JPH08510685A - 触媒およびこれを不飽和カルボン酸エステルの製造で使用する方法 - Google Patents
触媒およびこれを不飽和カルボン酸エステルの製造で使用する方法Info
- Publication number
- JPH08510685A JPH08510685A JP7500722A JP50072295A JPH08510685A JP H08510685 A JPH08510685 A JP H08510685A JP 7500722 A JP7500722 A JP 7500722A JP 50072295 A JP50072295 A JP 50072295A JP H08510685 A JPH08510685 A JP H08510685A
- Authority
- JP
- Japan
- Prior art keywords
- support
- catalyst
- compounds
- palladium
- alkali metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 146
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 57
- 150000001733 carboxylic acid esters Chemical class 0.000 title description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000010931 gold Substances 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 229910052737 gold Inorganic materials 0.000 claims abstract description 48
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 29
- -1 palladium group metals Chemical class 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002585 base Substances 0.000 claims abstract description 19
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000011133 lead Substances 0.000 claims abstract description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 68
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 229910052763 palladium Inorganic materials 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 150000002895 organic esters Chemical class 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 206010028980 Neoplasm Diseases 0.000 claims description 2
- 201000011510 cancer Diseases 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 6
- 238000009736 wetting Methods 0.000 claims 6
- 239000011260 aqueous acid Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000011324 bead Substances 0.000 description 84
- 239000000243 solution Substances 0.000 description 82
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 64
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 48
- 235000011056 potassium acetate Nutrition 0.000 description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 23
- 238000005470 impregnation Methods 0.000 description 19
- 238000005507 spraying Methods 0.000 description 19
- 239000011734 sodium Substances 0.000 description 17
- 229910002708 Au–Cu Inorganic materials 0.000 description 15
- 230000009467 reduction Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229960000583 acetic acid Drugs 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 235000019353 potassium silicate Nutrition 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 10
- 239000004111 Potassium silicate Substances 0.000 description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 9
- IZPZQHISQHRLFP-UHFFFAOYSA-J [Na+].[Na+].[Na+].[Na+].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Cl-].[Cl-].[Cl-].[Cl-] IZPZQHISQHRLFP-UHFFFAOYSA-J 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 9
- 229910052913 potassium silicate Inorganic materials 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 150000002344 gold compounds Chemical class 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 5
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000006223 plastic coating Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910017398 Au—Ni Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000005973 Carvone Substances 0.000 description 2
- 229910016502 CuCl2—2H2O Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- ZHQLTKAVLJKSKR-UHFFFAOYSA-N homophthalic acid Chemical compound OC(=O)CC1=CC=CC=C1C(O)=O ZHQLTKAVLJKSKR-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002265 redox agent Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008213 purified water 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
- 229960000948 quinine Drugs 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- LHYPLJGBYPAQAK-UHFFFAOYSA-M sodium;pentanoate Chemical compound [Na+].CCCCC([O-])=O LHYPLJGBYPAQAK-UHFFFAOYSA-M 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical group [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical group C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 1. オレフィン系化合物、酸素およびカルボン酸から気相中でエチレン系不 飽和有機エステルを製造するための触媒として用いるに適切な組成物において、 (i)1種以上のパラジウム族金属および/またはそれらの化合物、(ii)金 および/またはそれの化合物、および(iii)銅、ニッケル、コバルト、鉄、 マンガン、鉛、銀およびそれらの化合物から成る群から選択される1種以上の助 触媒を含んでおり、ここで、パラジウム族金属に対する該助触媒内の金属のグラ ム−原子比が約0.4以下である組成物。 2. 該パラジウム族金属に対する該助触媒内の金属のグラム−原子比が約0 .04から約0.2である請求の範囲1記載の組成物。 3. 上記助触媒が銅および/またはそれの化合物、ニッケルおよび/または それの化合物およびそれらの混合物である請求の範囲1記載の組成物。 4. 該パラジウム族金属に対する金のグラム−原子比が約0.1から約0. 5である請求の範囲1記載の組成物。 5. 担体支持体を更に含んでおり、この上に(i)、(ii)および(ii i)を堆積させる請求の範囲1記載の組成物。 6. 該支持体がシリカである請求の範囲5記載の組成物。 7. 該支持体が、1種以上のアルカリ金属塩基および1種以上のアルカリ金 属ケイ酸塩で処理したものである請求の範囲6記載の組成物。 8. 上記支持体が、(a)アルカリ金属水酸化物水溶液とアルカリ金属ケイ 酸塩水溶液の混合物で該支持体を湿らせ、(b)この湿らせた支持体を熟成させ た後、(c)この湿らせて熟成させた支持体を乾燥さ せる、ことによって処理したものである請求の範囲7記載の組成物。 9. オレフィン系化合物、酸素およびカルボン酸から気相中でエチレン系不 飽和有機エステルを製造する時の触媒として用いるに適切な組成物において、( i)1種以上のパラジウム族金属および/またはそれらの化合物、(ii)金お よび/またはそれの化合物、および(iii)銅、ニッケル、コバルト、鉄、マ ンガン、鉛、銀およびそれらの化合物から成る群から選択される1種以上の助触 媒を含んでおり、ここで、(i)、(ii)および(iii)を支持材料の上に 堆積させ、そしてここで、上記支持材料が、上記堆積を行うに先立って1種以上 のアルカリ金属塩基および1種以上のアルカリ金属ケイ酸塩で処理したものであ る組成物。 10. 上記パラジウム族金属がパラジウムであり、上記助触媒が銅および/ またはそれの化合物、ニッケルおよび/またはそれの化合物またはそれらの混合 物であり、そして該パラジウムに対する該助触媒内の金属のグラム−原子比が約 0.04から約0.2である請求の範囲9記載の組成物。 11. 該パラジウムに対する金のグラム−原子比が約0.1から約0.5で ある請求の範囲10記載の組成物。 12. 上記支持体が、(a)1種以上のアルカリ金属水酸化物と1種以上の アルカリ金属ケイ酸塩の混合物で該支持体を湿らせ、(b)この湿らせた支持体 を熟成させた後、(c)この湿らせて熟成させた支持体を乾燥させる、ことによ って処理したものである請求の範囲9記載の組成物。 13. 上記支持体がシリカである請求の範囲9記載の組成物。 14. オレフィン系化合物、酸素およびカルボン酸から気相中でエチレン系 不飽和有機エステルを製造する時の触媒として用いるに適切な組成物において、 (i)1種以上のパラジウム族金属および/またはそれらの化合物および(ii )金および/またはそれの化合物を含んでおり、ここで、(i)および(ii) を支持材料の上に堆積させ、そしてここで、上記支持材料が、上記堆積を行うに 先立って1種以上のアルカリ金属塩基および1種以上のアルカリ金属ケイ酸塩で 処理したものである組成物。 15. 該パラジウムに対する金のグラム−原子比が約0.1から約0.5で ある請求の範囲14記載の組成物。 16. 上記支持体が、(a)1種以上のアルカリ金属水酸化物と1種以上の アルカリ金属ケイ酸塩の混合物で該支持体を湿らせ、(b)この湿らせた支持体 を熟成させた後、(c)この湿らせて熟成させた支持体を乾燥させる、ことによ って処理したものである請求の範囲14記載の組成物。 17. 上記支持体がシリカである請求の範囲14記載の組成物。 18. エチレン系不飽和エステルの製造方法において、(i)1種以上のパ ラジウム族金属および/またはそれらの化合物と(ii)金および/またはそれ の化合物と(iii)銅、ニッケル、コバルト、鉄、マンガン、鉛、銀およびそ れらの化合物から成る群から選択される1種以上の助触媒を含んでいてパラジウ ム族金属に対する該助触媒内の金属のグラム−原子比が約0.4以下である触媒 組成物を有効量で存在させて、少なくとも1種のオレフィン系化合物と少なくと も1種のカルボン酸と分子状酸素を気相中で反応させることを含む方法。 19. 該パラジウム族金属に対する該助触媒内の金属のグラム−原子比が約 0.04から約0.2である請求の範囲18記載の方法。 20. 上記助触媒が銅および/またはそれの化合物、ニッケルおよび/また はそれの化合物およびそれらの混合物である請求の範囲18記載の方法。 21. 該パラジウム族金属に対する金のグラム−原子比が約0.1から約0 .5である請求の範囲18記載の方法。 22. 上記触媒組成物を担体支持体の上に堆積させる請求の範囲18記載の 方法。 23. 該支持体がシリカである請求の範囲22記載の方法。 24. 上記支持体の上に上記触媒を堆積させるに先立って、この支持体を、 1種以上のアルカリ金属塩基および1種以上のアルカリ金属ケイ酸塩で処理する 請求の範囲23記載の方法。 25. 上記支持体が、(a)1種以上のアルカリ金属水酸化物と1種以上の アルカリ金属ケイ酸塩の混合物で該支持体を湿らせ、(b)この湿らせた支持体 を熟成させた後、(c)この湿らせて熟成させた支持体を乾燥させる、ことによ って処理したものである請求の範囲18記載の方法。 26. エチレン系不飽和エステルの製造方法において、(i)1種以上のパ ラジウム族金属および/またはそれらの化合物と(ii)金および/またはそれ の化合物と(iii)銅、ニッケル、コバルト、鉄、マンガン、鉛、銀およびそ れらの化合物から成る群から選択される1種以上の助触媒を含んでいる触媒が支 持材料の上に堆積しておりそしてここで上記支持材料が上記堆積を行うに先立っ て1種以上のアルカリ金属 塩基および1種以上のアルカリ金属ケイ酸塩で処理したものである触媒組成物を 有効量で存在させて、少なくとも1種のオレフィン系化合物と少なくとも1種の カルボン酸と分子状酸素を気相中で反応させることを含む方法。 27. 上記パラジウム族金属がパラジウムであり、上記助触媒が銅および/ またはそれの化合物、ニッケルおよび/またはそれの化合物またはそれらの混合 物であり、そして該パラジウムに対する該助触媒内の金属のグラム−原子比が約 0.04から約0.2である請求の範囲26記載の方法。 28. 該パラジウムに対する金のグラム−原子比が約0.1から約0.5で ある請求の範囲27記載の方法。 29. 上記支持体が、(a)1種以上のアルカリ金属水酸化物と1種以上の アルカリ金属ケイ酸塩の混合物で該支持体を湿らせ、(b)この湿らせた支持体 を熟成させた後、(c)この湿らせて熟成させた支持体を乾燥させる、ことによ って処理したものである請求の範囲26記載の方法。 30. 上記支持体がシリカである請求の範囲27記載の方法。 31. エチレン系不飽和エステルの製造方法において、(i)1種以上のパ ラジウム族金属および/またはそれらの化合物と(ii)金および/またはそれ の化合物を含んでいる触媒が支持材料の上に堆積しておりそしてここで上記支持 材料が上記堆積を行うに先立って1種以上のアルカリ金属塩基および1種以上の アルカリ金属ケイ酸塩で処理したものである触媒組成物を有効量で存在させて、 少なくとも1種のオレフィン系化合物と少なくとも1種のカルボン酸と分子状酸 素を気相中で反応 させることを含む方法。 32. 該パラジウムに対する金のグラム−原子比が約0.1から約0.5で ある請求の範囲31記載の方法。 33. 上記支持体が、(a)1種以上のアルカリ金属水酸化物と1種以上の アルカリ金属ケイ酸塩の混合物で該支持体を湿らせ、(b)この湿らせた支持体 を熟成させた後、(c)この湿らせて熟成させた支持体を乾燥させる、ことによ って処理したものである請求の範囲31記載の方法。 34. 上記支持体がシリカである請求の範囲31記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/067,445 | 1993-05-25 | ||
US08/067,445 US5347046A (en) | 1993-05-25 | 1993-05-25 | Catalyst and process for using same for the preparation of unsaturated carboxylic acid esters |
PCT/US1994/005382 WO1994027720A1 (en) | 1993-05-25 | 1994-05-11 | Catalyst and process for using same for the preparation of unsaturated carboxylic acid esters |
Publications (2)
Publication Number | Publication Date |
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JPH08510685A true JPH08510685A (ja) | 1996-11-12 |
JP3698322B2 JP3698322B2 (ja) | 2005-09-21 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP50072295A Expired - Lifetime JP3698322B2 (ja) | 1993-05-25 | 1994-05-11 | 触媒およびこれを不飽和カルボン酸エステルの製造で使用する方法 |
Country Status (10)
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US (1) | US5347046A (ja) |
EP (1) | EP0708684A1 (ja) |
JP (1) | JP3698322B2 (ja) |
KR (1) | KR960702348A (ja) |
CN (1) | CN1123527A (ja) |
AU (1) | AU6912994A (ja) |
BR (1) | BR9406696A (ja) |
CA (1) | CA2161952A1 (ja) |
TW (1) | TW254934B (ja) |
WO (1) | WO1994027720A1 (ja) |
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JP2002516748A (ja) * | 1998-06-02 | 2002-06-11 | セラニーズ・インターナショナル・コーポレーション | 金属パラジウム、銅および金を含む酢酸ビニル触媒およびその製造方法 |
JP2012526110A (ja) * | 2009-05-07 | 2012-10-25 | セラニーズ・インターナショナル・コーポレーション | 均一触媒を用いるアセチレン及びカルボン酸からのビニルエステルの製造 |
JP2014012268A (ja) * | 2012-05-03 | 2014-01-23 | Clariant International Ag | 酢酸塩を用いたシェル触媒の前含浸 |
JP2015521540A (ja) * | 2012-06-19 | 2015-07-30 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Publiclimited Company | 触媒組成物 |
WO2018235705A1 (ja) * | 2017-06-23 | 2018-12-27 | エヌ・イーケムキャット株式会社 | 酢酸ビニル合成用パラジウム-金担持触媒の製造方法 |
JP2019005746A (ja) * | 2017-06-21 | 2019-01-17 | 中国石油化工股▲ふん▼有限公司 | クメンを製造するための触媒及びその適用 |
WO2022113429A1 (ja) * | 2020-11-27 | 2022-06-02 | 昭和電工株式会社 | 酢酸ビニル製造用触媒の製造方法及び酢酸ビニルの製造方法 |
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DE4323980C1 (de) * | 1993-07-16 | 1995-03-30 | Hoechst Ag | Palladium und Kalium sowie Cadmium, Barium oder Gold enthaltender Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung zur Herstellung von Vinylacetat |
CA2135021A1 (en) * | 1993-11-19 | 1995-05-20 | David J. Gulliver | Process for the preparation of catalysts for use in the production of vinyl acetate |
US5665668A (en) * | 1994-01-25 | 1997-09-09 | Grigorova; Bojidara | Method of making a catalyst |
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- 1994-05-11 AU AU69129/94A patent/AU6912994A/en not_active Abandoned
- 1994-05-11 BR BR9406696A patent/BR9406696A/pt not_active Application Discontinuation
- 1994-05-11 CA CA002161952A patent/CA2161952A1/en not_active Abandoned
- 1994-05-11 EP EP94917387A patent/EP0708684A1/en not_active Withdrawn
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JP2002516748A (ja) * | 1998-06-02 | 2002-06-11 | セラニーズ・インターナショナル・コーポレーション | 金属パラジウム、銅および金を含む酢酸ビニル触媒およびその製造方法 |
JP2012526110A (ja) * | 2009-05-07 | 2012-10-25 | セラニーズ・インターナショナル・コーポレーション | 均一触媒を用いるアセチレン及びカルボン酸からのビニルエステルの製造 |
JP2014012268A (ja) * | 2012-05-03 | 2014-01-23 | Clariant International Ag | 酢酸塩を用いたシェル触媒の前含浸 |
JP2015521540A (ja) * | 2012-06-19 | 2015-07-30 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Publiclimited Company | 触媒組成物 |
JP2019005746A (ja) * | 2017-06-21 | 2019-01-17 | 中国石油化工股▲ふん▼有限公司 | クメンを製造するための触媒及びその適用 |
WO2018235705A1 (ja) * | 2017-06-23 | 2018-12-27 | エヌ・イーケムキャット株式会社 | 酢酸ビニル合成用パラジウム-金担持触媒の製造方法 |
JPWO2018235705A1 (ja) * | 2017-06-23 | 2020-04-23 | エヌ・イーケムキャット株式会社 | 酢酸ビニル合成用パラジウム−金担持触媒の製造方法 |
US10981161B2 (en) | 2017-06-23 | 2021-04-20 | N.E. Chemcat Corporation | Method for producing palladium-gold loaded catalyst for vinyl acetate synthesis |
WO2022113429A1 (ja) * | 2020-11-27 | 2022-06-02 | 昭和電工株式会社 | 酢酸ビニル製造用触媒の製造方法及び酢酸ビニルの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2161952A1 (en) | 1994-12-08 |
CN1123527A (zh) | 1996-05-29 |
AU6912994A (en) | 1994-12-20 |
US5347046A (en) | 1994-09-13 |
JP3698322B2 (ja) | 2005-09-21 |
BR9406696A (pt) | 1996-03-19 |
TW254934B (ja) | 1995-08-21 |
KR960702348A (ko) | 1996-04-27 |
WO1994027720A1 (en) | 1994-12-08 |
EP0708684A1 (en) | 1996-05-01 |
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