JP5376804B2 - シリカ支持体、それから製造されるヘテロポリ酸触媒およびシリカ支持ヘテロポリ酸触媒を使用するエステル合成 - Google Patents
シリカ支持体、それから製造されるヘテロポリ酸触媒およびシリカ支持ヘテロポリ酸触媒を使用するエステル合成 Download PDFInfo
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- JP5376804B2 JP5376804B2 JP2007532944A JP2007532944A JP5376804B2 JP 5376804 B2 JP5376804 B2 JP 5376804B2 JP 2007532944 A JP2007532944 A JP 2007532944A JP 2007532944 A JP2007532944 A JP 2007532944A JP 5376804 B2 JP5376804 B2 JP 5376804B2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 78
- 239000003054 catalyst Substances 0.000 title claims description 61
- 239000011964 heteropoly acid Substances 0.000 title claims description 43
- 239000000377 silicon dioxide Substances 0.000 title claims description 28
- 150000002148 esters Chemical class 0.000 title claims description 17
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000008187 granular material Substances 0.000 claims description 24
- 239000000741 silica gel Substances 0.000 claims description 22
- 229910002027 silica gel Inorganic materials 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- 150000001336 alkenes Chemical class 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 11
- -1 ethylene, propylene Chemical group 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 239000012808 vapor phase Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 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 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 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 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001168730 Simo Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 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
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 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 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 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
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound 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 IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- ACTPFSYIGLFGLY-UHFFFAOYSA-N silicic acid;trioxotungsten;hydrate Chemical compound O.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 ACTPFSYIGLFGLY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
12−モリブド燐酸 − H3[PMo12O40].xH2O
12−タングスト珪酸 − H4[SiW12O40].xH2O
12−モリブド珪酸 − H4[SiMo12O40].xH2O
タングスト珪酸セシウム水素 − Cs3H[SiW12O40].xH2O
タングスト燐酸カリウム − K6[P2W18O62].xH2O
モリブド二燐酸アンモニウム − (NH4)6[P2Mo18O62].xH2O
Claims (30)
- 1−オレフィンをモノカルボン酸および水と蒸気相にてシリカゲル支持へテロポリ酸触媒の存在下に反応させることによるエステルの製造方法において、シリカゲル支持体は顆粒の形態であり、これら顆粒は100〜300℃の範囲の温度にて0.1〜200時間の範囲の時間にわたり水蒸気での処理にかけられ、このシリカゲル支持体の処理は、ヘテロポリ酸が支持体に適用される前または同時に行われることを特徴とするエステルの製造方法。
- 支持体顆粒の平均粒子直径が2〜10mmである請求項1に記載の方法。
- 支持体顆粒の平均粒子直径が2.5〜8mmである請求項2に記載の方法。
- シリカゲル顆粒が球状、チューブ状および/または円筒状である請求項1〜3のいずれか一項に記載の方法。
- 水蒸気での処理が130〜250℃の範囲の温度である請求項1〜4のいずれか一項に記載の方法。
- シリカ純度が少なくとも99%w/wである請求項1〜5のいずれか一項に記載の方法。
- 支持体顆粒が0.3〜1.8ml/gの範囲の気孔容積および少なくとも7ニュートン力の単一粒子平均破砕強度を有する請求項1〜6のいずれか一項に記載の方法。
- 気孔容積が0.6〜1.2ml/gの範囲である請求項7に記載の方法。
- 触媒を支持する前の支持体の平均気孔直径が10〜500Åである請求項1〜8のいずれか一項に記載の方法。
- 水蒸気での処理を0.1〜50bargの全圧力にて行う請求項1〜9のいずれか一項に記載の方法。
- モノカルボン酸がC1〜C4カルボン酸である請求項1〜10のいずれか一項に記載の方法。
- モノカルボン酸が酢酸である請求項11に記載の方法。
- 1−オレフィンがエチレン、プロピレンまたはその混合物である請求項1〜12のいずれか一項に記載の方法。
- ヘテロポリ酸がタングスト燐酸、タングスト珪酸、モリブド珪酸、モリブド燐酸およびその塩よりなる群から選択される少なくとも1種のへテロポリ酸である請求項1〜13のいずれか一項に記載の方法。
- 支持体に対し沈着/含浸されるヘテロポリ酸の量がヘテロポリ酸および支持体の全重量に対し10〜60重量%の範囲である請求項1〜14のいずれか一項に記載の方法。
- 水の量がオレフィンとモノカルボン酸と水との合計量に対し1〜15モル%の範囲である請求項1〜15のいずれか一項に記載の方法。
- オレフィンをモノカルボン酸に関しモル過剰で存在させる請求項1〜16のいずれか一項に記載の方法。
- ガス空時速度が毎時100〜5000の範囲である請求項1〜17のいずれか一項に記載の方法。
- 温度が150〜200℃の範囲である請求項1〜18のいずれか一項に記載の方法。
- 圧力が5〜20bargの範囲である請求項1〜19のいずれか一項に記載の方法。
- プロセスを固定床プロセスとして行う請求項1〜20のいずれか一項に記載の方法。
- 1−オレフィンを蒸気相にてモノカルボン酸および水と反応させることによりエステルを製造する際に使用するシリカゲル支持ヘテロポリ酸触媒の製造方法において、触媒は支持体上に少なくとも1種のヘテロポリ酸を含浸および/または沈着させることにより生成させ、前記支持体はシリカゲル顆粒を100〜300℃の範囲の温度にて水蒸気で0.1〜200時間の範囲の時間にわたり処理することにより作成されたことを特徴とするシリカゲル支持ヘテロポリ酸触媒の製造方法。
- 顆粒が球状、チューブ状および/または円筒状である請求項22に記載の方法。
- シリカゲル顆粒が2〜10mmの範囲の平均粒子直径を有する請求項22または23に記載の方法。
- 水蒸気での処理を130〜250℃の範囲の温度にて行う請求項22〜24のいずれか一項に記載の方法。
- 水蒸気での処理を0.1〜50bargの全圧力にて行う請求項22〜25のいずれか一項に記載の方法。
- 支持体が0.3〜1.8ml/gの気孔容積および少なくとも7ニュートン力の単一粒子破砕強度を有する請求項22〜26のいずれか一項に記載の方法。
- ヘテロポリ酸がタングスト燐酸、タングスト珪酸、モリブド珪酸、モリブド燐酸およびその塩よりなる群から選択される請求項22に記載の方法。
- 支持体上に沈着/含浸されるヘテロポリ酸の量が、ヘテロポリ酸および支持体の全重量に対し10〜60重量%の範囲である請求項28に記載の方法。
- 1−オレフィンをモノカルボン酸および水と蒸気相にて反応させることによるエステルの製造に際し使用するためのシリカゲル支持ヘテロポリ酸触媒において、触媒は請求項22〜29のいずれか一項に記載の方法により生成されることを特徴とするシリカゲル支持ヘテロポリ酸触媒。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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GB0421012A GB0421012D0 (en) | 2004-09-22 | 2004-09-22 | Ester synthesis |
GB0421012.6 | 2004-09-22 | ||
GB0428060A GB0428060D0 (en) | 2004-12-22 | 2004-12-22 | Ester synthesis |
GB0428060.8 | 2004-12-22 | ||
PCT/GB2005/003470 WO2006032843A1 (en) | 2004-09-22 | 2005-09-08 | Silica support, heteropolyacid catalyst produced therefrom and ester synthesis using the silica supported heteropolyacid catalyst |
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JP2008513534A JP2008513534A (ja) | 2008-05-01 |
JP2008513534A5 JP2008513534A5 (ja) | 2008-10-30 |
JP5376804B2 true JP5376804B2 (ja) | 2013-12-25 |
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US (1) | US7432393B2 (ja) |
EP (1) | EP1791637B1 (ja) |
JP (1) | JP5376804B2 (ja) |
KR (1) | KR20070057853A (ja) |
BR (1) | BRPI0515565A (ja) |
CA (1) | CA2580581C (ja) |
MX (1) | MX2007003347A (ja) |
RU (1) | RU2395487C2 (ja) |
WO (1) | WO2006032843A1 (ja) |
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US9199845B2 (en) | 2006-11-22 | 2015-12-01 | Bp Chemicals Limited | Process for producing alkenes oxygenates by using supported heteropolyacid catalysts |
MX2012009845A (es) * | 2010-02-24 | 2012-11-30 | Bp Plc | Procedimiento para preparar un alqueno. |
KR20130008536A (ko) * | 2010-02-24 | 2013-01-22 | 비피 피이. 엘. 시이. | 알켄 제조 방법 |
CN102060995B (zh) * | 2010-11-19 | 2012-06-06 | 中南大学 | 一种硅胶负载二硫代氨基甲酸盐重金属螯合树脂的制备方法 |
KR101583464B1 (ko) * | 2013-07-24 | 2016-01-12 | 한국에너지기술연구원 | 철-치환 혼종다종산이 함침된 메조포러스 셀 형태 흡착제, 그 제조방법 및 그를 이용한 이산화탄소 분리방법 |
JP6910252B2 (ja) | 2017-09-05 | 2021-07-28 | 昭和電工株式会社 | シリカ担体の製造方法 |
JP6986908B2 (ja) | 2017-09-05 | 2021-12-22 | 昭和電工株式会社 | 脂肪族カルボン酸エステルの製造方法 |
CN110302834B (zh) * | 2019-06-28 | 2022-07-01 | 苏州仕净科技股份有限公司 | 一种用于氮氧化物治理的催化剂制备方法及催化剂 |
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GB1371905A (en) * | 1971-07-27 | 1974-10-30 | Bp Chem Int Ltd | Olefin hydration catalyst and use thereof in alcohol production |
US4038211A (en) | 1973-12-17 | 1977-07-26 | National Distillers And Chemical Corporation | Olefin hydration catalyst |
US3969274A (en) * | 1974-03-14 | 1976-07-13 | National Distillers And Chemical Corporation | Fixed bed catalyst |
GB9809210D0 (en) * | 1998-04-29 | 1998-07-01 | Bp Chem Int Ltd | Olefin hydration process |
GB9902676D0 (en) * | 1999-02-06 | 1999-03-31 | Bp Chem Int Ltd | Silica supported catalysts |
AU6784701A (en) | 2000-06-27 | 2002-01-08 | Showa Denko Kabushiki Kaisha | Catalyst for use in producing lower aliphatic carboxylic acid ester, process forproducing the catalyst and process for producing lower aliphatic carboxylic aci d ester using the catalyst |
WO2002020158A2 (en) | 2000-09-07 | 2002-03-14 | Showa Denko K. K. | Catalyst for producing lower aliphatic carboxylic acid esters |
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 |
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- 2005-09-08 EP EP05782749.5A patent/EP1791637B1/en not_active Not-in-force
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WO2006032843A1 (en) | 2006-03-30 |
KR20070057853A (ko) | 2007-06-07 |
RU2395487C2 (ru) | 2010-07-27 |
CA2580581A1 (en) | 2006-03-30 |
CA2580581C (en) | 2012-10-30 |
EP1791637A1 (en) | 2007-06-06 |
BRPI0515565A (pt) | 2008-07-29 |
US7432393B2 (en) | 2008-10-07 |
EP1791637B1 (en) | 2017-03-01 |
US20080004466A1 (en) | 2008-01-03 |
JP2008513534A (ja) | 2008-05-01 |
MX2007003347A (es) | 2007-05-21 |
RU2007115155A (ru) | 2008-11-10 |
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