CN110499341B - Method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws - Google Patents
Method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws Download PDFInfo
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
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- 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
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- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
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Abstract
The invention belongs to the technical field of plant straw utilization, and particularly relates to a method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws. The method for simultaneously producing the ethanol, the fulvic acid and the carbon dioxide by using the straws comprises the steps of preparing the straws, pretreating, carrying out enzymolysis, fermenting and distilling to obtain the ethanol and the carbon dioxide, wherein the method also comprises the steps of carrying out solid-liquid separation on a product obtained after the enzymolysis, a product obtained after the fermentation and/or a residue obtained after the distillation, preferably carrying out solid-liquid separation on the product obtained after the enzymolysis, and carrying out sulfonation reaction on the obtained solid phase to obtain the fulvic acid. The invention converts more than 70% of lignin in the residue into water-soluble lignosulphonate (fulvic acid) through a chemical reaction-sulfonation reaction.
Description
Technical Field
The invention belongs to the technical field of plant straw utilization, and particularly relates to a method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws.
Background
The crop straw fiber mainly comprises organic components such as cellulose, hemicellulose, lignin and the like. The lignin in the plant can be divided into acid soluble lignin and acid insoluble lignin, and the proportion of the acid soluble lignin to the acid insoluble lignin is not nearly the same in different types of straws in different regions (see table 1).
TABLE 1
Bioethanol is one of the best petroleum fuel substitutes, cellulosic plant biomass resources are rich, the total energy stored in plant biomass dry matter is 10 times of the current total energy consumption of human beings, the plant biomass dry matter can be regenerated again, and how to extract bioethanol from the plant biomass resources without pollution is a strategic subject of countries in the world.
The production of ethanol from cellulosic materials is currently recognized as one of the best routes for producing ethanol. However, in most cellulosic ethanol production processes, cellulose and hemicellulose are converted and utilized, and lignin is mainly combusted as fuel, so that the utilization value is low. Currently, the yield of straws in China is 8 hundred million tons, the yield of straws has the production potential of 1 hundred million tons of ethanol, and the quantity of the produced lignin waste residues is very large. However, up to now, more than 95% of lignin produced in the production of cellulosic ethanol is still burned out mainly as waste after concentration, which not only causes great waste of resources, but also pollutes the environment. Therefore, the potential value of the lignin residues generated in the cellulosic ethanol production process is developed to be of great strategic significance.
CN102504276A discloses a method for simultaneously preparing carbon dioxide, bioethanol, humic acid and fulvic acid without pollution to all cellulosic plant organisms. Comprises cleaning and cutting equipment, dissolving equipment, catalyzing equipment, humation equipment and ethanol, humic acid and fulvic acid separation equipment. Compared with the method for preparing carbon dioxide and bioethanol by using cellulose alone, humic acid and fulvic acid are extracted from coal alone, renewable resources are utilized by 100%, no waste is discharged, and the method belongs to the fields of low-carbon economy and circular economy.
However, CN102504276A only adopts a physical method, namely a solid-liquid separation method to obtain part of lignin (fulvic acid) in acid-soluble lignin, the yield is very low, and industrialization is difficult.
Study on Lignin sulfonation reaction in Lignin ethanol fermentation waste residue [ Zhang, li text, etc. [ J ] study on Lignin sulfonation reaction in Lignin ethanol fermentation waste residue []Jiangsu agricultureScience, 2013, 41 (11): 324-326 reports that a large amount of waste residues are generated in the process of producing cellulosic ethanol by using corn straws, wherein the waste residues contain a large amount of lignin. Taking the ethanol fermentation waste residue of the corn straws as a raw material and using Na 2 SO 3 The lignin is subjected to sulfonation process treatment, the influence of single factors such as sulfonation time, reaction temperature, pH value and catalyst dosage on the sulfonation degree is researched, and the optimum lignin sulfonation conditions are obtained through an orthogonal test as follows: taking 20g of cellulosic ethanol waste residue (the weight percentage is that the lignin content is 55 percent), mixing the cellulosic ethanol waste residue with 20mL of hot water, adding 10 percent (mass fraction) of sodium hydroxide solution to dissolve the lignin, filtering, adding anhydrous sodium sulfate and 0.055g of ferric chloride into the filtrate, adjusting the pH value of the solution to 10.5 by using sodium hydroxide or dilute sulfuric acid, controlling the volume of reaction liquid to be less than 150mL, transferring the solution into a 250mL three-neck flask, heating to 90 ℃ under the condition of continuous stirring, and reacting for 5 hours to obtain sodium lignosulfonate. In the research, in order to contribute to the sulfonation reaction, a catalyst, namely ferric chloride, is added in the sulfonation reaction to change the distribution of benzene rings on lignin and electron clouds on side chains of the benzene rings, so that the sulfonation reaction is facilitated, and a sodium hydroxide solution is added before the sulfonation reaction to dissolve the lignin, so that the types of reagents used in the sulfonation reaction process are more, and the operation is complicated.
The present invention has been made in view of this situation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws comprises the steps of preparing materials, pretreating, carrying out enzymolysis, fermenting and distilling the straws to obtain the ethanol and the carbon dioxide, and also comprises the steps of carrying out solid-liquid separation on a product obtained after the enzymolysis, a product obtained after the fermentation and/or a residue obtained after the distillation, preferably carrying out solid-liquid separation on the product obtained after the enzymolysis, and carrying out sulfonation reaction on the obtained solid phase to obtain the fulvic acid.
In the invention, the solid-liquid phase separation can be carried out after enzymolysis, liquid phase materials enter a fermentation unit, and solid phase materials are sulfonated; solid-liquid phase separation can also be carried out after fermentation, liquid phase materials enter a distillation unit, and solid phase materials are sulfonated; the solid-liquid phase separation can also be carried out after distillation, the liquid phase material enters a dehydration unit, and the solid phase material is sulfonated.
The inventor researches to discover that all acid-insoluble lignin and partial acid-soluble lignin are retained in residues after enzymolysis or fermentation or distillation, and more than 70% of lignin in the residues is converted into water-soluble lignosulphonate (fulvic acid) through a chemical reaction, namely a sulfonation reaction; CN102504276A is only a physical method- -part of lignin (fulvic acid) in acid-soluble lignin is obtained by solid-liquid separation, the yield is very low, and industrialization is difficult.
Specifically, the method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws provided by the invention comprises the following three schemes:
the first one is: a method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws comprises the steps of preparing materials, pretreating, carrying out enzymolysis, fermenting and distilling the straws to obtain ethanol and carbon dioxide, and also comprises the steps of carrying out solid-liquid separation on a product obtained after the enzymolysis, and carrying out sulfonation reaction on an obtained solid phase to obtain the fulvic acid.
The second method is as follows: a method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws comprises the steps of preparing the straws, pretreating, carrying out enzymolysis, fermenting and distilling to obtain the ethanol and the carbon dioxide, and also comprises the steps of carrying out solid-liquid separation on the fermented product, and carrying out sulfonation reaction on the obtained solid phase to obtain the fulvic acid.
The third is: a method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws comprises the steps of preparing the straws, pretreating, carrying out enzymolysis, fermenting and distilling to obtain the ethanol and the carbon dioxide, and also comprises the steps of carrying out solid-liquid separation on the distilled residues and carrying out sulfonation reaction on the obtained solid phase to obtain the fulvic acid.
More specifically, the invention provides three schemes of a method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws as follows:
a method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws comprises the following steps:
1) Preparing and pretreating straws to obtain a pretreated material;
2) Carrying out enzymolysis on the pretreated material to obtain an enzymolysis product;
3) Carrying out solid-liquid separation on the product after enzymolysis to obtain a solid phase and a liquid phase;
4) Fermenting the liquid phase to obtain carbon dioxide and a fermented product;
5) And (3) performing sulfonation reaction on the solid phase to obtain fulvic acid, and distilling and dehydrating the fermented product to obtain the commercial ethanol.
The process flow diagram is shown in figure 1.
Or the method for simultaneously producing the ethanol, the fulvic acid and the carbon dioxide by using the straws comprises the following steps:
1) Preparing and pretreating straws to obtain a pretreated material;
2) Carrying out enzymolysis on the pretreated material to obtain an enzymolysis product;
3) Fermenting the product after enzymolysis to obtain carbon dioxide and a fermented product;
4) Carrying out solid-liquid separation on the fermented product to obtain a solid phase and a liquid phase;
5) And (3) performing sulfonation reaction on the solid phase to obtain fulvic acid, and distilling and dehydrating the liquid phase to obtain the commercial ethanol.
The process flow diagram is shown in figure 2.
Or the method for simultaneously producing the ethanol, the fulvic acid and the carbon dioxide by using the straws comprises the following steps:
1) Preparing and pretreating straws to obtain a pretreated material;
2) Carrying out enzymolysis on the pretreated material to obtain an enzymolysis product;
3) Fermenting the product after enzymolysis to obtain carbon dioxide and a fermented product;
4) Distilling the fermented product to obtain a distilled residue;
5) Carrying out solid-liquid separation on the distilled residue to obtain a solid phase and a liquid phase;
6) And (3) carrying out sulfonation reaction on the solid phase to obtain fulvic acid, and dehydrating the liquid phase to obtain the commercial ethanol.
The process flow diagram is shown in FIG. 3.
In the invention, the above schemes can be combined with each other, namely, the product after enzymolysis and the product after fermentation can be subjected to solid-liquid separation at the same time, the product after fermentation and the residue after distillation can be subjected to solid-liquid separation at the same time, the product after enzymolysis and the residue after distillation can be subjected to solid-liquid separation at the same time, and the product after enzymolysis, the product after fermentation and the residue after distillation can be subjected to solid-liquid separation. Then the obtained solid phases are combined, and a sulfonating agent is added for sulfonation reaction.
In a preferred embodiment of the present invention, the product after enzymatic hydrolysis is preferably subjected to solid-liquid separation.
Further, the sulfonation reaction is as follows: adding a sulfonating agent into the solid phase, and reacting at the temperature of 155-180 ℃ in a liquid ratio of 1: reacting for 2-6 hours under the condition of 3-10; the reaction is preferably carried out at a temperature of 165 to 170 ℃ for 4 hours.
The research on the lignin sulfonation reaction in the lignocellulose ethanol fermentation waste residue obtains the best conditions of lignin sulfonation through an orthogonal test: taking 20g of cellulosic ethanol waste residue (the weight percentage is 55 percent of lignin content), mixing the cellulosic ethanol waste residue with 20mL of hot water, adding 10 percent (mass fraction) of sodium hydroxide solution to dissolve the lignin, filtering, adding anhydrous sodium sulfate and 0.055g of ferric chloride into the filtrate, adjusting the pH value of the solution to 10.5 by using sodium hydroxide or dilute sulfuric acid, controlling the volume of reaction liquid to be less than 150mL, transferring the reaction liquid into a 250mL three-neck flask, heating to 90 ℃ under the condition of continuous stirring, and reacting for 5 hours to obtain the sodium lignosulfonate. In the research, in order to facilitate the sulfonation reaction, a catalyst, namely ferric chloride, is added in the sulfonation reaction to change the distribution of benzene rings on lignin and electron clouds on side chains thereof, so as to facilitate the sulfonation reaction, and a sodium hydroxide solution is also added before the sulfonation reaction to dissolve the lignin.
In the invention, because the straws are pretreated and then subjected to enzymolysis, the degradation speed of cellulose is obviously improved, the yield of glucose is increased, and the straw is pretreated, so that the shell layer of lignin is damaged, the lignin is dissolved without adding a sodium hydroxide solution before adding a sulfonating agent for sulfonation reaction, and the catalyst iron chloride is not required to be added when adding the sulfonating agent for sulfonation reaction.
Further, the sulfonating agent is ammonium sulfite or sodium sulfite, preferably ammonium sulfite, and the dosage of the sulfonating agent is 20-40%, preferably 30% of the total amount of the solid phase. Here in mass percent.
In the sulfonation reaction of the present invention, the liquid ratio is controlled to be 1: 3-10.
Further, the pretreatment is steam explosion, acid method steam explosion, high-temperature steaming or traditional pulping.
The cellulosic material contains three main components, cellulose, hemicellulose and lignin, in approximate proportions of 4:3:3. the cellulose is a macromolecular compound consisting of a plurality of anhydroglucose chain links; hemicellulose is composed of polymers of pentoses (mainly xylose and arabinose), hexoses (mainly glucose and mannose), and many sugar acids; lignin is a complex amorphous polymer of phenylpropane. Hemicellulose is easy to degrade and can be hydrolyzed by acid method, alkali method and enzyme method to obtain monosaccharide and oligosaccharide. Cellulose exists mostly in a crystalline state, and the winding and wrapping of lignin form a strong barrier to the degradation of cellulose. In order to make reasonable use of the cellulosic material, the cellulose must first be converted to its constituent unit, glucose. Two major factors affecting the degradation of cellulose molecules are the crystalline structure of cellulose and the lignin wrapped around it, so that the destruction of the lignin protective layer and the alteration of the crystalline structure of cellulose will promote the degradation of cellulose. Pretreatment of cellulosic feedstocks prior to enzymatic degradation, direct microbial degradation, and acid-catalyzed hydrolysis has been shown to significantly increase the rate of degradation of cellulose and increase the yield of glucose.
Therefore, the pretreatment in the invention is steam explosion, acid method steam explosion, high-temperature steaming or traditional pulping.
Specifically, the steam explosion is to adopt steam, and the temperature is kept for 8 to 10 minutes under the pressure of 1 to 3 MPa;
the acid method steam explosion is to add 1 to 5 percent of sulfuric acid, the pressure is 1 to 3MPa, and the temperature is kept for 8 to 10 minutes;
the high-temperature steaming is to add water and preserve heat for 30 to 40 minutes at the temperature of between 170 and 180 ℃;
the traditional pulping is to add 5 to 15 percent of sodium hydroxide or ammonium sulfite or sodium sulfite, and to keep the temperature for 30 minutes at the temperature of between 140 and 170 ℃ to obtain the semi-chemical pulp with the potassium permanganate value of between 20 and 30K.
Here, the amount of the chemical solution added during the pretreatment means mass percentage with respect to the weight of the straw.
In the invention, after the straw raw material is prepared and pretreated, enzymolysis is carried out, so that the degradation speed of cellulose can be obviously improved, and the yield of glucose can be increased.
Further, the enzymolysis is to adjust the pH of the material to 4.5-5.5, and the material is added with an enzyme preparation and then reacts for 48-96 hours at the temperature of 40-55 ℃.
Wherein, the dosage of the enzyme preparation is 3-8%.
The dosage of the enzyme preparation is the mass percentage relative to the weight of the materials.
Further, the fermentation is to adjust the pH value of the liquid phase to 4.5-5.5, add yeast and ferment for 24-48 hours at the temperature of 35-45 ℃.
Wherein the using amount of the yeast is 0.5-3%.
The amount of yeast used herein means a mass percentage based on the weight of the liquid phase.
Further, the stock preparation is dry stock preparation.
In the present invention, the enzyme preparation used in the enzymolysis process is an enzyme preparation commonly used in the art, and can be selected by a person skilled in the art according to actual situations. Preferably, the enzyme preparation is at least one of cohn CT-3, novacin CTec2, oxalic acid green enzyme, SUKAGlucan beta-glucanase and SUKACell cellulase.
After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the inventor researches and discovers that all acid-insoluble lignin and part of acid-soluble lignin are reserved in the residue after enzymolysis, fermentation or distillation, and more than 70% of lignin in the residue is converted into water-soluble lignosulphonate (fulvic acid) through a chemical reaction, namely a sulfonation reaction.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic of the process flow of the present invention wherein solid-liquid separation is after enzymatic hydrolysis;
FIG. 2 is a schematic of the process flow of the present invention wherein the solid-liquid separation is after fermentation;
FIG. 3 is a schematic of the process scheme of the present invention wherein the solid-liquid separation is after distillation.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
1) Preparing and pretreating 10kg of rice straws to obtain a pretreated material; the pretreatment is steam explosion, namely steam is adopted, and the temperature is kept for 8 to 10 minutes under the pressure of 1 to 3 MPa;
2) Adjusting the pH value of the pretreated material to 4.5, adding 3% of enzyme preparation, and reacting at 40 ℃ for 48 hours to obtain a product after enzymolysis;
3) Carrying out solid-liquid separation on the product after enzymolysis to obtain a solid phase and a liquid phase;
4) Fermenting the liquid phase to obtain ethanol and carbon dioxide; and (2) carrying out sulfonation reaction on the solid phase to obtain fulvic acid, wherein the sulfonation reaction is to add ammonium sulfite into the solid phase, the dosage of the ammonium sulfite is 30% of the total amount of the solid phase, and water is added to ensure that the liquid ratio of the ammonium sulfite to the solid phase is 1:6, reacting for 4 hours at the temperature of 165 ℃.
Example 2
1) Preparing and pretreating 10kg of wheat straw to obtain a pretreated material; the pretreatment is acid-process steam explosion, namely 1 percent of sulfuric acid is added, the pressure is 3MPa, and the temperature is kept for 10 minutes;
2) Adjusting the pH value of the pretreated material to 5.5, adding 8% of enzyme preparation, and reacting at 55 ℃ for 96 hours to obtain an enzymolysis product; the enzyme preparation is Novoverin CTec2;
3) Carrying out solid-liquid separation on the product after enzymolysis to obtain a solid phase and a liquid phase;
4) Fermenting the liquid phase to obtain ethanol and carbon dioxide; and (2) carrying out sulfonation reaction on the solid phase to obtain fulvic acid, wherein the sulfonation reaction is to add ammonium sulfite into the solid phase, the dosage of the ammonium sulfite is 20% of the total amount of the solid phase, and water is added to ensure that the liquid ratio is 1:8, reacting at 168 ℃ for 2 hours.
Example 3
1) Preparing and pretreating 10kg of cotton stalks to obtain pretreated materials; the pretreatment is high-temperature steaming, namely adding water, and preserving heat for 30 minutes at the temperature of 180 ℃;
2) Adjusting the pH value of the pretreated material to 5.0, adding 5% of enzyme preparation, and reacting at 50 ℃ for 60 hours to obtain a product after enzymolysis; the enzyme preparation is oxalate enzyme;
3) And (3) fermenting the product after enzymolysis to obtain a mixed solution containing carbon dioxide and ethanol solution and solid waste residues.
4) And (2) carrying out solid-liquid separation on the mixed solution, continuously distilling and dehydrating the liquid to obtain a finished product ethanol, and carrying out sulfonation reaction on the solid phase to obtain fulvic acid, wherein the sulfonation reaction is to add sodium sulfite into the solid phase, the dosage of the sodium sulfite is 40% of the total amount of the solid phase, and water is added to ensure that the liquid ratio is 1:4, reacting for 6 hours at the temperature of 170 ℃.
Example 4
1) Preparing and pretreating 10kg of corn straws to obtain a pretreated material; the pretreatment is high-temperature steaming, namely adding water, and preserving heat for 40 minutes at the temperature of 170 ℃;
2) Adjusting the pH value of the pretreated material to 4.8, adding 3% of enzyme preparation, and reacting at the temperature of 40 ℃ for 48 hours to obtain a product after enzymolysis; the enzyme preparation is SUKAGlucan beta-glucanase;
3) Adjusting the pH value of the product after enzymolysis to 4.0, adding 0.5% yeast, and fermenting at 36 deg.C for 48 hr to obtain a mixed solution of carbon dioxide and ethanol solution and solid waste residue;
4) Distilling the mixed solution to obtain crude ethanol and residue, and dehydrating the crude ethanol to obtain the finished product ethanol. And (3) carrying out solid-liquid separation on the residue, and carrying out sulfonation reaction on the obtained solid phase to obtain fulvic acid, wherein the sulfonation reaction is to add ammonium sulfite into the solid phase, the dosage of the ammonium sulfite is 30% of the total amount of the solid phase, and water is added to ensure that the liquid ratio is 1:7, reacting for 4 hours at the temperature of 165 ℃.
Example 5
1) Preparing and pretreating 10kg of wheat straw to obtain a pretreated material; the pretreatment is traditional pulping, namely 5 percent of sodium hydroxide is added, and the temperature is kept at 140 ℃ for 30 minutes to obtain semi-chemical pulp with the potassium permanganate value of 20K;
2) Adjusting the pH value of the semi-chemical pulp to 5.0, adding 8% enzyme preparation, and reacting at 55 ℃ for 80h to obtain an enzymolysis product; the enzyme preparation is SUKACell cellulase;
3) Carrying out solid-liquid separation on the product after enzymolysis to obtain a solid phase and a liquid phase;
4) Adjusting the pH value of the liquid phase to 5.0, adding 3% yeast, and fermenting at 40 deg.C for 50 hr to obtain ethanol and carbon dioxide; and (2) carrying out sulfonation reaction on the solid phase to obtain fulvic acid, wherein the sulfonation reaction is to add ammonium sulfite into the solid phase, the dosage of the ammonium sulfite is 30% of the total amount of the solid phase, and water is added to ensure that the liquid ratio is 1:8, reacting for 4 hours at the temperature of 165 ℃.
Example 6
1) Preparing and pretreating 10kg of rice straws to obtain a pretreated material; the pretreatment is traditional pulping, namely 15 percent of ammonium sulfite is added, and the temperature is kept at 170 ℃ for 30 minutes to obtain semi-chemical pulp with the potassium permanganate value of 30K;
2) Adjusting the pH value of the semi-chemical pulp to 4.9, adding 5% of enzyme preparation, and reacting at the temperature of 50 ℃ for 72 hours to obtain a product after enzymolysis; the enzyme preparation is oxalate enzyme;
3) Carrying out solid-liquid separation on the product after enzymolysis to obtain a solid phase and a liquid phase;
4) Adjusting the pH value of the liquid phase to 4.9, adding 1% of yeast, and fermenting at 38 ℃ for 48 hours to obtain ethanol and carbon dioxide; and (2) carrying out sulfonation reaction on the solid phase to obtain fulvic acid, wherein the sulfonation reaction is to add ammonium sulfite into the solid phase, the dosage of the ammonium sulfite is 30% of the total amount of the solid phase, and water is added to ensure that the liquid ratio is 1:3, reacting for 4 hours at the temperature of 165 ℃.
Example 7
1) Preparing and pretreating 10kg of straw stalks to obtain a pretreated material; the pretreatment is traditional pulping, namely 10 percent of sodium sulfite is added, and the temperature is kept at 155 ℃ for 30 minutes to obtain semi-chemical pulp with the potassium permanganate value of 25K;
2) Adjusting the pH value of the semi-chemical pulp to 4.9, adding 5% of enzyme preparation, and reacting at the temperature of 50 ℃ for 72 hours to obtain a product after enzymolysis; the enzyme preparation is Kandien CT-3;
3) Carrying out solid-liquid separation on the product after enzymolysis to obtain a solid phase and a liquid phase;
4) Adjusting the pH value of the liquid phase to 4.9, adding 1% of yeast, and fermenting at 38 ℃ for 48 hours to obtain ethanol and carbon dioxide; and (2) carrying out sulfonation reaction on the solid phase to obtain fulvic acid, wherein the sulfonation reaction is to add ammonium sulfite into the solid phase, the dosage of the ammonium sulfite is 30% of the total amount of the solid phase, and water is added to ensure that the liquid ratio is 1:3, reacting for 4 hours at 168 ℃.
Example 8
1) Preparing and pretreating 10kg of wheat straw to obtain a pretreated material; the pretreatment is acid-process steam explosion, namely 5 percent of sulfuric acid is added, the pressure is 1MPa, and the temperature is kept for 8 minutes;
2) Adjusting the pH value of the pretreated material to 4.7, adding 6% enzyme preparation, and reacting at 50 ℃ for 72 hours to obtain an enzymolysis product; the enzyme preparation is condien CT-3;
3) Carrying out solid-liquid separation on the product after enzymolysis to obtain a solid phase and a liquid phase;
4) Fermenting the liquid phase to obtain ethanol and carbon dioxide; and (2) carrying out sulfonation reaction on the solid phase to obtain fulvic acid, wherein the sulfonation reaction is to add ammonium sulfite into the solid phase, the dosage of the ammonium sulfite is 20% of the total amount of the solid phase, and water is added to ensure that the liquid ratio is 1:8, reacting for 2 hours at the temperature of 170 ℃.
Example 9
1) Preparing and pretreating 10kg of straw stalks to obtain a pretreated material; the pretreatment is steam explosion, namely steam is adopted, and the temperature is kept for 8 to 10 minutes under the pressure of 1 to 3 MPa;
2) Adjusting the pH value of the pretreated material to 4.5, adding 3% of enzyme preparation, and reacting at 40 ℃ for 48 hours to obtain a product after enzymolysis; the enzyme preparation is condien CT-3;
3) Carrying out solid-liquid separation on the product after enzymolysis to obtain a solid phase A and a liquid phase A;
4) Fermenting the liquid phase A to obtain a mixed solution containing carbon dioxide, an ethanol solution and solid waste residues; carrying out solid-liquid separation on the mixed solution of the solid waste residues to obtain a solid phase B and a liquid phase B; and combining the solid phase A and the solid phase B for sulfonation reaction to obtain fulvic acid, wherein the sulfonation reaction is to add ammonium sulfite into the solid phase, the dosage of the ammonium sulfite is 30% of the total amount of the solid phase, and water is added to ensure that the liquid ratio is 1:6, reacting for 4 hours at the temperature of 165 ℃. And distilling and dehydrating the ethanol-containing solution and the liquid phase B to obtain the commercial ethanol.
Comparative example 1
Taking 10kg of straw stalk as a raw material, cleaning, cutting into sections or pieces, dissolving at a high temperature of 200-300 ℃, catalyzing, decomposing to obtain carbon dioxide, a humic acid mixture containing bioethanol and rich fulvic acid, and separating the mixture by an ethanol separator, a humic acid separator and a fulvic acid separator to obtain ethanol, solid humic acid and liquid fulvic acid.
Comparative example 2
1) Preparing and pretreating 10kg of rice straws to obtain a pretreated material; the pretreatment is steam explosion, namely steam is adopted, and the temperature is kept for 8 to 10 minutes under the pressure of 1 to 3 MPa;
2) Adjusting the pH value of the pretreated material to 4.5, adding 3% of enzyme preparation, and reacting at 40 ℃ for 48 hours to obtain a product after enzymolysis; the enzyme preparation is Kandien CT-3;
3) Carrying out solid-liquid separation on the product after enzymolysis to obtain a solid phase and a liquid phase;
4) Fermenting the liquid phase to obtain ethanol and carbon dioxide; and (2) performing sulfonation reaction on the solid phase to obtain fulvic acid, wherein the sulfonation reaction is to mix the solid phase in 20mL of hot water, then add 10% (mass fraction) of sodium hydroxide solution to dissolve lignin, filter, add anhydrous sodium sulfate and 0.055g of ferric chloride into the filtrate, adjust the pH value of the solution to 10.5 by using sodium hydroxide or dilute sulfuric acid, control the volume of the reaction liquid to be less than 150mL, transfer the reaction liquid into a 250mL three-neck flask, heat the reaction liquid to 90 ℃ under the condition of continuous stirring, and react for 5 hours to obtain sodium lignosulfonate (fulvic acid).
Test example 1
This test example compares the conversion of lignin produced in the inventive and comparative examples to sodium lignosulfonate (fulvic acid). The results are shown in Table 2:
wherein, the calculation formula is as follows:
conversion of lignin into sodium lignosulfonate (fulvic acid) = (total lignin amount in residue-amount of acid-insoluble lignin remaining after sulfonation reaction)/total lignin amount in residue × 100%
TABLE 2
| Method | Conversion of Lignin to sodium Lignosulfonate (fulvic acid)% |
| Example 1 | 77 |
| Example 2 | 74 |
| Example 3 | 72 |
| Example 4 | 82 |
| Example 5 | 80 |
| Example 6 | 78 |
| Example 7 | 76 |
| Example 8 | 75 |
| Comparative example 1 | 10 |
| Comparative example 2 | 42 |
Although the present invention has been described with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the invention.
Claims (4)
1. A method for simultaneously producing ethanol, fulvic acid and carbon dioxide by using straws is characterized by comprising the steps of preparing materials, pretreating, carrying out enzymolysis, fermenting and distilling the straws to obtain the ethanol and the carbon dioxide, wherein the method also comprises the steps of carrying out solid-liquid separation on a product after the enzymolysis, a product after the fermentation and/or a residue after the distillation, and carrying out sulfonation reaction on the obtained solid phase to obtain the fulvic acid; the sulfonation reaction is as follows: adding a sulfonating agent into the solid phase, and reacting for 2-6 hours at the temperature of 155-180 ℃ and the liquid ratio of 1; the sulfonating agent is ammonium sulfite, and the dosage of the sulfonating agent is 20-40% of the total amount of the solid phase;
the pretreatment is steam explosion, acid method steam explosion, high-temperature steaming or traditional pulping; the steam explosion is to adopt steam, and the temperature is kept for 8 to 10 minutes under the pressure of 1 to 3 MPa; the acid method steam explosion is to add 1 to 5 percent of sulfuric acid, the pressure is 1 to 3MPa, and the temperature is kept for 8 to 10 minutes; the high-temperature steaming is to add water and preserve heat for 30 to 40 minutes at the temperature of between 170 and 180 ℃; the traditional pulping is to add 5 to 15 percent of sodium hydroxide, ammonium sulfite or sodium sulfite, and keep the temperature for 30 minutes at the temperature of between 140 and 170 ℃ to obtain semi-chemical pulp with the potassium permanganate value of between 20 and 30K;
the enzymolysis is to adjust the pH of the material to 4.5-5.5, and the material is added with an enzyme preparation and then reacts for 48-96 hours at the temperature of 40-55 ℃, wherein the dosage of the enzyme preparation is 3-8%;
the fermentation is to adjust the pH value of the liquid phase to 4.5-5.5, add yeast and ferment for 24-48 hours at the temperature of 35-45 ℃; the using amount of the yeast is 0.5-3%.
2. The method of claim 1, wherein the sulfonation is carried out at a temperature of 165 to 170 ℃ for 4 hours.
3. The method according to claim 1, wherein the amount of ammonium sulfite used in the sulfonation reaction is 28% to 32% of the total amount of the solid phase.
4. A method according to any one of claims 1-3, characterized in that the stock preparation is dry stock preparation.
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| CN107586805A (en) * | 2017-11-07 | 2018-01-16 | 临颍路得生物科技有限公司 | Comprehensively utilize five joint production process of biological straw |
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| 碱法蔗渣制浆黑液木质素磺化反应研究;穆环珍等;《环境化学》;20030730(第04期);全文 * |
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