CN116121314A - Process for preparing acrylamide aqueous solution by microbiological method - Google Patents
Process for preparing acrylamide aqueous solution by microbiological method Download PDFInfo
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- CN116121314A CN116121314A CN202211718378.6A CN202211718378A CN116121314A CN 116121314 A CN116121314 A CN 116121314A CN 202211718378 A CN202211718378 A CN 202211718378A CN 116121314 A CN116121314 A CN 116121314A
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- acrylamide
- nitrile hydratase
- acrylonitrile
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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
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/60—Cleaning or rinsing ion-exchange beds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
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Abstract
The invention discloses a process for preparing an acrylamide aqueous solution by a microbial method, and relates to the technical field of acrylamide preparation. The preparation process comprises the following steps: culturing a nitrile hydratase strain to obtain a seed solution of the nitrile hydratase strain; culturing seed solution of nitrile hydratase strain to obtain fermentation liquor; preparing an aqueous suspension of nitrile hydratase bacteria cells; performing reduced pressure distillation on an acrylonitrile raw material, and removing heavy components to obtain a purified acrylonitrile raw material; mixing acrylamide with the purified acrylonitrile; adding an aqueous suspension of nitrile hydratase bacteria cells and deionized water into a hydration reaction kettle, then dropwise adding acrylonitrile, and reacting to obtain a crude acrylamide aqueous solution; removing cation and anion impurity ions from the crude acrylamide aqueous solution to obtain a pure acrylamide solution. The invention has the advantages that: the content of residual acrylonitrile in the prepared acrylamide aqueous solution is less than or equal to 0.01%, the purity of the acrylamide aqueous solution is improved, and the repeated use batch of the nitrile hydratase bacteria is increased.
Description
Technical Field
The invention relates to the technical field of acrylamide preparation, in particular to a process for preparing an acrylamide aqueous solution by a microbiological method.
Background
Acrylamide can be used as a coagulant, a petroleum recovery agent, a paper strength enhancer in the paper industry, or a thickener for papermaking, and is a raw material for producing polyacrylamide. There are two main methods for preparing acrylamide by hydration of acrylonitrile: one is a copper catalyst method in which acrylonitrile is hydrated in the presence of a copper catalyst (metallic copper, reduced copper, or skeletal copper) to obtain an aqueous acrylamide solution; another is a microbial method in which a hydration reaction is carried out using a microbial cell containing a nitrile hydratase, a cell treated product or the like as a catalyst. In the two methods, the microbial method is higher in conversion rate and selectivity of acrylonitrile than the copper catalytic method, so that most industrial devices now use the microbial method to prepare an aqueous acrylamide solution.
In the prior art, patent CN201010258271.9 discloses a preparation process of an acrylamide aqueous solution without a polymerization inhibitor, wherein the polymerization inhibitor is removed from the prepared acrylamide aqueous solution, so that the purity of acrylamide is improved, and high-quality polyacrylamide can be produced. However, the hydratase used in the hydration process of acrylamide cannot maintain the hydration activity, the amount of the hydratase used in the hydration process is increased, the content of residual acrylonitrile in acrylamide obtained by catalyzing the hydration reaction is high, the purity of the aqueous acrylamide solution is reduced, and the number of repeated use batches of the hydratase is small.
Disclosure of Invention
The invention aims to solve the technical problems that the hydratase used in the hydration process of acrylamide in the prior art cannot keep the hydration activity, the content of residual acrylonitrile in acrylamide obtained by catalytic hydration reaction is high, the purity of the acrylamide aqueous solution is reduced, and the number of repeated use batches of the hydratase is small.
In order to solve the technical problems, the technical scheme of the invention is as follows: the method comprises the following steps:
s1, inoculating a nitrile hydratase strain into a seed culture medium, and culturing for 30-55 hours on a shaking table with the rotation speed of 200-220 rpm at the temperature of 27-30 ℃ to obtain a seed solution of the nitrile hydratase strain;
s2, inoculating seed liquid of nitrile hydratase strain into a shake flask or a fermentation tank filled with a fermentation medium, and culturing for 36-72 hours at the temperature of 27-30 ℃ and the pH value of 7.5-8.5 to obtain fermentation liquor; centrifuging the fermentation liquor to obtain nitrile hydratase bacteria;
s3, preparing the aqueous suspension of the nitrile hydratase bacteria cells obtained in the step S2 according to the concentration of 10-25 g stem cells/L for later use;
s4, performing reduced pressure distillation on the acrylonitrile raw material, collecting a fraction at 75-79 ℃ by controlling micro negative pressure in the distillation process, and removing heavy components to obtain a purified acrylonitrile raw material;
s5, mixing acrylamide into the purified acrylonitrile, wherein the content of the mixed acrylamide in the acrylonitrile is 100ppm;
s6, adding the aqueous suspension of the nitrile hydratase bacteria cells and deionized water into a hydration reaction kettle, regulating the pH value of the mixed solution to 8-9, then dropwise adding acrylonitrile into the hydration reaction kettle, and reacting for 2-6 hours at the temperature of 15-25 ℃ to obtain a crude acrylamide aqueous solution, wherein the mass ratio of the nitrile hydratase bacteria to the deionized water to the acrylonitrile is 1-1.5:17.5-19:5-7;
s7, respectively flowing the crude acrylamide aqueous solution through a cation exchange column and an anion exchange column to remove cation and anion impurity ions, thereby obtaining the pure acrylamide aqueous solution.
Further, in the step S1, the composition of the seed culture medium is as follows: glucose 2%, yeast extract 0.5%, peptone 0.1%, KH2PO4 0.05%, K2HPO4 0.05%, mgSO4.7H2O 0.05%, pH 7-7.2, and the balance water.
Further, in the step S2, the composition of the fermentation medium is as follows: glucose 2%, yeast extract 0.5%, urea 0.7%, KH2PO4 0.05%, K2HPO4 0.05%, mgSO4.7H2O 0.05%, monosodium glutamate 1%, coCl 210 ppm, pH 7.5-8.5, and water in balance.
Further, in the step S6, the dropping speed of the acrylonitrile is 1-2 mL/min, and the stirring speed is 200rpm during the reaction.
Further, in the step S7, after the cation exchange column and the anion exchange column fail, the regeneration treatment is performed by using 5% hydrochloric acid and 5% liquid alkali respectively, and during the regeneration, the feeding ratio of the acid or alkali to the water is controlled, and the mixture is directly fed and mixed through a nozzle to clean, and then the water is used for washing after the cleaning.
The invention has the advantages that: the method comprises the steps of preparing an aqueous suspension of nitrile hydratase bacteria cells after culturing and fermenting to obtain the nitrile hydratase bacteria, using the aqueous suspension as a catalyst, wherein acrylamide added into acrylonitrile during the catalytic hydration reaction can play a role in activating the nitrile hydratase bacteria, so that the nitrile hydratase bacteria can keep activity in the hydration process for a long time, removing cation and anion impurity ions from a crude acrylamide aqueous solution, the content of residual acrylonitrile in the prepared acrylamide aqueous solution is less than or equal to 0.01%, the purity of the acrylamide aqueous solution is improved, and the nitrile hydratase bacteria are repeatedly used in batches.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. The following examples will provide those skilled in the art with a more complete understanding of the present invention and are not intended to limit the invention to the embodiments described.
The specific implementation mode adopts the following technical scheme: the method comprises the following steps:
s1, inoculating a nitrile hydratase strain into a seed culture medium, and culturing for 30-55 hours on a shaking table with the rotation speed of 200-220 rpm at the temperature of 27-30 ℃ to obtain a seed solution of the nitrile hydratase strain, wherein the seed culture medium comprises the following components: glucose 2%, yeast extract 0.5%, peptone 0.1%, KH2PO4 0.05%, K2HPO4 0.05%, mgSO4.7H2O 0.05%, pH 7-7.2, and the balance water.
S2, inoculating seed liquid of nitrile hydratase strain into a shake flask or a fermentation tank filled with a fermentation medium, and culturing for 36-72 hours at the temperature of 27-30 ℃ and the pH value of 7.5-8.5 to obtain fermentation liquor; centrifuging the fermentation liquor to obtain nitrile hydratase bacteria, wherein the fermentation medium comprises the following components: glucose 2%, yeast extract 0.5%, urea 0.7%, KH2PO4 0.05%, K2HPO4 0.05%, mgSO4.7H2O 0.05%, monosodium glutamate 1%, coCl 210 ppm, pH 7.5-8.5, and water in balance.
S3, preparing the aqueous suspension of the nitrile hydratase bacteria cells obtained in the step S2 according to the concentration of 10-25 g stem cells/L for later use.
S4, performing reduced pressure distillation on the acrylonitrile raw material, collecting a fraction at 75-79 ℃ by controlling micro negative pressure in the distillation process, and removing heavy components to obtain the purified acrylonitrile raw material.
S5, mixing acrylamide into the purified acrylonitrile, wherein the content of the mixed acrylamide in the acrylonitrile is 100ppm.
S6, adding the aqueous suspension of the nitrile hydratase bacteria cells and deionized water into a hydration reaction kettle, regulating the pH value of the mixed solution to 8-9, then dropwise adding acrylonitrile into the hydration reaction kettle, wherein the dropwise adding speed of the acrylonitrile is 1-2 mL/min, reacting for 2-6 hours at the temperature of 15-25 ℃, stirring during the reaction, and the stirring speed is 200rpm, so as to obtain a crude acrylamide aqueous solution, wherein the mass ratio of the nitrile hydratase bacteria to the deionized water to the acrylonitrile is 1-1.5:17.5-19:5-7.
S7, respectively flowing the crude acrylamide aqueous solution through a cation exchange column and an anion exchange column to remove cation and anion impurity ions, obtaining pure acrylamide aqueous solution, after the cation exchange column and the anion exchange column are invalid, respectively adopting 5% hydrochloric acid and 5% liquid alkali to carry out regeneration treatment, controlling the feeding ratio of acid or alkali and water during regeneration, directly feeding and mixing through a nozzle to carry out cleaning, and then washing with water after the cleaning is finished.
Example 1:
s1, inoculating a nitrile hydratase strain into a seed culture medium, and culturing for 30 hours on a shaking table with the rotation speed of 200rpm at the temperature of 27 ℃ to obtain a seed solution of the nitrile hydratase strain;
s2, inoculating seed liquid of nitrile hydratase strain into a shake flask or a fermentation tank filled with a fermentation medium, and culturing for 36 hours at 27 ℃ and pH7.5 to obtain fermentation liquid; centrifuging the fermentation liquor to obtain nitrile hydratase bacteria;
s3, preparing the aqueous suspension of the nitrile hydratase bacteria cells obtained in the step S2 according to the concentration of 10g stem cells/L for later use;
s4, performing reduced pressure distillation on the acrylonitrile raw material, collecting a fraction at 75-79 ℃ by controlling micro negative pressure in the distillation process, and removing heavy components to obtain a purified acrylonitrile raw material;
s5, mixing acrylamide into the purified acrylonitrile, wherein the content of the mixed acrylamide in the acrylonitrile is 100ppm;
s6, adding the aqueous suspension of the nitrile hydratase bacteria cells and deionized water into a hydration reaction kettle, regulating the pH value of the mixed solution to 8, then dropwise adding acrylonitrile into the hydration reaction kettle, and reacting for 2 hours at the temperature of 15 ℃ to obtain a crude acrylamide aqueous solution, wherein 2L of the aqueous suspension of the nitrile hydratase bacteria cells, 350g of deionized water and 100g of acrylonitrile;
s7, respectively flowing the crude acrylamide aqueous solution through a cation exchange column and an anion exchange column to remove cation and anion impurity ions to obtain a pure acrylamide aqueous solution, wherein the acrylamide content in the obtained acrylamide aqueous solution is 33%, and the acrylonitrile content is less than or equal to 0.01%.
Example 2:
s1, inoculating a nitrile hydratase strain into a seed culture medium, and culturing for 50 hours on a shaking table with the rotation speed of 210rpm at 29 ℃ to obtain a seed solution of the nitrile hydratase strain;
s2, inoculating seed liquid of nitrile hydratase strain into a shake flask or a fermentation tank filled with a fermentation medium, and culturing for 48 hours at 29 ℃ and pH8 to obtain fermentation liquid; centrifuging the fermentation liquor to obtain nitrile hydratase bacteria;
s3, preparing the aqueous suspension of the nitrile hydratase bacteria cells obtained in the step S2 according to the concentration of 20g stem cells/L for later use;
s4, performing reduced pressure distillation on the acrylonitrile raw material, collecting a fraction at 75-79 ℃ by controlling micro negative pressure in the distillation process, and removing heavy components to obtain a purified acrylonitrile raw material;
s5, mixing acrylamide into the purified acrylonitrile, wherein the content of the mixed acrylamide in the acrylonitrile is 100ppm;
s6, adding the aqueous suspension of the nitrile hydratase bacteria cells and deionized water into a hydration reaction kettle, regulating the pH value of the mixed solution to 8.5, then dropwise adding acrylonitrile into the hydration reaction kettle, and reacting for 5 hours at the temperature of 20 ℃ to obtain a crude acrylamide aqueous solution, wherein 1.5L of the aqueous suspension of the nitrile hydratase bacteria cells, 370g of deionized water and 120g of acrylonitrile;
s7, respectively flowing the crude acrylamide aqueous solution through a cation exchange column and an anion exchange column to remove cation and anion impurity ions, thereby obtaining a pure acrylamide aqueous solution, wherein the acrylamide content in the acrylamide aqueous solution is 33.5 percent, and the acrylonitrile content is less than or equal to 0.01 percent.
Example 3:
s1, inoculating a nitrile hydratase strain into a seed culture medium, and culturing for 55 hours on a shaking table with the rotation speed of 220rpm at the temperature of 30 ℃ to obtain a seed solution of the nitrile hydratase strain;
s2, inoculating seed liquid of nitrile hydratase strain into a shake flask or a fermentation tank filled with a fermentation medium, and culturing at 30 ℃ and pH8.5 for 72 hours to obtain fermentation liquor; centrifuging the fermentation liquor to obtain nitrile hydratase bacteria;
s3, preparing the aqueous suspension of the nitrile hydratase bacteria cells obtained in the step S2 according to the concentration of 25g stem cells/L for later use;
s4, performing reduced pressure distillation on the acrylonitrile raw material, collecting a fraction at 75-79 ℃ by controlling micro negative pressure in the distillation process, and removing heavy components to obtain a purified acrylonitrile raw material;
s5, mixing acrylamide into the purified acrylonitrile, wherein the content of the mixed acrylamide in the acrylonitrile is 100ppm;
s6, adding the aqueous suspension of the nitrile hydratase bacteria cells and deionized water into a hydration reaction kettle, regulating the pH value of the mixed solution to 9, then dropwise adding acrylonitrile into the hydration reaction kettle, and reacting for 6 hours at the temperature of 25 ℃ to obtain a crude acrylamide aqueous solution, wherein 1.2L of the aqueous suspension of the nitrile hydratase bacteria cells, 380g of deionized water and 140g of acrylonitrile;
s7, respectively flowing the crude acrylamide aqueous solution through a cation exchange column and an anion exchange column to remove cation and anion impurity ions, thereby obtaining a pure acrylamide aqueous solution, wherein the acrylamide content in the acrylamide aqueous solution is 34 percent, and the acrylonitrile content is less than or equal to 0.01 percent.
Comparative example:
adding 20g of mycelium and 350g of deionized water into a hydration reaction kettle, slowly adding 100g of acrylonitrile under the stirring effect, carrying out hydration reaction at 20 ℃ and normal pressure, and converting the acrylonitrile into acrylamide under the action of a microbial catalyst to obtain an acrylamide aqueous solution, wherein the acrylamide content is 30% and the acrylonitrile content is less than or equal to 0.1%. The method comprises the steps of preparing an aqueous suspension of nitrile hydratase bacteria cells after culturing and fermenting the nitrile hydratase bacteria to obtain the nitrile hydratase bacteria, using the aqueous suspension as a catalyst, enabling acrylamide added into acrylonitrile to play a role in activating the nitrile hydratase bacteria during the hydration reaction, enabling the nitrile hydratase bacteria to keep active in the hydration process for a long time, removing cation and anion impurity ions from a crude acrylamide aqueous solution, and increasing the purity of the acrylamide aqueous solution by less than or equal to 0.01% after the residual acrylonitrile content in the prepared acrylamide aqueous solution, wherein the nitrile hydratase bacteria are repeatedly used in batches.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A process for preparing an acrylamide aqueous solution by a microbiological method is characterized by comprising the following steps: the method comprises the following steps:
s1, inoculating a nitrile hydratase strain into a seed culture medium, and culturing for 30-55 hours on a shaking table with the rotation speed of 200-220 rpm at the temperature of 27-30 ℃ to obtain a seed solution of the nitrile hydratase strain;
s2, inoculating seed liquid of nitrile hydratase strain into a shake flask or a fermentation tank filled with a fermentation medium, and culturing for 36-72 hours at the temperature of 27-30 ℃ and the pH value of 7.5-8.5 to obtain fermentation liquor; centrifuging the fermentation liquor to obtain nitrile hydratase bacteria;
s3, preparing the aqueous suspension of the nitrile hydratase bacteria cells obtained in the step S2 according to the concentration of 10-25 g stem cells/L for later use;
s4, performing reduced pressure distillation on the acrylonitrile raw material, collecting a fraction at 75-79 ℃ by controlling micro negative pressure in the distillation process, and removing heavy components to obtain a purified acrylonitrile raw material;
s5, mixing acrylamide into the purified acrylonitrile, wherein the content of the mixed acrylamide in the acrylonitrile is 100ppm;
s6, adding the aqueous suspension of the nitrile hydratase bacteria cells and deionized water into a hydration reaction kettle, regulating the pH value of the mixed solution to 8-9, then dropwise adding acrylonitrile into the hydration reaction kettle, and reacting for 2-6 hours at the temperature of 15-25 ℃ to obtain a crude acrylamide aqueous solution, wherein the mass ratio of the nitrile hydratase bacteria to the deionized water to the acrylonitrile is 1-1.5:17.5-19:5-7;
s7, respectively flowing the crude acrylamide aqueous solution through a cation exchange column and an anion exchange column to remove cation and anion impurity ions, thereby obtaining the pure acrylamide aqueous solution.
2. The process for preparing an aqueous acrylamide solution by a microbiological method according to claim 1, characterized in that: in the step S1, the composition of the seed culture medium is as follows: glucose 2%, yeast extract 0.5%, peptone 0.1%, KH2PO4 0.05%, K2HPO4 0.05%, mgSO4.7H2O 0.05%, pH 7-7.2, and the balance water.
3. The process for preparing an aqueous acrylamide solution by a microbiological method according to claim 1, characterized in that: in the step S2, the composition of the fermentation medium is as follows: glucose 2%, yeast extract 0.5%, urea 0.7%, KH2PO4 0.05%, K2HPO4 0.05%, mgSO4.7H2O 0.05%, monosodium glutamate 1%, coCl 210 ppm, pH 7.5-8.5, and water in balance.
4. The process for preparing an aqueous acrylamide solution by a microbiological method according to claim 1, characterized in that: in the step S6, the dropping speed of the acrylonitrile is 1-2 mL/min, and the stirring speed is 200rpm during the reaction.
5. The process for preparing an aqueous acrylamide solution by a microbiological method according to claim 1, characterized in that: in the step S7, after the cation exchange column and the anion exchange column are out of order, 5% hydrochloric acid and 5% liquid alkali are respectively adopted for regeneration treatment, during regeneration, the feeding proportion of acid or alkali and water is controlled, the mixture is directly fed and mixed through a nozzle for cleaning, and water is used for flushing after the cleaning is finished.
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