CN1186484A - Process for producing cyclohexanonoxim and caprolactam - Google Patents
Process for producing cyclohexanonoxim and caprolactam Download PDFInfo
- Publication number
- CN1186484A CN1186484A CN96194378A CN96194378A CN1186484A CN 1186484 A CN1186484 A CN 1186484A CN 96194378 A CN96194378 A CN 96194378A CN 96194378 A CN96194378 A CN 96194378A CN 1186484 A CN1186484 A CN 1186484A
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- Prior art keywords
- formic acid
- mixture
- cyclohexanone
- oxime
- desired method
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- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 72
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 39
- 230000008569 process Effects 0.000 title description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 13
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000006237 Beckmann rearrangement reaction Methods 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 116
- 235000019253 formic acid Nutrition 0.000 claims description 59
- 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 55
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 29
- QJMMOFKVXUHETR-UHFFFAOYSA-N formic acid;hydroxylamine Chemical compound ON.OC=O QJMMOFKVXUHETR-UHFFFAOYSA-N 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 18
- 150000003057 platinum Chemical class 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 230000002829 reductive effect Effects 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- -1 formic acid ester Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 5
- 238000006462 rearrangement reaction Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 230000008707 rearrangement Effects 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- RBLWMQWAHONKNC-UHFFFAOYSA-N hydroxyazanium Chemical compound O[NH3+] RBLWMQWAHONKNC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005864 Sulphur Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 235000001508 sulfur Nutrition 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 230000004913 activation Effects 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Catalysts (AREA)
Abstract
The production of cyclohexanonoxim by the reaction of cyclohexanone with a hydroxyl ammonium salt, i.e. hydroxyl ammonium formiate, and the production of caprolactam by the Beckmann rearrangement of cyclohexanonoxim in a C1-C4 carboxylic acid.
Description
The present invention relates to method by pimelinketone and hydroxyl ammonium salt prepared in reaction cyclohexanone-oxime.
The present invention also further relates to the method for preparing hexanolactam.
The reactant aqueous solution of having described the inorganic or organic acid salt by pimelinketone and azanol according to claim DE-C1493198 prepares the method for cyclohexanone-oxime, remove the separation of carrying out salt/acid in the residual water solution that contains free acid behind the oxime therein, and, the amount of isolated acid be used to prepare the hydroxylammonium salt starting soln.The shortcoming of this method is that cost of equipment is big; And when using carboxylic acid (particularly acetate), although the use of sulfuric acid and ammonia causes the content of ammonium sulfate or ammonium phosphate must be removed than lack also in the past in the treating processes of acid/salt mixture.
EP-A620042 has described at strong inorganic acid or C
1-C
5In the monobasic aliphatic carboxylic acid (for example formic acid and acetate), in the presence of hydrogenation catalyst, by prepare the method for hydroxyl ammonium salt with the hydrogen reduction nitrogen protoxide, wherein hydrogenation catalyst is to obtain by also subsequently platinum salt being reduced to platinum with sulphuring treatment platinum salt in small, broken bits.But, the preparation of hydroxylammonium formate had not both clearly been described, the preparation of cyclohexanone-oxime and hexanolactam is not described yet.
The purpose of this invention is to provide the method for preparing cyclohexanone-oxime, the ammonium sulfate that must remove that is wherein generated or the amount of other salt are than lower in the prior art or in fact be zero; In addition, the present invention also under avoiding producing ammonium sulfate equally or reducing to minimum situation to its generation of major general, provides from the method for the preparing caprolactam with cyclohexanone-oxime that generates thus.
We find that purpose of the present invention can realize by the method for pimelinketone and hydroxyl ammonium salt prepared in reaction cyclohexanone-oxime (wherein using the hydroxylammonium formate as hydroxyl ammonium salt).
We also further find by pimelinketone and the method for hydroxylammonium formate prepared in reaction cyclohexanone-oxime and the method for preparing hexanolactam.
The preparation of cyclohexanone-oxime of the present invention is finished by pimelinketone and the reaction of hydroxylammonium formate in aqueous formic acid.
The mol ratio of hydroxylammonium formate and pimelinketone is selected from 1.3: 1 to 1: 1 usually, preferred 1.2: 1 to 1: 1.
In addition, according to the present invention, the hydroxylammonium formate reacts in aqueous formic acid; The concentration of used hydroxylammonium formate is selected from 10 to 16 by weight percentage, and preferred 12 to 14%.Formic acid concn in aqueous formic acid by weight percentage normally 10 to 15, preferred 12 to 14%.
Temperature is selected from 70 to 90 ℃ usually, preferred 75 to 80 ℃.
Pressure is selected from 90 usually to 120kPa, and preferred 100 to 120kPa, and preferred especially 105 to 110kPa.
PH is selected from 0.5 to 2.5 usually, and preferred 1.2 to 1.8.Usually, during the hydroxylammonium formate solution that directly obtains without further processing when preferred use is synthetic from the hydroxylammonium formate, this pH forms automatically by the shock absorption of ammonium formiate/formic acid system.
This reaction divides one or more stages, both can also can carry out continuously in batches; The preferred branch two stages, continuously preferred especially and divide two stages to carry out.
In the preferred embodiment of dividing two stages and carrying out continuously, normally 1.5 to the 3 hours residence time in each stage.
Find so far based on the yield of pimelinketone normally 94 to 98%.
In preferred embodiments, use in the presence of hydrogenation catalyst the hydroxylammonium formate that in aqueous formic acid, makes with the hydrogen reduction nitrogen protoxide.
Normally by hydrogenation catalyst is suspended in aqueous formic acid, and the mixture of nitrogen protoxide and hydrogen led to this suspension into carries out with regard to the preparation of this purpose hydroxylammonium formate.
In the process of preparation hydroxylammonium formate, hydrogen and nitric oxide production mol ratio preferably remained on 1.5: 1 to 6: 1, preferred especially 3: 1 to 5: 1.
The content of formic acid is selected from 50 usually to 500g in every liter of formic acid/water mixture, and preferred 100 to 250g.Observation so far be presented at by weight formic acid concn be higher than at 60% o'clock no longer may hydrogenation.
Nitric oxide production hydrogenation is preferably carried out under 35 to 60 ℃ temperature usually at 30 to 80 ℃.In addition, the pressure during the hydrogenation is selected from 100 usually to 3000kPa, and preferred 150 to 2000kPa.
The ratio of formic acid and catalyzer is selected from usually that platinum/graphite catalyst 10 is to 100g in every liter of aqueous formic acid, and preferred 30 to 80g.In preferred embodiments, before hydrogenation, catalyzer (is suitable in formic acid) handling (activation) with hydrogen in acid solution.
The hydrogenation catalyst of available common known preparation hydroxyl ammonium salt is as catalyzer of the present invention.Particularly preferred hydrogenation catalyst is by the described method preparation of DE-A4311420; In the method, with sulphuring treatment platinum in small, broken bits, and will be reduced to metal platinum with the platinum that this mode is handled subsequently.
Specially suitable platinum salt is water-soluble salt, for example halogenide, nitrate and vitriol; The example that is exemplified is :-platinum (IV) compound, and for example chloroplatinic acid and basic metal thereof and ammonium salt, Tetrachloroplatinum or tetrachloro dihydroxyl platinic acid: and-platinum (II) compound, for example Tetrachloroplatinate and an alkali metal salt thereof or platinum chloride (II); The mixture of all right in principle the main consuming body salt and other metal-salt (for example arsenic, antimony, selenium or tellurium salt).
The sulphur that serves as the part poisonous substance of Shi Yonging is sulphur in small, broken bits in a preferred method, for example commercially available flowers of sulfur (Schwefelblute).The granular size that the preferred sulphur that uses has is lower than 500 μ m, preferably is lower than 50um; The sulphur that especially preferably has following particle size dispersion, wherein 20% particle is lower than 1 μ m, and the particle that 50% particle is lower than 5 μ m and 90% is lower than 10 μ m.Suitable sulphur is from for example Kumulus WG
Colloid sulphur (BASF sale) or obtain with ordinary method (particularly screening) by for example flowers of sulfur or levigated sulphur.
Usually, in the aqueous solution, be by finishing with sulphur in small, broken bits contact platinum salt brine solution with sulphuring treatment platinum salt in small, broken bits.Described sulphur also can be used as colloid sulphur solution and uses.Preferably the form with aqeous suspension adds sulphur.
Can use other solvent except preferred solvent water in principle or it is added in the entry; Can also dry powdered form be introduced in the solution of platinum salt by sulphur.
In addition, can in reaction mixture, add the solvability that improves initial compounds or the material of dispersive ability; According to observation up to now, the wetting conventional surfactants that improves solvability and sulphur that is useful on all is particularly suitable for this purpose.
Suitable tensio-active agent (also can be known as dispersion agent) is for example seen UllmannsEncyklopadie der technischen Chemie, the 4th edition, and 23 volumes, Verlag Chemie, Weinheim, 1983, the 31-39 pages or leaves; The example that is exemplified is: polyacrylic ester, poly-sulfonic acid vinyl acetate, polyvinylpyrrolidone, TAMOL
(BASF), Schaeffer salt and Sulfite lignin.
In particularly preferred embodiments, (be disclosed in for example Ullmanns Encyclopadie der techn.Chemie with Sulfite lignin as tensio-active agent, the 4th edition, 16 volumes, the 253rd page is waited Verlag Chemie, 1978), preferred as alkali Sulfite lignin (for example sodium lignosulfonate and lignin sulfonic acid potassium), this is owing to be easy to they are removed with washing water when the catalyzer that cleaning is made, and since they be easy to degraded and do not cause environmental pollution.
Usually with sulphur, or be valuably add moisture sulphur suspension in the platinum salt before, tensio-active agent is added reaction mixture.
Usually, the weight ratio of tensio-active agent and sulphur is selected from 0.1 to 50% by weight percentage, and preferred 1 to 15%.
Temperature during handling platinum salt with finely-divided sulfur is selected from 20 to 95 ℃ usually, and preferred 40 to 95 ℃, preferred especially 50 to 85 ℃.
PH during handling platinum salt with finely-divided sulfur is being selected from 1.5 to 11.5 usually, and is preferred 2.5 to 8.5, preferred especially 4.5 to 8.5, and most preferably 7.0 to 7.5.
Time with finely-divided sulfur is handled platinum salt, promptly, be selected from 0.5 to 60 minute usually, preferred 2 to 15 minutes from adding finely-divided sulfur to the time that adds reductive agent.
The mol ratio of platinum and sulphur is selected from 90 to 10 moles of % usually, preferred 75 to 35 moles of %.
After partly poisoning with sulphur, should platinum salt be reduced to metal platinum by in handle the reaction mixture that platinum salt generates with finely-divided sulfur, adding reductive agent.
Appropriate reductant is all known reductive agents that are generally used for platinum salt is reduced to platinum; Hydrazine for example, formaldehyde, the formate of formic acid or basic metal or alkaline-earth metal (for example formate of sodium, potassium and calcium); Special preferable formic acid.
The mol ratio of platinum and reductive agent is selected from 0.5 to 100 mole of % usually, preferred 5 to 85 moles of %.
Temperature during reduction reaction is selected from 20 to 95 ℃ usually, and preferred 40 to 95 ℃, preferred especially 50 to 85 ℃.
PH during reduction reaction depends on the amount and the character of reductive agent basically.For example, when using formic acid, pH is selected from 0.5 to 3.5 usually, and preferred 1.0 to 2.5.
After the reduction fully, handle catalyzer in the mode of routine usually, for example from reaction mixture, it is separated by filtering with water cleaning suitably.
In preferred embodiments, reduction reaction and, if necessary, in the presence of support of the catalyst, carry out with the treating processes of finely-divided sulfur, described carrier for example is graphite or activated carbon, preferred graphite.Particularly preferably in before handling with finely-divided sulfur platinum salt being mixed with graphite in small, broken bits, common, the granular size of this graphite is 0.1 to 1000 μ m, preferred 0.1 to 300 μ m, preferred especially 5 to 100 μ m.
Carbon (or graphite or activated carbon) is selected from 99.99 to 10 moles of % usually with the mol ratio of platinum, and preferred 99.99 to 30 moles of % especially are preferably 99.99 to 90 moles of % under the situation of platinum, preferred especially 99.98 to 95.0 moles of %.
In another embodiment preferred, the formic acid that will use in the cyclohexanone-oxime preparation process and discharge is removed from the reaction mixture that generates.Then, the formic acid of being removed can be used further to prepare hydroxylammonium formate and cyclohexanone-oxime.Preferred especially such embodiment is wherein with formic acid esterification: (a) cyclohexanone-oxime is removed from the reaction mixture that generates, contained the mixture A of water and formic acid basically; And (b) with C
1-C
4-alkanol mixes with mixture A, under normal condition, is manthanoate with formic acid esterification, thereby obtains mixture B; (c) from mixture B, isolate the manthanoate that step (b) generates by distillation; (d) manthanoate that step (c) is obtained is with the mode hydrolysis of routine, thus contained basically formic acid and corresponding in step (a) mixture C of used alcohol; (e) from mixture, remove the formic acid that derives from step (d), and be used to prepare hydroxylammonium formate and/or cyclohexanone-oxime.
Usually, from the reaction mixture that the preparation of cyclohexanone-oxime, generates, obtain cyclohexanone-oxime by phase disengagement method, for example at 70 to 75 ℃, the phase on phase separator.Obtain the mixture A that forms by water, formic acid and possible impurity (for example hydroxylammonium formate of ammonium formiate and trace) basically simultaneously.
According to the present invention, with C
1-C
4-alkanol (methyl alcohol for example, ethanol, just-, different-propyl alcohol, just-, different-, secondary-and uncle-butanols) adding mixture A, used chain triacontanol base is in formic acid by weight percentage common excessive 10 to 40, preferred 20 to 40%.
Since the boiling point of methyl-formiate low (under 100kPa 31.8 ℃), thus easily remove, therefore, especially preferably use methanol esterification formic acid.
Carry out esterification with ordinary method, it is 40 to 80 ℃ and to keep-up pressure be 150 to 500kPa that the mixture A that for example will add alkanol is heated to temperature.
Esterification generates the mixture B that contains manthanoate.Go out manthanoate among the mixture B by fractionation by distillation.In preferred embodiments, during esterification, remove the manthanoate of generation continuously.
Esterification is carried out in the presence of acid catalyst usually, this acid (preferred mineral acid, for example sulfuric acid, hydrochloric acid or phosphoric acid) with based on formic acid by weight at the most 2% amount use.
Preferred this step is carried out in the stirred reactor of distillation column is housed, and removes formed formic acid C continuously by distilling
1-C
4Alkyl ester.
Also can use strongly-acid ion-exchanger (Amberlite for example
Or Duolite
) replacement acid.In this case, in tubular reactor, carry out this reaction usually, by distilling the formic acid C that removes formation continuously
1-C
4Alkyl ester.
The pH value is usually 0.5 to 2.5.
Manthanoate (formic acid C
1-C
4Alkyl ester) common mode hydrolysis, i.e. cracking formic acid and C with routine
1-C
4-alkanol.This hydrolysis both can also can be carried out in alkaline medium in acidity.
In preferred embodiments, in stirred vessel, under the situation of acid or base catalysis, be hydrolyzed in due form.
In another embodiment preferred, in containing the fixed bed type reactor of alkaline ion exchanger, be hydrolyzed.
In preferred two embodiments, the reactor used rectifier that preferably is equipped with separates H to reach
2O/HCOOH/C
1-C
4The purpose of-alkanol/manthanoate system.
After the hydrolysis, from reaction mixture, separate formic acid, for example remove low boiling component in the reaction mixture by distillation by ordinary method.Preferably with isolating formic acid (preferably the form with the aqueous solution exists) be used for synthetic hydroxylammonium formate and/or be used for the synthesizing cyclohexane 1 ketoxime, thereby cause the circulation of formic acid.
In particularly preferred embodiments, in esterification, use methyl alcohol and, in hydrolysis (temperature range: 40-80 ℃, pressure range: 100-500kPa, pH scope: 8-11) cause Methanol Recovery and methyl-formiate to reclaim with the form of ester.In this step, have the form that very lower boiling methyl-formiate can distillate and remove, and methyl alcohol can be used as side stream and be drawn out of, aqueous formic acid then remains and preferably be used further to hydroxylammonium as bottoms synthetic.
Do not contain by product, particularly other organic impurity (TOC, total organic carbon) in the formic acid that the advantage that this method has is to reclaim.Owing to removed by product, in circulation, avoided the accumulation of unwanted by product.
According to the present invention, at C
1-C
4Under the existence of-carboxylic acid (for example formic acid, acetate, propionic acid or butyric acid, preferable formic acid and acetate, special preferable formic acid), the Beckmann rearrangement by cyclohexanone-oxime prepares hexanolactam.
The mol ratio of cyclohexanone-oxime and carboxylic acid is preferably selected from 1: 1 to 1: 30, more preferably 1: 1 to 1: 10.
Cyclohexanone-oxime is usually with at C
1-C
4The form of the solution the in-carboxylic acid is used, and this concentration that is generally carboxylic acid aqueous solution is 10 to 70% by weight usually, and preferred 15 to 50%.Preferred especially the use and the same carboxylic acid of carboxylic acid that in rearrangement reaction, uses as solvent, special preferable formic acid.
Temperature is selected from 50 to 150 ℃ usually, preferred 70 to 120 ℃.
Pressure is selected from 100 usually to 1000kPa, and preferred 100 to 200kPa.
According to observation up to now, the pH value forms under the situation that does not have intervention, and need not to use buffer reagent usually.
In addition, rearrangement reaction is carried out with ordinary method, promptly both can be continuous, also can divide one or more stages in batches, and preferably divide several stages to carry out.
Usually, the residence time is 2 to 10 hours, preferred 3 to 6 hours.
In preferred embodiments, use one of method noted earlier preparation according to the present invention with record cyclohexanone-oxime in the dependent claims.
In preferred embodiments, after resetting, remove the C that when resetting beginning, uses by distillation to hexanolactam
1-C
4-carboxylic acid, and preferably it is used further to the rearrangement of cyclohexanone-oxime.
The aftertreatment of hexanolactam prepared in accordance with the present invention can ordinary method be carried out, and for example uses solvent extraction lactan crude product, the method by describing in following file: EP-B22261 for example, DE-A3735054, US2813858, EP-B411455.
Hexanolactam prepared in accordance with the present invention is as the starting material of preparation polycaprolactam and corresponding copolymers thereof.
The present invention prepares the advantage that the method for cyclohexanone-oxime has and is not generate salt.In addition, used carboxylic acid is capable of circulation.An advantage is to carry out oxime rearrangement with carboxylic acid again, and this is because remove ammonium sulfate having been avoided resembling in the ordinary method of prior art equally.
The preparation of EXAMPLE Example 1 hydroxylammonium formate
640 grams (calculating with dry substance) graphite carrier in small, broken bits (0.1 to 300 μ m) is suspended in 500 ml waters and the 100 milliliters of chloroazotic acid, adds the platinum (as the chloroplatinic acid hexahydrate) of 0.5% (by weight), and stir these mixture overnight at 80 ℃.Second day, suspension with after the 400 ml waters dilutions, is cooled to 30 ℃, and then with yellow soda ash with pH regulator to 7.5.
Then, with the 150 milligrams of elementary sulfurs in small, broken bits (particle size dispersion: 20%<1 μ m that is suspended in 50 ml waters; 50%<5 μ m; 90%<10 μ m) adds reaction mixture.After 10 minutes, in this reaction mixture, add the formic acid of 100 milliliters of purity 99% again.
At 40 ℃, will be suspended in 1250 milliliter of 25% (by weight) formic acid with the 50 gram catalyzer that this mode is handled, and use H
2Handle (activation).
Subsequently, will be by 70% (by volume) H
2(purity 99.95%) and 30% (by volume) NO (purity 99.5%) blended mixture leads to into above-mentioned suspension with 100 liters/hour.
Lead to into amount to 300 go up state gaseous mixture after, obtain the solution of 1320 milliliters of following compositions: 145.3 grams per liter HCOOH, 51.2 grams per liter NH
2OH is (as NH
2OHHCOOH) 4.8 grams per liter NH
3(as HCOONH
4) total amount of waste gas is 99.8 liters.Selectivity: 65.3% NH
2OH is (as NH
2OHHCOOH) 10.7% NH
3(as HCOONH
4) 24.0% N
2O space-time yield: 0.84 mol
RVliq. hour, based on conversion 0.55 mol of NO
RVliq. hour, based on the NH that forms
2OH.The preparation of embodiment 2 cyclohexanone-oximes
Hybrid ring hexanone and azanol in 2 liters of stirred reactors.Wherein azanol is to add with the form of hydroxylammonium formate solution.
Keep following condition: stirring velocity: 100 rev/mins of temperature: 80 ℃ of pressure: normal atmosphere residence time: 2 hours.
Reaction is performed such, and promptly passes through at first with NH
2OH joins to react in the pimelinketone to reach with excessive (20 moles of %) and transforms purpose completely.After removing formed cyclohexanone-oxime (in phase separator as top phase), following phase (is had unreacted NH
2OH) return stirred reactor with fresh hydroxylammonium formate solution.Productive rate: based on the preparation of about 92% embodiment of pimelinketone 3 hexanolactams
The solution of 20% (by weight) cyclohexanone-oxime (from embodiment 2) in formic acid (purity 100%) was refluxed 5 hours at 105 ℃.Then, remove formic acid removal, and it is used further to rearrangement reaction, the lactan liquid crude product that generates is sent to further processing (prior art: use solvent extraction, distillation) by distillation.
Claims (11)
1, by the method for pimelinketone and hydroxyl ammonium salt prepared in reaction cyclohexanone-oxime, wherein use the hydroxylammonium formate as hydroxyl ammonium salt.
2, as the desired method for preparing cyclohexanone-oxime of claim 1, wherein said hydroxylammonium formate is by in the presence of hydrogenation catalyst, makes with the hydrogen reduction nitrogen protoxide in aqueous formic acid.
3, as the desired method of claim 2, hydrogenation catalyst wherein makes by following step basically: (a) then platinum salt is reduced to platinum with finely-divided sulfur processing platinum salt with (b).
4, as each desired method of claim 1 to 3, wherein (a) isolates cyclohexanone-oxime from the reaction mixture that generates, and contained the mixture A of water and formic acid basically; (b) with C
1-C
4-alkanol mixes with mixture A, and under normal condition, with formic acid esterification formic acid ester, obtains mixture B; (c) from mixture B, isolate the manthanoate that in step (b), generates by distillation; (d) in a usual manner hydrolysis from the manthanoate that step (c) obtains, contained basically formic acid and with the mixture C of used corresponding alcohol in step (a); (e) from mixture, separate formic acid from step (d), and in order to preparation hydroxylammonium formate and/or cyclohexanone-oxime.
5, the method for preparing hexanolactam by the Beckmann rearrangement of cyclohexanone-oxime, wherein said rearrangement reaction is at the C as solvent
1-C
4-carboxylic acid carries out under existing.
6, as the desired method of claim 5, cyclohexanone-oxime wherein makes by pimelinketone and the reaction of hydroxylammonium formate.
7, as the desired method of claim 6, wherein said hydroxylammonium formate is by in the presence of hydrogenation catalyst, makes with the hydrogen reduction nitrogen protoxide in aqueous formic acid.
8, as the desired method of claim 7, hydrogenation catalyst wherein makes by following step basically: (a) then platinum salt is reduced to platinum with finely-divided sulfur processing platinum salt with (b).
9, as each desired method of claim 6 to 8, wherein (a) isolates cyclohexanone-oxime from the reaction mixture that the preparation cyclohexanone oxime generates, and contained the mixture A of water and formic acid basically; (b) with C
1-C
4-alkanol mixes with mixture A, and under normal condition, with formic acid esterification formic acid ester, obtains mixture B; (c) from mixture B, isolate the manthanoate that in step (b), generates by distillation; (d) in a usual manner hydrolysis from the manthanoate that step (c) obtains, contained basically formic acid and with the mixture C of used corresponding alcohol in step (a); (e) from mixture, divide and leave away from the formic acid of step (d), and in order to preparation hydroxylammonium formate and/or cyclohexanone-oxime.
10,, wherein remove the C that when rearrangement reaction begins, uses the reaction mixture that after the cyclohexanone-oxime cyclisation, generates by distilling as each desired method of claim 5 to 9
1-C
4-carboxylic acid.
11, as the desired method of claim 10, the wherein C that is removed
1-C
4-carboxylic acid is used for the rearrangement of cyclohexanone-oxime.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19520271.6 | 1995-06-02 | ||
DE19520271A DE19520271A1 (en) | 1995-06-02 | 1995-06-02 | Process for the preparation of cyclohexanone oxime and caprolactam |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1186484A true CN1186484A (en) | 1998-07-01 |
Family
ID=7763514
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN96194378A Pending CN1186484A (en) | 1995-06-02 | 1996-05-24 | Process for producing cyclohexanonoxim and caprolactam |
Country Status (12)
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---|---|
EP (1) | EP0828707A1 (en) |
JP (1) | JPH11506440A (en) |
KR (1) | KR19990022175A (en) |
CN (1) | CN1186484A (en) |
AU (1) | AU6000196A (en) |
BR (1) | BR9608960A (en) |
CZ (1) | CZ359197A3 (en) |
DE (1) | DE19520271A1 (en) |
EA (1) | EA199700443A1 (en) |
PL (1) | PL323676A1 (en) |
TW (1) | TW342383B (en) |
WO (1) | WO1996038407A1 (en) |
Cited By (3)
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---|---|---|---|---|
CN1091763C (en) * | 1999-07-26 | 2002-10-02 | 巴陵石化鹰山石油化工厂 | Method for preventing hydroxylamine decomposition in inorganic liquid for manufacturing caprolactam by hydroxylamine phosphate oximation method |
CN109453820A (en) * | 2018-11-27 | 2019-03-12 | 中国天辰工程有限公司 | A kind of liquid phase Beckmann rearrangement catalyst and its preparation method and application |
CN115819344A (en) * | 2023-01-13 | 2023-03-21 | 神马实业股份有限公司 | Process method for producing caprolactam and coproducing sulfuric ester by liquid phase Beckmann rearrangement |
Families Citing this family (1)
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CN102626645B (en) * | 2012-03-27 | 2013-11-27 | 长沙理工大学 | Application of fluorgypsum in ketoxime Beckmann rearrangement |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2721199A (en) * | 1953-12-15 | 1955-10-18 | Du Pont | Production of amides or lactams from oximes |
NL301053A (en) * | 1963-11-27 | |||
US4105575A (en) * | 1976-10-12 | 1978-08-08 | Imc Chemical Group, Inc. | Partial resolution of pentaerythritol waste liquors |
DE4311420A1 (en) * | 1993-04-07 | 1994-10-13 | Basf Ag | Hydrogenation catalyst based on a platinum metal partially poisoned with finely divided sulfur |
-
1995
- 1995-06-02 DE DE19520271A patent/DE19520271A1/en not_active Withdrawn
-
1996
- 1996-05-24 CN CN96194378A patent/CN1186484A/en active Pending
- 1996-05-24 KR KR1019970708654A patent/KR19990022175A/en not_active Application Discontinuation
- 1996-05-24 BR BR9608960A patent/BR9608960A/en not_active Application Discontinuation
- 1996-05-24 AU AU60001/96A patent/AU6000196A/en not_active Abandoned
- 1996-05-24 EA EA199700443A patent/EA199700443A1/en unknown
- 1996-05-24 PL PL96323676A patent/PL323676A1/en unknown
- 1996-05-24 JP JP8536165A patent/JPH11506440A/en active Pending
- 1996-05-24 WO PCT/EP1996/002240 patent/WO1996038407A1/en not_active Application Discontinuation
- 1996-05-24 CZ CZ973591A patent/CZ359197A3/en unknown
- 1996-05-24 EP EP96917419A patent/EP0828707A1/en not_active Withdrawn
- 1996-05-30 TW TW085106432A patent/TW342383B/en active
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1091763C (en) * | 1999-07-26 | 2002-10-02 | 巴陵石化鹰山石油化工厂 | Method for preventing hydroxylamine decomposition in inorganic liquid for manufacturing caprolactam by hydroxylamine phosphate oximation method |
CN109453820A (en) * | 2018-11-27 | 2019-03-12 | 中国天辰工程有限公司 | A kind of liquid phase Beckmann rearrangement catalyst and its preparation method and application |
CN115819344A (en) * | 2023-01-13 | 2023-03-21 | 神马实业股份有限公司 | Process method for producing caprolactam and coproducing sulfuric ester by liquid phase Beckmann rearrangement |
Also Published As
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WO1996038407A1 (en) | 1996-12-05 |
CZ359197A3 (en) | 1998-04-15 |
PL323676A1 (en) | 1998-04-14 |
BR9608960A (en) | 1999-05-04 |
MX9708928A (en) | 1998-03-31 |
TW342383B (en) | 1998-10-11 |
JPH11506440A (en) | 1999-06-08 |
EP0828707A1 (en) | 1998-03-18 |
KR19990022175A (en) | 1999-03-25 |
DE19520271A1 (en) | 1996-12-05 |
EA199700443A1 (en) | 1998-06-25 |
AU6000196A (en) | 1996-12-18 |
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