• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a continuous process for the manufacture of methionine by alkaline hydrolysis of hydantoin of methionine in the aqueous phase, removal of NH3 and CO2 from the hydrolysis medium, and neutralization of the methioninate salt obtained, according to which, after elimination of NH3 and CO2, the hydrolysis reaction medium is concentrated to precipitate Na2CO3, said Na2CO3 being separated and then recycled for alkaline hydrolysis, this being carried out in the presence of NaOH and Na2CO3.
    公开号:FR3035400A1
    申请号:FR1553547
    申请日:2015-04-21
    公开日:2016-10-28
    发明作者:Nicolas Capelle；Patrick Rey
    申请人:Adisseo France SAS；
    IPC主号:
    专利说明:

    [0001] The invention relates to an improvement of the methionine production process from the hydantoin of methionine. Methionine is an essential amino acid in humans, so it must be provided by its diet. But its major market is that of animal nutrition for which it is produced in hundreds of thousands of tons per year. It is essentially made by chemical synthesis. One of the known chemical processes for obtaining methionine, see for example US2557920A, comprises a step of converting the hydantoin of methionine by alkaline hydrolysis, or saponification, methioninate salt and then neutralization of methioninate methionine . The hydrolysis of the hydantoin of methionine is carried out in the presence of sodium hydroxide and / or sodium carbonate, in the aqueous phase. It is manifested by a simultaneous removal of carbon dioxide and ammonia which leads to methionine salt, sodium methioninate. Carbon dioxide and ammonia are removed from the hydrolysis medium, and then the hydrolysis reaction medium containing the methioninate salt is neutralized with sulfuric acid to yield methionine. This is then separated and purified by crystallization. The typical reaction conditions of the above steps are as follows: Alkaline hydrolysis can be carried out in the presence of an excess of sodium hydroxide, from 1.3 to 3.5 eq, preferably from 1.7 to 2. , 5 eq., For temperatures between 150 and 200 ° C. After removal of ammonia and carbon dioxide from the saponification medium, the neutralization is generally carried out by adding concentrated sulfuric acid until a pH of between 3 and 6 is reached at temperatures between 70.degree. and 130 ° C. The methionine can then be purified by crystallization, subsequently, by cooling. The methionine is then separated from the sodium sulfate formed by filtration at 30-50 ° C. The predominant disadvantage of this synthesis is the formation of large volumes of sodium sulphate at the end of the neutralization, which can not be recycled in the methionine production process and which are difficult to recover. The prior art provides some answers to this problem, with processes for producing aqueous solutions of sodium methioninate which are used in place of solid methionine. According to these processes, a saponification of the methionine hydantoin is carried out in the presence of sodium hydroxide, and a part of the sodium carbonate formed during the alkaline hydrolysis is separated and can be recycled to the saponification stage, allowing to obtain an aqueous methioninate solution less concentrated in sodium carbonate. Thus according to US4391987A, the sodium carbonate is separated by cold precipitation, at a temperature ranging from -10 ° C to 5 ° C. This has the disadvantage of using refrigerants and having to cool a saponification solution at more than 100 ° C, resulting in a significantly high energy cost. US6126972A improves this separation by concentrating the saponification solutions to precipitate hot (100-130 ° C) sodium carbonate and separate by hot filtration (100-130 ° C). The purpose of this separation is to obtain sodium methioninate, which can subsequently be granulated via a fluidized bed. The invention is part of the development of a process for the production of solid methionine, of high purity, which has the advantage of being much more effective for animal nutrition, at equal weight than its salt, the methionine of sodium, and to date, it is still not remedied the excessive co-production of sodium sulfate during the neutralization of methionine methionine. The invention provides a solution with a method of manufacturing methionine having an additional step to significantly reduce the amount of sodium sulfate formed. This process can be carried out on an industrial scale via a continuous or batch process. The yields of methionine are almost quantitative and the quality of the methionine is not affected by the modification.
    [0002] Thus, the process of the invention comprises alkaline hydrolysis of hydantoin of methionine in aqueous phase, removal of NH3 and CO2 from the hydrolysis medium, and neutralization of the methioninate salt, said method comprising a step concentration of the hydrolysis reaction medium, after removal of NH3 and CO2, this concentration for precipitating Na2CO3, said Na2CO3 being separated and recycled to the previous alkaline hydrolysis step. The alkaline hydrolysis step of the process of the invention is therefore carried out in the presence of NaOH and of Na2CO3, which makes it possible, on the one hand, to significantly reduce the quantity of sodium hydroxide required, this reduction being compensated by a contribution of sodium carbonate from the process itself, and secondly, to reduce the amount of sodium sulfate formed after the neutralization. A reduction of 3035400 to 50% (w / w) of the amount of sodium sulfate per kg of methionine produced can be measured. The hydrolysis medium comprises sodium methioninate and sodium carbonate which have different solubility profiles, depending on the temperature and their respective concentrations. The difficulty lies in a reproducible compromise between a crystallization of a maximum amount of sodium carbonate and that of a minimal amount of sodium methioninate which will determine the conditions of neutralization of methioninate methionine. The inventors first observed that a sodium carbonate extraction step could be inserted into an industrial methionine synthesis process in order to solve the problem of coproduction of sodium sulphate and furthermore defined conditions. in which the above compromise was achieved so as not to affect the performance of the neutralization step to obtain methionine. They are described below and may be considered alone or in combination. Advantageously, the concentration, or enrichment, of the sodium carbonate medium is carried out by removing the water from the medium until a concentration of the methioninate salt varies from 20 to 70%, advantageously from 30 to 50%, expressed by mass of sodium methioninate relative to the mass of the medium.
    [0003] Any technique well known to those skilled in the art can be used to concentrate the medium. Elimination of water by evaporation at a temperature ranging from 90 to 100 ° C under atmospheric pressure is particularly effective. It allows crystallization of a maximum amount of sodium carbonate while maintaining a maximum content of methioninate salt in solution in the medium for the next neutralization step. According to another variant, the elimination of water is carried out by evaporation under vacuum at a temperature ranging from 30 to 90 ° C., preferably 40 to 60 ° C. The alkaline hydrolysis medium of hydrantoin may comprise pure methionine hydantoin, hydantoin unpurified or partially purified from its synthetic medium. The hydantoin of methionine can be obtained from 2-hydroxy-4-methylthiobutyronitrile (HMTBN). In this case, it is preferably not isolated from the reaction medium and the latter is directly subjected to the saponification conditions. It is then preferable that the proportion of the hydantoin of the methionine in said reaction medium is at least 10%. Advantageously, a prior removal of the ammonia and carbon dioxide produced during the synthesis of the methionine hydantoin is carried out.
    [0004] Preferably, for the alkaline hydrolysis of the hydantoin of methionine, the molar ratio of the sum of the bases to the sum of the sulfur-containing products (Na / S) is at least 2, preferably between 2, 5 and 4. Such a ratio makes it possible to achieve saponification yields greater than 98%. In particular, it makes it possible to limit the formation of methionine dipeptides. The quantity of sulfur is, of course, mainly provided by the hydantoin of the methionine of the reaction medium, where it is formed from HMTBN; it also comes, in minor amounts, from the unconsumed HMTBN and hydantoin from the methionine present as impurities in the recycled sodium carbonate and introduced into the saponification medium. The sodium is supplied by the sodium hydroxide added as saponification reagent and by the sodium carbonate recovered at the end of the concentration of the hydrolysis medium and recycled. Preferably, the molar ratio of NaOH / Na2CO3 in the hydrolysis medium ranges from 0.5 to 3, preferably 2. The crystallized sodium carbonate in the hydrolysis medium is separated by any technique well known to man. of the art, for example by filtration. According to an advantageous variant of the process of the invention, the sodium carbonate is filtered at a temperature ranging from 70 to 130 ° C., preferably from 90 to 110 ° C. This hot filtration is carried out after a sufficient concentration of the saponification flow to precipitate the desired amount of sodium carbonate.
    [0005] In a preferred embodiment of the process of the invention, after separation, the recovered Na 2 CO 3 is dissolved beforehand in the water removed during the concentration of the sodium carbonate hydrolysis medium, and then recycled to the stage of hydrolysis of methionine hydantoin. The flow of sodium methioninate can then be neutralized with sulfuric acid as in the conventional methionine production process, but also with carbon dioxide, in the form of pressurized gas, which makes it possible to neutralize the medium. in the form of sodium bicarbonate and methionine, which precipitates from the medium and can be separated by filtration. The neutralization is advantageously carried out at a temperature ranging from 10 to 60 ° C.
    [0006] The method of the invention is illustrated in the following examples, in support of the following single figure. The figure shows the synthesis block diagram of methionine incorporating a step of concentration of the hydrolysis medium in sodium carbonate, according to the invention. Methionine is made from 2-hydroxy-4-methylthiobutyronitrile (HMTBN) which is converted to methionine hydantoin by any known technique, such as ammonia hydrolysis, in the presence of ammonium bicarbonate. The methionine hydantoin is then saponified with sodium hydroxide, and the saponification sap is neutralized. According to the invention, a saponification juice concentration step is thus added, it makes it possible to precipitate the sodium carbonate, which is separated from the sodium methioninate by filtration, resuspended in aqueous suspension and then recycled at the stage of saponification. Compared to the conventional method, the co-production of sodium sulfate is greatly reduced. Example 1: Saponification step In an autoclave, 92 g of 50% (w / w) sodium hydroxide, 52 g of sodium carbonate and 520 g of synthesis flux of methionine hydantoin, containing 139 g of sodium hydroxide were charged. hydantoin and derivatives (hydantoic acid, methioninamide, ureido-butyramide). The medium is heated at 180 ° C. for 30 minutes, the autogenous pressure is 10 bars. After cooling, the determination of the reaction medium by liquid chromatography makes it possible to calculate a methionine yield greater than 98%. Before being engaged in the concentration step for crystallization of sodium carbonate, the saponification flow is pre-concentrated by stripping with nitrogen.
    [0007] EXAMPLE 2 Sodium carbonate separation step 1100 g of a saponification flow from the above concentration and containing 150 g of sodium methioninate and 110 g of sodium carbonate are concentrated at 90-110 ° C. by evaporation. 600 g of water containing ammonium carbonate are thus eliminated. The resulting medium, in which a part of the sodium carbonate has precipitated, is filtered at 90 ° C. under nitrogen pressure (150 mbar). 165 g of a solid, containing sodium carbonate and sodium methioninate, is separated, which can be recycled to the saponification stage. 340 g of mother liquor containing 125 g of sodium methioninate are recovered for the next neutralization stage.
    [0008] Example 3: Neutralization step / Crystallization of Methionine In a reactor, 740 g of mother liquors of sodium carbonate filtration obtained in Example 2, containing 190 g of sodium methioninate and 50 g of sodium carbonate, are charged. having not crystallized in the previous step. The resulting medium is neutralized at 90-100 ° C to pH 4.5 by the addition of 135 g of 92.5% sulfuric acid. The methionine is crystallized in the stream by cooling to 40 ° C. It is separated by filtration under nitrogen pressure and after washing with 100 g of water, 200 g of juice containing 2.2% of methionine are obtained. After drying at 100 ° C., 170 g of methionine dry cake are obtained at 95% purity and containing 4% of residual sodium sulphate. 5
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. Continuous process for producing methionine by alkaline hydrolysis of methionine hydantoin in the aqueous phase, removal of NH3 and CO2 from the hydrolysis medium, and neutralization of the obtained methioninate salt, characterized in that after removal of NH 3 and CO2, the hydrolysis reaction medium is concentrated to precipitate Na2CO3, said Na2CO3 being separated and then recycled for alkaline hydrolysis, the latter being carried out in the presence of NaOH and Na2CO3.
    [0002]
    2. Method according to claim 1, characterized in that the hydrolysis reaction medium contains methioninate salt and in that the concentration is carried out by removing the water from the medium to a concentration of the methioninate salt varying from 20 to 70%, by weight of sodium methioninate relative to the mass of the medium, preferably from 30 to 50%.
    [0003]
    3. Method according to claim 2, characterized in that the removal of the water is carried out by evaporation at a temperature ranging from 90 to 110 ° C under atmospheric pressure.
    [0004]
    4. Method according to claim 2, characterized in that the removal of water is carried out by evaporation under vacuum at a temperature ranging from 30 to 90 ° C, preferably 40 to 60 ° C. 20
    [0005]
    5. Method according to any one of claims 1 to 4, characterized in that the Na2CO3 is separated by filtration at a temperature ranging from 70 to 130 ° C.
    [0006]
    6. Method according to any one of claims 1 to 5, characterized in that after separation, Na2CO3 is dissolved in the evaporated water and recycled to hydrolysis hydantoin methionine. 25
    [0007]
    7. Method according to any one of claims 1 to 6, characterized in that the Na / S molar ratio for the alkaline hydrolysis of the hydantoin of methionine is at least 2.0, preferably between 2 , 5 and 4.
    [0008]
    8. Process according to claim 7, characterized in that the molar ratio of NaOH / Na2CO3 varies from 1 to 3.
    [0009]
    9. Process according to any one of claims 1 to 8, characterized in that the hydrolysis medium is neutralized with sulfuric acid.
    [0010]
    10. Process according to any one of claims 1 to 8, characterized in that the hydrolysis medium is neutralized with carbon dioxide.
    [0011]
    Process according to claim 9 or 10, characterized in that the hydrolysis medium is neutralized at a temperature ranging from 10 to 60 ° C. 3035400 8
    [0012]
    12. Process according to any one of claims 1 to 11, characterized in that the hydantoin of methionine is obtained from 2-hydroxy-4-methylthiobutyronitrile (HMTBN) and is not isolated from the reaction medium. .
    [0013]
    13. Process according to claim 12, characterized in that the proportion of hydantoin of the methionine in said reaction medium is at least 10%.
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    公开号 | 公开日
    ES2737735T3|2020-01-15|
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    RU2017134700A3|2019-08-23|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2557920A|1946-11-07|1951-06-19|Dow Chemical Co|Method for production of amino acids|
    US6126972A|1998-05-16|2000-10-03|Degussa-Huls Ag|Process for the preparation of aqueous sodium methioninate solutions and use of those solutions in the production of a granulate|
    CH529118A|1969-02-08|1972-10-15|Degussa|Process for the production of methionine|
    US4069251A|1969-02-08|1978-01-17|Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler|Continuous process for the manufacture of methionine|
    DE3105007A1|1981-02-12|1982-09-09|Degussa Ag, 6000 Frankfurt|METHOD FOR PRODUCING AQUEOUS SODIUM METHIONINATE SOLUTIONS |
    CN1178909C|1999-05-21|2004-12-08|住友化学工业株式会社|Prepn. of methionine|
    JP2010111642A|2008-11-07|2010-05-20|Sumitomo Chemical Co Ltd|Method for producing methionine|WO2018210615A1|2017-05-15|2018-11-22|Evonik Degussa Gmbh|Process for preparing methionine|
    EP3404018A1|2017-05-15|2018-11-21|Evonik Degussa GmbH|Process for preparing methionine|
    CN108658819A|2017-06-13|2018-10-16|宁夏紫光天化蛋氨酸有限责任公司|A kind of clean preparation method of methionine|
    CN108658820A|2017-06-13|2018-10-16|宁夏紫光天化蛋氨酸有限责任公司|Reduce the methionine production method of by-product sodium sulphate|
    EP3431465A1|2017-07-21|2019-01-23|Evonik Degussa GmbH|Process for preparing methionine|
    EP3730479A4|2017-12-19|2021-09-22|Sumitomo Chemical Company Limited|Method for manufacturing methionine|
    CN110483348B|2019-09-03|2021-12-07|蓝星安迪苏南京有限公司|Mixtures comprising hydroxy analogues of methionine and oligomers thereof and process for preparing same|
    法律状态:
    2016-02-23| PLFP| Fee payment|Year of fee payment: 2 |
    2016-10-28| PLSC| Search report ready|Effective date: 20161028 |
    2017-02-23| PLFP| Fee payment|Year of fee payment: 3 |
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    2021-01-15| ST| Notification of lapse|Effective date: 20201214 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1553547A|FR3035400B1|2015-04-21|2015-04-21|PROCESS FOR THE PRODUCTION OF METHIONINE|FR1553547A| FR3035400B1|2015-04-21|2015-04-21|PROCESS FOR THE PRODUCTION OF METHIONINE|
    JP2017553259A| JP6778212B2|2015-04-21|2016-04-15|How to make methionine|
    SG11201708366QA| SG11201708366QA|2015-04-21|2016-04-15|Method for making methionine|
    KR1020177025796A| KR20170140167A|2015-04-21|2016-04-15|Methionine manufacturing method|
    CN201680023411.XA| CN107531621A|2015-04-21|2016-04-15|The method for preparing methionine|
    US15/567,742| US10494335B2|2015-04-21|2016-04-15|Method for making methionine|
    ES16721196T| ES2737735T3|2015-04-21|2016-04-15|Methionine Manufacturing Procedure|
    EP16721196.0A| EP3286167B1|2015-04-21|2016-04-15|Method for making methionine|
    RU2017134700A| RU2708258C2|2015-04-21|2016-04-15|Method of producing methionine|
    PCT/FR2016/050883| WO2016170252A1|2015-04-21|2016-04-15|Method for making methionine|
    TW105112132A| TWI686379B|2015-04-21|2016-04-19|Methionine manufacturing process|
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