CN101358218A - Method for producing xylose coupled cogeneration of propanone, butanol and ethanol using stalk - Google Patents

Method for producing xylose coupled cogeneration of propanone, butanol and ethanol using stalk Download PDF

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Publication number
CN101358218A
CN101358218A CNA2008101414189A CN200810141418A CN101358218A CN 101358218 A CN101358218 A CN 101358218A CN A2008101414189 A CNA2008101414189 A CN A2008101414189A CN 200810141418 A CN200810141418 A CN 200810141418A CN 101358218 A CN101358218 A CN 101358218A
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xylose
butanols
propanone
cogeneration
stalks
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CN101358218B (en
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王建设
王绍鹏
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ZHENGZHOU DAYANG GREASE CHEMICAL EQUIPMENT CO Ltd
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    • 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

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Abstract

The invention provides a method for producing xylose co-produced with acetone, butanol and ethanol by utilizing straws. The straws are hydrated by acid to be filtered to be divided into xylose hydrolysis fluid and xylose residue; the xylose residue is zymohydrolyzed, fermented and rectified to prepare the acetone, the butanol and the ethanol; the xylose hydrolysis fluid is used for preparing the xylose. The method of producing xylose co-produced with acetone, butanol and ethanol by utilizing straws of the invention realizes the maximization of the cellulose straw substances, not only the straw resources are fully utilized to realize changing waste into valuable and the added value of products is improved to realize the economic value of the straws, but also the new raw material source and methods for the production of the acetone and the ethanol are developed and more economic benefits and social benefits are brought to the enterprises and the society.

Description

A kind of producing xylose with stalks cogeneration of propanone, butanols and alcoholic acid method utilized
Technical field
The invention belongs to technical field of biochemical industry, relate to a kind of producing xylose with stalks cogeneration of propanone, butanols and alcoholic acid method utilized.
Background technology
Crop stalk is the photosynthetic product of sunlight, is large renewable resources, and only China just gathers in the crops about 800,000,000 tons every year, and except that sub-fraction was used as feed, all the other major parts had all been wasted.Along with the progress of technology, developed the technology of utilizing producing xylose with stalks, Xylitol, for a new way has been opened up in the utilization again of stalk.But in the technology of utilizing producing xylose with stalks, Xylitol, also exist some shortcomings, liquid part after the acid hydrolysis of stalk process, the filtration is used to produce wood sugar, but the xylose residue after filtering is not then utilized fully, there is part to be used to prepare ethanol, but do not realize the maximization of straw utilization, still have the waste on certain resource.
Acetone and butanols are widely used in organic synthesis plastics, resin, paint, medicine and national defense industry.Acetone can be used as paint, cinefilm, plastics, petroleum refining dewaxing, vegetables oil extraction, the solvent of pharmacy and the raw material of synthetic organic chemical manufacturing industry.Butanols still is that a kind of potential is combined power fuel greatly except that can be used as solvent, and its fuel value and gasoline are suitable, are the substitutes of gasoline.Existing acetone, production of butanol technology have two kinds of methods, and a kind of is the petrochemical industry synthesis method, and another kind is a biological fermentation process.What petrochemical industry synthesized that the method raw material of acetone, butanols adopts is exhausted day by day petroleum resources, along with the minimizing petrochemical industry synthesis method of oil also will come to an end.It is corn that biological fermentation process is given birth to the raw material that adopts, and not only cost is too high, has also brought competitive pressure to feedstuff industry simultaneously.Utilize Maize Production acetone, butanols be directly corn screen, broken, propose embryo, gelatinization, connect the boiling that disappears etc. and handle in earlier stage, ferment, distill production acetone and butanols again.It is higher to utilize corn fermentation to produce the cost of method of acetone and butanols like this.
Summary of the invention
The purpose of this invention is to provide a kind of producing xylose with stalks cogeneration of propanone, butanols and alcoholic acid method utilized, realized utilization of resources maximization.
For achieving the above object, the present invention is by the following technical solutions: a kind of producing xylose with stalks cogeneration of propanone that utilizes, butanols and alcoholic acid method, crushed stalk adds diluted acid after with hot-water soak and is hydrolyzed, filtration is divided into xylose hydrolysis fluid and xylose residue, xylose hydrolysis fluid is through evaporation, decolouring, filter, ion-exchange, concentrate and crystallization production wood sugar, the hot water that in xylose residue, adds 35~60 ℃, the weight ratio of xylose residue and hot water is 1: 3~6, adding alkaline matter accent pH value is 4~7, add cellulase more in batches, every gram xylose residue adds 200~600ncu cellulase, then 40~55 ℃ of following continuous enzymolysis 60~120 hours; The enzymolysis membrane sepn that finishes filters and to be divided into decomposed solution and filter residue, and filter residue returns the continuation enzymolysis; In parting liquid, add nitrogenous source class material, the mass percent concentration of adjusting sugar in the parting liquid is 4~6%, carries out cooking disinfection 30~45 minutes under 120~150 ℃ then, sends into fermentor tank after being cooled to 35~41 ℃, the inoculation bacterial classification was 34~39 ℃ of following anaerobically fermentings 36~72 hours; Fermented liquid carries out rectifying and tells acetone, butanols and ethanol.
After the described crushed stalk with 60~90 ℃ of hot-water soaks 1~3 hour.
Described diluted acid is that mass percent concentration is 0.3~6% dilute sulphuric acid or dilute hydrochloric acid, and the add-on of diluted acid is 5~8 times of stalk weight.
Temperature is 100~130 ℃ during described hydrolysis, and pressure is 0.1~0.3MPa during hydrolysis, and hydrolysis time is 3~8 hours.
Described bacterial classification is clostridium acetobutylicum, acetone Clostridium butylicum, clostridium saccharobutyricum or Pasteur's gemma clostridium.
Described nitrogenous source class material is ammonium sulfate, monoammonium sulfate, ammonium chloride, dregs of beans, cottonseed meal, peanut meal, corn or rapeseed meal, and the add-on of nitrogenous source class material is 1~5% of a decomposed solution weight.
Described alkaline matter is calcium hydroxide, lime carbonate, yellow soda ash, sodium hydroxide, salt of wormwood or potassium hydroxide.
Slightly heat up in a steamer earlier before the described rectification working process.
Use the enzymolysis producer during described enzymolysis.
Described stalk is one or more in maize straw, wheat stalk, broomcorn straw, Sunflower Receptacle stalk, straw, corn cob, bagasse, Pericarppium arachidis hypogaeae or the cotton seed hulls.
Raw material used in the present invention is a straw-like materials, straw-like materials mainly is to be become to be grouped into for three kinds by hemicellulose, Mierocrystalline cellulose and xylogen, the main moiety of hemicellulose material is an xylan, the hemicellulose material is difficult for by cellulase hydrolysis, and the main moiety of Mierocrystalline cellulose is a hexosan, and Mierocrystalline cellulose is difficult for by dilute acid hydrolysis again.In order to utilize the Mierocrystalline cellulose straw-like materials fully, the present invention uses the hot-water soak stalk earlier, remove the material that pectin in the raw material and tannin etc. hinder hydrolysis, utilize diluted acid to make hydrolysis of hemicellulose be converted into pentose then, pentose is the good raw material of producing wood sugar, Xylitol or furfural; And under equal conditions hemicellulose acid hydrolysis speed is 100 times of cellulosic acid hydrolysis rate, be difficult for then being generated monose-glucose with a spot of cellulase hydrolysis by acid-hydrolyzed Mierocrystalline cellulose, so not only reduced the consumption of cellulase, also improved cellulosic utilization ratio greatly, add strain fermentation in the glucose and obtain acetone, butanols and alcoholic acid mixture, rectifying is with mixture separation.The present invention utilizes producing xylose with stalks cogeneration of propanone, butanols and alcoholic acid method to realize the maximization that the Mierocrystalline cellulose straw-like materials utilizes, not only utilize the straw resource fully, realized turning waste into wealth, improved value-added content of product, realized its economic worth, simultaneously also new raw material resources and method have been opened up, for enterprise and society have brought more economic benefit and social benefit for the production of acetone, butanols.
Embodiment
Embodiment 1: corn cob is pulverized back with 90 ℃ of hot-water soaks 1 hour, adding mass percent concentration then and be 0.3% dilute sulphuric acid is hydrolyzed, the dilute sulphuric acid add-on is 8 times of corn cob weight, temperature is 100 ℃ during hydrolysis, pressure is 0.1MPa during hydrolysis, hydrolysis time is 8 hours, filters to be divided into xylose hydrolysis fluid and xylose residue, and xylose hydrolysis fluid is through evaporation, decolouring, filtration, ion-exchange, concentrated and crystallization production wood sugar; The hot water that in xylose residue, adds 35 ℃, the weight ratio of xylose residue and hot water is 1: 6, and adding calcium hydroxide accent pH value is 4, adds cellulase more in batches, every gram xylose residue adds the 200ncu cellulase, sends into the enzymolysis producer then 40 ℃ of following continuous enzymolysis 120 hours; The enzymolysis membrane sepn that finishes filters and to be divided into decomposed solution and filter residue, and filter residue returns the continuation enzymolysis; In parting liquid, add ammonium sulfate, the add-on of ammonium sulfate is 1% of a decomposed solution weight, concentrating the mass percent concentration of adjusting sugar in the parting liquid is 6%, under 120 ℃, carried out cooking disinfection 45 minutes then, send into fermentor tank after being cooled to 35 ℃, inoculation clostridium acetobutylicum bacterial classification was 34 ℃ of following anaerobically fermentings 72 hours; Fermented liquid slightly heats up in a steamer earlier and carries out rectifying again and tell acetone, butanols and ethanol, and acetone, butanols, alcoholic acid mass ratio are 27: 62.2: 10.1.
Embodiment 2: it is back with 80 ℃ of hot-water soaks 2 hours that maize straw, wheat stalk and broomcorn straw are mixed pulverizing, adding mass percent concentration then and be 3% dilute hydrochloric acid is hydrolyzed, the dilute hydrochloric acid add-on is maize straw, wheat stalk and broomcorn straw gross weight 7 times, temperature is 120 ℃ during hydrolysis, pressure is 0.2MPa during hydrolysis, hydrolysis time is 5 hours, filtration is divided into xylose hydrolysis fluid and xylose residue, and xylose hydrolysis fluid is through evaporation, decolouring, filtration, ion-exchange, concentrated and crystallization production wood sugar; The hot water that in xylose residue, adds 45 ℃, the weight ratio of xylose residue and hot water is 1: 5.5, and adding lime carbonate accent pH value is 5, adds cellulase more in batches, every gram xylose residue adds the 400ncu cellulase, sends into the enzymolysis producer then 50 ℃ of following continuous enzymolysis 90 hours; The enzymolysis membrane sepn that finishes filters and to be divided into decomposed solution and filter residue, and filter residue returns the continuation enzymolysis; In parting liquid, add monoammonium sulfate, the add-on of monoammonium sulfate is 3% of a decomposed solution weight, concentrating the mass percent concentration of adjusting sugar in the parting liquid is 5%, under 140 ℃, carried out cooking disinfection 40 minutes then, send into fermentor tank after being cooled to 38 ℃, inoculation clostridium saccharobutyricum bacterial classification was 37 ℃ of following anaerobically fermentings 50 hours; Fermented liquid slightly heats up in a steamer earlier and carries out rectifying again and tell acetone, butanols and ethanol, and acetone, butanols, alcoholic acid mass ratio are 28: 61: 10.1.
Embodiment 3: pulverize Pericarppium arachidis hypogaeae and cotton seed hulls mixing back with 60 ℃ of hot-water soaks 3 hours, adding mass percent concentration then and be 6% dilute sulphuric acid is hydrolyzed, the dilute sulphuric acid add-on is Pericarppium arachidis hypogaeae and cotton seed hulls gross weight 5 times, temperature is 130 ℃ during hydrolysis, pressure is 0.3MPa during hydrolysis, hydrolysis time is 3 hours, filters to be divided into xylose hydrolysis fluid and xylose residue, and xylose hydrolysis fluid is through evaporation, decolouring, filtration, ion-exchange, concentrated and crystallization production wood sugar; The hot water that in xylose residue, adds 60 ℃, the weight ratio of xylose residue and hot water is 1: 3, and adding sodium hydroxide accent pH value is 7, adds cellulase more in batches, every gram xylose residue adds the 500ncu cellulase, sends into the enzymolysis producer then 55 ℃ of following continuous enzymolysis 60 hours; The enzymolysis membrane sepn that finishes filters and to be divided into decomposed solution and filter residue, and filter residue returns the continuation enzymolysis; In parting liquid, add corn, the add-on of corn is 2% of a decomposed solution weight, the mass percent concentration that adds sugar in the water adjustment parting liquid is 4%, under 150 ℃, carried out cooking disinfection 30 minutes then, send into fermentor tank after being cooled to 41 ℃, inoculation clostridium acetobutylicum bacterial classification was 39 ℃ of following anaerobically fermentings 36 hours; Fermented liquid slightly heats up in a steamer earlier and carries out rectifying again and tell acetone, butanols and ethanol, and acetone, butanols, alcoholic acid mass ratio are 27.4: 62: 10.1.
Embodiment 4: pulverize bagasse and straw mixing back with 70 ℃ of hot-water soaks 2.5 hours, adding mass percent concentration then and be 5% dilute hydrochloric acid is hydrolyzed, the dilute hydrochloric acid add-on is bagasse and straw gross weight 6 times, temperature is 110 ℃ during hydrolysis, pressure is 0.15MPa during hydrolysis, hydrolysis time is 6 hours, filters to be divided into xylose hydrolysis fluid and xylose residue, and xylose hydrolysis fluid is through evaporation, decolouring, filtration, ion-exchange, concentrated and crystallization production wood sugar; The hot water that in xylose residue, adds 50 ℃, the weight ratio of xylose residue and hot water is 1: 4, and adding yellow soda ash accent pH value is 6, adds cellulase more in batches, every gram xylose residue adds the 600ncu cellulase, sends into the enzymolysis producer then 45 ℃ of following continuous enzymolysis 100 hours; The enzymolysis membrane sepn that finishes filters and to be divided into decomposed solution and filter residue, and filter residue returns the continuation enzymolysis; In parting liquid, add dregs of beans, the add-on of dregs of beans is 5% of a decomposed solution weight, the mass percent concentration of adjusting sugar in the parting liquid is 5%, under 130 ℃, carried out cooking disinfection 35 minutes then, send into fermentor tank after being cooled to 40 ℃, inoculation Pasteur gemma clostridium species was 38 ℃ of following anaerobically fermentings 60 hours; Fermented liquid slightly heats up in a steamer earlier and carries out rectifying again and tell acetone, butanols and ethanol, and acetone, butanols, alcoholic acid mass ratio are 28.2: 61: 10.
More than with specific embodiment technical scheme of the present invention is described; but be not to be restriction to technical scheme of the present invention; those skilled in the art should understand that; still can make amendment or be equal to replacement invention; and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed among protection scope of the present invention.

Claims (10)

1, a kind of producing xylose with stalks cogeneration of propanone that utilizes, butanols and alcoholic acid method, crushed stalk adds diluted acid after with hot-water soak and is hydrolyzed, filtration is divided into xylose hydrolysis fluid and xylose residue, xylose hydrolysis fluid is through evaporation, decolouring, filter, ion-exchange, concentrate and crystallization production wood sugar, it is characterized in that: the hot water that in xylose residue, adds 35~60 ℃, the weight ratio of xylose residue and hot water is 1: 3~6, adding alkaline matter accent pH value is 4~7, add cellulase more in batches, every gram xylose residue adds 200~600ncu cellulase, then 40~55 ℃ of following continuous enzymolysis 60~120 hours; The enzymolysis membrane sepn that finishes filters and to be divided into decomposed solution and filter residue, and filter residue returns the continuation enzymolysis; In parting liquid, add nitrogenous source class material, the mass percent concentration of adjusting sugar in the parting liquid is 4~6%, carries out cooking disinfection 30~45 minutes under 120~150 ℃ then, sends into fermentor tank after being cooled to 35~41 ℃, the inoculation bacterial classification was 34~39 ℃ of following anaerobically fermentings 36~72 hours; Fermented liquid carries out rectifying and tells acetone, butanols and ethanol.
2, producing xylose with stalks cogeneration of propanone, butanols and the alcoholic acid method utilized as claimed in claim 1 is characterized in that: after the described crushed stalk with 60~90 ℃ of hot-water soaks 1~3 hour.
3, producing xylose with stalks cogeneration of propanone, butanols and the alcoholic acid method utilized as claimed in claim 2 is characterized in that: described diluted acid is that mass percent concentration is 0.3~6% dilute sulphuric acid or dilute hydrochloric acid, and the add-on of diluted acid is 5~8 times of stalk weight.
4, producing xylose with stalks cogeneration of propanone, butanols and the alcoholic acid method utilized as claimed in claim 3 is characterized in that: temperature is 100~130 ℃ during described hydrolysis, and pressure is 0.1~0.3MPa during hydrolysis, and hydrolysis time is 3~8 hours.
5, as each described producing xylose with stalks cogeneration of propanone, butanols and alcoholic acid method utilized of claim 1 to 4, it is characterized in that: described bacterial classification is clostridium acetobutylicum, acetone Clostridium butylicum, clostridium saccharobutyricum or Pasteur's gemma clostridium.
6, producing xylose with stalks cogeneration of propanone, butanols and the alcoholic acid method utilized as claimed in claim 5, it is characterized in that: described nitrogenous source class material is ammonium sulfate, monoammonium sulfate, ammonium chloride, dregs of beans, cottonseed meal, peanut meal, corn or rapeseed meal, and the add-on of nitrogenous source class material is 1~5% of a decomposed solution weight.
7, producing xylose with stalks cogeneration of propanone, butanols and the alcoholic acid method utilized as claimed in claim 6, it is characterized in that: described alkaline matter is calcium hydroxide, lime carbonate, yellow soda ash, sodium hydroxide, salt of wormwood or potassium hydroxide.
8, producing xylose with stalks cogeneration of propanone, butanols and the alcoholic acid method utilized as claimed in claim 7 is characterized in that: slightly heat up in a steamer earlier before the described rectification working process.
9, producing xylose with stalks cogeneration of propanone, butanols and the alcoholic acid method utilized as claimed in claim 8 is characterized in that: use the enzymolysis producer during described enzymolysis.
10, producing xylose with stalks cogeneration of propanone, butanols and the alcoholic acid method utilized as claimed in claim 9, it is characterized in that: described stalk is one or more in maize straw, wheat stalk, broomcorn straw, Sunflower Receptacle stalk, straw, corn cob, bagasse, Pericarppium arachidis hypogaeae or the cotton seed hulls.
CN2008101414189A 2008-09-22 2008-09-22 Method for producing xylose coupled cogeneration of propanone, butanol and ethanol using stalk Expired - Fee Related CN101358218B (en)

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CN102260230A (en) * 2011-05-17 2011-11-30 中国林业科学研究院林产化学工业研究所 Method for preparing furfural by using two-step hydrolysis of biomass
CN101492700B (en) * 2009-03-05 2012-07-04 王建设 Intensive processing method for stalk articles or agricultural castoff
CN101928733B (en) * 2009-11-05 2012-08-29 王建设 Method and device for producing biological butanol with straw-like materials or agricultural and forestry wastes
CN101597625B (en) * 2009-07-23 2012-08-29 南京林业大学 Method for preparing fuel ethanol by low-energy consumption wood raw material
CN102876736A (en) * 2012-07-25 2013-01-16 中国科学院成都生物研究所 Method for producing acetone, ethanol and butanol by taking straw as raw material
CN103320548A (en) * 2013-06-24 2013-09-25 稼禾生物股份有限公司 Method for preparing xylooligosaccharide and cellulose by using crop straws
US20130252293A1 (en) * 2011-01-28 2013-09-26 Institute Of Process Engineering, Chinese Academy Of Sciences Process for producing bio-based product from straw hemicellulose and fully utilizing the components thereof
CN101942382B (en) * 2009-07-06 2014-01-15 中国科学院过程工程研究所 Device and method for producing butanol by fermenting straw dilute acid hydrolyzed pentaglucose
CN103757072A (en) * 2014-01-10 2014-04-30 杭州师范大学 Method for preparing xylan and xylo-oligosaccharide from rice straw
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CN104357490A (en) * 2014-10-27 2015-02-18 梁利和 Method for producing alcohol by adding waste molasses into cellulose sweet mash
CN104774877A (en) * 2015-04-10 2015-07-15 山东龙力生物科技股份有限公司 Method for co-producing ethanol, acetone and butanol by lignocellulose biomass
US20160230134A1 (en) * 2012-12-21 2016-08-11 Verbio Vereinigte Bioenergie Ag Method and plant for producing biogas from lignocellulose-containing biomass
CN107058405A (en) * 2017-06-27 2017-08-18 合肥市老海新材料有限公司 A kind of ecological, environmental protective bio-ethanol and preparation method thereof
CN107502627A (en) * 2017-08-16 2017-12-22 哈尔滨工业大学 A kind of method of the rice straw split-phase bioconversion butanol based on carboxylic acid platform
CN108265085A (en) * 2017-12-29 2018-07-10 中溶科技股份有限公司 A kind of method using agricultural crop straw co-producing butanol, acetone
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CN101942382B (en) * 2009-07-06 2014-01-15 中国科学院过程工程研究所 Device and method for producing butanol by fermenting straw dilute acid hydrolyzed pentaglucose
CN101597625B (en) * 2009-07-23 2012-08-29 南京林业大学 Method for preparing fuel ethanol by low-energy consumption wood raw material
CN101928733B (en) * 2009-11-05 2012-08-29 王建设 Method and device for producing biological butanol with straw-like materials or agricultural and forestry wastes
US20130252293A1 (en) * 2011-01-28 2013-09-26 Institute Of Process Engineering, Chinese Academy Of Sciences Process for producing bio-based product from straw hemicellulose and fully utilizing the components thereof
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WO2023123805A1 (en) * 2021-12-30 2023-07-06 浙江华康药业股份有限公司 System and method for preparing refined xylose and fermentable sugar by using corn straw
CN114276885A (en) * 2022-01-05 2022-04-05 湖南华诚生物资源股份有限公司 Method for preparing ethanol from fresh momordica grosvenori
CN114276885B (en) * 2022-01-05 2024-05-17 江西海富生物工程有限公司 Method for preparing ethanol from fresh fructus momordicae

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