CN111304261B - Method for producing ethanol by fermentation - Google Patents
Method for producing ethanol by fermentation Download PDFInfo
- Publication number
- CN111304261B CN111304261B CN202010276260.7A CN202010276260A CN111304261B CN 111304261 B CN111304261 B CN 111304261B CN 202010276260 A CN202010276260 A CN 202010276260A CN 111304261 B CN111304261 B CN 111304261B
- Authority
- CN
- China
- Prior art keywords
- fermentation
- temperature
- mash
- ethanol
- liquefied
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/20—Preparation of compounds containing saccharide radicals produced by the action of an exo-1,4 alpha-glucosidase, e.g. dextrose
-
- 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 relates to the technical field of biological fuels, and discloses a method for producing ethanol by fermentation, wherein the method comprises the following steps: inoculating a fermentation strain into liquefied mash of a starchiness raw material in the presence of saccharifying enzyme for fermentation, wherein the fermentation temperature is controlled in the fermentation process as follows: controlling the fermentation temperature to be 30-32 ℃ before the 6 th to 10 th hours after the fermentation starts, then raising the fermentation temperature by 0.5-2 ℃ for continuous fermentation for 25-30 hours, and then controlling the fermentation temperature to be 32-34 ℃ until the fermentation is finished; the method can effectively improve the concentration of the ethanol in the fermented mash.
Description
Technical Field
The invention relates to the technical field of biological fuels, in particular to a method for producing ethanol by fermentation.
Background
The current biofuel ethanol productivity is about 296 ten thousand tons/year, and the biofuel ethanol consumption in 2020 is estimated to be about 1200 ten thousand tons/year; and the existing alcohol in northeast area is idle for 150 ten thousand tons/year, the newly increased biofuel ethanol for 885 ten thousand tons/year is arranged in a staged and proper amount, wherein the corn raw material is 630 ten thousand tons/year, the quality safety index is disqualified, the flexible rice raw material is 50 ten thousand tons/year, the cassava raw material is 145 ten thousand tons/year, the raw material of straw and the like is 60 ten thousand tons/year, and the total capacity can be about 1330 ten thousand tons/year.
At present, the raw materials for producing fuel ethanol mainly comprise corn, cassava and the like. Along with the innovation and stable promotion of grain collection and storage systems in China, the digestion progress of aged grains such as corns, unhusked rice and the like is naturally accelerated, especially unhusked rice with higher stock, however, the starch wine yield of raw materials is lower due to the control of fermentation conditions in the prior art, especially the aged unhusked rice is used as the raw material for preparing ethanol, and the starch wine yield is lower.
Therefore, the development of a method for producing ethanol by fermentation, which can obtain higher starch wine yield, has great significance.
Disclosure of Invention
The invention aims to solve the problem of low starch wine yield (particularly under the condition of using aged rice as a raw material and not shelling) in the prior art, and provides a method for producing ethanol by fermentation so as to achieve the aim of obtaining high starch wine yield.
In order to achieve the object of the present invention, the present invention provides a method for producing ethanol by fermentation, wherein the method comprises the following steps: inoculating a fermenting strain in the liquefied mash of a starchy material in the presence of a saccharifying enzyme for fermentation to obtain a fermented mash containing ethanol, wherein the fermentation temperature is controlled in the fermentation process as follows:
after fermentation starts, the fermentation temperature of the first stage is controlled to be 30-32 ℃ before the 6-10h, then the fermentation temperature is increased by 0.5-2 ℃ for continuous fermentation for 25-30h in the second stage, and then the fermentation temperature is controlled to be 32-34 ℃ in the third stage until the fermentation is finished.
By adopting the technical scheme of the invention, the starch raw material, especially the aged rice without shelling, is used as the raw material for fermenting and producing the ethanol, so that the fermentation effect can be effectively improved, the starch wine yield can reach 50.69%, and the energy consumption can be reduced to within 370kg of standard coal/t fuel ethanol.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The present invention relates generally to improvements in processes for producing ethanol using a starchy material, and generally, to processes for producing ethanol using a starchy material that involve four steps of size mixing, liquefaction, fermentation, and separation. Specifically:
firstly, size mixing
The size mixing is a step of mixing the starchy raw material with size mixing liquid to obtain powder slurry, wherein the size mixing liquid can be water, such as tap water or process water. The slurry may also be a supernatant produced in a fermentation ethanol production process, but the direct use of the supernatant has an adverse effect on the fermentation. Accordingly, the inventors of the present invention have conducted a large number of experiments, and as a result, have found that the liquefaction effect and subsequent fermentation effect of the starchy material can be ensured while reusing a large amount of the supernatant liquid by treating the supernatant liquid produced in the present invention to obtain reclaimed water and combining the supernatant liquid and the reclaimed water in a specific ratio.
Accordingly, in a first aspect, the present invention provides a conditioning fluid, wherein the conditioning fluid is provided by a clear fluid, a medium water and optionally water, wherein the weight ratio of clear fluid to medium water is 1:0.15-0.75; the content of suspended matters in the clear liquid is 5000-5500mg/L; the reclaimed water is reclaimed water generated in the process of preparing ethanol by fermentation.
Because clear liquid produced in the process of preparing ethanol by fermentation is unfavorable for ethanol fermentation, the clear liquid needs to be treated to obtain reclaimed water, and then the reclaimed water is further treated to eliminate or reduce factors unfavorable for ethanol fermentation in the reclaimed water and then is reused as slurry, but the treatment process and the production cost of the reclaimed water are increased; or in order to reduce the adverse effect of clear liquid on ethanol fermentation, only a small amount of clear liquid can be used for regulating slurry, but the added value of the clear liquid cannot be realized, and the production cost cannot be effectively reduced; the inventor of the invention discovers through researches that clear liquid generated in the process of preparing ethanol by adopting the technical scheme of the invention and reclaimed water obtained by processing part of the obtained clear liquid are matched in a specific proportion, so that the dosage of the clear liquid and the reclaimed water in the slurry is obviously increased, the production cost is reduced, and a higher fermentation effect is also obtained.
In the present invention, in order to further obtain a better ethanol fermentation effect, preferably, the weight ratio of the clear liquid to the reclaimed water is 1:0.4-0.6.
In the present invention, in order to further increase the amount of the supernatant and the reclaimed water in the slurry and to obtain a preferable ethanol fermentation effect, it is preferable that the COD of the supernatant has a value of 40000 to 45000mg/L (for example, 40000mg/L, 41000mg/L, 42000mg/L, 43000mg/L, 44000mg/L, 45000mg/L, or any value between the above values).
More preferably, BOD in the supernatant 5 The value of (a) is 32000-36000mg/L (e.g., 32000mg/L, 33000mg/L, 34000mg/L, 35000mg/L, 36000mg/L, or any value in between).
More preferably, the conductivity of the supernatant is 7000-8000 μS/cm (e.g., 7000 μS/cm, 7200 μS/cm, 7400 μS/cm, 7600 μS/cm, 7800 μS/cm, 8000 μS/cm, or any value therebetween).
In the present invention, preferably, the preparation method of the clear liquid includes solid-liquid separation of waste mash produced in the process of preparing ethanol by fermentation, and the obtained liquid phase is clear liquid, wherein the obtained solid phase material can be used as feed.
In the present invention, the method for solid-liquid separation of the waste mash produced in the fermentation process for producing ethanol is not particularly limited, and may be at least one of the methods for solid-liquid separation conventionally used in the art, preferably centrifugation, pressure filtration, concentration and drying, more preferably centrifugation, pressure filtration, concentration and drying, further preferably centrifugation, pressure filtration, concentration and drying are sequentially performed.
In the present invention, the conditions of the centrifugation are not particularly limited, and in order to enhance the effect of the centrifugation, it is preferable that the conditions of the centrifugation include a rotation speed of 2500 to 3500rpm, and a feed temperature of 85℃or less.
In the present invention, the conditions of the press filtration are not particularly limited, and in order to enhance the effect of the press filtration, it is preferable that the conditions of the press filtration include a filter cloth pore size of 60 to 100 mesh and a pressure of 0.4 to 0.8MPa.
In the invention, the pressures are gauge pressures.
In the present invention, the conditions of the concentration are not particularly limited, and in order to enhance the effect of the concentration, it is preferable that the conditions of the concentration are such that 60 to 81t of clear liquid is obtained per hour, including a concentration temperature of 80 to 90 ℃.
In the present invention, the drying conditions are not particularly limited, and in order to enhance the drying effect, it is preferable that the drying conditions are such that 4 to 5t of solid phase material (water content of 10 to 13 wt%) is obtained per hour, including a drying temperature of 170 to 190 ℃.
In the present invention, in order to increase the amount of the supernatant liquid and the reclaimed water in the slurry and to obtain a preferable ethanol fermentation effect, it is preferable that the content of the suspended matters in the reclaimed water is 200 to 350mg/L (for example, 200mg/L, 250mg/L, 300mg/L, 350mg/L, or any value between the above values).
More preferably, the COD value of the reclaimed water is 700-1000mg/L (e.g., 700mg/L, 750mg/L, 800mg/L, 840mg/L, 880mg/L, 920mg/L, 960mg/L, 1000mg/L, or any value therebetween).
More preferably, BOD in said reclaimed water 5 Is 560-800mg/L (e.g., 560mg/L, 600mg/L, 640mg/L, 680mg/L, 720mg/L, 760mg/L, 800mg/L, or any value therebetween).
More preferably, the electrical conductivity of the reclaimed water is 3000-4000. Mu.S/cm (e.g., 3000. Mu.S/cm, 3200. Mu.S/cm, 3400. Mu.S/cm, 3600. Mu.S/cm, 3800. Mu.S/cm, 4000. Mu.S/cm, or any value in between).
In the present invention, preferably, the method for preparing reclaimed water comprises the steps of: (I) Carrying out primary precipitation treatment on the clear liquid to obtain primary treatment liquid, wherein the content of suspended matters in the obtained pretreatment liquid is 2500-3500mg/L; (II) carrying out secondary biological treatment on the obtained pretreatment liquid to obtain secondary treatment liquid; (III) carrying out three-stage precipitation treatment on the obtained secondary treatment liquid to obtain reclaimed water.
Preferably, the primary precipitation treatment in step (I) is performed in a first precipitation tank.
Preferably, the method of the secondary biological treatment in the step (II) comprises the steps of firstly conveying the primary treatment liquid obtained in the step (I) into an IC reactor for anaerobic reaction treatment, and then conveying the effluent of the IC reactor into an A/O reactor for aerobic reaction treatment.
Preferably, the tertiary precipitation treatment in step (III) is performed in a second precipitation tank.
In the present invention, in order to further obtain a better ethanol fermentation effect, preferably, the sum of the weights of the clear liquid and the reclaimed water in the slurry accounts for 35-55% of the total weight of the slurry, and the balance is water.
(II) liquefaction
In the present invention, liquefaction refers to a process of hydrolyzing a starchy material into small molecular substances (dextrin, oligosaccharide, etc.), and can be performed by using a liquefaction method conventionally used in the art. However, the inventors of the present invention found that the two-pass heating is particularly advantageous for improving the liquefaction effect of the starchy material.
Accordingly, in a second aspect, the present invention provides a process for liquefying a starchy material, wherein the process comprises the steps of: (1) In the presence of enzyme, carrying out primary temperature rise and secondary temperature rise on starch-containing raw material slurry to obtain pre-liquefied slurry, wherein the primary temperature rise rate is lower than the secondary temperature rise rate; (2) Spraying and liquefying the pre-liquefied slurry obtained in the step (1); (3) And (3) continuously liquefying the material obtained by spraying and liquefying in the step (2) (obtaining liquefied mash).
In the present invention, in order to enhance the liquefaction effect, the enzyme is preferably used in an amount of 8 to 10U relative to 1 g of the starchy material.
Preferably, the enzyme used for the liquefaction is selected from amylases. Amylases typically include alpha-amylase, beta-amylase, glucoamylase, and isoamylase.
Alpha-amylase, also known as starch 1, 4-dextrinase, liquefying enzyme, is capable of randomly and irregularly cleaving alpha-1, 4-glycosidic bonds within the starch chain, hydrolyzing starch into maltose, oligosaccharides containing 6 glucose units and oligosaccharides with branched chains, and is commonly used for starch liquefaction. The liquefying enzyme may comprise an alpha-amylase conventionally used in the art, such as a high temperature resistant alpha-amylase which may be of the Norwechat company.
Beta-amylase is also called starch 1, 4-maltosidase, and can cleave 1, 4-glycosidic bonds from the non-reducing end of starch molecules to produce maltose. The products of this enzyme action on starch are maltose and limiting dextrins.
The isoamylase is also called starch alpha-1, 6-glucosidase and branching enzyme, and acts on alpha-1, 6-glycosidic bond at branching point of amylopectin molecule to cut the whole side chain of amylopectin into amylose.
In the present invention, the pH of the slurry is preferably 5 to 6, more preferably 5.4 to 5.8.
Preferably, the starch feedstock is present in the slip in an amount of 28 to 40 wt.%, more preferably 32 to 35 wt.%.
The slip may be obtained by conventional slip methods, such as by mixing the starchy material with a slip, preferably using a slip as described in the first aspect.
In the present invention, in order to further enhance the effect of liquefaction, it is preferable that the temperature rising rate of the primary temperature rising is lower than the temperature rising rate of the secondary temperature rising by 0.3 to 0.6 ℃/min (e.g., 0.3 ℃/min, 0.4 ℃/min, 0.5 ℃/min, 0.6 ℃/min, or any value in between the foregoing values).
More preferably, the rate of the primary temperature increase is 0.5 to 1℃/min (e.g., 0.5C/min, 0.6C/min, 0.7C/min, 0.8C/min, 0.9C/min, 1℃/min, or any value therebetween).
Further preferably, the rate of the secondary temperature increase is 1-1.5 ℃/min (e.g., 1 ℃/min, 1.1 ℃/min, 1.2 ℃/min, 1.3 ℃/min, 1.4 ℃/min, 1.5 ℃/min, or any value in between the foregoing).
In the present invention, in order to further enhance the liquefaction effect, it is preferable that the temperature of the material is raised to 50-60℃ (e.g., 50℃, 52℃, 54℃, 56℃, 58℃, 60℃, or any value between the above values) by one heating.
More preferably, the secondary temperature rise causes the temperature of the material to rise to 80-85 ℃ (e.g., 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, or any value therebetween).
More preferably, the method further comprises maintaining for 10-20min after one temperature increase.
More preferably, the method further comprises maintaining for 20-30min after the second temperature increase.
In the present invention, the conditions for the jet liquefaction are not particularly limited, and in order to enhance the effect of the jet liquefaction, the conditions for the jet liquefaction preferably include: the spraying temperature is 95-100 ℃, the spraying inlet pressure is 0.6-0.8MPa, the spraying outlet pressure is 0.18-0.25MPa, and the steam consumption is 0.3-0.5t/t of pre-liquefied powder slurry.
In the present invention, in order to further improve the liquefaction effect, preferably, the method of continuing liquefaction includes first cooling the material obtained by spraying liquefaction to 86-88 ℃ for 2-2.5 hours, and then cooling to 30-32 ℃ for the second time.
Preferably, the primary cooling mode is flash evaporation cooling.
Preferably, the secondary cooling mode is heat exchange cooling.
In the present invention, the source of the starchy material is not particularly limited, and may be starch-containing materials conventionally used in the art, and preferably the starchy material is selected from cereal materials and/or potato materials.
More preferably, the starchy material is a cereal material.
More preferably, the starchy material is a cereal material that has a long shelf life (e.g., greater than 2 years).
More preferably, the cereal raw material is selected from at least one of rice, corn, wheat, barley and sorghum.
More preferably, the cereal material is rice. More preferably Chen Daogu which has a storage time of 3 years or more.
The method of the present invention is applicable to a cereal raw material containing chaff or a cereal raw material not containing chaff, and when the cereal raw material contains chaff, the content of chaff in the cereal raw material is preferably 10 to 20% by weight in order to enhance the liquefying effect and thus the fermenting effect.
In the present invention, in order to further improve the liquefaction effect and the fermentation effect, the starch material preferably has a particle size of less than 1.8mm, and more preferably the starch material has a particle size of less than 1mm and a content of the material of not less than 90% by weight.
(III) fermentation
Fermentation refers to a process of preparing microbial cells themselves, or direct metabolites or secondary metabolites by the vital activities of microorganisms under aerobic or anaerobic conditions, and fermentation may be performed using methods conventionally used in the art. However, the inventor of the present invention found that the stepwise control of the fermentation temperature is advantageous for improving the fermentation effect, and the method is particularly suitable for fermentation preparation of ethanol from unhulled aged rice as a raw material.
Accordingly, in a third aspect, the present invention provides a method of fermentative ethanol production, wherein the method comprises: inoculating a fermenting strain in the liquefied mash of a starchy material in the presence of a saccharifying enzyme for fermentation to obtain a fermented mash containing ethanol, wherein the fermentation temperature is controlled in the fermentation process as follows: after the fermentation starts, the fermentation temperature of the first stage is controlled to be 30-32 ℃ before the 6-10h, then the fermentation temperature is increased by 0.5-2 ℃ (such as 0.5 ℃, 1 ℃, 1.5 ℃, 2 ℃ or any value between the values) in the second stage, the fermentation is continued for 25-30h, and then the fermentation temperature is controlled to be 32-34 ℃ in the third stage until the fermentation is finished.
More preferably, the fermentation temperature of the second stage is controlled to be 32-34 ℃, the fermentation temperature of the third stage is controlled to be 32-34 ℃, and the fermentation temperature of the second stage is different from the fermentation temperature of the third stage.
More preferably, the absolute value of the difference between the temperature of the second stage and the temperature of the third stage is 0.5-1 ℃. Controlling the fermentation temperature of the second stage to be different from the fermentation temperature of the third stage can further improve the fermentation efficiency.
Preferably, the total time of the fermentation is 60-72 hours.
In the present invention, in order to enhance the effect of fermentation, it is preferable that the apparent sugar concentration in the liquefied mash is 23 to 26 ° BX.
Preferably, the DE value in the liquefied mash is 16-21%.
Preferably, the pH of the liquefied mash is 4.2-4.5 and the acidity is 2.5-4.5mol/L. The acidity is the molar mass of the strong base consumed to neutralize the acidic substances (including inorganic acids, organic acids, strong acid weak base salts, etc.) in each liter of liquefied mash.
In the present invention, in order to enhance the fermentation effect, the saccharifying enzyme is preferably used in an amount of 100 to 180U relative to 1 g of the starchy material.
In the invention, the saccharifying enzyme is also called starch alpha-1, 4-glucosidase, and acts on the non-reducing end of starch molecules, and takes glucose as a unit to sequentially act on alpha-1, 4-glycosidic bonds in the starch molecules to generate glucose. Products after the saccharifying enzyme acts on the amylopectin include glucose and oligosaccharides with alpha-1, 6-glycosidic bonds; the product after the action on amylose is almost entirely glucose. The saccharifying enzyme may be a saccharifying enzyme of novelin.
In a preferred embodiment of the invention, the fermentation is carried out in the presence of a protease.
Preferably, the protease is an acid protease, more preferably an acid protease having an optimum pH of 2.5-3.5.
Preferably, the protease is used in an amount of 15-20U relative to 1 gram of starchy material.
In the present invention, the fermentation broth is not particularly limited, and may be a fermentation broth conventionally used in the art, for example, a yeast. The mother liquor can be obtained by seed culture, and then inoculated.
In the present invention, the inoculation amount of the fermentation seed is not particularly limited, and in order to enhance the effect of fermentation, it is preferable that the inoculation amount of the fermentation seed is such that the number of viable bacteria in 1 ml of the liquefied mash is 2X 10 7 -2.5×10 8 cfu。
In the present invention, in order to enhance the effect of ethanol fermentation, it is preferable that an inorganic nitrogen source is also added to the liquefied mash. Preferably, an inorganic nitrogen source and a bactericide may also be added during the ethanol fermentation.
In the present invention, in order to further enhance the effect of ethanol fermentation, the inorganic nitrogen source is preferably at least one selected from urea, ammonium sulfate, ammonium chloride and aqueous ammonia, and more preferably ammonium sulfate.
Preferably, relative to 1kg of starchRaw materials of the material NH 4 + The inorganic nitrogen source is used in an amount of 1.8 to 2.5g.
In the present invention, in order to further enhance the effect of ethanol fermentation, it is preferable that a bactericide is further added during the ethanol fermentation.
Preferably, the bactericide is at least one selected from the group consisting of penicillin, ambroxol and mycopeptide, more preferably ambroxol.
Preferably, relative to lm 3 The dosage of the ambroxol is 3-7g.
In the invention, the liquefied mash of the starchy raw material is prepared by liquefying slurry containing the starchy raw material.
The method of preparing liquefied mash of the starchy material may be obtained according to conventional methods, preferably with reference to the method of liquefying starchy material as described in the second aspect.
In the invention, the obtained fermented mash can be distilled to obtain ethanol solution for practical needs.
(IV) separation
Separation refers to the step of separating ethanol from beer and can be performed using separation methods conventionally used in the art. However, the inventor of the invention finds that the method is particularly suitable for separating ethanol from the fermented mash prepared by fermenting old rice with shells serving as a raw material, by distilling the fermented mash to obtain crude mash with specific volume and ethanol-containing steam and rectifying the obtained crude mash, thereby being more beneficial to improving the ethanol separation effect.
Accordingly, in a fourth aspect, the present invention provides a method of separating ethanol from beer, wherein the method comprises: distilling the beer containing ethanol to obtain a raw beer, ethanol-containing steam, and a first portion of waste beer, wherein the beer is formed in an amount of 30-40% by volume of the beer; then separating the crude mash to obtain clear wine and waste fermented glutinous rice, and purifying the obtained ethanol-containing steam and clear wine to obtain ethanol solution and a second part of waste mash; the resulting ethanol solution is then optionally dehydrated.
In the invention, the obtained fermented mash contains sediment, and the fermented mash is directly distilled and purified to easily block equipment, preferably, the sediment in the fermented mash can be removed firstly, and then the fermented mash with the sediment removed is distilled and purified. Wherein, the sediment contains ethanol, and the sediment can be subjected to solid-liquid separation to obtain thin mash and wet distiller's grains.
In the present invention, the thin mash obtained is preferably distilled and purified together with the sedimented beer.
In the present invention, in order to enhance the purification effect, preferably, the method further comprises cooling the obtained ethanol-containing vapor to form a crude wine, and then purifying the crude wine and sake.
In the invention, preferably, the first part of waste mash and the second part of waste mash are subjected to solid-liquid separation to obtain a liquid phase and a solid phase, wherein the obtained liquid phase is clear liquid, and the obtained solid phase can be used as feed.
In the method, because the obtained first part of waste mash and the obtained second part of waste mash have higher solid content, pipelines, equipment and the like are easy to be blocked, so that the stability of the fermentation ethanol preparation process is poor, in order to improve the stability of a separation section, preferably, the method further comprises the steps of recycling the obtained clear liquid to dilute the newly obtained first part of waste mash and the newly obtained second part of waste mash, and then carrying out solid-liquid separation on the diluted first part of waste mash and the diluted second part of waste mash.
More preferably, 20-30% by volume of the resulting supernatant is returned to dilute the first portion of waste mash newly obtained in step (3) and the second portion of waste mash newly obtained in step (4).
In the present invention, in order to enhance the effects of acid removal and concentration, it is preferable that the distillation is performed in a crude column whose operating conditions include: the theoretical plate number is 30-35, the tower bottom temperature is 80-85 ℃, the tower top temperature is 53-62 ℃, and the tower top pressure is-0.072 MPa to-0.068 MPa.
In the present invention, in order to enhance the effect of solid-liquid separation, the method of separating the resulting raw mash is preferably selected from the group consisting of a centrifuge method, a membrane filtration method and a cyclone separation method, and more preferably from the group consisting of cyclone separation methods. The cyclone separation process is generally carried out by means of a cyclone separator.
In the invention, in order to improve the yield of the ethanol, the method preferably further comprises returning the obtained waste fermented glutinous rice to a crude tower for separation treatment again, so that part of the ethanol in the waste fermented glutinous rice is recovered.
In the present invention, in order to improve the purity and yield of ethanol, it is preferable that the purification treatment includes rectification, and more preferable that the rectification includes primary rectification and secondary rectification.
In the present invention, in order to improve the effect of the rectification, preferably, the working conditions of the primary rectification include: the theoretical plate number is 66-70, the tower top temperature is 122-135 ℃, the middle temperature is 124-142 ℃, and the tower top pressure is 0.38-0.55MPa.
In the present invention, in order to further enhance the effect of the rectification, preferably, the working conditions of the secondary rectification include: the theoretical plate number is 40-50, the tower top temperature is 88-98 ℃, the tower bottom temperature is 115-124 ℃, and the tower top pressure is 0.035-0.095MPa.
In the present invention, the method of dehydration is not particularly limited, and in order to enhance the effect of dehydration, it is preferable that the method of dehydration is selected from a method of molecular sieve dehydration, a method of corn meal adsorption dehydration or a method of osmotic gasification membrane adsorption separation, and more preferably from a method of molecular sieve dehydration.
In the present invention, preferably, the molecular sieve is selected from 3A molecular sieves.
In the present invention, preferably, the molecular sieve has a water adsorption capacity of greater than 15 wt%.
In the present invention, preferably, the working conditions for dehydrating the molecular sieve include: the adsorption temperature is 100-130 ℃, the adsorption pressure is 0.04-0.055MPa, and the adsorption time is 30-35min.
(V) others
The invention also relates to a method of liquefying a starchy material, the method comprising: the slurrying and liquefying are performed according to the steps (one) and (two) as described above. The specific manner of slurrying and liquefying may be combined in any of the ways previously described.
The invention also relates to a method for producing ethanol by fermentation, which comprises the following steps: the steps of slurrying, liquefying and fermenting are performed as described in (one) to (three) above. The specific modes of pulping, liquefying and fermenting can be combined in any of the ways described above.
In particular, the present invention provides a method of liquefying a starchy material, wherein the method comprises:
(a) Mixing the starchiness raw material with the size mixing liquid to obtain powder slurry;
(b) Liquefying the slurry obtained in the step (a) by contacting with enzyme.
Wherein the slip in step (a) is preferably prepared according to the step (one) as described above, and the liquefaction in step (b) is preferably performed according to the step (two) as described above.
Specifically, the invention also provides a method for preparing ethanol from a starchy raw material, wherein the method comprises the step of fermenting liquefied mash of the starchy raw material obtained by liquefying the method in the presence of saccharifying enzyme to obtain fermented mash containing ethanol. Wherein the conditions of the ethanol fermentation include: the fermentation time is 60-72h, and the fermentation temperature is 30-34 ℃. Preferably, the saccharifying enzyme is as described in (III) above. Preferably, the fermentation is performed according to the step (III) as described above. Preferably, the method further comprises distilling the beer to obtain an ethanol solution.
Specifically, the invention also provides a method for preparing ethanol from rice raw materials, wherein the method comprises the following steps: liquefying the rice raw material to obtain liquefied mash; then carrying out ethanol fermentation on the obtained liquefied mash to obtain ethanol-containing fermented mash; then distilling the obtained fermented mash to obtain coarse mash, ethanol-containing steam and a first part of waste mash, wherein 30-40% by volume of the fermented mash forms ethanol-containing steam; then separating the obtained coarse mash to obtain clear wine and waste fermented glutinous rice, and purifying the obtained ethanol-containing steam and the obtained clear wine to obtain ethanol solution and a second part of waste mash; the resulting ethanol solution is then optionally dehydrated. Among them, the above steps are preferably performed as the steps of (one) to (four) as described above for size mixing, liquefying, fermenting and separating.
In addition, it should be noted that the four parts described above are not separately present, and descriptions of the respective parts may be used interchangeably for the same terms or the same steps, and for brevity, a repeated discussion is not provided herein.
The present invention will be described in detail by examples. In the following examples of the present invention,
The amylase is alpha-amylase, and is purchased from Jenergy (China) bioengineering Co., ltd, and the enzyme activity is 150000U/g;
saccharifying enzyme is purchased from Shandong biological engineering Co., ltd, and the enzyme activity is 260000U/g;
the protease is acid protease, and is purchased from Jenergy (China) bioengineering Co., ltd, and has an enzyme activity of 260000U/g;
molecular sieves were purchased from Shanghai ring molecular sieves limited under the designation 3A molecular sieves;
the aged rice is aged rice stored for 3 years, the starch content is 56 wt% and the water content is 11 wt%;
an Jun Thai is commercially available from Longtai technologies Inc. of Liuzhou, with a sterilization rate of 85%;
dry yeasts are purchased from Angel Yeast Co., ltd, the total yeast content is not less than 2X 10 10 Individual/g;
the liquefaction sprayer is purchased from Shanghai megalight injection liquefaction technology Co., ltd, and the brand is HYZ-15;
the method for measuring COD in clear liquid and reclaimed water is described in GB 11914-89 (chemical oxygen demand measurement);
BOD in clear and reclaimed water 5 Reference is made to GB7488-87 five-day culture method (BOD 5 )；
The method for determining Suspended Substances (SS) in clear liquid and reclaimed water is referred to the gravimetric method (GB 11901-89);
the determination method of the conductivity of the clear liquid and the reclaimed water is referred to (GB 11007-1989) a conductivity meter test method;
Appearance sugars were determined by a brix meter;
the DE value refers to the percentage of reducing sugar (calculated as glucose) in the dry matter of the syrup, and the measuring method of the reducing sugar and the syrup is a filin reagent method;
the residual reducing sugar refers to reducing sugar remained in fermented mash obtained after the ethanol fermentation is finished, and the measuring method is a Filin reagent method;
the residual total sugar refers to sugar (including reducing sugar, disaccharide, starch and the like) remained in the fermented mash obtained after the ethanol fermentation is finished, and the measuring method is a Filin reagent method;
acidity refers to the molar mass of NaOH consumed by neutralizing acidic substances (including inorganic acid, organic acid, strong acid weak alkali salt and the like) in each liter of liquefied mash, and the measuring method is an acid-base neutralization method;
the ethanol yield is characterized by the starch wine yield, and the calculation formula is as follows: starch wine yield = 99.5% x fuel ethanol yield +.total weight of raw starch x 100%;
the energy consumption refers to the weight (kg) of standard coal converted from water, electricity and steam consumed by each 1 ton of 99.5 volume percent ethanol produced in the process of preparing the ethanol by fermentation;
the feed index is measured by referring to a method for measuring crude protein in GB/T6432-2018 feed, a method for measuring crude fat in GB/T6433-2006 feed, a method for measuring the content of crude fiber in GB/T6434-2006 feed, a method for measuring the content of water and other volatile substances in GB/T6435-2014 feed, a method for measuring crude ash in GB/T6438-2007 feed and a standard for health of GB 13078-2017 feed.
Preparation example 1
The dried yeast was mixed with sterilized water in an amount of 0.005g per 1mL of sterilized water, and activated at 35℃and 180rpm for 25 minutes to obtain a yeast-activated liquid.
Example 1
(1) Size mixing
The rice raw material (rice stored for three years, water content 11% by weight, grain size <1.8mm, wherein the content of raw material with grain size <1.0mm is 97% by weight, rice hull content 10% by weight) and slurry (55% by weight of process water, 30% by weight of clear liquid 2, 15% by weight of water 2) were mixed to prepare slurry according to a weight ratio of 1:2, and the pH value of the slurry was adjusted to 5.6.
(2) Liquefaction process
Adding amylase (the adding amount is 8U/g of rice raw material) into the obtained slurry, heating to 55 ℃, and maintaining at the temperature for 15min at a heating rate of 0.75 ℃/min; then heating to 85 ℃, wherein the heating rate is 1.3 ℃/min, and maintaining at the temperature for 25min to obtain pre-liquefied powder slurry;
performing jet liquefaction on the obtained pre-liquefied slurry, wherein the jet liquefaction conditions are as follows: the injection temperature was 97 ℃, the injection inlet pressure was 0.66MPa, and the injection outlet pressure was 0.22MPa: the steam consumption is 0.4t/t of pre-liquefied slurry; and then the material obtained by spray liquefaction is subjected to flash evaporation and cooling to 87 ℃ for 2 hours, and then cooled to 31 ℃ to obtain liquefied mash, and 3.3kg of liquefied mash is obtained per kg of rice raw material. The appearance sugar content, DE value, pH value, acidity of the liquefied mash were measured, and the results are shown in Table 3.
Filtering and sterilizing part of liquefied mash with 1.8mm pore size filter screen, adding acid protease (18U/g rice material), inoculating yeast activating solution of preparation 1 into the filtered and sterilized liquefied mash at 5 vol% of inoculating amount, and culturing at 30deg.C to obtain yeast with a content of 2×10 8 cfu/mL of yeast wine.
(3) Fermentation
Adding ammonium sulfate (8.4 kg/t rice material), saccharifying enzyme (0.68 kg/t rice material), acid proteinase (0.06 kg/t rice material), bactericide (An Jun Tay, 5 g/m) 3 Liquefied mash) to prepare an ethanol fermentation medium, inoculating the yeast mash into the prepared ethanol fermentation medium, wherein the inoculation amount of the yeast mash is 25ml/100ml medium; controlling the fermentation temperature to be 31 ℃ within a period of time from the beginning of fermentation to 8 hours of fermentation; controlling the fermentation temperature to be 32 ℃ within a period from 9 hours to 36 hours, and controlling the fermentation temperature to be 33 ℃ and the total fermentation time to be 68 hours from 37 hours to obtain the fermentation containing ethanolAnd (5) mash. The apparent sugar content, the content of residual reducing sugar, the content of residual total sugar, acidity and ethanol concentration in the beer were measured and the results are shown in Table 3. And (5) conveying the sediment at the bottom of the fermentation tank to a sediment separator, and separating to obtain thin mash and wet vinasse.
(4) Separation
Feeding the fermented mash and thin mash after sediment removal in the step (3) into a coarse tower for distillation to obtain coarse mash, ethanol-containing steam (generated by 35% of the total volume of the fermented mash and thin mash) and a first part of waste mash, and feeding the obtained first part of waste mash into a waste mash tank; the working condition of the crude tower is that the theoretical plate number is 32, the temperature of the tower bottom is 83 ℃, the temperature of the tower top is 57 ℃, and the pressure of the tower top is-0.07 MPa.
Collecting the obtained coarse mash from the upper middle part of the coarse tower, and then entering a cyclone separator, separating to obtain sake liquid and waste fermented glutinous rice, and returning the obtained waste fermented glutinous rice to the coarse tower, wherein the working condition of the cyclone separator is 0.6MPa; the clear wine liquid is sent into a second rectifying tower for impurity removal and concentration (purification treatment), the working condition of the second rectifying tower is that the theoretical plate number is 43, the tower top temperature is 95 ℃, the tower bottom temperature is 121 ℃, and the tower top pressure is 0.075MPa. Condensing the obtained ethanol vapor from the top of the crude tower to form crude liquor, laterally extracting the purified and concentrated clear liquor from the middle side line of the second rectifying tower, and sending the purified and concentrated clear liquor and the obtained crude liquor into a first rectifying tower for further impurity removal and concentration (purification treatment), wherein the working condition of the first rectifying tower is that the theoretical plate number is 68, the tower top temperature is 129 ℃, the tower middle temperature is 135 ℃ and the tower top pressure is 0.45MPa; feeding the second part of waste mash extracted from the first rectifying tower and the second rectifying tower into a waste mash tank;
The ethanol solution extracted from the top of the first rectifying tower is sent to the upper part of the second rectifying tower to form ethanol-containing gas phase, and the obtained ethanol-containing gas phase is dehydrated by a 3A molecular sieve (the adsorption temperature is 120 ℃, the adsorption pressure is 0.05MPa, and the adsorption time is 33 min) to obtain a fuel ethanol product, wherein the purity (volume percent) of the fuel ethanol product and the starch wine yield are shown in Table 3.
Separating the waste mash extracted from the waste mash tank by a horizontal decanter centrifuge (with the rotating speed of 3000rpm and the feeding temperature of 70 ℃), plate-frame filter pressing (with the filter cloth of 80 meshes and the pressure of 0.6 MPa), concentrating by a falling film evaporator (with the temperature of 85 ℃) and tube bundle roller drying (with the temperature of 180 ℃) to obtain solid matters (which are used as feed together with the obtained wet vinasse, the feed ingredients are shown in table 5) and clear liquid 2, wherein the 20 volume percent of the obtained clear liquid is returned to the waste mash tank, a part of the rest clear liquid is used for size mixing, a part of the clear liquid is used for processing to obtain reclaimed water 2 (the obtained clear liquid is sent to a primary sedimentation tank for processing to obtain primary processing liquid, the content of suspended matters (SS) in the obtained primary processing liquid is 3000mg/L, the obtained primary processing liquid is sent to an IC reactor for anaerobic reaction processing (the anaerobic processing temperature of 36 ℃, the pH value of 7 and the hydraulic retention time of 91 h), the effluent of the IC reactor is sent to an A/O reactor for aerobic processing (the aerobic processing temperature of 25 ℃ and the pH value of 7.5, the DO value of 2 mg/L), and the hydraulic retention time of 49 h) is sent to the rice slurry prepared in the secondary sedimentation tank (step 1). The water quality of the obtained clear liquid 2 and the water quality of the reclaimed water 2 are shown in tables 1 and 2 respectively.
Example 2
(1) Size mixing
The rice raw material (rice stored for three years, water content 11% by weight, grain size <1.8mm, wherein the content of raw material with grain size <1.0mm is 97% by weight, rice hull content 10% by weight) and slurry (45% by weight of process water, 35% by weight of clear liquid 1, 20% by weight of reclaimed water 1) were mixed to prepare slurry according to a weight ratio of 1:2, and the pH value of the slurry was adjusted to 5.6.
(2) Liquefaction process
Adding amylase (the adding amount is 8U/g of rice raw material) into the obtained slurry, heating to 50 ℃, and maintaining at the temperature for 10min at the heating rate of 0.5 ℃/min; then heating to 85 ℃, wherein the heating rate is 1 ℃/min, and maintaining at the temperature for 30min to obtain pre-liquefied powder slurry;
performing jet liquefaction on the obtained pre-liquefied slurry, wherein the jet liquefaction conditions are as follows: the injection temperature was 95 ℃, the injection inlet pressure was 0.8MPa, and the injection outlet pressure was 0.25MPa: the steam consumption is 0.5t/t of pre-liquefied slurry; then the material obtained by spray liquefaction is cooled to 87 ℃ for 2 hours through flash evaporation, then cooled to 31 ℃ to obtain liquefied mash, and 3.33kg of liquefied mash is obtained per kg of rice raw material. The appearance sugar content, DE value, pH value, acidity of the liquefied mash were measured, and the results are shown in Table 3.
Filtering and sterilizing part of liquefied mash with 1.8mm pore size filter screen, adding acid protease (18U/g rice material), inoculating yeast activating solution of preparation 1 into the filtered and sterilized liquefied mash at 5 vol% of inoculating amount, and culturing at 30deg.C to obtain yeast with a content of 2×10 8 cfu/mL of yeast wine.
(3) Fermentation
Adding ammonium sulfate (8.4 kg/t rice material), saccharifying enzyme (0.68 kg/t rice material), acid proteinase (0.06 kg/t rice material), bactericide (An Jun Tay, 5 g/m) 3 Liquefying mash) to prepare an ethanol fermentation medium, inoculating the yeast mash into the ethanol fermentation medium obtained in the step (1), wherein the inoculation amount of the yeast mash is 25ml/100ml of the medium; controlling the fermentation temperature to be 30 ℃ within a period of time from the beginning of fermentation to the 10 th hour of fermentation; and controlling the fermentation temperature to be 32 ℃ in a period from 11 hours to 35 hours of fermentation, and controlling the fermentation temperature to be 34 ℃ and the total fermentation time to be 72 hours from 36 hours of fermentation to obtain the ethanol-containing fermented mash. The apparent sugar content, the content of residual reducing sugar, the content of residual total sugar, acidity and ethanol concentration in the beer were measured and the results are shown in Table 3. And (3) conveying the sediment at the bottom of the fermentation tank to a sediment separator, and separating the obtained thin mash and wet vinasse.
(4) Separation
Feeding the fermented mash and thin mash after sediment removal in the step (3) into a coarse tower for distillation to obtain coarse mash, ethanol-containing steam (generated by 40% of the total volume of the fermented mash and thin mash) and a first part of waste mash, and feeding the obtained first part of waste mash into a waste mash tank; the working condition of the crude tower is that the theoretical plate number is 35, the temperature of the tower bottom is 80 ℃, the temperature of the tower top is 53 ℃, and the pressure of the tower top is-0.072 MPa.
Collecting the obtained coarse mash from the upper middle part of the coarse tower, and then entering a cyclone separator, separating to obtain sake liquid and waste fermented glutinous rice, and returning the obtained waste fermented glutinous rice to the coarse tower, wherein the working condition of the cyclone separator is 0.6MPa; and (3) sending the obtained sake liquid into a second rectifying tower for impurity removal and concentration (purification treatment), wherein the working condition of the second rectifying tower is that the theoretical plate number is 50, the tower top temperature is 98 ℃, the tower bottom temperature is 124 ℃, and the tower top pressure is 0.095MPa. Condensing the obtained ethanol vapor from the top of the crude tower to form crude liquor, laterally extracting the purified and concentrated clear liquor from the middle side line of the second rectifying tower, and sending the purified and concentrated clear liquor and the obtained crude liquor into a first rectifying tower for further impurity removal and concentration (purification treatment), wherein the working condition of the first rectifying tower is that the theoretical plate number is 70, the tower top temperature is 122 ℃, the tower middle temperature is 135 ℃ and the tower top pressure is 0.38MPa; feeding the second part of waste mash extracted from the first rectifying tower and the second rectifying tower into a waste mash tank;
the ethanol solution extracted from the top of the first rectifying tower is sent to the upper part of the second rectifying tower to form ethanol-containing gas phase, and the obtained ethanol-containing gas phase is dehydrated by a 3A molecular sieve (the adsorption temperature is 100 ℃, the adsorption pressure is 0.055MPa, and the adsorption time is 35 min)) to obtain a fuel ethanol product, wherein the purity (volume percent) of the fuel ethanol product and the starch liquor yield are shown in Table 3.
The waste mash extracted from the waste mash tank was subjected to separation by a decanter centrifuge (rotation speed: 3000rpm, material temperature: 70 ℃ C.), plate-and-frame press filtration (filter cloth: 80 mesh, pressure: 0.6 MPa), concentration by a falling film evaporator (temperature: 85 ℃ C.), and tube bundle drum drying (temperature: 180 ℃ C.) in this order to obtain a solid (used as a feed with the obtained wet distillers' grains, the feed components are shown in Table 5) and a clear liquid 1, and the obtained clear liquid was fed back to the waste mash tank in an amount of 20% by volume. The remaining obtained clear liquid is used for preparing rice flour slurry in the step (1) and further processing to obtain reclaimed water 1 (the obtained clear liquid is sent to a primary sedimentation tank for processing to obtain primary processing liquid, the content of suspended matters (SS) in the obtained primary processing liquid is 3000mg/L, the obtained primary processing liquid is sent to an IC reactor for anaerobic reaction processing (the temperature of anaerobic processing is 35 ℃, the pH value is 7.5, the hydraulic retention time is 85 h), the effluent of the IC reactor is sent to an A/O reactor for aerobic processing (the temperature of aerobic processing is 35 ℃, the pH value is 6, the DO value is 1mg/L, the hydraulic retention time is 45 h), and then the effluent of the A/O reactor is sent to a secondary sedimentation tank for sedimentation processing to obtain reclaimed water), and the obtained reclaimed water is used for preparing rice flour slurry in the step (1). The water quality of the obtained clear liquid 1 and the water quality of the reclaimed water 1 are shown in tables 1 and 2 respectively.
Example 3
(1) Size mixing
The rice raw material (rice stored for three years, water content 11% by weight, grain size <1.8mm, wherein the content of raw material with grain size <1.0mm is 97% by weight, rice hull content 10% by weight) and slurry (65% by weight of process water, 25% by weight of clear liquid 3, 10% by weight of water 3) were mixed to prepare a slurry at a weight ratio of 1:2, and the pH of the slurry was adjusted to 5.6.
(2) Liquefaction process
Adding amylase (the adding amount is 8U/g of rice raw material) into the obtained slurry, heating to 60 ℃, and maintaining at the temperature for 20min at a heating rate of 1 ℃/min; then heating to 85 ℃, wherein the heating rate is 1.5 ℃/min, and maintaining at the temperature for 20min to obtain pre-liquefied powder slurry;
performing jet liquefaction on the obtained pre-liquefied slurry, wherein the jet liquefaction conditions are as follows: the injection temperature was 100deg.C, the injection inlet pressure was 0.6MPa, and the injection outlet pressure was 0.18MPa: the steam consumption is 0.3t/t of pre-liquefied slurry; then the material obtained by spray liquefaction is cooled to 87 ℃ for 2 hours through flash evaporation, then cooled to 31 ℃ to obtain liquefied mash, and 2.94kg of liquefied mash is obtained per kg of rice raw material. The appearance sugar content, DE value, pH value, acidity of the liquefied mash were measured, and the results are shown in Table 3.
Filtering and sterilizing part of liquefied mash with 1.8mm pore size filter screen, adding acid protease (18U/g rice material), inoculating yeast activating solution of preparation 1 into the filtered and sterilized liquefied mash at 5 vol% of inoculating amount, and culturing at 30deg.C to obtain yeast with a content of 2×10 8 cfu/mL of yeast wine.
(3) Fermentation
Adding ammonium sulfate (8.4 kg/t rice material), saccharifying enzyme (0.68 kg/t rice material), acid proteinase (0.06 kg/t rice material), bactericide (An Jun Tay, 5 g/m) 3 Liquefied mash) to prepare an ethanol fermentation medium, inoculating the yeast mash toIn the ethanol fermentation culture medium obtained in the step (1), the inoculum size of the yeast wine is 25mL/100mL of the culture medium; controlling the fermentation temperature to be 32 ℃ within a period of time from the beginning of fermentation to the 6 th hour of fermentation; and controlling the fermentation temperature to be 32.5 ℃ within a period from 7 hours to 36 hours of fermentation, and controlling the fermentation temperature to be 32 ℃ from 37 hours of fermentation, wherein the total fermentation time is 65 hours, so as to obtain the ethanol-containing fermented mash. The apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the beer were measured and the results are shown in Table 3. And (3) conveying the sediment at the bottom of the fermentation tank to a sediment separator, and separating the obtained thin mash and wet vinasse.
(4) Separation
Feeding the fermented mash and thin mash after sediment removal in the step (3) into a coarse tower for distillation to obtain coarse mash, ethanol steam (generated by 30% of the total volume of the fermented mash and thin mash) and a first part of waste mash, and feeding the obtained first part of waste mash into a waste mash tank; the working condition of the crude tower is that the theoretical plate number is 30, the temperature of the tower bottom is 85 ℃, the temperature of the tower top is 62 ℃, and the pressure of the tower top is-0.068 MPa.
Collecting the obtained coarse mash from the upper middle part of the coarse tower, and then entering a cyclone separator, separating to obtain sake liquid and waste fermented glutinous rice, and returning the obtained waste fermented glutinous rice to the coarse tower, wherein the working condition of the cyclone separator is 0.6MPa; the clear wine liquid is sent into a second rectifying tower for impurity removal and concentration (purification treatment), the working condition of the second rectifying tower is that the theoretical plate number is 40, the tower top temperature is 88 ℃, the tower bottom temperature is 115 ℃, and the tower top pressure is 0.035MPa. Condensing the obtained ethanol vapor from the top of the crude tower to form crude liquor, laterally extracting the purified and concentrated clear liquor from the middle side line of the second rectifying tower, and sending the purified and concentrated clear liquor and the obtained crude liquor into a first rectifying tower for further impurity removal and concentration (purification treatment), wherein the working condition of the first rectifying tower is that the theoretical plate number is 70, the tower top temperature is 129 ℃, the tower middle temperature is 135 ℃ and the tower top pressure is 0.45MPa; feeding the second part of waste mash extracted from the first rectifying tower and the second rectifying tower into a waste mash tank;
the ethanol solution extracted from the top of the first rectifying tower is sent to the upper part of the second rectifying tower to form ethanol-containing gas phase, and the obtained ethanol-containing gas phase is dehydrated by a 3A molecular sieve ((adsorption temperature is 130 ℃, adsorption pressure is 0.04MPa, and adsorption time is 30 min)) to obtain a fuel ethanol product, wherein the purity (volume percent) of the fuel ethanol product and the starch liquor yield are shown in Table 3.
The waste mash extracted from the waste mash tank was subjected to separation by a decanter centrifuge (rotation speed: 3000rpm, feed temperature: 70 ℃ C.), plate-and-frame press filtration (filter cloth: 80 mesh, pressure: 0.6 MPa), concentration by a falling film evaporator (temperature: 85 ℃ C.), and tube bundle drum drying (temperature: 180 ℃ C.) in this order to obtain a solid (used as a feed with the obtained wet distillers' grains, feed components are shown in Table 5) and a supernatant 3, and the obtained supernatant was fed back to the waste mash tank in an amount of 20% by volume. The remaining obtained clear liquid is used for preparing rice flour slurry in the step (1) and further processing to obtain reclaimed water 3 (the obtained clear liquid is sent to a primary sedimentation tank for processing to obtain primary processing liquid, the content of suspended matters (SS) in the obtained primary processing liquid is 3000mg/L, the obtained primary processing liquid is sent to an IC reactor for anaerobic reaction processing (the anaerobic processing temperature is 38 ℃, the pH value is 6.5, the hydraulic retention time is 95 h), the effluent of the IC reactor is sent to an A/O reactor for aerobic processing (the aerobic processing temperature is 15 ℃, the pH value is 6, the DO value is 3mg/L, the hydraulic retention time is 55 h), and then the effluent of the A/O reactor is sent to a secondary sedimentation tank for sedimentation processing to obtain reclaimed water), and the obtained reclaimed water is used for preparing rice flour slurry in the step (1). The quality of the obtained clear liquid 3 and the quality of the reclaimed water 3 are shown in tables 1 and 2 respectively.
Example 4
Ethanol was prepared as in example 1, except that the serum was conditioned as serum 4 and the reclaimed water as reclaimed water 4; in the step (4), the obtained clear liquid 4 is sent into a primary sedimentation tank for treatment to obtain primary treatment liquid, and the content of Suspended Substances (SS) in the primary treatment liquid is 3155mg/L; the obtained primary treatment liquid is sent into an IC reactor for anaerobic reaction treatment (the temperature of anaerobic treatment is 36 ℃, the pH value is 6.7, the hydraulic retention time is 96 h), the effluent of the IC reactor is sent into an A/O reactor for aerobic treatment (the temperature of aerobic treatment is 20 ℃, the pH value is 6.4, the DO value is 3mg/L, and the hydraulic retention time is 47 h), and then the effluent of the A/O reactor is sent into a secondary sedimentation tank for sedimentation treatment to obtain reclaimed water), and the reclaimed water is used for preparing rice slurry in the step (1). The quality of the obtained clear liquid 4 and the quality of the obtained reclaimed water 4 are shown in tables 1 and 2 respectively.
The apparent sugar content, DE value, pH value, acidity of the liquefied mash, apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the fermented mash, purity of fuel ethanol product, starch wine yield, and the results are shown in Table 3, and the obtained feed ingredients are shown in Table 5.
Example 5
Ethanol was prepared as in example 1 (and both the supernatant and the reclaimed water were also the supernatant 2 and the reclaimed water 2 obtained as in example 1), except that in step (3), the fermentation temperature was controlled to 31℃during the period from the start of fermentation to 8 hours of fermentation; and (3) controlling the fermentation temperature to 33 ℃ and the total fermentation time to 68 hours from the 9 th to the end of fermentation to obtain the ethanol-containing fermented mash. The resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration, purity of fuel ethanol, starch wine yield, and the results are shown in Table 3, and the obtained feed ingredients are shown in Table 5.
Example 6
Ethanol was prepared as in example 1 (and both supernatant and reclaimed water were also used as in supernatant 2 and reclaimed water 2 obtained as in example 1) except that in step (2), the first temperature was raised at a rate of 0.75 ℃/min and the second temperature was raised at a rate of 1.5 ℃/min. The resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, DE value, pH value, acidity of the liquefied mash, apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the fermented mash, purity of fuel ethanol product, starch wine yield, and the results are shown in Table 3, and the obtained feed ingredients are shown in Table 5.
Example 7
Ethanol was prepared as in example 1 (and both the supernatant and the reclaimed water used were also the supernatant 2 and the reclaimed water 2 obtained as in example 1), except that in step (2), amylase (added in an amount of 8U/g of rice raw material) was added to the resulting slurry, which was then warmed to 55℃at a warming rate of 0.75℃per minute and maintained at that temperature for 15 minutes; then the temperature is raised to 90 ℃ with the temperature rising rate of 1.3 ℃/min and maintained at the temperature for 25min, and the pre-liquefied powder slurry is obtained. The resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, DE value, pH value, acidity of the liquefied mash, apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the fermented mash, purity of fuel ethanol product, starch wine yield, and the results are shown in Table 3, and the obtained feed ingredients are shown in Table 5.
Example 8
Ethanol was prepared as in example 1 (and both the supernatant and the reclaimed water used were also the supernatant 2 and the reclaimed water 2 obtained as in example 1), except that in step (2), amylase (added in an amount of 8U/g of rice raw material) was added to the resulting slurry, which was then warmed to 55℃at a warming rate of 0.75℃per minute and maintained at that temperature for 15 minutes; then the temperature is raised to 85 ℃, the temperature raising rate is 0.75 ℃/min, and the temperature is maintained for 25min, so as to obtain the pre-liquefied powder slurry. The resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, DE value, pH value, acidity of the liquefied mash, apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the fermented mash, purity of fuel ethanol product, starch wine yield, and the results are shown in Table 4, and the obtained feed ingredients are shown in Table 5.
Example 9
Ethanol was prepared as in example 1 (and both the supernatant and the reclaimed water used were also the supernatant 2 and the reclaimed water 2 obtained as in example 1), except that in step (2), amylase (added in an amount of 8U/g of rice raw material) was added to the resulting slurry, which was then warmed to 55℃at a warming rate of 1.8℃per minute and maintained at that temperature for 15 minutes; then heating to 85 ℃, wherein the heating rate is 1.3 ℃/min, and maintaining at the temperature for 25min to obtain pre-liquefied powder slurry; the resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, DE value, pH value, acidity of the liquefied mash, apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the fermented mash, purity of fuel ethanol product, starch wine yield, and the results are shown in Table 4, and the obtained feed ingredients are shown in Table 5.
Example 10
Ethanol was prepared as in example 1 (and both supernatant and reclaimed water were also used as in supernatant 2 and reclaimed water 2 obtained as in example 1) except that the size contained 55 wt.% process water, 15 wt.% supernatant 2 and 30 wt.% reclaimed water 2. The resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, DE value, pH value, acidity of the liquefied mash, apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the fermented mash, purity of fuel ethanol product, starch wine yield, and the results are shown in Table 4, and the obtained feed ingredients are shown in Table 5.
Example 11
Ethanol was prepared as in example 1 (and both supernatant and reclaimed water were also used as in supernatant 2 and reclaimed water 2 obtained as in example 1) except that the size contained 55 wt.% process water, 25 wt.% supernatant 2 and 20 wt.% reclaimed water 2. The resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, DE value, pH value, acidity of the liquefied mash, apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the fermented mash, purity of fuel ethanol product, starch wine yield, and the results are shown in Table 4, and the obtained feed ingredients are shown in Table 5.
Example 12
Ethanol was prepared as in example 1, except that the size was replaced with water; the resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, DE value, pH value, acidity of the liquefied mash, apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the fermented mash, purity of fuel ethanol product, starch wine yield, and the results are shown in Table 4, and the obtained feed ingredients are shown in Table 5.
Example 13
Ethanol was prepared as in example 1, except that the supernatant in the conditioned slurry was replaced with an equal amount of reclaimed water (and the reclaimed water used was reclaimed water 2 obtained as in example 1); the resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, DE value, pH value, acidity of the liquefied mash, apparent sugar content, residual reducing sugar content, residual total sugar content, acidity and ethanol concentration in the fermented mash, purity of fuel ethanol product, starch wine yield, and the results are shown in Table 4, and the obtained feed ingredients are shown in Table 5.
Comparative example 1
Ethanol was prepared as in example 1 (and both the supernatant and the reclaimed water used were also supernatant 2 and reclaimed water 2 obtained as in example 1) except that fermentation was performed at 32℃for 68 hours in step (3) to obtain ethanol-containing beer. The resulting supernatant and reclaimed water of step (4) are not used for slurrying.
The apparent sugar content, residual reducing sugar, residual total sugar content, acidity content and ethanol concentration in the beer were measured, the purity of the fuel ethanol product, the starch wine yield, and the results are shown in Table 4, and the feed ingredients obtained are shown in Table 5.
TABLE 1
| SS(g/100ml) | COD(g/100ml) | BOD 5 (g/100ml) | Conductivity of | |
| Clear liquid 1 | 5492 | 44980 | 36578 | 7980 |
| Clear liquid 2 | 5326 | 42032 | 33611 | 7800 |
| Clear liquid 3 | 5037 | 40009 | 32020 | 7215 |
| Clear liquid 4 | 5011 | 41044 | 33006 | 7300 |
TABLE 2
| SS(g/100ml) | COD(g/100ml) | BOD 5 (g/100ml) | Conductivity of | |
| Reclaimed water 1 | 346 | 992 | 787 | 3790 |
| Reclaimed water 2 | 310 | 917 | 723 | 3620 |
| Reclaimed water 3 | 263 | 708 | 560 | 3308 |
| Reclaimed water 4 | 295 | 612 | 503 | 3429 |
TABLE 3 Table 3
/>
TABLE 4 Table 4
TABLE 5
| Numbering device | Moisture/wt% | Crude protein/wt% | Crude fat/wt% | Crude fiber/wt% | Safety index |
| Example 1 | 10 | 20.3 | 7.2 | 35 | Toxin-free superscalar |
| Example 2 | 10.2 | 19.7 | 7 | 34.5 | Toxin-free superscalar |
| Example 3 | 10.5 | 19.8 | 6.7 | 34.6 | Toxin-free superscalar |
| Example 4 | 11.5 | 18.2 | 6 | 35 | Toxin-free superscalar |
| Example 5 | 11.2 | 18.3 | 5.8 | 30 | Toxin-free superscalar |
| Example 6 | 11.4 | 18.8 | 6.1 | 33.8 | Toxin-free superscalar |
| Example 7 | 11.6 | 18.4 | 6.3 | 34.2 | Toxin-free superscalar |
| Example 8 | 12 | 18.7 | 5.9 | 33.7 | Toxin-free superscalar |
| Example 9 | 11.3 | 18.6 | 6 | 34 | Toxin-free superscalar |
| Example 10 | 11.5 | 19 | 6.2 | 33 | Toxin-free superscalar |
| Example 11 | 11.3 | 18.5 | 6 | 34.8 | Toxin-free superscalar |
| Example 12 | 11 | 18.6 | 6.3 | 33 | Toxin-free superscalar |
| Example 13 | 11.1 | 18.5 | 6.2 | 33.5 | Toxin-free superscalar |
| Comparative example 1 | 12 | 18.5 | 6.1 | 32.5 | Toxin-free superscalar |
The results show that the ethanol prepared by the method can reach a starch wine yield of more than 50%; as can be seen from a comparison of example 1 and comparative example 1, the fermentation effect of example 1 using the technical scheme of the invention for stepwise controlling fermentation temperature is better, the starch liquor yield can reach 50.69%, and the energy consumption can be reduced to 370kg of standard coal/t fuel ethanol.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for producing ethanol by fermentation, comprising: inoculating a fermenting strain in the liquefied mash of a starchy material in the presence of a saccharifying enzyme for fermentation to obtain a fermented mash containing ethanol, wherein the fermentation temperature is controlled in the fermentation process as follows:
after fermentation starts, the fermentation temperature of the first stage is controlled to be 30-32 ℃ before the 6-10h, then the fermentation temperature is increased by 0.5-2 ℃ for continuous fermentation for 25-30h in the second stage, and then the fermentation temperature is controlled to be 32-34 ℃ in the third stage until the fermentation is finished;
The fermentation temperature of the second stage is controlled to be 32-34 ℃, the fermentation temperature of the third stage is controlled to be 32-34 ℃, and the fermentation temperature of the second stage is different from the fermentation temperature of the third stage;
the liquefied mash of the starchy raw material is prepared by liquefying slurry containing the starchy raw material;
the liquefying mode comprises the following steps: firstly, carrying out primary temperature rise and secondary temperature rise on starch-containing raw material slurry in the presence of amylase to obtain pre-liquefied slurry, wherein the primary temperature rise rate is lower than the secondary temperature rise rate; then spraying and liquefying the obtained pre-liquefied slurry; then continuously liquefying the material obtained by spraying and liquefying;
the temperature rising rate of the primary temperature rising is 0.3-0.6 ℃/min lower than that of the secondary temperature rising, and the temperature of the material is raised to 50-60 ℃ by the primary temperature rising; the temperature of the materials is raised to 80-85 ℃ by the secondary temperature rise;
the primary heating rate is 0.5-1 ℃/min;
the rate of the secondary temperature rise is 1-1.5 ℃/min;
the method also comprises maintaining for 10-20min after primary temperature rise, and maintaining for 20-30min after secondary temperature rise;
the conditions for jet liquefaction include: the spraying temperature is 95-100 ℃, the spraying inlet pressure is 0.6-0.8MPa, the spraying outlet pressure is 0.18-0.25MPa, and the steam consumption is 0.3-0.5t/t of pre-liquefied slurry;
The continuous liquefaction mode comprises the steps of firstly cooling the material obtained by spraying liquefaction to 86-88 ℃ for 2-2.5h, and then cooling to 30-32 ℃ for the second time;
the primary cooling mode is flash evaporation cooling;
the secondary cooling mode is heat exchange cooling.
2. The method of claim 1, wherein the total time of fermentation is 60-72 hours.
3. The method of claim 1, wherein the apparent sugar concentration in the liquefied mash is 23-26 ° BX;
and/or the DE value in the liquefied mash is 16-21 wt.%;
and/or the pH value of the liquefied mash is 4.2-4.5, and the acidity is 2.5-4.5 mol/L.
4. A process according to any one of claims 1 to 3, wherein the saccharifying enzyme is used in an amount of 100 to 180U relative to 1 gram of starchy material.
5. A method according to any one of claims 1-3, wherein the fermentation broth is a yeast.
6. The method according to any one of claims 1 to 3, wherein the fermentation broth is inoculated in an amount such that the viable count in 1 ml of the liquefied mash is 2X 10 7 -2.5×10 8 cfu。
7. The method of claim 1, wherein the starch feedstock is present in the slip in an amount of 28-40 wt%;
And/or the starchy material is selected from cereal material and/or potato material.
8. The method according to claim 1 or 7, wherein the starch feedstock is present in the slip in an amount of 32-35 wt%;
and/or, the starchy material is a cereal material;
and/or the starch feedstock has a particle size <1.8mm.
9. The method of claim 7, wherein the cereal raw material is selected from at least one of rice, corn, wheat, barley, and sorghum;
and/or, the cereal material comprises 10-20wt% of chaff;
and/or the content of the raw materials with the granularity of less than 1mm in the starchy raw materials is more than or equal to 90 weight percent.
10. The method of claim 9, wherein the cereal material is rice.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010276260.7A CN111304261B (en) | 2020-04-09 | 2020-04-09 | Method for producing ethanol by fermentation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010276260.7A CN111304261B (en) | 2020-04-09 | 2020-04-09 | Method for producing ethanol by fermentation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111304261A CN111304261A (en) | 2020-06-19 |
| CN111304261B true CN111304261B (en) | 2023-08-08 |
Family
ID=71151902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010276260.7A Active CN111304261B (en) | 2020-04-09 | 2020-04-09 | Method for producing ethanol by fermentation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111304261B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2212467A1 (en) * | 2007-11-01 | 2010-08-04 | Eau-Viron Incorporated | Methods and apparatus for hydrolyzing cellulosic material |
| CN102559776A (en) * | 2012-03-19 | 2012-07-11 | 上海天之冠可再生能源有限公司 | Alcohol fermentation production method of pasting, diluting, liquefying and saccharifying thick mash surface |
| CN105755057A (en) * | 2014-12-17 | 2016-07-13 | 中粮生化能源（肇东）有限公司 | Method for fermentative production of alcohol |
| CN108103112A (en) * | 2018-02-09 | 2018-06-01 | 广东中科天元新能源科技有限公司 | A kind of technique that alcohol fuel is produced as raw material using cornstarch matter |
| CN109762851A (en) * | 2018-12-27 | 2019-05-17 | 吉林中粮生化有限公司 | A kind of method of paddy processing production alcohol fuel and by-product rice DDGS |
| CN110511864A (en) * | 2019-08-28 | 2019-11-29 | 宿州市皖神面制品有限公司 | A kind of thinning workshop section multiple-effect tandem flash distillation energy saving technique |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL2027244T5 (en) * | 2006-05-19 | 2015-12-31 | Heineken Supply Chain Bv | A method of producing a bright, yeast fermented beverage |
-
2020
- 2020-04-09 CN CN202010276260.7A patent/CN111304261B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2212467A1 (en) * | 2007-11-01 | 2010-08-04 | Eau-Viron Incorporated | Methods and apparatus for hydrolyzing cellulosic material |
| CN102559776A (en) * | 2012-03-19 | 2012-07-11 | 上海天之冠可再生能源有限公司 | Alcohol fermentation production method of pasting, diluting, liquefying and saccharifying thick mash surface |
| CN105755057A (en) * | 2014-12-17 | 2016-07-13 | 中粮生化能源（肇东）有限公司 | Method for fermentative production of alcohol |
| CN108103112A (en) * | 2018-02-09 | 2018-06-01 | 广东中科天元新能源科技有限公司 | A kind of technique that alcohol fuel is produced as raw material using cornstarch matter |
| CN109762851A (en) * | 2018-12-27 | 2019-05-17 | 吉林中粮生化有限公司 | A kind of method of paddy processing production alcohol fuel and by-product rice DDGS |
| CN110511864A (en) * | 2019-08-28 | 2019-11-29 | 宿州市皖神面制品有限公司 | A kind of thinning workshop section multiple-effect tandem flash distillation energy saving technique |
Non-Patent Citations (1)
| Title |
|---|
| 黄芳一.《发酵过程》.华中师范大学出版社,2019,(第4版),83. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111304261A (en) | 2020-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Maiorella et al. | Alcohol production and recovery | |
| CN101157890B (en) | Fuel ethanol production equipment and method | |
| US4460687A (en) | Fermentation method | |
| EP0330686B1 (en) | Process and apparatus for the continuous production of ethanol from cereals and method of operating said apparatus | |
| CN110468161B (en) | Application of corn and rice in wheat ethanol fermentation process and method for producing ethanol by fermenting raw materials by using mixed raw materials | |
| US5559031A (en) | Apparatus for the continuous production of ethanol from cereals | |
| CN101538588A (en) | Technology for coupling the liquefaction process of corn alcohol and the concentration process of vinasse clear liquid | |
| CN1298859C (en) | Production of alcohol fuel | |
| US20210222207A1 (en) | Method for producing ethanol fuel by using elaeagnus angustifolia l. as raw material | |
| CN101974567A (en) | Method for ecologically producing alcohol by taking tuberous crop as raw material | |
| CN111187790B (en) | Method for preparing ethanol by using rice raw material | |
| CN102605003B (en) | Method for producing alcohol from potato raw materials | |
| CN111304261B (en) | Method for producing ethanol by fermentation | |
| CN101676393B (en) | Method for preparing alcohol by utilizing potato materials | |
| CN111500648B (en) | Method for liquefying starchy material | |
| CN111440828A (en) | Method for preparing slurry and liquefying starchy material and method for preparing ethanol | |
| CN101210257B (en) | Method for producing high-butanol acetone-butanol by biological process | |
| CN113943758B (en) | Method for producing ethanol | |
| CN111424057A (en) | Process for producing ethanol | |
| CN112322667A (en) | Clostridium butyricum fermentation method using waste pichia pastoris as nitrogen source | |
| CN111254166A (en) | Method for co-producing alcohol and biogas by utilizing cassava and method for generating power by utilizing biogas | |
| CN114250251B (en) | Method for producing ethanol | |
| CN112175999B (en) | Fermentation treatment method of corn soaking liquid, liquid phase product obtained by using fermentation treatment method and application of liquid phase product | |
| CN102909109B (en) | Methods for degerming and pretreating corns and method for brewing alcohol by adopting corns | |
| CN101487026B (en) | Method for preparing ethanol from tuber crops raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |