CN1128251A - 烯烃水合方法 - Google Patents
烯烃水合方法 Download PDFInfo
- Publication number
- CN1128251A CN1128251A CN95119690A CN95119690A CN1128251A CN 1128251 A CN1128251 A CN 1128251A CN 95119690 A CN95119690 A CN 95119690A CN 95119690 A CN95119690 A CN 95119690A CN 1128251 A CN1128251 A CN 1128251A
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- Prior art keywords
- clay
- ion
- acid
- carrier
- catalyst
- Prior art date
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- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 23
- 238000006703 hydration reaction Methods 0.000 title claims description 32
- 230000036571 hydration Effects 0.000 title claims description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 16
- 239000004927 clay Substances 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 29
- -1 hydrogen ions Chemical class 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012808 vapor phase Substances 0.000 claims abstract description 4
- 239000000440 bentonite Substances 0.000 claims abstract description 3
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 238000010306 acid treatment Methods 0.000 claims description 13
- 125000004429 atom Chemical group 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 235000013495 cobalt Nutrition 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 241000908838 Parietaria mottle virus Species 0.000 claims description 2
- 241001168730 Simo Species 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Chemical group 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001439 antimony ion Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012477 high molecular weight ligand Substances 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Chemical group 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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 1
- 239000002994 raw material Substances 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 230000000887 hydrating effect Effects 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及在催化剂体系存在下烯烃水合成相应醇的汽相方法。催化剂体系包括载于粘土载体上的杂多酸催化剂。这粘土载体是热酸处理过的粘土。其制备方法是用热酸连续浸洗市售膨润土粘土,使粘土中阳离子被氢离子交换,从而得到表面大于50米2/克的粘土载体。使用这种粘土作载体不仅可以提高方法的时空产率,而且可以延长载体寿命,因而减少载体更换的频度。
Description
本发明涉及烯烃水合方法,该方法使用含有载于热酸处理过的粘土上的杂多酸催化剂的催化剂体系。
众所周知,使用沉积在硅质载体上的磷酸催化剂在汽相通过烯烃(如乙烯或丙烯)的水合转化为相应醇的方法。许多现有技术发表物都描述了这样的方法,包括以下专利申请所公开的:、GB-A-1570650,US-A-4808559,GB-A-1371905,US-A-4038211,US-A-4012452,GB-A-1476534,GB-A-1306141,US-A-3996338和CAN-A-844004。在这些公开发表物中均用各种参数对所用的硅质载体的性质进行限定,这些参数包括:孔体积、表面积、粉碎强度和载体的纯度。但是没有一篇发表物明确公开过为本发明目的的这类载体与一种杂多酸催化剂的组合。
有些现有技术发表物,如GB-A-1281120描述了使用杂多酸催化剂的烯烃水合液相法。又如US-A-2173187描述了使用杂多酸催化剂使烯烃水合而成相应醇的汽相法,此杂多酸的配位阴离子包括周期表中第VI族的A亚族中的一种元素。此文献写到:此催化剂可以在有或没有载体下使用。据说若使用载体最好是硅胶,但也列也其它硅质载体如硅酸、日本酸性粘土、膨润土、硅藻土或石棉。但是都没有公开过使用热酸处理过的粘土(此后称“HAT”粘土)作为杂多酸催化剂的载体。
现已发现,对以上所论及的方面,尤其是使用HAT粘土的仔细控制,可以改善杂多酸催化剂体系的功能。
据此,本发明是在催化剂体系存在下烯烃水合成相应醇的汽相方法,此催化剂体系包括载于一种粘土上的杂多酸催化剂,其特征在于粘土载体是经热酸处理过的粘土。
此方法适宜于在如下的反应条件下进行:
a.通过反应器的水对烯烃的摩尔比适宜范围在0.1~3.0,较好为0.1~1.0;
b.水/烯烃混合物的气体时空速度(GHSV)适宜为0.010~0.25克/分/厘米3催化剂体系,较好为0.03~0.10克/分/厘米3催化剂体系;
c.杂多酸催化剂的浓度是以催化剂体系的总重为基5-40%(重/重),较好为10-30%(重/重)。
本说明书所使用的术语“热酸处理过的粘土”(此后称HAT粘土)是指:或为分层粘土(layered clays)或为带支柱粘土(pillared clays),其中粘土不含额外的酸或其它阳离子,但是可以在一个或多个氧化物构成的多层之间有支柱(pillars),上述氧化物例如是氧化铝、氧化镓、氧化锆、氧化铁和氧化铬。
粘土特别是蒙脱石粘土是具有层状结构的铝硅酸盐,在加入极性介质如水、醇或胺时这种粘土会膨胀,这将造成层的分离。在极性介质中层是分开的,但一旦除去极性介质如干燥,膨胀结构就塌陷和收缩,返回与极性介质相接触之前的原来的尺寸大小。这种塌缩是由于使用一种能保持层的分离的所谓:“支柱”的技术加以阻止的。这种支柱的例子有:一种或多数种的铝、镓、硅或锆的氧化物,它们可以单独使用也可以与其它氧化物,如希土氧化物(尤其是氧化铈)联合使用。支柱通常是靠静电引力留在该处。例如二甲基胺丙基三甲氧基硅烷可用作氧化硅支柱的前体,此前体在水性酸条件下发生水解而得到配位氧化硅阳离子,它通过静电引力保留在粘土中,这样处理的粘土然后通常进行煅烧而产生带支柱粘土,这种支柱粘土在水热条件下是不稳定的。Figueras,F.在专著“Catalysis Review-Science &Enginering”Vol.30,No.3,457-499页(1988)中对于这种带支柱粘土、它的制法和作为催化剂的应用有过评述。
HAT粘土适宜的制备方法为用热酸连续地浸洗市售的膨润土型粘土,如蒙脱土或一种带支柱粘土,这样能使粘土中的阳离子如钠或钙离子被氢离子所置换,从而使粘土载体具有大于50米2/克的平均表面积。
这种类型粘土的例子包括K10粘土,它是用热酸处理标准的层状粘土(如膨润土)而得到的。这种方法除去了未处理粘土中存在的金属,所得到的粘土适宜地具有约150米2/克的表面积。此酸处理方法可破坏粘土的层状结构。热酸处理过的粘土(HAT粘土)适于制粒粘或挤压方法成型为粒状、珠状或球形。这种处理方法适宜地可按已发表的US-A-5,086,031所描述的方法进行(参见其实例),此处将此文献并入本发明作为参考。成型的HAT粘土适宜地具有2~10毫米的平均粒径,较好为4-6毫米。适宜地,HTA粘土的平均孔体积范围在0.3-1.2毫升/克,较好为0.6-1.0毫升/克。此载体的平均粉碎强度适宜地为至少2公斤力,较好为至少5公斤力,更好为至少6公斤力和最好为至少7公斤力。所列的粉碎强度是基于每批50个珠/球在CHATTILLON测试仪上测定的平均值,此仪器测量在平行板之间压碎一个粒子所必须的最小力。此载体的松密度(bulk density)适且地至少为380克/升,较好为至少440克/升。
HAT粘土载体(使用前)适宜地具有平均孔径为10-1000埃,较好为30-600埃。
为获得最佳性能,HAT粘土载体适宜地应不含有可能对体系的催化活性产生不良效果的外加金属或元素。因此,HTA粘土载体的纯度相对于铝硅酸盐含量来说适宜地至少为99%(重/重),即对体系的催化活性有不良影响的杂质含量应小于1%(重/重),较好小于0.60%(重/重)和最好小于0.30%(重/重)。
本说明书所用的术语“杂多酸”是指包括游离酸及它们的盐。用于制备本发明方法的烯烃水合催化剂的杂多酸因此包括游离酸和它们的配位型的盐,其中阴离子是高分子量的配位体。典型的阴离子含有2-18个氧链的多价金属原子,这些金属原子称之为外围原子,它们以对称方式围绕一个或几个中心原子。外围原子通常是一个或几个的钼、钨、钒、铌、钽和其它金属。中心原子通常是硅或磷,但也可能包括元素周期表中第I-VIII族中任一大类原子。例如这可以包括:锂离子;铜离子;二价的铍、锌、钴或镍离子;三价的硼、铝、镓、铁、铈、砷、锑、磷、铋、铬或铑离子;四价的硅、锗、锡、钛、锆、钒、硫、碲、镍、铂、钍、铪、铈离子和其它希土离子;五价的磷、砷、钒、锑离子;六价的碲离子;和七价的碘离子。这些杂多酸也称之为“多氧阴离子(polyoxoanions)”,“多氧金属酸盐(polyoxometalltes)”或“金属氧化物簇(metal oxide cluster)”。
一些众所周知的阴离子的结构是以本领域原研究者命名的,如称之为Keggin,Wells-Dawson和Anderson-Evans-Perloff结构。
杂多酸通常具有大分子量,如其范围在700-8500和包括双重配位(dimeric complexes)。在极性溶剂如水或其它含氧溶剂中杂多酸有较高溶解度,尤其是若它们是游离酸和在几种盐的情况下。另外,选择适且的反离子(counterions)也可以控制它们的溶解度。杂多酸用于本发明作为催化剂的具体例子有:
1-12-钨磷酸 - H3[PW12O40].xH2O
1-12-钼磷酸 - H3[PMo12O40].xH2O
1-12-钨硅酸 - H4[SiW12O40].xH2O
1-12-钼硅酸 - H4[SiMo12O40].xH2O
钨磷酸钾 - K6[P2W18O62].xH2O
钼磷酸钠 - Na3[PMo12O40].xH2O
钼磷酸铵 - (NH4)6[P2Mo18O62].xH2O
钨镍酸钠 - Na4[NiW6O24H6].xH2O
钼二钴酸铵 - (NH4)[Co2Mo10O36].xH2O
钨硅酸氢铯 - Cs3H[SiW12O40].xH2O
钼二钒磷酸钾 - K5[PMoV2O40].xH2O
钨硅酸氢铜 - CuH2[SiW12O40].xH2O
钨硅酸氢锂 - Li3H[SiW12O40].xH2O
浸渍的HAT粘土载体适宜地可以这样制备:将载体用杂多酸溶液浸渍。而此杂多酸溶液则是溶解杂多酸于例如醇或蒸馏水的溶剂中来制备的。将载体加到这样形成的杂多酸溶液中,浸泡几个小时,并不时搅拌。然后使用布氏漏斗过滤以除去过量的酸。也可以使用其它浸渍技术如初湿(incipient wetness)技术。
这样形成的湿催化剂放在烘箱中升温几个小时进行干燥,然后在保干器中冷却至室温。可以得到干燥催化剂的重量、所使用的HAT粘土载体的重量和在载体上的酸的重量,方法是从前者减去后者即可测得以克、升表示的催化剂负载量。这些催化剂(称重后)用作烯烃水合工艺。
应当指出,本文上述的和以某些具体化合物化学式表示的杂多酸和多价氧化态只适用于被浸渍在HAT粘土载体上之前,和特别是在进行烯烃水合方法之前的游离酸。另外,杂多酸的水合程度也可能影响催化剂的酸度,因而也影响到它的活性。因此浸渍操作和/或烯烃水合工艺条件都可能改变杂多酸中金属的氧化态和水合度,即在工业条件下实际的催化物质可能并不保持在用于浸渍载体的杂多酸中的金属的氧化态和水合度。当然正如可预期的这水合度与氧化态也可能和反应后使用过的催化剂不同。
载体杂多酸催化剂也可以进行改性,通过向其内加入磷酸或其它无机酸。
烯烃水合反应是在温度为150-350℃的范围内进行。在这个温度范围内,乙烯水合而成乙醇的温度为它的露点至350℃和较好在200-300℃;而丙烯水合而成异丙醇的温度则在它的露点至300℃和较好在150-250℃。
水合反应是在1000-25000Kpa的压力下进行。
进行水合的烯烃适宜地为乙烯或丙烯和所生成的相应的醇分别是乙醇和异丙醇。这些烯烃可以在纯态下使用也可以是烯烃的混合物,以生成相应的醇的混合物。因此来自例如炼厂(如流态化催化裂解工艺)和包括C2和C3的饱和或不饱和烃的混合物的混合烃进料也可以用于本发明目的。此方法在汽相进行,即无论烯烃和水都是在汽相通过催化剂体系,当然每一气相反应物有小部分溶于催化剂体系。据认为水合反应是在这样溶解的反应物之间发生。在反应期作为副产物的相应于烯烃的醚也生成。
水合反应是这样进行:将催化剂体系置入反应器中,密封反应器和然后加热催化剂体系至反应温度。视所需的最终产物而定,催化剂体系加热至170-300℃的温度。例如,最终产物是从乙烯而得的乙醇,催化剂体系适宜地加热到225-280℃的温度,较好的230-260℃,更好为235-245℃。另一方面,如果最终产物是从丙烯而得的异丙醇,则催化剂体系适宜地加热至180-225℃的温度,较好为185-205℃。当催化剂体系已达到所需温度时,汽相的烯烃和水的进料通过反应器。通过反应器的水对烯烃的摩尔比适宜地为0.1-3.0,较好为0.1-1.0和更好为0.25-0.45。通过反应器的水蒸汽/烯烃混合物的空速要根据反应物是乙烯或丙烯而加以微小调整。例如,在乙烯的情况下,它与水蒸汽混合物的空速适宜为0.010-0.100克/分/厘米3催化剂体系,较好为0.020-0.050克/分/厘米3催化剂体系。在丙烯与水混合物的情况下空速适宜为0.010-0.100克/分/厘米3催化剂体系,较好为0.02-0.07克/分/厘米3催化剂体系。
水合反应是在1000-25000Kpa的压力下进行。在此压力范围内,乙烯的水合适宜在3000-10000Kpa压力下进行,而丙烯的水合适宜在2000-7600Kpa压力下进行。
可以测量催化剂体系的活性,方法是监测在标准测试条件下(具体见下述实例)一小时周期内产生的醇、醚和未反应烯烃的总量。
可用气相色谱法测量产生的醇和醚,而未反应的烯烃则使用湿式正取代流量计量来计量。
因此,现已发现使用本文所述的具体的HAT粘土载体,不仅有可能提高方法的时空产率(以下称“STY”),而且也可以延长载体的寿命,从而减少载体在工厂中更换或取代的频度。
下面参考实例进一步阐述本发明。
实例1
一般程序和所用设备的描述
将有载体的催化剂(20毫升,下述)装入一微型反应器中。充入惰性气体氮(413毫升/分)加压至6800Kpa,和温度升至260℃(以每分钟升1℃的速度升温)。在实例中催化剂的用量下面将说明。当温度稳定在260℃时,在保持惰性气流(氮气)下通入水(速度为0.11毫升液体/分)。如此保持水/氮气流至少30分钟。然后停止氮气流和在气体时空速度(GHSV)约为1240/小时下通入乙烯。水对乙烯的摩尔比为0.3。监测催化剂活性(见表1的结果)。这结果是收集2-3小时的产物并进行气体和液体进料的气相色谱分析。在260℃和240℃对催化剂进行评估。
在本实例中,进行乙烯水合是使用载于加热酸浸洗过的蒙脱石粘土(称之为K10,ex Sud Chemie)上的硅钨酸。此载体的表面积为220-270米2/克,孔体积约为0.318毫升/克和松密度约为300-370。这载体的催化剂是这样制备的:将硅钨酸[H4SiW12O40](44.5克)溶于蒸馏水(28.1毫升)中。此溶液加到孔径为1.0-1.4毫米的K10粘土(28.1克,ex Sud Chemie)上。使此溶液浸渍粘土载体24小时并不时搅拌。过滤从浸渍过的载体中除去过量的酸。在120℃此载带HPA的粘土干燥过液。干燥后载体催化剂的质量为39.83克。
本实例的目的是在上面概述的标准条件下试验和然后观测降低施加温度的效果。水对乙烯的摩尔比定在0.33。使用的催化剂体积为20厘米3和使用的载体催化剂的质量为20.5克。所用载体催化剂的粒径为1.0-1.4毫米。GHSV是在标准温度和压力下计算的。所用的反应条件和取得的结果列于下面表1。
比较试验(不按本发明)
载体催化剂是这样制备的:将硅钨酸[H4SiW12O40·26H20](12.0克,ex BDH)溶解在蒸馏水(100毫升)中,此溶液注入在酸交换的蒙脱石粘土(LBB/1,500-1000μm,72.3克)上。通过旋转蒸发(133.3Pa,约95℃)除去过量的水,接着在120℃干燥过夜。在保干器内冷却催化剂和粉碎成0.2-2.0毫米的粒子。此载体催化剂按下述进行试验。
在比较实验中制备的此载体催化剂装入一微型反应器中,通入氮气(413毫升/分)使压力增至6800Kpa和以每分钟2℃的速度将温度升至反应温度(220-240℃)。当温度稳定时,保持氮气流下以0.11毫升液体/分的速度下导入水。保持水/氮气流至少30分钟。停止氮气流和在1240/小时的GHSV下通入乙烯。水/乙烯的摩尔比大约为0.3。收集2-3小时的产物和对气体和液体进料进行气相色谱分析来监测催化剂的活性(见下表1的结果)。
结果表明:载于没有用热酸处理过的粘土载体上的杂多酸催化剂在选择性和STY方面明显不如载于热酸处理过的粘土载体上的杂多酸催化剂。
表1
例号 | HOS | 温度(℃) | H2O∶C2H4摩尔比 | GHSVC2H4 | 克/升催化剂/小时 | 转化率%(摩尔) | C2选择性%(摩尔) | STY克/升催化剂/小时 | ||||
C2H4 | H2O | C2H4 | H2O | 乙醇 | 乙醚 | 乙醇 | 乙醚 | |||||
例 1 | 10 | 260 | 0.34 | 1114 | 1392 | 300 | 3.4 | 9.3 | 82 | 18 | 65 | 11 |
14 | 260 | 0.33 | 1148 | 1435 | 300 | 3.5 | 9.9 | 82 | 18 | 68 | 12 | |
20 | 260 | 0.30 | 1237 | 1546 | 300 | 2.9 | 8.8 | 86 | 14 | 63 | 8 | |
CT | 15 | 230 | 0.32 | 1163 | 1454 | 300 | 2 | 4 | 72 | 28 | 26 | 8 |
21 | 240 | 0.32 | 1170 | 1462 | 300 | 2 | 4 | 69 | 31 | 25 | 9 | |
24 | 250 | 0 37 | 1009 | 1262 | 300 | 2 | 5 | 72 | 28 | 33 | 10 |
CT-不按本发明的比较试验
Claims (20)
1.烯烃水合成相应醇的汽相方法,此方法是在含有载于粘土载体上的杂多酸催化剂存在下进行的,其特征在于所说的粘土载体是热酸处理过的粘土。
2.权利要求1的方法,其中所述方法是使用下述反应条件进行的:
a.通过反应器的水对烯烃摩尔比的范围是0.1-3.0,
b.水/烯烃混合物的气体时空速度(GHSV)为0.010-0.25克/分/厘米3催化剂体系;和
c.以催化剂体系的总重为基,杂多酸催化剂的浓度为5-40%)重/重)。
3.权利要求1的方法,其中热酸处理过的粘土是这样制备的,用热酸连续地浸洗市售的膨润土型粘土,使粘土中的阳离子被氢离子置换从而得到表面积大于50米2/克的粘土载体。
4.权利要求1的方法,其中粘土经制粒或挤压而成型为粒状或珠状或球形。
5.权利要求1的方法,其中热酸处理过的粘土具有2-10毫米的平均粒径;0.3-1.2毫升/克的平均孔体积;10-1000埃的平均孔径(使用前),至少为380克/升的松密度以及至少为2公斤力的粉碎强度。
6.权利要求1的方法,其中热酸处理过的粘土载体不含外加金属或元素,其纯度相对于载体的铝硅酸盐含量至少为99%(重/重)。
7.权利要求1的方法,其中所用的杂多酸催化剂选自游离的杂多酸和它们的配位盐,包括与一个阴离子配位的中心原子,其中阴离子
是一个高分子量的配位体,和包括围绕一中心原子或离子的2-18个氧链的多价金属的外围原子,中心原子或离子是来自周期表第I-VIII族的元素。
8.权利要求7的方法,其中多价金属外围原子是一个或多个的钼、钨、钒、铌和钽,和中心原子或离子是选自:锂离子;铜离子;二价的铍、锌、钴或镍离子;三价的硼、铝、镓、铁、铈、砷、锑、磷、铋、铬或铑离子;四价的硅、锗、锡、钛、锆、钒、硫、碲、锰、镍、铂、钍、铪、铈离子和其它希土离子;五价的磷、砷、钒、锑离子;六价的碲离子;和七价的碘离子。
9.权利要求1的方法,其中杂多酸催化剂选自下列化合物组成的组:
1-12-钨磷酸 - H3[PW12O40].xH2O
1-12-钼磷酸 - H3[PMo12O40].xH2O
1-12-钨硅酸 - H4[SiW12O40].xH2O
1-1 2-钼硅酸 - H4[SiMo12O40].xH2O
钨磷酸钾 - K6[P2W18O62].xH2O
钼磷酸钠 - Na3[PMo12O40].xH2O
钼磷酸铵 - (NH4)[P2Mo18O62].xH2O
钨镍酸钠 - Na4[NiW6O24H6].xH2O
钼二钴酸铵 - (NH4)[Co2Mo10O36].xH2O
钨硅酸氢铯 - Cs3H[SiW12O40].xH2O
钼二钒磷酸钾 - K5[PMoV2O40].xH2O
钨硅酸氢铜 - CuH2[SiW12O40].xH2O
钨硅酸氢锂 - Li3H[SiW12O40].xH2O 。
10.权利要求1的方法,其中烯烃水合反应所用的载体杂多酸催化剂可通过加入磷酸或其它无机酸而改性。
11.权利要求1的方法,其中水合反应是在压力范围1000-25000Kpa下进行。
12.权利要求1的方法,其中待水合的烯烃是纯烯烃或可得到相应醇的混合物的烯烃混合物。
13.权利要求12的方法,其中烯烃反应物的原料是来自炼厂的混合烃进料和包括C2和C3的饱和和不饱和的烃的混合物。
14.权利要求1的方法,其中烯烃水合反应是在温度150-350℃下进行的。
15.权利要求1的方法,其中乙烯水合成乙醇是在温度为自进料气的露点至350℃下进行的。
16.权利要求15的方法,其中所说水合反应是在200-300℃温度下进行的。
17.权利要求15或16的方法,其中乙烯与水蒸汽的混合物的空速是0.020-0.050克/分/厘米3催化剂体系。
18.权利要求1的方法,其中丙烯水合成异丙醇是在温度为自进料气的露点至300℃下进行的。
19.权利要求17的方法,其中水合反应是在150-250℃的温度下进行的。
20.权利要求18或19的方法,其中丙烯和水蒸汽的混合物的空速是0.020-0.070克/分/厘米3催化剂体系。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9423648A GB9423648D0 (en) | 1994-11-23 | 1994-11-23 | Olefin hydration process |
GB9423648.6 | 1994-11-23 |
Publications (1)
Publication Number | Publication Date |
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CN1128251A true CN1128251A (zh) | 1996-08-07 |
Family
ID=10764864
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Application Number | Title | Priority Date | Filing Date |
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CN95119690A Pending CN1128251A (zh) | 1994-11-23 | 1995-11-23 | 烯烃水合方法 |
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US (1) | US5629459A (zh) |
EP (1) | EP0713847A3 (zh) |
JP (1) | JPH08225473A (zh) |
KR (1) | KR960017601A (zh) |
CN (1) | CN1128251A (zh) |
CA (1) | CA2163415A1 (zh) |
GB (1) | GB9423648D0 (zh) |
MY (1) | MY131706A (zh) |
Families Citing this family (11)
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US6060419A (en) | 1998-01-05 | 2000-05-09 | Sunoco, Inc. (R&M) | Wells-Dawson type heteropolyacids, their preparation and use as oxidation catalysts |
US6043184A (en) * | 1998-01-05 | 2000-03-28 | Sunoco, Inc. (R&M) | Heteropoly acids supported on polyoxometallate salts and their preparation |
GB9806408D0 (en) * | 1998-03-25 | 1998-05-20 | Bp Chem Int Ltd | Olefin hydration process |
GB9809210D0 (en) * | 1998-04-29 | 1998-07-01 | Bp Chem Int Ltd | Olefin hydration process |
JP2002079088A (ja) * | 2000-09-07 | 2002-03-19 | Showa Denko Kk | 低級脂肪族カルボン酸エステル製造用触媒、該触媒の製造方法、及び該触媒を用いた低級脂肪族カルボン酸エステルの製造方法 |
JP2002079089A (ja) * | 2000-09-07 | 2002-03-19 | Showa Denko Kk | 低級脂肪族カルボン酸エステル製造用触媒、該触媒の製造方法、及び該触媒を用いた低級脂肪族カルボン酸エステルの製造方法 |
KR100515586B1 (ko) * | 2002-10-14 | 2005-09-16 | 주식회사 엘지화학 | 활성이 우수한 인산촉매를 이용한 이소프로필알코올의제조방법 |
US7514577B2 (en) * | 2006-05-31 | 2009-04-07 | Exxonmobil Chemical Patents Inc. | Pd- and Pt-substituted polyoxometalates and process for their preparation |
US7820868B2 (en) * | 2007-01-19 | 2010-10-26 | Exxonmobil Chemical Patents Inc. | Transition metal substituted polyoxometalates and process for their preparation |
US7645907B2 (en) * | 2007-03-23 | 2010-01-12 | Exxonmobil Chemical Patents Inc. | Transition metal substituted polyoxometalates and process for their preparation |
EP3875446A4 (en) | 2018-11-02 | 2022-08-03 | Showa Denko K.K. | ALCOHOL PRODUCTION METHOD AND ALCOHOL PRODUCTION CATALYST |
Family Cites Families (12)
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DE1069583B (de) * | 1959-11-26 | Süd-Chemie A.G., München 2 | Verfahren zur Herstellung von Katalysatoren aus Bentonit | |
US2173187A (en) * | 1937-02-25 | 1939-09-19 | Du Pont | Process for hydrating olefins |
GB981237A (en) * | 1961-02-21 | 1965-01-20 | Hibernia Chemie G M B H | Process for the production of a catalyst for the catalytic hydration of olefins intoalcohols |
DE1156772B (de) * | 1961-02-21 | 1963-11-07 | Bergwerksgesellschaft Hibernia | Verfahren zur Herstellung eines Katalysators fuer die Herstellung von Alkoholen durch katalytische Hydratation von Olefinen |
DE1193929B (de) * | 1962-12-17 | 1965-06-03 | Hibernia Chemie Ges Mit Beschr | Verfahren zur Herstellung von Alkoholen durch katalytische Hydratation von Olefinen |
JPS4936203B1 (zh) * | 1969-05-08 | 1974-09-28 | ||
JPS644815B2 (zh) * | 1979-12-22 | 1989-01-26 | Buriteitsushu Pitorooriamu Co Plc Za | |
JPS57130935A (en) * | 1981-02-09 | 1982-08-13 | Tokuyama Soda Co Ltd | Hydrating method of olefin |
US4542250A (en) * | 1982-01-09 | 1985-09-17 | The British Petroleum Company, P.L.C. | Use of stabilized pillared interlayered clays as catalyst in alkylation reactions |
JPS58181758A (ja) * | 1982-04-16 | 1983-10-24 | 岩尾磁器工業株式会社 | 多孔質セラミツクスの製造方法 |
GB8518026D0 (en) * | 1985-07-17 | 1985-08-21 | British Petroleum Co Plc | Chemical process |
GB9214688D0 (en) * | 1992-07-10 | 1992-08-19 | Bp Chem Int Ltd | Olfin hydration catalysts |
-
1994
- 1994-11-23 GB GB9423648A patent/GB9423648D0/en active Pending
-
1995
- 1995-11-09 EP EP95308013A patent/EP0713847A3/en not_active Withdrawn
- 1995-11-13 US US08/556,409 patent/US5629459A/en not_active Expired - Fee Related
- 1995-11-21 CA CA002163415A patent/CA2163415A1/en not_active Abandoned
- 1995-11-22 JP JP7328220A patent/JPH08225473A/ja active Pending
- 1995-11-23 MY MYPI95003595A patent/MY131706A/en unknown
- 1995-11-23 CN CN95119690A patent/CN1128251A/zh active Pending
- 1995-11-23 KR KR1019950043250A patent/KR960017601A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EP0713847A3 (en) | 1996-07-24 |
US5629459A (en) | 1997-05-13 |
GB9423648D0 (en) | 1995-01-11 |
KR960017601A (ko) | 1996-06-17 |
CA2163415A1 (en) | 1996-05-24 |
MY131706A (en) | 2007-08-30 |
JPH08225473A (ja) | 1996-09-03 |
EP0713847A2 (en) | 1996-05-29 |
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