CN112941112A - Method for preparing ethanol by using starchy raw material and cellulose raw material - Google Patents
Method for preparing ethanol by using starchy raw material and cellulose raw material Download PDFInfo
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- 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
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- 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
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Bioinformatics & Cheminformatics (AREA)
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Abstract
The invention relates to the field of fuel ethanol production, and discloses a method for preparing ethanol by using a starchy material and a cellulose material. In this method, after a starchy raw material is subjected to size mixing, the starchy raw material slurry obtained by the size mixing is subjected to fiber separation to obtain a starchy raw material fiber and a starch slurry. The starchy raw material fiber enters a process of producing ethanol by cellulose fermentation, the starch slurry enters a process of producing ethanol by starch fermentation, and the two processes are integrated, so that the high-efficiency utilization of equipment is realized, and the dosage of an enzyme preparation is reduced. The method of the invention can also reduce the usage amount of raw materials and enzymes, and reduce water consumption, energy consumption and steam consumption.
Description
Technical Field
The invention relates to the field of fuel ethanol production, and discloses a method for preparing ethanol by using a starchy material and a cellulose material.
Background
As the key point of renewable fuels, developing fuel ethanol has great significance for adjusting the energy structure of China, developing petroleum substitute resources, improving the specific gravity of clean fuel, improving the emission of automobile exhaust and the quality of atmospheric environment, developing low-carbon economy, promoting the virtuous cycle and sustainable development of agricultural production and consumption, realizing agricultural efficiency improvement and increasing the income of farmers.
However, in the process of producing ethanol from starchy raw materials at present, the enzymolysis efficiency of liquefying enzyme is low in the liquefying process, and cellulose contained in the starchy raw materials cannot be fully utilized, so that the utilization rate of the raw materials is low, and the improvement of the ethanol yield is influenced.
Disclosure of Invention
The invention aims to improve the ethanol yield in the process of producing ethanol by using starchy raw materials, and provides a method for preparing ethanol by using the starchy raw materials and cellulose raw materials.
In order to achieve the above object, the present invention provides a method for producing ethanol using a starchy material and a cellulosic material, the method comprising:
(1) sequentially crushing, mixing and separating fibers of the starchy raw material to obtain starchy raw material fibers and starch slurry;
(2) sequentially hydrolyzing, carrying out enzymolysis, fermenting 1# and carrying out 1# rough distillation on the starchy raw material fiber obtained in the step (1) and the cellulose raw material crushed material to obtain 1# rough distillation fraction;
(3) sequentially liquefying, fermenting and roughly distilling the starch slurry obtained in the step (1) to obtain roughly distilled fraction No. 2 and waste mash No. 2;
(4) and (3) rectifying the 1# crude distillation fraction obtained in the step (2) and the 2# crude distillation fraction obtained in the step (3) to obtain ethanol.
By adopting the technical scheme, the ethanol produced by the starchy raw material and the ethanol produced by the cellulose raw material are integrated, so that the high-efficiency utilization of equipment is realized; the starchy raw material slurry is subjected to fiber separation, and the separated cellulose component is integrated into the process for preparing the ethanol from the cellulose raw material, so that the dosage of an enzyme preparation in the process of liquefying the starchy raw material is reduced, the utilization rate of the raw material is improved, and the yield of the ethanol is improved.
Under the preferred condition, in the cellulose hydrolysis step, the waste acid is recycled and the crushed cellulose raw material is pickled, so that cleaner materials enter an acid hydrolysis and steam explosion system, the impurity removal cost is reduced while equipment is protected, and the utilization rate of acid is improved.
Under the optimal conditions, the water consumption and the energy consumption are greatly reduced through the circulation of steam and water in the system.
Under the optimal condition, in the step of cellulose enzymolysis, the cellulase is added into the mixing auger, so that the materials are subjected to pre-enzymolysis in the mixing auger before the enzymolysis is carried out, and the subsequent enzymolysis operation is facilitated.
The invention effectively reduces energy consumption, water consumption and steam consumption by matching a plurality of processes, simultaneously reduces the usage amount of raw materials and enzyme, and improves the fermentation effect.
Drawings
FIG. 1 is a flow diagram of the present invention for producing ethanol using a starchy feedstock and a cellulosic feedstock.
FIG. 2 is a schematic diagram of a compounding auger in a preferred embodiment of the present invention for producing ethanol from a starchy feedstock and a cellulosic feedstock.
Description of the reference numerals
1 motor 2 reduction box 3 material inlet 4 enzyme adding port 5 blade
6 main shaft 7 discharge hole
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the term "mature mash" refers to a mash obtained by separating a fermented mash after fermentation.
In the present invention, the term "distillation" refers to the rough distillation and rectification of the mature mash from fermentation.
The invention provides a method for preparing ethanol by using a starchy raw material and a cellulose raw material, which comprises the following steps:
(1) sequentially crushing, mixing and separating fibers of the starchy raw material to obtain starchy raw material fibers and starch slurry;
(2) sequentially hydrolyzing, carrying out enzymolysis, fermenting 1# and carrying out 1# rough distillation on the starchy raw material fiber obtained in the step (1) and the cellulose raw material crushed material to obtain 1# rough distillation fraction;
(3) sequentially liquefying, fermenting and roughly distilling the starch slurry obtained in the step (1) to obtain roughly distilled fraction No. 2 and waste mash No. 2;
(4) and (3) rectifying the 1# crude distillation fraction obtained in the step (2) and the 2# crude distillation fraction obtained in the step (3) to obtain ethanol.
In the present invention, the kind of the starchy material is not particularly limited, and may be a starchy material conventionally used in the art, such as corn, wheat, sweet potato, tapioca, potato, and the like, and preferably corn.
In the present invention, the method for pulverizing the starchy raw material may be a method conventionally used in the art, for example, a pulverizer may be used to pulverize the starchy raw material, and then the pulverized starchy raw material may be sieved to obtain starchy raw material particles. Wherein the average particle diameter of the starchy raw material particles can be 20-80 meshes.
In the present invention, the process of size mixing may include: adding water for size mixing into the starchy raw material particles and mixing to obtain starchy raw material slurry; wherein the solid content in the starchy raw material slurry can be 30-40 wt%, preferably 32-38 wt%; the temperature of the size mixing can be 35-80 ℃, preferably 40-75 ℃. Wherein the size mixing process may further comprise a step of adjusting the pH, for example, adjusting the pH of the starchy raw material slurry to 3 to 8, preferably 4 to 7, by adding acid.
In the present invention, a heat source can be provided for the size mixing step by using the conventional technical means in the field to make the size mixing temperature reach the preset temperature, for example, the heat source can be provided by water bath heating, resistance wire heating or steam heating. Preferably, steam is used as the heat source for the size mixing step, i.e., the steam exchanges heat with the starch slurry, the steam temperature decreases, and the starch slurry temperature increases.
Preferably, the conditioned condensate obtained by heat exchange of steam in the conditioning step is used as at least part of the acid water in the following acid hydrolysis step of fermentation of cellulosic feedstock to produce ethanol, and more preferably, the gas explosion steam generated in the acid hydrolysis step of fermentation of cellulosic feedstock to produce ethanol is used as at least part of the heat source for the conditioning step. In this preferable case, the heat and water can be sufficiently utilized, and the energy and water consumption can be reduced.
In the invention, the purpose of the fiber separation is to separate the starchy raw material fiber in the starchy raw material slurry from the starchy raw material slurry, so that the starch slurry entering the liquefaction step contains a small amount of starchy raw material fiber or even a trace amount of starchy raw material fiber, thereby improving the liquefaction efficiency and reducing the use amount of enzyme in the liquefaction process. On the other hand, the starchy raw material fiber obtained by separation is conveyed to the process of producing ethanol by cellulose, so that the starchy raw material fiber can be fully utilized. Among them, the method conventionally used in the art for achieving the object of fiber separation is applicable to the present invention. Preferably, the defibration is performed by means of a grinding disc using a selective grinding technique.
In the present invention, the purpose of the liquefaction is to convert the starch slurry into fermentable sugars. Therefore, the method which is conventionally used in the field and can realize the purpose of liquefying the starchy raw materials is suitable for the invention. Specifically, the process of liquefying may include: adding amylase into the starch slurry for liquefaction to obtain liquefied liquid, wherein the addition amount of the amylase is 10-80U/g of dry base starch raw material, and preferably 15-60U/g of dry base starch raw material; the liquefaction temperature is 55-120 ℃, and the preferred temperature is 70-105 ℃; the liquefaction pH is between 3 and 8, preferably between 4 and 7; the liquefaction time is 0.2-10h, preferably 0.5-5 h.
In the present invention, in step (3), the purpose of the 2# fermentation is to subject the liquefied liquid to fermentation to produce 2# fermented mash containing ethanol. Therefore, methods conventionally used in the art to achieve fermentation objectives are suitable for use in the present invention. Preferably, the method for # 2 fermentation comprises: inoculating the 2# strain into the liquefied liquid obtained by liquefaction for fermentation to obtain 2# mature mash. Wherein, the parameters of the 2# fermentation process can include: the pH value of the fermentation is 2-7, preferably 3-6; the temperature is 25-40 ℃, preferably 30-35 ℃; the time is 2-5 days.
In a preferred embodiment of the present invention, the method further comprises: part of the # 2 mature mash was refluxed to # 2 fermentation step.
In the present invention, the 2# strain may be a strain conventionally used in the art for producing ethanol by fermentation of starchy material, such as saccharomyces cerevisiae.
In the present invention, the # 2 strain may be activated before inoculation, and the activation method may be a method conventionally used in the art, for example, the # 2 strain may be inoculated into an activation tank, mixed with water and activated to obtain # 2 seed solution. If necessary, a carbon source, such as a liquefied solution of a starchy material, may be added to the activation tank to activate the 2# strain. Wherein, the pH value of the activation can be 2-7, and is preferably 3-6; the activation temperature can be 25-40 ℃, and preferably 30-35 ℃; the time can be 6-16 h.
In the invention, the 2# strain can be subjected to at least one stage of propagation before inoculation, and the propagation can be performed in a shake flask and/or a propagation tank. For example, the first stage of expanding culture can be carried out in a shake flask, and the second stage of expanding culture can be carried out in an expanding culture tank, so as to obtain the No. 2 seed liquid. Wherein, the pH value in each stage of the expanding culture process can be 2-7, preferably 3-6; the expanding culture temperature of each stage can be 25-40 ℃, and preferably 30-35 ℃; the time of each stage of propagation can be 6-16h respectively.
In the present invention, the # 2 medium used in each propagation process may be a medium conventionally used in the art, such as a corn liquefied solution, preferably a corn liquefied solution with a solid content of 10-30%, and preferably a pH of 6-8, and the pH may be adjusted by using ammonia water.
In the present invention, in the 2# fermentation, the 2# strain inoculation amount can be selected in a wide range, for example, the 2# strain inoculation amount can be 1 × 10 with respect to 1 g of the liquefied liquid4-1×107cfu。
In the present invention, colony forming units of the species can be determined by methods well known in the art, such as methylene blue stain viable count.
In the present invention, the purpose of the 2# crude is to predistillate the 2# mature mash to obtain a 2# crude fraction with lower ethanol purity and 2# waste mash. Therefore, any method conventionally used in the art to achieve the purpose of crude distillation is suitable for the present invention. Preferably, in the step (3), the 2# crude distillation is performed in a 2# crude distillation column, and the 2# crude distillation column is provided with a 2# crude distillation column reboiler. The temperature of the crude distillation in the 2# crude distillation tower can be 70-90 ℃.
In the present invention, a heat source can be provided for the # 2 rough distillation step by using the conventional technical means in the field, for example, the heat source can be provided by water bath heating, resistance wire heating or steam heating. Preferably, the heat source for the # 2 coarse distillation column reboiler is from steam which is heat exchanged with # 2 mature mash in the # 2 coarse distillation column reboiler to form # 2 coarse distillation condensate, and the # 2 mature mash is heated and reboiled. Wherein, preferably, at least part of the steam comes from the gas explosion steam generated in the steam explosion step in the cellulose ethanol production process.
In a preferred embodiment of the present invention, in order to reduce water consumption, the method further comprises recycling the # 2 caide distillate to the acid hydrolysis step for use as at least a partial partition of acid water.
In the present invention, the process of rectifying the 2# rough distillation fraction and the 1# rough distillation fraction obtained in the following 1# rough distillation step is preferably performed in the same rectification system, in which case, one set of rectification equipment can be saved, the utilization rate of the equipment can be improved, and the input cost can be reduced. The rectification method is described in detail below, and is not repeated here.
In the present invention, in order to achieve efficient utilization of the material, the 2# waste mash can be reprocessed to convert it to DDGS. Wherein the DDGS is distillers' grain protein and can be used for producing feed products.
In a preferred embodiment of the present invention, the No. 2 mash obtained in step (3) is subjected to solid-liquid separation to obtain a mash clear solution and a mash wet cake; preferably, the waste mash clear liquid is subjected to evaporation concentration to obtain waste mash concentrated solution and evaporation condensate; and mixing the wet waste mash cake and the waste mash concentrated solution, and drying the obtained mixture to obtain the DDGS.
Wherein, in order to further reduce the water consumption in the ethanol production process and improve the utilization rate of the materials, the evaporation condensate is preferably circulated to a plurality of steps for producing ethanol by fermentation. It is understood that the process can be recycled to the process for producing ethanol by fermenting starchy materials, and can also be recycled to the process for producing ethanol by fermenting cellulosic materials. Preferably, the method further comprises: at least part of the evaporation condensate is recycled to the acid mixing step of the cellulose ethanol production process to be uniformly mixed with the acid-washing material, the starchy raw material fiber and the acid liquor, and/or at least part of the evaporation condensate is recycled to the size mixing step to be used as at least part of size mixing water.
In the present invention, the kind of the cellulose raw material is not particularly limited, and may be a cellulose raw material conventionally used in the art, such as corn stover, sorghum stover, rice straw, straw of cereal plants which may be wheat straw, straw of oil plants including soybean stover, cotton straw, and the like, preferably corn stover. It will be understood that the straw includes the stem and leaves of the plant and optionally the roots.
In the present invention, the method of pulverizing the cellulose raw material to obtain a pulverized cellulose raw material may be a method conventionally used in the art, and for example, the cellulose raw material may be pulverized using a pulverizer. Preferably, the cellulose raw material is firstly crushed into coarse crushed materials with the average length of 5-10cm through primary crushing, then impurity removal treatment is carried out, and secondary crushing is carried out to obtain fine crushed materials with the average length of 0.5-3cm, and fine crushed materials with the average length of 1-2cm are preferred.
The method for removing impurities can be a conventional technical means in the field as long as impurities in the cellulose raw material can be removed. For example, a dust collector may be used to remove dust-like impurities from the coarsely pulverized material, an impurity remover may be used to remove sand and stone impurities from the coarsely pulverized material, and a magnetic adsorption method may be used to remove iron impurities therefrom. The skilled person can combine the aforementioned methods to perform the impurity removal operation as required.
In the present invention, in the step (2), the hydrolysis method may be a method conventionally used in the art for hydrolysis of a cellulose raw material, and for example, hydrolysis may be performed using an acid, or hydrolysis may be performed using a base. The invention preferably uses acid for hydrolysis, and specifically comprises the following steps: 1) acid washing is carried out on the crushed cellulose raw material to obtain a first waste acid solution and an acid washing material; 2) uniformly mixing the acid-washed material, the starchy raw material fiber and an acid solution to obtain a mixed acid material, and performing acid hydrolysis on the mixed acid material to obtain an acid-hydrolyzed material; 3) and performing steam explosion on the acid hydrolysis material to obtain a hydrolyzed material and gas explosion steam.
In the present invention, the pickling method may not be particularly limited, and for example, pickling may be performed using a rinsing machine. When at least part of the acid for pickling is preferably the first waste acid clear liquid and/or the second waste acid clear liquid, through the pickling step, not only can the waste acid generated in the hydrolysis process be fully utilized to carry out primary acid hydrolysis on the raw material, but also impurities contained in the crushed material of the cellulose raw material are removed, and the loss of the impurities (mainly dust) on equipment in the steam explosion step is reduced.
Wherein the first waste acid solution can be directly discharged, or the first waste acid solution can be recovered after solid-liquid separation. Preferably, the first waste acid solution is subjected to solid-liquid separation to obtain a first waste acid clear solution and ash. More preferably, said first spent acid liquor is recycled to said pickling step as at least part of the pickling acid. The ash can be directly discharged or discarded.
In the invention, the acid-washing material, the starchy raw material fiber and the acid liquor are uniformly mixed to obtain the mixed acid material. The concentration of the acid solution may not be particularly limited, and in a preferred embodiment of the present invention, the acid solution is a sulfuric acid solution having a mass fraction of 1 to 3%.
In a preferred embodiment of the present invention, the weight ratio of the acid solution to the pickling material is 1: 1-3.
In the present invention, the manner of mixing the acid-washed material, the starchy raw material fiber and the acid solution may not be particularly limited, and preferably, the acid solution is atomized and then mixed with the acid-washed material and the starchy raw material fiber, and then further mixed with stirring.
In the present invention, an acid solution prepared from a raw material acid and an acid preparation water may be prepared as needed according to a conventional method in the art.
The concentration of the starting acid is not particularly limited, but preferably an acid solution having a mass fraction of acid molecules of 30% or less. The kind of the raw material acid is not particularly limited, and may be, for example, hydrochloric acid, sulfuric acid, nitric acid or the like, and preferably sulfuric acid.
In the present invention, the acid solution may be prepared according to a method conventional in the art according to needs, and the acid solution is preferably prepared by using acid preparation water at least partially from at least one of size mixing condensate, 1# crude distillation condensate, 2# crude distillation condensate, rectification condensate and column bottom condensate, and more preferably from size mixing condensate, 1# crude distillation condensate, 2# crude distillation condensate, rectification condensate and column bottom condensate in the process of preparing ethanol.
In the invention, preferably, the mixed acid material is first subjected to a first dehydration treatment to obtain a dehydrated material and a second waste acid solution. Preferably, the second waste acid liquid is subjected to solid-liquid separation to obtain a second waste acid clear liquid and acid sludge. More preferably, the first spent acid liquor and/or the second spent acid liquor are recycled to the pickling step as at least part of the pickling acid and the acid sludge is returned to the mixed acid step.
In the present invention, the first dehydration method may be a method conventionally used in the art, such as dehydration by centrifugation, filtration, extrusion and sedimentation, and preferably, the waste acid solution is separated from the mixed acid material by extrusion. More preferably, the moisture content of the dewatered material is preferably 40-60% by weight.
In the present invention, the method for acid hydrolysis of the dewatered material may be a method conventionally used in the art, and preferably, the dewatered material is subjected to pressure and heat treatment, and the cellulose material is subjected to acid hydrolysis under the pressure and heat conditions to obtain an acid hydrolyzed material.
The pressure and heat treatment conditions can be conventional methods in the field, and only the condition that a high-temperature and high-pressure environment is provided for the dehydrated material to carry out acid hydrolysis is met. Preferably, said high pressure means a pressure of 1.4 to 2.0MPa, more preferably 1.5 to 1.6 MPa; the high temperature is 180-200 ℃, more preferably 185-195 ℃; the treatment time is 10-120 s.
In the invention, the acid hydrolysis material is subjected to steam explosion to obtain a hydrolyzed material and gas explosion steam. The method of steam explosion is not particularly limited as long as the acid hydrolyzed material can be released to normal pressure, and for example, the acid hydrolyzed material can be sprayed through a spray valve to reduce the pressure to normal pressure. In the present invention, the steam explosion may be intermittent steam explosion or continuous steam explosion, and is preferably intermittent steam explosion.
In the present invention, the method for performing solid-liquid separation on the first waste acid solution may not be particularly limited, and may be, for example, settling, filtering or centrifuging, and only the ash and slag in the first waste acid solution need to be separated.
In the present invention, the method for performing solid-liquid separation on the second waste acid solution may not be particularly limited, and may be at least one of grid separation, sedimentation, filtration or centrifugation, and it is preferable that the acid sludge in the second waste acid solution is separated by grid separation, and then the second waste acid solution is settled to obtain the second waste acid clear solution.
In a preferred embodiment of the present invention, the evaporation condensate obtained in the process of producing ethanol from the starchy raw material is recycled to the acid mixing step in the hydrolysis step, and is mixed with the acid solution, the acid-washed material and the starchy raw material fiber, and then enters the acid hydrolysis step. In this case, the utilization rate of the starchy material and the moisture can be improved, and the yield of ethanol can also be improved.
In the present invention, the method of subjecting the hydrolyzed material to enzymatic hydrolysis to convert the hydrolyzed material into fermentable sugars may be performed according to a method of subjecting cellulose to enzymatic hydrolysis, which is conventional in the art. In a preferred embodiment of the present invention, the method of enzymatic hydrolysis comprises: conveying the hydrolyzed material by a mixing auger, and carrying out enzymolysis to obtain an enzymolysis liquid; the efficiency of the enzymatic step can be improved, for example, the same degree of enzymatic hydrolysis is achieved during the enzymatic process, less cellulase is used and/or the enzymatic time is shorter.
Preferably, the method further comprises: and in the mixing auger, mixing the hydrolyzed material with cellulase. It will be appreciated that the point at which the hydrolysed material and cellulase enzyme begin to mix, i.e. the point at which the cellulase enzyme is added, should be located in the first half of the mixing auger, preferably in the range from the start of the mixing auger to the front 1/4.
In the present invention, the compounding auger has paddles in a paddle configuration, such as the paddle configuration shown in fig. 2. The preferred compounding auger as shown in figure 2 that is preferred to the compounding auger, the compounding auger includes motor 1, reducing gear box 2, pan feeding mouth 3, adds enzyme mouth 4, paddle 5, main shaft 6 and discharge gate 7, and wherein, the material after the hydrolysis passes through feed inlet 3 and gets into in the compounding auger, cellulase gets into from adding enzyme mouth 4 in the compounding auger, cellulase and the material intensive mixing after the hydrolysis under the promotion of paddle 5 and stirring effect to carry out enzymolysis in advance for the viscosity of the material after the hydrolysis reduces along material advancing direction gradually, then, the material after the enzymolysis in advance is discharged from discharge gate 7.
In the present invention, the shape, structure, number and distribution of the blades 2 are not particularly limited, and may be selected by those skilled in the art according to actual conditions.
In the invention, the total dosage of the cellulase in the step (2), including the dosage of the optional cellulase added in the mixing auger and the dosage of the cellulase added in the subsequent enzymolysis step, can be selected in a wide range, preferably the total dosage of the cellulase is 8-20 enzyme activity units, more preferably 10-15 enzyme activity units, based on the dry weight of each gram of the raw material containing cellulose.
The enzymatic activity of the cellulase is determined according to NREL LAP-006 which is a standard method provided by National Renewable Energy Laboratory (NREL) and used for determining the enzymatic activity of the cellulase, wherein the enzymatic activity unit of the cellulase is microgram of enzyme required for converting 1 g of Whatman No.1 filter paper into glucose within 1 minute under the determination condition specified by the standard method.
In the present invention, in order to achieve a better enzymolysis effect, the step of enzymolysis preferably includes sequentially performing the first enzymolysis and the second enzymolysis. The first enzymolysis and second enzymolysis equipment can respectively and independently comprise at least two enzymolysis tanks connected in series. The first enzymolysis and the second enzymolysis are performed under the same conditions, which may be conditions of conventional enzymolysis in the art. In the first enzymolysis and/or the second enzymolysis process, cellulase can be supplemented.
In the invention, the cellulase can be added in the first enzymolysis stage and the second enzymolysis stage, or not, and the cellulase can be adjusted by a person skilled in the art according to needs.
In the present invention, the enzyme used in the enzymatic hydrolysis step may further include one or more of hemicellulase, pectinase and protease, and the ratio of the total weight of hemicellulase, pectinase and protease to the total weight of cellulase is 1:1 to 100, preferably 1:1 to 10, based on the total weight of cellulase added.
In the present invention, the temperature of the enzymatic hydrolysis may be any optimum temperature for the cellulase, and is generally 45 to 55 ℃, more preferably 48 to 52 ℃.
In the present invention, the pH value for the enzymatic hydrolysis may be any optimum pH for the action of the cellulase, and is generally 3.0 to 7.0, more preferably 4.5 to 5.5. Since the pH value does not fluctuate much during the enzymatic hydrolysis, the pH value of the enzymatic hydrolysis can be adjusted according to methods commonly used in the art before the addition of the enzyme, for example, the pH of the material to be hydrolyzed can be adjusted to 3.0-7.0, more preferably to 4.5-5.5, with sulfuric acid solution or sodium hydroxide.
In the present invention, the time of the first enzymatic hydrolysis and the time of the second enzymatic hydrolysis may be selected within a wide range. Preferably, the time of the first enzymolysis is 1 to 10 hours, and more preferably 2 to 6 hours; the time of the second enzymolysis is 25 to 48 hours, and more preferably 30 to 40 hours.
In the present invention, the cellulase may be an enzyme conventionally used in the art, such as a commercially available cellulase which can be produced by norvistin with high efficiency.
In the invention, the purpose of the 1# fermentation is to ferment the enzymolysis liquid to obtain the 1# mature mash containing ethanol. Thus, methods conventionally used in the art to achieve the goal of fermenting cellulose to ethanol are suitable for use in the present invention. Preferably, in step (2), the method for # 1 fermentation comprises: inoculating the 1# strain into the enzymolysis liquid for fermentation to obtain 1# mature mash.
Wherein, the parameters of the 1# fermentation process can include: the pH value of the fermentation is 2-7, preferably 3-6; the temperature is 30-36 ℃, preferably 32-35 ℃; the time is 32 to 48 hours, preferably 32 to 40 hours.
In the present invention, the # 1 strain may be yeast conventionally used in the art for fermentation to produce ethanol, preferably pichia stipitis and/or saccharomyces cerevisiae. The inoculation amount of the yeast used for the 1# fermentation can be 10 per gram of zymolytic fluid3-108cfu, preferably 104-106cfu. The yeast used in the fermentation of the invention can be yeast solid preparation or yeast strain, such as YEPD yeast which can be preserved at 4 ℃.
In the present invention, colony forming units of the species can be determined by methods well known in the art, such as methylene blue stain viable count.
In the present invention, the # 1 strain may be activated before inoculation, and the activation method may be a method conventionally used in the art, for example, the # 1 strain may be inoculated into an activation tank, mixed with water and activated to obtain # 1 seed solution. If necessary, a carbon source, such as a liquefied solution of a starchy material, may be added to the activation tank to activate the # 1 strain. Wherein, the pH value of the activation can be 2-7, and is preferably 3-6; the activation temperature can be 25-40 ℃, and preferably 30-35 ℃; the time can be 6-16 h.
In the invention, the strain No.1 can be subjected to at least one stage of propagation before inoculation, and the propagation can be performed in a shake flask and/or a propagation tank. For example, the first stage of expanding culture can be carried out in a shake flask, and the second stage of expanding culture can be carried out in an expanding culture tank, so as to obtain the No.1 seed liquid. Wherein, the pH value in each stage of the expanding culture process can be 2-7, preferably 3-6; the expanding culture temperature of each stage can be 30-36 ℃, and preferably 32-35 ℃; the time for each stage of propagation can be 32-48 hours, preferably 32-40 hours.
In the present invention, the # 1 medium used in each propagation process may be a medium conventionally used in the art, and may be, for example, peptone, inorganic salts, nitrogen source required for yeast, inorganic salts, trace elements, vitamins and corn liquefied liquid, preferably corn liquefied liquid having a solid content of 10-20%, preferably pH 6-8, pH adjusted using ammonia water.
In a preferred embodiment of the present invention, the method further comprises: part of the # 1 mature mash was refluxed to # 1 fermentation step.
In a preferred embodiment of the present invention, in order to increase the yield of ethanol, the process of the present invention further comprises subjecting the CO produced in the fermentation step # 1 and the fermentation step # 2 to2Washing is performed and the resulting washing liquid is returned to the mature mash # 1 and/or the mature mash # 2.
In the present invention, the purpose of the # 1 crude distillation is to preliminarily distill the # 1 matured mash to obtain a # 1 crude distillation fraction with lower ethanol purity and # 1 waste mash. Therefore, any method conventionally used in the art to achieve the purpose of crude distillation is suitable for the present invention. Preferably, in the step (2), the 1# crude distillation is performed in a 1# crude distillation column, and the 1# crude distillation column is provided with a 1# crude distillation column reboiler. The temperature of the crude distillation in the No.1 crude distillation tower can be 70-90 ℃.
In the present invention, the heat source can be provided for the 1# rough distillation step by using the conventional technical means in the field, for example, the heat source can be provided by water bath heating, resistance wire heating or steam heating. Preferably, steam is used as a heat source for the # 1 roughing step, the steam exchanges heat with # 1 mature mash in the # 1 roughing column reboiler to form # 1 roughing condensate, and the # 1 mature mash is heated and reboiled. Wherein at least part of the steam comes from the gas explosion steam generated in the steam explosion step in the cellulose ethanol production process.
In a preferred embodiment of the present invention, in order to reduce water consumption, the method further comprises recycling the # 1 caide distillate to the acid hydrolysis step for use as at least a partial partition of acid water.
In the invention, the No.1 waste mash can be subjected to solid-liquid separation to obtain No.1 solid waste and No.1 clear liquid. The No.1 clear liquid can enter a sewage treatment system for treatment, and the No.1 solid waste can be directly discharged or incinerated for treatment.
In the invention, the rectification is to distill the 1# crude distillation fraction and the 2# crude distillation fraction to obtain ethanol with higher purity, and the methods which are conventionally used in the field and can achieve the rectification purpose are all suitable for the invention. Preferably, in step (4), the rectification is carried out in a rectification column, which is equipped with a rectification column reboiler.
In the present invention, the rectification may be performed in at least one rectification column provided with a rectification column reboiler, and for example, may be performed in 2 rectification columns provided with rectification column reboilers.
In the present invention, the heat source can be provided for the rectification step by using the conventional technical means in the field, for example, the heat source can be provided by water bath heating, resistance wire heating or steam heating. Preferably, the heat source of the rectifying tower reboiler is fresh steam, and the fresh steam exchanges heat in the rectifying tower reboiler to form rectifying condensate.
In a preferred embodiment of the invention, the method further comprises recycling said rectified condensate to said acid hydrolysis step for use as at least a partial partition of acid water.
In a preferred embodiment of the invention, the process further comprises recycling the column bottoms condensate produced in the rectification step to the acid hydrolysis step for use as at least a portion of the acid water. The column condensate generally refers to column condensate produced in the first rectification process as described below.
In the present invention, the rectification method can be a method conventionally used in the art, and preferably the first rectification is performed on the 1# crude distillation fraction and the 2# crude distillation fraction in a first rectification column at the temperature of 100 ℃ and 140 ℃, and the second rectification is performed on the obtained first rectification fraction in a second rectification column at the temperature of 140 ℃ and 160 ℃ to obtain a second rectification fraction. Wherein, through the first rectification process, the fusel oil can be obtained besides the obtained first rectification fraction.
In a preferred embodiment of the invention, the distillation step for producing ethanol from starchy and cellulosic feedstocks comprises a 1# rough run, a 2# rough run and a rectification step, in particular: conveying 1# mature mash from the 1# fermentation step to a 1# rough distillation step, and performing 1# rough distillation through a 1# rough distillation tower provided with a 1# rough distillation tower reboiler to obtain a 1# rough distillation fraction and 1# waste mash; conveying 2# mature mash from the 2# fermentation step to a 2# rough distillation step, and performing 2# rough distillation through a 2# rough distillation tower provided with a 2# rough distillation tower reboiler to obtain 2# rough distillation fraction and 2# waste mash; and conveying the 1# crude distillation fraction and the 2# crude distillation fraction to a first rectifying tower provided with a first rectifying tower reboiler for first rectification to obtain a first rectifying fraction, and conveying the first rectifying fraction to a second rectifying tower provided with a second rectifying tower reboiler for second rectification to obtain ethanol.
In the present invention, the ethanol obtained by the distillation may be subjected to a second dehydration treatment to obtain fuel ethanol. The second dehydration method may be a method conventionally used in the art, and for example, ethanol may be obtained by dehydration using a molecular sieve and/or membrane separation. The working condition of the molecular sieve can be that the adsorption temperature of the sieve is 120-140 ℃, the adsorption pressure is 0.02-0.06MPa, and the regeneration condition is-0.02-0.06 MPa.
Preferably, before the fuel ethanol is obtained after the second dehydration unit, the finished product wine gas obtained by the second dehydration is used for heat exchange with the mature mash, and the finished product wine gas after the heat exchange obtains the fuel ethanol.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the reagents used are all commercially available unless otherwise specified.
The raw material acid is 98% concentrated sulfuric acid, and the acid consumption is calculated by the volume of the concentrated sulfuric acid consumed for producing 1t of ethanol.
The No.1 strain for producing ethanol from cellulose material is YEPD yeast.
The 2# strain for producing ethanol from starchy material is Saccharomyces cerevisiae (Angel super high activity dry Saccharomyces cerevisiae) purchased from Angel Yeast of Hubei.
Alpha-amylase was purchased from novacin.
The cellulase is a commercial product of high-efficiency cellulase under the trademark of Klaine-Kyoweixin.
The starchy raw material is corn, and the cellulose raw material is corn straw.
In the following examples, 30 ten thousand tons/year corn fuel ethanol and 5 ten thousand tons/year cellulose fuel ethanol are co-produced in the process of co-producing ethanol from starch material and cellulose material, wherein the obtained fuel ethanol is 99.5 vol% ethanol.
Example 1
This example illustrates the preparation of ethanol in the process of the invention
The steps in this embodiment are operated with reference to a flowchart shown in fig. 1.
(1) Preparation of ethanol from starchy material
Crushing, size mixing and fiber separation: the starchy raw material is crushed and then sieved by a 20-mesh sieve to obtain starchy raw material particles. And (3) sending the starchy raw material particles into a size mixing tank to be mixed with size mixing water for size mixing to obtain starchy raw material size, wherein the size mixing temperature is 80 ℃, and the amount of the size mixing water is used for ensuring that the solid content in the obtained starchy raw material size is 30 wt%. Then, the starchy raw material slurry is subjected to fiber separation by using a fiber separator to obtain starch slurry and starchy raw material fibers.
Fresh steam is used as a heat source in the pulp mixing step, pulp mixing condensate is obtained through heat exchange, and the pulp mixing condensate is conveyed to the following process of producing ethanol from cellulose raw materials and is used as acid preparation water. The starchy raw material fiber is conveyed to the acid mixing step in the process of producing ethanol by using the cellulose raw material and is mixed with the acid-washed material and the acid liquor.
Liquefaction: uniformly mixing starch slurry and alpha-amylase, and liquefying to obtain liquefied liquid; wherein, relative to 1 g of starchy raw material, the dosage of the alpha-amylase is 20 enzyme activity units, and the liquefying conditions are as follows: the temperature of liquefaction was 90 ℃, the time of liquefaction was 90 minutes, and the pH of liquefaction was 5.6.
2# fermentation: adding the 2# strain into an activation tank, and mixing with water for activation for 10 h. Inoculating activated 2# seed liquid into the liquefied liquid, performing 2# fermentation to obtain 2# fermented mash, and separating thallus to obtain 2# mature mash. Wherein the inoculation amount of the 2# strain is 10 relative to 1 g of the liquefied liquid5cfu. The conditions of the 2# fermentation include: at 31.5 deg.C and pH 4.5The fermentation time was 65 hours.
2# crude distillation: and carrying out coarse distillation on the 2# mature mash in a 2# coarse distillation tower equipped with a 2# coarse distillation tower reboiler at 82 ℃ to obtain 2# waste mash and 2# coarse distillation fraction.
And the heat source of the 2# rough distillation is steam, wherein at least the heat source is gas explosion steam for preparing ethanol from the cellulose raw material, and the 2# rough distillation condensate is obtained after the steam exchanges heat. The 2# crude distillate is sent to the cellulosic feedstock to the ethanol stream for use as at least a portion of the acid water.
2# waste mash treatment: and (3) carrying out solid-liquid separation on the No. 2 waste mash by using a plate and frame filter to obtain waste mash clear liquid and waste mash wet cake. And carrying out four-effect evaporation on the clear liquid of the waste mash to obtain evaporation condensate and waste mash concentrated solution. And drying the waste mash concentrated solution and the waste mash wet cake by using a dryer to obtain the DDGS.
Wherein, the evaporation condensate is conveyed to the acid mixing step in the process of producing ethanol by using the cellulose raw material and is mixed with the acid washing material and the acid liquor.
(2) Preparation of ethanol from cellulosic material
Crushing: the method comprises the following steps of crushing a cellulose raw material into a long section with the average length of about 7cm through a primary crusher, and then removing impurities in an impurity removing machine, wherein a dust remover is arranged above the impurity removing machine and used for removing dust. And (3) secondarily crushing the material after impurity removal, and crushing the crushed material into fragments with the average length of about 1.5cm to obtain a crushed cellulose raw material.
Hydrolysis: and (2) pickling the crushed cellulose raw material in a rinsing machine to obtain a first waste acid solution and a pickling material, settling the first waste acid solution in a settling tank to obtain a first waste acid clear solution and ash, recycling the first waste acid clear solution as at least part of acid for pickling, and discarding the ash.
In a blending tank, 98% concentrated sulfuric acid is diluted into 2% dilute sulfuric acid under the action of blending acid water. And (2) then, carrying out mixed acid treatment on the acid-washed material, the starchy raw material fiber and the evaporation condensate from the step (1) and a dilute sulfuric acid atomized liquid in a mixed conveyor to obtain a mixed acid material, wherein the weight ratio of the dilute sulfuric acid to the acid-washed material is 1: 1.8.
and conveying the mixed acid material to a cooking system, and performing first dehydration treatment on the mixed acid material at a feeder of the cooking system through extrusion to obtain a dehydrated material and a second waste acid solution. And (3) feeding the dehydrated material obtained by extrusion into a cooking system for pressurizing and heating treatment to obtain an acid hydrolyzed material, wherein the pressure is 1.5Mpa, the temperature is 190 ℃, and the treatment time is 30 s. And opening the blow-off valve to release the acid hydrolysis material in the cooking system to the normal pressure environment to obtain the gas explosion steam and the hydrolyzed material.
Separating acid sludge in the second waste acid liquid through grid separation, then settling to obtain a second waste acid clear liquid, and conveying the acid sludge to a mixing conveyor for mixed acid treatment. And storing the first waste acid clear liquid and the second waste acid clear liquid into a waste acid clear liquid storage tank, and circulating to a rinsing machine to wash the cellulose raw material crushed material during acid washing.
Enzymolysis: and conveying the hydrolyzed material to a mixing auger, wherein the structure of the mixing auger is shown in figure 2. The material mixing auger comprises a motor 1, a reduction gearbox 2, a feeding port 3, an enzyme adding port 4, a paddle 5, a main shaft 6 and a discharge port 7, wherein hydrolyzed materials enter the material mixing auger through the feed port 3, cellulase enters the material mixing auger from the enzyme adding port 4, the cellulase and the hydrolyzed materials are fully mixed under the pushing and stirring action of the paddle 5 and subjected to pre-enzymolysis, so that the viscosity of the hydrolyzed materials is gradually reduced along the advancing direction of the materials, and then the materials subjected to pre-enzymolysis are discharged from the discharge port 7.
Conveying the material subjected to pre-enzymolysis to two serially-connected enzymolysis tanks of a first enzymolysis device for carrying out first enzymolysis for 8 hours, wherein the enzymolysis temperature is 50 ℃; then, second enzymolysis is carried out in 10 serially connected enzymolysis tanks in a second enzymolysis unit, the total enzymolysis time is 36h, and the enzymolysis temperature is 50 ℃. Wherein the dosage of the cellulase is 12 enzyme activity units based on the dry weight of each gram of the raw material containing cellulose.
1# fermentation: adding the strain No.1 into an expansion tank for primary and secondary expansion culture, and then obtaining the seed solution No. 1. The first-stage propagation and the second-stage propagation have the same propagation conditions: pH of 4.5 and temperature of 35 deg.C, expanding cultureThe time is 16h, and the inoculation amount is 105cfu/mL culture medium, the culture medium is the liquefied liquid obtained in the step (1), and the pH is adjusted to 4.5 by using ammonia water.
And (3) conveying the 1# enzymolysis liquid and the 1# seed liquid to a fermentation tank for fermentation to obtain fermentation mash, and separating thalli to obtain 1# mature mash. Wherein the inoculation amount is 10 per 1 g of the above enzymolysis solution5cfu. The fermentation conditions include: fermenting at 35 deg.C and pH 4.5 for 40 hr, and filtering to obtain No.1 mature mash.
1# crude distillation: and carrying out rough distillation on the No.1 mature mash in a No.1 rough distillation tower equipped with a No.1 rough distillation tower reboiler at 82 ℃ to obtain No.1 waste mash and No.1 rough distillation fraction. Fresh steam is used for providing a heat source for a reboiler of the 1# coarse distillation tower, and the 1# coarse distillation condensate is obtained after heat exchange and is conveyed to the acid mixing step to be used as at least part of acid water.
1# waste mash treatment: and (3) carrying out solid-liquid separation on the No.1 waste mash to obtain No.1 clear liquid and No.1 solid waste. Wherein, the 1# clear liquid is conveyed to a sewage treatment system, and the 1# solid waste is incinerated.
(3) Rectification
And (3) performing first rectification on the 2# crude distillation fraction obtained in the step (1) and the 1# crude distillation fraction obtained in the step (2) in a first rectifying tower provided with a first rectifying tower reboiler at 120 ℃, performing second rectification on the obtained secondary distillation fraction in a second rectifying tower provided with a second rectifying tower reboiler at 157 ℃, performing second dehydration by using a molecular sieve to obtain finished product wine gas, wherein the finished product wine gas is used for performing heat exchange with the mature mash, and the finished product wine gas after heat exchange is used for obtaining fuel ethanol.
Fresh steam is used for providing a heat source for a first rectifying tower reboiler and a second rectifying tower reboiler, rectified condensate obtained after heat exchange is conveyed to be mixed with acid for at least partially distributing acid water; the column bottom condensate obtained in the first rectification column is also fed to the acid-mixing step for at least partial distribution of the acid water.
In addition, CO is produced in the propagation and fermentation process performed in the # 1 fermentation step and the fermentation process performed in the # 2 fermentation step2Introduction of CO into2To CO2The tank was washed and then refluxed to 1# matured mash and 2# matured mash, respectively.
In the process of coproducing ethanol from starchy raw materials and cellulose raw materials, the usage amount of alpha-amylase is 0.5kg/t ethanol, the usage amount of cellulase is 0.5t/t ethanol, the total water consumption is 12.5t/t ethanol, and the total steam consumption is 8.9t/t ethanol.
Wherein, in the part of producing ethanol from starchy raw materials, the starchy raw materials (corn) are used in an amount of 3t every time 1t of ethanol is produced.
Example 2
This example illustrates the preparation of ethanol in the process of the invention
The operation was carried out according to the method described in example 1, except that the mixing auger was replaced with a conveying auger having only a conveying function.
In the process of coproducing ethanol from starchy raw materials and cellulose raw materials, the usage amount of cellulase reaching the same enzymolysis degree is 0.7t/t ethanol.
Wherein, the using amount of the starchy raw material, the using amount of the alpha-amylase, the total water consumption and the total steam consumption are basically the same as those of the embodiment 1 when 1t of ethanol is generated.
Example 3
This example illustrates the preparation of ethanol in the process of the invention
The operation was carried out as described in example 1, except that the gas explosion steam neutralization treatment was followed by wastewater treatment.
In the process of coproducing ethanol from starchy raw materials and cellulose raw materials, the total steam consumption is 9t/t ethanol.
Wherein the amount of starchy raw material, the amount of alpha-amylase, the amount of cellulase and the total water consumption are substantially the same as those in example 1 for every 1t of ethanol produced.
Comparative example 1
This comparative example illustrates the preparation of reference ethanol
The procedure was followed as described in example 1, except that no defibration was performed.
In this case, the amount of alpha-amylase used to achieve the same degree of liquefaction was 0.55kg/t ethanol compared to example 1.
In the process of coproducing ethanol from starchy raw materials and cellulose raw materials, the usage amount of alpha-amylase is 0.5kg/t ethanol, the usage amount of cellulase is 0.5t/t ethanol, the total water consumption is 15t/t ethanol, and the total steam consumption is 10.5t/t ethanol.
Wherein, in the part of producing ethanol from starchy raw material, the starchy raw material (corn) is used in an amount of 3.3t per 1t of ethanol produced.
According to the invention, the cellulose raw material and the starchy raw material are co-produced, the starchy raw material is subjected to fiber treatment, steam, waste acid and waste materials obtained in the production process are recovered, and the mixing auger is used for carrying out pre-enzymolysis, so that the consumption of corn, alpha-amylase and cellulose for producing 1t of ethanol can be obviously reduced, and the water consumption, the acid consumption and the steam consumption can be reduced.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of producing ethanol from a starchy material and a cellulosic material, the method comprising:
(1) sequentially crushing, mixing and separating fibers of the starchy raw material to obtain starchy raw material fibers and starch slurry;
(2) sequentially hydrolyzing, carrying out enzymolysis, fermenting 1# and carrying out 1# rough distillation on the starchy raw material fiber obtained in the step (1) and the cellulose raw material crushed material to obtain 1# rough distillation fraction;
(3) sequentially liquefying, fermenting and roughly distilling the starch slurry obtained in the step (1) to obtain roughly distilled fraction No. 2 and waste mash No. 2;
(4) and (3) rectifying the 1# crude distillation fraction obtained in the step (2) and the 2# crude distillation fraction obtained in the step (3) to obtain ethanol.
2. The method of claim 1, wherein in step (2), the method of hydrolyzing comprises:
1) acid washing is carried out on the crushed cellulose raw material to obtain a first waste acid solution and an acid washing material;
2) uniformly mixing the acid-washed material, the starchy raw material fiber and an acid solution to obtain a mixed acid material, and performing acid hydrolysis on the mixed acid material to obtain an acid-hydrolyzed material;
3) performing steam explosion on the acid hydrolysis material to obtain a hydrolyzed material and gas explosion steam;
preferably, the first waste acid liquid is subjected to solid-liquid separation to obtain a first waste acid clear liquid and ash;
preferably, before the acid hydrolysis of the mixed acid material, the method further comprises a first dehydration treatment of the mixed acid material to obtain a dehydrated material and a second waste acid solution;
preferably, performing solid-liquid separation on the second waste acid liquid to obtain a second waste acid clear liquid and acid sludge;
more preferably, the first spent acid liquor and/or the second spent acid liquor are recycled to the pickling step as at least part of the pickling acid and the acid sludge is returned to the mixed acid step.
3. The method of claim 2, wherein in step (2), the enzymatic hydrolysis method comprises: conveying the hydrolyzed material by a mixing auger, and carrying out enzymolysis to obtain an enzymolysis liquid;
preferably, the method further comprises: mixing the hydrolyzed material with cellulase in the mixing auger;
preferably, the mixing auger has paddles with a paddle structure.
4. The method of claim 3, wherein in the step (2), the method of # 1 fermentation comprises: inoculating the 1# strain into the enzymolysis liquid for fermentation to obtain 1# mature mash.
5. The process according to claim 2, wherein in step (2), the # 1 crude distillation is carried out in a # 1 crude distillation column, and the # 1 crude distillation column is provided with a # 1 crude distillation column reboiler;
preferably, the heat source of the No.1 coarse distillation tower reboiler is steam, at least part of the steam is from the gas explosion steam, and the steam exchanges heat in the No.1 coarse distillation tower reboiler to form No.1 coarse distillation condensate;
preferably, the method further comprises recycling the # 1 caide distillate to the acid hydrolysis step for use as at least a portion of the acid water.
6. The method of claim 1, wherein in step (3), the 2# fermentation method comprises: inoculating the 2# strain into the liquefied liquid obtained by liquefaction for fermentation to obtain 2# mature mash.
7. The process according to claim 2, wherein in step (3), the # 2 crude distillation is carried out in a # 2 crude distillation column, the # 2 crude distillation column being provided with a # 2 crude distillation column reboiler;
preferably, the heat source of the 2# coarse distillation tower reboiler is steam, at least part of the heat source is the gas explosion steam, and the steam exchanges heat in the 2# coarse distillation tower reboiler to form 2# coarse distillation condensate;
preferably, the method further comprises recycling the # 2 caide distillate to the acid hydrolysis step for use as at least a portion of the acid water.
8. The method of claim 1, wherein the method further comprises: carrying out solid-liquid separation on the No. 2 waste mash obtained in the step (3) to obtain waste mash clear liquid and waste mash wet cake;
preferably, evaporating and concentrating the waste mash clear liquid to obtain waste mash concentrated liquid and evaporation condensate, mixing the waste mash wet cake and the waste mash concentrated liquid, and drying the obtained mixture to obtain DDGS;
more preferably, the method further comprises: recycling at least part of the evaporation condensate to the acid mixing step of claim 2 to mix with the acid wash stock, the starchy raw fibers and the acid liquor uniformly, and/or
Recycling at least a portion of said evaporative condensate to said size mixing step for use as at least a portion of the size mixing water.
9. The method according to claim 2, wherein the rectification is carried out in a rectification column provided with a rectification column reboiler;
preferably, the heat source of the rectifying tower reboiler is fresh steam, and the fresh steam exchanges heat in the rectifying tower reboiler to form rectifying condensate;
preferably, the method further comprises recycling the rectified condensate to the acid hydrolysis step for use as at least a portion of the acid water;
preferably, the process further comprises recycling column bottoms condensate produced in the rectifying step to the acid hydrolysis step for use as at least a portion of the acid water.
10. The method of claim 2, wherein the method further comprises: recycling at least part of the gas explosion steam to the size mixing step in the step (1) to be used as at least part of a heat source of the size mixing step.
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