CN108658821B - Clean production method of D, L-methionine and product thereof - Google Patents
Clean production method of D, L-methionine and product thereof Download PDFInfo
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- CN108658821B CN108658821B CN201710443926.1A CN201710443926A CN108658821B CN 108658821 B CN108658821 B CN 108658821B CN 201710443926 A CN201710443926 A CN 201710443926A CN 108658821 B CN108658821 B CN 108658821B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
Abstract
The invention relates to a clean production method of D, L-methionine and a product thereof, wherein saponification liquid containing methionine salt and carbonate with certain concentration is subjected to carbon dioxide acidification crystallization and solid-liquid separation to obtain a methionine crystal product and a crystallization mother liquor, the crystallization mother liquor is subjected to bipolar membrane electrodialysis for sodium removal and decarburization concentration, and finally carbon dioxide acidification crystallization is carried out again, the purity of the methionine crystal product obtained in the whole process is more than 99.4 wt%, and carbon dioxide and sodium hydroxide obtained in the production process can be recycled and repeatedly used in the process and the previous process.
Description
Technical Field
The invention belongs to the field of production of organic compounds, and particularly relates to a clean production method of D, L-methionine and a product thereof.
Background
The L-methionine is also called methionine, is one of basic units forming protein, is only amino acid containing sulfur in essential amino acid, is involved in methyl transfer, phosphorus metabolism and synthesis of adrenaline, choline and creatine in animals, and is also a raw material for synthesizing protein and cystine.
Currently, the hydantoin method for preparing methionine mainly has two ways: one is to adopt hydrocyanic acid to replace traditional sodium cyanide or potassium cyanide and 3-methylmercapto propionaldehyde to react and produce cyanohydrin, then react with carbon dioxide, ammonia and produce hydantoin, potassium carbonate hydrolyzes hydantoin, carbon dioxide neutralizes methionine potassium, separate methionine and potassium bicarbonate, the potassium bicarbonate mother liquor containing methionine circulates to the hydantoin and hydrolyzes the step, there is almost no waste water waste residue to discharge in the whole technological process of this method, it is a relatively clean, low production cost methionine production technology; the other method is characterized in that cyanohydrin, carbon dioxide and ammonia are used as raw materials or sodium cyanide, 3-methylthiopropanal, carbon dioxide and ammonia are used as raw materials to prepare hydantoin, hydrolysis is carried out under the action of sodium hydroxide to generate saponified solution containing sodium carbonate and sodium methionine, and methionine and sodium sulfate are obtained through sulfuric acid acidification and crystallization respectively; concentrating the methionine-containing sodium sulfate mother liquor at high temperature, particularly heating to 100-120 ℃, then precipitating a large amount of sodium sulfate crystals (the solubility of methionine is the largest and the solubility of sodium sulfate is the lowest), carrying out suction filtration while the solution is hot at high temperature, cooling the filtrate to 40 ℃, crystallizing methionine, washing with water, drying to obtain a methionine product, wherein nearly 10% of total methionine remains in the sodium sulfate mother liquor, circulating the mother liquor to a saponification liquor acidification step, and circulating the steps Allylamine, 3-methylthiopropylamine, and carbon dioxide), the mechanism of which is: methionine is heated, and is firstly decomposed into 3-methylthio propylamine and carbon dioxide, namely decarboxylation is firstly carried out, the 3-methylthio propylamine is continuously heated and decomposed into dimethyl disulfide and allylamine, a substance with foul smell is generated, the substance can remain in sodium sulfate mother liquor and discharged condensed water, the sodium sulfate mother liquor which is circulated for a long time has foul smell, the operating environment of a sodium sulfate workshop is severe, the surrounding environment is influenced, partial decomposition of methionine is also caused, the COD of the discharged mother liquor is high, biochemical treatment is difficult to carry out, the sodium sulfate mother liquor containing methionine is circulated for a long time, the product quality of subsequent methionine is reduced, and the reasons for the reduction are mainly that: first, decomposition of methionine and polymerization of methionine, especially forming a dimer of methionine, and organic impurities after decomposition of methionine are accumulated in the system, and the crystallized methionine has an offensive odor; and secondly, the sodium formate and the sodium 2-hydroxy-4-methylthiobutyrate in the saponification liquid are accumulated in the system, so that the quality of the methionine product is influenced, the quality of sulfuric acid is influenced finally, the sodium sulfate product not only contains methionine but also contains sodium formate, so that the use of sodium sulfate is influenced, and particularly the sodium sulfate product contains about 0.5% of methionine. The most prominent problems in the methionine production process are environmental protection and the byproduct sodium sulfate with low value (1 ton of methionine and 1.2-1.8 tons of sodium sulfate byproduct), while the best method for solving the environmental protection problem is incineration, which inevitably consumes more energy, increases the methionine loss and the production cost, and cannot find a fundamental effective solution for the problem of the byproduct sodium sulfate with a large amount of low value.
Based on the methionine production process technology, the researchers of the invention are dedicated to developing a clean production method of D, L methionine, which saves energy consumption and is environment-friendly.
Disclosure of Invention
The applicant researches and discovers that only by controlling the proper ratio of sodium methionine to sodium carbonate in the saponified solution, D, L-methionine can be produced by adopting carbon dioxide acidification crystallization, and the bipolar membrane electrodialysis has the characteristic of desalting, the sodium carbonate in the saponified solution is reduced, so that when the sodium methionine is acidified by introducing the carbon dioxide, the generated sodium bicarbonate is not enough to reach the saturated state, the methionine can be crystallized and separated out, and the purity is high.
The invention aims to provide an energy-saving and environment-friendly clean production method of D, L methionine, which can overcome the problems of environmental protection, low-value sodium sulfate byproduct, energy waste and decomposition of methionine and inorganic salt in the traditional D, L-methionine production method
In order to achieve the purpose, the invention provides the following technical scheme:
the clean production method of the D, L-methionine comprises the following steps of introducing saponification liquid containing methionine salt and carbonate into carbon dioxide for acidification and crystallization, carrying out solid-liquid separation, respectively collecting D, L-methionine crystals and crystallization mother liquor, drying the collected D, L-methionine crystals to obtain D, L-methionine, decarbonizing the crystallization mother liquor to obtain mother liquor decarbonization liquid, removing salt ions of 20-70 wt% of total salt ions in the mother liquor decarbonization liquid through bipolar membrane electrodialysis, carrying out secondary decarbonization to obtain decarbonization liquid of the methionine salt and the carbonate and carbon dioxide, and finally returning the decarbonization liquid of the methionine salt and the carbonate to the step of carbon dioxide acidification and crystallization for recycling.
Further, the acidification crystallization is carried out by introducing carbon dioxide under the conditions that the temperature is 0-70 ℃ and the pressure is 0.1-1.0 MPa.
Further, the bipolar membrane electrodialysis treatment comprises the steps of introducing a mother liquor decarbonization solution into a salt chamber, introducing water or a dilute alkali solution into an alkali chamber, introducing direct current into a cathode and an anode, and controlling the pH value of the salt chamber to be 6.5-10.0 and the temperature to be 15-50 ℃.
Further, the carbon dioxide recovered by the decarburization is recycled to the acidification crystallization step.
Further, the saponification liquid contains less than 4wt% of sodium carbonate and 10-25 wt% of sodium methionine or the saponification liquid contains less than 20wt% of potassium carbonate and 10-25 wt% of potassium methionine.
Further, the saponification liquid is prepared by the following method: preparing a mixed aqueous solution of 5- (2-methylthioethyl) -hydantoin and ammonium bicarbonate by using 2-hydroxy-4-methylthiobutyronitrile, carbon dioxide, ammonia and water as raw materials, carrying out steam stripping to obtain a 5- (2-methylthioethyl) -hydantoin aqueous solution, adding sodium hydroxide for alkaline hydrolysis, and carrying out steam stripping after the alkaline hydrolysis is finished to obtain a saponified solution with the sodium carbonate content of less than 4wt% and the sodium methionine content of 10-25 wt%;
or the saponification liquid is prepared by the following method: preparing hydantoin by using cyanohydrin, carbon dioxide and ammonia as raw materials or using sodium cyanide, 3-methylthiopropanal, carbon dioxide and ammonia as raw materials, adjusting the pH value of the hydantoin to be 3.0-6.0 through alkaline hydrolysis and acidification to obtain a mixed solution containing 2.5-10 wt% of sodium carbonate and 10-25 wt% of sodium methionine, and diluting the mixed solution until the content of the sodium carbonate is within 4wt% and the content of the sodium methionine is 4-10 wt%; and removing sodium through bipolar membrane electrodialysis, decarbonizing, and concentrating to obtain a saponified solution with the sodium carbonate content of less than 4wt% and the sodium methionine content of 10-25 wt%.
Further, the decarburization condition is 0-0.6 Mpa and 70-150 ℃.
Further, the saponification liquid is obtained by the following steps: preparing a mixed aqueous solution of 5- (2-methylthioethyl) -hydantoin and ammonium bicarbonate by taking 2-hydroxy-4-methylthiobutyronitrile, carbon dioxide, ammonia and water as raw materials, carrying out steam stripping to obtain a 5- (2-methylthioethyl) -hydantoin aqueous solution, adding potassium hydroxide for alkaline hydrolysis, and carrying out steam stripping after the alkaline hydrolysis is finished to obtain a saponified solution containing within 20wt% of potassium carbonate and 10-25 wt% of potassium methionine; further, the heating decarburization condition is 0-0.6 Mpa and 100-180 ℃.
2. The D, L-methionine with high purity and low impurity is prepared by the clean production method of the D, L-methionine, and the purity of the D, L-methionine is more than 99.4%.
The clean production method of D, L-methionine can eliminate the problem of by-product sodium sulfate, avoid the energy consumption that the subsequent purification concentration of sodium sulfate needs, easy to operate, the methionine purity that is got can be up to more than 99.4%, the invention does not need to concentrate the sodium bicarbonate filtrate containing methionine repeatedly, can avoid methionine to be heated and decomposed for a long time and produce the foul gas, and the method has low costs, does not have a large amount of acidity and foul waste water discharge, green environmental protection, bipolar membrane electrodialysis by-product sodium hydroxide circulate to hydrolyze 5- (2-methylthio ethyl) -hydantoin step, does not need to supplement fresh sodium hydroxide, the carbon dioxide produced by decarbonization also circulates to the saponification liquid acidification step, economical and applicable, worth the market popularization and application.
The method can be applied to saponification solutions with different contents of methionine salt and carbonate obtained in different modes to realize various clean production modes of methionine.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a flow chart of a clean production method of D, L-methionine;
wherein V1 is a saponified liquid concentration adjusting device, ED1 is a bipolar membrane electrodialysis device, E1 is a decarburization concentration device, T1 is a carbon dioxide recovery device, R1 is a carbon dioxide acidification crystallization device, S1 is a solid-liquid separation device, and E2 is a decarburization device;
10-25 wt% of sodium methionine and 2.5-10 wt% of sodium carbonate are added into the saponified solution ①;
10-25 wt% of sodium methionine and 0-4 wt% of sodium carbonate in ② parts of saponified solution;
the saponified solution ③ contains 10-25 wt% of potassium methionine and 0-20 wt% of potassium carbonate.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The experimental procedures, in which specific conditions are not specified in the examples, are generally carried out under conventional conditions or under conditions recommended by the manufacturers.
Example 1
The method comprises the steps of taking 2-hydroxy-4-methylthiobutyronitrile, carbon dioxide, ammonia and water as raw materials, adding the raw materials into a closed reactor according to a certain proportion, after reaction, decompressing to normal pressure to obtain a mixed aqueous solution of 5- (2-methylthioethyl) -hydantoin and ammonium bicarbonate (ammonium bicarbonate and ammonium carbonate solution), discharging unreacted ammonium bicarbonate in a reaction system to obtain a 5- (2-methylthioethyl) -hydantoin aqueous solution, adding a certain amount of a sodium hydroxide aqueous solution, after alkaline hydrolysis is finished, obtaining 599 g of sodium methionine and sodium carbonate saponified solution, wherein the sodium methionine content is 16.8%, the sodium carbonate content is 3.07%, adding the obtained saponified solution into a 2L stirring reactor, bipolar maintaining to 45 ℃, simultaneously introducing carbon dioxide, the pressure of introducing the carbon dioxide is 0.2MPa, after acidification reaction, performing solid-liquid separation, respectively collecting D, L-methionine crystal and crystallized mother solution, washing D, small amount of water, L-methionine crystal, 51.18 g of the dried methionine product, the purity is 99.4%, the methionine crystal is obtained by 7%, the yield is obtained by controlling the pH value of the sodium carbonate crystal and the sodium carbonate crystal mother solution by adding the sodium carbonate crystal mother solution into a bipolar membrane, the anode chamber, the bipolar membrane is obtained by adding the bipolar membrane, the bipolar membrane is obtained by controlling the bipolar membrane, the bipolar membrane is obtained by adding the bipolar membrane, the bipolar membrane is formed by the bipolar membrane, the bipolar membrane is from the bipolar membrane, the bipolar membrane is from the bipolar membrane is from the bipolar membrane, the bipolar membrane is from the bipolar membrane, the bipolar membrane is from the bipolar membrane, the bipolar membrane is from the bipolar membrane.
Example 2
Adding 1mol of 3-methylthiopropanal, sodium cyanide, carbon dioxide, ammonia and 800 g of water into a closed reactor, wherein the feeding molar ratio of the 3-methylthiopropanal to the sodium cyanide to the carbon dioxide to the ammonia is 1:1.05:2:4, then heating to 80 ℃, carrying out heat preservation stirring for 10min, immediately heating to 120 ℃, carrying out heat preservation stirring for 20min, then heating the pressure of a reaction system to 2MPa, after the reaction is finished, releasing the pressure to normal pressure, discharging unreacted hydrocarbon in the reaction system to obtain a hydantoin aqueous solution, adding 1.5mol of a 40% sodium hydroxide aqueous solution, immediately heating to 178 ℃, carrying out heat preservation stirring for 30 min, and controlling the pressure of the reaction system to 2.5 MPa; after the reaction is finished, cooling to 100 ℃, decompressing to normal pressure, removing carbon dioxide and ammonia in a reaction system to obtain 970 g of sodium methionine and sodium carbonate saponified solution, wherein the content of sodium methionine is 17.36 percent, the content of sodium carbonate is 8.40 percent, adding water into the saponified solution to dilute the saponified solution until the content of sodium methionine is 5.4 percent and the content of sodium carbonate is 2.61 percent, and separating 50 weight percent of total sodium ions in the solution in the form of sodium hydroxide solution by virtue of bipolar membrane electrodialysis to respectively obtain sodium removal solution and sodium hydroxide solution with the pH of 7.2; the sodium-removing liquid is decarbonized and concentrated at the high temperature of 110 ℃ and 0.2MPa to obtain the mixed liquid of 18.51 wt% of sodium methionine and 1.61 wt% of sodium carbonate.
Adding the obtained mixed solution into a stirring reactor of 2L, keeping the temperature to 50 ℃, introducing carbon dioxide, introducing the pressure of the carbon dioxide to 0.2MPa, after the acidification reaction is finished, carrying out solid-liquid separation, respectively collecting D, L-methionine crystals and crystallization mother liquor, washing the D, L-methionine crystals with a small amount of water, drying to obtain 57.58 g of methionine product with the purity of 99.5% and the single yield of methionine of 42%, carrying out high-temperature decarburization treatment on the crystallization mother liquor at 120 ℃ to obtain decarbonization solution of sodium carbonate and sodium methionine, wherein the mass percentage of the sodium methionine is 10.1%, the mass percentage of the sodium carbonate is 3.67%, introducing the decarbonization solution into a bipolar membrane electrodialysis sodium removal system, carrying out bipolar membrane electrodialysis on the decarbonization solution to obtain a saponification solution with the mass percentage of 9.9.9%, the mass percentage of the sodium carbonate is 1.4%, concentrating to obtain a saponification solution with the mass percentage of sodium methionine content of 16%, the mass percentage of the sodium carbonate, carrying out acidification solution of the pH value of the hydrolysis membrane from 5% to 5.7%, and gradually reducing the pH value of the hydrolysis ion by-sodium hydroxide, wherein the hydrolysis membrane is reduced by the hydrolysis membrane.
Example 3
Adding 2-hydroxy-4-methylthiobutyronitrile, carbon dioxide, ammonia and water as raw materials into a closed reactor, carrying out steam stripping to obtain a mixed aqueous solution of 5- (2-methylthioethyl) -hydantoin and ammonium bicarbonate (ammonium bicarbonate and ammonium carbonate solution), carrying out steam stripping to obtain a 5- (2-methylthioethyl) -hydantoin aqueous solution, adding a 50% by mass potassium hydroxide aqueous solution, mixing, rapidly heating to 185 ℃, keeping the temperature for 15min and keeping the pressure at 2.0 MPa. After the reaction is finished, the pressure is released to normal pressure, then gas stripping is carried out, carbon dioxide and ammonia released in the reaction are removed until ammonia is not detected as the gas stripping end point, and 786 g of mixed saponification liquid containing potassium methionine and potassium carbonate is obtained, wherein the mass percentage of the potassium methionine is 22.4%, and the mass percentage of the potassium carbonate is 18.9%.
Adding the obtained mixed solution into a stirring reactor of 2L, keeping the temperature to 60 ℃, introducing carbon dioxide, introducing the pressure of the carbon dioxide to 0.4MPa, after the acidification reaction is finished, performing solid-liquid separation, respectively collecting D, L-methionine crystals and crystallization mother liquor, washing the D, L-methionine crystals with a small amount of water, drying to obtain 345.84 g of methionine product with the purity of 99.5% and the single yield of methionine of 44%, subjecting the crystallization mother liquor to high-temperature decarburization treatment at 160 ℃ to obtain 561 g of decarbonization solution of potassium carbonate and potassium methionine, the mass percentage of potassium methionine is 11.9%, the mass percentage of potassium carbonate is 9.8%, introducing the decarbonization solution into a bipolar membrane electrodialysis system (shown in figure 1), subjecting the decarbonization solution to a bipolar membrane electrodialysis system to obtain 561 g of potassium carbonate and potassium methionine solution, the mass percentage of 11.8%, the mass percentage of potassium carbonate is 6.7%, concentrating to obtain a saponification solution, wherein the mass percentage of potassium methionine is 20.7%, the mass percentage of potassium carbonate is 11.75%, the hydrolysis solution of hydantoin is subjected to hydrolysis by-hydrolysis in a cycle, and the pH value of the hydrolysis solution is reduced from that of 2-5% and the hydrolysis by-5% of hydantoin salt, and the hydrolysis rate of the hydrolysis solution is reduced from that of ethyl hydroxide by a hydrolysis by a cycle.
FIG. 1 is a flow chart of a clean production method of D, L-methionine of the invention, in FIG. 1, V1 is a saponified liquid concentration adjusting device, ED1 is a bipolar membrane electrodialysis device, E1 is a decarburization concentration device, T1 is a carbon dioxide recovery device, R1 is a carbon dioxide acidification crystallization device, S1 is a solid-liquid separation device, and E2 is a decarburization device, wherein saponified liquid ① contains 10-25 wt% of sodium methionine and 2.5-10 wt% of sodium carbonate, saponified liquid ② contains 10-25 wt% of sodium methionine and 0-4 wt% of sodium carbonate, and saponified liquid ③ contains 10-25 wt% of potassium methionine and 0-20 wt% of potassium carbonate.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. Introducing saponification liquid containing methionine salt and carbonate into carbon dioxide for acidification and crystallization, performing solid-liquid separation, respectively collecting D, L-methionine crystals and crystallization mother liquor, drying the collected D, L-methionine crystals to obtain D, L-methionine, decarbonizing the crystallization mother liquor to obtain mother liquor decarbonization liquid, removing salt ions of 20-70 wt% of total salt ions in the mother liquor by bipolar membrane electrodialysis, performing secondary decarbonization to obtain decarbonization liquid of methionine salt and carbonate and carbon dioxide, and finally returning the decarbonization liquid of methionine salt and carbonate to the step of carbon dioxide acidification and crystallization for recycling;
the saponification liquid contains less than 4wt% of sodium carbonate and 10-25 wt% of sodium methionine or the saponification liquid contains less than 20wt% of potassium carbonate and 10-25 wt% of potassium methionine.
2. The clean production method of D, L-methionine as claimed in claim 1, wherein the acidification crystallization is conducted by introducing carbon dioxide under the conditions of 0-70 deg.C and 0.1-1.0 MPa pressure.
3. The clean production method of D, L-methionine as claimed in claim 1, wherein the bipolar membrane electrodialysis is performed by passing mother solution decarbonization solution into salt compartment, passing water or dilute alkali solution into alkali compartment, passing direct current through cathode and anode, and controlling pH value of salt compartment to 6.5-10.0 and temperature to 15-50 ℃.
4. The clean production method of D, L-methionine as claimed in claim 1, wherein the carbon dioxide recovered after the secondary decarbonization is recycled to the acidification crystallization step.
5. The clean production method of D, L-methionine according to claim 1, wherein the saponified solution is prepared by using 2-hydroxy-4-methylthiobutyronitrile, carbon dioxide, ammonia and water as raw materials to prepare a mixed aqueous solution of 5- (2-methylthioethyl) -hydantoin and ammonium bicarbonate, performing steam stripping to obtain a 5- (2-methylthioethyl) -hydantoin aqueous solution, adding sodium hydroxide for alkaline hydrolysis, and performing steam stripping after the alkaline hydrolysis is finished to obtain a saponified solution with a sodium carbonate content of less than 4wt% and a sodium methionine content of 10-25 wt%;
or the saponification liquid is prepared by the following method: preparing hydantoin by using cyanohydrin, carbon dioxide and ammonia as raw materials or using sodium cyanide, 3-methylthiopropanal, carbon dioxide and ammonia as raw materials, adjusting the pH value of the hydantoin to be 3.0-6.0 through alkaline hydrolysis and acidification to obtain a mixed solution containing 2.5-10 wt% of sodium carbonate and 10-25 wt% of sodium methionine, and diluting the mixed solution until the content of the sodium carbonate is within 4wt% and the content of the sodium methionine is 4-10 wt%; and removing sodium through bipolar membrane electrodialysis, decarbonizing, and concentrating to obtain a saponified solution with the sodium carbonate content of less than 4wt% and the sodium methionine content of 10-25 wt%.
6. The clean production method of D, L-methionine as claimed in claim 5, wherein the decarbonization conditions are 0-0.6 MPa, 70-150 ℃.
7. The clean production method of D, L-methionine according to claim 1, wherein the saponified solution is obtained by using 2-hydroxy-4-methylthiobutyronitrile, carbon dioxide, ammonia and water as raw materials to prepare a mixed aqueous solution of 5- (2-methylthioethyl) -hydantoin and ammonium bicarbonate, performing steam stripping to obtain an aqueous solution of 5- (2-methylthioethyl) -hydantoin, adding potassium hydroxide for alkaline hydrolysis, and performing steam stripping after the alkaline hydrolysis is finished to obtain a saponified solution containing within 20wt% of potassium carbonate and 10-25 wt% of potassium methionine.
8. The clean production method of D, L-methionine as claimed in claim 7, wherein the decarbonization conditions are 0-0.6 MPa, 100-180 ℃.
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| CN109734637B (en) * | 2019-02-14 | 2021-02-26 | 天宝动物营养科技股份有限公司 | Methionine crystallization mother liquor treatment method |
| CN112679397B (en) * | 2020-12-21 | 2023-08-01 | 宁夏紫光天化蛋氨酸有限责任公司 | Preparation method of DL-methionine |
| CN112661683A (en) * | 2020-12-22 | 2021-04-16 | 宁夏紫光天化蛋氨酸有限责任公司 | DL-methionine production method without discharged wastewater |
| CN116535338B (en) * | 2023-04-25 | 2023-11-03 | 重庆渝化新材料有限责任公司 | Potassium salt recycling process in production process of D, L-methionine |
| CN116675631B (en) * | 2023-06-07 | 2023-12-12 | 重庆渝化新材料有限责任公司 | Cyclic production method of D, L-methionine |
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| CN102399177B (en) * | 2010-09-15 | 2016-02-24 | 李宽义 | The environment-friendly clean process method of serialization synthetic methionine |
| CN104130169A (en) * | 2014-07-08 | 2014-11-05 | 重庆紫光化工股份有限公司 | Environment-friendly clean production method of D,L-methionine |
| CN105671587B (en) * | 2015-12-10 | 2018-02-13 | 浙江工业大学 | A kind of method and its device for preparing methionine and reclaiming accessory substance carbon dioxide |
| CN106083674B (en) * | 2016-06-03 | 2018-11-06 | 宁夏紫光天化蛋氨酸有限责任公司 | A kind of production method reducing carbonate in methionine saponification liquor |
| CN106349131B (en) * | 2016-08-26 | 2018-04-20 | 宁夏紫光天化蛋氨酸有限责任公司 | A kind of isolation and purification method of methionine |
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