CN110317838A - Method for preparing ethanol by adopting cassava alcohol residues - Google Patents
Method for preparing ethanol by adopting cassava alcohol residues Download PDFInfo
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- CN110317838A CN110317838A CN201810265075.0A CN201810265075A CN110317838A CN 110317838 A CN110317838 A CN 110317838A CN 201810265075 A CN201810265075 A CN 201810265075A CN 110317838 A CN110317838 A CN 110317838A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 238000000034 method Methods 0.000 title claims abstract description 126
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 title claims abstract description 48
- 125000003158 alcohol group Chemical group 0.000 title abstract 4
- 241000658379 Manihot esculenta subsp. esculenta Species 0.000 title 1
- 230000008569 process Effects 0.000 claims abstract description 81
- 238000000855 fermentation Methods 0.000 claims abstract description 54
- 230000004151 fermentation Effects 0.000 claims abstract description 53
- 240000003183 Manihot esculenta Species 0.000 claims abstract description 47
- 239000007790 solid phase Substances 0.000 claims abstract description 39
- 229920005610 lignin Polymers 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 235000019441 ethanol Nutrition 0.000 claims description 120
- 230000003301 hydrolyzing effect Effects 0.000 claims description 52
- 239000002893 slag Substances 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 32
- 230000002478 diastatic effect Effects 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 108010059892 Cellulase Proteins 0.000 claims description 17
- 229940106157 cellulase Drugs 0.000 claims description 17
- 239000006052 feed supplement Substances 0.000 claims description 16
- 239000012265 solid product Substances 0.000 claims description 16
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 10
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 238000007701 flash-distillation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000009471 action Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 53
- 239000000463 material Substances 0.000 description 20
- 239000000758 substrate Substances 0.000 description 15
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- -1 Mesh Chemical compound 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
-
- 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
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
-
- 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
Landscapes
- 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 provides a method for preparing ethanol by adopting cassava alcohol residues. The method comprises the following steps: carrying out a first hydrolysis process on the cassava alcohol residues under the catalysis of alkali to obtain a first solid-phase product; under the catalysis of acid, carrying out a second hydrolysis process on the first solid-phase product to obtain a second solid-phase product; and carrying out saccharification and fermentation on the second solid-phase product to obtain the ethanol. Under the action of alkali, the cassava alcohol residues can be hydrolyzed by the first hydrolysis process, so that lignin is dissolved in water, and meanwhile, some phenolic substances can be generated, and the adsorption of the phenolic substances on the first solid-phase product can inhibit the subsequent alcohol fermentation process. In the second hydrolysis process, under the action of acid, the phenolic substance reacts with the acid and then is removed from the first solid-phase product, so as to obtain a second solid-phase product. The second hydrolysis process can remove the above phenolic substances inhibiting the fermentation process, and thus the second hydrolysis process is beneficial to improving the yield of ethanol in the fermentation process.
Description
Technical field
The present invention relates to biological chemical fields, in particular to a kind of method for preparing ethyl alcohol using cassava alcohol slag.
Background technique
China since Car-Use Ethanol Gasoline Promotion, has successively been established, using corn wheat as the Ji of raw material since 2001
Woods alcohol fuel, Henan day hat, Anhui rich Yuan Dengshuojia alcohol fuel company and cassava are China Oil and Food Import and Export Corporation's North Sea alcohol fuel of raw material
Co., Ltd.Currently, striving grain with grain-production alcohol fuel and people, country, which has expressly provided, to forbid continuing developing grain alcohol item
Mesh, and there are no relevant regulations in terms of cassava produces alcohol fuel, therefore are had become not using cassava production alcohol fuel
Come the trend developed.However, how generated cassava alcohol slag handles, gives during using cassava production alcohol fuel
Enterprise causes great burden.
According to the literature, 1 ton of Cassava-based ethanol of every production can about generate 0.33 ton of cassava alcohol slag, produce 300000 tons of cassava per year
Alcohol fuel factory generates about 100,000 tons of cassava alcohol slag for 1 year.Currently, the processing mode of cassava alcohol slag, is mainly burned
Or landfill, not still to the significant wastage of resource, while seriously polluting environment.
Contain higher cellulose and hemicellulose in cassava alcohol slag, if by preprocess method appropriate to cassiri
Smart slag is pre-processed, and is converted ethyl alcohol for the cellulose in cassava alcohol slag, will be mitigated environmental pollution, is cassava alcohol slag
It recycles and a practicable approach is provided.And existing there is a problem of that alcohol yied is low using cassava alcohol slag method.
Summary of the invention
It is existing to solve the main purpose of the present invention is to provide a kind of method for preparing ethyl alcohol using cassava alcohol slag
There is a problem of that alcohol yied is low using the method that cassava alcohol slag prepares ethyl alcohol.
To achieve the goals above, a kind of method that ethyl alcohol is prepared using cassava alcohol slag is provided according to the present invention, side
Method includes: that cassava alcohol slag is carried out the first hydrolytic process, obtains the first solid product under the catalytic action of alkali；In acid
Under catalytic action, the first solid product is subjected to the second hydrolytic process, obtains second solid phase product；And by second solid phase product into
Row diastatic fermentation, obtains ethyl alcohol.
Further, this method further includes adding in the first hydrolytic process to the reaction system of the first hydrolytic process
The step of heat；Preferably, the temperature of the first hydrolytic process is 150~220 DEG C, and heating time is 1~2h.
Further, alkali is the mixed liquor of the hydrogen peroxide of 30wt% and the ammonium hydroxide of 5~15wt%, and the volume of hydrogen peroxide is ammonia
The 10~20% of water volume.
Further, method further includes heating in the second hydrolytic process to the reaction system of the second hydrolytic process
The step of；Preferably, the heating temperature of the second hydrolytic process is 160~210 DEG C, and heating time is 40~75min.
Further, acid is the aqueous sulfuric acid of 3~5wt% of concentration.
Further, before carrying out diastatic fermentation process, the above method further include: in being washed to second solid phase product
Property after, then using ethanol water carry out alcohol wash processing；And ethyl alcohol is recycled by the way of flash distillation after alcohol washes processing, it obtains
Second solid phase product.
Further, the volume fraction of the middle ethyl alcohol of ethanol water is 10~20%, and temperature is 80~100 DEG C, and alcohol is washed
The time for the treatment of process is 30~60min.
Further, diastatic fermentation includes carrying out the mixture of second solid phase product, cellulase, inorganic salts and yeast
The process of fermentation.
Further, the total amount relative to the reaction system of diastatic fermentation, the additional amount of cellulase are 15~25FPU/
g。
Further, inorganic salts are selected from urea and diammonium hydrogen phosphate；Preferably, the dosage of urea is 2~4g/L；It is preferred that
Ground, the dosage of diammonium hydrogen phosphate are 1~2g/L.
Further, this method further includes the steps that supplementing the second hydrolysate during diastatic fermentation；Preferably, it mends
The number for filling second solid phase product process is 2~4 times, and the time interval of the adjacent process of feed supplement twice is for 24 hours；Preferably, it mends
After filling second solid phase product, the concentration of second solid phase product is 200~260g/L.
Further, the contents on dry basis of the lignin in second solid phase product be less than 10wt%, moisture content be 5~
20wt%；Preferably, the partial size of cassava alcohol slag is less than 0.9mm.
It applies the technical scheme of the present invention, in the presence of alkali, carrying out the first hydrolytic process can be such that cassava alcohol slag sends out
Unboiled water solution, to make lignin dissolution into water.In second hydrolytic process, under the action of an acid, the inhibition that the first hydrolysis generates
The substance of alcoholic fermentation is reacted with acid to be removed, this can further decrease inhibition of the lignin to fermentation process, so as to
Greatly improve the content of ethyl alcohol.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
It is existing the method for ethyl alcohol to be prepared using cassava alcohol slag that there are alcohol yieds is low as described in background technique
The problem of.In order to solve the above-mentioned technical problem, this application provides a kind of method for preparing ethyl alcohol using cassava alcohol slag, the party
Method includes that cassava alcohol slag is carried out the first hydrolytic process, obtains the first solid product under the catalytic action of alkali；In urging for acid
Under change effect, the first solid product is subjected to the second hydrolytic process, obtains second solid phase product；And second solid phase product is carried out
Diastatic fermentation obtains ethyl alcohol.
Due to containing a large amount of lignin in cassava alcohol slag, the presence of lignin will affect the production of ethyl alcohol in fermentation process
Rate.Originally in the presence of alkali, carrying out the first hydrolytic process can be such that cassava alcohol slag hydrolyzes, so that lignin dissolution be made to arrive
In water, while some phenolic substancess can also be generated, which, which is adsorbed on the first solid product, can inhibit subsequent
Alcoholic fermentation process.In second hydrolytic process, under the action of an acid, above-mentioned phenolic substances reacted with acid after from the first solid product
Upper removing obtains second solid phase product.Second hydrolytic process can remove the phenolic substances of above-mentioned inhibition fermentation process, thus
After the second hydrolytic process, be conducive to the yield for improving ethyl alcohol in fermentation process.
While the superiority in order to prove processing method in the application, inventor have made intensive studies: first to cassiri
Smart slag carries out sour processing, then carries out subsequent alkali process and fermentation process again.It is made using the technique that the method prepares ethyl alcohol
Ethanol production it is lower.It traces it to its cause as in sour treatment process, No. 5 positions of lignin G unit can be used as reaction site can be with
Condensation reaction occurs for lignin other structures unit, and then generates condensation property lignin, and the generation of condensation property lignin is so that wood
Element removing becomes difficult, thus affects the process of alcohol prepared by fermenting.
And as first carried out alkali process to cassava alcohol slag, that most of lignin can be removed by hydrolysis, through the first solid-liquid
After separation, the first solid product is obtained.When first solid product to be carried out to the second hydrolytic process under subsequent acidic environment, suppression
The phenolic substances of preparing alcohol fermentation is reacted with acid to be removed, so as to reduce its inhibition to fermentation.Thus pass through the second water
The content for be conducive to improving ethyl alcohol obtained in fermentation process of solution preocess.It is thus this for cassava alcohol slag to contain wood
For the more material of quality, it is clear that the sour treatment effect of progress is more preferable after first carrying out alkali process, this is because in alkali process process
Middle lignin can be easier to be removed, so that the hydrolysis of advantageous fibre element enzyme greatly improves the content of ethyl alcohol in turn.
Specifically, the above method includes: cassava alcohol slag to be carried out the first hydrolytic process, so under the catalytic action of alkali
First time separation of solid and liquid process is carried out afterwards, obtains the first solid slag (the first solid product) and filtrate；It, will under the catalytic action of acid
First solid slag carries out the second hydrolytic process, then carries out second of separation of solid and liquid process, and obtaining the second solid slag, (second solid phase produces
Object)；And the second solid slag is subjected to diastatic fermentation, obtain ethyl alcohol.
Be conducive to improve the removal rate of lignin using above-mentioned preparation method, while the yield of ethyl alcohol can also be improved.?
In a kind of preferred embodiment, method further includes carrying out in the first hydrolytic process to the reaction system of the first hydrolysis
The step of heating.
Under base catalysis, cassava alcohol slag is able to carry out initial hydrolysis.In the first hydrolytic process, the first hydrolysis is produced
Objects system is heated, and the lignin in above-mentioned solid reactant can be made further to be hydrolyzed, to improve lignin
Removal rate, and then be conducive to improve ethyl alcohol yield.
Preferably, the temperature of the first hydrolytic process is 150~220 DEG C, and heating time is 1~2h.First hydrolytic process
The heating time of temperature includes but is not limited to above range, and limited be conducive to further increase within the above range it is wooden
The removal rate of element.
Preferably, in the first hydrolytic process, alkali is the mixed liquor of the hydrogen peroxide of 30wt% and the ammonium hydroxide of 5~15wt%, double
The volume of oxygen water is the 10~20% of the volume of ammonium hydroxide.
In a preferred embodiment, the above method further includes in the second hydrolytic process, to the second hydrolytic process
Reaction system the step of being heated.In second of hydrolytic process, the second hydrolysate system is heated, Neng Goujia
The extent of reaction of phenols and acid that fast first hydrolytic process generates further improves to improve the removal rate of phenolic substances
The yield of ethyl alcohol during diastatic fermentation.
Preferably, the heating temperature of the second hydrolytic process is 160~210 DEG C, and heating time is 40~75min.Second water
The heating time of the temperature of solution preocess includes but is not limited to above range, and is limited and be conducive within the above range further
Improve the removal rate of phenolic substances in the second hydrolytic process.
Preferably, in the second hydrolytic process, acid is the aqueous sulfuric acid of 3~5wt% of concentration.
During diastatic fermentation, nutriment needed for needing to be added fermenting microbe.Preferably, above-mentioned diastatic fermentation packet
Include the process that the mixture of second solid phase product, cellulase, inorganic salts and yeast ferments.
In a preferred embodiment, before carrying out diastatic fermentation process, the above method further include: consolidate second
After phase product is washed to neutrality, alcohol is then carried out using ethanol water and washes processing；And using the side of flash distillation after alcohol washes processing
Formula recycles ethyl alcohol, obtains second solid phase product.It will further can be obtained through the second hydrolytic process using aforesaid operations process
The lignin on solid product surface improve ethyl alcohol during diastatic fermentation so as to further decrease the content of lignin
Yield.
It is highly preferred that the volume fraction of the middle ethyl alcohol of ethanol water is 10~20%, temperature is 80~100 DEG C, and alcohol is washed
The time for the treatment of process is 30~60min.
In a preferred embodiment, the total amount relative to the reaction system of diastatic fermentation, the addition of cellulase
Amount is 15~25FPU/g.Cellulase, which is added, can speed up the percent hydrolysis of cellulose.And the additional amount of cellulase includes but
Be not limited to above range, and limited be conducive to further increase within the above range cellulose in fermentation process be hydrolyzed into it is small
The percent hydrolysis of molecule carbohydrate, and then improve the yield of ethyl alcohol.
During diastatic fermentation, need to be added nutriment of the inorganic salts as fermenting microbe indispensability.A kind of preferred
In embodiment, inorganic salts include but is not limited to urea and diammonium hydrogen phosphate.Preferably, the dosage of urea is 2~4g/L；It is preferred that
Ground, the dosage of diammonium hydrogen phosphate are 1~2g/L.
In order to improve the yield of ethyl alcohol during diastatic fermentation, it is preferable that this method further includes during diastatic fermentation
The step of supplementing second solid phase product.
Preferably, the number for supplementing second solid phase product is 2~4 times, and the time interval of the adjacent process of feed supplement twice is
24h；
Preferably, after supplementing second solid phase product, the concentration of second solid phase product is 200~260g/L.By diastatic fermentation
The concentration of second solid phase product limits within the above range in the process, is conducive to improve fermentation efficiency.
Preferably, the contents on dry basis of lignin is less than 10wt% in second solid phase product, and moisture content is 5~20wt%；
Preferably, the partial size of cassava alcohol slag is less than 0.9mm.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
The contents on dry basis of lignin is 20%~23wt% in cassava alcohol slag in the embodiment of the present application, and moisture content is
5%-10wt%.
Embodiment 1
It is added in 1L autoclave after weak aqua ammonia is mixed with hydrogen peroxide, wherein the weight percentage of weak aqua ammonia is
The volume of the ammonium hydroxide 500mL of 10wt%, hydrogen peroxide (30wt%) are 50mL, obtain lye (pre-treatment solvents).By 60g cassiri
Smart slag is added in autoclave, after closed, impregnates cassava alcohol slag in pre-treatment solvents, to carry out the first water
Solution preocess, wherein the time impregnated is 3h.After immersion, start temperature program, at 170 DEG C, handles 1h.After treatment
Carry out decrease temperature and pressure, after pressure drops to normal pressure, will treated that cassava alcohol slag is filtered, filter residue (the is obtained after filtering
One solid product).
Above-mentioned filter residue is put into autoclave, and the dilution heat of sulfuric acid 300mL that weight percentage is 3% is added,
To carry out the second hydrolytic process, wherein the temperature of the second hydrolytic process is 150 DEG C, the processing time is 50min.After treatment,
After pressure drops to normal pressure, material is released, and carries out the solid material (second for filtering after being washed to neutrality, obtaining after filtering
Solid product).It to dry matter is 10wt%, substrate material as fermentation into above-mentioned solid material plus after water.
Urea and diammonium hydrogen phosphate (additive amount is respectively 2g/L, 1g/L) are added into above-mentioned substrate material, then 121
Sterilize 30min at DEG C, after sterilizing, is cooled to room temperature.Cellulase and work are added in material after stating sterilizing then up
Saccharomyces cerevisiae after change carries out diastatic fermentation at 35 DEG C, wherein the additional amount of cellulase is 15FPU/g substrate, is added and lives
Saccharomyces cerevisiae after change makes the amount of the saccharomyces cerevisiae of fermentation liquid reach 108cfu/mL.Fermentation carries out feed supplement afterwards for 24 hours, and feed supplement is hair
The substrate material of ferment.It feed supplement 2 times, is divided into for 24 hours.Make the concentration of substrate of total material in 200g/L, above-mentioned material fermentation after feed supplement
After 96h, the concentration of ethyl alcohol can achieve 50g/L.
Embodiment 2
It is added in 1L autoclave after weak aqua ammonia is mixed with hydrogen peroxide, wherein the weight percentage of weak aqua ammonia is
The volume of the ammonium hydroxide 500mL of 10wt%, the hydrogen peroxide being added (30wt%) are 100mL, obtain lye (pre-treatment solvents).It will
60g cassava alcohol slag is added in autoclave, after closed, impregnates cassava alcohol slag in pre-treatment solvents, with
The first hydrolytic process is carried out, wherein the time impregnated is 4h.After immersion, start temperature program, at 190 DEG C, handles 1h.
After treatment carries out decrease temperature and pressure, and after pressure drops to normal pressure, by treated, cassava alcohol slag is filtered, after filtering
To filter residue (the first solid product).
Above-mentioned filter residue is put into autoclave, and the dilution heat of sulfuric acid 400mL that weight percentage is 4% is added,
To carry out the second hydrolytic process, wherein the temperature of the second hydrolytic process is 170 DEG C, the processing time is 60min.After treatment,
After pressure drops to normal pressure, material is released, and carries out the solid material (second for filtering after being washed to neutrality, obtaining after filtering
Solid product).It to dry matter is 10wt%, substrate material as fermentation into above-mentioned solid-state material plus after water.
Urea and diammonium hydrogen phosphate (additive amount is respectively 2g/L, 1g/L) are added into above-mentioned substrate material, then 121
Sterilize 30min at DEG C, after sterilizing, after being cooled to room temperature.State then up sterilizing after material in be added cellulase and
Saccharomyces cerevisiae after activation carries out diastatic fermentation at 35 DEG C, and cellulase is added, and the additional amount of cellulase is 15FPU/g
Substrate, the saccharomyces cerevisiae after activation is added, makes the amount of the saccharomyces cerevisiae of fermentation liquid reach 108Cfu/mL, fermentation are mended afterwards for 24 hours
Material, feed supplement be the substrate material to ferment, feed supplement 2 times, are divided into for 24 hours.Make the concentration of substrate of total material in 240g/L after feed supplement, on
Material fermentation 120h is stated, the concentration of ethyl alcohol can achieve 60g/L.
Embodiment 3
With the difference of embodiment 1 are as follows: without heating in the first hydrolytic process, the second hydrolytic process is also without heating.
The concentration of ethyl alcohol can achieve 21g/L.
Embodiment 4
With the difference of embodiment 1 are as follows: the heating temperature in the first hydrolytic process is 250 DEG C, heating time 1h.Ethyl alcohol it is dense
Degree can achieve 28g/L.
Embodiment 5
With the difference of embodiment 1 are as follows: the heating temperature in the second hydrolytic process is 280 DEG C, heating time 1h.Ethyl alcohol it is dense
Degree can achieve 30g/L
Embodiment 6
With the difference of embodiment 1 are as follows: lye is sodium hydroxide.The concentration of ethyl alcohol can achieve 24g/L.
Embodiment 7
With the difference of embodiment 1 are as follows: acid solution is the nitric acid of 3~5wt%.The concentration of ethyl alcohol can achieve 33g/L.
Embodiment 8
With the difference of embodiment 1 are as follows: the additional amount of cellulase is 10FPU/g.The concentration of ethyl alcohol can achieve 37g/L.
Embodiment 9
With the difference of embodiment 1 are as follows: the dosage 8g/L of urea.The concentration of ethyl alcohol can achieve 43g/L.
Embodiment 10
With the difference of embodiment 1 are as follows: the dosage of diammonium hydrogen phosphate is 5g/L.The concentration of ethyl alcohol can achieve 40g/L.
Embodiment 11
With the difference of embodiment 1 are as follows: without feed supplement.The concentration of ethyl alcohol can achieve 20g/L.
Embodiment 12
With the difference of embodiment 1 are as follows: the concentration of substrate is 300g/L during diastatic fermentation.The concentration of ethyl alcohol can achieve
42g/L。
Embodiment 13
With the difference of embodiment 1 are as follows: the contents on dry basis of the lignin in cassava alcohol slag is 15wt%, and moisture content is
20wt%.
The concentration of ethyl alcohol can achieve 38g/L.
Embodiment 14
With the difference of embodiment 1 are as follows: it is washed using the solid material that deionized water obtains the second hydrolytic process to neutrality,
Then it uses the volume fraction of ethyl alcohol to carry out alcohol for 15% ethanol water and washes journey, recycle second finally by the mode of flash distillation
Alcohol obtains second solid phase product.The concentration of ethyl alcohol can achieve 55g/L.
Comparative example 1
The untreated cassava alcohol slag of 20g is put into 300mL triangular flask, adds 100mL water, while urea and phosphorus is added
Sour hydrogen diammonium (additive amount is respectively 0.2g and 0.1g), then sterilize at 121 DEG C 30min, after sterilizing, is cooled to room
Temperature.Saccharomyces cerevisiae after cellulase and activation are added in material after stating sterilizing then up, carries out saccharification hair at 35 DEG C
Ferment, wherein the additional amount of cellulase is 15FPU/g substrate, the saccharomyces cerevisiae 1mL of activation is added, so that the quantity of yeast is not
Lower than 108cfu/mL.Fermentation carries out feed supplement afterwards for 24 hours, and feed supplement is the substrate material of fermentation.It feed supplement 2 times, is divided into for 24 hours.Feed supplement
Making concentration of alcohol of the concentration of substrate of total material in 200g/L, the 96h post-fermentation mash that ferments afterwards is 17g/L.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
Comparing embodiment 1 to 14 and comparative example 1 using method provided by the present application it is found that be conducive to improve the production of ethyl alcohol
Amount.
Comparing embodiment 1 and 3 to 5 is it is found that by the limit temperature of the first hydrolytic process and the second hydrolytic process in the application
Preferably be conducive to improve the yield of ethyl alcohol in range.
Comparing embodiment 1,7 and 8 is it is found that using the production for being conducive to improve ethyl alcohol in the application lye preferably and acid solution
Amount.
Comparing embodiment 1 and 8 to 10 is it is found that be limited to the application for the dosage of cellulase, urea and diammonium hydrogen phosphate
Preferably be conducive to improve the yield of ethyl alcohol in range.
Comparing embodiment 1,11 is it is found that feed supplement process is conducive to improve the yield of ethyl alcohol.
Comparing embodiment 1,12 is it is found that the concentration of substrate during diastatic fermentation is limited in the application preferably range
Be conducive to improve the yield of ethyl alcohol.
Comparing embodiment 1,13 is it is found that be limited to this for the contents on dry basis of the lignin in cassava alcohol slag and moisture content
Be conducive to improve the yield of ethyl alcohol in application preferably range.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (12)
1. a kind of method for preparing ethyl alcohol using cassava alcohol slag, which is characterized in that the described method includes:
Under the catalytic action of alkali, the cassava alcohol slag is subjected to the first hydrolytic process, obtains the first solid product；
Under the catalytic action of acid, first solid product is subjected to the second hydrolytic process, obtains second solid phase product；And
The second solid phase product is subjected to diastatic fermentation, obtains ethyl alcohol.
2. the method according to claim 1, wherein the method also includes in first hydrolytic process,
The step of reaction system of first hydrolytic process is heated；
Preferably, the temperature of first hydrolytic process is 150~220 DEG C, and heating time is 1~2h.
3. method according to claim 1 or 2, which is characterized in that the alkali is the hydrogen peroxide and 5~15wt% of 30wt%
Ammonium hydroxide mixed liquor, the volume of the hydrogen peroxide is the 10~20% of the ammonium hydroxide volume.
4. according to the method in any one of claims 1 to 3, which is characterized in that the method also includes described second
In hydrolytic process, the step of heating to the reaction system of second hydrolytic process；Preferably, second hydrolytic process
Heating temperature be 160~210 DEG C, heating time be 40~75min.
5. according to the method described in claim 4, it is characterized in that, the aqueous sulfuric acid that the acid is 3~5wt% of concentration.
6. the method according to claim 1, wherein before carrying out the diastatic fermentation process, the method
Further include: after the second solid phase product is washed to neutrality, alcohol is then carried out using ethanol water and washes processing；And described
Alcohol recycles ethyl alcohol by the way of flash distillation after washing processing, obtains the second solid phase product.
7. according to the method described in claim 6, it is characterized in that, the volume fraction of the middle ethyl alcohol of the ethanol water is 10
~20%, temperature is 80~100 DEG C, and the alcohol is used to wash the time for the treatment of process as 30~60min.
8. the method according to claim 1, wherein the diastatic fermentation include by the second solid phase product,
The process that the mixture of cellulase, inorganic salts and yeast ferments.
9. according to the method described in claim 8, it is characterized in that, the total amount of the reaction system relative to the diastatic fermentation,
The additional amount of the cellulase is 15~25FPU/g.
10. according to the method described in claim 8, it is characterized in that, the inorganic salts are selected from urea and diammonium hydrogen phosphate；
Preferably, the dosage of the urea is 2~4g/L；
Preferably, the dosage of the diammonium hydrogen phosphate is 1~2g/L.
11. the method according to claim 1, wherein the method also includes during the diastatic fermentation
The step of supplementing the second solid phase product；
Preferably, the number of the supplement second solid phase product process is 2~4 times, and between the time of the adjacent process of feed supplement twice
It is divided into for 24 hours；
Preferably, after supplementing the second solid phase product, the concentration of the second solid phase product is 200~260g/L.
12. the method according to claim 1, wherein the butt of the lignin in the second solid phase product contains
Amount is less than 10wt%, and moisture content is 5~20wt%；Preferably, the partial size of the cassava alcohol slag is less than 0.9mm.
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