CN1150585A - 酯合成 - Google Patents
酯合成 Download PDFInfo
- Publication number
- CN1150585A CN1150585A CN96112172A CN96112172A CN1150585A CN 1150585 A CN1150585 A CN 1150585A CN 96112172 A CN96112172 A CN 96112172A CN 96112172 A CN96112172 A CN 96112172A CN 1150585 A CN1150585 A CN 1150585A
- Authority
- CN
- China
- Prior art keywords
- described method
- acid
- water
- carboxylic acid
- aforementioned
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title claims description 5
- 238000003786 synthesis reaction Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 150000001336 alkenes Chemical class 0.000 claims abstract description 33
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 29
- -1 aliphatic mono-carboxylic acid Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011541 reaction mixture Substances 0.000 claims abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 30
- 238000007600 charging Methods 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 230000032050 esterification Effects 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 239000011734 sodium 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
- 229910052721 tungsten Inorganic materials 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000002093 peripheral effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- 229910002012 Aerosil® Inorganic materials 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 241000908838 Parietaria mottle virus Species 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 2
- 241001168730 Simo Species 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- SQYYWZFCALQDLV-UHFFFAOYSA-I [NH4+].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[Mo+5] Chemical compound [NH4+].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[Mo+5] SQYYWZFCALQDLV-UHFFFAOYSA-I 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 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
- 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
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000006471 dimerization reaction Methods 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [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
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 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
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229940093916 potassium phosphate Drugs 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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 compound [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 Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 5
- 150000001735 carboxylic acids Chemical class 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 101150002998 LCAT gene Proteins 0.000 description 55
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 27
- 238000004458 analytical method Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 230000009466 transformation Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 235000016768 molybdenum Nutrition 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 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
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GDKWXCWTFCPDFQ-UHFFFAOYSA-N [Si].OP(O)(O)=O Chemical compound [Si].OP(O)(O)=O GDKWXCWTFCPDFQ-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
Landscapes
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Abstract
本发明涉及一种制备低级脂族酯的方法，所述方法包括在杂多酸催化剂存在下，低级烯烃与饱和低级脂族单羧酸在汽相中反应，其特征在于在反应中在反应混合物中加入以烯烃、脂族单羧酸和水的总量计，为1-10摩尔％的水，水的存在增加了所需酯的产率。反应混合物中也可以含有二醚，使副产物变得最少。本方法特别适于在水存在下由乙烯和乙酸生产乙酸乙酯。
Description
本发明涉及在酸催化剂存在下通过烯烃与低级羧酸反应合成酯的方法。
烯烃可以与低脂族羧酸反应形成相应的酯是公知的。在GB-A-1259390中描述了一种这样的方法，其中烯类不饱和化合物与含羧酸和含钼或钨的游离杂多酸的液体介质接触。该方法是均相法，其中杂多酸催化剂是非载带的。另一个制备酯的方法在JP-A-05294894中描述，其中低级脂肪酸被低级烯烃酯化，形成低级脂肪酸酯。在该文件中，酯化反应在由载于载体上的至少一种金属，例如Li，Cu，Mg或K的杂多酸盐组成的催化剂存在下进行。其中所用的杂多酸是磷钨酸，所述载体是二氧化硅。
现已发现，通过在反应混合物中共同加入水可以明显改进该方法的效果。
因此，本发明是一种制备低级脂族酯的方法，所述方法包括在杂多酸催化剂存在下，低级烯烃和饱和低级脂族单羧酸在汽相中反应，其特征在于，在反应过程中，在反应混合物中加入以烯烃，脂族单羧酸和水总量计为1-10mol％的水。
本发明的一个特征是水作为反应混合物的一个组分加入。令人惊奇的是，发现基于全部进料，水在反应混合物中的存在量为1-10摩尔％，优选1-7摩尔％，更优选1-5摩尔％，提高了催化剂的程定性，因而提高了本方法的效果。此外，水的存在还减小了对生成不想要的副产物，如齐聚物和其它未知物，包括二***和乙醇的选择性。
此外还发现在反应混合物中加入一定量的二醚如二***作为共同进料也能减少不想要的副产物的形成。二醚的共同加入量以包括烯烃、脂族羧酸、水和二***的反应混合物总量计为1-6摩尔％，优选为1-3摩尔％。该二醚共同进料可以是由反应物烯烃经反应生成的副产物二醚。当所用的是烯烃的混合物时，例如乙烯和丙烯的混合物，二醚也可以是不对称二醚。因此共同进料二醚可以是反应的副产物，该副产物被循环到反应混合物中。
这里和全文中所用术语“杂多酸”的意思包括游离酸。因此用于制备本发明酯化催化剂的杂多酸还包括游离酸和其配位型的盐，其中阴离子是高分子量本体配位体。特别是，该阴离子是联结着2-18个氧的多价金属原子，其称为***原子。这些***原子以对称方式包围着一个或多个中心原子。这些***原子通常是一个或多个钼、钨、钒、铌、钽和其它金属。中心原子通常是硅或磷，但可以包括元素周期表中I-VIII族的任何一个原子。这些原子包括，例如二价铜离子；二价铍、锌、钴或镍离子；三价硼，铝、镓、铁、铈、砷、锑、磷、铋、铬或铑离子；四价硅、锗、锡、钛、锆、钒、硫、碲、锰、镍、铂、钍、铪、铈离子和其它稀土离子；五价磷、砷、钒、锑离子；六价碲离子；和七价碘离子。这些杂多酸还叫作“多氧合阴离子(polyoxoanions)”、“多氧金属盐(polyoxometallates)”或“金属氧化物簇”。一些已知阴离子的结构用这一领域最早研究者命名，如Keggin结构、Wells-Dawson结构和Anderson-Evans-Perloff结构。
杂多酸通常是高分子量的，例如为700-8500，并且含有二聚配合物。它们在极性溶剂中如水或其它氧饱和的溶剂中有相对较高的溶解度特别是如果它们是游离酸和一些盐时，其溶解度可通过选择适当的抗衡离子控制。可用于本发明作催化剂的杂多酸的具体例子包括：
12-钨磷酸 H3[PW12O40]·XH2O
12-钼磷酸 H3[PMo12O40]·XH2O
12-钨硅酸 H4[SiW12O40]·XH2O
12-钼硅酸 H4[SiMo12O40]·XH2O
钨磷酸钾 K6[P2W18O62]·XH2O
钼磷酸钠 Na3[PMo12O40]·XH2O
钼二磷酸铵 (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
杂多酸催化剂无论以游离酸或其盐形式使用时适于载带，优选载于硅载体上。合适的硅载体为压出物或丸状。
所用的硅载体特别优选从无定形的、无孔合成二氧化硅特别是发烟二氧化硅如由火焰水解SiCl4得到的产物制得。这种硅载体的具体例子包括由AEROSIL200(both ex Degnssa)压丸制成的Support350。该压丸方法可通过美国专利US 5,086,031(见实施例)描述的方法完成，列为本文参考文献。该压丸或挤出方法不包括任何蒸汽处理步骤和载体的多孔结构是在无孔二氧化硅压丸或挤出步骤中形成的空隙。二氧化硅载体的合适形式为具有平均粒径2至10mm，优选4至6mm的小丸或颗粒或小球。合适的硅载体孔体积为0.3-1.2ml/g，优选0.6-1.0ml/g。载体应具有至少2kg力的抗碎强度，合适地为至少5kg力，优选6kg和更优选至少7kg。所引用的抗碎强度是在CHATTILLON测试器上每50颗粒/小珠测定的平均值，所述测试器是用来测定在平行板之间压碎小球所需的最小力。载体的堆积密度应至少为380g/l，优选至少为440g/l。
载体应具有平均孔半径(在使用前)为10至500，优选的平均孔半径为30至100。
为达到最好效果，硅载体最好不合对体系催化活性产生不利影响的外来金属元素。硅载体应至少有99％w/w的纯度，即杂质低于1％W/W，优选低于0.6％W/W，和更优选低于0.30％W/W。
其它丸状二氧化硅为Grace57和1371级二氧化硅。特别是，Grace二氧化硅No.1371具有平均堆积密度约0.39g/ml、平均孔体积约1.15ml/g和平均粒度约0.1-3.5mm。这些丸状物可直接使用或经压碎到平均粒度0.5-2mm并在用作杂多酸催化剂载体前过筛。
浸渍的载体的制备是将杂多酸，优选钨硅酸，溶解于如蒸馏水中，然后将载体加到形成的水溶液中。载体应在该酸溶液中浸数小时，定期进行手工搅拌，此后用Buchner漏斗过滤以除去过量的酸。
由此形成的湿催化剂应置于于烘箱中干燥数小时，此后让其在干燥器中冷却到室温。从干燥的催化剂重量，所用载体的重量和通过前者减去后者得出在载体上的酸的重量，可确定催化剂的装载量(g/l)。
另外，载体可用上述的湿润技术用催化剂浸渍并同时在旋转蒸发器中干燥。
该载体催化剂(以重量计)随后可以用于酯化方法。以杂多酸和载体的总重量计，用于酯化反应而沉积/浸渍在载体上的杂多酸的量为10-60wt％，优选30-50wt％。
在酯化反应中，适用的烯烃反应剂为乙烯、丙烯或其混合物。当使用烯烃混合物时，形成的产物不可避免的是酯混合物。所用的烯烃反应物可以是石油加工产品或含某些烃混合物的化学纯烯烃。
饱和低级脂族单羧酸反应物合适地为C1-C4羧酸，并优选乙酸。
相对于脂族单羧酸反应物，反应混合物最好含过量的烯烃反应物。因此在反应混合物中烯烃与低级羧酸的摩尔比为1∶1至15∶1，优选10∶1至14∶1。
反应在高于上述的反应器所含有的反应物酸、就地形成的任何醇、产物酯和水的露点条件下于汽相中进行。以烯烃、羧酸和水的总量计，水量为1-10mole％，合适地为1-7mole％，优选1-5mole％。露点是所给样品气体在空气中冷凝的温度。任何气体样品的露点取决于它的组成。载体杂多酸催化剂适于用于固定床，其可以是填料塔的形式。反应物烯烃和酸蒸汽适当地以GHSV为100-5000/小时，优选300-2000/小时通过催化剂。
酯化反应应在温度150-200℃、反应压力至少为400KPa下进行，压力优选500-3000KPa，其取决于烯烃与酸的摩尔比以及所用水的量。
如到反应混合物中的水应为蒸汽并能与方法中的酯和醇形成混合物。通过精馏回收反应产物。当酯生成时，不管是单一或酯混合物，其可以相对高的产率和纯度水解成相应的醇或醇混合物。通过使用该技术，从烯烃生产醇方法的效果比传统烯烃水合生产醇的方法有明显的改进。
本发明将参考以下实施例和对比试验被进一步说明。实施例
在所有实施例中，所采用的反应条件和得到的结果被列在表中。在这些表中，使用了以下的缩写：
HOS 操作时间
Bed(T/M/B) 床(顶部/中部/底部)
HAC 乙酸
C2H4 乙烯
H2O 水
EtAc 乙酸乙酯
EtoH 乙醇
DEE 二***
GHSV 气时空速
g/Lcat/h 每升催化剂每小时克
STP 标准温度和压力
STY 时空产率实施例1A.催化剂制备催化剂1：
二氧化硅颗粒(Grace1371级，530m2/g，堆积密度0.39g/ml，孔体积1.15ml/g，约1-3mm，70g，ex WR Grace)在溶于250ml蒸馏水中的硅钨酸[H4SiW12O40·26H2O](65.53g，ex Japan New Metals)溶液中浸渍24小时，并间歇地搅动，以便在二氧化硅载体上浸渍硅磷酸催化剂。在此期间，过量的催化剂溶液被滗析和滤出。生成的催化剂浸渍的载体于120℃在流动的氮气中干燥过夜。如此形成的载体催化剂在干燥器中冷却和再称重。形成的载体催化剂的杂多酸催化剂负载量为92g/L。催化剂2：
二氧化硅颗粒(Grace 57级，表面积510m2/g，堆积密度0.649g/ml，孔体积1.0267ml/g，约5-8mm，57.7g，ex WR Grace)在12-钨硅酸[H4SiW12O40·26H2O](ex Johnson Matthey，69.4g溶于200ml蒸馏水)溶液中浸渍24小时，间歇地搅拌，以使用催化剂浸渍载体。此后过量的硅钨酸催化剂溶液经滗析和过滤除去。形成的催化剂浸渍的载体于120℃和流动氮气下干燥过夜。由此形成的干燥的载体催化剂在干燥器中冷却并且杂多酸催化剂的负载量为190g/L。催化剂3：
重复以上制备催化剂2的方法，发现具有的杂多酸催化剂负载量为192g/L。B.催化剂的成形：
所有以上生产的催化剂经破碎和过筛以得到需要的粒径，以便装载在酯化反应器中。C.催化剂测试：
所用反应器为三段式Severn-Sciences反应器，用Hastelloy C-276制造，能承受达到300℃和15000KPa(150巴)压力的冰醋酸(长度650mm，外直径22mm，内直径16mm)。沿着反应器内壁有一温度计套管(外径5mm)和在两端有1.77cm外径的Swagelock VCR接头。在被控制和进入质量流量控制器前，乙烯和氮气从钢瓶中以1000KPa(10巴)放出并经Haskel增压压缩机压缩到5000-12000KPa(50-120巴)。液体进料***有一个保持在10KPa-80KPa(0.1-0.8巴)氮气层中的2dm3的储存罐。
在装入收集器前，用冷却夹套将产物气流冷凝成液体。大部分液体产物在室温收集。
预热区位于催化剂床的上游。预热区与催化剂床之间用玻璃毛塞分开。另外一个玻璃毛塞子用于催化剂床的下游以减小死体积和有助于使催化剂床保持在反应器中部。
反应是通进将反应器用氮气加压到1000KPa(10巴)开始的，建立起需要的流速(其与后面烯烃的进料速度相同)，然后在1小时内将反应器温度升至需要的操作条件(170℃或180℃)。以所需的流速打开用于乙酸/水混合物的液体泵，通常2-3小时后，烯烃从收集罐以液流射入反应器。调整流量到需要的进料摩尔比和GHSV。以一定的间隔收集反应器流出物。液体产物被排放出来，称重然后用GC分析。气流在液体收集点的下游取样并用GC分析。在测验期间所有出来的气体用湿气计测量。
以上的方法/催化剂用来用乙酸酯化乙烯。所用催化剂1-3的相对量，和其进行酯化反应的床的大小和长度如下：
*催化剂1的参数用于表2操作
| 参数 | 催化剂1 | 催化剂2 | 催化剂3 |
| 体积(cm3) | 25 | 25 | 25 |
| 重量(g) | 11.3(11.4*) | 12 | 12 |
| 粒度(mm) | 1-2(0.5-1*) | 0.5-1 | 0.5-1 |
| 床长度 | 8.75(14*) | 14 | 14 |
表1操作条件：(在进料中加水，1摩尔％)使用催化剂1
*在该对比试验中不加水(不根据本发明)产品分析(表1续)
*不使用水，这是一个对比试验。(不根据本发明)
| 参数 | 操作1 | 操作2 | 操作3* |
| HOS | 17-20 | 42-45 | 70-73(21-24) |
| 温度(℃)使用的床(T/M/B) | 170173/-/170 | 170172.5/-169.5 | 170170/-168 |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(@STP) | 980 | 980 | 974 |
| C2H4 GHSV/h | 905 | 905 | 905 |
| HAC GHSV/h | 66 | 66 | 69 |
| H2O GHSV/h | 9 | 9 | 9 |
| C2H4(g/Lcat/h) | 1131 | 1131 | 1131 |
| HAC(g/Lcat/h) | 177 | 177 | 185 |
| H2O(g/Lcat/h) | 8 | 8 | 0 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2O mole％比 | 92.3/6.7/1.0 | 92.3/6.7/1.0 | 92.9/7.2/0 |
| C2H4/HAC/H2O wt％比 | 85.9/13.5/0.6 | 85.9/13.5/0.6 | 85.9/14.1/0 |
| C2H4/HAC摩尔比 | 13.7 | 13.7 | 13.1 |
| 产品/分析 | 操作1 | 操作2 | 操作3* |
| HAC转化率 | 66 | 64 | 27 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 97.30.41.80.00.30.1 | 97.80.31.30.00.60.04 | 91.60.10.00.01.46.8 |
| EtAc产率 | 95 | 59 | 25 |
| EtAc STY(g/Lcat/h) | 180 | 160 | 44 |
| 碳平衡(mol％) | 104 | 105 | 100 |
| 氧平衡(mol％) | 95 | 102 | 81 |
| 质量平衡 | 103 | 105 | 99 |
| 回收水(％) | 69 | 73 | - |
表2操作条件：(在进料中加水，1摩尔％)使用催化剂上
产品分析(表2续)
| 参数 | 操作4 | 操作5 | 操作6 | 操作7 |
| HOS | 19-22 | 44-77 | 68.75-71.75 | 91-94 |
| 温度(℃)使用的床(T/M/B) | 180181.5/186/182.5 | 170181.5/185/183 | 170181.3/184.5/181.2 | 170181.4/184/181.1 |
| 压力(KPa) | 1000 | 1000 | 1000 | 1000 |
| 总进料GHSV/h(αSTP) | 980 | 980 | 990 | 980 |
| C2H4 GHSV/h | 905 | 905 | 905 | 905 |
| HAC GHSV/h | 66 | 66 | 69 | 66 |
| H2O GHSV/h | 9 | 9 | 9 | 9 |
| C2H4(g/Lcat/h) | 1131 | 1131 | 1131 | 1131 |
| HAC(g/Lcat/h) | 177 | 177 | 177 | 177 |
| H2O(g/Lcat/h) | 8 | 8 | 8 | 8 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 | 4 |
| C2H4/HAC/H2O摩尔％比 | 92.3/6.7/1.0 | 92.3/6.7/1.0 | 92.3/6.7/1.0 | 92.3/6.7/1.0 |
| C2H4/HAC/H2O wt％比 | 86/13.40/0.6 | 86/13.4/0.6 | 86/13.4/0.6 | 86/13.4/0.6 |
| C2H4/HAC摩尔比 | 13.7 | 13.7 | 13.7 | 13.7 |
| 产品/分析 | 操作4 | 操作5 | 操作6 | 操作7 |
| 乙烯转化率(％) | 5.3 | 3.9 | 4.1 | 6.0 |
| HAC(转化率) | 71 | 64 | 60 | 54 |
| 产物选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 95.90.72.30.00.80.3 | 97.20.61.80.00.30.1 | 97.80.51.30.00.30.0 | 98.10.61.00.00.20.0 |
| EtAc产率 | 68 | 63 | 59 | 53 |
| EtAc STY(g/Lcat/h) | 194 | 183 | 164 | 148 |
| 碳平衡(mol％) | 100 | 199 | 100 | 97 |
| 氧平衡(mol％) | 93 | 89 | 93 | 88 |
| 质量平衡 | 100 | 99 | 99 | 96 |
| 回收水(％) | 53 | 56 | 62 | 65 |
表3操作条件：(在进料中加水，1摩尔％)使用催化剂2
产品分析(表3续)
| 参数 | 操作8 | 操作9 | 操作10 |
| HOS | 179.5/189/182.8 | 38.5-41.5 | 62.5-65.5 |
| 温度(℃)使用的床(T/M/B) | 18017.5/189/182.8 | 170179.6/187.5/182.9 | 170179.4/186.5/182.8 |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(αSTP) | 981 | 981 | 981 |
| C2H4 GHSV/h | 905 | 905 | 905 |
| HAC GHSV/h | 66 | 66 | 66 |
| H2O GHSV/h | 10 | 10 | 10 |
| C2H4(g/Lcat/h) | 1131 | 1131 | 1131 |
| HAC(g/Lcat/h) | 177 | 177 | 177 |
| H2O(g/Lcat/h) | 8 | 8 | 8 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2O mole％比 | 92.3/6.7/1.0 | 92.3/6.7/1.0 | 92.3/6.7/1.0 |
| C2H4/HAC/H2O wt％比 | 85.9/13.5/0.6 | 85.9/13.5/0.6 | 85.9/13.5/0.6 |
| C2H4/HAC摩尔比 | 13.7 | 13.7 | 13.7 |
| 产品/分析 | 操作8 | 操作9 | 操作10 |
| 乙烯转化率 | 7.3 | 3.9 | 3.3 |
| HAC转化率 | 81 | 77 | 75 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 92.70.83.80.01.61.1 | 95.20.72.80.00.90.5 | 96.00.72.20.00.80.3 |
| EtAc产率 | 75 | 73 | 72 |
| EtAc STY(g/Lcat/h) | 213 | 211 | 201 |
| 碳平衡(mol％) | 100 | 102 | 103 |
| 氧平衡(mol％) | 99 | 96 | 98 |
| 质量平衡 | 100 | 102 | 103 |
| 回收水(％) | 45 | 43 | 51 |
表4操作条件：(在进料中加水，5摩尔％)使用催化剂2
产品分析(表4续)
| 参数 | 操作11 | 操作12 | 操作13 |
| HOS | 90.5-95.5 | 134.5-137.5 | 158.5-161.5 |
| 温度(℃)使用的床(T/M/B) | 180179.3/188.5/182.4 | 180179.6/188.5/183.4 | 180179.5/188.5/183.4 |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(@STP) | 975 | 975 | 975 |
| C2H4GHSV/h | 866 | 866 | 866 |
| HAC GHSV/h | 61 | 61 | 61 |
| H2O GHSV/h | 48 | 48 | 48 |
| C2H4(g/Lcat/h) | 1083 | 1083 | 1083 |
| HAC(g/Lcat/h) | 164 | 164 | 164 |
| H2O(g/Lcat/h) | 38 | 38 | 38 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2O mole％ | 88.8/6.3/4.9 | 88.8/6.3/4.9 | 88.8/6.3/4.9 |
| C2H4/HAC/H2O wt％比 | 84.2/12.8/3 | 84.2/12.8/3 | 84.2/12.8/3 |
| C2H4/HAC摩尔比 | 14.2 | 14.2 | 14.2 |
| 产品/分析 | 操作11 | 操作12 | 操作13 |
| 乙烯转化率 | 4.4 | 4.0 | 4.3 |
| HAC转化率 | 68 | 72 | 72 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 85.23.710.50.00.60.01 | 82.93.713.00.00.40.02 | 82.03.913.60.00.50.07 |
| EtAc产率 | 58 | 60 | 59 |
| EtAc STY(g/Lcat/h) | 203 | 215 | 210 |
| 碳平衡(mol％) | 102 | 103 | 103 |
| 氧平衡(mol％) | 87 | 87 | 89 |
| 质量平衡 | 101 | 102 | 102 |
| 回收水(％) | 43 | 39 | 42 |
表5操作条件：(在进料中加水，5摩尔％)使用催化剂3
| 参数 | 操作14 | 操作15 | 操作16 |
| HOS | 16-19 | 40-43 | 112.5-115.5 |
| 温度(℃)使用的床(T/M/B) | 180179.1/191/183.2 | 180179.1/190.5/183.5 | 180179.2/190/183.8 |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(@STP) | 980 | 980 | 980 |
| C2H4 GHSV/h | 866 | 866 | 866 |
| HAC GHSV/h | 64 | 64 | 64 |
| H2O GHSV/h | 50 | 50 | 50 |
| C2H4(g/Lcat/h) | 1083 | 1083 | 1083 |
| HAC(g/Lcat/h) | 170 | 170 | 170 |
| H2O(g/Lcat/h) | 40 | 40 | 40 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2Omole％ | 88.4/6.5/5.1 | 88.4/6.5/5.1 | 92.3/6.7/1.0 |
| C2H4/HAC/H2O wt％比 | 83.7/13.2/3.1 | 83.7/13.2/3.1 | 86/13.4/0.6 |
| C2H4/HAC摩尔比 | 13.6 | 13.6 | 13.6 |
产品分析(表5续)
| 产品/分析 | 操作14 | 操作15 | 操作16 |
| 乙烯转化率 | 6.6 | 7.6 | 6.3 |
| HAC转化率 | 86 | 85 | 83 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 73.43.722.00.00.60.2 | 74.03.721.50.00.70.1 | 73.23.522.90.00.50.0 |
| EtAc产率 | 63 | 63 | 60 |
| EtAc STY(g/Lcat/h) | 219 | 221 | 224 |
| 碳平衡(mol％) | 106 | 104 | 105 |
| 氧平衡(mol％) | 103 | 101 | 95 |
| 质量平衡 | 105 | 104 | 104 |
| 回收水(％) | 40 | 40 | 36 |
表6操作条件：(在进料中加水，5摩尔％)使用催化剂
| 参数 | 操作17 | 操作18 | 操作19 |
| HOS | 160.5-163.5 | 208.5-211.5 | 285.5-288.5 |
| 温度(℃)使用的床(T/M/B) | 180179.2/190/184.1 | 180179.3/190/184.3 | 180179.3/190/184.2 |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(αSTP) | 980 | 980 | 980 |
| C2H4 GHSV/h | 866 | 866 | 866 |
| HAC GHSV/h | 64 | 64 | 64 |
| H2O GHSV/h | 50 | 50 | 50 |
| C2H4(g/Lcat/h) | 1083 | 1083 | 1083 |
| HAC(g/Lcat/h) | 170 | 170 | 170 |
| H2O(g/Lcat/h) | 40 | 40 | 40 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2O摩尔％比 | 88.4/6.5/5.1 | 88.4/6.5/5.1 | 88.4/6.5/5.1 |
| C2H4/HAC/H2O wt％比 | 83.7/13.2/3.1 | 83.7/13.2/3.1 | 83.7/13.2/3.1 |
| C2H4/HAC摩尔比 | 13.6 | 13.6 | 13.6 |
产品分析(表6续)
| 产品/分析 | 操作17 | 操作18 | 操作19 |
| 乙烯转化率 | 8.8 | 8.7 | 8.4 |
| HAC转化率 | 85 | 86 | 88 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 73.23.622.60.00.50.1 | 73.03.922.60.00.50.1 | 73.73.722.10.00.50.1 |
| EtAc产率 | 62 | 63 | 65 |
| EtAc STY(g/Lcat/h) | 217 | 217 | 225 |
| 碳平衡(mol％) | 104 | 104 | 105 |
| 氧平衡(mol％) | 103 | 103 | 103 |
| 质量平衡 | 103 | 104 | 104 |
| 回收水(％) | 40 | 41 | 38 |
表7操作条件：(在进料加水5摩尔％)使用催化剂3
*另外共进料2摩尔％DEE§-在操作中不使用二乙基醚
| 参数 | 操作20 | 操作21* | 操作22* |
| HOS | 375.5-378.5 | 448.5-451.5 | 472.5-475.5 |
| 温度(℃)使用的床(T/M/B) | 180179.3/190/184.4 | 180179.3/186.5/183.4 | 180179.3/186.5/183.4 |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(αSTP) | 980 | 980 | 980 |
| C2H4GHSV/h | 866 | 866 | 866 |
| HAC GHSV/h | 64 | 64 | 64 |
| H2O GHSV/h | 50 | 50 | 50 |
| DEEGHSV/h | 0 | 0 | 0 |
| C2H4(g/Lcat/h) | 1083 | 1083 | 1083 |
| HAC(g/Lcat/h) | 170 | 170 | 170 |
| H2O(g/Lcat/h) | 40 | 40 | 40 |
| DEE(g/Lcat/h) | 0 | 71 | 71 |
| 进料接触时间[1/GHSV](秒) | 3.7 | 3.6 | 3.6 |
| C2H4/HAC/H2O mole％比 | 88.4/6.5/5.1§ | 86.5/6.4/5/2.1 | 86.5/6.4/2.1 |
| C2H4/HAC/H2O wt％比 | 83.7/13.2/3.1§ | 79.4/12.5/2.9/5.2 | 79.4/12.5/2.9/5.2 |
| C2H4/HAC摩尔比 | 13.6 | 13.6 | 13.6 |
产品分析(表7续)
| 产品/分析 | 操作20 | 操作21 | 操作22 |
| 乙烯转化率 | 8.7 | 2.7 | 2.4 |
| HAC转化率 | 85 | 81 | 80 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 74.13.621.60.00.50.1 | 71.95.022.90.00.20.0 | 70.85.423.30.00.50.0 |
| EtAc产率 | 63 | 59 | 57 |
| EtAc STY(g/Lcat/h) | 226 | 226 | 222 |
| 碳平衡(mol％) | 103 | 105 | 105 |
| 氧平衡(mol％) | 98 | 101 | 98 |
| 质量平衡 | 102 | 105 | 104 |
| 回收水(％) | 38 | 60 | 63 |
表8操作条件：(在进料中加5摩尔％水和2摩尔％DEE)使用催化剂3
| 参数 | 操作23 | 操作24 |
| HOS | 479.5-500.5 | 544.5-547.5 |
| 温度(℃)使用的床(T/M/B) | 180179.3/186.5/183.4 | 180179.4/187/183.4 |
| 压力(KPa) | 1000 | 1000 |
| 总进料GHSV/h(αSTP) | 1001 | 1001 |
| C2H4 GHSV/h | 866 | 866 |
| HAC GHSV/h | 64 | 64 |
| H2O GHSV/h | 50 | 50 |
| DEEGHSV/h | 21 | 21 |
| C2H4(g/Lcat/h) | 1083 | 1083 |
| HAC(g/Lcat/h) | 170 | 170 |
| H2O(g/Lcat/h) | 40 | 40 |
| DEE(g/Lcat/h) | 71 | 71 |
| 进料接触时间[1/GHSV](秒) | 3.6 | 3.6 |
| C2H4/HAC/H2O摩尔％比 | 86.5/6.4/5/2.1 | 86.5/6.4/5/2.1 |
| C2H4/HAC/H2O wt％比 | 79.4/12/5/2.9/5.2 | 79.4/12.5/2.9/5.2 |
| C2H4/HAC摩尔比 | 13.6 | 13.6 |
产品分析(表8续)
| 产品/分析 | 操作23 | 操作24 |
| 乙烯转化率 | 1.4 | 1.3 |
| HACC转化率 | 84 | 82 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 70.65.123.90.00.30.0 | 71.15.223.50.00.30.0 |
| EtAc产率 | 59 | 58 |
| EtAc STY(g/Lcat/h) | 226 | 224 |
| 碳平衡(mol％) | 107 | 106 |
| 氧平衡(mol％) | 103 | 99 |
| 质量平衡 | 106 | 105 |
| 回收水(％) | 61 | 63 |
表9
实施例2：催化剂制备：催化剂4：
| 液体产物数据GCMS180℃，1000KPa(10barg)，乙烯/乙酸＝14 | |||
| 有机物(wt％) | 操作号 | ||
| 7 17 23 | |||
| 水(进料中，摩尔％) | 1 | 5 | 5(+2％DEE) |
| 乙酸(未反应原料)乙酸乙酯二乙基醚乙醇乙醛C6齐聚物C8齐聚物杂氧化物芳烃未知物 | 52.346.50.050.650.0020.00150.00550.00650.0450.11 | 21.267.337.80.0400000.01 | 16.3693.3110.00900000 |
| 平衡：其它(烃及含氧化合物) | |||
将12-钨磷酸[H3PW12O40·24H2O](175g)溶于蒸馏水(250ml)中。将硝酸锂[LiNO3·2H2O](0.652g)溶于蒸馏水(～5ml)中。将硝酸锂溶液滴加到铝磷酸溶液中形成溶液“A”。
将溶液“A”加入丸状二氧化硅载体(Grace1371级，1-3mm，99.5g，exWR(Grace)中并让其浸渍24小时，不时地搅拌，以使二氧化硅浸渍钨磷酸催化剂。此后，滗析和过滤掉过量的溶液“A”。得到的催化剂浸渍的载体在流动的氮气中首先于150℃干燥3小时然后上升至200℃并于此温度下进行5小时干燥。由此得到的载体催化剂在干燥器中冷却并再称重。得到的载体催化剂最终重量为164.4g，净催化剂负载量为64.9g，化学式为Li0.1H2.9PW12O40·24H2O/SiO2，相应的负载量为255g/L。催化剂5
丸状二氧化硅载体(Grace1371级，1-3mm，70g，ex WR Grace)浸渍在12-钨硅酸[H4SiW12O40·26H2O](65.53g溶于蒸馏水)溶液中24小时，间歇地搅拌，以使载体浸渍催化剂。此后通过滗析和过滤除去过量的钨硅酸溶液。得到的催化剂浸渍的载体在流动的氮气流中于120℃干燥过夜。经干燥的由此得到的载体催化剂在干燥器中冷却，具有的最终重量为86.2g，净催化剂负载量16.2g，化学式为H4SiW12O40·26H2O/SiO2，相应的负载量为92g/l。
以上催化剂用于用乙酸酯化乙烯。每种催化剂相对的使用量，进行酯化反应的催化床的大小和长度如下：
| 参数 | 催化剂4 | 催化剂5 |
| 体积(cm3) | 25 | 25 |
| 重量(g) | 15.5 | 11.2-11.4 |
| 粒度(mm) | 1-2 | 1-2(表11)&0.5-1(表12，13和14) |
| 床长度 | 8.5 | 8.75 |
表10(催化剂4-15.5g)操作条件：
| 参数 | 操作25 | 操作26 | 操作27 |
| HOS | 1-3 | 19-21 | 25-27 |
| 温度(℃)使用的床(T/M/B) | 170173.5/170.5 | 170172/-/169 | 170172/-/169 |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(αSTP) | 979 | 979 | 979 |
| C2H4 GHSV/h | 905 | 905 | 905 |
| HAC GHSV/h | 65 | 65 | 65 |
| H2O GHSV/h | 9 | 9 | 9 |
| C2H4(g/Lcat/h) | 1131 | 1131 | 1131 |
| HAC(g/Lcat/h) | 173 | 173 | 173 |
| H2O(g/Lcat/h) | 8 | 8 | 8 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2O摩尔％比 | 92.4/6.6/1.0 | 92.4/6.6/1.0 | 92.4/6.6/1.0 |
| C2H4/HAC/H2O wt％比 | 86.2/13.2/0.6 | 86.2/13.2/0.6 | 86.2/13.2/0.6 |
| C2H4/HAC摩尔比 | 14.0 | 14.0 | 14.0 |
产品分析(表10续)
| 产品/分析 | 操作25 | 操作26 | 操作27 |
| HOS | 51 | 47 | 45 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 89.70.50.90.07.01.90 | 98.00.50.70.00.40.49 | 97.70.41.00.00.70.26 |
| EtAc产率 | 45 | 46 | 44 |
| EtAc STY(g/Lcat/h) | 128 | 122 | 118 |
| 碳平衡(mol％) | 102 | 102 | 105 |
| 氧平衡(mol％) | 86 | 89 | 100 |
| 质量平衡 | 101 | 101 | 104 |
| 回收水(％) | 90 | 70 | 81 |
表11(催化剂5-13.3g)操作条件：
| 参数 | 操作28 | 操作29 | 操作30 |
| HOS | 1-2 | 17-20 | 21-24 |
| 温度(℃)使用的床(T/M/B) | 170176/174 | 170173/-/170 | 170173/-/170 |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(αSTP) | 980 | 980 | 980 |
| C2H4 GHSV/h | 905 | 905 | 905 |
| HAC GHSV/h | 66 | 66 | 66 |
| H2O GHSV/h | 9 | 9 | 9 |
| C2H4(g/Lcat/h) | 1131 | 1131 | 1131 |
| HAC(g/Lcat/h) | 177 | 177 | 177 |
| H2O(g/Lcat/h) | 8 | 8 | 8 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2O摩尔％比 | 92.3/6.7/1.0 | 92.3/6.7/1.0 | 92.4/6.6/1.0 |
| C2H4/HAC/H2Owt％比 | 85.9/13.5/0.6 | 85.9/13.5/0.6 | 86.2/13.2/0.6 |
| C2H4/HAC摩尔比 | 13.7 | 13.7 | 13.7 |
产品分析(表11续)
| 产品/分析 | 操作28 | 操作29 | 操作30 |
| HAC转化率 | 62 | 66 | 64 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 86.02.43.30.02.45.9 | 97.30.41.80.00.30.1 | 97.60.41.40.00.60.1 |
| EtAc产率 | 53 | 65 | 62 |
| EtAc STY(g/Lcat/h) | 151 | 180 | 171 |
| 碳平衡(mol％) | 101 | 104 | 105 |
| 氧平衡(mol％) | 98 | 95 | 99 |
| 质量平衡 | 101 | 103 | 105 |
| 回收水(％) | 70 | 69 | 67 |
表12(催化剂5-11.2g)操作条件：
| 参数 | 操作31 | 操作32 | 操作33 |
| HOS | 19.25-22.5 | 23-26 | 43.25-45.25 |
| 温度(℃)使用的床(T/M/B) | 170172.5/176/- | 170172.5/175.5/- | 180182/187/- |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(@STP) | 980 | 980 | 980 |
| C2H4 GHSV/h | 905 | 905 | 905 |
| HAC GHSV/h | 66 | 66 | 66 |
| H2O GHSV/h | 9 | 9 | 9 |
| C2H4(g/Lcat/h) | 1131 | 1131 | 1131 |
| HAC(g/Lcat/h) | 177 | 177 | 177 |
| H2O(g/Lcat/h) | 8 | 8 | 8 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2O摩尔％比 | 92.3/6.7/1.0 | 92.3/6.7/1.0 | 92.3/6.7/1.0 |
| C2H4/HAC/H2O wt％比 | 86/13.4/0.6 | 86/13.4/0.6 | 86/13.4/0.6 |
| C2H4/HAC摩尔比 | 13.7 | 13.7 | 13.7 |
产品分析(表12续)
| 产品/分析 | 操作31 | 操作32 | 操作33 |
| HAC转化率 | 72 | 72 | 82 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 96.00.52.90.00.40.2 | 94.40.52.70.01.60.7 | 94.90.73.30.00.70.3 |
| EtAc产率 | 69 | 68 | 78 |
| EtAc STY(g/Lcat/h) | 203 | 194 | 210 |
| 碳平衡(mol％) | 101 | 103 | 108 |
| 氧平衡(mol％) | 91 | 97 | 104 |
| 质量平衡 | 100 | 103 | 108 |
| 回收水(％) | 47 | 48 | 48 |
表13(催化剂5-11.2g)操作条件：
| 参数 | 操作34 | 操作35 | 操作36 |
| HOS | 47-50 | 67.25-70.25 | 71-74 |
| 温度(℃)使用的床(T/M/B) | 180181.5/186.5/- | 190191.5/196/- | 190191.5/195.5/- |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(αSTP) | 980 | 980 | 980 |
| C2H4 GHSV/h | 905 | 905 | 905 |
| HAC GHSV/h | 66 | 66 | 66 |
| H2O GHSV/h | 9 | 9 | 9 |
| C2H4(g/Lcat/h) | 1131 | 1131 | 1131 |
| HAC(g/Lcat/h) | 177 | 177 | 177 |
| H2O(g/Lcat/h) | 8 | 8 | 8 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2O摩尔％比 | 92.3/6.7/1.0 | 92.3/6.7/1.0 | 92.3/6.7/1.0 |
| C2H4/HAC/H2Owt％比 | 86/13.4/0.6 | 86/13.4/0.6 | 86/13.4/0.6 |
| C2H4/HAC摩尔比 | 13.7 | 13.7 | 13.7 |
产品分析(表13续)
| 产品/分析 | 操作34 | 操作35 | 操作36 |
| HAC转化率 | 79 | 74 | 72 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 95.20.73.20.00.60.2 | 94.70.72.80.01.60.3 | 94.90.72.20.01.30.8 |
| EtAc产率 | 75 | 70 | 68 |
| EtAc STY(g/Lcat/h) | 206 | 202 | 191 |
| 碳平衡(mol％) | 105 | 102 | 104 |
| 氧平衡(mol％) | 102 | 94 | 99 |
| 质量平衡 | 105 | 102 | 104 |
| 回收水(％) | 47 | 52 | 54 |
表14(催化剂5-11.4g)操作条件：
| 参数 | 操作号37 | 操作号38 | 操作号39 |
| HOS | 19-22 | 44-47 | 68.75-71.75 |
| 温度(℃)使用的床(T/M/B) | 180181.5/186/182.5 | 180181.5/185/182 | 180181.3/184.5/181.2 |
| 压力(KPa) | 1000 | 1000 | 1000 |
| 总进料GHSV/h(@STP) | 980 | 980 | 980 |
| C2H4 GHSV/h | 905 | 905 | 905 |
| HAC GHSV/h | 66 | 66 | 66 |
| H2O GHSV/h | 9 | 9 | 9 |
| C2H4(g/Lcat/h) | 1131 | 1131 | 1131 |
| HAC(g/Lcat/h) | 177 | 177 | 177 |
| H2O(g/Lcat/h) | 8 | 8 | 8 |
| 进料接触时间[1/GHSV](秒) | 4 | 4 | 4 |
| C2H4/HAC/H2O摩尔％比 | 92.3/6.7/1.0 | 92.3/6.7/1.0 | 92.3/6.7/1.0 |
| C2H4/HAC/H2Owt％比 | 86/13.4/0.6 | 86/13.4/0.6 | 86/13.4/0.6 |
| C2H4/HAC摩尔比 | 13.7 | 13.7 | 13.7 |
产品分析(表14续)
| 产品/分析 | 操作37 | 操作38 | 操作39 |
| HAC转化率 | 71 | 64 | 60 |
| 产品选择性(wt％)EtAcEtOHDEE乙醛齐聚物其它 | 95.90.72.30.00.80.3 | 97.20.61.80.00.30.1 | 97.80.51.30.00.30.0 |
| EtAc产率 | 68 | 63 | 59 |
| EtAc STY(g/Lcat/h) | 194 | 183 | 164 |
| 碳平衡(mol％) | 100 | 100 | 100 |
| 氧平衡(mol％) | 94 | 89 | 93 |
| 质量平衡 | 100 | 99 | 99 |
| 回收水(％) | 53 | 56 | 62 |
Claims (31)
1.一种制备低级脂族酯的方法，所述方法包括在杂多酸催化剂存在下，低级烯烃与饱和低级脂族单羧酸在汽相中反应，其特征在于在反应过程中在反应混合物中加入以烯烃、脂族单羧酸和水的总量计为1-10摩尔％的水。
2.根据权利要求1所述的方法，其中以烯烃、脂族单羧酸和水总量计，加入水量为1-7摩尔％。
3.根据权利要求1或2所述的方法，其中以烯烃、脂族单羧酸和水总量计，加入水量为1-5摩尔％。
4.根据上述任一项权利要求所述的方法，其中杂多酸催化剂载于挤出物或丸状形式的硅载体上。
5.根据权利要求4所述的方法，其中硅载体由无定形、无孔合成二氧化硅制成。
6.根据权利要求4或5所述方法，其中硅载体由通过火焰水解SiCl4得到的发烟二氧化硅制成。
7.根据权利要求4-6任意一项所述方法，其中硅载体是通过挤压AEROSILR200(both ex Degussa)制成的Support 350。
8.根据权利要求4-7任意一项所述的方法，其中二氧化硅载体是具有平均粒直径2-10mm，孔体积0.3-1.2ml/g，抗压强度至少2kg力和堆积密度至少380g/l的丸状或颗粒或小球。
9.根据权利要求4-8任意一项所述的方法，其中硅载体至少有99％W/W的纯度。
10.根据权利要求4所述方法，其中硅载体是丸状二氧化硅载体，其平均堆积密度约为0.39g/ml，平均孔体积约为1..15ml/g和平均粒度约为0.1-3.5mm。
11.根据权利要求10所述的方法，其中丸状二氧化硅载体直接使用或经压碎至平均粒度为0.5-2mm，以载带杂多酸催化剂。
12.根据前面所述权利要求的任何一项所述方法，其中用来制备酯化催化剂的杂多酸选自游离酸和其配位型的盐，其中的阴离子是高分子量本体配位体，含联结着2-18个氧的多价金属***原子，其以对称方式包围着选自元素周期表中I-VIII族的中心原子。
13.根据权利要求12所述的方法，其中***原子是钼、钨、钒、铌和钽中一个或多个，中心原子或离子选自硅、磷，二价铜离子；二价铍、锌、钴或镍离子；三价硼、铝、镓、铁、铈、砷、锑、磷、铋、铬或铑离子；四价硅、锗、锡、钛、锆、钒、硫、碲、锰、镍、铂、钍、铪、铈离子和其它稀土离子；五价磷、砷、钒、锑离子；六价碲离子；和七价的碘离子。
14.根据前述权利要求中任意一项所述方法，其中杂多酸的分子量为700-8500，并含有二聚配位体。
15.根据前述权利要求中任意一项所述方法，其中杂多酸包括以下化合物中至少一种：
12-钨磷酸 H3[PW12O40]·XH2O
12-钼磷酸 H3[PMo12O40]·XH2O
12-钨硅酸 H4[SiW12O40]·XH2O
12-钼硅酸 H4[SiMo12O40]·XH2O
钨磷酸钾 K6[P2W18O62]·XH2O
钼磷酸钠 Na3[PMo12O40]·XH2O
钼二磷酸铵 (NH4)6[P2Mo18O62]·XH2O
钨镍酸钠 Na4[NiW6O24H6]·XH2O
钼二钴酸铵 (NH4)[Co2Mo10O36]·XH2O
钨硅酸氢铈 Cs3H[SiW12O40]·XH2O
钼二钒磷酸钾 K5[PMoV2O40]·XH2O
16.根据权利要求4-15任意一项所述的方法，其中沉积/浸渍在载体上用于酯化反应的杂多酸的量以杂多酸和载体的总重量计为10-60wt％。
17.根据前述权利要求中任意一项所述的方法，其中所用的烯烃反应物是乙烯、丙烯或其混合物。
18.根据前述权利要求中任意一项所述的方法，其中饱和的低级脂族单羧酸反应物是C1-C4的羧酸。
19.根据前述权利要求中任意一项所述的方法，其中脂族单羧酸反应物是乙酸。
20.根据前述权利要求中任意一项所述的方法，其中相对于脂族单羧酸反应物，反应混合物中有摩尔过量的烯烃反应物。
21.根据前述权利要求中任意一项所述的方法，其中反应混合物中烯烃与低级羧酸的摩尔比为1∶1至15∶1。
22.根据权利要求18所述的方法，其中反应混合物中烯烃与低级羧酸的摩尔比为10∶1至14∶1。
23.根据前述权利要求中的任意一项所述的方法，其中反应在高于反应器所含反应物酸、任何就地形成的醇、产物酯和水的露点的汽相中进行。
24.根据前述权利要求中任意一项所述的方法，其中载带的杂多酸催化剂可以填料塔的形式作为固定床使用。
25.根据前述权利要求中任意一项所述的方法，其中杂多酸可以通过加磷酸或其它无机酸进一步改性。
26.根据前述权利要求中任意一项所述的方法，其中反应物烯烃和酸的蒸汽以GHSV为100-5000/小时通过催化剂。
27.根据前述权利要求中任意一项所述的方法，其中酯化反应在温度150-200℃和反应压力至少400KPa下进行。
28.根据权利要求中任意一项所述方法，其中在反应混合物中加入的二醚共同进料中二醚的量，以反应混合物所含烯烃、脂族羧酸、水和二醚总量计，为1-6摩尔％。
29.根据权利要求28所述方法，其中二醚相当于在反应中由反应物烯烃就地形成的副产物二醚，其被回收和再循环到反应混合物中。
30.根据权利要求28或29所述方法，其中二醚是二乙基醚。
31.根据权利要求28或29所述方法，其中二醚是不对称醚。
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9515813.5A GB9515813D0 (en) | 1995-08-02 | 1995-08-02 | Ester synthesis |
| GBGB9603770.0A GB9603770D0 (en) | 1996-02-22 | 1996-02-22 | Ester synthesis |
| GBGB9613227.9A GB9613227D0 (en) | 1996-06-25 | 1996-06-25 | Ester synthesis |
| GB9515813.5 | 1996-06-25 | ||
| GB9603770.0 | 1996-06-25 | ||
| GB9613227.9 | 1996-06-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1150585A true CN1150585A (zh) | 1997-05-28 |
| CN1085197C CN1085197C (zh) | 2002-05-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96112172A Expired - Lifetime CN1085197C (zh) | 1995-08-02 | 1996-08-02 | 酯合成 |
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| Country | Link |
|---|---|
| US (2) | US5861530A (zh) |
| EP (2) | EP0959064B1 (zh) |
| JP (2) | JP3911048B2 (zh) |
| KR (1) | KR100293337B1 (zh) |
| CN (1) | CN1085197C (zh) |
| CA (1) | CA2182558C (zh) |
| DE (2) | DE69618032T2 (zh) |
| MY (1) | MY116546A (zh) |
| SA (1) | SA96170381B1 (zh) |
| SG (1) | SG49973A1 (zh) |
| TW (1) | TW338764B (zh) |
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| EP0959064B1 (en) | 1995-08-02 | 2001-12-12 | BP Chemicals Limited | Ester synthesis |
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- 1996-07-22 EP EP99113642A patent/EP0959064B1/en not_active Expired - Lifetime
- 1996-07-22 DE DE69618032T patent/DE69618032T2/de not_active Expired - Lifetime
- 1996-07-22 DE DE69607536T patent/DE69607536T2/de not_active Expired - Lifetime
- 1996-07-22 EP EP96305369A patent/EP0757027B1/en not_active Expired - Lifetime
- 1996-07-26 US US08/687,811 patent/US5861530A/en not_active Ceased
- 1996-07-29 SG SG1996010358A patent/SG49973A1/en unknown
- 1996-08-01 JP JP20397496A patent/JP3911048B2/ja not_active Expired - Lifetime
- 1996-08-01 CA CA002182558A patent/CA2182558C/en not_active Expired - Lifetime
- 1996-08-02 KR KR1019960032397A patent/KR100293337B1/ko not_active IP Right Cessation
- 1996-08-02 MY MYPI96003185A patent/MY116546A/en unknown
- 1996-08-02 CN CN96112172A patent/CN1085197C/zh not_active Expired - Lifetime
- 1996-10-04 TW TW085112155A patent/TW338764B/zh not_active IP Right Cessation
- 1996-10-21 SA SA96170381A patent/SA96170381B1/ar unknown
-
2005
- 2005-07-13 JP JP2005204950A patent/JP2005298527A/ja active Pending
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2007
- 2007-02-28 US US11/712,545 patent/USRE41341E1/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6624325B1 (en) | 1999-06-03 | 2003-09-23 | Showa Denko K. K. | Catalyst for use in producing lower fatty acid ester, process for producing the catalyst, and process for producing lower fatty acid ester using the catalyst |
| CN104117378A (zh) * | 2014-06-29 | 2014-10-29 | 陈昆 | 酯化反应催化剂的制备方法 |
| CN104117378B (zh) * | 2014-06-29 | 2016-03-02 | 陈昆 | 酯化反应催化剂的制备方法 |
| CN110152648A (zh) * | 2018-02-12 | 2019-08-23 | 中国石油化工股份有限公司 | 锡催化剂的制备方法、锡催化剂及其应用 |
| CN110152648B (zh) * | 2018-02-12 | 2022-01-04 | 中国石油化工股份有限公司 | 锡催化剂的制备方法、锡催化剂及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| USRE41341E1 (en) | 2010-05-18 |
| KR100293337B1 (ko) | 2001-07-12 |
| DE69618032T2 (de) | 2002-06-27 |
| DE69607536D1 (de) | 2000-05-11 |
| SA96170381B1 (ar) | 2007-01-20 |
| DE69607536T2 (de) | 2001-02-08 |
| KR980002006A (ko) | 1998-03-30 |
| CA2182558C (en) | 2006-10-24 |
| CN1085197C (zh) | 2002-05-22 |
| CA2182558A1 (en) | 1997-02-03 |
| TW338764B (en) | 1998-08-21 |
| EP0959064A1 (en) | 1999-11-24 |
| DE69618032D1 (de) | 2002-01-24 |
| JP2005298527A (ja) | 2005-10-27 |
| EP0757027A1 (en) | 1997-02-05 |
| JPH09118647A (ja) | 1997-05-06 |
| EP0959064B1 (en) | 2001-12-12 |
| EP0757027B1 (en) | 2000-04-05 |
| SG49973A1 (en) | 1998-06-15 |
| JP3911048B2 (ja) | 2007-05-09 |
| MY116546A (en) | 2004-02-28 |
| US5861530A (en) | 1999-01-19 |
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