CN106395850B - Method for producing zeolite and method for producing epsilon-caprolactam - Google Patents
Method for producing zeolite and method for producing epsilon-caprolactam Download PDFInfo
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- CN106395850B CN106395850B CN201610597172.0A CN201610597172A CN106395850B CN 106395850 B CN106395850 B CN 106395850B CN 201610597172 A CN201610597172 A CN 201610597172A CN 106395850 B CN106395850 B CN 106395850B
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- Prior art keywords
- zeolite
- mixture
- reaction
- crystals
- caprolactam
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- 239000010457 zeolite Substances 0.000 title claims abstract description 152
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 140
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000013078 crystal Substances 0.000 claims abstract description 110
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- 239000000203 mixture Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 239000011541 reaction mixture Substances 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 15
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 15
- 238000010304 firing Methods 0.000 claims abstract description 14
- 150000002291 germanium compounds Chemical class 0.000 claims abstract description 14
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 17
- 229910052796 boron Inorganic materials 0.000 claims description 17
- 238000006237 Beckmann rearrangement reaction Methods 0.000 claims description 12
- 229910052732 germanium Inorganic materials 0.000 claims description 12
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 abstract description 50
- 238000011282 treatment Methods 0.000 abstract description 27
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 235000005985 organic acids Nutrition 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000001914 filtration Methods 0.000 description 32
- 238000001035 drying Methods 0.000 description 29
- 238000004140 cleaning Methods 0.000 description 28
- 229910001873 dinitrogen Inorganic materials 0.000 description 23
- 238000005406 washing Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 18
- 239000012528 membrane Substances 0.000 description 16
- 238000011085 pressure filtration Methods 0.000 description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 15
- -1 allylamines Chemical class 0.000 description 15
- 229910017604 nitric acid Inorganic materials 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000012495 reaction gas Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000011369 resultant mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002036 drum drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 2
- HSNJERRVXUNQLS-UHFFFAOYSA-N 1-(4-tert-butylphenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(C(C)(C)C)C=C1 HSNJERRVXUNQLS-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JKYPBYBOZSIRFW-UHFFFAOYSA-N 3-(4-chlorophenyl)oxolane-2,5-dione Chemical compound C1=CC(Cl)=CC=C1C1C(=O)OC(=O)C1 JKYPBYBOZSIRFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BZGBXNBROBZKLC-UHFFFAOYSA-N 4-cyano-n-methoxy-n-methylbenzamide Chemical compound CON(C)C(=O)C1=CC=C(C#N)C=C1 BZGBXNBROBZKLC-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KTDMLSMSWDJKGA-UHFFFAOYSA-M methyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](C)(CCC)CCC KTDMLSMSWDJKGA-UHFFFAOYSA-M 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006146 oximation reaction Methods 0.000 description 1
- PYUBPZNJWXUSID-UHFFFAOYSA-N pentadecapotassium;pentaborate Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] PYUBPZNJWXUSID-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000010453 quartz Substances 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
- 230000035484 reaction time Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PKLMYPSYVKAPOX-UHFFFAOYSA-N tetra(propan-2-yloxy)germane Chemical compound CC(C)O[Ge](OC(C)C)(OC(C)C)OC(C)C PKLMYPSYVKAPOX-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- VJHDVMPJLLGYBL-UHFFFAOYSA-N tetrabromogermane Chemical compound Br[Ge](Br)(Br)Br VJHDVMPJLLGYBL-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- QQXSEZVCKAEYQJ-UHFFFAOYSA-N tetraethylgermanium Chemical compound CC[Ge](CC)(CC)CC QQXSEZVCKAEYQJ-UHFFFAOYSA-N 0.000 description 1
- CUDGTZJYMWAJFV-UHFFFAOYSA-N tetraiodogermane Chemical compound I[Ge](I)(I)I CUDGTZJYMWAJFV-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZRLCXMPFXYVHGS-UHFFFAOYSA-N tetramethylgermane Chemical compound C[Ge](C)(C)C ZRLCXMPFXYVHGS-UHFFFAOYSA-N 0.000 description 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/047—Germanosilicates; Aluminogermanosilicates
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/86—Borosilicates; Aluminoborosilicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
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- 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)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for producing zeolite and a method for producing epsilon-caprolactam. An object of the present invention is to provide a method for producing a zeolite having excellent catalytic activity, and another object of the present invention is to provide the following method: the zeolite thus obtained is used as a catalyst to react cyclohexanone oxime with a high conversion rate and to obtain epsilon-caprolactam with a high selectivity, thereby enabling the production of epsilon-caprolactam with good productivity. The present invention provides the following methods: the zeolite is produced by mixing at least 1 compound selected from boron compounds and germanium compounds, tetraalkyl orthosilicate, water and quaternary ammonium hydroxide, subjecting the resulting mixture to a hydrothermal synthesis reaction, subjecting the reaction mixture containing the resulting zeolite crystals to solid-liquid separation, firing the resulting zeolite crystals, and subjecting the fired zeolite crystals to a contact treatment with an aqueous solution containing at least one acid selected from inorganic acids and organic acids.
Description
Technical Field
The present invention relates to a method for producing zeolites. In addition, the present invention relates to a process for producing epsilon-caprolactam from cyclohexanone oxime using zeolite as a catalyst.
Background
Conventionally, as one of the methods for producing epsilon-caprolactam, there have been known: a process for producing a cyclohexanone oxime by Beckmann rearrangement in a gas phase using a zeolite as a catalyst. As a method for producing the zeolite, for example, japanese patent laying-open No. 5-170732 (patent document 1) proposes the following method: after firing a crystal obtained by a hydrothermal synthesis reaction of a silicon compound, an aqueous solution of a basic substance selected from ammonia, lower alkylamines, allylamines, and alkylammonium hydroxides and an ammonium salt, or aqueous ammonia is brought into contact with the crystal. Further, jp 9-12540 a (patent document 2) describes a production method for producing epsilon-caprolactam by beckmann rearrangement of cyclohexanone oxime in a gas phase at a temperature of 250 to 450 ℃ on a zeolite catalyst, wherein MFI zeolite having OH groups on the surface thereof, which are arranged symmetrically to each other based on a defect in the central metal atom, is used as the zeolite catalyst.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 5-170732
Patent document 2: japanese patent laid-open No. 9-12540.
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide a method for producing a zeolite which is more excellent in terms of catalytic activity. Another object of the present invention is to provide the following method: which can produce epsilon-caprolactam with good productivity by reacting cyclohexanone oxime with high conversion using zeolite as a catalyst to produce epsilon-caprolactam with high selectivity.
Means for solving the problems
The present inventors have conducted extensive studies to achieve the above object, and as a result, the present invention has been completed.
That is, the present invention provides a method for producing zeolite comprising the following step (1), the following step (2), the following step (3), the following step (4), and the following step (5). By the above method, a zeolite having hydroxyl groups arranged symmetrically to each other can be produced, and a zeolite having excellent catalytic activity can be produced.
Step (1): mixing at least 1 compound selected from boron compounds and germanium compounds, tetraalkyl orthosilicate, water, and quaternary ammonium hydroxide salt
Step (2): subjecting the mixture obtained in the step (1) to a hydrothermal synthesis reaction to obtain a reaction mixture containing zeolite crystals
Step (3): a step of obtaining zeolite crystals by subjecting a reaction mixture containing the zeolite crystals obtained in the step (2) to solid-liquid separation
Step (4): a step of firing the zeolite crystals obtained in the step (3)
Step (5): and (3) a step of contacting the zeolite crystal calcined in the step (4) with an aqueous solution containing at least one acid selected from an inorganic acid and an organic acid to obtain a zeolite.
Further, the present invention provides a method for producing epsilon-caprolactam, which comprises the following step (1), the following step (2), the following step (3), the following step (4), the following step (5) and the following step (6). By the above method, cyclohexanone oxime is reacted at a high conversion rate, epsilon-caprolactam can be obtained at a high selectivity, and epsilon-caprolactam can be produced at a good productivity.
Step (1): mixing at least 1 compound selected from boron compounds and germanium compounds, tetraalkyl orthosilicate, water, and quaternary ammonium hydroxide salt
Step (2): subjecting the mixture obtained in the step (1) to a hydrothermal synthesis reaction to obtain a reaction mixture containing zeolite crystals
Step (3): a step of obtaining zeolite crystals by subjecting a reaction mixture containing the zeolite crystals obtained in the step (2) to solid-liquid separation
Step (4): a step of firing the zeolite crystals obtained in the step (3)
Step (5): a step of contacting the zeolite crystal calcined in the step (4) with an aqueous solution containing at least one acid selected from an inorganic acid and an organic acid to obtain zeolite
Step (6): a step of causing a beckmann rearrangement reaction of cyclohexanone oxime in a gas phase in the presence of the zeolite obtained in the step (5).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a zeolite having excellent catalytic performance can be produced, and when the obtained zeolite is used as a catalyst, cyclohexanone oxime is reacted in a gas phase by Beckmann rearrangement reaction to produce cyclohexanone oxime at a high conversion rate, and epsilon-caprolactam can be obtained at a high selectivity and can be produced with good productivity.
Detailed Description
The zeolite to be produced by the present invention may contain silicon and oxygen as elements constituting the framework, and may be crystalline silica having a framework substantially composed of only silicon and oxygen, or may be crystalline metallosilicate containing other elements as elements constituting the framework. Examples of the crystalline metallosilicate include aluminosilicate and titanosilicate, and 2 or more of them may be contained.
Various structures are known as zeolites, and a zeolite having a Pentasil-type structure is preferable as the zeolite produced in the present invention. The Pentasil-type structure includes ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ATN, ATO, ATT, ATV, AWO, AWW, BEA, BIK, BOG, BPH, BRE, CAN, CAS, CFI, CGF, CGS, CHA, CHI, CLO, CON, CZP, DAC, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, EUO, FAU, FER, GME, GOO, HEU, IFR, ISV, ITE, JBW, LIU, LEV, LOV, LTA, LOT, PHAT, STT, SMT, SLE, SLS, the zeolite produced in the present invention is preferably a zeolite having an MFI structure, such as a WEN, YUG, and ZON structure or a structure formed by a combination of 2 or more of these structures. The structure of the zeolite can be analyzed using an X-ray diffraction apparatus.
In the present invention, zeolite is produced by a method comprising the following step (1), the following step (2), the following step (3), the following step (4), and the following step (5). Through the above series of steps, a zeolite having excellent catalytic performance can be produced.
Step (1): mixing at least 1 compound selected from boron compounds and germanium compounds, tetraalkyl orthosilicate, water, and quaternary ammonium hydroxide salt
Step (2): subjecting the mixture obtained in the step (1) to a hydrothermal synthesis reaction to obtain a reaction mixture containing zeolite crystals
Step (3): a step of obtaining zeolite crystals by subjecting a reaction mixture containing the zeolite crystals obtained in the step (2) to solid-liquid separation
Step (4): a step of firing the zeolite crystals obtained in the step (3)
Step (5): and (3) a step of contacting the zeolite crystal calcined in the step (4) with an aqueous solution containing at least one acid selected from an inorganic acid and an organic acid to obtain a zeolite.
In the step (1), examples of the tetraalkyl orthosilicate include tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, and the like, and tetraethyl orthosilicate is preferable. The tetraalkyl orthosilicate may be used alone or in combination of 2 or more.
In the step (1), examples of the boron compound include boric acid, ammonium borate, ammonium tetrafluoroborate, lithium metaborate, lithium tetraborate, lithium tetrafluoroborate, sodium metaborate, sodium tetraborate, sodium perborate, sodium tetrahydroborate, sodium tetraethylborate, sodium tetraphenylborate, sodium tetrafluoroborate, potassium metaborate, potassium tetraborate, potassium pentaborate, potassium tetrafluoroborate, calcium borate, magnesium borate, zinc borate, trimethyl borate, trimethylene borate, triethyl borate, tetrafluoroboric acid, tri-n-butyl boric acid, triisopropyl borate, triethanolamine borate, nitrosyl tetrafluoroborate, etc., and boric acid, preferably trimethyl borate or triethyl borate, more preferably boric acid. The boron compound may be used alone or in combination of 2 or more.
In the step (1), examples of the germanium compound include germanium oxide, germanium chloride, germanium bromide, germanium iodide, tetraethyl germanium, tetramethyl germanium, tetraisopropoxy germanium, and the like, and germanium oxide is preferable. The germanium compounds can be used alone, also can use more than 2.
In the step (1), only one of the boron compound and the germanium compound may be used, or both may be used in combination.
The quaternary ammonium hydroxide mixed in the step (1) is used as a structure-directing agent. By structure directing agent is meant an organic compound used to form the zeolite structure. The structure directing agent can form a precursor of a zeolite structure by organizing polysilicate ions and polymetallic silicate ions around the structure directing agent (see "science and engineering of zeolite", lecture サイエンティフィク, 2000, p.33-34). Examples of the quaternary ammonium hydroxide salt used in the step (1) include compounds represented by the following formula (I).
R1R2R3R4N＋OH- （I）
(in the formula (I), R1、R2、R3And R4Each independently represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group. In addition, R is1、R2、R3And R4They may be the same groups as each other or different groups. ).
As R in the aforementioned formula (I)1、R2、R3Or R4Examples of the alkyl group include methyl, ethyl, propyl, and butyl, and propyl is preferred. As R in the aforementioned formula (I)1、R2、R3Or R4Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group and the like. As R in the aforementioned formula (I)1、R2、R3Or R4Examples of the aralkyl group include benzyl and tolylmethyl. As R in the aforementioned formula (I)1、R2、R3Or R4Examples of the aryl group include phenyl and tolyl.
The quaternary ammonium hydroxide salt represented by the formula (I) is preferably tetraalkylammonium hydroxide. Examples of the tetraalkylammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, triethylmethylammonium hydroxide, tri-n-propylmethylammonium hydroxide, and tri-n-butylmethylammonium hydroxide, with tetra-n-propylammonium hydroxide being preferred.
The mixture obtained in the step (1) may contain at least 1 compound selected from boron compounds and germanium compounds, tetraalkyl orthosilicate, water, and tetraalkyl ammonium hydroxide. For example, in order to adjust the hydroxide ion concentration in the mixture, a basic compound such as sodium hydroxide or potassium hydroxide, or a silicon compound other than tetraalkylorthosilicate such as silica may be mixed, and it is preferable to mix the basic compound. When tetraalkylammonium hydroxide is mixed as the quaternary ammonium hydroxide salt, a tetraalkylammonium salt such as tetraalkylammonium bromide may be mixed in order to adjust the concentration of tetraalkylammonium ions in the mixture.
In the step (1), by mixing at least 1 compound selected from boron compounds and germanium compounds, tetraalkyl orthosilicate, water, and tetraalkylammonium hydroxide, a zeolite having a higher catalytic activity can be obtained, and when the zeolite is used as a catalyst, cyclohexanone oxime can be reacted at a higher conversion rate, epsilon-caprolactam can be obtained at a high selectivity, and epsilon-caprolactam can be produced with a higher productivity.
The amount of water contained in the mixture obtained in the step (1) is preferably 5 mol or more and 100 mol or less, and more preferably 10mol or more and 60 mol or less, based on 1mol of the silicon element contained in the mixture.
The amount of the quaternary ammonium ion contained in the mixture is preferably 0.1 mol or more and 0.6 mol or less, and more preferably 0.2mol or more and 0.5 mol or less, based on 1mol of the silicon element contained in the mixture.
The amount of hydroxide ions contained in the mixture is preferably 0.01mol or more and 0.6 mol or less, and more preferably 0.05 mol or more and 0.5 mol or less, based on 1mol of silicon element contained in the mixture.
The amount of the silicon element contained in the mixture is preferably 5 moles or more and 100 moles or less, more preferably 5 moles or more and 40 moles or less, further preferably 5 moles or more and 20 moles or less, and further preferably 8 moles or more and 13 moles or less, relative to 1 mole of the total amount of the boron element and the germanium element contained in the mixture.
When the amounts of the respective components contained in the mixture are set to the above ranges, a zeolite having more excellent catalytic activity can be obtained, and when the zeolite is used as a catalyst, cyclohexanone oxime can be reacted at a higher conversion rate, epsilon-caprolactam can be obtained at a high selectivity, and epsilon-caprolactam can be produced with more excellent productivity.
The hydrothermal synthesis reaction in the step (2) is a reaction in which a compound is synthesized under heat and pressure or a reaction in which a crystal is grown.
In the step (2), the reaction temperature at which the mixture obtained in the step (1) is subjected to hydrothermal synthesis reaction is preferably 80 ℃ or higher and 160 ℃ or lower, more preferably 120 ℃ or higher and 140 ℃ or lower. When the reaction temperature is in the above range, a zeolite having a higher catalytic activity can be obtained, and when the zeolite is used as a catalyst, cyclohexanone oxime can be reacted at a higher conversion rate, and epsilon-caprolactam can be obtained at a high selectivity, and epsilon-caprolactam can be produced with a higher productivity. The reaction time is preferably 1 hour or more and 200 hours or less. The pressure during the hydrothermal synthesis reaction is preferably 0.1MPa or more and 5MPa or less. The hydrothermal synthesis reaction is carried out by, for example, enclosing the mixture in a reaction vessel such as an autoclave and stirring the mixture under the conditions of the reaction temperature and the pressure in a sealed state.
In the step (3), the solid-liquid separation of the reaction mixture containing the zeolite crystals obtained in the step (2) may be performed by, for example, concentration, filtration, decantation, or the like, and preferably filtration. As a method of filtration, a membrane separation method using a microfiltration membrane (MF membrane) or an ultrafiltration membrane (UF membrane) is preferable. The material and pore size of the MF membrane or UF membrane can be appropriately set. The filtration system may be a cross-flow system or a total volume filtration system, and the cross-flow system is preferred from the viewpoint of enabling easy and efficient cleaning. Further, the filtration may be an external pressure filtration or an internal pressure filtration. The filtration may be either pressure filtration or suction filtration, and is preferably pressure filtration. The pressure during filtration may be set as appropriate, and may be either constant flow filtration in which filtration is performed while keeping the flow rate of the filtrate constant, or constant pressure filtration in which filtration is performed while keeping the membrane pressure difference constant. The cross-flow system is a system in which: a method of flowing a liquid to be treated in parallel to a filtration membrane surface, preventing contamination of the filtration membrane due to sedimentation of sludge, and filtering a part of the liquid to be treated in a flow direction of the liquid to be treated.
The slurry temperature during solid-liquid separation is preferably 0 ℃ to 160 ℃, and the pressure acting on the slurry during solid-liquid separation is preferably 0.1MPa to 5 MPa. The solid-liquid separation does not need to remove all dissolved components and solvents.
The liquid obtained by the solid-liquid separation usually contains silicic acid or an oligomer thereof as an active ingredient, and may contain unreacted quaternary ammonium hydroxide or the like, and therefore, it can be reused in the step (1) and mixed as a raw material.
After the solid-liquid separation, the crystals may be washed with an organic solvent such as methanol or ethanol, or water as appropriate, in order to completely remove dissolved components other than the zeolite crystals remaining in the crystals. Examples of the cleaning treatment include the following methods: (A) a method of adding water to the above crystals and washing and filtering the crystals with water by a cross-flow method; (B) a method of adding water to the above crystals and washing and filtering the crystals with water by total amount filtration; (C) a method of mixing the crystals with water, stirring the mixture, allowing the mixture to stand, and separating the supernatant by decantation. Among the methods (a) to (C), the method (a) is preferred from the viewpoint of easy and efficient cleaning. In the case of performing the washing filtration, a membrane separation method using an MF membrane or a UF membrane is preferable as a method for washing filtration. The material and pore size of the MF membrane or UF membrane can be appropriately set. The cleaning filtration may be an external pressure filtration or an internal pressure filtration. The washing filtration may be either pressure filtration or suction filtration, and is preferably pressure filtration. The pressure applied to the slurry during the washing filtration may be set as appropriate, and may be either constant flow filtration in which filtration is performed while keeping the flow rate of the filtrate constant, or constant pressure filtration in which filtration is performed while keeping the membrane pressure difference constant. The cleaning liquid obtained by the cleaning treatment, particularly the cleaning liquid at the initial stage of cleaning, may contain silicic acid, its oligomer, quaternary ammonium hydroxide, and the like as active ingredients, and therefore, can be reused in the step (1) and mixed as a raw material.
The temperature of the slurry during the cleaning treatment is preferably 0 ℃ to 100 ℃, and the pressure acting on the slurry during the cleaning treatment is preferably 0.1MPa to 5 MPa. In the washing treatment, the zeolite crystals and the liquid do not necessarily need to be completely separated, and for example, they may be appropriately washed with a cross-flow filtration apparatus or the like, concentrated, and recovered as a slurry. The washing treatment is preferably performed so that the pH of the washing liquid obtained by washing with water at 25 ℃ is 7 to 9.
The resulting zeolite crystals may be dried. The drying method in drying is not particularly limited, and methods generally used in the art, such as evaporation drying, spray drying, drum drying, and air flow drying, can be used. Further, the drying conditions may be appropriately set.
In the step (4), the zeolite crystals obtained through the step (3) and, if necessary, cleaning treatment, drying, etc. are calcined. The firing is usually performed appropriately at a temperature of 400 ℃ to 600 ℃ in an oxygen-containing gas atmosphere, for example, in an air atmosphere or in a mixed gas atmosphere of air and nitrogen. The firing time is preferably 0.5 hours or more and 12 hours or less. Before and after the firing in the gas atmosphere containing oxygen, the firing may be performed in an inert gas atmosphere such as nitrogen.
The amount of the silicon element contained in the zeolite crystal obtained in the step (4) is preferably 10mol or more and 400 mol or less, more preferably 20mol or more and 150 mol or less, and further preferably 40 mol or more and 100 mol or less, based on 1mol of the total amount of the boron element and the germanium element contained in the zeolite crystal. When the zeolite crystal contains both a boron compound and a germanium compound, the amount of the silicon element is a value of 1mol based on the total amount of the boron element and the germanium element contained in the zeolite crystal.
The amounts of boron and germanium elements contained in the zeolite crystal can be determined by Inductively Coupled Plasma (ICP) spectroscopic analysis, for example. The amount of silicon element can be determined by, for example, ICP spectrometry, or by subtracting the content of elements other than silicon element from the total amount of elements contained in the calcined zeolite crystal.
In the step (5), the zeolite crystal calcined in the step (4) is subjected to a contact treatment with an aqueous solution containing at least one acid selected from an inorganic acid and an organic acid. The phrase "subjecting the zeolite crystals to a contact treatment with an aqueous solution" means contacting the zeolite crystals with the aqueous solution. In the step (5), boron and germanium elements and alkali metal elements or alkaline earth metal elements derived from the basic compound, which are included in the zeolite crystal, can be removed.
Examples of the inorganic acid contained in the aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, and phosphoric acid, and examples of the organic acid contained in the aqueous solution include formic acid, acetic acid, propionic acid, benzoic acid, citric acid, oxalic acid, terephthalic acid, and p-toluenesulfonic acid. The inorganic acid may be used alone or in combination of 2 or more, and the organic acid may be used alone or in combination of 2 or more. In the step (5), an aqueous solution containing only one of the inorganic acid and the organic acid may be used, or an aqueous solution containing both of them may be used.
The at least one acid selected from an inorganic acid and an organic acid is preferably an inorganic acid, more preferably nitric acid or hydrochloric acid, and still more preferably nitric acid.
The hydrogen ion concentration of at least one acid selected from the group consisting of inorganic acids and organic acids contained in the aqueous solution is preferably 0.001mol/L or more and 20mol/L or less, and more preferably 0.01mol/L or more and 10mol/L or less. In the step (5), it is preferable that an aqueous solution containing 1 to 100 equivalents of at least one acid selected from the group consisting of inorganic acids and organic acids is added to 1 equivalent of the total of at least one element selected from the group consisting of boron and germanium and an alkali metal element or an alkaline earth metal element derived from a basic compound in the calcined zeolite crystal, and the contact treatment is performed. The aqueous solution may contain at least one acid selected from the group consisting of the inorganic acids and the organic acids, and may also contain salts such as ammonium nitrate, ammonium chloride, ammonium sulfate, and ammonium carbonate.
The slurry temperature at the time of the contact treatment in the step (5) is preferably 0 ℃ or more and 100 ℃ or less, more preferably 45 ℃ or more and 95 ℃ or less. When the slurry temperature in the contact treatment is in the above range, a zeolite having more excellent catalytic activity can be obtained, and when this zeolite is used as a catalyst, cyclohexanone oxime can be reacted at a higher conversion rate, and epsilon-caprolactam can be obtained at a high selectivity, and epsilon-caprolactam can be produced with more excellent productivity. The pressure acting on the slurry during the contact treatment is preferably 0.1MPa or more and 5MPa or less.
The treatment time in the contact treatment is preferably 0.1 hour or more and 100 hours or less. The amount of the aqueous solution used is preferably 80 parts by weight or more and 5000 parts by weight or less based on 100 parts by weight of the zeolite crystals after firing. The contact treatment with the aqueous solution may be carried out by a batch method or a continuous method, and for example, the zeolite crystals fired in a stirring tank may be immersed in the aqueous solution and stirred, or the aqueous solution may be circulated through a tubular container filled with the fired zeolite crystals. In the case of the batch type, the contact treatment may be performed again after the solid-liquid separation described later. The number of contact treatments is preferably 1 to 10 times.
The mixture obtained by the contact treatment is subjected to solid-liquid separation by concentration, filtration, decantation, or the like, thereby obtaining zeolite. The slurry temperature at the time of solid-liquid separation is preferably 0 ℃ to 160 ℃, and the pressure acting on the slurry at the time of solid-liquid separation is preferably 0.1MPa to 5 MPa. In the solid-liquid separation, it is not necessary to remove all dissolved components and solvents.
After the step (5), the crystals may be washed with an organic solvent such as methanol or ethanol, or water to completely remove dissolved components other than zeolite remaining in the crystals. The temperature of the slurry during the cleaning treatment is preferably 0 ℃ to 100 ℃, and the pressure acting on the slurry during the cleaning treatment is preferably 0.1MPa to 5 MPa. The zeolite and liquid need not be completely separated during the cleaning process.
The resulting zeolite may be dried. The drying method in drying is not particularly limited, and examples thereof include methods generally used in the art, such as evaporation drying, spray drying, drum drying, and air flow drying. Further, the drying conditions may be appropriately set.
The zeolite obtained by the production method comprising the steps (1) to (5) can be used in various applications including catalysts for organic synthesis reactions, and among them, can be suitably used as a catalyst for producing epsilon-caprolactam by causing a beckmann rearrangement reaction of cyclohexanone oxime in a gas phase. That is, epsilon-caprolactam can be produced by a method comprising the steps (1) to (5) and the step (6).
Step (6): a step of causing a Beckmann rearrangement reaction of cyclohexanone oxime in a gas phase in the presence of the zeolite obtained in the step (5)
In the step (6), cyclohexanone oxime undergoes Beckmann rearrangement to produce epsilon-caprolactam.
The zeolite as the catalyst can be shaped and used according to the size, shape, etc. of the reactor or the like to be used. Shaping can be carried out by methods such as extrusion, compression, sheeting, flow, tumbling, spraying, and the like. The molding method can be used to mold the material into a desired shape, for example, a spherical shape, a cylindrical shape, a plate shape, an annular shape, a clover shape, a granular shape, or the like. The molding may be performed after the step (3), after the step (4), or after the step (5). In the case where the cleaning treatment is performed in the step (3), the forming may be performed after the cleaning treatment. In addition, the formed zeolite may be subjected to a contact treatment with steam, for example, in order to improve mechanical strength. The zeolite may be substantially composed of only zeolite, or may contain zeolite and other components, and for example, may be substantially obtained by molding only zeolite, may be obtained by mixing zeolite with a binder, a reinforcing material, or the like and molding, or may be obtained by supporting zeolite on a carrier.
The reaction temperature in the beckmann rearrangement reaction in the step (6) is preferably 250 ℃ to 500 ℃, more preferably 300 ℃ to 450 ℃, and the reaction pressure is preferably 0.005MPa to 0.5MPa, more preferably 0.005MPa to 0.2 MPa. The step (6) may be carried out in the form of a fixed bed, or may be carried out in the form of a fluidized bed. The feeding rate of the starting cyclohexanone oxime was set to the average feeding rate of 1g of the catalyst (unit: g/h), i.e., the space velocity WHSV (unit: h)-1) Preferably for 0.1h-1Above and for 20h-1Below, more preferably 0.2h-1Above and for 10h-1The following.
The cyclohexanone oxime may be introduced into the reaction system alone, or may be introduced together with an inert gas such as nitrogen, argon, or carbon dioxide. In addition, the following method is also effective: a method of allowing ether to coexist as described in Japanese patent application laid-open No. 2-250866; a method of allowing a lower alcohol to coexist as described in Japanese patent application laid-open No. 2-275850; a method of allowing an alcohol and/or an ether to coexist with water as described in Japanese patent application laid-open No. 5-201965; a method of allowing ammonia to coexist as described in Japanese patent laid-open No. 5-201966; and a method of allowing methylamine to coexist as described in Japanese patent application laid-open No. 6-107627.
The cyclohexanone oxime may be produced, for example, by oximation of cyclohexanone with hydroxylamine or a salt thereof, or by ammoximation of cyclohexanone with ammonia and hydrogen peroxide in the presence of a catalyst such as titanosilicate, or by oxidation of cyclohexylamine.
The step (6) may be carried out in combination with an operation of calcining the catalyst in an oxygen-containing gas atmosphere such as air, and the carbonaceous material precipitated on the catalyst can be burnt and removed by the catalyst calcining treatment, and the conversion of cyclohexanone oxime and the continuity of the selectivity of epsilon-caprolactam can be improved. For example, when the step (6) is carried out by a fixed bed system, the following method can be suitably employed: after the cyclohexanone oxime and, if necessary, other components are supplied together into a fixed bed reactor packed with a solid catalyst to perform a beckmann rearrangement reaction, the supply of the cyclohexanone oxime is stopped, and then, an oxygen-containing gas is supplied to perform firing, and further, the beckmann rearrangement reaction and firing are repeated. When the step (6) is carried out by a fluidized bed method, the following method can be suitably employed: the cyclohexanone oxime and, if necessary, other components are supplied to a fluidized bed reactor in which a solid catalyst is flowing, and the beckmann rearrangement reaction is carried out, and the solid catalyst is continuously or intermittently taken out from the reactor, calcined in a calciner, and then returned to the reactor again.
As the work-up operation of the product obtained by the above reaction, a known method can be suitably employed, and for example, epsilon-caprolactam can be isolated by cooling and condensing the reaction product gas, and then performing operations such as extraction, distillation, crystallization, and the like.
Examples
The following examples of the present invention are given, but the present invention is not limited thereto. Note that the space velocity WHSV of cyclohexanone oxime (unit: h)-1) The feed rate of cyclohexanone oxime (unit: g/h) divided by the weight of catalyst (unit: g) to calculate. The amount (mole) of silicon element contained in the mixture obtained in step (1) is 1 mole relative to the total amount of boron element and germanium element contained in the mixture obtained in step (1)The amount of the silicon compound, the boron compound and the germanium compound mixed in the step (1) is calculated from the amounts of the silicon compound, the boron compound and the germanium compound. The amounts of boron and germanium elements contained in the zeolite crystals fired in step (4) are determined by ICP spectrometry, and the amount of silicon element is determined by subtracting the content of elements other than silicon element from the total amount of elements contained in the zeolite crystals fired. When the number of moles of cyclohexanone oxime supplied is denoted by X, the number of moles of unreacted cyclohexanone oxime is denoted by Y, and the number of moles of epsilon-caprolactam produced is denoted by Z, the conversion of cyclohexanone oxime and the selectivity of epsilon-caprolactam are calculated by the following formulae, respectively.
Conversion (%) of seeded cyclohexanone oxime = [ (X-Y)/X ] × 100
Selectivity (%) of seed epsilon-caprolactam, (= [ Z/(X-Y) ] × 100.
Example 1
(a) Manufacture of zeolites
[ Process (1) ]
Tetraethyl orthosilicate [ Si (OC) ] is charged into a glass beaker2H5）4]115g, 39.7% by weight of tetra-n-propylammonium hydroxide aqueous solution (containing 0.9% by weight of potassium, 1.0% by weight of hydrogen bromide, 58.4% by weight of water) 153g, boric acid 3.4g and water 269g, and vigorously stirred at room temperature for 120 minutes to obtain a mixture. The amount of silicon element contained in the resultant mixture was 10.0 mol with respect to 1mol of boron element contained in the aforementioned mixture.
[ Process (2) ]
The mixture obtained in the step (1) was put into a stainless autoclave and stirred at 120 ℃ for 24 hours to carry out a hydrothermal synthesis reaction.
[ Process (3) ]
The reaction mixture obtained in the step (2) is subjected to pressure filtration.
[ cleaning step and drying step ]
The crystals comprising the zeolite crystals obtained in the step (3) are washed with ion-exchanged water several times until the pH of the washing liquid becomes 9 or less, and then dried at 100 ℃ or higher.
[ Process (4) ]
The zeolite crystals obtained in the drying step were calcined at 530 ℃ for 1 hour under a nitrogen gas flow, and then calcined at 530 ℃ for 1 hour under an air flow, to obtain powdery white crystals.
[ Process (5) ]
5.0g of the powdery white crystals obtained in the step (4) was charged into an autoclave, 150g of a 0.2mol/L nitric acid aqueous solution was added thereto, and the mixture was stirred at 90 ℃ for 1 hour, followed by filtration to separate the crystals. This crystal was further treated with the same aqueous nitric acid solution as described above repeatedly 2 times.
[ cleaning step 2 and drying step 2]
The zeolite-containing crystals finally obtained in the step (5) are washed with ion-exchanged water several times until the pH of the washing solution becomes 5 or more, and then dried at 100 ℃ or more. Classifying the dried powder by a sieve, and separating out particles with the particle size of more than 0.50mm and less than 0.85 mm. The zeolite thus obtained is used as a catalyst in the following (b).
(b) Production of epsilon-caprolactam (step (6))
0.375g of the zeolite obtained in the above (a) was packed in a quartz glass reaction tube having an inner diameter of 1cm to form a catalyst layer, and then preheated at 350 ℃ for 1 hour under a flow of nitrogen gas of 4.2L/h. Subsequently, after the temperature of the catalyst layer was lowered to 316 ℃ under a flow of nitrogen gas of 4.2L/h, a mixture of gasified cyclohexanone oxime/methanol =1/1.8 (weight ratio) was mixed at 8.4g/h (WHSV of cyclohexanone oxime =8 h)-1) The reaction is carried out by supplying the reaction mixture into the reaction tube at the supply rate of (2). The reaction gas was collected from the start of the reaction to 5.5 hours to 5.75 hours after the start of the reaction, and analyzed by gas chromatography. The conversion of cyclohexanone oxime was 95.5% and the selectivity for epsilon-caprolactam was 95.1%.
Example 2
(a) Manufacture of zeolites
[ Process (1) ]
Adding raw silicon into a glass beakerAcid tetraethyl ester [ Si (OC)2H5）4]115g, 105g of a 39.7% by weight aqueous tetra-n-propylammonium hydroxide solution (containing 0.9% by weight of potassium, 1.0% by weight of hydrogen bromide, and 58.4% by weight of water), 3.4g of boric acid, 0.13g of potassium hydroxide, and 118g of water were vigorously stirred at room temperature for 120 minutes, thereby obtaining a mixture. The amount of silicon element contained in the resultant mixture was 10.0 mol with respect to 1mol of boron element contained in the aforementioned mixture.
[ Process (2) ]
The mixture obtained in the step (1) was put into a stainless autoclave and stirred at 140 ℃ for 24 hours to carry out a hydrothermal synthesis reaction.
[ Process (3) ]
The reaction mixture obtained in the step (2) is subjected to pressure filtration.
[ cleaning step and drying step ]
The crystals comprising the zeolite crystals obtained in the step (3) are washed with ion-exchanged water several times until the pH of the washing liquid becomes 9 or less, and then dried at 100 ℃ or higher.
[ Process (4) ]
The zeolite crystals obtained in the drying step were calcined at 530 ℃ for 1 hour under a nitrogen gas flow, and then calcined at 530 ℃ for 1 hour under an air flow, to obtain powdery white crystals.
[ Process (5) ]
5.0g of the powdery white crystals obtained in the step (4) was charged into an autoclave, 150g of a 0.2mol/L nitric acid aqueous solution was added thereto, and the mixture was stirred at 90 ℃ for 1 hour, followed by filtration to separate the crystals. This crystal was further treated with the same aqueous nitric acid solution as described above repeatedly 2 times.
[ cleaning step 2 and drying step 2]
The zeolite-containing crystals finally obtained in the step (5) are washed with ion-exchanged water several times until the pH of the washing solution becomes 5 or more, and then dried at 100 ℃ or more. Classifying the dried powder by a sieve, and separating out particles with the particle size of more than 0.50mm and less than 0.85 mm. The zeolite thus obtained is used as a catalyst in the following (b).
(b) Production of epsilon-caprolactam (step (6))
0.375g of the zeolite obtained in the above (a) was packed in a quartz glass reaction tube having an inner diameter of 1cm to form a catalyst layer, and then preheated at 350 ℃ for 1 hour under a flow of nitrogen gas of 4.2L/h. Subsequently, after the temperature of the catalyst layer was lowered to 316 ℃ under a flow of nitrogen gas of 4.2L/h, a mixture of gasified cyclohexanone oxime/methanol =1/1.8 (weight ratio) was mixed at 8.4g/h (WHSV of cyclohexanone oxime =8 h)-1) The reaction is carried out by supplying the reaction mixture into the reaction tube at the supply rate of (2). The reaction gas was collected from the start of the reaction to 5.5 hours to 5.75 hours after the start of the reaction, and analyzed by gas chromatography. The conversion of cyclohexanone oxime was 90.5% and the selectivity for epsilon-caprolactam was 95.5%.
Example 3
(a) Manufacture of zeolites
A catalyst was prepared in the same manner as in example 2, except that the temperature in step (2) was changed to 120 ℃.
(b) Production of epsilon-caprolactam (step (6))
0.375g of the zeolite obtained in the above (a) was packed in a quartz glass reaction tube having an inner diameter of 1cm to form a catalyst layer, and then preheated at 350 ℃ for 1 hour under a flow of nitrogen gas of 4.2L/h. Subsequently, after the temperature of the catalyst layer was lowered to 316 ℃ under a flow of nitrogen gas of 4.2L/h, a mixture of gasified cyclohexanone oxime/methanol =1/1.8 (weight ratio) was mixed at 8.4g/h (WHSV of cyclohexanone oxime =8 h)-1) The reaction is carried out by supplying the reaction mixture into the reaction tube at the supply rate of (2). The reaction gas was collected from the start of the reaction to 5.5 hours to 5.75 hours after the start of the reaction, and analyzed by gas chromatography. The conversion of cyclohexanone oxime was 89.6% and the selectivity for epsilon-caprolactam was 95.0%.
Example 4
(a) Manufacture of zeolites
A catalyst was prepared in the same manner as in example 2, except that the temperature in step (2) was changed to 105 ℃.
(b) Production of epsilon-caprolactam (step (6))
0.375g of the zeolite obtained in the above (a) was packed in a quartz glass reaction tube having an inner diameter of 1cm to form a catalyst layer, and then preheated at 350 ℃ for 1 hour under a flow of nitrogen gas of 4.2L/h. Subsequently, after the temperature of the catalyst layer was lowered to 316 ℃ under a flow of nitrogen gas of 4.2L/h, a mixture of gasified cyclohexanone oxime/methanol =1/1.8 (weight ratio) was mixed at 8.4g/h (WHSV of cyclohexanone oxime =8 h)-1) The reaction is carried out by supplying the reaction mixture into the reaction tube at the supply rate of (2). The reaction gas was collected from the start of the reaction to 5.5 hours to 5.75 hours after the start of the reaction, and analyzed by gas chromatography. The conversion of cyclohexanone oxime was 87.6% and the selectivity for epsilon-caprolactam was 94.1%.
Example 5
(a) Manufacture of zeolites
A catalyst was prepared in the same manner as in example 2, except that the temperature in step (2) was changed to 150 ℃.
(b) Production of epsilon-caprolactam (step (6))
0.375g of the zeolite obtained in the above (a) was packed in a quartz glass reaction tube having an inner diameter of 1cm to form a catalyst layer, and then preheated at 350 ℃ for 1 hour under a flow of nitrogen gas of 4.2L/h. Subsequently, after the temperature of the catalyst layer was lowered to 316 ℃ under a flow of nitrogen gas of 4.2L/h, a mixture of gasified cyclohexanone oxime/methanol =1/1.8 (weight ratio) was mixed at 8.4g/h (WHSV of cyclohexanone oxime =8 h)-1) The reaction is carried out by supplying the reaction mixture into the reaction tube at the supply rate of (2). The reaction gas was collected from the start of the reaction to 5.5 hours to 5.75 hours after the start of the reaction, and analyzed by gas chromatography. The conversion of cyclohexanone oxime was 82.6% and the selectivity for epsilon-caprolactam was 95.0%.
Example 6
(a) Manufacture of zeolites
[ Process (1) ]
Tetraethyl orthosilicate [ Si (OC) ] is charged into a glass beaker2H5）4]115g of 39.7% by weight aqueous tetra-n-propylammonium hydroxide solution (containing 0.9% by weight of potassium, 1.0% by weight of hydrogen bromide, and 58.4% by weight of water)67g, boric acid 1.76g and water 140g, and vigorously stirred at room temperature for 120 minutes, thereby obtaining a mixture. The amount of silicon element contained in the resultant mixture was 19.4 mol with respect to 1mol of boron element contained in the aforementioned mixture.
[ Process (2) ]
The mixture obtained in the step (1) was put into a stainless autoclave and stirred at 120 ℃ for 24 hours to carry out a hydrothermal synthesis reaction.
[ Process (3) ]
The reaction mixture obtained in the step (2) is subjected to pressure filtration.
[ cleaning step and drying step ]
The crystals comprising the zeolite crystals obtained in the step (3) are washed with ion-exchanged water several times until the pH of the washing liquid becomes 9 or less, and then dried at 100 ℃ or higher.
[ Process (4) ]
The zeolite crystals obtained in the drying step were calcined at 530 ℃ for 1 hour under a nitrogen gas flow, and then calcined at 530 ℃ for 1 hour under an air flow, to obtain powdery white crystals.
[ Process (5) ]
5.0g of the powdery white crystals obtained in the step (4) was charged into an autoclave, 150g of a 0.2mol/L nitric acid aqueous solution was added thereto, and the mixture was stirred at 90 ℃ for 1 hour, followed by filtration to separate the crystals. This crystal was further treated with the same aqueous nitric acid solution as described above repeatedly 2 times.
[ cleaning step 2 and drying step 2]
The zeolite-containing crystals finally obtained in the step (5) are washed with ion-exchanged water several times until the pH of the washing solution becomes 5 or more, and then dried at 100 ℃ or more. Classifying the dried powder by a sieve, and separating out particles with the particle size of more than 0.50mm and less than 0.85 mm. The zeolite thus obtained is used as a catalyst in the following (b).
(b) Production of epsilon-caprolactam (step (6))
Filling 0.375g of zeolite obtained in the above (a)The reaction tube was filled with a quartz glass reaction tube having an inner diameter of 1cm to form a catalyst layer, and the catalyst layer was preheated at 350 ℃ for 1 hour under a flow of nitrogen gas of 4.2L/h. Subsequently, after the temperature of the catalyst layer was lowered to 316 ℃ under a flow of nitrogen gas of 4.2L/h, a mixture of gasified cyclohexanone oxime/methanol =1/1.8 (weight ratio) was mixed at 8.4g/h (WHSV of cyclohexanone oxime =8 h)-1) The reaction is carried out by supplying the reaction mixture into the reaction tube at the supply rate of (2). The reaction gas was collected from the start of the reaction to 5.5 hours to 5.75 hours after the start of the reaction, and analyzed by gas chromatography. The conversion of cyclohexanone oxime was 88.7% and the selectivity for epsilon-caprolactam was 95.0%.
Example 7
(a) Manufacture of zeolites
[ Process (1) ]
Tetraethyl orthosilicate [ Si (OC) ] is charged into a glass beaker2H5）4]115g, 90g of a 39.7 wt% aqueous tetra-n-propylammonium hydroxide solution (containing 0.9 wt% of potassium, 1.0 wt% of hydrogen bromide, and 58.4 wt% of water), 0.85g of boric acid, and 299g of water were vigorously stirred at room temperature for 120 minutes to obtain a mixture. The amount of silicon element contained in the resultant mixture was 40.1 mol with respect to 1mol of boron element contained in the aforementioned mixture.
[ Process (2) ]
The mixture obtained in the step (1) was put into a stainless autoclave and stirred at 120 ℃ for 24 hours to carry out a hydrothermal synthesis reaction.
[ Process (3) ]
The reaction mixture obtained in the step (2) is subjected to pressure filtration.
[ cleaning step and drying step ]
The crystals comprising the zeolite crystals obtained in the step (3) are washed with ion-exchanged water several times until the pH of the washing liquid becomes 9 or less, and then dried at 100 ℃ or higher.
[ Process (4) ]
The zeolite crystals obtained in the drying step were calcined at 530 ℃ for 1 hour under a nitrogen gas flow, and then calcined at 530 ℃ for 1 hour under an air flow, to obtain powdery white crystals.
[ Process (5) ]
5.0g of the powdery white crystals obtained in the step (4) was charged into an autoclave, 150g of a 0.2mol/L nitric acid aqueous solution was added thereto, and the mixture was stirred at 90 ℃ for 1 hour, followed by filtration to separate the crystals. This crystal was further treated with the same aqueous nitric acid solution as described above repeatedly 2 times.
[ cleaning step 2 and drying step 2]
The zeolite-containing crystals finally obtained in the step (5) are washed with ion-exchanged water several times until the pH of the washing solution becomes 5 or more, and then dried at 100 ℃ or more. And (4) grading the dry powder by using a sieve, and separating out particles with the particle size of more than 0.50mm and less than 0.85 mm. The zeolite thus obtained is used as a catalyst in the following (b).
(b) Production of epsilon-caprolactam (step (6))
0.375g of the zeolite obtained in the above (a) was packed in a quartz glass reaction tube having an inner diameter of 1cm to form a catalyst layer, and then preheated at 350 ℃ for 1 hour under a flow of nitrogen gas of 4.2L/h. Subsequently, after the temperature of the catalyst layer was lowered to 316 ℃ under a flow of nitrogen gas of 4.2L/h, a mixture of gasified cyclohexanone oxime/methanol =1/1.8 (weight ratio) was mixed at 8.4g/h (WHSV of cyclohexanone oxime =8 h)-1) The reaction is carried out by supplying the reaction mixture into the reaction tube at the supply rate of (2). The reaction gas was collected from the start of the reaction to 5.5 hours to 5.75 hours after the start of the reaction, and analyzed by gas chromatography. The conversion of cyclohexanone oxime was 62.9% and the selectivity for epsilon-caprolactam was 93.2%.
Example 8
(a) Manufacture of zeolites
[ Process (1) ]
Tetraethyl orthosilicate [ Si (OC) ] is charged into a glass beaker2H5）4]115g, 80g of a 39.7 wt% aqueous tetra-n-propylammonium hydroxide solution (containing 0.9 wt% of potassium, 1.0 wt% of hydrogen bromide, and 58.4 wt% of water), 0.49g of boric acid, and 302g of water were vigorously stirred at room temperature for 120 minutes to obtain a mixture. What is needed isThe amount of silicon element contained in the obtained mixture was 69.6 mol with respect to 1mol of boron element contained in the mixture.
[ Process (2) ]
The solution obtained in the step (1) was put into a stainless autoclave, stirred at 120 ℃ for 24 hours, and subjected to a hydrothermal synthesis reaction.
[ Process (3) ]
The reaction mixture obtained in the step (2) is subjected to pressure filtration.
[ cleaning step and drying step ]
The crystals comprising the zeolite crystals obtained in the step (3) are washed with ion-exchanged water several times until the pH of the washing liquid becomes 9 or less, and then dried at 100 ℃ or higher.
[ Process (4) ]
The zeolite crystals obtained in the drying step were calcined at 530 ℃ for 1 hour under a nitrogen gas flow, and then calcined at 530 ℃ for 1 hour under an air flow, to obtain powdery white crystals.
[ Process (5) ]
5.0g of the powdery white crystals obtained in the step (4) was charged into an autoclave, 150g of a 0.2mol/L nitric acid aqueous solution was added thereto, and the mixture was stirred at 90 ℃ for 1 hour, followed by filtration to separate the crystals. This crystal was further treated with the same aqueous nitric acid solution as described above repeatedly 2 times.
[ cleaning step 2 and drying step 2]
The zeolite-containing crystals finally obtained in the step (5) are washed with ion-exchanged water several times until the pH of the washing solution becomes 5 or more, and then dried at 100 ℃ or more. Classifying the dried powder by a sieve, and separating out particles with the particle size of more than 0.50mm and less than 0.85 mm. The zeolite thus obtained is used as a catalyst in the following (b).
(b) Production of epsilon-caprolactam (step (6))
0.375g of the zeolite obtained in the above (a) was packed in a quartz glass reaction tube having an inner diameter of 1cm to form a catalyst layer, and the catalyst layer was purged with 4.2L/h of nitrogen gasA preheating treatment was carried out at 350 ℃ for 1 hour. Subsequently, after the temperature of the catalyst layer was lowered to 316 ℃ under a flow of nitrogen gas of 4.2L/h, a mixture of gasified cyclohexanone oxime/methanol =1/1.8 (weight ratio) was mixed at 8.4g/h (WHSV of cyclohexanone oxime =8 h)-1) The reaction is carried out by supplying the reaction mixture into the reaction tube at the supply rate of (2). The reaction gas was collected from the start of the reaction to 5.5 hours to 5.75 hours after the start of the reaction, and analyzed by gas chromatography. The conversion of cyclohexanone oxime was 44.3% and the selectivity for epsilon-caprolactam was 92.2%.
Example 9
(a) Manufacture of zeolites
[ Process (1) ]
Tetraethyl orthosilicate [ Si (OC) ] is charged into a glass beaker2H5）4]97g, 39.7 wt% tetra-n-propylammonium hydroxide aqueous solution (containing 0.9 wt% of potassium, 1.0 wt% of hydrogen bromide, 58.4 wt% of water) 57g, germanium oxide 0.7g and water 268g were vigorously stirred at room temperature for 120 minutes to obtain a mixture. The amount of silicon element contained in the resultant mixture was 69.6 moles with respect to 1 mole of germanium element contained in the aforementioned mixture.
[ Process (2) ]
The mixture obtained in the step (1) was put into a stainless autoclave and stirred at 140 ℃ for 24 hours to carry out a hydrothermal synthesis reaction.
[ Process (3) ]
The reaction mixture obtained in the step (2) is subjected to pressure filtration.
[ cleaning step and drying step ]
The crystals comprising the zeolite crystals obtained in the step (3) are washed with ion-exchanged water several times until the pH of the washing liquid becomes 9 or less, and then dried at 100 ℃ or higher.
[ Process (4) ]
The zeolite crystals obtained in the drying step were calcined at 530 ℃ for 1 hour under a nitrogen gas flow, and then calcined at 530 ℃ for 1 hour under an air flow, to obtain powdery white crystals.
[ Process (5) ]
5.0g of the powdery white crystals obtained in the step (4) was charged into an autoclave, 150g of a 0.2mol/L nitric acid aqueous solution was added thereto, and the mixture was stirred at 90 ℃ for 1 hour, followed by filtration to separate the crystals. This crystal was further treated with the same aqueous nitric acid solution as described above repeatedly 2 times.
[ cleaning step 2 and drying step 2]
The zeolite-containing crystals finally obtained in the step (5) are washed with ion-exchanged water several times until the pH of the washing solution becomes 5 or more, and then dried at 100 ℃ or more. Classifying the dried powder by a sieve, and separating out particles with the particle size of more than 0.50mm and less than 0.85 mm. The zeolite thus obtained is used as a catalyst in the following (b).
(b) Production of epsilon-caprolactam (step (6))
0.375g of the zeolite obtained in the above (a) was packed in a quartz glass reaction tube having an inner diameter of 1cm to form a catalyst layer, and then preheated at 350 ℃ for 1 hour under a flow of nitrogen gas of 4.2L/h. Subsequently, after the temperature of the catalyst layer was lowered to 316 ℃ under a flow of nitrogen gas of 4.2L/h, a mixture of gasified cyclohexanone oxime/methanol =1/1.8 (weight ratio) was mixed at 8.4g/h (WHSV of cyclohexanone oxime =8 h)-1) The reaction is carried out by supplying the reaction mixture into the reaction tube at the supply rate of (2). The reaction gas was collected from the start of the reaction to 5.5 hours to 5.75 hours after the start of the reaction, and analyzed by gas chromatography. The conversion of cyclohexanone oxime was 24.8% and the selectivity for epsilon-caprolactam was 89.6%.
Comparative example 1
(a) Manufacture of zeolites
79.6g of silicic acid sol (LUDOX), 22.2g of tetra-n-propylammonium hydroxide, 89.0g of deionized water, and 3.9g of trimethyl borate were put into a stainless autoclave and stirred to obtain a mixture. The amount of silicon element contained in the resultant mixture was 14.1 mol with respect to 1mol of boron element contained in the aforementioned mixture. To the resulting mixture was added 25 wt% ammonia solution. The hydrothermal synthesis reaction was carried out in a closed autoclave at 185 ℃ and a stirrer speed of 100 rpm for 7 days. After the resulting reaction mixture was cooled, it was taken out of the autoclave and filtered through a pressure filter, followed by washing with 89.0g of deionized water. The resultant product was dried at 110 ℃ over 12 hours, and then fired at 550 ℃ under air for 12 hours, thereby obtaining a powder.
8.8g of a mixture of nitrogen and water vapor (each containing 50% by weight) was introduced into 8.9g of the obtained powder at 550 ℃ for 2 hours in a quartz tube having a diameter of 4cm, thereby obtaining 8.8g of the powder. Thereafter, the obtained powder and an aqueous hydrochloric acid solution (pH 6) were added to a 100 ml-capacity flask, stirred at room temperature for 24 hours, and dried. Classifying the dried powder by a sieve, and separating out particles with the particle size of more than 0.50mm and less than 0.85 mm.
The reaction was carried out in the same manner as in (b) of example 1 except that the obtained crystals were used as a catalyst. The conversion of cyclohexanone oxime was 2.4% and the selectivity for epsilon-caprolactam was 48.6%.
[ Table 1]
Claims (7)
1. A method for producing zeolite, which comprises the following step (1), the following step (2), the following step (3), the following step (4), and the following step (5):
step (1): a step of mixing at least 1 compound selected from a boron compound and a germanium compound, tetraalkylorthosilicate, water, and quaternary ammonium hydroxide to obtain a mixture, wherein the amount of silicon element contained in the mixture is 5 moles or more and 100 moles or less with respect to 1 mole of the total amount of boron element and germanium element contained in the mixture;
step (2): subjecting the mixture obtained in the step (1) to a hydrothermal synthesis reaction to obtain a reaction mixture containing zeolite crystals;
step (3): a step of subjecting a reaction mixture containing the zeolite crystals obtained in the step (2) to solid-liquid separation to obtain zeolite crystals;
step (4): firing the zeolite crystal obtained in the step (3);
step (5): and (3) a step of contacting the zeolite crystal calcined in the step (4) with an aqueous solution containing at least one acid selected from an inorganic acid and an organic acid to obtain a zeolite.
2. The production method according to claim 1, wherein the amount of the silicon element contained in the mixture obtained in the step (1) is 5 mol or more and 40 mol or less based on 1mol of the total amount of the boron element and the germanium element contained in the mixture.
3. The production method according to claim 1 or 2, wherein the tetraalkyl orthosilicate is tetraethyl orthosilicate.
4. The production method according to claim 1 or 2, wherein the quaternary ammonium hydroxide salt is tetra-n-propyl ammonium hydroxide.
5. The production method according to claim 1 or 2, wherein the boron compound is boric acid.
6. The production method according to claim 1 or 2, wherein the reaction temperature at the hydrothermal synthesis reaction in the step (2) is 120 ℃ or more and 140 ℃ or less.
7. A process for producing epsilon-caprolactam, which comprises the following step (1), the following step (2), the following step (3), the following step (4), the following step (5) and the following step (6):
step (1): a step of mixing at least 1 compound selected from a boron compound and a germanium compound, tetraalkylorthosilicate, water, and quaternary ammonium hydroxide to obtain a mixture, wherein the amount of silicon element contained in the mixture is 5 mol or more and 100 mol or less relative to 1mol of the total amount of boron element and germanium element contained in the mixture;
step (2): subjecting the mixture obtained in the step (1) to a hydrothermal synthesis reaction to obtain a reaction mixture containing zeolite crystals;
step (3): a step of subjecting a reaction mixture containing the zeolite crystals obtained in the step (2) to solid-liquid separation to obtain zeolite crystals;
step (4): firing the zeolite crystal obtained in the step (3);
step (5): a step of contacting the zeolite crystal calcined in the step (4) with an aqueous solution containing at least one acid selected from an inorganic acid and an organic acid to obtain zeolite;
step (6): and (3) a step of causing a beckmann rearrangement reaction of cyclohexanone oxime in a gas phase in the presence of the zeolite obtained in the step (5).
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| GB2226307A (en) * | 1988-12-09 | 1990-06-27 | Eniricerche Spa | "Crystalline, porous borosilicate isostructural with levynite" |
| CN1484615A (en) * | 2000-11-03 | 2004-03-24 | �Ʒ� | Crystalline aluminosilicate zeolitic composition uzm-4 and processes using the composition |
| CA2477491C (en) * | 2002-03-07 | 2009-04-28 | Showa Denko K.K. | Mww type zeolite substance, precursor substance therefor, and process for producing these substances |
| CN101654436A (en) * | 2008-08-20 | 2010-02-24 | 住友化学株式会社 | Method for producing epsilon caprolactam and method for producing pentasil type zeolite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1009465A3 (en) * | 1995-05-04 | 1997-04-01 | Degussa | -CAPROLACTAME MANUFACTURING PROCESS. |
| JP2000256309A (en) * | 1999-03-04 | 2000-09-19 | Sumitomo Chem Co Ltd | Production of epsilon-caprolactam |
| JP2001072658A (en) * | 1999-06-28 | 2001-03-21 | Mitsubishi Chemicals Corp | Production of amide compound |
| US7081552B2 (en) * | 2004-08-17 | 2006-07-25 | Solutia Inc. | Catalysts for cycloalkanes oxidation and decomposition of cycloalkyl hydroperoxide |
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2015
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| GB2226307A (en) * | 1988-12-09 | 1990-06-27 | Eniricerche Spa | "Crystalline, porous borosilicate isostructural with levynite" |
| CN1484615A (en) * | 2000-11-03 | 2004-03-24 | �Ʒ� | Crystalline aluminosilicate zeolitic composition uzm-4 and processes using the composition |
| CA2427614C (en) * | 2000-11-03 | 2009-09-08 | Uop Llc | Crystalline aluminosilicate zeolitic composition: uzm-4 and processes using the composition |
| CA2477491C (en) * | 2002-03-07 | 2009-04-28 | Showa Denko K.K. | Mww type zeolite substance, precursor substance therefor, and process for producing these substances |
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