CN113832195A - Method for producing fuel ethanol by using grass straws - Google Patents

Method for producing fuel ethanol by using grass straws Download PDF

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CN113832195A
CN113832195A CN202010590789.6A CN202010590789A CN113832195A CN 113832195 A CN113832195 A CN 113832195A CN 202010590789 A CN202010590789 A CN 202010590789A CN 113832195 A CN113832195 A CN 113832195A
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ethanol
grass
straws
slurry
producing fuel
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毕衍金
牛彦生
宋明信
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Shandong Quanlin Group Co ltd
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Shandong Quanlin Group Co ltd
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/02Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06Ethanol, i.e. non-beverage
    • C12P7/08Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
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    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/02Monosaccharides
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/14Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2201/00Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

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Abstract

The invention discloses a method for producing fuel ethanol by utilizing grass straws, which comprises the following process flows: cooking, black liquor extraction, slurry enzymolysis and fermentation of enzymolysis liquid. The method provided by the invention effectively improves the efficiency of producing ethanol by straws, recycles waste materials in the production process to prepare fertilizer, and increases economic benefits while protecting the environment.

Description

Method for producing fuel ethanol by using grass straws
Technical Field
The invention relates to a method for producing ethanol by taking grass straws as a raw material.
Background
Energy and environmental issues have become a focus of increasing global attention, and with the exhaustion of fossil energy and the severity of greenhouse gas emissions, the development of clean renewable energy has become an urgent issue. The utilization of biomass energy has attracted attention.
Biomass is the most abundant renewable resource in the nature, and the total amount of carbon fixed in green plants by photosynthesis on the earth can reach 2 x 10 every year11Ton, biomass 1.7X 1011Ton. Chinese biomass resource is rich, wherein the annual total amount of crop straws is 7 multiplied by 108Ton, about 2X 10 of forest waste8Ton, and the total amount of cellulose biomass available per year can reach about 2 multiplied by 109And more than ton. Cellulosic biomass is composed mainly of cellulose, hemicellulose and woodThe lignin composition converts cellulose and hemicellulose into saccharides for fermentation to produce ethanol, and can be used in the aspects of fuel energy, industrial raw materials and the like.
In the prior art, polysaccharide in cellulose is usually converted into monosaccharide and fermented into ethanol by adopting modes such as enzymolysis or hydrolysis, but the problem of low polysaccharide conversion rate exists, and no effective solution is provided for waste materials generated in the whole process flow.
Chinese patent No. 200710009497.3 discloses a method for preparing fuel ethanol by using plant fiber, comprising: selecting plants rich in cellulose, xylan and araban as raw materials, and controlling the ratio of the sum of the contents of xylan and araban in the raw materials to the content of cellulose to be more than or equal to 0.5; mixing the above materials, steaming for 3-5 hr, spreading, and cooling to 50-60 deg.C; adding 4-8 units of cellulase per gram of raw material into the raw material, stirring for 1-2 hours to saccharify the raw material, and cooling to 28-32 ℃; adding yeast, stirring, sealing, and fermenting for 3-5 days to obtain mature fermented mash; and heating the fermented glutinous rice, and dehydrating the generated ethanol-steam mixed gas to obtain the fuel ethanol. Although this application provides a method for producing ethanol using plant fibers, it does not make full use of the waste materials in the production process.
Chinese patent application No. 200410096175.3 discloses a method for preparing ethanol from acid-out filtrate of pulping black liquor. Uniformly mixing acid precipitation filtrate obtained from pulping black liquor and wheat bran according to the weight ratio of 6-8:1, hydrolyzing at the temperature of 100-120 ℃ for 3-5 hours, standing, and separating supernatant and fiber residue; adjusting pH of the supernatant to 5-6, adding into a fermentation tank, adding fermentation enzyme under stirring at 40-50 deg.C for 45-55 hr to obtain fermentation liquid with ethanol content of 6-8%, and distilling the fermentation liquid to obtain ethanol product. The method provides a method for producing ethanol by using black liquor and waste residues of wheat bran in the papermaking process, but the conversion rate of treating polysaccharide to convert monosaccharide by adopting an acid hydrolysis mode is not enough to meet the requirement of industrial production.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for producing ethanol by taking grass straws as a raw material, which adopts an ammonium sulfite method for pretreatment and then carries out enzymolysis fermentation, thereby achieving the effects of improving the yield of the ethanol, protecting the environment and increasing the economic benefit.
The invention specifically adopts the following technical scheme:
a method for producing fuel ethanol by grass straws comprises the following steps:
1) adding ammonium sulfite into a grass straw raw material for pretreatment to obtain slurry;
2) extracting black liquor in the pulp to obtain pure pulp with the concentration of 10-13%;
3) performing enzymolysis on the slurry to obtain an enzymolysis product;
4) and fermenting the enzymolysis product to obtain the ethanol.
The invention adopts an enzymolysis method to degrade glucan which accounts for the main content in cellulose and xylan which accounts for the main content in hemicellulose, so that glucose and xylose are generated, good conditions are provided for the next fermentation, and the yield of ethanol can be improved.
The invention further comprises the following steps:
preparing grass straw raw materials, feeding the grass straw raw materials into a boiler, adding 15-28% ammonium sulfite solution according to a liquid-to-liquid ratio of 1: 4-8, introducing steam for heating, raising the temperature to 150 ℃ and 180 ℃, preserving the heat for 220 minutes, and steaming to obtain the slurry.
Then extracting the black liquor in the pulp to obtain pure pulp with the concentration of 10-13%.
The invention further comprises the following steps:
and carrying out enzymolysis on the clean slurry, and adjusting the pH of the slurry to 4.0-5.5. Adding an enzyme preparation with the concentration of 5-8% and reacting at the temperature of 40-55 ℃ for 48-72 hours. The enzymolysis product is glucose converted from glucan and xylose converted from xylan, the conversion rate of glucan is 80-90%, and the conversion rate of xylan is 75-90%.
The invention further comprises the following steps:
the fermentation is to add yeast with the concentration of 7.0-10.0 mg/g into the enzymolysis product to react for 36-48 hours at the temperature of 28-40 ℃ to obtain the ethanol.
The invention further comprises the following steps:
the enzyme preparation is at least one of cohn CT-3, Novoxin CTec2, and oxalic acid green enzyme.
The yeast is at least one of Angel high temperature resistant yeast and Senel high temperature resistant yeast.
The invention has the beneficial effects that:
(1) the straw is prepared and then is steamed and boiled by an ammonium sulfite method to prepare the slurry for producing the ethanol, so that residual biomass after agricultural production is effectively utilized, and the influence of straw burning on the environment is prevented;
(2) the enzymolysis method is adopted to decompose cellulose and hemicellulose in the straws, so that the saccharification rate is greatly improved, and the polysaccharide conversion is more thorough.
Detailed Description
The following are specific embodiments of the present invention, which are intended to further illustrate the invention and not to limit it.
Example 1:
the method adopts cotton stalks as raw materials to prepare ethanol and simultaneously identifies the components of biomass contained in the cotton stalks, and the specific method is as follows:
(1) a plurality of cotton stalks are selected and put into a screw extruder for dehydration, and then the biomass components contained in the cotton stalks are detected, and the results are shown in the following table 1:
TABLE 1 ingredient determination results of cotton stalks after being prepared by a screw extruder
Figure BDA0002556175520000041
As can be seen from Table 1, the cotton stalks contained 46.72% total sugars, and the increased conversion rate produced more ethanol per unit weight of cotton stalk.
(2) Adding an ammonium sulfite solution with the concentration of 22-28% into a cotton stalk prepared by a screw extruder, mixing according to the material-liquid ratio of 1:6, heating and cooking at 165-170 ℃, and preserving heat for 180 min; after the cooking is finished, filling the pulp into a disc grinder for pulping to obtain pulp; the components of the slurry were measured and the results are shown in table 2 below:
TABLE 2 determination of the composition of the cooked and ground cotton stalks
Figure BDA0002556175520000042
As can be seen from Table 2, the carbohydrates were further liberated by cooking and refining, while the lignin content of the pulp was reduced.
(3) Washing and separating the pulp to obtain pulp containing fibers and black liquor;
(4) adding acetic acid-sodium acetate buffer solution into the slurry containing the fibers to adjust the pH value to 4.7-4.8, adding 6% of Novoxin CTec2 enzyme preparation, and reacting at the temperature of 49-50 ℃ for 72 hours to obtain an enzymolysis product; the results of the tests for obtaining enzymatic products are shown in table 3 below:
TABLE 3 fiber-containing slurries enzymolysis parameters and test results
Figure BDA0002556175520000051
As can be seen from Table 3, the conversion of the haplotypes of glucan and xylan into monosaccharides, which is a key step in the fermentative production of ethanol, was obtained by the aforementioned pretreatment.
(5) Adding Angel high-temperature-resistant yeast with the concentration of 8.0mg/g into an enzymolysis product, and reacting at the temperature of 30 ℃ for 36 hours to obtain ethanol and fermentation residues; the results obtained from the fermentation product testing are shown in table 4 below:
TABLE 4 fermentation parameters and test results
Figure BDA0002556175520000052
As can be seen from Table 4, the conversion rate of the ethanol production method of the invention for converting glucan in straw cellulose into ethanol can reach 92.4%, and the ethanol production method can be well applied to industrial production.
In the embodiment, the cotton stalks are pretreated by ammonium sulfite and ground into pulp, 6 percent of Novitin CTec2 is added for enzymolysis, the conversion rates of glucan and xylan reach more than 80 percent, glucose and xylose are fermented together, the conversion rate of alcohol to sugar reaches 92 percent, and 3.88 tons of cotton stalk raw materials can be consumed by calculating to produce one ton of ethanol; only glucose is fermented singly, the conversion rate of alcohol to sugar reaches 98%, and 4.25 tons of cotton stalk raw materials can be consumed for producing one ton of ethanol.
Example 2
The method adopts corn straws as raw materials, prepares the ethanol by applying the method of the invention, and identifies the components of biomass contained in the corn straws, and the specific method is as follows:
(1) selecting a plurality of corn straws, placing the corn straws into a screw extruder for dehydration, and detecting biomass components contained in the straws, wherein the results are shown in table 5:
TABLE 5 ingredient determination results of corn stover after feed preparation by screw extruder
Figure BDA0002556175520000061
As can be seen from Table 5, the corn stover contained 45.9% total sugar, and increased conversion resulted in more ethanol being produced per unit weight of corn stover.
(2) Adding a 19% ammonium sulfite solution into the corn straws prepared by a screw extruder, mixing according to the material-liquid ratio of 1:6, heating and cooking at 165 ℃ and preserving heat for 120 min; after the cooking is finished, filling the pulp into a disc grinder for pulping to obtain pulp; the components of the slurry were measured, and the results are shown in table 6:
TABLE 6 ingredient determination results of corn stover after cooking and grinding
Figure BDA0002556175520000062
As can be seen from Table 6, the carbohydrates were further liberated by cooking and refining, while the lignin content of the pulp was reduced.
(3) Washing and separating the pulp to obtain pulp containing fibers and black liquor;
(4) adding sulfuric acid into the slurry containing fibers to adjust the pH value to 4.7-4.8, adding 5% of Novixin CTec2 enzyme preparation, and reacting at the temperature of 49-50 ℃ for 72 hours to obtain an enzymolysis product; the results of the tests for obtaining enzymatic products are shown in table 7:
TABLE 7 fiber-containing slurries enzymolysis parameters and test results
Figure BDA0002556175520000071
As can be seen from Table 7, the conversion of the haplotypes of glucan and xylan into monosaccharides, which is a key step in the fermentative production of ethanol, was obtained by the aforementioned pretreatment.
(5) Adding Angel high-temperature-resistant yeast with the concentration of 8.0mg/g into an enzymolysis product, and reacting for 48 hours at the temperature of 35 ℃ to obtain ethanol and fermentation residues; the results obtained from the fermentation product testing are shown in Table 8:
TABLE 8 fermentation parameters and test results
Figure BDA0002556175520000072
Figure BDA0002556175520000081
As can be seen from Table 8, the conversion rate of glucan in the straw cellulose into ethanol by the ethanol production method of the present invention can reach 84.1%, and the conversion rate of monosaccharide after conversion into ethanol is 99.3%, so that the ethanol production method can be well applied to industrial production.
In the embodiment, the corn straws are pretreated by ammonium sulfite and ground into slurry, 5% of novacin CTec2 is added for enzymolysis, the conversion rates of glucan and xylan reach more than 80%, glucose and xylose are fermented together, the conversion rate of alcohol to monosaccharide reaches 84.1%, the conversion rate of alcohol to monosaccharide reaches 99.3%, and the result shows that the saccharides after enzymolysis are completely fermented.

Claims (7)

1. A method for producing fuel ethanol by grass straws is characterized by comprising the following steps:
1) adding ammonium sulfite into a grass straw raw material for pretreatment to obtain slurry;
2) extracting black liquor in the pulp to obtain pure pulp with the concentration of 10-13%;
3) performing enzymolysis on the slurry to obtain an enzymolysis product;
4) and fermenting the enzymolysis product to obtain the ethanol.
2. The method for producing fuel ethanol by using the grass straws as claimed in claim 1, wherein the pretreatment comprises the following steps:
preparing grass straw raw materials, feeding the grass straw raw materials into a boiler, adding 15-28% ammonium sulfite solution according to a liquid-to-liquid ratio of 1: 4-8, introducing steam for heating, raising the temperature to 150 ℃ and 180 ℃, preserving the heat for 220 minutes, and steaming to obtain the slurry.
3. The method of claim 1, wherein the pH of the slurry is adjusted to 4.0-5.5, and the slurry is reacted at 40-55 ℃ for 48-72 hours after an enzyme preparation with a concentration of 5-8% is added.
4. The method for producing fuel ethanol from grass straws as claimed in claim 1 or 3, wherein the enzymatic hydrolysis product is glucose converted from glucan and xylose converted from xylan, the conversion rate of glucan is 80-90%, and the conversion rate of xylan is 75-90%.
5. The method for producing fuel ethanol by using grass straws as claimed in claim 1, wherein the ethanol is obtained by adding yeast with the concentration of 7.0-10.0 mg/g into the enzymolysis product and reacting at 28-40 ℃ for 36-48 hours.
6. The method for producing fuel ethanol by using grass straws as claimed in claim 1 or 3, wherein the enzyme preparation is at least one of coyohn CT-3, Nuoweixin CTec2 and oxalic acid green enzyme.
7. The method for producing fuel ethanol by using the grass straws as claimed in claim 1 or 5, wherein the yeast is at least one of Angel high temperature resistant yeast and Angel high temperature resistant yeast.
CN202010590789.6A 2020-06-24 2020-06-24 Method for producing fuel ethanol by using grass straws Pending CN113832195A (en)

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