CN105017111A - Preparation method of methionine sodium - Google Patents
Preparation method of methionine sodium Download PDFInfo
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- CN105017111A CN105017111A CN201510412094.8A CN201510412094A CN105017111A CN 105017111 A CN105017111 A CN 105017111A CN 201510412094 A CN201510412094 A CN 201510412094A CN 105017111 A CN105017111 A CN 105017111A
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- sodium
- methioninate
- aqueous solution
- preparation
- carbonate
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- IREPZTZSVPKCAR-WCCKRBBISA-M sodium;(2s)-2-amino-4-methylsulfanylbutanoate Chemical compound [Na+].CSCC[C@H](N)C([O-])=O IREPZTZSVPKCAR-WCCKRBBISA-M 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 82
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 66
- 239000007864 aqueous solution Substances 0.000 claims abstract description 53
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 50
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 42
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 41
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 33
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 25
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 25
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 21
- 239000000292 calcium oxide Substances 0.000 claims abstract description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 15
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 230000029142 excretion Effects 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- -1 methylmercaptoethyl Chemical group 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001424 calcium ion Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 4
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 abstract description 14
- 235000011116 calcium hydroxide Nutrition 0.000 abstract description 12
- SBKRXUMXMKBCLD-UHFFFAOYSA-N 5-(2-methylsulfanylethyl)imidazolidine-2,4-dione Chemical compound CSCCC1NC(=O)NC1=O SBKRXUMXMKBCLD-UHFFFAOYSA-N 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- 235000012255 calcium oxide Nutrition 0.000 description 10
- 229940087373 calcium oxide Drugs 0.000 description 10
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 8
- 229930182817 methionine Natural products 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 125000001360 methionine group Chemical group N[C@@H](CCSC)C(=O)* 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- LWJVROOSERVUAF-UHFFFAOYSA-N N-carbamoyl-2-hydroxy-N-(2-methylsulfanylethyl)acetamide Chemical compound CSCCN(C(N)=O)C(=O)CO LWJVROOSERVUAF-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BTUDTSGOEFVJTD-WCCKRBBISA-N (2s)-2-amino-4-methylsulfanylbutanoic acid;sodium Chemical compound [Na].CSCC[C@H](N)C(O)=O BTUDTSGOEFVJTD-WCCKRBBISA-N 0.000 description 3
- CQSQMXIROIYTLO-UHFFFAOYSA-N 2-methylpropanethial Chemical compound CC(C)C=S CQSQMXIROIYTLO-UHFFFAOYSA-N 0.000 description 3
- GSYTVXOARWSQSV-BYPYZUCNSA-N L-methioninamide Chemical compound CSCC[C@H](N)C(N)=O GSYTVXOARWSQSV-BYPYZUCNSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MWLKEJXYXYRWIH-UHFFFAOYSA-N 2-amino-4-methylsulfanylbutanenitrile Chemical compound CSCCC(N)C#N MWLKEJXYXYRWIH-UHFFFAOYSA-N 0.000 description 2
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000007873 sieving 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 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
- 239000005864 Sulphur Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- RPHZRUDLEUBFCM-UHFFFAOYSA-L calcium;methanedisulfonate Chemical class [Ca+2].[O-]S(=O)(=O)CS([O-])(=O)=O RPHZRUDLEUBFCM-UHFFFAOYSA-L 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229960003624 creatine Drugs 0.000 description 1
- 239000006046 creatine Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960005139 epinephrine Drugs 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000002741 methionine derivatives Chemical class 0.000 description 1
- 108010085203 methionylmethionine Proteins 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of methionine sodium, specifically a preparation method of a methionine sodium aqueous solution and a methionine sodium solid. The preparation method comprises specific steps as follows: using a 5-(methylthioethyl)-hydantoin aqueous solution containing sodium carbonate or sodium bicarbonate as a raw material, and hydrolyzing the raw material by adding calcium oxide or calcium hydrate so as to obtain a methionine sodium aqueous solution containing calcium carbonate and ammonia; separating the methionine sodium aqueous solution containing calcium carbonate and ammonia to remove calcium carbonate precipitate, and continuously discharging ammonia out of a filtrate obtained after separation of the calcium carbonate precipitate so as to obtain a methionine sodium aqueous solution; and concentrating the methionine sodium aqueous solution and drying so as to obtain a methionine sodium solid. The prepared methionine sodium contains no sodium carbonate or sodium bicarbonate and has high purity. The preparation method can be used to realize continuous production and is suitable for large-scale industrial production of methionine sodium.
Description
Technical field
The invention belongs to chemical field, be specifically related to the preparation method of the Sodium L-methioninate aqueous solution and Sodium L-methioninate solid.
Background technology
Methionine(Met), it is one of fundamental unit forming protein, unique amino acid containing sulphur in indispensable amino acid, except participating in the synthesis of the transfer of methyl in animal body, the metabolism of phosphorus and suprarenin, choline, creatine, or the raw material of synthetic protein and Gelucystine.So methionine(Met), the methionine salt aqueous solution and surrogate such as methionine hydroxy analog (MHA), particularly Sodium L-methioninate (patent DE3105009C) to be widely used as the fodder additives of raise poultry, pig and other economy animal in the whole world.
As required, Sodium L-methioninate can be solid-state form, also can be the form of liquid.The methionine concentration of commercially available sodium methionine solution is 40wt%, and its biological value is equal to solid-state methionine(Met).At present, mainly contain following three kinds of methods and prepare this type of sodium methionine solution:
Method 1: the highly purified methionine(Met) of separation is dissolved in the aqueous sodium hydroxide solution of equivalent;
Method 2:5-(2-methylmercaptoethyl)-glycolylurea aqueous solution is with sodium hydroxide and/or sodium carbonate hydrolysis;
Method 3: the sodium hydroxide of methionine amide and/or sodium carbonate hydrolysis;
Although method 1 gives the purest product, the sodium methionine solution that the method obtains is expensive and final more uneconomical than the production of methionine(Met) itself, and this is mainly attributed to additional method step when preparing than solid methionine(Met) product;
In method 2, 5-(2-methylmercaptoethyl)-glycolylurea adopts known method, utilize common starting raw material methylthiopropionaldehyde and prussic acid or sodium cyanide, under the existence of ammonia and carbonic acid gas, prepare by directly to synthesize, then through SPC-D or sodium hydroxide hydrolysis, and be hydrolyzed 5-(2-methylmercaptoethyl)-glycolylurea to need to add excessive alkali, the object adding alkali is in order to complete hydrolysis 5-(2-methylmercaptoethyl)-glycolylurea, avoid the generation of methionylmethionine sodium salt, excessive alkali finally forms sodium carbonate and stays in the Sodium L-methioninate aqueous solution, obtain the Sodium L-methioninate aqueous solution containing sodium carbonate, the method is in order to obtain the Sodium L-methioninate aqueous solution or Sodium L-methioninate solid, first sodium carbonate in the Sodium L-methioninate aqueous solution must be removed (as patent DE-OS3104997, US-PS4931987, CN1321979C, CN1184896C), and containing a small amount of sodium carbonate in the Sodium L-methioninate after purifying, and affect its quality,
In method 3, the preparation of methionine amide is comparatively complicated, and be difficult to control, usually with methylthiopropionaldehyde, prussic acid, ammonia is raw material, namely methylthiopropionaldehyde and prussic acid react, prepare 2-2-hydroxy-4-methylthio butyronitrile, 2-2-hydroxy-4-methylthio butyronitrile is again through ammonification, prepare 2-amino-4-methylthio butanenitrile, and form 2-amino-4-methylthio butanenitrile dimer, catalyzer alkaline hydrolysis is made through ketone, obtain methionine amide, again through sodium hydroxide hydrolysis, obtain the Sodium L-methioninate aqueous solution, containing a small amount of free alkali sodium hydroxide (as patent CN1040533C).
For above technique Problems existing, in conjunction with the methionine(Met) production technique of Chongqing Unisplendour Chemical Co., Ltd, the invention provides a kind of preparation not containing sodium carbonate and the Sodium L-methioninate aqueous solution of sodium bicarbonate and the method for solid Sodium L-methioninate.
Summary of the invention
In view of this, the object of the invention is to overcome the defect described in above-mentioned technique, from cost, environmental protection propose a kind of novelty, easy handling not containing sodium carbonate and the Sodium L-methioninate aqueous solution of sodium bicarbonate and the preparation method of solid Sodium L-methioninate.
For achieving the above object, the invention provides following technical scheme:
With 5-(the methylmercaptoethyl)-glycolylurea aqueous solution containing sodium carbonate or sodium bicarbonate for raw material, add calcium oxide or calcium hydroxide hydrolysis, obtain the Sodium L-methioninate aqueous solution containing calcium carbonate and ammonia; Be separated precipitation of calcium carbonate by containing calcium carbonate with the Sodium L-methioninate aqueous solution of ammonia, obtain the Sodium L-methioninate aqueous solution.
Calcium oxide or calcium hydroxide hydrolysis is used mainly to utilize calcium hydroxide and sodium carbonate or reaction of sodium bicarbonate in the present invention, the sodium hydroxide generated can increase alkalescence, be conducive to 5-(methylmercaptoethyl)-glycolylurea hydrolysis and generate Sodium L-methioninate, simultaneous oxidation calcium or calcium hydroxide also have the effect of decolouring.The present invention is the Ca of reaction
2+ion and CO
3 2-generate precipitation of calcium carbonate, dissolution of calcium carbonate is little, easily removes.
Preferably, the mol ratio of described 5-(methylmercaptoethyl)-glycolylurea and sodium carbonate or sodium bicarbonate is 1:0.4 ~ 1.5; Preferred, 5-(the methylmercaptoethyl)-glycolylurea aqueous solution containing sodium carbonate or sodium bicarbonate is with 3-methylthiopropionaldehyde, sodium cyanide and carbonic acid gas and ammonia for raw material obtains, and pH is 8.5 ~ 10.5.Most preferred, the mol ratio of described 5-(methylmercaptoethyl)-glycolylurea and sodium carbonate or sodium bicarbonate is 1:0.5 ~ 1, and the pH of 5-(the methylmercaptoethyl)-glycolylurea aqueous solution containing sodium carbonate or sodium bicarbonate is 8.5 ~ 10.
In the present invention, the interpolation molar weight of described calcium oxide or calcium hydroxide is more than or equal to the molar weight sum of 5-(methylmercaptoethyl)-glycolylurea and sodium carbonate or sodium bicarbonate.
In hydrolysis reaction of the present invention, hydrolysising condition is 120 DEG C ~ 200 DEG C in temperature, and pressure is that 0.2 ~ 3.0MPa Water Under solution all can realize goal of the invention in 10 ~ 60 minutes, is 170 DEG C ~ 180 DEG C in temperature, pressure is 0.8 ~ 2.0MPa, and the time is best results under 15 ~ 30 minutes conditions.
In the present invention, described separation also comprises the ammonia of discharging in filtrate after going precipitation of calcium carbonate, make filtrate free ammonia content lower than 50ppm, after ammonia excretion, the content of Sodium L-methioninate is 8 ~ 20wt%, and ammonia excretion mode is air lift or negative pressure ammonia excretion.
In order to make in the Methionine calcium salt that obtains, not containing calcium ion, also comprising the steps after described ammonia excretion, the solution after ammonia excretion is removed residual calcium ion by ion-exchange.
In order to production cost can be reduced further, after precipitation of calcium carbonate is removed in separation, collect precipitation of calcium carbonate, then precipitation of calcium carbonate is calcined, obtain calcium oxide, the calcium oxide obtained is circulated to hydrolysing step, achieve the recycle of byproduct of reaction calcium oxide.
The further preferred version of the present invention, by the obtained Sodium L-methioninate aqueous solution through concentrated, dry, obtains Sodium L-methioninate solid.Preferably, the Sodium L-methioninate aqueous solution is concentrated into Sodium L-methioninate massfraction by described simmer down to is 40% ~ 60%; Described drying is spraying dry, and tap density circle of the Sodium L-methioninate obtained after spraying dry is in scope 350 ~ 600kg/m
3, gained Sodium L-methioninate moisture lower than 0.5%, the purity of Sodium L-methioninate is greater than 98.5%.
Owing to adopting spraying dry, its obtained Sodium L-methioninate is particulate form, and without the need to pulverizing and sieving, avoid a large amount of dust pollutions, avoiding impure mineral has, and ensure that the purity of product.
Beneficial effect of the present invention is: the invention discloses the Sodium L-methioninate aqueous solution and solid Sodium L-methioninate product that preparation does not contain sodium carbonate and sodium bicarbonate, this preparation method is simple, can continuous prodution Sodium L-methioninate, industrialization scale operation can be realized, yield is high, production cost is low, and obtained product purity is high, the purity of Sodium L-methioninate solid is greater than 98.5%, Sodium L-methioninate solid can unrestricted flow, can be used as animal feedstuff additive, without the need to pulverizing and sieving, avoid a large amount of dust pollutions, avoid impure mineral to have, ensure that the purity of product.
Embodiment
To be described in detail the preferred embodiments of the present invention below.The experimental technique of unreceipted actual conditions in embodiment, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
Embodiment 1
By the 5-of 500 grams (methylmercaptoethyl)-glycolylurea aqueous solution, (5-(methylmercaptoethyl)-glycolylurea content is 13.42wt%, carbonate content is 4.10wt%) and the calcium hydroxide powder of 43.7 gram 98% add in the autoclave of 1000ml, closed reactor, be warming up to 180 DEG C immediately, insulated and stirred 15 minutes, then room temperature (18 ~ 25 DEG C) is cooled to, pressure release is to normal pressure (100KPa), obtain the liquid containing white precipitate, suction filtration white precipitate, then precipitation is washed with water, merging filtrate, again by filtrate ammonia excretion to ammonia content lower than 50ppm, solution after ammonia excretion removes residual calcium ion through ion exchange resin, obtain the Sodium L-methioninate aqueous solution 400 grams, Sodium L-methioninate content is 16.48wt%, being evaporated to Sodium L-methioninate concentration is 40 ~ 60wt%, obtains the Sodium L-methioninate aqueous solution, by analysis, sodium carbonate or sodium bicarbonate do not detected.
Embodiment 2
By the 5-of 500 grams (methylmercaptoethyl)-glycolylurea aqueous solution, (5-(methylmercaptoethyl)-glycolylurea content is 13.42wt%, carbonate content is 4.10wt%) and the lime powder of 33.7 gram 98% add in the autoclave of 1000ml, closed reactor, be warming up to 170 DEG C immediately, insulated and stirred 15 minutes, then room temperature (18 ~ 25 DEG C) is cooled to, pressure release is to normal pressure (100KPa), obtain the liquid containing white precipitate, suction filtration white precipitate, then precipitation is washed with water, merging filtrate, ammonia excretion to ammonia content lower than 50ppm, solution after ammonia excretion removes residual calcium ion through ion exchange resin, obtain the Sodium L-methioninate aqueous solution 378 grams, Sodium L-methioninate content is 17.44wt%, being evaporated to Sodium L-methioninate concentration is 40 ~ 60wt%, obtains the Sodium L-methioninate aqueous solution, by analysis, sodium carbonate or sodium bicarbonate do not detected.
Embodiment 3
By the 5-of 500 grams (methylmercaptoethyl)-glycolylurea aqueous solution, (5-(methylmercaptoethyl)-glycolylurea content is 13.42wt%, carbonate content is 4.10wt%) and the lime powder of 33.7 gram 98% add in the autoclave of 1000ml, closed reactor, be warming up to 180 DEG C immediately, insulated and stirred 15 minutes, then room temperature (18 ~ 25 DEG C) is cooled to, pressure release is to normal pressure (100KPa), obtain the liquid containing white precipitate, suction filtration white precipitate, then precipitation is washed with water, merging filtrate, ammonia excretion to ammonia content lower than 50ppm, solution after ammonia excretion removes residual calcium ion through ion exchange resin, obtain the Sodium L-methioninate aqueous solution 378 grams, Sodium L-methioninate content is 17.44wt%, being evaporated to Sodium L-methioninate concentration is 40 ~ 60wt%, obtains the Sodium L-methioninate aqueous solution, by analysis, sodium carbonate or sodium bicarbonate do not detected.
Then above-mentioned solution is carried out spraying dry, obtain Powdered Sodium L-methioninate 66.59 grams, the content of Sodium L-methioninate is 99%, and tap density is 0.58g/ml.
Embodiment 4
By the 5-of 500 grams (methylmercaptoethyl)-glycolylurea aqueous solution, (5-(methylmercaptoethyl)-glycolylurea content is 13.42wt%, carbonate content is 4.10wt%) and the lime powder of 33.7 gram 98% add in the autoclave of 1000ml, closed reactor, be warming up to 180 DEG C immediately, insulated and stirred 15 minutes, then room temperature (18 ~ 25 DEG C) is cooled to, pressure release is to normal pressure (100KPa), obtain the liquid containing white precipitate, suction filtration white precipitate, then precipitation is washed with water, merging filtrate, ammonia excretion to ammonia content lower than 50ppm, solution after ammonia excretion removes residual calcium ion through ion exchange resin, obtain the Sodium L-methioninate aqueous solution 378 grams, Sodium L-methioninate content is 17.44wt%, being evaporated to Sodium L-methioninate concentration is 40 ~ 60wt%, obtains the Sodium L-methioninate aqueous solution, by analysis, sodium carbonate or sodium bicarbonate do not detected.
The white solid calcium carbonate obtained by above-mentioned suction filtration is calcined, and obtains lime powder, and lime powder recycled is to the hydrolysis of 5-(methylmercaptoethyl)-glycolylurea aqueous solution.
Embodiment 5
By the 5-of 500 grams (methylmercaptoethyl)-glycolylurea aqueous solution, (5-(methylmercaptoethyl)-glycolylurea content is 13.42wt%, carbonate content is 3.27wt%) and the calcium hydroxide powder of 43.7 gram 98% add in the autoclave of 1000ml, closed reactor, be warming up to 120 DEG C immediately, insulated and stirred 60 minutes, then room temperature (18 ~ 25 DEG C) is cooled to, pressure release is to normal pressure (100KPa), obtain the liquid containing white precipitate, suction filtration white precipitate, then precipitation is washed with water, merging filtrate, again by filtrate ammonia excretion to ammonia content lower than 50ppm, solution after ammonia excretion removes residual calcium ion through ion exchange resin, obtain the Sodium L-methioninate aqueous solution 400 grams, Sodium L-methioninate content is 16.40wt%, being evaporated to Sodium L-methioninate concentration is 40 ~ 60wt%, obtains the Sodium L-methioninate aqueous solution, by analysis, sodium carbonate or sodium bicarbonate do not detected.
Embodiment 6
By the 5-of 500 grams (methylmercaptoethyl)-glycolylurea aqueous solution, (5-(methylmercaptoethyl)-glycolylurea content is 13.42wt%, carbonate content is 12.26wt%) and the calcium hydroxide powder of 43.7 gram 98% add in the autoclave of 1000ml, closed reactor, be warming up to 200 DEG C immediately, insulated and stirred 10 minutes, then room temperature (18 ~ 25 DEG C) is cooled to, pressure release is to normal pressure (100KPa), obtain the liquid containing white precipitate, suction filtration white precipitate, then precipitation is washed with water, merging filtrate, again by filtrate ammonia excretion to ammonia content lower than 50ppm, solution after ammonia excretion removes residual calcium ion through ion exchange resin, obtain the Sodium L-methioninate aqueous solution 400 grams, Sodium L-methioninate content is 16.65wt%, being evaporated to Sodium L-methioninate concentration is 40 ~ 60wt%, obtains the Sodium L-methioninate aqueous solution, by analysis, sodium carbonate or sodium bicarbonate do not detected.
In above-described embodiment 1 ~ 6, 5-(methylmercaptoethyl)-glycolylurea aqueous solution containing sodium carbonate or sodium bicarbonate is with 3-methylthiopropionaldehyde, sodium cyanide and carbonic acid gas and ammonia are that raw material obtains, pH is 8.5 ~ 10.5, the mol ratio of 5-(methylmercaptoethyl)-glycolylurea and sodium carbonate or sodium bicarbonate is 1:0.4 ~ 1.5, the molar weight that calcium oxide or calcium hydroxide add is more than or equal to the molar weight sum of 5-(methylmercaptoethyl)-glycolylurea and sodium carbonate or sodium bicarbonate, calcium oxide or calcium hydroxide hydrolysising condition are 120 DEG C ~ 200 DEG C in temperature, pressure is that 0.2 ~ 3.0MPa Water Under solution all can obtain above-mentioned effect in 10 ~ 60 minutes.5-(methylmercaptoethyl)-glycolylurea aqueous solution pH containing sodium carbonate or sodium bicarbonate is 8.5 ~ 10, the mol ratio of 5-(methylmercaptoethyl)-glycolylurea and sodium carbonate or sodium bicarbonate is 1:0.5 ~ 1, calcium oxide or calcium hydroxide hydrolysising condition are 170 DEG C ~ 180 DEG C in temperature, pressure is 0.8 ~ 2.0MPa, and the time is best results under 15 ~ 30 minutes conditions.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (10)
1. the preparation method of Sodium L-methioninate, it is characterized in that: with 5-(the methylmercaptoethyl)-glycolylurea aqueous solution containing sodium carbonate or sodium bicarbonate for raw material, add calcium oxide or calcium hydroxide hydrolysis, obtain the Sodium L-methioninate aqueous solution containing calcium carbonate and ammonia; Be separated precipitation of calcium carbonate by containing calcium carbonate with the Sodium L-methioninate aqueous solution of ammonia, obtain the Sodium L-methioninate aqueous solution.
2. the preparation method of Sodium L-methioninate according to claim 1, is characterized in that: the mol ratio of described 5-(methylmercaptoethyl)-glycolylurea and sodium carbonate or sodium bicarbonate is 1:0.4 ~ 1.5.
3. the preparation method of Sodium L-methioninate according to claim 1, is characterized in that: the interpolation molar weight of described calcium oxide or calcium hydroxide is more than or equal to the molar weight sum of 5-(methylmercaptoethyl)-glycolylurea and sodium carbonate or sodium bicarbonate.
4. the preparation method of Sodium L-methioninate according to claim 1, is characterized in that: described calcium oxide or calcium hydroxide hydrolysising condition are 120 DEG C ~ 200 DEG C in temperature, and pressure is 0.2 ~ 3.0MPa Water Under solution 10 ~ 60 minutes.
5. the preparation method of Sodium L-methioninate according to claim 1, is characterized in that: described separation also comprises the ammonia of discharging in filtrate after going precipitation of calcium carbonate, make filtrate free ammonia content lower than 50ppm.
6. the preparation method of Sodium L-methioninate according to claim 1, is characterized in that: also comprise the steps after described ammonia excretion, and the solution after ammonia excretion is removed residual calcium ion by ion-exchange.
7. the preparation method of Sodium L-methioninate according to claim 1, it is characterized in that: described 5-(methylmercaptoethyl)-glycolylurea aqueous solution containing sodium carbonate or sodium bicarbonate is with 3-methylthiopropionaldehyde, sodium cyanide and carbonic acid gas and ammonia for raw material obtains, and pH is 8.5 ~ 10.5.
8. the preparation method of Sodium L-methioninate according to claim 1, is characterized in that: be separated after removing precipitation of calcium carbonate, collect precipitation of calcium carbonate, then precipitation of calcium carbonate calcined, obtain calcium oxide, the calcium oxide obtained is circulated to hydrolysing step.
9. the preparation method of Sodium L-methioninate according to any one of claim 1 ~ 8, is characterized in that: by the obtained Sodium L-methioninate aqueous solution through concentrated, dry, obtain Sodium L-methioninate solid.
10. the preparation method of Sodium L-methioninate according to claim 9, is characterized in that: it is 40% ~ 60% that the Sodium L-methioninate aqueous solution is concentrated into Sodium L-methioninate massfraction by described simmer down to; Described drying is spraying dry.
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| WO2018227840A1 (en) * | 2017-06-13 | 2018-12-20 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine production method for reducing by-product sodium sulfate |
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| CN109232339A (en) * | 2018-11-09 | 2019-01-18 | 禄丰天宝磷化工有限公司 | Cleaning process for co-production of D, L-methionine, D, L-methionine hydroxy analogue and calcium salt thereof |
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Effective date of registration: 20160525 Address after: 755000 Ningxia central defence industrial park Applicant after: NINGXIA ZIGUANG TIANHUA METHIONINE CO., LTD. Address before: 402160 Yongchuan District, Chongqing Chemical Road, No. 426 Applicant before: Chongqing Unisplendour Chemical Co., Ltd. |
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