CN110317838B - Method for preparing ethanol by adopting cassava alcohol residues - Google Patents
Method for preparing ethanol by adopting cassava alcohol residues Download PDFInfo
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- CN110317838B CN110317838B CN201810265075.0A CN201810265075A CN110317838B CN 110317838 B CN110317838 B CN 110317838B CN 201810265075 A CN201810265075 A CN 201810265075A CN 110317838 B CN110317838 B CN 110317838B
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 238000000034 method Methods 0.000 title claims abstract description 109
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 title claims abstract description 52
- 125000003158 alcohol group Chemical group 0.000 title claims abstract description 45
- 241000658379 Manihot esculenta subsp. esculenta Species 0.000 title 1
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 63
- 230000007062 hydrolysis Effects 0.000 claims abstract description 62
- 239000007790 solid phase Substances 0.000 claims abstract description 57
- 238000000855 fermentation Methods 0.000 claims abstract description 53
- 230000004151 fermentation Effects 0.000 claims abstract description 53
- 240000003183 Manihot esculenta Species 0.000 claims abstract description 51
- 229920005610 lignin Polymers 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 108010059892 Cellulase Proteins 0.000 claims description 17
- 229940106157 cellulase Drugs 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 11
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 11
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 11
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000001502 supplementing effect Effects 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 239000005696 Diammonium phosphate Substances 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- 239000000463 material Substances 0.000 description 24
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 239000011343 solid material Substances 0.000 description 7
- 238000002791 soaking Methods 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000002478 diastatic effect Effects 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
-
- 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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Abstract
The invention provides a method for preparing ethanol by adopting cassava alcohol residues. The method comprises the following steps: carrying out a first hydrolysis process on the cassava alcohol residues under the catalysis of alkali to obtain a first solid-phase product; under the catalysis of acid, carrying out a second hydrolysis process on the first solid-phase product to obtain a second solid-phase product; and carrying out saccharification and fermentation on the second solid-phase product to obtain the ethanol. Under the action of alkali, the cassava alcohol residues can be hydrolyzed by the first hydrolysis process, so that lignin is dissolved in water, and meanwhile, some phenolic substances can be generated, and the adsorption of the phenolic substances on the first solid-phase product can inhibit the subsequent alcohol fermentation process. In the second hydrolysis process, under the action of acid, the phenolic substance reacts with the acid and then is removed from the first solid-phase product, so as to obtain a second solid-phase product. The second hydrolysis process can remove the above phenolic substances inhibiting the fermentation process, and thus the second hydrolysis process is beneficial to improving the yield of ethanol in the fermentation process.
Description
Technical Field
The invention relates to the field of biochemical engineering, and particularly relates to a method for preparing ethanol by using cassava alcohol residues.
Background
Since the popularization of ethanol gasoline for vehicles since 2001, several fuel ethanol companies such as Jilin fuel ethanol, Henan Tianguan, Anhufeng Yuan and the like which take corn and wheat as raw materials and Zhongliang North sea fuel ethanol limited company which takes cassava as a raw material have been established in China. At present, grains are used for producing fuel ethanol, and the grains are struggled with people, the national plain regulation prohibits the continuous development of grain ethanol projects, and no relevant regulation exists in the aspect of producing fuel ethanol by cassava, so that the production of fuel ethanol by utilizing cassava becomes the future development trend. However, in the process of producing fuel ethanol by utilizing cassava, how to treat the generated cassava alcohol residues causes great burden to enterprises.
The literature reports that about 0.33 tons of cassava alcohol residues are produced per 1 ton of cassava ethanol produced, about 10 million tons of cassava alcohol residues are produced per year in a cassava fuel ethanol plant producing 30 million tons of cassava ethanol annually. At present, the cassava alcohol residues are mainly incinerated or buried, which not only wastes resources greatly, but also pollutes the environment seriously.
The cassava alcohol residues contain higher cellulose and hemicellulose, and if the cassava alcohol residues are pretreated by a proper pretreatment method, the cellulose in the cassava alcohol residues is converted into ethanol, so that the environmental pollution is reduced, and a feasible way is provided for recycling the cassava alcohol residues. And the existing method for adopting cassava alcohol residues has the problem of low ethanol yield.
Disclosure of Invention
The invention mainly aims to provide a method for preparing ethanol by adopting cassava alcohol residues, which solves the problem of low ethanol yield of the existing method for preparing ethanol by adopting cassava alcohol residues.
In order to achieve the above objects, there is provided according to the present invention a method for preparing ethanol using cassava alcohol residues, the method comprising: carrying out a first hydrolysis process on the cassava alcohol residues under the catalysis of alkali to obtain a first solid-phase product; under the catalysis of acid, carrying out a second hydrolysis process on the first solid-phase product to obtain a second solid-phase product; and carrying out saccharification and fermentation on the second solid-phase product to obtain the ethanol.
Further, the method also comprises the step of heating the reaction system of the first hydrolysis process in the first hydrolysis process; preferably, the temperature of the first hydrolysis process is 150-220 ℃, and the heating time is 1-2 h.
Further, the alkali is a mixed solution of 30wt% of hydrogen peroxide and 5-15 wt% of ammonia water, and the volume of the hydrogen peroxide is 10-20% of the volume of the ammonia water.
Further, the method further comprises the step of heating the reaction system of the second hydrolysis process in the second hydrolysis process; preferably, the heating temperature of the second hydrolysis process is 160-210 ℃, and the heating time is 40-75 min.
Further, the acid is a sulfuric acid aqueous solution with the concentration of 3-5 wt%.
Further, before the saccharification and fermentation process, the method further comprises the following steps: washing the second solid-phase product with water to neutrality, and then carrying out alcohol washing treatment by adopting an ethanol water solution; and recovering ethanol in a flash evaporation mode after alcohol washing treatment to obtain a second solid-phase product.
Furthermore, the volume fraction of ethanol in the ethanol water solution is 10-20%, the temperature is 80-100 ℃, and the time of the alcohol washing treatment process is 30-60 min.
Further, the saccharification and fermentation comprises a process of fermenting the mixture of the second solid phase product, cellulase, inorganic salt and yeast.
Furthermore, the addition amount of the cellulase is 15-25 FPU/g relative to the total amount of a reaction system of saccharification and fermentation.
Further, the inorganic salt is selected from urea and diammonium phosphate; preferably, the dosage of the urea is 2-4 g/L; preferably, the dosage of the diammonium hydrogen phosphate is 1-2 g/L.
Further, the method further comprises the step of supplementing the second hydrolysate during the saccharification and fermentation process; preferably, the times of the processes of supplementing the second solid phase product are 2-4 times, and the time interval between two adjacent supplementing processes is 24 hours; preferably, after the second solid-phase product is supplemented, the concentration of the second solid-phase product is 200-260 g/L.
Further, the dry content of lignin in the second solid-phase product is less than 10wt%, and the moisture content is 5-20 wt%; preferably, the grain size of the cassava alcohol residues is less than 0.9 mm.
By applying the technical scheme of the invention, the cassava alcohol residues can be hydrolyzed by performing the first hydrolysis process under the action of alkali, so that the lignin is dissolved in water. In the second hydrolysis process, substances which are generated by the first hydrolysis and inhibit the alcoholic fermentation are removed by the reaction with acid under the action of acid, so that the inhibition of lignin on the fermentation process can be further reduced, and the content of ethanol can be greatly improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing method for preparing ethanol by using cassava alcohol residues has the problem of low ethanol yield. In order to solve the technical problems, the application provides a method for preparing ethanol by using cassava alcohol residues, which comprises the steps of carrying out a first hydrolysis process on the cassava alcohol residues under the catalysis of alkali to obtain a first solid-phase product; under the catalysis of acid, carrying out a second hydrolysis process on the first solid-phase product to obtain a second solid-phase product; and carrying out saccharification and fermentation on the second solid-phase product to obtain the ethanol.
Due to the large amount of lignin contained in the cassava alcohol residues, the presence of lignin can affect the yield of ethanol in the fermentation process. Under the action of alkali, the cassava alcohol residues can be hydrolyzed by the first hydrolysis process, so that lignin is dissolved in water, and meanwhile, some phenolic substances can be generated, and the subsequent alcohol fermentation process can be inhibited by adsorbing the phenolic substances on the first solid-phase product. In the second hydrolysis process, under the action of acid, the phenolic substance reacts with the acid and then is removed from the first solid-phase product, so as to obtain a second solid-phase product. The second hydrolysis process can remove the above phenolic substances inhibiting the fermentation process, and thus the second hydrolysis process is beneficial to improving the yield of ethanol in the fermentation process.
Meanwhile, in order to prove the superiority of the treatment method in the present application, the inventors conducted intensive studies: firstly, carrying out acid treatment on the cassava alcohol residues, and then carrying out subsequent alkali treatment and fermentation processes. The ethanol prepared by the process for preparing the ethanol by the method has lower yield. The reason for this is that in the acid treatment process, the 5 th position of the lignin G unit can be used as a reaction site to perform condensation reaction with other lignin structural units, so as to generate condensed lignin, and the generation of the condensed lignin makes lignin removal difficult, thereby affecting the process of preparing ethanol by fermentation.
If the cassava alcohol residues are subjected to alkali treatment, most of lignin can be removed through hydrolysis, and a first solid-phase product is obtained after first solid-liquid separation. When the first solid phase product is subjected to a second hydrolysis process in a subsequent acidic environment, phenolic substances inhibiting the alcoholic fermentation are removed from reacting with acid, so that the inhibition of the fermentation can be reduced. The second hydrolysis process is thus advantageously carried out to increase the ethanol content obtained during the fermentation. Therefore, for the cassava alcohol residues which contain more lignin, the acid treatment effect is better after the alkali treatment, and the lignin is easier to remove in the alkali treatment process, so that the hydrolysis of cellulase is facilitated, and the content of ethanol is greatly improved.
Specifically, the method comprises the following steps: carrying out a first hydrolysis process on the cassava alcohol residues under the catalysis of alkali, and then carrying out a first solid-liquid separation process to obtain first solid residues (first solid-phase products) and filtrate; under the catalysis of acid, the first solid slag is subjected to a second hydrolysis process, and then a second solid-liquid separation process is carried out to obtain second solid slag (a second solid-phase product); and carrying out saccharification and fermentation on the second solid residue to obtain the ethanol.
The preparation method is beneficial to improving the removal rate of lignin and simultaneously can improve the yield of ethanol. In a preferred embodiment, the method further comprises the step of heating the reaction system of the first hydrolysis reaction during the first hydrolysis.
Under the action of alkali catalysis, the cassava alcohol residues can be subjected to preliminary hydrolysis. In the first hydrolysis process, the first hydrolysate system is heated, so that lignin in the solid reactants can be further hydrolyzed, the removal rate of the lignin is improved, and the yield of the ethanol is improved.
Preferably, the temperature of the first hydrolysis process is 150-220 ℃, and the heating time is 1-2 h. The heating time of the temperature of the first hydrolysis process includes, but is not limited to, the above range, and it is preferable to further increase the removal rate of lignin by limiting it to the above range.
Preferably, in the first hydrolysis process, the alkali is a mixed solution of 30wt% of hydrogen peroxide and 5-15 wt% of ammonia water, and the volume of the hydrogen peroxide is 10-20% of the volume of the ammonia water.
In a preferred embodiment, the above method further comprises a step of heating the reaction system of the second hydrolysis process in the second hydrolysis process. In the second hydrolysis process, the second hydrolysate system is heated, so that the reaction degree of phenols and acid generated in the first hydrolysis process can be accelerated, the removal rate of the phenols is improved, and the yield of ethanol in the saccharification and fermentation process is further improved.
Preferably, the heating temperature of the second hydrolysis process is 160-210 ℃, and the heating time is 40-75 min. The heating time of the temperature of the second hydrolysis process includes, but is not limited to, the above range, and it is preferable to limit it to the above range to further improve the removal rate of the phenolic substances in the second hydrolysis process.
Preferably, in the second hydrolysis process, the acid is a sulfuric acid aqueous solution with the concentration of 3-5 wt%.
In the saccharification and fermentation process, nutrients required by fermentation strains are required to be added. Preferably, the saccharification and fermentation comprises a process of fermenting a mixture of the second solid phase product, cellulase, inorganic salt and yeast.
In a preferred embodiment, the method further comprises, prior to performing the saccharification fermentation process: washing the second solid-phase product with water to neutrality, and then carrying out alcohol washing treatment by adopting an ethanol water solution; and recovering ethanol in a flash evaporation mode after alcohol washing treatment to obtain a second solid-phase product. By adopting the operation process, the lignin on the surface of the solid-phase product obtained by the second hydrolysis process can be further reduced, so that the content of the lignin can be further reduced, and the yield of the ethanol in the saccharification and fermentation process can be improved.
More preferably, the volume fraction of ethanol in the ethanol water solution is 10-20%, the temperature is 80-100 ℃, and the time of the alcohol washing treatment process is 30-60 min.
In a preferred embodiment, the cellulase is added in an amount of 15 to 25FPU/g relative to the total amount of the reaction system for the saccharification and fermentation. The addition of cellulase can accelerate the hydrolysis rate of cellulose. The addition amount of the cellulase includes, but is not limited to, the above range, and the limitation of the addition amount to the above range is beneficial to further improve the hydrolysis rate of cellulose into small molecular saccharides in the fermentation process, thereby improving the yield of ethanol.
In the process of saccharification and fermentation, inorganic salt is required to be added as a necessary nutrient substance for the fermentation strain. In a preferred embodiment, the inorganic salts include, but are not limited to, urea and diammonium phosphate. Preferably, the dosage of the urea is 2-4 g/L; preferably, the dosage of the diammonium hydrogen phosphate is 1-2 g/L.
In order to increase the yield of ethanol during the saccharification and fermentation process, the method preferably further comprises the step of supplementing the second solid phase product during the saccharification and fermentation process.
Preferably, the times of supplementing the second solid-phase product are 2-4 times, and the time interval between two adjacent supplementing processes is 24 hours;
preferably, after the second solid-phase product is supplemented, the concentration of the second solid-phase product is 200-260 g/L. The concentration of the second solid phase product in the saccharification and fermentation process is limited in the range, which is beneficial to improving the fermentation efficiency.
Preferably, the dry content of the lignin in the second solid-phase product is less than 10wt%, and the moisture content is 5-20 wt%; preferably, the grain size of the cassava alcohol residues is less than 0.9 mm.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
In the embodiment of the application, the dry basis content of lignin in the cassava alcohol residues is 20-23 wt%, and the water content is 5-10 wt%.
Example 1
And (3) mixing dilute ammonia water and hydrogen peroxide, and adding the mixture into a 1L high-pressure reaction kettle, wherein the weight percentage of the dilute ammonia water is 500mL of 10wt% ammonia water, and the volume of the hydrogen peroxide (30 wt%) is 50mL, so as to obtain an alkali liquor (pretreatment solvent). Adding 60g of cassava alcohol residues into a high-pressure reaction kettle, sealing, and soaking the cassava alcohol residues in a pretreatment solvent for a first hydrolysis process, wherein the soaking time is 3 hours. After soaking, starting a temperature raising program, and treating for 1h at 170 ℃. And after the treatment is finished, reducing the temperature and the pressure, after the pressure is reduced to normal pressure, filtering the treated cassava alcohol residues, and filtering to obtain filter residues (first solid-phase products).
And (3) putting the filter residue into a high-pressure reaction kettle, and adding 300mL of dilute sulfuric acid solution with the weight percentage of 3% to perform a second hydrolysis process, wherein the temperature of the second hydrolysis process is 150 ℃, and the treatment time is 50 min. And after the treatment is finished, discharging the material after the pressure is reduced to normal pressure, washing the material to be neutral, filtering the material, and filtering the material to obtain a solid material (a second solid-phase product). Adding water into the solid material until the dry matter is 10wt%, and using the solid material as a base material for fermentation.
Adding urea and diammonium hydrogen phosphate (the addition amounts are 2g/L and 1g/L respectively) into the base material, sterilizing at 121 deg.C for 30min, and cooling to room temperature after sterilization. Adding cellulase and activated Saccharomyces cerevisiae into the sterilized materials, performing diastatic fermentation at 35 deg.C, wherein the addition amount of cellulase is 15FPU/g substrate, and adding activated Saccharomyces cerevisiae to make the amount of Saccharomyces cerevisiae in the fermentation broth reach 108cfu/mL. Feeding after fermenting for 24h, wherein the feeding is a substrate material for fermentation. The feed was fed 2 times with an interval of 24 h. After the material is supplemented, the substrate concentration of the total material is 200g/L, and after the material is fermented for 96 hours, the concentration of ethanol can reach 50 g/L.
Example 2
And (3) mixing dilute ammonia water and hydrogen peroxide, and adding the mixture into a 1L high-pressure reaction kettle, wherein the weight percentage of the dilute ammonia water is 500mL of 10wt% ammonia water, and the volume of the added hydrogen peroxide (30 wt%) is 100mL, so as to obtain an alkali liquor (pretreatment solvent). Adding 60g of cassava alcohol residues into a high-pressure reaction kettle, sealing, and soaking the cassava alcohol residues in a pretreatment solvent for a first hydrolysis process, wherein the soaking time is 4 hours. After soaking, starting a temperature raising program, and treating for 1h at 190 ℃. And after the treatment is finished, reducing the temperature and the pressure, after the pressure is reduced to normal pressure, filtering the treated cassava alcohol residues, and filtering to obtain filter residues (first solid-phase products).
And (3) putting the filter residue into a high-pressure reaction kettle, and adding 400mL of dilute sulfuric acid solution with the weight percentage of 4% to perform a second hydrolysis process, wherein the temperature of the second hydrolysis process is 170 ℃, and the treatment time is 60 min. And after the treatment is finished, discharging the material after the pressure is reduced to normal pressure, washing the material to be neutral, filtering the material, and filtering the material to obtain a solid material (a second solid-phase product). Adding water into the solid material until the dry matter is 10wt%, and using the solid material as a base material for fermentation.
Adding urea and diammonium hydrogen phosphate (the addition amounts are respectively 2g/L and 1g/L) into the base material, sterilizing at 121 deg.C for 30min, and cooling to room temperature after sterilization. Adding cellulase and activated Saccharomyces cerevisiae into the sterilized materials, performing diastatic fermentation at 35 deg.C, adding cellulase in an amount of 15FPU/g substrate, and adding activated Saccharomyces cerevisiae to make the amount of Saccharomyces cerevisiae in the fermentation liquid reach 108cfu/mL, and feeding after fermenting for 24h, wherein the feeding is a substrate material for fermentation, and the feeding is carried out for 2 times at an interval of 24 h. After feeding, the substrate concentration of the total material is 240g/L, the material is fermented for 120h, and the concentration of ethanol can reach 60 g/L.
Example 3
The differences from example 1 are: the first hydrolysis process is not heated, and the second hydrolysis process is not heated. The concentration of the ethanol can reach 21 g/L.
Example 4
The differences from example 1 are: the heating temperature in the first hydrolysis process is 250 ℃, and the heating time is 1 h. The concentration of the ethanol can reach 28 g/L.
Example 5
The differences from example 1 are: the heating temperature in the second hydrolysis process is 280 ℃, and the heating time is 1 h. The concentration of the ethanol can reach 30g/L
Example 6
The differences from example 1 are: the alkali solution is sodium hydroxide. The concentration of the ethanol can reach 24 g/L.
Example 7
The differences from example 1 are: the acid solution is 3-5 wt% of nitric acid. The concentration of the ethanol can reach 33 g/L.
Example 8
The differences from example 1 are: the cellulase was added in an amount of 10 FPU/g. The concentration of the ethanol can reach 37 g/L.
Example 9
The differences from example 1 are: the dosage of the urea is 8 g/L. The concentration of the ethanol can reach 43 g/L.
Example 10
The differences from example 1 are: the dosage of the diammonium hydrogen phosphate is 5 g/L. The concentration of the ethanol can reach 40 g/L.
Example 11
The differences from example 1 are: no feeding was performed. The concentration of the ethanol can reach 20 g/L.
Example 12
The differences from example 1 are: the concentration of the substrate in the saccharification and fermentation process is 300 g/L. The concentration of the ethanol can reach 42 g/L.
Example 13
The differences from example 1 are: the dry basis content of lignin in the cassava alcohol residues is 15wt%, and the water content is 20 wt%.
The concentration of the ethanol can reach 38 g/L.
Example 14
The differences from example 1 are: and washing the solid material obtained in the second hydrolysis process to be neutral by using deionized water, then performing alcohol washing by using an ethanol water solution with the volume fraction of ethanol being 15%, and finally recovering the ethanol in a flash evaporation manner to obtain a second solid-phase product. The concentration of the ethanol can reach 55 g/L.
Comparative example 1
Putting 20g of unprocessed cassava alcohol residues into a 300mL triangular flask, adding 100mL of water, adding urea and diammonium hydrogen phosphate (the addition amounts are 0.2g and 0.1g respectively), sterilizing at 121 ℃ for 30min, and cooling to room temperature after sterilization. Adding cellulase and activated Saccharomyces cerevisiae into the sterilized materials, performing diastatic fermentation at 35 deg.C, wherein the addition amount of cellulase is 15FPU/g substrate, and adding activated Saccharomyces cerevisiae 1mL to make the amount of yeast not less than 108cfu/mL. Feeding after fermenting for 24h, wherein the feeding is a substrate material for fermentation. The feed was fed 2 times with an interval of 24 h. After feeding, the substrate concentration of the total material is 200g/L, and the ethanol concentration in the fermented mash after 96h fermentation is 17 g/L.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
comparing examples 1 to 14 with comparative example 1, it can be seen that the method provided herein advantageously increases the yield of ethanol.
Comparing examples 1 and 3 to 5, it can be seen that limiting the temperatures of the first and second hydrolysis processes to the preferred ranges herein is advantageous for increasing the yield of ethanol.
Comparing examples 1, 6 and 7, it can be seen that the use of alkaline and acid solutions preferred in the present application is advantageous for increasing the yield of ethanol.
Comparing examples 1 and 8 to 10, it can be seen that limiting the amounts of cellulase, urea and diammonium phosphate to the preferred ranges herein facilitates improved ethanol production.
Comparing examples 1 and 11, it can be seen that the feeding process is beneficial to increase the yield of ethanol.
Comparing examples 1 and 12, it is found that limiting the concentration of the substrate during the saccharification and fermentation process to the preferred range of the present application is advantageous for increasing the yield of ethanol.
Comparing examples 1, 13, it is known that limiting the dry content and moisture content of lignin in cassava alcohol residues to the preferred ranges of the present application is advantageous for increasing the yield of ethanol.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A method for preparing ethanol by using cassava alcohol residues is characterized by comprising the following steps:
under the catalysis of alkali, carrying out a first hydrolysis process on the cassava alcohol residues to obtain a first solid-phase product;
carrying out a second hydrolysis process on the first solid-phase product under the catalysis of acid to obtain a second solid-phase product; washing the second solid-phase product with water to neutrality, and then carrying out alcohol washing treatment by adopting an ethanol water solution to obtain a second solid-phase product; and
carrying out saccharification and fermentation on the second solid-phase product to obtain ethanol;
the temperature of the first hydrolysis process is 170-190 ℃, and the heating time is 1-2 h;
the alkali is a mixed solution of 30wt% of hydrogen peroxide and 5-15 wt% of ammonia water; the volume of the hydrogen peroxide is 10-20% of that of the ammonia water;
the heating temperature of the second hydrolysis process is 160-210 ℃, and the heating time is 40-75 min;
the acid is a sulfuric acid aqueous solution with the concentration of 3-5 wt%;
the dry content of lignin in the second solid-phase product is less than 10wt%, and the moisture content is 5-20 wt%.
2. The method according to claim 1, wherein ethanol is recovered by flash evaporation after the alcohol washing treatment to obtain the second solid-phase product.
3. The method according to claim 2, wherein the volume fraction of ethanol in the ethanol aqueous solution is 10-20%, the temperature is 80-100 ℃, and the time of the ethanol washing treatment process is 30-60 min.
4. The method of claim 1, wherein the saccharification and fermentation comprises a process of fermenting a mixture of the second solid phase product, cellulase enzymes, inorganic salts, and yeast.
5. The method according to claim 4, wherein the cellulase is added in an amount of 15 to 25FPU/g relative to the total amount of the reaction system for the saccharification and fermentation.
6. The method according to claim 4, wherein the inorganic salt is selected from urea and diammonium phosphate.
7. The method according to claim 6, wherein the amount of urea is 2-4 g/L.
8. The method according to claim 6, wherein the amount of diammonium phosphate is 1-2 g/L.
9. The method of claim 1, further comprising the step of replenishing the second solid phase product during the saccharification and fermentation process.
10. The method according to claim 9, wherein the number of the processes for supplementing the second solid phase product is 2-4, and the time interval between two adjacent feeding processes is 24 h.
11. The method of claim 9 or 10, wherein the concentration of the second solid phase product after replenishing the second solid phase product is 200 to 260 g/L.
12. The method according to claim 1, wherein the cassava alcohol residues have a particle size of less than 0.9 mm.
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