CN103641760B - The preparation method of cheap highly purified D, L-2-2-hydroxy-4-methylthio butyramide - Google Patents
The preparation method of cheap highly purified D, L-2-2-hydroxy-4-methylthio butyramide Download PDFInfo
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- CN103641760B CN103641760B CN201310585647.0A CN201310585647A CN103641760B CN 103641760 B CN103641760 B CN 103641760B CN 201310585647 A CN201310585647 A CN 201310585647A CN 103641760 B CN103641760 B CN 103641760B
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- methylthio
- methylthio butyramide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 144
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 56
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 50
- CQSQMXIROIYTLO-UHFFFAOYSA-N 2-methylpropanethial Chemical compound CC(C)C=S CQSQMXIROIYTLO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000002425 crystallisation Methods 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000006703 hydration reaction Methods 0.000 claims abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 13
- 239000011707 mineral Substances 0.000 claims abstract description 13
- 230000036571 hydration Effects 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 66
- 239000007789 gas Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 31
- 239000012043 crude product Substances 0.000 claims description 30
- 238000001953 recrystallisation Methods 0.000 claims description 30
- 230000008025 crystallization Effects 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 28
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 25
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 13
- -1 inorganic acid ammonium salt Chemical class 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 230000009615 deamination Effects 0.000 claims description 8
- 238000006481 deamination reaction Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 150000007530 organic bases Chemical group 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000000967 suction filtration Methods 0.000 description 24
- 238000004128 high performance liquid chromatography Methods 0.000 description 20
- 238000006386 neutralization reaction Methods 0.000 description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- PICCHNWCTUUCAQ-UHFFFAOYSA-N 2-hydroxypentanethioic s-acid Chemical compound CCCC(O)C(O)=S PICCHNWCTUUCAQ-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- PICCHNWCTUUCAQ-BYPYZUCNSA-N (2s)-2-hydroxypentanethioic s-acid Chemical compound CCC[C@H](O)C(S)=O PICCHNWCTUUCAQ-BYPYZUCNSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 239000001166 ammonium sulphate Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 241000857212 Varanus nebulosus Species 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000013016 damping Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- MKRQHUHJZKUMOL-UHFFFAOYSA-N [Zn].OC(C(=S)O)CCC Chemical class [Zn].OC(C(=S)O)CCC MKRQHUHJZKUMOL-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 210000004767 rumen Anatomy 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OAGSFHDUINSAMQ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium;hydrate Chemical compound O.[Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OAGSFHDUINSAMQ-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HRJXMHAOFRMRCR-UHFFFAOYSA-K O.[Na+].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] Chemical compound O.[Na+].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] HRJXMHAOFRMRCR-UHFFFAOYSA-K 0.000 description 1
- 229910000566 Platinum-iridium alloy Inorganic materials 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MKRQHUHJZKUMOL-WCCKRBBISA-N [Zn].O[C@H](C(=S)O)CCC Chemical compound [Zn].O[C@H](C(=S)O)CCC MKRQHUHJZKUMOL-WCCKRBBISA-N 0.000 description 1
- PNNIIULEYDEVIV-UHFFFAOYSA-N acetic acid;sodium;hydrate Chemical compound O.[Na].CC(O)=O PNNIIULEYDEVIV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 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 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000019621 digestibility Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- YDKKQXNAIYTHFB-UHFFFAOYSA-L disodium;butanedioate;hydrate Chemical compound O.[Na+].[Na+].[O-]C(=O)CCC([O-])=O YDKKQXNAIYTHFB-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical class [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 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
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is directed to chemical field, relate to a kind of preparation method of highly purified D, L-2-2-hydroxy-4-methylthio butyramide of cheapness.The method adopts iS-One legal system to obtain prussic acid gas mixture and methylthiopropionaldehyde under the katalysis of alkali, fully reacts to obtain 2-2-hydroxy-4-methylthio butyronitrile system; 2-2-hydroxy-4-methylthio butyronitrile system carries out hydration in the presence of a mineral acid, and after reaction terminates, regulate reaction solution pH to 5.0 ~ 6.5 with ammonia or ammoniacal liquor, crystallisation by cooling, obtains D, L-2-2-hydroxy-4-methylthio butyramide.The method is simple to operate, production cost is low, and the D of acquisition, L-2-2-hydroxy-4-methylthio butyramide purity is high, yield is high, is applicable to the production of subsequent product.
Description
Technical field
The present invention is directed to chemical field, relate to a kind of preparation method of highly purified D, L-2-2-hydroxy-4-methylthio butyramide of cheapness.
Background technology
Methionine hydroxy analog (MHA) is also known as D, L-2-hydroxy-4-methylthiobutyric acid, have that toxicity is little, rumen digestibility is low, promote the synthesis of rumen microorganism, the protein saved in daily ration, the production performance improving cow, the production performance and immunological competence, the discharge of minimizing ammonia that improve animal, the feature such as contaminate environment is less, production technique is simple, price is lower, be the most economical effective a kind of amino acid source of animal.Although methionine hydroxy analog has above-mentioned advantage, commercially replacing more expensive amino acid gradually, still there is following problem in it:
(1) there is stronger corrodibility and irritating smell, store, transport, use inconvenience, expensive dedicated liquid charging system must be used;
(2) viscosity is very large, not easily mixes in feed pre-mixing material;
(3) meet water and release a large amount of heats, cause feed fermentation of generating heat in storage and transport process to become sour; Acidity is very large, and pH is about 1, and other composition generation acid-base reactions easily and in feed or premixing feedstuff, damage the nutritive ingredient in feed.
For solving the problems referred to above that D, L-2-hydroxy-4-methylthiobutyric acid exists, being prepared into metallo-chelate is that one is effectively improved one's methods.Such as:
Publication number is in the patent documentation of CN1493560, the D adopting commercial grade is proposed, L-2-hydroxy-4-methylthiobutyric acid and calcium oxide or calcium hydroxide carry out neutralization reaction as raw material and prepare D, L-2-2-hydroxy-4-methylthio calcium butyrate, final drying and crushing obtains pulverous HMBC product.Due to commercially available D, containing the dimer of about 22% and polymer thereof in L-2-hydroxy-4-methylthiobutyric acid, and these polymers exist mainly with the form of ester or acid anhydrides, these polymers are caused to be difficult to and calcium oxide or calcium hydroxide reaction, finally be adsorbed on its surface, product is difficult to drying, and then affects product quality.
Publication number is in the patent documentation of CN101348451, and also disclosing with D, L-2-hydroxy-4-methylthiobutyric acid is the method that HMBC prepared by raw material.Also because D, L-2-hydroxy-4-methylthiobutyric acid purity is low, monomer content is low, there is the problems such as product yield is low, dry difficulty in the method.
Improve one's methods and all finally affect the quality of the inner complex of preparation because of the quality of D, L-2-hydroxy-4-methylthiobutyric acid for above two kinds, and wherein the purity of D, L-2-hydroxy-4-methylthiobutyric acid and monomer content are major influence factors.
D, L-2-2-hydroxy-4-methylthio butyramide is preparation D, a kind of important intermediate of L-2-hydroxy-4-methylthiobutyric acid, directly D can be prepared by it, the inner complex of L-2-hydroxy-4-methylthiobutyric acid, also first can obtain D by it, L-2-hydroxy-4-methylthiobutyric acid prepares D again, the inner complex of L-2-hydroxy-4-methylthiobutyric acid.Such as:
Publication number is in the patent documentation of CN102399176, disclose a kind of preparation method of HMBC, its with content up to more than 99% 2-2-hydroxy-4-methylthio butyronitrile for raw material, add concentrated hydrochloric acid hydrolysis, with the sodium hydroxide neutralization of 30%, water recrystallization obtains the D of high-content, L-2-2-hydroxy-4-methylthio butyramide, D, L-2-2-hydroxy-4-methylthio butyramide is hydrolyzed with excessive calcium hydroxide again, obtains HMBC.
Publication number is in the patent documentation of CN102079719, disclose another kind of D, the preparation method of L-2-2-hydroxy-4-methylthio calcium butyrate, its with content lower than 90% feed grade D, L-2-hydroxy-4-methylthiobutyric acid or other content 75% ~ 90% D, L-2-hydroxy-4-methylthiobutyric acid is starting raw material, ammonium salt is generated with ammonia react, and then dehydration obtains D, L-2-2-hydroxy-4-methylthio butyramide, through extraction, concentrate and crystallization purifying, obtain the D that content is greater than 98.5%, L-2-2-hydroxy-4-methylthio butyramide, D, L-2-2-hydroxy-4-methylthio butyramide is hydrolyzed and generates D, L-2-hydroxy-4-methylthiobutyric acid salt, last and inorganic calcium salt reacts and generates D, L-2-2-hydroxy-4-methylthio calcium butyrate.
Therefore, obtain the D of high-quality, L-2-hydroxy-4-methylthiobutyric acid metallo-chelate, prevents D, and dimer and polymeric interference in L-2-hydroxy-4-methylthiobutyric acid, the quality of D, L-2-2-hydroxy-4-methylthio butyramide is very crucial.The present invention improves the preparation of D, L-2-2-hydroxy-4-methylthio butyramide and the method for separation and purification thereof, and to obtaining the D of high-quality, L-2-2-hydroxy-4-methylthio butyramide, is convenient to the production of subsequent product.
Summary of the invention
In view of this, the invention provides a kind of preparation method of D, L-2-2-hydroxy-4-methylthio butyramide, the method is simple to operate, production cost is low, obtained D, L-2-2-hydroxy-4-methylthio butyramide can obtain high yield and high purity through simple recrystallization, is applicable to the production of subsequent product.
For achieving the above object, technical scheme of the present invention is:
The preparation method of D, L-2-2-hydroxy-4-methylthio butyramide, comprises the following steps:
A, with methane, ammonia and oxygen for raw material, adopt iS-One method composition principle, be prepared into prussic acid gas mixture I; Described prussic acid gas mixture I obtains prussic acid gas mixture II through deamination process;
B, described prussic acid gas mixture II under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile system with methylthiopropionaldehyde;
C, described 2-2-hydroxy-4-methylthio butyronitrile system carry out hydration reaction in the presence of a mineral acid, after reaction terminates, reaction solution pH to 5.0 ~ 6.5 are regulated with ammonia or ammoniacal liquor, crystallisation by cooling, solid-liquid separation obtains D, the crystalline mixture of L-2-2-hydroxy-4-methylthio butyramide and inorganic acid ammonium salt is D, L-2-2-hydroxy-4-methylthio butyramide crude product.
Described iS-One method (Andrussow method) is the industrial process completed the 1950's, is the main method of producing prussic acid.The main raw material that it adopts has methane, ammonia and oxygen, therefore is again methane oxidation proceses of ammonia.This method is under the condition more than normal pressure, l000 DEG C, material mixed gas is led to the silk screen that people is made up of platinum, rhodium alloy catalyst platinum and rhodium, or the wire-mesh catalyst bed be made up of platinum iridium alloy, and the oxidative ammonolysis carried out, its reaction formula is 2CH
4+ 2NH
3+ 3O
2→ 2HCN+6H
2o.At present, this technology is very ripe, has special prussic acid synthetic tower for the preparation of hydrocyanic acid gas.
Described deamination process refers to and passes in acid by prussic acid gas mixture I standby for iS-One legal system, sloughs the operation of ammonia.The Main Function that described acid rises is absorbing ammonia G&W steam, therefore preferably sulfuric acid, and further preferred mass mark is the sulfuric acid of 75% ~ 90%.The prussic acid gas mixture of the present invention before and after deamination process all can be used for the preparation of 2-2-hydroxy-4-methylthio butyronitrile, and prussic acid gas mixture II character just after deamination process is more excellent.Industrially, special acid tower can be set for deamination process.
Further, described prussic acid gas mixture I is preferably made up of the component of following mass percent: hydrocyanic acid gas 8.8% ± 2%, water vapour 3.9% ± 2%, ammonia 1.6% ± 2%, hydrogen 1.1% ± 2%, nitrogen 76.0% ± 2%, oxygen 1.5% ± 2%, carbon monoxide 5.6% ± 2%, carbonic acid gas 1.1% ± 2%, methane 0.4% ± 2%.Described prussic acid gas mixture II is preferably made up of the component of following mass percent: hydrocyanic acid gas 9.4% ± 2%, hydrogen 1.6% ± 2%, nitrogen 79.4% ± 2%, oxygen 1.7% ± 2%, carbon monoxide 5.8% ± 2%, carbonic acid gas 1.5% ± 2%, methane 0.6% ± 2%.
Described prussic acid gas mixture II is particularly suitable as the raw material of preparation 2-2-hydroxy-4-methylthio butyronitrile.Its reaction is except obtained 2-2-hydroxy-4-methylthio butyronitrile, also containing residual qualities mark in reaction solution is the prussic acid of 0.05% ~ 0.5% and the water of 2% ~ 5%, just because of the existence of residual hydrogen cyanic acid and water, this system (namely 2-2-hydroxy-4-methylthio butyronitrile is together with reaction solution) can long-term storage and not decomposing.The reaction system of 2-2-hydroxy-4-methylthio butyronitrile also can be adjusted to pH with acid further and 2 ~ 4 to deposit, like this, even if still keep longer stability at normal temperatures.The acid of described adjustment pH can be sulfuric acid, phosphoric acid etc., massfraction preferably 85%.2-2-hydroxy-4-methylthio butyronitrile system, without the need to carrying out any separation and purification, can be directly used in the production of MHA.
Further, described methylthiopropionaldehyde is not purified methylthiopropionaldehyde, wherein containing the heavy constituent of the methylthiopropionaldehyde of massfraction 94.5% ~ 96%, the light constituent of massfraction 3.5% ~ 5.3% and massfraction 0.2% ~ 0.5%; Described light constituent is thiomethyl alcohol, methyl alcohol, propenal and water; Described restructuring is divided into dipolymer and the trimer of methylthiopropionaldehyde.
Step B is the nucleophilic addition under base catalysis.The alkali of described katalysis is organic bases and/or mineral alkali; The consumption of the alkali of described katalysis is the pH maintaining reaction system is 4.0 ~ 6.5, and preferred pH is 5.0 ~ 5.5.The preferred low-molecular-weight amine compound of described organic bases, the further aminated compounds of preferred 3 ~ 20 carbon atoms, this compounds with methylthiopropionaldehyde arbitrarily than mixing, can be conducive to fast reaction speed.The aminated compounds of described 3 ~ 20 carbon atoms comprises triethylamine, tri-isopropanolamine, DMA, imidazoles, picoline, pyridine etc., use wherein one or more can, particularly preferably triethylamine and/or pyridine.Described mineral alkali is one or more in metal hydroxides, metal cyanides, metal carbonate and alkali metal bicarbonate salt, or is ammonia.Described metallic hydrogen oxidation compound, as sodium hydroxide or potassium hydroxide; Metal cyanides, as sodium cyanide or potassium cyanide; Metal carbonate, as sodium carbonate or salt of wormwood; Alkali metal bicarbonate salt, as sodium bicarbonate or saleratus.Independent a kind of mineral alkali or mixed base can.
Further, in the alkali of described katalysis, also add acid, form mixture or the damping fluid of bronsted lowry acids and bases bronsted lowry; Described acid comprises mineral acid and organic acid.Adding or the formation of damping fluid of acid, reaction system can be made to maintain in more stable pH value range.Described organic acid is the one in acetic acid, formic acid, citric acid, Phenylsulfonic acid, trifluoromethanesulfonic acid etc.; Described mineral acid is sulfuric acid or phosphoric acid.The damping fluid formed is as Trisodium Citrate-sodium hydrate buffer solution, sodium succinate-sodium hydrate buffer solution, acetic acid-sodium hydrate buffer solution etc., optimization citric acid-sodium hydrate buffer solution.
In described step B, the mol ratio of prussic acid and methylthiopropionaldehyde is 1:1.0 ~ 1.05; Reaction pressure is 0.09 ~ 0.5MPa, namely can react at the environment of negative pressure to malleation, for considering of equipment requirements and reaction efficiency, and preferably 0.1 ~ 0.3MPa, more preferably 0.1 ~ 0.15MPa; Temperature of reaction is 30 ~ 80 DEG C, preferably 35 ~ 60 DEG C, more preferably 40 ~ 45 DEG C.
In step C, during 2-2-hydroxy-4-methylthio butyronitrile hydration reaction, described mineral acid comprises sulfuric acid, concentrated hydrochloric acid, phosphoric acid etc., preferably sulfuric acid.When mineral acid is sulfuric acid, the mol ratio of 2-2-hydroxy-4-methylthio butyronitrile and sulfuric acid is 1:0.5 ~ 1, and preferred molar ratio is 1:0.7 ~ 1; The massfraction of sulfuric acid is 50% ~ 80%, and preferred mass mark is 65% ~ 75%; Temperature controls at 40 ~ 70 DEG C, and preferable temperature is 50 ~ 65 DEG C.The raw material of the method monitoring reactions such as available HPLC and product changing conditions, until the i.e. stopped reaction that reacts completely.In above-mentioned sulfuric acid concentration and temperature condition, the hydration reaction time is 0.5 ~ 2h, and the preferred reaction time is 1 ~ 2h.
After hydration reaction terminates, the adjustment of reaction solution pH is except with except ammonia or ammoniacal liquor, and can also regulate with other mineral alkalis, but the intensity of these alkali is not to destroy D, the amido linkage in L-2-2-hydroxy-4-methylthio butyramide is limited.The present invention is for the consideration of subsequent purification, and preferred weakly alkaline ammonia or ammoniacal liquor, neutralization can not additionally introduce other salts simultaneously.During adjustment pH, temperature controls within 30 DEG C, preferably 10 ~ 30 DEG C, is convenient to the reaction solution obtaining required potential of hydrogen accurately.
Further, the purification step to D, L-2-2-hydroxy-4-methylthio butyramide crude product is comprised after described step C:
1) by the hydration of D, L-2-2-hydroxy-4-methylthio butyramide crude product and 5 ~ 10 DEG C also, stirring and dissolving inorganic acid ammonium salt, solid-liquid separation obtains D, L-2-2-hydroxy-4-methylthio butyramide work in-process;
2) described D, the L-2-2-hydroxy-4-methylthio butyramide work in-process water dissolution of 2 ~ 4 times of crude product quality, crystallisation by cooling, is separated to obtain crystallization and recrystallization mother liquor; Crystallization is dried, and obtains highly purified D, L-2-2-hydroxy-4-methylthio butyramide finished product.
The consumption of water described in step 1) preferably makes inorganic acid ammonium salt dissolve the amount reached capacity.Step 2) described recrystallization mother liquor is capable of circulation to step 1), and for the dissolving of inorganic acid ammonium salt in the crude product produced next time, the product in such mother liquor is recycled further, also reduces water consumption, avoids the discharge of waste liquid simultaneously.
Another object of the present invention is to provide one to utilize D, D prepared by L-2-2-hydroxy-4-methylthio butyramide production equipment, the method of L-2-2-hydroxy-4-methylthio butyramide, the method is simple to operate, controllability is strong, production cost is low, obtained D, L-2-2-hydroxy-4-methylthio butyramide can obtain high yield and high purity through simple recrystallization, is applicable to the production of subsequent product.
For achieving the above object, technical scheme of the present invention is:
Utilize D, D prepared by L-2-2-hydroxy-4-methylthio butyramide production equipment, the method of L-2-2-hydroxy-4-methylthio butyramide, described production equipment comprises prussic acid synthetic tower, acid tower, reactor and tripping device, the sulfuric acid that massfraction is 75% ~ 90% is filled in described acid tower, described reactor is provided with pressure and temperature regulates supplementary unit, and the air outlet of prussic acid synthetic tower is communicated with the inlet mouth of acid tower by pipeline, and the air outlet of acid tower is communicated with reactor by the pipeline being provided with throttling valve;
A, with methane, ammonia and oxygen for raw material, adopt iS-One method composition principle, prepare prussic acid gas mixture I by prussic acid synthetic tower; Described prussic acid gas mixture I passes into acid tower and sloughs ammonia and water vapour, obtains prussic acid gas mixture II;
B, described prussic acid gas mixture II, under throttle valve control, pass in the methylthiopropionaldehyde in reactor with the speed of 250 ~ 350L/min, under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile system;
Under C, vigorous stirring, in reactor, add sulfuric acid mix with 2-2-hydroxy-4-methylthio butyronitrile system, carry out hydration reaction, the massfraction of sulfuric acid is 50% ~ 80%, and temperature of reaction controls 40 ~ 70 DEG C of fully reactions; After reaction terminates, regulate reaction solution pH to 5.0 ~ 6.5 with ammonia or ammoniacal liquor, crystallisation by cooling, obtains D through tripping device solid-liquid separation, the crystalline mixture of L-2-2-hydroxy-4-methylthio butyramide and ammonium sulfate, is D, L-2-2-hydroxy-4-methylthio butyramide crude product.
In described step C, when sulfuric acid mixes with 2-2-hydroxy-4-methylthio butyronitrile system, the sequencing added does not affect the carrying out of reaction, but dilutes the consideration of heat release for sulfuric acid, for preventing bumping, preferably in sulfuric acid, drips 2-2-hydroxy-4-methylthio butyronitrile.
Described tripping device can be whizzer, suction filter, gets rid of worry machine etc.Wherein, described reactor possesses the function of synthesis, hydration, neutralization and crystallization, the utility appliance such as cooling, heating, supercharging are equipped with also correspondingly, but reactor used in the present invention is not limited to this, the equipment such as hydrolytic reaction pot, crystallization kettle that also can arrange separately is in addition to complete corresponding function.The reaction conditions optimized in first inventive method, is also suitable for the method for this part band production equipment.
Further, described D, L-2-2-hydroxy-4-methylthio butyramide production equipment also comprises crystallization kettle and drying plant, and corresponding operation steps comprises:
1) D that obtains of step C, L-2-2-hydroxy-4-methylthio butyramide crude product in tripping device with the hydration of 5 ~ 10 DEG C also, stirring and dissolving ammonium sulfate, then obtain D by tripping device solid-liquid separation, L-2-2-hydroxy-4-methylthio butyramide work in-process;
2) described D, L-2-2-hydroxy-4-methylthio butyramide work in-process return crystallization kettle, and with the water dissolution of 2 ~ 4 times of crude product quality, crystallisation by cooling, tripping device is separated to obtain crystallization and recrystallization mother liquor; Crystallization is transferred to drying plant, dries, obtains highly purified D, L-2-2-hydroxy-4-methylthio butyramide finished product.
Advantageous Effects of the present invention is:
(1) the prussic acid gas mixture adopting iS-One legal system standby and not purified methylthiopropionaldehyde, raw material, without the need to rectifying purifying, is saved the production time, is improve production efficiency, also reduce production cost; The 2-2-hydroxy-4-methylthio butyronitrile system prepared, stable in properties, can long-term storage, is more conducive to the production of follow-up D, L-2-2-hydroxy-4-methylthio butyramide.
(2) the 2-2-hydroxy-4-methylthio butyronitrile system obtained just can be directly used in D without the need to separation and purification, the preparation of L-2-2-hydroxy-4-methylthio butyramide, and the D obtained, L-2-2-hydroxy-4-methylthio butyramide can obtain high yield and high purity through simple recrystallization, and product appearance is crystallinity gloss, be particularly suitable for the preparations such as follow-up D, L-2-hydroxy-4-methylthiobutyric acid trace metal inner complex, HMBC.
To sum up, the present invention prepares D, and the method for L-2-2-hydroxy-4-methylthio butyramide is simple to operate, production cost is low, and the D of acquisition, L-2-2-hydroxy-4-methylthio butyramide purity is high, yield is high, is applicable to the production of subsequent product.
Accompanying drawing explanation
Fig. 1 is D, L-2-2-hydroxy-4-methylthio butyramide production equipment structural representation.
Embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.The experimental technique of unreceipted actual conditions in preferred embodiment, usually conveniently condition.Embodiment 1-8 is the preparation of 2-2-hydroxy-4-methylthio butyronitrile; Embodiment 9-14 is the preparation of D, L-2-2-hydroxy-4-methylthio butyramide.
Embodiment 1
Detect from prussic acid synthetic tower prussic acid gas mixture I out, consisting of of prussic acid gas mixture I: hydrocyanic acid gas 8.87%, water vapour 3.88%, ammonia 1.64%, hydrogen 1.13%, nitrogen 76.01%, oxygen 1.48%, carbon monoxide 5.67%, carbonic acid gas 1.13%, methane 0.39%.
Prussic acid gas mixture I through 75% sulfuric acid tower absorb ammonia in gas mixture and water vapour thereof after, consisting of of the prussic acid gas mixture II obtained: hydrocyanic acid gas 9.35%, hydrogen 1.57%, nitrogen 79.44%, oxygen 1.71%, carbon monoxide 5.79%, carbonic acid gas 1.50%, methane 0.64%.
Embodiment 2
Prussic acid gas mixture II being passed into 223.3g massfraction is in the methylthiopropionaldehyde of 94.5%, containing 3.3g pyridine in methylthiopropionaldehyde.React under normal pressure, controlling temperature of reaction is 45 DEG C, and draft speed is 300L/min, and tail gas sodium hydroxide absorbs, and monitors the residual volume of methylthiopropionaldehyde with HPLC.When methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 270.64g, 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.5%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into two parts together with reaction solution (i.e. 2-2-hydroxy-4-methylthio butyronitrile system).Portion wherein adds 8.5g water, preserves 120 days, have no decomposition under 3 DEG C of conditions; Another part adds 8.5g water wherein, and be then 3 with the sulfuric acid acidation of 85% to pH, preserve 120 days under 20 DEG C of conditions, 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.1%.
Embodiment 3
Prussic acid gas mixture II being passed into 223.3g massfraction is in the methylthiopropionaldehyde of 94.5%, contains the water of 2.2g pyridine and 10g in methylthiopropionaldehyde.Under 0.15MPa, controlling temperature of reaction is 42 DEG C, and draft speed is 280L/min, and tail gas sodium hydroxide absorbs, and monitors the residual volume of methylthiopropionaldehyde with HPLC.When methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 279.54g, 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.07%.
Embodiment 4
Prussic acid gas mixture II being passed into 247.2g massfraction is in the methylthiopropionaldehyde of 94.5%, contains the water of 2.2g pyridine and 15g in methylthiopropionaldehyde.Under 0.5MPa, controlling temperature of reaction is 45 DEG C, and draft speed is 280L/min, and tail gas sodium hydroxide absorbs, and monitors the residual volume of methylthiopropionaldehyde with HPLC.When methylthiopropionaldehyde residual volume is less than 0.2%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 294.54g, 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.07%.
Embodiment 5
Prussic acid gas mixture II being passed into 227.3g massfraction is in the methylthiopropionaldehyde of 94.5%, contains the water of 3.3g pyridine and 4g in methylthiopropionaldehyde.Under 0.09MPa, controlling temperature of reaction is 80 DEG C, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 DEG C.Monitor the residual volume of methylthiopropionaldehyde with HPLC, when methylthiopropionaldehyde residual volume is less than 0.2%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 277.4g, 2-2-hydroxy-4-methylthio butyronitrile is 97%, prussic acid remnants 0.06%, moisture content 2%.
Embodiment 6
Prussic acid gas mixture II being passed into 237.3g massfraction is in the methylthiopropionaldehyde of 94.5%, containing 8.5g water in methylthiopropionaldehyde, adds a certain amount of catalyzer sodium carbonate in mixed system, keeps the pH of system to be 5.5 passing in prussic acid gas mixture process.Under 0.5MPa, controlling temperature of reaction is 30 DEG C, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 DEG C.Monitor the residual volume of methylthiopropionaldehyde with HPLC, when methylthiopropionaldehyde residual volume is less than 0.2%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 287.4g, 2-2-hydroxy-4-methylthio butyronitrile is 96%, prussic acid remnants 0.06%, moisture content 3%.
Embodiment 7
Prussic acid gas mixture II being passed into 233.3g massfraction is in the methylthiopropionaldehyde of 94.5%, containing 8.5g water in methylthiopropionaldehyde, in mixed system, adds a certain amount of catalyst of triethylamine, keeps the pH of system to be 5.5 passing in prussic acid gas mixture process.React under normal pressure, controlling temperature of reaction is 40 DEG C, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 DEG C.Monitor the residual volume of methylthiopropionaldehyde with HPLC, when methylthiopropionaldehyde residual volume is less than 0.2%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 287.4g, 2-2-hydroxy-4-methylthio butyronitrile is 96%, prussic acid remnants 0.06%, moisture content 3%.
Embodiment 8
Prussic acid gas mixture II being passed into 223.3g massfraction is in the methylthiopropionaldehyde of 94.5%, adds the damping fluid of a certain amount of sodium hydroxide and citric acid formation, in logical prussic acid gas mixture process, keep the pH of system to be 5.0 in mixed system.React under normal pressure, controlling temperature of reaction is 45 DEG C, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 DEG C.Monitor the residual volume of methylthiopropionaldehyde with HPLC, when methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 287.4g, 2-2-hydroxy-4-methylthio butyronitrile is 97%, prussic acid remnants 0.06%, moisture content 2%.
Embodiment 9
At 50 DEG C, add people 210g70% sulfuric acid (1.5mol) in the reactor under vigorous stirring, add under this temperature and vigorous stirring with cooling embodiment 2-in-1 become 2-2-hydroxy-4-methylthio butyronitrile 270.64g, control temperature of reaction at 55 DEG C.Dropwise, 60 minutes are reacted again at 55 DEG C, monitor the residual quantity of 2-2-hydroxy-4-methylthio butyronitrile with HPLC, be reaction end when 2-2-hydroxy-4-methylthio butyronitrile is transformed into 2-2-hydroxy-4-methylthio butyramide completely, the transformation efficiency of 2-2-hydroxy-4-methylthio butyronitrile is more than 99%.Then slowly in 2-2-hydroxy-4-methylthio butyramide vitriol reactant, add 25% ammoniacal liquor, neutralization reaction temperature is no more than 30 DEG C, in and terminal pH control 6.0, after neutralization, non-shock chilling to 0 DEG C crystallization, suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide crude product (being the mixed crystal of D, L-2-2-hydroxy-4-methylthio butyramide and ammonium sulfate, wet product) amounts to 450g, by analysis, D, L-2-2-hydroxy-4-methylthio butyramide is containing 65.7%, and ammonium sulfate is containing 26.7%.
To D obtained above, L-2-2-hydroxy-4-methylthio butyramide crude product adds the water of 5 DEG C of 150g, stir under 5 DEG C of conditions, then suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide work in-process 330g(wet product), D, L-2-2-hydroxy-4-methylthio butyramide content is 87.8%, and ammonium sulphate content is 3%.
D, L-2-2-hydroxy-4-methylthio butyramide work in-process 330g obtained above is added water, is heated to 85 DEG C, D, L-2-2-hydroxy-4-methylthio butyramide just dissolves completely and is as the criterion.Be cooled to 0 DEG C, crystallization, suction filtration, dry and obtain D, L-2-2-hydroxy-4-methylthio butyramide 289.7g, yield is 96%, and purity is 99.5%.Recrystallization mother liquor is applied mechanically to next batch recrystallization.
Embodiment 10
At 50 DEG C, add the sulfuric acid (1.57mol) that people 219.8g massfraction is 70% under vigorous stirring in the reactor, at this temperature and vigorous stirring and cooling, add the 2-2-hydroxy-4-methylthio butyronitrile 279.54g that embodiment 3 is synthesized, control temperature of reaction at 50 DEG C.Dropwise, 40 minutes are reacted again at 65 DEG C, monitor the residual quantity of 2-2-hydroxy-4-methylthio butyronitrile with HPLC, be reaction end when 2-2-hydroxy-4-methylthio butyronitrile is transformed into 2-2-hydroxy-4-methylthio butyramide completely, the transformation efficiency of 2-2-hydroxy-4-methylthio butyronitrile is more than 99%.Then slowly in 2-2-hydroxy-4-methylthio butyramide vitriol reactant, add 25% ammoniacal liquor, neutralization reaction temperature is no more than 30 DEG C, in and terminal pH control 5.0, after neutralization, non-shock chilling to 0 DEG C crystallization, suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide crude product (is the mixed crystal of D, L-2-2-hydroxy-4-methylthio butyramide and ammonium sulfate, wet product), amount to 451g, by analysis, D, L-2-2-hydroxy-4-methylthio butyramide is containing 69.2%, and ammonium sulfate is containing 25.7%.
To D obtained above, the water of 5 DEG C of 156g is added in L-2-2-hydroxy-4-methylthio butyramide crude product, stir under 5 DEG C of conditions, then suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide work in-process 335g(wet product), D, L-2-2-hydroxy-4-methylthio butyramide content is 91.2%, and ammonium sulphate content is 3.4%.
D, L-2-2-hydroxy-4-methylthio butyramide work in-process 335g obtained above is added the recrystallization mother liquor of embodiment 9, be heated to 85 DEG C, D, L-2-2-hydroxy-4-methylthio butyramide just dissolves completely and is as the criterion.Be cooled to 0 DEG C, crystallization, suction filtration, dry and obtain D, L-2-2-hydroxy-4-methylthio butyramide 300.7g, yield is 96.5%, and purity is 99.5%.Recrystallization mother liquor is applied mechanically to next batch recrystallization.
Embodiment 11
At 50 DEG C, add the sulfuric acid (1.53mol) that people 231g massfraction is 65% under vigorous stirring in the reactor, at this temperature and vigorous stirring and cooling, add the 2-2-hydroxy-4-methylthio butyronitrile 294.54g that embodiment 4 is synthesized, control temperature of reaction at 50 DEG C.Dropwise, 60 minutes are reacted again at 50 DEG C, monitor the residual quantity of 2-2-hydroxy-4-methylthio butyronitrile with HPLC, be reaction end when 2-2-hydroxy-4-methylthio butyronitrile is transformed into 2-2-hydroxy-4-methylthio butyramide completely, the transformation efficiency of 2-2-hydroxy-4-methylthio butyronitrile is more than 99%.Then slowly in 2-2-hydroxy-4-methylthio butyramide vitriol reactant, add 25% ammoniacal liquor, neutralization reaction temperature is no more than 30 DEG C, in and terminal pH control 5.5, after neutralization, non-shock chilling to 0 DEG C crystallization, suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide crude product (being the mixed crystal of D, L-2-2-hydroxy-4-methylthio butyramide and ammonium sulfate, wet product) amounts to 647.9g, by analysis, D, L-2-2-hydroxy-4-methylthio butyramide is containing 47.66%, and ammonium sulfate is containing 39.67%.
To D obtained above, L-2-2-hydroxy-4-methylthio butyramide crude product adds the water of 5 DEG C of 160g, stir under 5 DEG C of conditions, then suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide work in-process 354.82g(wet product), D, L-2-2-hydroxy-4-methylthio butyramide content is 90.50%, and ammonium sulphate content is 5.56%.
D, L-2-2-hydroxy-4-methylthio butyramide work in-process 354.82g obtained above is added the recrystallization mother liquor of embodiment 10, be heated to 85 DEG C, D, L-2-2-hydroxy-4-methylthio butyramide just dissolves completely and is as the criterion.Be cooled to 0 DEG C, crystallization, suction filtration, dry and obtain D, L-2-2-hydroxy-4-methylthio butyramide 318.44g, yield is 96.7%, and purity is 99.5%.Recrystallization mother liquor is applied mechanically to next batch recrystallization.
Embodiment 12
At 50 DEG C, add the sulfuric acid (1.54mol) that people 201g massfraction is 75% under vigorous stirring in the reactor, at this temperature and vigorous stirring and cooling, add the 2-2-hydroxy-4-methylthio butyronitrile 277.4g that embodiment 5 is synthesized, control temperature of reaction at 50 DEG C.Dropwise, 100 minutes are reacted again at 40 DEG C, monitor the residual quantity of 2-2-hydroxy-4-methylthio butyronitrile with HPLC, be reaction end when 2-2-hydroxy-4-methylthio butyronitrile is transformed into 2-2-hydroxy-4-methylthio butyramide completely, the transformation efficiency of 2-2-hydroxy-4-methylthio butyronitrile is up to more than 99.8%.Then slowly in 2-2-hydroxy-4-methylthio butyramide vitriol reactant, add 25% ammoniacal liquor, neutralization reaction temperature is no more than 20 DEG C, in and terminal pH control 6.5, after neutralization, non-shock chilling to 0 DEG C crystallization, suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide crude product (is the mixed crystal of D, L-2-2-hydroxy-4-methylthio butyramide and ammonium sulfate, wet product), amount to 460g, by analysis, D, L-2-2-hydroxy-4-methylthio butyramide is containing 65.2%, and ammonium sulfate is containing 26.0%.
To D obtained above, L-2-2-hydroxy-4-methylthio butyramide crude product adds the water of 6 DEG C of 160g, stir under 6 DEG C of conditions, then suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide work in-process 350g(wet product), D, L-2-2-hydroxy-4-methylthio butyramide content is 84%, and ammonium sulphate content is 7.4%.
D, L-2-2-hydroxy-4-methylthio butyramide work in-process 335g obtained above is added the recrystallization mother liquor of embodiment 11, be heated to 85 DEG C, D, L-2-2-hydroxy-4-methylthio butyramide just dissolves completely and is as the criterion.Be cooled to 0 DEG C, crystallization, suction filtration, dry and obtain D, L-2-2-hydroxy-4-methylthio butyramide 313g, yield is 95.3%, and purity is 99.5%.Recrystallization mother liquor is applied mechanically to next batch recrystallization.
Embodiment 13
At 50 DEG C, add the sulfuric acid (1.81mol) that people 221.2g massfraction is 80% under vigorous stirring in the reactor, at this temperature and vigorous stirring and cooling, add the 2-2-hydroxy-4-methylthio butyronitrile 287.4g that embodiment 6 is synthesized, control temperature of reaction at 50 DEG C.Dropwise, 40 minutes are reacted again at 50 DEG C, monitor the residual quantity of 2-2-hydroxy-4-methylthio butyronitrile with HPLC, be reaction end when 2-2-hydroxy-4-methylthio butyronitrile is transformed into 2-2-hydroxy-4-methylthio butyramide completely, the transformation efficiency of 2-2-hydroxy-4-methylthio butyronitrile is more than 99%.Then slowly in 2-2-hydroxy-4-methylthio butyramide vitriol reactant, add 25% ammoniacal liquor, neutralization reaction temperature is no more than 30 DEG C, in and terminal pH control 6.0, after neutralization, non-shock chilling to 0 DEG C crystallization, suction filtration, obtains D, L-2-2-hydroxy-4-methylthio butyramide crude product (is D, the mixed crystal of L-2-2-hydroxy-4-methylthio butyramide and ammonium sulfate, wet product) amount to 488.28g, by analysis, 2-2-hydroxy-4-methylthio butyramide is containing 63.63%, and ammonium sulfate is containing 32.44%.
To D obtained above, L-2-2-hydroxy-4-methylthio butyramide crude product adds the water of 10 DEG C of 165g, stir under 10 DEG C of conditions, then suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide work in-process 346.95g(wet product), 2-2-hydroxy-4-methylthio butyramide content is 89.55%, and ammonium sulphate content is 5.72%.
D, L-2-2-hydroxy-4-methylthio butyramide work in-process 346.95g obtained above is added the recrystallization mother liquor of embodiment 12, be heated to 85 DEG C, D, L-2-2-hydroxy-4-methylthio butyramide just dissolves completely and is as the criterion.Be cooled to 0 DEG C, crystallization, suction filtration, dry and obtain D, L-2-2-hydroxy-4-methylthio butyramide 304.90g, yield is 97.65%, and purity is 99.5%.Recrystallization mother liquor is applied mechanically to next batch recrystallization.
Embodiment 14
At 50 DEG C, the sulfuric acid (1.58mol) that people's 221.2g massfraction obtained above is 70% is added in the reactor under vigorous stirring, at this temperature and vigorous stirring and cooling, add the 2-2-hydroxy-4-methylthio butyronitrile 287.4g that embodiment 7 is synthesized, control temperature of reaction at 50 DEG C.Dropwise, 40 minutes are reacted again at 50 DEG C, monitor the residual quantity of 2-2-hydroxy-4-methylthio butyronitrile with HPLC, be reaction end when 2-2-hydroxy-4-methylthio butyronitrile is transformed into 2-2-hydroxy-4-methylthio butyramide completely, the transformation efficiency of 2-2-hydroxy-4-methylthio butyronitrile is more than 99%.Then slowly in 2-2-hydroxy-4-methylthio butyramide vitriol reactant, add 25% ammoniacal liquor, neutralization reaction temperature is no more than 30 DEG C, in and terminal pH control 6.0, after neutralization, non-shock chilling to 0 DEG C crystallization, suction filtration, obtains D, L-2-2-hydroxy-4-methylthio butyramide crude product (is D, the mixed crystal of L-2-2-hydroxy-4-methylthio butyramide and ammonium sulfate, wet product) amount to 624.18g, by analysis, 2-2-hydroxy-4-methylthio butyramide is containing 49.77%, and ammonium sulfate is containing 38.06%.
To D obtained above, L-2-2-hydroxy-4-methylthio butyramide crude product adds the water of 8 DEG C of 160g, stir under 8 DEG C of conditions, then suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide work in-process 346.95g(wet product), 2-2-hydroxy-4-methylthio butyramide content is 89.55%, and ammonium sulphate content is 5.72%.
D, L-2-2-hydroxy-4-methylthio butyramide work in-process 346.95g obtained above is added the recrystallization mother liquor of embodiment 13, be heated to 85 DEG C, D, L-2-2-hydroxy-4-methylthio butyramide just dissolves completely and is as the criterion.Be cooled to 0 DEG C, crystallization, suction filtration, dry and obtain D, L-2-2-hydroxy-4-methylthio butyramide 304.90g, yield is 97.65%, and purity is 99.5%.Recrystallization mother liquor is applied mechanically to next batch recrystallization.
Embodiment 15 prepares MHA zinc
By the D that embodiment 9 obtains, L-2-2-hydroxy-4-methylthio butyramide 289.7g(1.934mol) add 40% sodium hydroxide 290.2g(2.9mol) in, be heated with stirring to 90 DEG C, hydrolysis reaction 1.5 hours, HPLC detects D, L-2-2-hydroxy-4-methylthio butyramide transforms complete, be cooled to 60 DEG C, under vigorous stirring, 30% solder(ing)acid 703g(1.55mol is dripped) with 2 hours, dropwise, continue 60 DEG C of stirring reactions 1 hour, filter insoluble solids, then filtrate be cooled to 5 DEG C, filter, cold water washing, merging filtrate and washings are circulated to next batch reaction, the D obtained, L-2-hydroxy-4-methylthiobutyric acid zinc filter cake adds water heating just to dissolving completely, Heating temperature is 90 DEG C, and then add a small amount of water by its saturated D, L-2-hydroxy-4-methylthiobutyric acid zinc solution dilutes, concentration after dilution is 85% of former saturation concentration, add the Natvosol of 100ppm (with D, L-2-hydroxy-4-methylthiobutyric acid zinc meter) vigorous stirring, then 0 DEG C is cooled to, separate out a large amount of white crystals, filter, 100 DEG C of vacuum dryings obtain D, L-2-hydroxy-4-methylthiobutyric acid zinc white powder crystal 318.9g, yield 92%, purity is that 99.6%(HPLC detects), tap density (g/ml) is 0.67.
The preparation of embodiment 16D, L-2-2-hydroxy-4-methylthio calcium butyrate
Add the 2-2-hydroxy-4-methylthio butyramide 300.7g(2.0mol of embodiment 10 gained in the reactor), add water 1200ml, adds calcium hydroxide 112.1g(1.5mol in batches under stirring).Neutralization reaction is reacted in 100 DEG C, until sampling high performance liquid chromatography detects the residual volume of 2-2-hydroxy-4-methylthio butyramide lower than 0.1%.After completion of the reaction, be cooled to 60 DEG C, the calcium hydroxide of filtration residue, the filtrate obtained adds the Natvosol of 2-2-hydroxy-4-methylthio butyramide quality 300ppm, be cooled to 0 DEG C of crystallisation by cooling again, suction filtration obtains crystal and crystalline mother solution, and the 100 DEG C of dryings of crystal vacuum, obtain D, the Powdered crystal 337.9g of L-2-2-hydroxy-4-methylthio calcium butyrate, purity is that 99.7%(HPLC measures), yield is 99.5%, and tap density (g/ml) is 0.70.
Embodiment 17 utilizes D, and D prepared by L-2-2-hydroxy-4-methylthio butyramide production equipment, L-2-2-hydroxy-4-methylthio butyramide
As shown in Figure 1, D, L-2-2-hydroxy-4-methylthio butyramide production equipment comprises prussic acid synthetic tower 1, acid tower 2, reactor 3 and tripping device 4-suction filtration machine, fills the sulfuric acid that massfraction is 75% ~ 90% in described acid tower 2; Described reactor 3 is provided with pressure and temperature regulates supplementary unit; The air outlet of prussic acid synthetic tower 1 is communicated with by the inlet mouth of pipeline with acid tower 2, and the air outlet of acid tower 2 is communicated with reactor 3 by the pipeline being provided with throttling valve.
According to the requirement of iS-One method synthesis prussic acid, send into raw material to prussic acid synthetic tower 1, react to obtain prussic acid gas mixture I, prussic acid gas mixture I passes into acid tower 2 and sloughs ammonia and water vapour, obtains prussic acid gas mixture II.Prussic acid gas mixture II is under throttle valve control, and passing into 227.3kg massfraction in reactor 3 with the speed of 350L/min is in the methylthiopropionaldehyde of 94.5%, containing 3.3kg pyridine and 4kg water in methylthiopropionaldehyde.Under 0.09MPa, controlling temperature of reaction is 80 DEG C, and tail gas sodium hydroxide absorbs, and monitors the residual volume of methylthiopropionaldehyde with HPLC.When methylthiopropionaldehyde residual volume is less than 0.2%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 277.1kg, 2-2-hydroxy-4-methylthio butyronitrile is 97%, prussic acid remnants 0.06%.
In reactor 3, adding people 215.6kg massfraction in 50 DEG C under vigorous stirring is the sulfuric acid of 70%, and add simultaneously, cool, temperature controls at 50 DEG C.Add complete, 40 minutes are reacted again in 65 DEG C, monitor the residual quantity of 2-2-hydroxy-4-methylthio butyronitrile with HPLC, be reaction end when 2-2-hydroxy-4-methylthio butyronitrile is transformed into 2-2-hydroxy-4-methylthio butyramide completely, the transformation efficiency of 2-2-hydroxy-4-methylthio butyronitrile is up to more than 99.8%.Then slowly in 2-2-hydroxy-4-methylthio butyramide vitriol reactant, add 25% ammoniacal liquor, neutralization reaction temperature is no more than 20 DEG C, in and terminal pH control 6.5, after neutralization, non-shock chilling to 0 DEG C crystallization, suction filtration, obtain D, L-2-2-hydroxy-4-methylthio butyramide crude product (being the mixed crystal of D, L-2-2-hydroxy-4-methylthio butyramide and ammonium sulfate, filter cake) amounts to 461kg, by analysis, D, L-2-2-hydroxy-4-methylthio butyramide is containing 65.5%, and ammonium sulfate is containing 25.8%.
The water of 5 DEG C of 160kg is added, stirring and dissolving ammonium sulfate, then suction filtration under 5 DEG C of conditions in the filter cake of suction filtration machine, obtain D, L-2-2-hydroxy-4-methylthio butyramide work in-process 350kg(wet product), D, L-2-2-hydroxy-4-methylthio butyramide content is 84%, and ammonium sulphate content is 7.4%.
D, L-2-2-hydroxy-4-methylthio butyramide work in-process obtained above return in reactor 3, are dissolved in water, are heated to 85 DEG C, and amount of water just dissolves completely with D, L-2-2-hydroxy-4-methylthio butyramide and is as the criterion.Be cooled to 0 DEG C, crystallization, suction filtration, obtain crystallization and recrystallization mother liquor.Crystallization is transferred to drying plant and dries, and obtain D, L-2-2-hydroxy-4-methylthio butyramide 313kg, yield is 95.3%, and purity is 99.5%.Recrystallization mother liquor is applied mechanically to next batch recrystallization.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (9)
- The preparation method of 1.D, L-2-2-hydroxy-4-methylthio butyramide, is characterized in that: comprise the following steps:A, with methane, ammonia and oxygen for raw material, adopt iS-One method composition principle, be prepared into prussic acid gas mixture I; Described prussic acid gas mixture I obtains prussic acid gas mixture II through deamination process;B, described prussic acid gas mixture II under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile system with methylthiopropionaldehyde;C, described 2-2-hydroxy-4-methylthio butyronitrile system carry out hydration reaction in the presence of a mineral acid, after reaction terminates, reaction solution pH to 5.0 ~ 6.5 are regulated with ammonia or ammoniacal liquor, crystallisation by cooling, solid-liquid separation obtains D, the crystalline mixture of L-2-2-hydroxy-4-methylthio butyramide and inorganic acid ammonium salt is D, L-2-2-hydroxy-4-methylthio butyramide crude product;The purification step to D, L-2-2-hydroxy-4-methylthio butyramide crude product is comprised after described step C:1) by the hydration of D, L-2-2-hydroxy-4-methylthio butyramide crude product and 5 ~ 10 DEG C also, stirring and dissolving inorganic acid ammonium salt, solid-liquid separation obtains D, L-2-2-hydroxy-4-methylthio butyramide work in-process;2) described D, the L-2-2-hydroxy-4-methylthio butyramide work in-process water dissolution of 2 ~ 4 times of crude product quality, crystallisation by cooling, is separated to obtain crystallization and recrystallization mother liquor; Crystallization is dried, and obtains highly purified D, L-2-2-hydroxy-4-methylthio butyramide finished product.
- 2. the preparation method of D, L-2-2-hydroxy-4-methylthio butyramide according to claim 1, is characterized in that: the deamination process described in steps A be prussic acid gas mixture I is passed into massfraction be 75% ~ 90% sulfuric acid carry out deamination process.
- 3. D according to claim 1, the preparation method of L-2-2-hydroxy-4-methylthio butyramide, it is characterized in that: the methylthiopropionaldehyde described in step B is not purified methylthiopropionaldehyde, wherein containing the heavy constituent of the methylthiopropionaldehyde of massfraction 94.5% ~ 96%, the light constituent of massfraction 3.5% ~ 5.3% and massfraction 0.2% ~ 0.5%; Described light constituent is thiomethyl alcohol, methyl alcohol, propenal and water; Described restructuring is divided into dipolymer and the trimer of methylthiopropionaldehyde.
- 4. the preparation method of D, L-2-2-hydroxy-4-methylthio butyramide according to claim 1, is characterized in that: the alkali described in step B is organic bases and/or mineral alkali; The consumption of described alkali is the pH maintaining reaction system is 4.0 ~ 6.5.
- 5. D according to claim 1, the preparation method of L-2-2-hydroxy-4-methylthio butyramide, is characterized in that: in described step B, and the mol ratio of prussic acid and methylthiopropionaldehyde is 1:1.0 ~ 1.05, reaction pressure is 0.09 ~ 0.5MPa, and temperature of reaction is 30 ~ 80 DEG C.
- 6. the preparation method of D, L-2-2-hydroxy-4-methylthio butyramide according to claim 1, is characterized in that: in described step C, and described mineral acid is sulfuric acid, and the mol ratio of 2-2-hydroxy-4-methylthio butyronitrile and sulfuric acid is 1:0.5 ~ 1; The massfraction of described sulfuric acid is 50% ~ 80%, and temperature of reaction controls at 40 ~ 70 DEG C.
- 7. the preparation method of D, L-2-2-hydroxy-4-methylthio butyramide according to claim 1, is characterized in that: in described step C, regulates the temperature of reaction solution pH to control at 10 ~ 30 DEG C with ammonia or ammoniacal liquor.
- 8. the preparation method of D, L-2-2-hydroxy-4-methylthio butyramide according to claim 1, is characterized in that: described recrystallization mother liquor is circulated to step 1), for the dissolving of inorganic acid ammonium salt in the crude product produced next time.
- 9. utilize D, D prepared by L-2-2-hydroxy-4-methylthio butyramide production equipment, the method of L-2-2-hydroxy-4-methylthio butyramide, it is characterized in that: described production equipment comprises prussic acid synthetic tower (1), acid tower (2), reactor (3) and tripping device (4), the sulfuric acid that massfraction is 75% ~ 90% is filled in described acid tower (2), described reactor (3) is provided with pressure and temperature regulates supplementary unit, the air outlet of prussic acid synthetic tower (1) is communicated with by the inlet mouth of pipeline with acid tower (2), the air outlet of acid tower (2) is communicated with reactor (3) by the pipeline being provided with throttling valve,A, with methane, ammonia and oxygen for raw material, adopt iS-One method composition principle, prepare prussic acid gas mixture I by prussic acid synthetic tower (1); Described prussic acid gas mixture I passes into acid tower (2) and sloughs ammonia and water vapour, obtains prussic acid gas mixture II;B, described prussic acid gas mixture II, under throttle valve control, pass in the methylthiopropionaldehyde in reactor (3) with the speed of 250 ~ 350L/min, under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile system;Under C, vigorous stirring, in reactor (3), add sulfuric acid mix with 2-2-hydroxy-4-methylthio butyronitrile system, carry out hydration reaction, the massfraction of sulfuric acid is 50% ~ 80%, and temperature of reaction controls 40 ~ 70 DEG C of fully reactions; After reaction terminates, regulate reaction solution pH to 5.0 ~ 6.5, crystallisation by cooling with ammonia or ammoniacal liquor, D is obtained through tripping device (4) solid-liquid separation, the crystalline mixture of L-2-2-hydroxy-4-methylthio butyramide and ammonium sulfate is D, L-2-2-hydroxy-4-methylthio butyramide crude product;The purification step to D, L-2-2-hydroxy-4-methylthio butyramide crude product is comprised after described step C:1) by the hydration of D, L-2-2-hydroxy-4-methylthio butyramide crude product and 5 ~ 10 DEG C also, stirring and dissolving inorganic acid ammonium salt, solid-liquid separation obtains D, L-2-2-hydroxy-4-methylthio butyramide work in-process;2) described D, the L-2-2-hydroxy-4-methylthio butyramide work in-process water dissolution of 2 ~ 4 times of crude product quality, crystallisation by cooling, is separated to obtain crystallization and recrystallization mother liquor; Crystallization is dried, and obtains highly purified D, L-2-2-hydroxy-4-methylthio butyramide finished product.
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| CN102399176A (en) * | 2011-11-17 | 2012-04-04 | 浙江新和成股份有限公司 | Preparation method of high-content 2-hydroxy-4-(methylthio) butyl calcium |
| CN103347854A (en) * | 2011-02-23 | 2013-10-09 | 赢创德固赛有限公司 | Method for producing 2-hydroxy-4-(methylthio)butanenitrile from 3-(methylthio)propanal and hydrogen cyanide |
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| CN103347854A (en) * | 2011-02-23 | 2013-10-09 | 赢创德固赛有限公司 | Method for producing 2-hydroxy-4-(methylthio)butanenitrile from 3-(methylthio)propanal and hydrogen cyanide |
| CN102399176A (en) * | 2011-11-17 | 2012-04-04 | 浙江新和成股份有限公司 | Preparation method of high-content 2-hydroxy-4-(methylthio) butyl calcium |
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Effective date of registration: 20160728 Address after: 755000 the Ningxia Hui Autonomous Region central defender, Shapotou District, Guangzhou Road West Patentee after: NINGXIA ZIGUANG TIANHUA METHIONINE CO., LTD. Address before: 402161 Yongchuan District, Chongqing Chemical Road, No. 426 Patentee before: Chongqing Unisplendour Chemical Co., Ltd. |