产品加工研究所 Straw enzymolysis composition and preparation method and application thereof

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Application publication date: 20161109