CN103420883A - Method for using crude hydrocyanic acid gas for preparing 2-hydroxy-4-methylmercapto-butyronitrile - Google Patents
Method for using crude hydrocyanic acid gas for preparing 2-hydroxy-4-methylmercapto-butyronitrile Download PDFInfo
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- methylthio butyronitrile
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 238000000034 method Methods 0.000 title claims abstract description 45
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 title claims abstract 5
- 239000007789 gas Substances 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 59
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000009615 deamination Effects 0.000 claims abstract description 10
- 238000006481 deamination reaction Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 53
- CQSQMXIROIYTLO-UHFFFAOYSA-N 2-methylpropanethial Chemical compound CC(C)C=S CQSQMXIROIYTLO-UHFFFAOYSA-N 0.000 claims description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal bicarbonate salt Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 238000013016 damping Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 150000007516 brønsted-lowry acids Chemical class 0.000 claims description 2
- 150000007528 brønsted-lowry bases Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 5
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 abstract 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000000354 decomposition reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- 238000004321 preservation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 4
- 229930195722 L-methionine Natural products 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229960004452 methionine Drugs 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
- 239000000047 product Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 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
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 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 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000463 material Substances 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 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
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-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
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003610 charcoal Substances 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
- YDKKQXNAIYTHFB-UHFFFAOYSA-L disodium;butanedioate;hydrate Chemical compound O.[Na+].[Na+].[O-]C(=O)CCC([O-])=O YDKKQXNAIYTHFB-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 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
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention aims at the chemical engineering field, and relates to a method for using crude hydrocyanic acid gas for preparing 2-hydroxy-4-methylmercapto-butyronitrile. Based on the Andrussow method composition principle, the method takes methane, ammonia gas and oxygen gas as raw material to obtain hydrocyanic acid mixed gas I through preparation; the hydrocyanic acid mixed gas I is subjected to deamination treatment to obtain hydrocyanic acid mixed gas II; under the alkaline catalytic action, the hydrocyanic acid mixed gas II is fully reacted with methylmercapto-propionaldehyde to obtain the 2-hydroxy-4-methylmercapto-butyronitrile. The raw material without rectification and purification is adopted for the method and is low in price and easy to get, and the prepared 2-hydroxy-4-methylmercapto-butyronitrile is high in yield and purity. Moreover, an obtained 2-hydroxy-4-methylmercapto-butyronitrilereaction system not purified and separated is stable in property, capable of being stored for a long time and convenient to use in production of down-stream products.
Description
Technical field
The present invention is directed to chemical field, relate to the method for utilizing thick hydrocyanic acid gas to prepare 2-2-hydroxy-4-methylthio butyronitrile.
Background technology
2-2-hydroxy-4-methylthio butyronitrile is to produce D, the important intermediate of L-Methionine or MHA.The yield size of 2-2-hydroxy-4-methylthio butyronitrile and cost drop into, and to the D of final production, quality and the cost of L-Methionine or MHA have material impact.
In theory, the preparation of 2-2-hydroxy-4-methylthio butyronitrile is known, mainly comprises following two kinds of modes:
(1) methylthiopropionaldehyde reacts and makes with prussic acid under the catalysis of alkali;
(2) methylthiopropionaldehyde reacts and makes with alkali metal cyanide under the sodium bisulfite effect.
The disclosed method of US5756803 is a kind of concrete grammar that mode (1) prepares 2-2-hydroxy-4-methylthio butyronitrile.The damping fluid that the method is used citric acid and sodium hydroxide to form is as catalyzer, and the pH of solution is controlled at 4 left and right, and the catalysis methylthiopropionaldehyde reacts with prussic acid, obtains 2-2-hydroxy-4-methylthio butyronitrile.Wherein, prussic acid excessive 2%～5%.The use of buffered soln and excessive prussic acid are conducive to the prolonged preservation of product 2-2-hydroxy-4-methylthio butyronitrile.The 2-2-hydroxy-4-methylthio butyronitrile obtained obtains MHA by mineral acid hydrolysis, or reacts with bicarbonate of ammonia, generates the 5-(2-methylmercaptoethyl)-glycolylurea, the salt of wormwood hydrolysis, the carbonic acid gas neutralization obtains D, L-Methionine.
The disclosed method of US2745745 is a kind of concrete grammar that mode (2) prepares 2-2-hydroxy-4-methylthio butyronitrile.The 2-2-hydroxy-4-methylthio butyronitrile obtained, reaction needs after finishing, with the organic solvent-benzene extraction, to obtain containing 2-2-hydroxy-4-methylthio butyronitrile benzole soln, dry, steaming removes organic solvent-benzene, obtain 2-2-hydroxy-4-methylthio butyronitrile, then with inorganic acid reaction, obtain MHA.
Obviously, in these bibliographical informations, no matter take which kind of mode to synthesize 2-2-hydroxy-4-methylthio butyronitrile, in order to obtain high yield, all need purer prussic acid, and prussic acid is excessive often, the rectifying purifying that prussic acid is extra and excessive use all can cause the increase of cost, the increase of this cost, particularly in technical scale, will cause huge financial loss.Moreover method as disclosed as US2745745, under unsuitable catalyzer is used, may cause the formation of cyaniding byproduct in process thing, and then be that subsequent purification and downstream production make troubles.
For these reasons and prior art, still need further the preparation method of 2-2-hydroxy-4-methylthio butyronitrile is improved.
Summary of the invention
In view of this, the object of the present invention is to provide the method for utilizing thick hydrocyanic acid gas to prepare 2-2-hydroxy-4-methylthio butyronitrile, the raw material that the method is used is cheap and easy to get, the 2-2-hydroxy-4-methylthio butyronitrile yield of preparation is high, purity is high, but its reaction system long-term storage, be convenient to the production for derived product.
For achieving the above object, the technical solution used in the present invention is as follows:
Utilize thick hydrocyanic acid gas to prepare the method for 2-2-hydroxy-4-methylthio butyronitrile, comprise the following steps:
A, take methane, ammonia and oxygen as raw material, adopt iS-One method composition principle, be prepared into prussic acid gas mixture I;
B, prussic acid gas mixture I deamination are processed to obtain prussic acid gas mixture II;
C, prussic acid gas mixture II and methylthiopropionaldehyde, under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile.
Wherein, described thick hydrocyanic acid gas just refers to the prussic acid gas mixture standby by iS-One legal system.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 be again the methane oxidation proceses of ammonia.This method is under the condition more than normal pressure, l000 ℃, the silk screen that the logical people of material mixed gas is made by platinum, rhodium alloy catalyst platinum and rhodium, or the wire-mesh catalyst bed of being made by platinum iridium alloy, and the oxidative ammonolysis carried out, its reaction formula is 2CH
4+ 2NH
3+ 30
2→ 2HCN+6H
20.At present, this technology is very ripe, and the preparation of special prussic acid synthetic tower for hydrocyanic acid gas arranged.
Described deamination is processed and is referred to that the prussic acid gas mixture I that iS-One legal system is standby passes in acid, sloughs the operation of ammonia.The Main Function that acid rises is absorbing ammonia G&W steam, so preferably sulfuric acid, the sulfuric acid that further preferred concentration is 75%～90%.The prussic acid gas mixture of the present invention before and after deamination is processed all can be used for the preparation of 2-2-hydroxy-4-methylthio butyronitrile, and just the prussic acid gas mixture II character after deamination is processed is more excellent.Industrial, special acid tower can be set and process for deamination.
Further, described prussic acid gas mixture I preferably is comprised 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 preferably is comprised 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%.
Further, described methylthiopropionaldehyde is not purified methylthiopropionaldehyde, wherein containing methylthiopropionaldehyde 94.5%～96%, light constituent 3.5%～5.3% and heavy constituent 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.
Further, the preferred 1:1.0 of mol ratio of prussic acid and methylthiopropionaldehyde～1.05 in described step C; Described reaction pressure is 0.09～0.5MPa, and in negative pressure, the environment to malleation can be reacted, 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 ℃, preferably 35～60 ℃, and more preferably 40～45 ℃.
Step C is the nucleophilic addition under base catalysis.Further, the alkali of described katalysis is one or more in low-molecular-weight amine compound and mineral alkali; The consumption of the alkali of described katalysis is that the pH that maintains reaction system is 4.0～6.5, and preferably pH is 5.0～5.5.
Described low-molecular-weight amine compound is the aminated compounds of 3～20 carbon atoms preferably, and this compounds can, with methylthiopropionaldehyde arbitrarily than mixing, 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.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, also add acid in the alkali of described katalysis, 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, can make reaction system maintain in more stable pH value scope.Described organic acid is a kind of in acetic acid, formic acid, citric acid, Phenylsulfonic acid and trifluoromethanesulfonic acid; Described mineral acid is sulfuric acid or phosphoric acid.The damping fluid that forms 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.
Another object of the present invention is to provide the method for utilizing 2-2-hydroxy-4-methylthio butyronitrile production equipment to prepare 2-2-hydroxy-4-methylthio butyronitrile, the method equipment is simple, and controllability is strong, is applicable to the industrially scalable application.
Its technical scheme is as follows:
Utilize 2-2-hydroxy-4-methylthio butyronitrile production equipment to prepare the method for 2-2-hydroxy-4-methylthio butyronitrile, described 2-2-hydroxy-4-methylthio butyronitrile production equipment comprises prussic acid synthetic tower, acid tower and reactor, fill 75%～90% sulfuric acid in described acid tower, described reactor is provided with pressure and temperature regulation supplementary unit, 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 that is provided with throttling valve;
A, take methane, ammonia and oxygen as raw material, adopt iS-One method composition principle, by the prussic acid synthetic tower, prepare prussic acid gas mixture I;
B, prussic acid gas mixture I pass into acid tower and slough ammonia and water vapour, obtain prussic acid gas mixture II;
C, 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.
The present invention also has a purpose to be to provide the reaction system of 2-2-hydroxy-4-methylthio butyronitrile, and this reaction system stable in properties, can long-term storage.
The reaction system of this 2-2-hydroxy-4-methylthio butyronitrile is not carried out the system of separation and purification after being reaction, and the 2-2-hydroxy-4-methylthio butyronitrile obtained by following reactions steps forms together with its reaction solution:
A, take methane, ammonia and oxygen as raw material, adopt iS-One method composition principle, be prepared into prussic acid gas mixture I;
B, prussic acid gas mixture I deamination are processed to obtain prussic acid gas mixture II;
C, prussic acid gas mixture II and methylthiopropionaldehyde, under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile.
In described system except containing the 2-2-hydroxy-4-methylthio butyronitrile made, the prussic acid that also to contain remaining massfraction be 0.05%～0.5% and 2%～5% water.Just because of the existence of residual hydrogen cyanic acid and water, but the 2-2-hydroxy-4-methylthio butyronitrile long-term storage in this reaction system and decomposing hardly.
Further, this reaction system is adjusted to pH with acid and 2～4 is deposited.Like this, even still keep at normal temperatures longer stability.The acid of described adjusting pH can be sulfuric acid, phosphoric acid etc., concentration preferably 85%.
Described 2-2-hydroxy-4-methylthio butyronitrile reaction system, without carrying out any separation and purification, can be directly used in the production of derived product, again due to its can be steady in a long-term preservation, be particularly suitable for D, the production of L-Methionine and 2-hydroxy-4-(methylthio) base butyric acid.
Useful technique effect of the present invention is:
(1) adopt standby thick hydrocyanic acid gas and the not purified methylthiopropionaldehyde of iS-One legal system, raw material, without the rectifying purifying, is saved the production time, has improved production efficiency, has also reduced production cost; Prepare 2-2-hydroxy-4-methylthio butyronitrile by the method, yield is more than 99%, and purity is more than 96%.
(2) utilize 2-2-hydroxy-4-methylthio butyronitrile production equipment to prepare the method for 2-2-hydroxy-4-methylthio butyronitrile, the equipment related to is simple, and controllability is strong, is applicable to the industrially scalable application.
(3) the 2-2-hydroxy-4-methylthio butyronitrile reaction system prepared, confirm through experiment, stable in properties, but long-term storage, and do not need to carry out separation and purification, can be directly used in the production of derived product.
The accompanying drawing explanation
The structural representation that Fig. 1 is 2-2-hydroxy-4-methylthio butyronitrile production equipment.
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, carry out according to normal condition.
Embodiment 1
To from the prussic acid synthetic tower, prussic acid gas mixture I is out detected, the 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 after 75% sulfuric acid tower absorbs the ammonia and water vapour thereof in gas mixture, the 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 is passed in the methylthiopropionaldehyde of 223.3g94.5%, contain the 3.3g pyridine in methylthiopropionaldehyde.Under normal pressure, react, controlling temperature of reaction is 45 ℃, and draft speed is 300L/min, and tail gas absorbs with sodium hydroxide, with the residual volume of HPLC monitoring methylthiopropionaldehyde.When the methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Be total to obtain weak yellow liquid 270.64g, the content of 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.5%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into to two parts together with reaction solution (being 2-2-hydroxy-4-methylthio butyronitrile reaction system).Portion wherein adds 8.5g water, under 3 ℃ of conditions, preserves 120 days, has no decomposition; Another part adds 8.5g water wherein, with 85% sulfuric acid acidation, to pH, is then 3, and under 20 ℃ of conditions, preservation is 120 days, and 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.1%.
Embodiment 3
Prussic acid gas mixture II is passed in the methylthiopropionaldehyde of 223.3g94.5%, contain the water of 2.2g pyridine and 10g in methylthiopropionaldehyde.Under 0.15MPa, controlling temperature of reaction is 42 ℃, and draft speed is 280L/min, and tail gas absorbs with sodium hydroxide, with the residual volume of HPLC monitoring methylthiopropionaldehyde.When the methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Be total to obtain weak yellow liquid 279.54g, the content of 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.07%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into to two parts together with reaction solution.Portion is wherein preserved 120 days under 3 ℃ of conditions, has no decomposition; The sulfuric acid acidation of another part of use 85% is 3 to pH, and under 20 ℃ of conditions, preservation is 130 days, and 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.3%.
Embodiment 4
Prussic acid gas mixture II is passed in the methylthiopropionaldehyde of 247.2g94.5%, contain the water of 2.2g pyridine and 15g in methylthiopropionaldehyde.Under 0.5MPa, controlling temperature of reaction is 45 ℃, and draft speed is 280L/min, and tail gas absorbs with sodium hydroxide, with the residual volume of HPLC monitoring methylthiopropionaldehyde.When the methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Be total to obtain weak yellow liquid 294.54g, the content of 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.07%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into to two parts together with reaction solution.Portion is wherein preserved 120 days under 3 ℃ of conditions, has no decomposition; It is 3 that the phosphoric acid of another part of use 85% is acidified to pH, under 20 ℃ of conditions, preserves 128 days, and 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.2%.
Embodiment 5
Prussic acid gas mixture II is passed in the methylthiopropionaldehyde of 227.3g94.5%, contain the water of 3.3g pyridine and 4g in methylthiopropionaldehyde.Under 0.09MPa, controlling temperature of reaction is 80 ℃, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 ℃.With the residual volume of HPLC monitoring methylthiopropionaldehyde, when the methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Be total to obtain weak yellow liquid 277.4g, the content of 2-2-hydroxy-4-methylthio butyronitrile is 97%, prussic acid remnants 0.06%, moisture content 2%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into to two parts together with reaction solution.Portion is wherein preserved 120 days under 3 ℃ of conditions, has no decomposition; Another part of use 85% sulfuric acid acidation is 2 to pH, and under 23 ℃ of conditions, preservation is 120 days, and 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.1%.
Embodiment 6
Prussic acid gas mixture II is passed in the methylthiopropionaldehyde of 237.3g94.5%, contain 8.5g water in methylthiopropionaldehyde, in mixed system, add a certain amount of catalyzer carbonic acid sodium, keeping the pH of system in passing into prussic acid gas mixture process is 5.5.Under 0.5MPa, controlling temperature of reaction is 30 ℃, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 ℃.With the residual volume of HPLC monitoring methylthiopropionaldehyde, when the methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Be total to obtain weak yellow liquid 287.4g, the content of 2-2-hydroxy-4-methylthio butyronitrile is 96%, prussic acid remnants 0.06%, moisture content 3%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into to two parts together with reaction solution.Portion is wherein preserved 120 days under 3 ℃ of conditions, has no decomposition; Another part of use 85% sulfuric acid acidation is 2 to pH, and under 23 ℃ of conditions, preservation is 120 days, and 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.1%.
Embodiment 7
Prussic acid gas mixture II is passed in the methylthiopropionaldehyde of 233.3g94.5%, contain 8.5g water in methylthiopropionaldehyde, in mixed system, add a certain amount of catalyst of triethylamine, keeping the pH of system in passing into prussic acid gas mixture process is 5.5.Under normal pressure, react, controlling temperature of reaction is 40 ℃, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 ℃.With the residual volume of HPLC monitoring methylthiopropionaldehyde, when the methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Be total to obtain weak yellow liquid 287.4g, the content of 2-2-hydroxy-4-methylthio butyronitrile is 96%, prussic acid remnants 0.06%, moisture content 3%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into to two parts together with reaction solution.Portion is wherein preserved 120 days under 3 ℃ of conditions, has no decomposition; Another part of use 75% sulfuric acid acidation is 2 to pH, and under 23 ℃ of conditions, preservation is 120 days, and 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.1%.
Embodiment 8
Prussic acid gas mixture II is passed in the methylthiopropionaldehyde of 223.3g94.5%, and to the damping fluid that adds in mixed system a certain amount of sodium hydroxide and citric acid to form, keeping the pH of system in logical prussic acid gas mixture process is 5.0.Under normal pressure, react, controlling temperature of reaction is 45 ℃, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 ℃.With the residual volume of HPLC monitoring methylthiopropionaldehyde, when the methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Be total to obtain weak yellow liquid 287.4g, the content of 2-2-hydroxy-4-methylthio butyronitrile is 97%, prussic acid remnants 0.06%, moisture content 2%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into to two parts together with reaction solution.Portion is wherein preserved 120 days under 3 ℃ of conditions, has no decomposition; Another part of use 90% sulfuric acid acidation is 3 to pH, and under 23 ℃ of conditions, preservation is 120 days, and 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.1%.
Embodiment 9
Take the bicarbonate of ammonia of 4mol, add the 1500g water dissolution, under room temperature, the 2-2-hydroxy-4-methylthio butyronitrile reaction system of embodiment 2 preparations is all added in ammonium bicarbonate aqueous solution and stirred.Mixed solution is poured in the four-hole round-bottomed flask of 2000 milliliters, be warming up to immediately 80 ℃, normal pressure heat-insulating stirs 2 hours.After stopped reaction, add the 1.74g gac to be decoloured, the filter activity charcoal, filtrate is poured in the beaker of 2000 milliliters, static, be cooled to 3 ℃, separate out a large amount of white solids, suction filtration, oven dry, obtain the 5-(2-methylmercaptoethyl)-glycolylurea 348g, purity 99%, yield 99%.Obtain filtrate 1585g, wherein the 5-(2-methylmercaptoethyl)-content of glycolylurea is 0.2%.The 5-(2-methylmercaptoethyl obtained)-glycolylurea can be further used for D, the preparation of L-Methionine.
Embodiment 10
As shown in Figure 1, the production equipment of 2-2-hydroxy-4-methylthio butyronitrile, comprise prussic acid synthetic tower 1, acid tower 2 and reactor 3, fill 75%～90% sulfuric acid in described acid tower 2, described reactor 3 is provided with pressure and temperature regulation supplementary unit, the air outlet of prussic acid synthetic tower 1 is communicated with the inlet mouth of acid tower 2 by pipeline, and the air outlet of acid tower 2 is communicated with reactor 3 by the pipeline that is provided with throttling valve.
According to the synthetic prussic acid requirement of iS-One method, 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, under throttle valve control, passes in the methylthiopropionaldehyde of 225kg94.5% in reactor 3 with the speed of 300L/min, contains the 3.3kg pyridine in methylthiopropionaldehyde.Under normal pressure, react, controlling temperature of reaction is 45 ℃, and tail gas absorbs with sodium hydroxide, with the residual volume of HPLC monitoring methylthiopropionaldehyde.When the methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Be total to obtain weak yellow liquid 271.3kg, the content of 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.5%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into to two parts together with reaction solution (being 2-2-hydroxy-4-methylthio butyronitrile reaction system).Portion wherein adds 8.5kg water, under 3 ℃ of conditions, preserves 120 days, has no decomposition; Another part adds 8.5kg water wherein, with 85% sulfuric acid acidation, to pH, is then 3, and under 20 ℃ of conditions, preservation is 120 days, and 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.1%.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme, and not breaking away from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (10)
1. utilize thick hydrocyanic acid gas to prepare the method for 2-2-hydroxy-4-methylthio butyronitrile, it is characterized in that: comprise the following steps:
A, take methane, ammonia and oxygen as raw material, adopt iS-One method composition principle, be prepared into prussic acid gas mixture I;
B, described prussic acid gas mixture I deamination are processed to obtain prussic acid gas mixture II;
C, described prussic acid gas mixture II and methylthiopropionaldehyde, under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile.
2. the method for preparing 2-2-hydroxy-4-methylthio butyronitrile according to claim 1, it is characterized in that: step B passes into by described prussic acid gas mixture I the sulfuric acid that concentration is 75%～90% to carry out the deamination processing.
3. the method for preparing 2-2-hydroxy-4-methylthio butyronitrile according to claim 1, it is characterized in that: described methylthiopropionaldehyde is not purified methylthiopropionaldehyde, wherein containing methylthiopropionaldehyde 94.5%～96%, light constituent 3.5%～5.3% and heavy constituent 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 method for preparing 2-2-hydroxy-4-methylthio butyronitrile according to claim 1, it is characterized in that: the mol ratio of prussic acid described in step C and methylthiopropionaldehyde is 1:1.0～1.05, and reaction pressure is 0.09～0.5MPa, and temperature of reaction is 30～80 ℃.
5. the method for preparing 2-2-hydroxy-4-methylthio butyronitrile according to claim 1 is characterized in that: the aminated compounds that the alkali of described katalysis is 3～20 carbon atoms and one or more in mineral alkali; The consumption of the alkali of described katalysis is that the pH that maintains reaction system is 4.0～6.5.
6. the method for preparing 2-2-hydroxy-4-methylthio butyronitrile according to claim 5, it is characterized in that: the aminated compounds of described 3～20 carbon atoms is one or more in triethylamine, tri-isopropanolamine, DMA, imidazoles, picoline and pyridine.
7. the method for preparing 2-2-hydroxy-4-methylthio butyronitrile according to claim 5, it is characterized in that: described mineral alkali is one or more in metal hydroxides, metal cyanides, metal carbonate and alkali metal bicarbonate salt.
8. according to the described method for preparing 2-2-hydroxy-4-methylthio butyronitrile of claim 5 to 7 any one, it is characterized in that: also add acid in the alkali of described katalysis, form mixture or the damping fluid of bronsted lowry acids and bases bronsted lowry; Described acid comprises mineral acid and organic acid; Described organic acid is a kind of in acetic acid, formic acid, citric acid, Phenylsulfonic acid and trifluoromethanesulfonic acid; Described mineral acid is sulfuric acid or phosphoric acid.
9. utilize 2-2-hydroxy-4-methylthio butyronitrile production equipment to prepare the method for 2-2-hydroxy-4-methylthio butyronitrile, it is characterized in that: described 2-2-hydroxy-4-methylthio butyronitrile production equipment comprises prussic acid synthetic tower (1), acid tower (2) and reactor (3), described acid tower fills 75%～90% sulfuric acid in (2), described reactor (3) is provided with pressure and temperature regulation supplementary unit, the air outlet of prussic acid synthetic tower (1) is communicated with the inlet mouth of acid tower (2) by pipeline, and the air outlet of acid tower (2) is communicated with reactor (3) by the pipeline that is provided with throttling valve;
A, take methane, ammonia and oxygen as raw material, adopt iS-One method composition principle, by prussic acid synthetic tower (1), prepare prussic acid gas mixture I;
B, described prussic acid gas mixture I pass into acid tower (2) and slough ammonia and water vapour, obtain prussic acid gas mixture II;
C, 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.
10.2-the reaction system of 2-hydroxy-4-methylthio butyronitrile is characterized in that: the 2-2-hydroxy-4-methylthio butyronitrile obtained by following reactions steps forms together with its reaction solution:
A, take methane, ammonia and oxygen as raw material, adopt iS-One method composition principle, be prepared into prussic acid gas mixture I;
B, described prussic acid gas mixture I deamination are processed to obtain prussic acid gas mixture II;
C, described prussic acid gas mixture II and methylthiopropionaldehyde, under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile.
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| CN2013103817151A CN103420883A (en) | 2013-08-28 | 2013-08-28 | Method for using crude hydrocyanic acid gas for preparing 2-hydroxy-4-methylmercapto-butyronitrile |
| CN201310722698.3A CN103664720A (en) | 2013-08-28 | 2013-12-24 | Method for using hydrocyanic acid mixed gas to prepare 2-hydroxy-4-methylthio-butyronitrile and continuous production method for 2-hydroxy-4-methylthio-butyronitrile |
| CN201310722890.2A CN103755608B (en) | 2013-08-28 | 2013-12-24 | Thick hydrocyanic acid is utilized to produce method and the device thereof of D, L-2-2-hydroxy-4-methylthio calcium butyrate continuously |
| CN201310721634.1A CN103664718B (en) | 2013-08-28 | 2013-12-24 | Utilize thick prussic acid continuous seepage D, the method for L-2-hydroxy-4-methylthiobutyric acid microelement chelate and device thereof |
| CN201310721668.0A CN103694177B (en) | 2013-08-28 | 2013-12-24 | Hydrocyanic acid gaseous mixture is utilized to produce 5-(2-methylmercaptoethyl continuously) method of-hydantoin and device thereof |
| CN201310722404.7A CN103724242B (en) | 2013-08-28 | 2013-12-24 | Hydrocyanic acid gaseous mixture is utilized to produce D, the method for METHIONINE salt and device thereof continuously |
| CN201310722863.5A CN103664719B (en) | 2013-08-28 | 2013-12-24 | Thick hydrocyanic acid is utilized to produce D continuously, the method for METHIONINE and device |
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| CN201310722863.5A Active CN103664719B (en) | 2013-08-28 | 2013-12-24 | Thick hydrocyanic acid is utilized to produce D continuously, the method for METHIONINE and device |
| CN201310721668.0A Active CN103694177B (en) | 2013-08-28 | 2013-12-24 | Hydrocyanic acid gaseous mixture is utilized to produce 5-(2-methylmercaptoethyl continuously) method of-hydantoin and device thereof |
| CN201310721634.1A Active CN103664718B (en) | 2013-08-28 | 2013-12-24 | Utilize thick prussic acid continuous seepage D, the method for L-2-hydroxy-4-methylthiobutyric acid microelement chelate and device thereof |
| CN201310722890.2A Active CN103755608B (en) | 2013-08-28 | 2013-12-24 | Thick hydrocyanic acid is utilized to produce method and the device thereof of D, L-2-2-hydroxy-4-methylthio calcium butyrate continuously |
| CN201310722698.3A Pending CN103664720A (en) | 2013-08-28 | 2013-12-24 | Method for using hydrocyanic acid mixed gas to prepare 2-hydroxy-4-methylthio-butyronitrile and continuous production method for 2-hydroxy-4-methylthio-butyronitrile |
| CN201310722404.7A Active CN103724242B (en) | 2013-08-28 | 2013-12-24 | Hydrocyanic acid gaseous mixture is utilized to produce D, the method for METHIONINE salt and device thereof continuously |
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| CN201310722863.5A Active CN103664719B (en) | 2013-08-28 | 2013-12-24 | Thick hydrocyanic acid is utilized to produce D continuously, the method for METHIONINE and device |
| CN201310721668.0A Active CN103694177B (en) | 2013-08-28 | 2013-12-24 | Hydrocyanic acid gaseous mixture is utilized to produce 5-(2-methylmercaptoethyl continuously) method of-hydantoin and device thereof |
| CN201310721634.1A Active CN103664718B (en) | 2013-08-28 | 2013-12-24 | Utilize thick prussic acid continuous seepage D, the method for L-2-hydroxy-4-methylthiobutyric acid microelement chelate and device thereof |
| CN201310722890.2A Active CN103755608B (en) | 2013-08-28 | 2013-12-24 | Thick hydrocyanic acid is utilized to produce method and the device thereof of D, L-2-2-hydroxy-4-methylthio calcium butyrate continuously |
| CN201310722698.3A Pending CN103664720A (en) | 2013-08-28 | 2013-12-24 | Method for using hydrocyanic acid mixed gas to prepare 2-hydroxy-4-methylthio-butyronitrile and continuous production method for 2-hydroxy-4-methylthio-butyronitrile |
| CN201310722404.7A Active CN103724242B (en) | 2013-08-28 | 2013-12-24 | Hydrocyanic acid gaseous mixture is utilized to produce D, the method for METHIONINE salt and device thereof continuously |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3339289A1 (en) | 2016-12-21 | 2018-06-27 | Evonik Degussa GmbH | Process for the preparation of methionine |
| WO2018114640A1 (en) | 2016-12-21 | 2018-06-28 | Evonik Degussa Gmbh | Method for preparing methionine |
| CN109160894A (en) * | 2018-10-15 | 2019-01-08 | 禄丰天宝磷化工有限公司 | Environment-friendly and clean production process of DL-2-amino-4-methylselenobutyric acid |
| CN111116437A (en) * | 2018-11-01 | 2020-05-08 | 山东新和成氨基酸有限公司 | Method and device for preparing 2-hydroxy-4-methylthiobutyric acid and its intermediates |
| CN111116437B (en) * | 2018-11-01 | 2021-02-05 | 山东新和成氨基酸有限公司 | Method and apparatus for producing 2-hydroxy-4-methylthiobutyric acid and intermediate thereof |
| CN109912472A (en) * | 2019-04-02 | 2019-06-21 | 禄丰天宝磷化工有限公司 | Method for continuously and rapidly synthesizing 2-hydroxy-4-methylthiobutyronitrile |
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| Publication number | Publication date |
|---|---|
| CN103664718B (en) | 2016-03-30 |
| CN103664718A (en) | 2014-03-26 |
| CN103694177B (en) | 2017-01-04 |
| CN103755608A (en) | 2014-04-30 |
| CN103664719B (en) | 2016-06-08 |
| CN103724242B (en) | 2016-06-08 |
| CN103664720A (en) | 2014-03-26 |
| CN103755608B (en) | 2016-06-08 |
| CN103694177A (en) | 2014-04-02 |
| CN103664719A (en) | 2014-03-26 |
| CN103724242A (en) | 2014-04-16 |
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