TWI385028B - 用於氧化乙烯之催化劑及其製造方法與用途 - Google Patents
用於氧化乙烯之催化劑及其製造方法與用途 Download PDFInfo
- Publication number
- TWI385028B TWI385028B TW095113805A TW95113805A TWI385028B TW I385028 B TWI385028 B TW I385028B TW 095113805 A TW095113805 A TW 095113805A TW 95113805 A TW95113805 A TW 95113805A TW I385028 B TWI385028 B TW I385028B
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- Taiwan
- Prior art keywords
- silver
- catalyst
- oxygen
- containing compound
- ppm
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 98
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 28
- 239000005977 Ethylene Substances 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000007254 oxidation reaction Methods 0.000 title description 15
- 230000003647 oxidation Effects 0.000 title description 13
- 229910052709 silver Inorganic materials 0.000 claims description 80
- 239000004332 silver Substances 0.000 claims description 79
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 75
- 238000000034 method Methods 0.000 claims description 42
- 229910052760 oxygen Inorganic materials 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 35
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229910052723 transition metal Inorganic materials 0.000 claims description 20
- 150000003624 transition metals Chemical class 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 150000001340 alkali metals Chemical class 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 230000001590 oxidative effect Effects 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 230000001737 promoting effect Effects 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- -1 silver carboxylate Chemical class 0.000 claims description 9
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 6
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 claims description 5
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 4
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- AXVCDCGTJGNMKM-UHFFFAOYSA-L C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ag+2] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ag+2] AXVCDCGTJGNMKM-UHFFFAOYSA-L 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000005263 alkylenediamine group Chemical group 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940071575 silver citrate Drugs 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 claims description 2
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000010455 vermiculite Substances 0.000 description 4
- 229910052902 vermiculite Inorganic materials 0.000 description 4
- 235000019354 vermiculite Nutrition 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant 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
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 241001379910 Ephemera danica Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- QCTNFXZBLBPELV-UHFFFAOYSA-N oxirane;silver Chemical compound [Ag].C1CO1 QCTNFXZBLBPELV-UHFFFAOYSA-N 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J37/0203—Impregnation the impregnation liquid containing organic 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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Description
本發明係關於適用於生產氧化烯之改良銀催化劑、其製備及其在氧化烯方法中之用途。更特定言之，本發明係關於製備能以含氧氣體在氣相中氧化烯烴(較佳為乙烯)之經承載且以金屬促進之銀催化劑以高效及選擇性生產氧化烯(較佳為環氧乙烷)。
生產用於將乙烯及氧轉化為環氧乙烷之經承載之銀催化劑在此項技術領域中已知。已提議多種修改方案以改良該等催化劑之活性及選擇性。該等修改涉及對使用之載體、生產方法、該載體上之銀的物理形式及該催化劑組合物之添加劑內含物的改良。用於製備適用於將乙烯予以氣相氧化為環氧乙烷之經承載的銀催化劑之方法為已知的，其涉及以銀鹽/胺溶液浸漬諸如氧化鋁之載體。美國專利3,702,359說明該等程序。
美國專利2,125,333揭示使用包括鈉或鉀之鹼金屬及其鹽作為各種銀環氧乙烷催化劑之添加劑。美國專利2,615,900列舉大量適用促進劑。美國專利2,773,844揭示多步銀沉積方法。美國專利3,575,888揭示使用具有約0.15與0.30 m2
/gm之間的孔隙體積及低於約10 m2
/gm之表面積的氧化鋁載體。在美國專利3,962,136及4,010,115中提到使用少量鹼金屬K、Rb及Cs在承載之銀催化劑中作為適用促進劑。美國專利4,005,049教示適用於氧化反應之銀/過渡金屬催化劑之製備。在美國專利4,536,482中，諸如Ag及Re之催化活性金屬與經共濺鍍之載體材料一起共濺鍍於特定載體。例如在美國專利3,962,136中展示藉由類似程序製備亦含有鹼金屬促進劑之銀催化劑。在美國專利4,766,105中展示用於製備經鹼金屬及錸促進且亦經選自硫、鉬、鎢、鉻及混合物之共促進劑促進之銀催化劑的類似程序。利用該等先前技術之程序的催化劑製備涉及以可含有各種促進劑之銀/胺溶液浸漬載體且隨後在強制空氣烘箱中將該經浸漬之載體加熱至高達約275℃之溫度以將銀還原為金屬銀且將揮發物自該催化劑中分離。
美國專利4,916,243展示藉由以銀/胺溶液及乳酸銀溶液浸漬惰性載體而製備的用於將乙烯氧化為環氧乙烷之銀催化劑。該經浸漬之載體隨後於經2"×2"方形加熱區傳送之鋼帶上加熱處理2.5分鐘，該加熱區藉由將熱空氣向上通過該帶而維持於500℃或於400℃歷時4分鐘。
美國專利5,444,034係關於銀催化劑之製備，其中以有機酸之銀鹽之烴溶液浸漬載體且其在諸如氮之惰性氣體下在高達500℃之溫度的階段中激活。
在其他環氧乙烷生產方法之描述中，將含氧氣體添加至饋料中提高功效。例如在美國專利5,112,795中，將5 ppm氧化氮添加至具有以下組成之氣體饋料中：8體積%氧、30體積%乙烯、約5 ppm氯乙烷及其餘之氮。
在其他方法中為增加功效，尤其增加選擇性，將該催化劑在特定溫度下及特定氣體混合物中處理。例如在美國2004/0049061及2004/002954中，可藉由在一般高於該催化劑正常初始操作溫度之溫度下在氧存在下熱處理該催化劑提高高選擇性環氧化催化劑之選擇性。
美國專利5,504,052及5,646,087展示用於將乙烯氧化為環氧乙烷之銀催化劑，其藉由以銀/胺溶液以及各種促進劑浸漬惰性載體並於300℃－500℃煅燒該經浸漬之載體來製備，同時將該催化劑維持在惰性氣氛下。因此，先前技術教示藉由在空氣中(意即大量氧)或在諸如氮之惰性氣氛下煅燒經浸漬之載體來製備催化劑。現已驚人地發現在諸如氮之惰性氣氛下煅燒經浸漬之載體且於該惰性氣氛中僅添加少量諸如分子氧之氧化氣體提高環氧乙烷催化劑之有效壽命、活性及選擇性。
本發明提供一種適用於自乙烯及氧以氣相生產環氧乙烷之催化劑之製法，其包括以包含催化有效量之含銀化合物、促進量之含鹼金屬化合物及促進量之含過渡金屬化合物的溶液浸漬惰性載體；於約200℃至約600℃之溫度下加熱該經浸漬之載體歷時足以將該含銀化合物中之銀轉化為金屬銀且大體上分解及移除所有有機材料之時間；在包含惰性氣體與以體積計約10 ppm至5%含氧氧化組份之氣體之組合氣氛下進行該加熱。
本發明亦提供一種適用於自乙烯及氧以氣相生產環氧乙烷之催化劑之製法，其包括以包含催化有效量之含銀化合物、促進量之含鹼金屬化合物及促進量之含過渡金屬化合物的溶液浸漬惰性載體；於約200℃至約600℃之溫度下加熱該經浸漬之載體歷時足以將該含銀化合物中之銀轉化為金屬銀且大體上分解及移除所有有機材料之時間；在包含惰性氣體與以體積計約10 ppm至1%含氧氧化組份之氣體之組合氣氛下進行該加熱。
本發明進一步提供一種適用於自乙烯及氧氣相生產環氧乙烷之催化劑之製法，其包括以包含催化有效量之含銀化合物、促進量之含鹼金屬化合物及促進量之含過渡金屬化合物的溶液浸漬惰性載體；於約200℃至約600℃之溫度加熱該經浸漬之載體歷時足以將該含銀化合物中之銀轉化為金屬銀且大體上分解及移除所有有機材料之時間；在包含惰性氣體與以體積計約10 ppm至500 ppm含氧氧化組份之氣體組合氣氛下進行該加熱。
本發明仍進一步提供一種用於將乙烯予以氧化為環氧乙烷之方法，其包含以分子氧在以上催化劑存在下於固定床型管式反應器中將乙烯予以氣相氧化。
藉由以溶解於足以使銀前驅體化合物沉積於載體之合適溶劑中之銀離子、化合物、錯合物及/或鹽浸漬多孔耐火載體來製備本發明之催化劑。隨後自該溶液移除該經浸漬之載體且藉由高溫煅燒將該沉積之銀化合物還原為金屬銀。同樣在沉積該銀之前、同時或隨後亦沉積於該載體上者為溶解於合適溶劑之鹼金屬之合適離子、化合物及/或鹽。同樣在沉積該銀及/或鹼金屬之前、同時或隨後亦沉積於載體上者為溶解於合適溶劑之合適過渡金屬離子、化合物、錯合物及/或鹽。
所用適用於該等催化劑之支撐物或載體可為在乙烯氧化饋料材料、產物及反應條件存在下相對惰性的多孔耐火催化劑載體或支撐物材料。該等習知材料為熟習此項技術者所已知且可為天然或合成來源且較佳為大孔結構，意即，具有約10 m2
/g或更小且較佳為約3 m2
/g或更小之表面積的結構。適用作本發明之環氧乙烷催化劑載體之載體的實例為氧化鋁、尤其α－氧化鋁、木炭、浮石、氧化鎂、氧化鋯、矽藻土、漂白土、碳化矽、包含矽石及/或碳化矽之多孔聚結物、矽石、氧化鎂、精選黏土、人工及天然沸石及陶瓷。較佳催化劑可以包含氧化鋁、矽石、矽石－氧化鋁或其組合之載體來製備。最佳之載體為主要含有α－氧化鋁之載體，尤其為含有高達約15重量%矽石之載體。在含α－氧化鋁載體之狀況下，較佳者為具有如由B.E.T.方法所量測之約0.03 m2
/g至約10 m2
/g、較佳約0.05 m2
/g至約5 m2
/g、更佳約0.1 m2
/g至約3 m2
/g之表面積且具有如由習知水吸收技術量測之以體積計約0.1 cc/g至約0.75 cc/g、較佳約0.25 cc/g至約0.55 cc/g之水孔體積的載體。測定特定表面積的B.E.T.方法詳細描述於Brunauer,S.,Em mett,P.H.及Teller,E.,J.Am.Chem.Soc.,60,309－16(1938)。孔體積及孔尺寸分佈由習知汞孔隙計方法來量測；參見Drake及Ritter,"Ind.Eng.Chem.Anal.Ed.,"17,787(1945)。該等載體可購自Norton Company。
為用於商業性環氧乙烷生產應用中，希望該等載體形成為規則狀小球、球體、環狀體、顆粒、厚塊、片狀、小球、車輪狀及具有適合應用於固定床反應器之尺寸的類似物。希望該等載體顆粒可具有在約3 mm至約10 mm之範圍且較佳在約4 mm至約8 mm之範圍內的"等效直徑"，其通常與該催化劑所置入之管式反應器之內部直徑一致。"等效直徑"為具有與所應用之該等載體顆粒相同的外表面(意即，忽略在該等顆粒之孔內的表面)對體積之比的球體之直徑。
以銀浸漬溶液、較佳銀之水溶液浸漬上述習知多孔耐火載體。亦以各種催化劑促進劑同時或在分開步驟中浸漬該載體。根據本發明所製備之較佳催化劑含有高達約45重量%之銀，其表現為金屬銀，沉積於多孔耐火載體之表面及全部孔中。以總催化劑之重量計約1－40%之表現為金屬銀之銀含量為較佳的，而8－35%銀含量更佳。沉積於該載體或存在於該載體之銀的量為催化有效量之銀的量，意即，經濟地催化乙烯與氧之反應以生產環氧乙烷之量。如本文所用，術語"催化有效量之銀"係指提供可量測之乙烯及氧至環氧乙烷的轉化及在催化劑壽命期間之選擇性及活性穩定性之銀的量。適用含銀化合物非獨占性包括草酸銀、硝酸銀、氧化銀、碳酸銀、羧酸銀、檸檬酸銀、鄰苯二甲酸銀、乳酸銀、丙酸銀、丁酸銀及高碳脂肪酸鹽及其組合。
該催化劑包含承載於多孔耐火載體上之催化有效量之銀、促進量之鹼金屬、促進量之過渡金屬。如本文所用，該術語"促進量"之催化劑之特定組份係指有效作用以當與不含有該組份的催化劑相比時提供該催化劑之一或多種特性之改良的該組份的量。當然，所使用之精確濃度將視(在其他因素中)所要之銀含量、載體之性質、液體之黏度及該銀化合物之溶解性而定。
除銀外，該催化劑亦含有選自鋰、鈉、鉀、銣、銫或其組合之鹼金屬促進劑，其中較佳為銫。沉積於載體或催化劑或存在於載體或催化劑上之鹼金屬之量將為促進量。該量以總催化劑之重量計較佳將在約10 ppm至約3000 ppm、更佳約15 ppm至約2000 ppm且甚至更佳約20 ppm至約1500 ppm且仍然甚至更佳約50 ppm至約1000 ppm之範圍，該量以金屬量測。
此催化劑亦含有包含來自元素週期表之第5b、6b、7b及8族之元素及其組合之過渡金屬促進劑。該過渡金屬較佳包含選自元素週期表第7b族之元素。更佳之過渡金屬為錸、鉬及鎢，其中鉬及錸最佳。沉積於載體或催化劑或存在於載體或催化劑之過渡金屬促進劑之量將為促進量。該過渡金屬促進劑可以約0.1微莫耳/公克總催化劑至10微莫耳/公克總催化劑、較佳約0.2微莫耳/公克總催化劑至5微莫耳/公克總催化劑且更佳約0.5微莫耳/公克總催化劑至4微莫耳/公克總催化劑之量存在，其以金屬表示。
用於浸漬該載體之銀溶液亦可包含諸如此項技術領域中已知之可選溶劑或錯合/溶解劑。多種溶劑或錯合/溶解劑可用以將銀在浸漬介質中溶解至所要濃度。適用錯合/溶解劑包括胺、氨、乳酸及其組合。胺包括具有1至5個碳原子的伸烷基二胺。在一較佳實施例中，該溶液包含草酸銀與乙二胺之水溶液。該錯合/溶解劑可以約0.1至約5.0莫耳乙二胺/莫耳銀、較佳約0.2至約4.0莫耳及更佳約0.3至約3.0莫耳乙二胺/莫耳銀之量存在於該浸漬溶液中。
當使用溶劑時，其可為水基或有機物基溶劑且可為極性或大體上或完全非極性。一般而言，該溶劑應具有足夠之溶劑化能力以溶解溶液組份。與此同時，較佳選擇該溶劑以避免具有對溶劑化促進劑的不良影響或與該溶劑化促進劑相互作用。有機物基溶劑之實例包括(但不限於)醇，尤其烷醇；二醇，尤其烷二醇；酮；醛；胺；四氫呋喃；硝基苯；甘醇二甲醚，尤其二甘醇二甲醚及四甘醇二甲醚；及其類似物。每分子具有1至約8個碳原子之有機物基溶劑較佳。可使用有機溶劑之混合物或水與一或多種有機溶劑之混合物，其限制條件為該等混合溶劑發揮如本文所要之功能。
銀鹽在溶液中之濃度在約0.1重量%至由所使用之特定鹽/溶解劑組合之溶解性所允許的最大值之範圍內。通常極適合使用含有以銀重量計0.5%至約45%之銀鹽溶液，較佳銀濃度為5重量%至30重量%。
以習知方式藉由過量溶液浸漬、微濕等實現選定載體之浸漬。一般將載體材料置入銀溶液直至該載體吸收足夠量之該溶液。用於浸漬多孔載體之銀溶液之量較佳不超過充滿該多孔載體的孔體積所需要之量。含銀液體藉由吸收、毛細作用及/或真空滲透至該載體之孔中。可使用存在或不存在中途乾燥之單一浸漬或連續浸漬，部分視溶液中銀鹽之濃度而定。浸漬程序描述於美國專利4,761,394,4,766,105m、4,908,343、5,057,481、5,187,140、5,102,848、5,011,807、5,099,041及5,407,888中，其以引用的方式併入本文中。可使用預沉積、共沉積及後沉積各種促進劑之已知先前程序。
催化特性之實例尤其包括可操作性(失控抗性)、選擇性、活性、轉化率、穩定性及產率。熟習此項技術者應瞭解，可由該"促進量"來增強一或多種個別催化特性，而其他催化特性可或可不增強或甚至減弱。應進一步瞭解，不同催化特性可在不同操作條件下增強。舉例而言，在一組操作條件下具有增強選擇性之催化劑可在其中改良展示於活性而非選擇性之不同組條件下操作，且環氧乙烷設備之操作者將有意改變操作條件以甚至在以其他催化特性為代價之情形下利用某些催化特性以藉由考慮到饋料成本、能量成本、副產物移除成本及其類似物來優化條件及結果。本發明之銀、載體、鹼金屬促進劑及過渡金屬促進劑之特定組合相對於銀及載體及無或僅有一種促進劑之相同組合將提供一或多種催化特性之改良。
浸漬後，將該浸漬有銀前驅體化合物及促進劑之載體煅燒或激活歷時足以將該銀組份還原為金屬銀且自該含銀載體中移除揮發性分解產物之時間。藉由以下方法完成該煅燒：將該經浸漬之載體加熱至(較佳以漸進之速率)約200℃至約600℃，較佳約250℃至約500℃且更佳約300℃至約450℃之範圍內的溫度，在0.5至35巴之範圍內的反應壓力下，歷時足以將所包含之銀轉化為銀金屬且分解所有或大體上所有所存在之有機材料並移除作為揮發物之該等有機材料的時間。適用加熱時間範圍為約1分鐘至約12小時，較佳約2分鐘至約6小時且更佳約2分鐘至約1小時。通常溫度愈高，所需要之還原時間愈短。在此項技術領域中已建議大範圍之加熱時間以熱處理該經浸漬之載體(例如，美國專利第3,563,914號暗示加熱低於300秒、美國專利第3,702,259號揭示於100℃至375℃之溫度下加熱2至8小時以還原催化劑中之銀鹽；且美國專利第3,962,136號暗示於相同溫度範圍加熱至8小時)，唯一重要的是，該還原時間與溫度相關從而完成銀鹽至催化活性金屬大體上完全之還原。連續或逐步加熱程式可用於此目的。
根據本發明，在加熱期間該經浸漬之載體維持在包含惰性氣體與以體積計約10 ppm至約5%含氧氧化組份的氣體之組合的氣氛下。為本發明之目的，惰性氣體定義為大體上不與在所選擇之催化劑製備條件下產生組份之催化劑反應的氣體。其包括氮、氬、氪、氦及其組合，其中較佳之惰性氣體為氮。含氧氧化組份之氣體可包括分子氧、CO2
、NO、NO2
、N2
O3
、N2
O4
或N2
O5
，或在煅燒條件下能夠形成NO、NO2
、N2
O3
、N2
O4
、N2
O5
之物質，或其組合，且視情況包含SO3
、SO2
、P2
O5
、P2
O3
或其組合。其中分子氧較佳且更佳者為O2
與NO或NO2
之組合。在一適用實施例中，該氣氛包含以體積計約10 ppm至約1%之含氧氧化組份之氣體。在另一適用實施例中，該氣氛包含約50 ppm至約500 ppm之含氧氧化組份之氣體。
通常藉由在本發明之催化劑存在下於約180℃至約330℃且較佳於約200℃至約325℃、更佳約225℃至約270℃範圍內之溫度下，視所要質量速度及產率在大氣壓力至約30個大氣壓力變化之壓力下使含氧氣體與乙烯連續接觸來進行商業上所實踐之環氧乙烷生產方法。通常使用約大氣壓力至約500 psi之範圍內的壓力。然而，在本發明之範圍內可使用較高壓力。在大規模反應器中滯留時間通常約為0.1－5秒。氧可以諸如空氣或來自諸如貯槽之市售遞送源之氧的含氧流供應至該反應。使用習知方法自該反應產物中分離及回收所得環氧乙烷。然而，為本發明之目的，該環氧乙烷方法設想以例如約0.5至6體積%之正常濃度包含二氧化碳再循環的正常氣體再循環。用於將乙烯氧化為環氧乙烷之通常方法包含以分子氧在固定床、管式反應器中在催化劑存在下氣相氧化乙烯。習知市售固定床乙烯氧化反應器一般為經催化劑填充之外徑約0.7至2.7吋且內徑約0.5至2.5吋且長約15－45呎的複數個平行延長管(於合適外殼中)之形式。
已展示本發明之催化劑為在以分子氧將乙烯氧化為環氧乙烷中之特定選擇性催化劑。用於在存在本發明之催化劑下進行該氧化反應之條件大致包含在先前技術中所描述之條件。例如，其牽涉到合適溫度、壓力、滯留時間、稀釋材料(諸如氮、二氧化碳、蒸汽、氬、甲烷或其他飽和烴)、存在或不存在控制催化作用之緩和劑(例如1,2－二氯乙烷、乙烯基氯或氯化聚苯化合物)、在不同反應器中使用再循環操作或應用連續轉化以增加環氧乙烷之產率的需要性及任何其他自可在製備環氧乙烷之方法中選擇的特定條件。可自習知源獲得用作反應物之分子氧。合適氧裝料可為相對純之氧、包含主要量之氧及少量一或多種稀釋劑(諸如氮、氬等)之經濃縮的氧流或諸如空氣之另一含氧流。本發明之催化劑在乙烯氧化反應中的使用絕不限於使用已知有效的條件中之特定條件。
藉由已知及在此項技術領域中所使用之習知方法來自該反應產物中分離及回收所得環氧乙烷。在環氧乙烷生產方法中使用本發明之銀催化劑在給定乙烯轉化率下產生比可能的習知催化劑更高的總乙烯至環氧乙烷之氧化選擇性。
在環氧乙烷生產中，反應物饋料混合物可含有0.5%至45%乙烯及3%至15%氧，及包含包括諸如氮、二氧化碳、甲烷、乙烷、氬及其類似物之物質的相對惰性材料之其餘部分。在本發明之銀催化劑之一較佳應用中，在含氧氣體含有約95%或更多氧時產生環氧乙烷。通常每次通過催化劑僅有一部分乙烯反應且在分離所要環氧乙烷產物及移除適當淨化氣流及二氧化碳以防止惰性氣體及/或副產物之不可控堆積後，將未反應之材料返回至該氧化反應器。僅為說明之目的，以下為在當前商業性環氧乙烷反應器裝置中通常使用之條件。
GHSV 1500－10,000入口壓力 150－400 psig入口饋料：乙烯 1－40% O2
3－12% CO2
2－40%乙烷 0－3%
氬及/或甲烷及/或氮：0.3－20 ppmv總稀釋氯代烴緩和劑冷卻劑溫度 180－315℃催化劑溫度 180℃ O2
轉化量 10－60% EO生產率(工作效率)2－16 lbs.EO/cu.ft.催化劑/小時以下為用以說明本發明之非限制性實例。
藉由取用1000 g由載體生產商所提供之氧化鋁載體且首先以1300 g於水中之1.25 M NaOH循環溶液處理其來獲得催化劑載體。當NaOH溶液與該載體接觸時，在30分鐘內溫度自室溫升至80℃且維持在此溫度1小時。處理後，排出該溶液且使用1300 g室溫下之循環去離子水清洗此載體1小時，此後將其排出。清洗程序重複四次。於150℃將該經處理之載體乾燥隔夜。
藉由以銀胺溶液真空浸漬該載體至在最終產物中具有目標之11.5%銀來製備催化劑A。將亦含有來自CsOH之銫促進劑的銀胺溶液應用至在410 ppm至650 ppm變化的最終催化劑中之目標濃度。該溶液亦含有來自高錸酸銨溶液之錸至280 ppm之在最終催化劑中目標錸。在最高溫度為400℃之純氮之環境下，在移經爐之帶上煅燒該經浸漬之載體。
藉由重複催化劑A之製備(除在氮及100 ppm氧環境下在移經爐之帶上煅燒該經浸漬之載體外)來製備催化劑B。
藉由重複催化劑A之製備(除在空氣環境下在移經爐之帶上煅燒該經浸漬之載體外)來製備催化劑C。
在重量工作效率為737之測試中比較催化劑且在圖1中呈示在該等載體上所製備之催化劑的選擇性效能。圖1展示隨時間在純氮中煅燒之催化劑(A)、在添加少量氧之氮中煅燒之催化劑(B)及在空氣中煅燒之催化劑(C)的選擇性。該資料清楚展示在添加少量氧之氮中煅燒之催化劑的改良效能。
雖然藉由參考較佳實施例特定展示及描述了本發明，但一般技術者將不難瞭解在不悖離本發明之範疇及精神下可做出各種變化及修改。希望申請專利範圍解釋為涵蓋所揭示之實施例、以上所討論之其替代物及其所有等價物。
圖1為實例中之催化劑對時間的選擇性曲線圖，(A)在純氮中煅燒之催化劑，(B)在添加有少量氧之氮中煅燒之催化劑及(C)在空氣中煅燒之催化劑。
Claims (25)
- 一種適用於自乙烯及氧以氣相生產環氧乙烷之催化劑的製法，其包括以包含催化有效量之含銀化合物、促進量之含鹼金屬化合物及促進量之含過渡金屬化合物的溶液浸漬惰性載體；於約200℃至約600℃之溫度下加熱歷足以將該含銀化合物中之銀轉化為金屬銀且大體上分解及移除所有有機材料之時間來煅燒該經浸漬之載體；在包含惰性氣體與以體積計約50 ppm至約500 ppm含氧氧化組份的氣體之組合氣氛下進行該加熱。
- 如請求項1之方法，其中該惰性載體包含α-氧化鋁。
- 如請求項1之方法，其中該溶液包含水溶液。
- 如請求項1之方法，其中該含銀化合物包含草酸銀、硝酸銀、氧化銀、碳酸銀、羧酸銀、檸檬酸銀、鄰苯二甲酸銀、乳酸銀、丙酸銀、丁酸銀、脂肪酸銀鹽及其組合。
- 如請求項1之方法，其中該溶液進一步包含選自由以下各物組成之群之組份：胺、醇、氨、乳酸及其組合。
- 如請求項1之方法，其中溶液進一步包含胺。
- 如請求項1之方法，其中該溶液進一步包含具有1至5個碳原子之伸烷基二胺。
- 如請求項1之方法，其中該溶液包含草酸銀及乙二胺。
- 如請求項1之方法，其中該含氧氧化組份之氣體包含CO2 、NO、NO2 、N2 O3 、N2 O4 或N2 O5 或能夠在煅燒條件下形成NO、NO2 、N2 O3 、N2 O4 或N2 O5 之物質或其組合， 且視情況包含SO3 、SO2 、P2 O5 、P2 O3 或其組合。
- 如請求項1之方法，其中該含氧之氧化組份之氣體包含O2 。
- 如請求項1之方法，其中該含氧之氧化組份之氣體包含O2 與NO或NO2 。
- 如請求項1之方法，其中該含鹼金屬之化合物包含鋰、鈉、鉀、銣、銫或其組合。
- 如請求項1之方法，其中該含鹼金屬之化合物包含飽。
- 如請求項1之方法，其中該過渡金屬包含選自元素週期表第5b、6b、7b及8族之元素及其組合。
- 如請求項1之方法，其中該過渡金屬包含選自元素週期表第7b族之元素及其組合。
- 如請求項1之方法，其中該過渡金屬包含錸、鉬、鎢或其組合。
- 如請求項1之方法，其中該過渡金屬包含鉬。
- 如請求項1之方法，其中該過渡金屬包含錸。
- 如請求項1之方法，其中該惰性氣體包含氮、氬、氪、氦或其組合。
- 如請求項1之方法，其中該惰性氣體包含氮。
- 如請求項1之方法，其中該加熱進行約1分鐘至約1小時。
- 如請求項1之方法，其中該惰性載體包含α-氧化鋁；該含銀化合物包含草酸銀、氧化銀、碳酸銀、乳酸銀及其組合；該含鹼金屬化合物包含鋰、鈉、鉀、銣、銫或其 組合；其中該過渡金屬包含錸；其中該惰性氣體包含氮、氬、氪、氦、二氧化碳或其組合；其中該氣氛包含以體積計約50 ppm至約500 ppm之含氧氧化組份之氣體。
- 如請求項1之方法，其中該惰性載體包含α-氧化鋁；該含銀化合物包含草酸銀、氧化銀、碳酸銀、乳酸銀及其組合；該含鹼金屬化合物包含銫；其中該過渡金屬包含錸；其中該惰性氣體包含氮；其中該氣氛包含以體積計約50 ppm至約500 ppm之含氧氧化組份之氣體。
- 一種催化劑，其根據如請求項1之方法製備。
- 一種將乙烯予以氧化為環氧乙烷之方法，其包括以分子氧在固定床型管式反應器中在催化劑存在下以氣相將乙烯予以氧化，其中該催化劑係根據如請求項1之方法製備。
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| WO2018017453A1 (en) * | 2016-07-18 | 2018-01-25 | Scientific Design Company, Inc. | Epoxidation process |
| US11439986B2 (en) * | 2017-12-13 | 2022-09-13 | Scientific Design Company, Inc. | Silver impregnation solution containing high-boiling oxygenated additive and its use in ethylene oxide catalyst preparation |
| TWI808125B (zh) | 2018-02-07 | 2023-07-11 | 德商巴斯夫歐洲公司 | 有效地將乙烯氧化轉化為環氧乙烷之催化劑 |
| DK3749449T3 (da) | 2018-02-07 | 2022-04-19 | Basf Se | Fremgangsmåde til fremstilling af en sølvimprægnerings-opløsning |
| EP3639923A1 (en) | 2018-10-15 | 2020-04-22 | Basf Se | Process for producing ethylene oxide by gas-phase oxidation of ethylene |
| EP3639924A1 (en) | 2018-10-15 | 2020-04-22 | Basf Se | Catalyst for producing ethylene oxide by gas-phase oxidation |
| EP3659703A1 (en) | 2018-11-28 | 2020-06-03 | Basf Se | Catalyst for producing ethylene oxide by gas-phase oxidation |
| CN109574133A (zh) * | 2018-12-29 | 2019-04-05 | 重庆科技学院 | 有机废水光降解方法 |
| WO2021038027A1 (en) | 2019-08-28 | 2021-03-04 | Basf Se | Process for preparing an epoxidation catalyst |
| EP3885038A1 (en) | 2020-03-27 | 2021-09-29 | Basf Se | Process for producing an epoxidation catalyst |
| WO2021191414A1 (en) * | 2020-03-27 | 2021-09-30 | Basf Se | Process for producing a silver-based epoxidation catalyst |
| JP2023532004A (ja) | 2020-06-26 | 2023-07-26 | ビーエーエスエフ ソシエタス・ヨーロピア | 多孔質アルファ－アルミナ触媒支持体を生成する方法 |
| US20230256420A1 (en) | 2020-06-26 | 2023-08-17 | Basf Se | Shaped catalyst body for the production of ethylene oxide |
| US20230256415A1 (en) | 2020-06-26 | 2023-08-17 | Basf Se | Production of porous alpha-alumina supports from boehmitic derived aluminas |
| EP4284552A1 (en) | 2021-01-26 | 2023-12-06 | Basf Se | Epoxidation catalyst |
| WO2022268348A1 (en) | 2021-06-25 | 2022-12-29 | Basf Se | High purity tableted alpha-alumina catalyst support |
| TW202421267A (zh) | 2022-10-12 | 2024-06-01 | 德商巴斯夫歐洲公司 | 環氧化催化劑 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525740A (en) * | 1993-03-01 | 1996-06-11 | Scientific Design Company, Inc. | Process for preparing silver catalyst and process of using same to produce ethylene oxide |
| CN1139886A (zh) * | 1993-12-30 | 1997-01-08 | 国际壳牌研究有限公司 | 环氧化催化剂和方法 |
| TW200407198A (en) * | 2002-06-28 | 2004-05-16 | Shell Int Research | A method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin |
Family Cites Families (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702309A (en) | 1954-08-13 | 1972-11-07 | Karl Ziegler | Polymerization of ethylene using reduced group iv-b,v-b and vi-b metal salts as the polymerization catalyst |
| US4774222A (en) * | 1982-06-16 | 1988-09-27 | Scientific Design Company, Inc. | Catalyst for oxidation of ethylene to ethylene oxide and process for preparing the catalyst |
| US4820675A (en) * | 1986-10-31 | 1989-04-11 | Shell Oil Company | Ethylene oxide catalyst & process for preparing the catalyst |
| US4766105A (en) * | 1986-10-31 | 1988-08-23 | Shell Oil Company | Ethylene oxide catalyst and process for preparing the catalyst |
| US4761394A (en) | 1986-10-31 | 1988-08-02 | Shell Oil Company | Ethylene oxide catalyst and process for preparing the catalyst |
| GB8626687D0 (en) * | 1986-11-07 | 1986-12-10 | Shell Int Research | Preparing silver catalyst |
| US4908343A (en) | 1987-02-20 | 1990-03-13 | Union Carbide Chemicals And Plastics Company Inc. | Catalyst composition for oxidation of ethylene to ethylene oxide |
| US5057481A (en) | 1987-02-20 | 1991-10-15 | Union Carbide Chemicals And Plastics Technology Corporation | Catalyst composition for oxidation of ethylene to ethylene oxide |
| EP0357292A1 (en) | 1988-08-30 | 1990-03-07 | Imperial Chemical Industries Plc | Production of ethylene oxide and catalysts therefor |
| JP2637537B2 (ja) | 1989-01-24 | 1997-08-06 | 株式会社日本触媒 | エチレンオキシド製造用銀触媒およびその製造方法 |
| CA1337722C (en) * | 1989-04-18 | 1995-12-12 | Madan Mohan Bhasin | Alkylene oxide catalysts having enhanced activity and/or stability |
| US5187140A (en) | 1989-10-18 | 1993-02-16 | Union Carbide Chemicals & Plastics Technology Corporation | Alkylene oxide catalysts containing high silver content |
| US5102848A (en) * | 1990-09-28 | 1992-04-07 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition for oxidation of ethylene to ethylene oxide |
| US5112795A (en) | 1990-10-12 | 1992-05-12 | Union Carbide Chemicals & Plastics Technology Corporation | Supported silver catalyst, and processes for making and using same |
| US5100859A (en) * | 1991-01-22 | 1992-03-31 | Norton Company | Catalyst carrier |
| US5145824A (en) * | 1991-01-22 | 1992-09-08 | Shell Oil Company | Ethylene oxide catalyst |
| US5407888A (en) | 1992-05-12 | 1995-04-18 | Basf Aktiengesellschaft | Silver catalyst |
| US6184175B1 (en) * | 1993-03-01 | 2001-02-06 | Scientic Design Company, Inc. | Process for preparing silver catalyst |
| US5447897A (en) * | 1993-05-17 | 1995-09-05 | Shell Oil Company | Ethylene oxide catalyst and process |
| US5364826A (en) * | 1993-09-13 | 1994-11-15 | Shell Oil Company | Process for preparing ethylene oxide catalysts |
| US5545603A (en) * | 1994-11-01 | 1996-08-13 | Shell Oil Company | Ethylene oxide catalyst and process |
| US5504052A (en) | 1994-12-02 | 1996-04-02 | Scientific Design Company, Inc. | Silver catalyst preparation |
| US5602070A (en) * | 1995-01-09 | 1997-02-11 | Scientific Design Company, Inc. | Process for preparing silver catalyst |
| US5705661A (en) * | 1995-09-25 | 1998-01-06 | Mitsubishi Chemical Corporation | Catalyst for production of ethylene oxide |
| US5625084A (en) * | 1996-01-31 | 1997-04-29 | Arco Chemical Technology, L.P. | Vapor phase oxidation of propylene to propylene oxide |
| US5801259A (en) * | 1996-04-30 | 1998-09-01 | Shell Oil Company | Ethylene oxide catalyst and process |
| WO1997046317A1 (en) * | 1996-06-05 | 1997-12-11 | Shell Internationale Research Maatschappij B.V. | Epoxidation catalyst and process |
| ES2156391T3 (es) * | 1996-07-01 | 2001-06-16 | Dow Chemical Co | Proceso para la oxidacion directa de olefinas a oxidos de olefinas. |
| US5780656A (en) * | 1997-04-14 | 1998-07-14 | Scientific Design Company, Inc. | Ethylene oxide catalyst and process |
| JP4210255B2 (ja) * | 1997-12-25 | 2009-01-14 | 株式会社日本触媒 | エチレンオキシド製造用銀触媒およびエチレンオキシドの製造方法 |
| TW426545B (en) * | 1997-12-25 | 2001-03-21 | Nippon Catalytic Chem Ind | Silver catalyst for production of ethylene oxide, method for production thereof, and method for production of ethylene oxide |
| DE19803890A1 (de) * | 1998-01-31 | 1999-08-05 | Erdoelchemie Gmbh | Silberhaltige Trägerkatalysatoren und Katalysator-Zwischenprodukte, Verfahren zu ihrer Herstellung und ihre Verwendung |
| EP0937498B1 (en) * | 1998-02-20 | 2004-08-18 | Nippon Shokubai Co., Ltd. | Silver catalyst for production of ethylene Oxide, method for production thereof, and method for production of ethylene oxide |
| US7232786B2 (en) * | 1998-09-14 | 2007-06-19 | Shell Oil Company | Catalyst composition |
| IN193645B (zh) * | 1998-11-17 | 2004-07-31 | Nippon Catalytic Chem Ind | |
| EP1086743B1 (en) | 1999-09-21 | 2006-08-16 | Nippon Shokubai Co., Ltd. | Catalyst for production of epoxides and methods for production thereof and epoxides |
| CN100553763C (zh) * | 2002-02-25 | 2009-10-28 | 国际壳牌研究有限公司 | 负载的银催化剂和使用该催化剂的环氧化方法 |
| EP1354626B1 (en) * | 2002-04-04 | 2005-07-13 | Nippon Shokubai Co., Ltd. | Alumina-silica supported silver catalyst and use thereof in the production of epoxide |
| US6750173B2 (en) * | 2002-04-08 | 2004-06-15 | Scientific Design Company, Inc. | Ethylene oxide catalyst |
| AU2003284183A1 (en) * | 2002-10-28 | 2004-05-25 | Shell Oil Company | A process for preparing an olefin oxide, a method of using the olefin oxide and a catalyst composition |
| US20060293180A1 (en) * | 2003-08-22 | 2006-12-28 | Thorsteinson Erlind M | Modified alumina carriers and silver-based catalysts for the production of alkylene oxides |
-
2005
- 2005-05-09 US US11/124,646 patent/US7759284B2/en active Active
-
2006
- 2006-04-18 TW TW095113805A patent/TWI385028B/zh not_active IP Right Cessation
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- 2006-05-09 AR ARP060101856A patent/AR054356A1/es active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525740A (en) * | 1993-03-01 | 1996-06-11 | Scientific Design Company, Inc. | Process for preparing silver catalyst and process of using same to produce ethylene oxide |
| CN1139886A (zh) * | 1993-12-30 | 1997-01-08 | 国际壳牌研究有限公司 | 环氧化催化剂和方法 |
| TW200407198A (en) * | 2002-06-28 | 2004-05-16 | Shell Int Research | A method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008540098A (ja) | 2008-11-20 |
| TW200642756A (en) | 2006-12-16 |
| US7759284B2 (en) | 2010-07-20 |
| WO2007000664A1 (en) | 2007-01-04 |
| CN101171080A (zh) | 2008-04-30 |
| US20060252639A1 (en) | 2006-11-09 |
| EP1893331B1 (en) | 2013-07-10 |
| EP1893331A1 (en) | 2008-03-05 |
| KR20080005505A (ko) | 2008-01-14 |
| RU2411997C2 (ru) | 2011-02-20 |
| JP4981792B2 (ja) | 2012-07-25 |
| RU2007145501A (ru) | 2009-06-20 |
| MX2007013763A (es) | 2008-04-07 |
| BRPI0611295A2 (pt) | 2010-08-31 |
| KR101324286B1 (ko) | 2013-11-01 |
| AR054356A1 (es) | 2007-06-20 |
| CN101171080B (zh) | 2012-07-11 |
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