CN104130169A - Environment-friendly clean production method of D,L-methionine - Google Patents
Environment-friendly clean production method of D,L-methionine Download PDFInfo
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- CN104130169A CN104130169A CN201410321782.9A CN201410321782A CN104130169A CN 104130169 A CN104130169 A CN 104130169A CN 201410321782 A CN201410321782 A CN 201410321782A CN 104130169 A CN104130169 A CN 104130169A
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- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 57
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- 238000000909 electrodialysis Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 35
- 229960004452 methionine Drugs 0.000 claims description 35
- 229930195722 L-methionine Natural products 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 26
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000029142 excretion Effects 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 239000012267 brine Substances 0.000 claims description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 150000008546 L-methionines Chemical class 0.000 claims description 6
- FFEARJCKVFRZRR-SCSAIBSYSA-N D-methionine Chemical compound CSCC[C@@H](N)C(O)=O FFEARJCKVFRZRR-SCSAIBSYSA-N 0.000 claims description 4
- 229930182818 D-methionine Natural products 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000010413 mother solution Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- BTUDTSGOEFVJTD-UHFFFAOYSA-N 2-amino-4-methylsulfanylbutanoic acid;sodium Chemical compound [Na].CSCCC(N)C(O)=O BTUDTSGOEFVJTD-UHFFFAOYSA-N 0.000 description 5
- IREPZTZSVPKCAR-WCCKRBBISA-M sodium;(2s)-2-amino-4-methylsulfanylbutanoate Chemical compound [Na+].CSCC[C@H](N)C([O-])=O IREPZTZSVPKCAR-WCCKRBBISA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 description 1
- YINJRVOAIYNHBT-UHFFFAOYSA-N CC(C(C(CCSC)N)=O)OC Chemical compound CC(C(C(CCSC)N)=O)OC YINJRVOAIYNHBT-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 125000000393 L-methionino group Chemical group [H]OC(=O)[C@@]([H])(N([H])[*])C([H])([H])C(SC([H])([H])[H])([H])[H] 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960003624 creatine Drugs 0.000 description 1
- 239000006046 creatine Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960005139 epinephrine Drugs 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an environment-friendly clean production method of D,L-methionine. The method comprises the following steps: (1) D,L-methionine salt water is adopted as a raw material, and is subjected to a bipolar membrane electrodialysis treatment in a bipolar membrane electrodialysis system, wherein the pH value in a salt chamber is controlled at 5.5-6.0, such that a D,L-methionine solution is obtained, and an alkali solution is obtained in an alkali chamber; and (2) D,L-methionine separated from the D,L-methionine solution obtained in the step (1). According to the invention, acid for neutralization is not needed, such that a by-product sulfate or hydrochloride is completely eliminated. The method causes no three-waste (waste gas, waste water, and solid waste) pollution, and helps reducing salt-containing waste water treatment cost. With the method, product quality is good, and yield is high. Also, according to the invention, the D,L-methionine salt is prepared with 2-hydroxy-4-methylthiobutyronitrile direct ammoniation, alkaline hydrolysis, and ammonia removing, such that carbonate is not produced. In the subsequent bipolar membrane electrodialysis treatment, energy consumption can be saved, and production cost can be reduced.
Description
Technical field
The present invention relates to a kind of D, the production method of L-Methionine, is specifically related to a kind of D, the environment friendly clean producing method of L-Methionine.
Background technology
D, L-Methionine has another name called methionine(Met), is one of fundamental unit forming in protein, is unique sulfur-containing amino acid in indispensable amino acid, and its structural formula is as follows:
D, L-Methionine is except participating in the metabolism of transfer, phosphorus of methyl in animal body and suprarenin, choline, creatine synthetic, or the raw material of synthetic protein and Gelucystine, therefore it is widely used in the fields such as medicine, food, feed and makeup, wherein very large as the consumption of fodder additives.But due to the restriction of technique and production cost, domestic output can not satisfy the demands, also need to be from external import.
Existing disclosed D, L-Methionine preparation method patent is many, and wherein the overwhelming majority prepares D by glycolylurea route, and L-Methionine, as CN1079095C, CN101602701A, CN1160043A, CN102633699A etc.This method is in order to obtain D, and L-Methionine, need to be by D, L-Methionine salt acid neutralization, and described acid is sulfuric acid, hydrochloric acid and carbonic acid etc.Vitriol or hydrochloride that sulfuric acid or hcl acidifying by-product are a large amount of, the a large amount of brine wastes that produce are difficult to process, and cause that complex process is loaded down with trivial details, production cost is higher, and also can dissolve a certain amount of D in acidified mother liquor, L-Methionine, causes that yield is lower, quality product is poor.Use carbonic acid acidifying, although salt of wormwood can recycled, due to the accumulation in order to reduce impurity, also to regularly discharge a certain amount of mother liquor, thereby cause D, the loss of L-Methionine product, in order to obtain highly purified D, L-Methionine, need to use a large amount of washings.
As can be seen here, conventional D, the L-Methionine production method three wastes are many, complex process, yield is low, cost is higher, and these are difficult to acceptance in industrial production.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of D, the environment friendly clean producing method of L-Methionine, does not produce by product, three-waste free pollution, and can improve product yield, reduce production costs.
For achieving the above object, the invention provides following technical scheme:
D of the present invention, the environment friendly clean producing method of L-Methionine, comprises the following steps:
1) with D, L-Methionine salt brine solution is raw material, enters bipolar membrane electrodialysis system and carries out bipolar membrane electrodialysis processing, and salt chamber is controlled pH=5.5 ~ 6.0 and obtained D, L-Methionine solution, and alkali chamber obtains alkaline solution;
2) D obtaining from step 1), isolates D in L-Methionine solution, L-Methionine.
Further, in described step 1), D, L-Methionine salt brine solution is made by following methods: 2-2-hydroxy-4-methylthio butyronitrile obtains 2-amino-4-methylthio group butyronitrile through aminating reaction, the basic hydrolysis of 2-amino-4-methylthio group butyronitrile is D, L-Methionine salt, has been hydrolyzed rear ammonia excretion, is then diluted to D, L-Methionine salt massfraction is 5% ~ 30%, refilter and remove micron, submicron and macromole impurity, obtain described D, L-Methionine salt brine solution.
Further, in described step 1), when 2-2-hydroxy-4-methylthio butyronitrile aminating reaction, the molar ratio of 2-2-hydroxy-4-methylthio butyronitrile and ammonia is 1:4 ~ 10, and temperature of reaction is 40 ~ 100 DEG C, and the reaction times is 5 ~ 50min, and reaction pressure is 0.2～3MPa.
Further, in described step 1), 2-amino-4-methylthio group butyronitrile basic hydrolysis alkali used is sodium hydroxide, and the molar ratio of 2-amino-4-methylthio group butyronitrile and sodium hydroxide is 1:1.05～1.5, temperature of reaction is 65～180 DEG C, and the reaction times is 60 ~ 120min.
Further, in described step 1), the mode of ammonia excretion is gas stripping column ammonia excretion or decompression ammonia excretion, and in the hydrolyzed solution after ammonia excretion, the content of ammonia is not higher than 50ppm.
Further, in described step 1), the alkaline solution recycled that alkali chamber obtains is to the basic hydrolysis step of 2-amino-4-methylthio group butyronitrile.
Further, in described step 1), bipolar membrane electrodialysis system one side and an other side are respectively equipped with the cathode compartment (I) of built-in negative electrode and are provided with anolyte compartment's (II) of built-in anode, between cathode compartment and anolyte compartment, be provided with film pair, one film forms the Bipolar Membrane (BP) by space and a cationic exchange membrane (C), the anode that described film is Bipolar Membrane to the relative position of Bipolar Membrane and cationic exchange membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, between two Bipolar Membrane, be provided with a cationic exchange membrane, cathode direction and the anode membrane of described film to Bipolar Membrane forms alkali chamber (III), anode membrane and Bipolar Membrane anode direction form salt chamber (IV).
Further, in described step 1), bipolar membrane electrodialysis processing is to pass into D in salt chamber, and L-Methionine salt brine solution passes into water or rare alkaline solution in alkali chamber, and negative electrode and anode pass into direct current.
Further, described step 2) in, by D, L-Methionine solution crystallisation by cooling or concentrated rear crystallisation by cooling, crystal solution is filtered, and after filter cake washing, oven dry, obtains D, L-Methionine; D after crystallization, L-Methionine Recycling Mother Solution cover is used D, and L-Methionine crystallization or cover are used D, the dilution of L-Methionine salt.
Beneficial effect of the present invention is:
1) the present invention adopts bipolar membrane electrodialysis technology by D, L-Methionine salt is converted into D, L-Methionine, reclaim corresponding alkali simultaneously, neutralize without acid adding, thereby eliminated by-product vitriol or hydrochloride completely, three-waste free pollution, reduce the processing cost of brine waste, and good product quality, yield is high.
2) in the present invention, adopt the direct ammonification of 2-2-hydroxy-4-methylthio butyronitrile, then hydrolysis, reclaims ammonia, its reaction formula following (being hydrolyzed to example with sodium hydroxide alkali):
Can draw from reaction formula, at preparation D, when L-Methionine salt, be not consume ammonia before and after reaction, and therefore reaction formula can be summarized as follows:
Compared with glycolylurea hydrolysis route, the above-mentioned synthetic D of the present invention, the operational path of L-Methionine salt can not produce carbonate, in the time that follow-up bipolar membrane electrodialysis is processed, can save energy consumption, reduces production costs.
3) alkaline solution that the present invention obtains in bipolar membrane electrodialysis can recycle, and separates D, and the mother liquor after L-Methionine can recycled, has saved D, the production cost of L-Methionine.
Brief description of the drawings
In order to make object of the present invention, technical scheme and beneficial effect clearer, the invention provides following accompanying drawing and describe:
Fig. 1 is the process flow sheet of bipolar membrane electrodialysis processing in the embodiment of the present invention 1.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
embodiment 1
1) preparation of 2-amino-4-methylthio group butyronitrile: at 85 DEG C, the ammoniacal liquor that is 40% by 625.5g massfraction imports in stainless steel high-pressure reactor, and this high-pressure reactor is equipped with agitator, thermometer, tensimeter, feed-pipe and thermal source.Then, in 2 minutes, add 96% 2-2-hydroxy-4-methylthio butyronitrile 272.9g with pump, warming while stirring to 60 DEG C, pressure reaches 1MPa, at the same temperature, continue to stir 15 minutes, be then cooled to 15 DEG C, decompression is to normal pressure, HPLC analyze reaction mixture, shows to have 2-amino-4-methylthio group butyronitrile of 99.5% theoretical amount to generate.
2) D, the preparation of L-Methionine sodium: add 220 grams, 40% sodium hydroxide in reactor, be preheated to 65 DEG C, then slowly drip 2-amino-4-methylthio group butyronitrile aqueous solution of above-mentioned acquisition, after dropwising, stir 40 minutes at 65 DEG C, be then warming up to 170 DEG C, under 170 DEG C and pressure 3.0MPa condition, continue to stir 1 hour, then be cooled to room temperature, obtain the liquid of reddish-brown, by analysis hydrolyzed solution, show to have 98.5% D normally measuring, L-Methionine sodium generates; This hydrolyzed liquid, through decompression ammonia excretion, obtains D, L-Methionine sodium water solution, and the content of ammonia, not higher than 50ppm, will add softening water through the liquid of ammonia excretion processing, and by D, the mass percent of L-Methionine sodium is diluted to 6%; Then by D, L-Methionine sodium diluent filters by ultra-filtration membrane, nanofiltration membrane combination with the flow velocity of 20L/h, removes micron, submicron and macromole impurity thereof, the D obtaining, 568.1 grams of L-Methionine sodium water solutions, D, L-Methionine sodium content is 5.9%, and the pH of feed liquid is 13.
3) above-mentioned D, L-Methionine sodium water solution enters bipolar membrane electrodialysis system and carries out bipolar membrane electrodialysis processing, the technical process of bipolar membrane electrodialysis processing as shown in Figure 1, bipolar membrane electrodialysis system one side and an other side are respectively equipped with the cathode compartment (I) of built-in negative electrode and are provided with anolyte compartment's (II) of built-in anode, between cathode compartment and anolyte compartment, be provided with film pair, one film forms the Bipolar Membrane (BP) by space and a cationic exchange membrane (C), the anode that described film is Bipolar Membrane to the relative position of Bipolar Membrane and cationic exchange membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, between two Bipolar Membrane, be provided with a cationic exchange membrane, cathode direction and the anode membrane of described film to Bipolar Membrane forms alkali chamber (III), anode membrane and Bipolar Membrane anode direction form salt chamber (IV), in salt chamber, pass into D, L-Methionine sodium water solution, passes into massfraction and is 2% sodium hydroxide solution in alkali chamber, and negative electrode and anode pass into direct current, pH in salt chamber is controlled at 5.6 for electrodialysis terminal, analyzes the D in salt chamber, L-Methionine, and its yield is greater than 99%, and the sodium hydroxide massfraction in alkali chamber is 8.2%.
4) obtain 40% aqueous sodium hydroxide solution by concentrated the sodium hydroxide of alkali chamber, be circulated to the hydrolysing step of 2-amino-4-methylthio group butyronitrile.By the D in salt chamber, L-Methionine solution is 20% through being concentrated into massfraction, is then cooled to 3 DEG C of crystallizations, and suction filtration obtains D, L-Methionine wet product, drying, obtains the D of content 99.5%, L-Methionine, D after crystallization, L-Methionine Recycling Mother Solution cover is used D, and L-Methionine crystallization or cover are used D, the dilution of L-Methionine sodium.
Finally explanation is, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is described in detail by above preferred embodiment, but those skilled in the art are to be understood that, can make various changes to it in the form and details, and not depart from the claims in the present invention book limited range.
Claims (9)
1. a D, the environment friendly clean producing method of L-Methionine, is characterized in that: comprise the following steps:
1) with D, L-Methionine salt brine solution is raw material, enters bipolar membrane electrodialysis system and carries out bipolar membrane electrodialysis processing, and salt chamber is controlled pH=5.5 ~ 6.0 and obtained D, L-Methionine solution, and alkali chamber obtains alkaline solution;
2) D obtaining from step 1), isolates D in L-Methionine solution, L-Methionine.
2. D according to claim 1, the environment friendly clean producing method of L-Methionine, it is characterized in that: in described step 1), D, L-Methionine salt brine solution is made by following methods: 2-2-hydroxy-4-methylthio butyronitrile obtains 2-amino-4-methylthio group butyronitrile through aminating reaction, the basic hydrolysis of 2-amino-4-methylthio group butyronitrile is D, L-Methionine salt, be hydrolyzed rear ammonia excretion, then be diluted to D, L-Methionine salt massfraction is 5% ~ 30%, refilters and removes micron, submicron and macromole impurity, obtain described D, L-Methionine salt brine solution.
3. D according to claim 2, the environment friendly clean producing method of L-Methionine, it is characterized in that: in described step 1), when 2-2-hydroxy-4-methylthio butyronitrile aminating reaction, the molar ratio of 2-2-hydroxy-4-methylthio butyronitrile and ammonia is 1:4 ~ 10, temperature of reaction is 40 ~ 100 DEG C, and the reaction times is 5 ~ 50min, and reaction pressure is 0.2～3MPa.
4. D according to claim 2, the environment friendly clean producing method of L-Methionine, it is characterized in that: in described step 1), 2-amino-4-methylthio group butyronitrile basic hydrolysis alkali used is sodium hydroxide, the molar ratio of 2-amino-4-methylthio group butyronitrile and sodium hydroxide is 1:1.05～1.5, temperature of reaction is 65～180 DEG C, and the reaction times is 60 ~ 120min.
5. D according to claim 2, the environment friendly clean producing method of L-Methionine, is characterized in that: in described step 1), the mode of ammonia excretion is gas stripping column ammonia excretion or decompression ammonia excretion, and in the hydrolyzed solution after ammonia excretion, the content of ammonia is not higher than 50ppm.
6. D according to claim 2, the environment friendly clean producing method of L-Methionine, is characterized in that: in described step 1), the alkaline solution recycled that alkali chamber obtains is to the basic hydrolysis step of 2-amino-4-methylthio group butyronitrile.
7. D according to claim 1, the environment friendly clean producing method of L-Methionine, it is characterized in that: in described step 1), bipolar membrane electrodialysis system one side and an other side are respectively equipped with the cathode compartment (I) of built-in negative electrode and are provided with anolyte compartment's (II) of built-in anode, between cathode compartment and anolyte compartment, be provided with film pair, one film forms the Bipolar Membrane (BP) by space and a cationic exchange membrane (C), the anode that described film is Bipolar Membrane to the relative position of Bipolar Membrane and cationic exchange membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, between two Bipolar Membrane, be provided with a cationic exchange membrane, cathode direction and the anode membrane of described film to Bipolar Membrane forms alkali chamber (III), anode membrane and Bipolar Membrane anode direction form salt chamber (IV).
8. D according to claim 7, the environment friendly clean producing method of L-Methionine, is characterized in that: in described step 1), bipolar membrane electrodialysis processing is to pass into D in salt chamber, L-Methionine salt brine solution, passes into water or rare alkaline solution in alkali chamber, negative electrode and anode pass into direct current.
9. D according to claim 1, the environment friendly clean producing method of L-Methionine, is characterized in that: described step 2) in, by D, L-Methionine solution crystallisation by cooling or concentrated rear crystallisation by cooling, crystal solution is filtered, after filter cake washing, oven dry, obtain D, L-Methionine; D after crystallization, L-Methionine Recycling Mother Solution cover is used D, and L-Methionine crystallization or cover are used D, the dilution of L-Methionine salt.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744280A (en) * | 2015-04-07 | 2015-07-01 | 湖北锡太化工有限公司 | Method of preparing sarcosine by bipolar membrane electrodialysis process |
| CN104844485A (en) * | 2015-04-16 | 2015-08-19 | 重庆紫光化工股份有限公司 | Clean production method of methionine |
| CN104892521A (en) * | 2015-03-16 | 2015-09-09 | 河北威远生化农药有限公司 | Synthesis and purification method for alpha-amino acid compound |
| CN106349131A (en) * | 2016-08-26 | 2017-01-25 | 宁夏紫光天化蛋氨酸有限责任公司 | Separation and purification method of methionine |
| CN108658821A (en) * | 2017-06-13 | 2018-10-16 | 宁夏紫光天化蛋氨酸有限责任公司 | D, clean preparation method of L-Methionine and products thereof |
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| CN104892521A (en) * | 2015-03-16 | 2015-09-09 | 河北威远生化农药有限公司 | Synthesis and purification method for alpha-amino acid compound |
| CN104892521B (en) * | 2015-03-16 | 2018-04-24 | 河北威远生物化工有限公司 | A kind of synthesis of alpha-amido acid compounds and purification process |
| CN104744280A (en) * | 2015-04-07 | 2015-07-01 | 湖北锡太化工有限公司 | Method of preparing sarcosine by bipolar membrane electrodialysis process |
| CN104844485A (en) * | 2015-04-16 | 2015-08-19 | 重庆紫光化工股份有限公司 | Clean production method of methionine |
| CN104844485B (en) * | 2015-04-16 | 2017-01-04 | 宁夏紫光天化蛋氨酸有限责任公司 | The clean preparation method of methionine |
| CN106349131A (en) * | 2016-08-26 | 2017-01-25 | 宁夏紫光天化蛋氨酸有限责任公司 | Separation and purification method of methionine |
| 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 |
| CN108658821A (en) * | 2017-06-13 | 2018-10-16 | 宁夏紫光天化蛋氨酸有限责任公司 | D, clean preparation method of L-Methionine and products thereof |
| CN109734637A (en) * | 2019-02-14 | 2019-05-10 | 禄丰天宝磷化工有限公司 | Methionine crystallization mother liquor treatment method |
| CN113087634A (en) * | 2019-12-23 | 2021-07-09 | 武汉远大弘元股份有限公司 | Preparation method of L-lysine-S-carboxymethyl-L-cysteine salt |
| CN113087634B (en) * | 2019-12-23 | 2023-03-24 | 武汉远大弘元股份有限公司 | Preparation method of L-lysine-S-carboxymethyl-L-cysteine salt |
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