CN101220379A - Method for producing ethyl alcohol by using sorgo stalk - Google Patents
Method for producing ethyl alcohol by using sorgo stalk Download PDFInfo
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- CN101220379A CN101220379A CNA2008100577136A CN200810057713A CN101220379A CN 101220379 A CN101220379 A CN 101220379A CN A2008100577136 A CNA2008100577136 A CN A2008100577136A CN 200810057713 A CN200810057713 A CN 200810057713A CN 101220379 A CN101220379 A CN 101220379A
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- sweet sorghum
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses an ethanol production method by utilizing sweet sorghum stalks, which pertains to the field of plant fuel. The invention includes the following steps that: the juice and the residue of the sweet sorghum stalks are separated, then the sweet sorghum residue is treated with diluted acid explosion pretreatment, fermentable sugar is obtained by the enzymolysis of a cellulase , then the sweet sorghum juice and the sorghum residue are processed to obtain the fermented sugar liquid, concentration and regulation of the fermented sugar liquid are carried out, and finally the ethanol is prepared by using the brewing yeast for fermentation. The method of the invention can make full use of the sweet sorghum stalks and has the advantages of short fermentation time, high enzymolysis efficiency of the cellulose, high ethanol yield, etc.
Description
Technical field
The invention belongs to the production method of biofuel, relate in particular to a kind of sweet sorghum stalk that utilizes and produce the alcoholic acid method.
Background technology
The excessive exploitation of oil, Sweet natural gas, coal and use make the world face serious energy dilemma and ecocrisis, seek the green energy resource of the continuable environmental protection of alternate, become the emphasis of world energy sources strategy.And biofuel ethanol is a kind of feasible alternative route, at present China mainly is the raw material production alcohol fuel with the grain in storage for years, not only strives grain with the people and strives ground, is difficult to extensive transport solution energy problem, and from the whole life of energy utilization, the CO of grain alcohol
2Burst size does not reduce, and can not reach the environmental protection purpose, utilizes the grain-production alcohol fuel simultaneously, and not only the cost height also causes the waste of grain.Therefore need to seek the plant material of new production biofuel, sweet sorghum stalk is rich in sugar and fiber, is a kind of raw material of more satisfactory production alcohol fuel.
Compare with other energy crops that can produce alcohol, sweet sorghum has incomparable advantage: first, in the biomass energy system, sweet sorghum is primary rival, per hectare can be gathered in the crops 2250～7500 kilograms seed, the stem stalk is rich in sugar, and output is high, and the output of the bright stalk of general per hectare is about 75 tons.The second, sweet sorghum is a high energy crop.Grow vigorous period, per hectare sweet sorghum synthetic every day carbohydrate can produce 48 liters of alcohol, and corn has only 15 liters, and wheat is 3 liters, just 9 liters of grain sorghums.The 3rd, sweet sorghum is the output height not only, and its adaptability is very wide, and drought resisting, waterlogging, salt tolerant alkali are " camels " in the crop.Sweet sorghum all can be cultivated at various types of soil of pH value 5～8.5, reaches 0.36%～0.53% saline-alkali soil ground in saltiness, sweet sorghum energy normal growth, and output can reach 4～5.5 tons.Because the arable area of China is limited, so saline and alkaline soil, the particularly saline-alkali soil of beach beach be the optimal zone of development fuel alcohol industry, and sweet sorghum produce one of optimum raw material crop of fuel alcohol exactly.
At present, utilizing sweet sorghum stalk to produce alcohol fuel mainly is to utilize the juice of sweet sorghum stalk or seed to carry out fermentative production with juice, as patent application " juice of sugar grass stalks is produced the alcoholic acid method " (application number: 200510076833.7), " utilizing sweet sorghum stalk to make the ethanol liquid fermentation technique " (application number is: 200410035604.6), " sweet sorghum stalk is produced the ethanol method " (application number is: 02151719.3), " a kind of alcohol fuel and reparation technology thereof " (application number is: 2007100022972.4), 200610134397.9) etc. (application number is: mainly utilize juice of sugar grass stalks to produce ethanol in " dry straw with sweet corn or sweet sorghum is the technology of raw material ethanol production ", " utilizing the method for sweet sorghum stalk and seed ethanol production thereof " (application number is: 200710057584.6), 200710010720.6) etc. (application number is: utilize juice of sugar grass stalks and seed to produce ethanol " with the method for sweet sorghum stalk ethanol production ", these inventions utilize the stalk juice fermentation only to utilize part soluble sugar in the sweet sorghum stalk, and with in the sweet sorghum slag with soluble sugar equivalent almost, the structure sugar that exists with Mierocrystalline cellulose and hemicellulose form discards or burns, not only cause a large amount of wastes, raw material availability is low, and has caused air and environmental pollution.Along with the raising of Mierocrystalline cellulose preconditioning technique, U.S. biomass processing application innovation association (CAFI) is in sour pre-treatment, and ammonia explosion pre-treatment has all obtained very big achievement; The world advanced zymin company is as Novi's letter and the reduction of outstanding person's energy section with the cellulase price; Make the non-structure sugar and the structure sugar production alcohol fuel that make full use of in the sweet sorghum stalk become possibility, this will improve raw material availability and ethanol yield greatly.
Summary of the invention
The purpose of this invention is to provide a kind of sweet sorghum stalk that utilizes and produce the alcoholic acid method, this method can make full use of non-structure sugar and the structure sugar in the sweet sorghum stalk, raw material availability height, and ethanol yield height.
For achieving the above object, the technical solution used in the present invention is:
Utilize sweet sorghum stalk to produce the alcoholic acid method, comprise the steps:
(1) sophisticated sweet sorghum stalk is squeezed, get stalk juice and sweet sorghum slag;
(2) the sweet sorghum slag is carried out diluted acid explosion pre-treatment;
(3) with cellulase with sweet sorghum slag enzymatic saccharification;
(4) mixed sugar liquid and regulate syrup concentration;
(5) activated yeast;
(6) fermentation promptly gets ethanol.
Squeezing described in the above-mentioned production alcoholic acid method steps (1) is meant pulverizes the thread segment that cuts into 10mm～25mm with sophisticated sweet sorghum stalk, squeeze then, in gained sweet sorghum slag, add 10～20% water again and carry out twice pressing, stalk juice and sweet sorghum slag; Again with the gained stalk juice at 85～100 ℃ of boiling 30～45min, centrifugal then, filter, go precipitation, clarifying stalk juice.
Described in the above-mentioned production alcoholic acid method steps (2) to the sweet sorghum slag carry out diluted acid explosion pre-treatment be meant above-mentioned gained sweet sorghum slag is air-dry or 30～45 ℃ of down oven dry, then with the sweet sorghum slag at 0.1～0.5%H
2SO
4Soaked in the solution 8～12 hours, and placed the steam explosion jar again, boost, under 1.3～1.9MPa pressure, keep 6～10min, moment pressure release, the sweet sorghum slag of the quick-fried back of collection vapour gained; Wash the sweet sorghum slag after sour explosion treatment with water, get pre-treatment slurries and solid regenerant, in the gained slurries, add Ca (OH)
2Regulate pH value to 9.5～10.5, stir 1～1.5h, sedimentation and filtration gets clarifying pre-treatment slurries.
Above-mentioned gained solid regenerant is added water to submerge in sweet sorghum slag enzymatic saccharification is meant with cellulase described in the above-mentioned production alcoholic acid method steps (3), regulating the pH value is 4.8～5.5, add cellulase 15～30FPU/g by sweet sorghum slag dry weight, β-glucose glycoside enzyme 20～30CBU/g, in 45～50 ℃ of enzymolysis 72～108h, stir once every 5～8h during this time, filter, obtain the enzymolysis liquid glucose.
Adjusting syrup concentration described in the above-mentioned production alcoholic acid method steps (4) is meant mixes above-mentioned gained stalk juice, pre-treatment slurries and enzymolysis liquid glucose, then mixed sugar liquid is carried out boiling and concentrates, syrup concentration is 16～24% mixed sugar liquid.
Activated yeast described in the above-mentioned production alcoholic acid method steps (5) is meant according to usual method and prepares yeast seed liquid, the yeast strain that is about to 4 ℃ of slant preservations is inoculated in the activated yeast substratum, cultivates 16～20h in the constant temperature shaking table under 28～32 ℃, 100～120rpm condition; And then transfer in the seed culture medium by 5% inoculum size, under 28～32 ℃, 100～120rpm condition, cultivate 18～24h in the constant temperature shaking table; Enlarged culturing gets final product successively; The moiety of wherein said activation medium and weight percent thereof are: 1.5～2% glucose, 1.5～2% peptones, 0.8～1% yeast extractive substance, 0.15～0.2%KH
2PO
4, 0.05～0.1%MgSO
4, pH value 5.0; The moiety of wherein said seed culture medium and weight percent thereof are: 1.5～2% glucose, 1.5～2% peptones, 0.8～1% yeast extractive substance.
Fermentation described in the above-mentioned production alcoholic acid method steps (6) is meant according to weight percent and adds 0.1～0.3% urea, 0.15～0.25%MgSO in above-mentioned gained mixed sugar liquid
47H
2O and 0.25～0.5%CaCl
22H
2O then at 100～120 ℃ of following sterilization 10～15min, pressed the access yeast saccharomyces cerevisiae seed liquor of juice volume ratio 5～10% again, in 32～35 ℃ of sealing and fermenting 32～48 hours; Ethanol is collected in distillation then, gets ethanol.
Squeezing described in the aforesaid method step (1) can be undertaken by squeezing machine.
Cellulase described in the aforesaid method step (4) is meant high temperature-resisting cellulase, beta-glucosidase or Walocel MT 20.000PV enzyme etc.; Described cellulase all can be bought from the market, buys as companies such as, company of outstanding person's energy section limited from Hunan You Teer biochemistry, Sigma companies.
Yeast saccharomyces cerevisiae described in the above-mentioned steps (6) can be bought from the market, also can buy from China Committee for Culture Collection of Microorganisms common micro-organisms center, as ethanol-tolerant yeast (Saccharomycescerevisiae 2.119).
The effect of the urea described in the aforesaid method step (6) is as nitrogenous source.
MgSO described in the aforesaid method step (6)
47H
2O and 0.5%CaCl
22H
2The effect of O is as nutritive salt.
The described fermentation time of aforesaid method step (6) can be according to discharging CO in the fermenting process
2The weightlessness control fermentation time that causes.
The part of not specifically noting in the aforesaid method is interpreted as used method or equipment usually.
Advantage of the present invention: (1) sweet sorghum stalk utilization ratio of the present invention height can all be fully utilized sugar of the structure in the stalk and non-structure sugar; (2) alcohol yied height of the present invention, owing to utilized juice and the Mierocrystalline cellulose of sweet sorghum, so its alcohol yied can reach the ethanol that every double centner stalk produces about 7.3 kilograms; (3) the saccharification efficient height of cellulase of the present invention, owing to adopt diluted acid explosion treatment technology, make hemicellulose, xylogen, cellulosic structure separate, sweet sorghum slag structure gapping interval increases, therefore improved the saccharification efficient of cellulase, with the at utmost hydrolysis of structure sugar that exists with Mierocrystalline cellulose and hemicellulose in the sweet sorghum slag, structure sugar transformation efficiency can reach more than 85%; (4) the present invention adopts the distillery yeast of ethanol-tolerant, can carry out high density fermentation, has shortened fermentation time, has improved fermentation efficiency, also can save a large amount of energy, improves plant factor and production efficiency; (5) fundamentally to have changed with grain be raw material production alcoholic acid present situation in the present invention.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
Utilize sweet sorghum stalk to produce ethanol, comprise the steps:
(1) sweet sorghum stalk is squeezed the juice water content 72.8%, sugar degree 13.9%, the sweet sorghum stalk double centner of crude fiber content 9.6% is pulverized the thread segment that cuts into 10mm～25mm, squeeze with squeezing machine, in gained sweet sorghum slag, add water then and carry out twice pressing, get sweet sorghum juice and the extremely low thread sweet sorghum slag of residual sugar content;
(2) with 100 ℃ of boilings of juice of sugar grass stalks 30 minutes, precipitation is gone in centrifuging, obtains clarifying sweet sorghum juice.
(3) sweet sorghum slag diluted acid explosion pre-treatment is used 0.1%H with sweet sorghum slag natural air drying
2SO
4Solution soaking 12 hours is inserted steam explosion jar stopping device; Keep 6min under 1.5MPa pressure, the quick-fried raw material of vapour is collected in the moment pressure release; Wash the sweet sorghum slag of sour explosion treatment with water, get pre-treatment slurries and solid regenerant, in the pre-treatment slurries, add Ca (OH)
2Regulate pH value to 10.5, stir 1h, sedimentation and filtration is abandoned precipitation, and filtrate is used H
2SO
4Neutralize 5.0, get clarifying pre-treatment slurries;
(4) sweet sorghum slag enzymatic saccharification is added water to submerge the pretreated solid regenerant of sweet sorghum slag, Ca (OH)
2Regulate pH value to 5.5, add cellulase (Hunan Youteer Biochemical Co., Ltd.'s production) 30FPU/g by sweet sorghum slag dry weight, (Novozym 188 for β-glucose glycoside enzyme, Novozymes Company produces) 30CBU/g, in 50 ℃ of enzymolysis 108h, stir once every 6h, filter, get the enzymolysis liquid glucose.
(5) yeast culture will (Saccharomycescerevisiae 2.119 at the ethanol-tolerant yeast of 4 ℃ of slant preservations, deriving from China Committee for Culture Collection of Microorganisms common micro-organisms center) three rings are inoculated in the 20mL yeast starter activation medium, cultivate 20h in 32 ℃, 120rpm constant temperature shaking table; And then transfer in the seed culture medium of 100ml by 5% inoculum size, in 32 ℃, 120rpm constant temperature shaking table, cultivate 20h; Enlarged culturing successively; Get yeast culture liquid.
(6) regulate syrup concentration step (2) gained sweet sorghum juice, step (3) gained pre-treatment slurries and step (4) gained enzymolysis liquid glucose mixed, mixed sugar liquid, mixed sugar liquid is carried out boiling concentrates, syrup concentration is 20% mixed sugar liquid.
(7) 0.3% urea, 0.25%MgSO are added in fermentation in the mixed sugar liquid of step (6)
47H
2O and 0.5%CaCl
22H
2O in 121 ℃ of sterilization 15min, adds in the mixed sugar liquid in the ratio of the juice 10% yeast saccharomyces cerevisiae activation solution with the ethanol-tolerant of step (5), then in 32 ℃ of sealing and fermenting 32h, ethanol concn reaches 8.3% (w/v) in the fermented liquid, and ethanol is collected in distillation, gets ethanol 7.56Kg.
Embodiment 2
Utilize sweet sorghum stalk to produce ethanol, comprise the steps:
(1) sweet sorghum stalk is squeezed the juice water content 72.8%, sugar degree 13.9%, the sweet sorghum stalk 100Kg of crude fiber content 9.6% pulverizes the thread segment that cuts into 10mm～25mm, squeeze with squeezing machine, in gained sweet sorghum slag, add water then and carry out twice pressing, get sweet sorghum juice and the extremely low thread sweet sorghum slag of residual sugar content.
(2) with 100 ℃ of boilings of step (1) gained juice of sugar grass stalks 30 minutes, precipitation is gone in centrifuging, obtains clarifying sweet sorghum juice.
(3) sweet sorghum slag diluted acid explosion pre-treatment is air-dry with step (1) gained sweet sorghum slag, uses 0.5%H
2SO
4Solution soaking 8 hours is inserted in the steam explosion jar stopping device; Boost rapidly, keep 6min under 1.5MPa pressure, the quick-fried raw material of vapour is collected in the moment pressure release; Wash the sweet sorghum slag of sour explosion treatment with water, get pre-treatment slurries and solid regenerant, add Ca (OH) in the slurries
2Regulate pH value to 10.5, stir 1h, sedimentation and filtration is abandoned precipitation, and filtrate is used H
2SO
4Neutralize 5.0, get clarifying pre-treatment slurries.
(4) sweet sorghum slag enzymatic saccharification.Add water to submerge the pretreated solid regenerant of sweet sorghum slag, Ca (OH)
2Regulate pH value to 5.0, add cellulase (Celluclast 1.5L, Novozymes Company produces) 15FPU/g by sweet sorghum slag dry weight, (Novozym 188 for β-glucose glycoside enzyme, Novozymes Company produces) 30CBU/g, in 50 ℃ of enzymolysis 72h, stir once every 6h.Obtain the enzymolysis liquid glucose.
(5) (Saccharomycescerevisiae 2.119 with the ethanol-tolerant yeast of 4 ℃ of slant preservations for activated yeast, derive from Chinese common micro-organisms culture presevation administrative center) be inoculated in the 20ml yeast starter activation medium, in 32 ℃, 120rpm constant temperature shaking table, cultivate 20h.And then transfer in the seed culture medium of 100ml by 5% inoculum size, in 32 ℃, 120rpm constant temperature shaking table, cultivate 18h.Enlarged culturing successively.
(6) regulate syrup concentration step (2) gained sweet sorghum juice, step (3) gained pre-treatment slurries and step (4) gained enzymolysis liquid glucose mixed,, mixed sugar liquid, mixed sugar liquid is carried out boiling concentrates, syrup concentration is 16% mixed sugar liquid.
(7) 0.3% urea is added in fermentation in step (6) gained mixed sugar liquid, adds 0.25%MgSO
47H
2O, 0.5%CaCl
22H
2O in 121 ℃ of sterilization 15min, adds the yeast saccharomyces cerevisiae activation solution in the mixed sugar liquid to by juice 10% again, and in 35 ℃ of sealing and fermenting 32h, ethanol concn is 6.6% (w/v) in the fermented liquid, and ethanol is collected in distillation, gets ethanol 7.28Kg.
Claims (8)
1. utilize sweet sorghum stalk to produce the alcoholic acid method, comprise the steps:
(1) sophisticated sweet sorghum stalk is squeezed, get stalk juice and sweet sorghum slag;
(2) the sweet sorghum slag is carried out diluted acid explosion pre-treatment;
(3) with cellulase with sweet sorghum slag enzymatic saccharification;
(4) mixed sugar liquid and regulate syrup concentration;
(5) activated yeast;
(6) fermentation gets ethanol.
2. according to the described production alcoholic acid of claim 1 method, it is characterized in that the squeezing described in its step (1) is meant the thread segment that sophisticated sweet sorghum stalk pulverizing is cut into 10mm～25mm, squeeze then, in gained sweet sorghum slag, add 10～20% water again and carry out twice pressing, stalk juice and sweet sorghum slag; Then with the gained stalk juice at 85～100 ℃ of boiling 30～45min, centrifugal, filter, go the precipitation, clarifying stalk juice.
3. according to claim 1 or 2 described production alcoholic acid methods, it is characterized in that described in its step (2) to the sweet sorghum slag carry out diluted acid explosion pre-treatment be meant above-mentioned gained sweet sorghum slag is air-dry or 30～45 ℃ of down oven dry, then with the sweet sorghum slag at 0.1～0.5%H
2SO
4Soaked in the solution 8～12 hours, and placed the steam explosion jar again, boost, under 1.3～1.9MPa pressure, keep 6～10min, moment pressure release, the sweet sorghum slag of the quick-fried back of collection vapour gained; Wash the sweet sorghum slag after sour explosion treatment with water, get pre-treatment slurries and solid regenerant, in the gained slurries, add Ca (OH)
2Regulate pH value to 9.5～10.5, stir 1～1.5h, sedimentation and filtration gets clarifying pre-treatment slurries.
4. according to the described production alcoholic acid of claim 3 method, it is characterized in that sweet sorghum slag enzymatic saccharification is meant with cellulase described in its step (3) adds water to submerge gained solid regenerant in the claim 3, regulating the pH value is 4.8～5.5, add cellulase 15～30FPU/g by sweet sorghum slag dry weight, β-glucose glycoside enzyme 20～30CBU/g, in 45～50 ℃ of enzymolysis 72～108h, during stir once every 5～8h, filter the enzymolysis liquid glucose.
5. according to the described production alcoholic acid of claim 4 method, it is characterized in that the adjusting syrup concentration described in its step (4) is meant that the enzymolysis liquid glucose with gained in gained pre-treatment slurries and the claim 4 in the stalk juice of gained in the claim 2, the claim 3 mixes, get mixed sugar liquid, then mixed sugar liquid is carried out boiling and concentrates, syrup concentration is 16～24% mixed sugar liquid.
6. according to the described production alcoholic acid of claim 5 method, it is characterized in that the activated yeast described in its step (5) is meant according to usual method prepares yeast seed liquid, the yeast strain that is about to 4 ℃ of slant preservations is inoculated in the activated yeast substratum, cultivates 16～20h in the constant temperature shaking table under 28～32 ℃, 100～120rpm condition; And then transfer in the seed culture medium by 5% inoculum size, under 28～32 ℃, 100～120rpm condition, cultivate 18～24h in the constant temperature shaking table; Enlarged culturing gets final product successively; The moiety of wherein said activation medium and weight percent thereof are: 1.5～2% glucose, 1.5～2% peptones, 0.8～1% yeast extractive substance, 0.15～0.2%KH
2PO
4, 0.05～0.1%MgSO
4, pH value 5.0; The moiety of wherein said seed culture medium and weight percent thereof are: 1.5～2% glucose, 1.5～2% peptones, 0.8～1% yeast extractive substance.
7. according to the described production alcoholic acid of claim 6 method, it is characterized in that the fermentation described in its step (6) is meant in the mixed sugar liquid according to weight percent gained in claim 5 and add 0.1～0.3% urea, 0.15～0.25%MgSO
47H
2O and 0.25～0.5%CaCl
22H
2O then at 100～120 ℃ of following sterilization 10～15min, pressed the access yeast saccharomyces cerevisiae seed liquor of juice volume ratio 5～10% again, in 32～35 ℃ of sealing and fermenting 32～48 hours; Distillation is collected then, gets ethanol.
8. according to the described production alcoholic acid of claim 6 method, it is characterized in that described yeast is ethanol-tolerant yeast Saccharomyces cerevisiae 2.119.
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|---|---|---|---|
| CN2008100577136A CN101220379B (en) | 2008-02-05 | 2008-02-05 | Method for producing ethyl alcohol by using sorgo stalk |
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| CN101220379B CN101220379B (en) | 2010-08-11 |
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| CN101343647B (en) * | 2008-08-28 | 2011-03-16 | 刘明全 | Method for preparing ethyl alcohol with sorgo stalk |
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| CN101875948B (en) * | 2009-04-28 | 2012-08-29 | 杨永福 | Method for producing fuel ethanol by sugar grass stalk juice |
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| CN102115702B (en) * | 2009-12-30 | 2012-10-24 | 中国科学院过程工程研究所 | Grain dry segmented steam explosion pretreatment method for fermenting liquor by using pure grain in solid state |
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| CN103773814A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Method for producing alcohol from sugar sorghum |
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