CN110201716B - Alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof - Google Patents
Alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof Download PDFInfo
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- CN110201716B CN110201716B CN201910424430.9A CN201910424430A CN110201716B CN 110201716 B CN110201716 B CN 110201716B CN 201910424430 A CN201910424430 A CN 201910424430A CN 110201716 B CN110201716 B CN 110201716B
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- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 alcohol amine Chemical group 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 47
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 39
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 39
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 36
- 150000001336 alkenes Chemical class 0.000 claims abstract description 29
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 230000002378 acidificating effect Effects 0.000 claims abstract description 24
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 7
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 87
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 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 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 17
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 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 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 7
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 21
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 32
- 238000004458 analytical method Methods 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 16
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- VUXKVKAHWOVIDN-UHFFFAOYSA-N Cyclohexyl formate Chemical compound O=COC1CCCCC1 VUXKVKAHWOVIDN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 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 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JAELLLITIZHOGQ-UHFFFAOYSA-N tert-butyl propanoate Chemical compound CCC(=O)OC(C)(C)C JAELLLITIZHOGQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- B01J37/082—Decomposition and pyrolysis
-
- 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
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- 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)
Abstract
The invention relates to mesoporous C/SiO modified by alcohol amine groups2A preparation method of a supported heteropolyacid catalyst and application thereof in catalyzing addition esterification of olefin and carboxylic acid. The alcohol amine group modified mesoporous C/SiO2The preparation method of the supported heteropolyacid catalyst comprises the steps of dissolving an organic template agent and an alcohol amine substance under an acidic condition, adding a silicon source, stirring to hydrolyze the silicon source, slowly dropwise adding an aqueous solution of heteropolyacid, fully stirring, carrying out hydrothermal crystallization for a period of time, filtering, washing, drying and roasting the crystallized solution. The alcohol amine group modified ordered mesoporous C/SiO2The supported heteropolyacid catalyst has simple preparation process, adjustable acidity and acid content and uniform and controllable aperture. Can efficiently and stably catalyze olefin and carboxylic acid to synthesize carboxylic ester with high conversion rate and high selectivity under the conditions of small catalyst dosage, higher temperature and no solvent, improve the atom utilization rate of the atom economic reaction, effectively reduce the energy consumption of separated products, and reduce the equipment investment。
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and relates to an alcohol amine group modified ordered mesoporous C/SiO2The preparation of the supported heteropolyacid catalyst and the application of the supported heteropolyacid catalyst in the production of carboxylic ester by the addition reaction of carboxylic acid and olefin.
Background
The carboxylic ester compound has good solubility, and has wide application in the fields of coating, daily chemical products, printing ink, industrial cleaning agent, surfactant and the like. The carboxylic ester is prepared by directly adding carboxylic acid and olefin, which is a green atom economic reaction synthetic route, the atom utilization rate can reach 100% theoretically, the process flow can be simplified, the separation energy consumption is saved, and the production cost of the carboxylic ester is reduced.
Patent US3678099 discloses a process flow for catalyzing the addition esterification reaction of acetic acid and isobutylene by using sulfonic acid modified ion exchange resin Amberlyst15 as a solid acid catalyst. It is composed ofThe molar ratio of isobutene to acetic acid is 1.31: 1; the reaction temperature is 150 ℃, the reaction pressure is 3MPa, and the final conversion rate of the acetic acid is 69.1%. The selectivity to tert-butyl acetate was 77.0% and to isobutylene dimer 21.1%. The above method shows that the sulfonic acid resin has high activity for the reaction, but the selectivity of the tert-butyl acetate is low. Patent CN102924272A reports a method for preparing MCM-41-SO3H, catalyzing carboxylic acid and olefin to synthesize carboxylic ester through addition esterification, wherein the final acrylic acid conversion rate is 55.0% and the tert-butyl acrylate generation selectivity is 92.6% under the reaction condition that the consumption of the polymerization inhibitor tert-butyl alcohol accounts for 9.0% of the mass of the acrylic acid. In order to improve the selectivity of carboxylic ester, the mesoporous molecular sieve catalyst adopted in the method is added with a polymerization inhibitor such as tertiary butyl alcohol, so that the tertiary butyl alcohol and diisobutylene form an azeotrope, and the separation energy consumption and equipment investment of subsequent products are increased. The heteropoly acid has the characteristics of strong acidity and good thermal stability, and is widely applied to the field of catalysis. Document [ Chinese Journal of Catalysis,1988, V9(4):404-]The use of heteropolyacids to catalyse the reaction of an olefin with a carboxylic acid is reported, where the results of the study show that tungstophosphoric acid (H) is used as the base3PW12O40·xH2O) is used as a catalyst to catalyze the reaction of 1-butene and acetic acid, the conversion rate of the acetic acid can reach 86% after the reaction time is 7 hours, and the selectivity of the product reaches more than 98%. The heteropoly acid used in the above report is dissolved in the reaction system, and separation of the reactant from the catalyst is difficult.
Disclosure of Invention
The invention aims to provide an ordered mesoporous C/SiO modified by alcohol amine groups2A method for synthesizing carboxylic ester by catalysis of a supported heteropolyacid catalyst overcomes the defects of poor thermal stability, easy dissolution in a polar solvent and single acidity of heteropolyacid.
The invention utilizes the strong acidity of heteropoly acid, and combines the characteristics of adjustable pore diameter, uniform pore distribution and large specific surface area of mesoporous material. The heteropolyacid is fixed on the surface of the mesoporous material by utilizing the alkalinity of the alcohol amine group to prepare the solid acid catalyst, and the defect position heteropolyacid is generated in the roasting process, so that the heteropolyacid has
And Lewis acid acidity, the defects of low specific surface area, easy dissolution in polar solvents, easy loss of active sites and single acidity of the heteropoly acid are overcome, and the heteropoly acid serving as a carboxylic ester catalyst has high activity and high selectivity by regulating the acid amount.
The technical scheme adopted by the invention is as follows:
the first purpose of the invention is to provide an alcohol amine group modified ordered mesoporous C/SiO2The supported heteropolyacid catalyst is prepared by dissolving an organic template agent and an alcohol amine substance under an acidic condition, adding a silicon source for hydrolysis, slowly dropwise adding an aqueous solution of heteropolyacid, fully stirring, carrying out hydrothermal crystallization, filtering, washing and drying the crystallized solution, and roasting.
Further, the catalyst is prepared by the following method:
(1) adding organic template and alcohol amine substance into H+Stirring for 1-3 h at 20-50 ℃ in 0.5-2.5 mol/L acidic aqueous solution, adding a silicon source after the template agent and the alcohol amine substance are completely dissolved, and stirring for 0.5-2 h at the temperature;
(2) dropwise adding 0.1-0.5 g/mL of heteropoly acid aqueous solution into the mixed solution in the step (1), preferably 0.2 g/mL; stirring at 20-50 ℃ for 20-24 h, and placing the stirred mixed suspension in a hydrothermal synthesis kettle for crystallization at 80-130 ℃ for 24-96 h, preferably at 100-120 ℃ for 48-72 h; cooling to room temperature and taking out the crystallized mixed solution;
(3) filtering or centrifugally washing the mixed solution obtained by crystallization in the step (2), placing the obtained filter cake or solid in an oven, drying at 50-100 ℃ for 8-12 h, roasting the obtained solid powder at 200-400 ℃ for 4-6 h in an inert atmosphere, wherein the inert atmosphere can be vacuum or N2Ar, He, preferably N2(ii) a Preferably, the roasting temperature is 300-350 ℃; obtaining the alcohol amine group modified ordered mesoporous C/SiO2A supported heteropolyacid catalyst.
Furthermore, the organic template is also a carbon source, and the organic template isSelected from nonionic surfactants; preferably a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123, EO)20PO70EO20，M＝5800)、 (F127，EO106PO70EO106，M＝12600)、(F108，EO132PO50EO132M10400); preferably P123;
the alcohol amine substance is selected from monoethanolamine, diethanolamine and triethanolamine; preferably diethanolamine;
the silicon source is selected from sodium silicate, tetraethyl orthosilicate, butyl silicate, silica sol, water glass and methyl silicate, and preferably tetraethyl orthosilicate;
the heteropoly acid is selected from phosphotungstic acid, silicotungstic acid and phosphomolybdic acid, and is preferably phosphotungstic acid.
Further, H of the acidic aqueous solution+The concentration is 1-2 mol/L;
the acid source of the acidic aqueous solution is hydrochloric acid, nitric acid and phosphoric acid, preferably hydrochloric acid;
h of the organic template agent and the acidic aqueous solution+The molar ratio is 0.001: 1-0.01: 1; the optimal ratio is 0.001: 1-0.005: 1;
the molar ratio of the organic template to the silicon source is 0.01-0.05: 1, preferably 0.01 to 0.025: 1;
the mass ratio of the heteropoly acid to the silicon source is 0.05-0.5: 1, preferably 0.1 to 0.4: 1;
the mass ratio of the alcohol amine substance to the heteropoly acid is 0.1-1.2: 1, preferably 0.2-0.8: 1.
the second purpose of the invention is to provide the above mentioned alcohol amine group modified ordered mesoporous C/SiO2The application of the supported heteropolyacid catalyst in catalyzing carboxylic acid and olefin to synthesize carboxylic ester.
The third purpose of the invention is to provide an alcohol amine group modified ordered mesoporous C/SiO2A process for the preparation of a supported heteropolyacid catalyst, the process comprising the steps of:
(1) adding organic template and alcohol amine substance into H+The concentration is 0.5-2.5 mStirring the solution in an ol/L acidic aqueous solution at the temperature of 20-50 ℃ for 1-3 h, adding a silicon source after the template agent and the alcohol amine substance are completely dissolved, and stirring the solution at the temperature for 0.5-2 h;
(2) dropwise adding 0.1-0.5 g/mL of heteropoly acid aqueous solution into the mixed solution in the step (1), preferably 0.2 g/mL; stirring at 20-50 ℃ for 20-24 h, and placing the stirred mixed suspension in a hydrothermal synthesis kettle for crystallization at 80-130 ℃ for 24-96 h, preferably at 100-120 ℃ for 48-72 h; cooling to room temperature and taking out the crystallized mixed solution;
(3) filtering or centrifugally washing the mixed solution obtained by crystallization in the step (2), placing the obtained filter cake or solid in an oven, drying at 50-100 ℃ for 8-12 h, roasting the obtained solid powder at 200-400 ℃ for 4-6 h in an inert atmosphere, wherein the inert atmosphere can be vacuum or N2Ar, He, preferably N2(ii) a Preferably, the roasting temperature is 300-350 ℃; obtaining the alcohol amine group modified ordered mesoporous C/SiO2A supported heteropolyacid catalyst.
Further, the organic template is also a carbon source, and is selected from a nonionic surfactant; preferably a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123, EO)20PO70EO20，M＝5800)、 (F127，EO106PO70EO106，M＝12600)、(F108，EO132PO50EO132M10400); preferably P123;
the alcohol amine substance is selected from monoethanolamine, diethanolamine and triethanolamine; preferably diethanolamine;
the silicon source is selected from sodium silicate, tetraethyl orthosilicate, butyl silicate, silica sol, water glass and methyl silicate, and preferably tetraethyl orthosilicate;
the heteropoly acid is selected from phosphotungstic acid, silicotungstic acid and phosphomolybdic acid, and is preferably phosphotungstic acid.
Further, H of the acidic aqueous solution+The concentration is 1-2 mol/L;
the acid source of the acidic aqueous solution is hydrochloric acid, nitric acid and phosphoric acid, preferably hydrochloric acid;
h of the organic template agent and the acidic aqueous solution+The molar ratio is 0.001: 1-0.01: 1; the optimal ratio is 0.001: 1-0.005: 1;
the molar ratio of the organic template to the silicon source is 0.01-0.05: 1, preferably 0.01 to 0.025: 1;
the mass ratio of the heteropoly acid to the silicon source is 0.05-0.5: 1, preferably 0.1 to 0.4: 1;
the mass ratio of the alcohol amine substance to the heteropoly acid is 0.1-1.2: 1, preferably 0.2-0.8: 1.
the fourth purpose of the invention is to provide the ordered mesoporous C/SiO modified by the alcohol amine group2The method for synthesizing carboxylic ester by catalyzing carboxylic acid and olefin through supported heteropolyacid, wherein the alcohol amine group modified ordered mesoporous C/SiO2The dosage of the supported heteropolyacid catalyst is 0.05 wt% to 10 wt% of the mass of the carboxylic acid.
Further, the carboxylic acid is one of linear carboxylic acid, alicyclic carboxylic acid and aromatic carboxylic acid, and the linear carboxylic acid can be selected from formic acid, acetic acid, acrylic acid and propionic acid;
the olefin is not required to be structurally, and common olefins can be applied to the invention, and are preferably selected from isobutene, butene and cyclohexene;
the molar ratio of the olefin to the carboxylic acid is 6: 1-1: 1, preferably 4: 1-1: 1;
the alcohol amine group modified ordered mesoporous C/SiO2The dosage of the supported heteropolyacid catalyst is 1wt.% to 5wt.% of the mass of the carboxylic acid;
the reaction temperature is 30-80 ℃, and preferably 30-50 ℃;
the reaction pressure is 0.5 to 1.5MPa (gauge pressure), preferably 0.7 to 1.2 MPa;
the stirring speed is 300-1000 r/min, preferably 400-1000 r/min, and more preferably 600-800 r/min;
the reaction time is 2-12 h, preferably 8-12 h, and more preferably 8-10 h.
The pressure in the technical scheme of the invention is gauge pressure.
The invention has the beneficial effects that:
the alcohol amine group modified ordered mesoporous C/SiO2The supported heteropolyacid catalyst is added with alcohol amine groups as a regulator in the synthesis stage, so that the damage of heteropolyacid particles to a framework is relieved, and the ordered pore structure of the carrier is facilitated; the decomposition of alcohol amine groups in the roasting process breaks metal oxygen bonds in heteropoly acid particles, and finally the catalyst has ordered mesoporous pore canals, and the acid center is adjustable and has
And Lewis acid is acidic, has no corrosion, is easy to separate, has no easy loss of active center, can catalyze olefin and carboxylic acid to synthesize carboxylic ester at high conversion rate under the conditions of higher temperature and no need of adding an olefin polymerization inhibitor, generates the carboxylic ester at high selectivity, and can simultaneously reduce the separation energy consumption of reaction products and the equipment investment cost. The method has the advantages of mild reaction conditions, few byproducts, environmental protection, reduction in production cost and the like.
Drawings
FIG. 1 is a small angle X-ray diffraction pattern of the catalysts obtained in examples 1 to 5 and comparative example 1.
FIG. 2 shows N in the catalysts obtained in examples 1 to 52Adsorption and desorption curve spectrogram
FIG. 3 is a pyridine infrared spectrum of the catalyst obtained in examples 1 to 5.
FIG. 4 is a TEM image of the catalyst obtained in example 3.
Detailed Description
The present invention is further illustrated by the following examples, which are experimental procedures not specifically identified, generally in accordance with procedures well known in the art.
In the scheme of the invention, the conversion rate calculation formula is as follows: conversion rate ═ 100% (amount of converted raw material/total amount of raw material) ×
In the scheme of the invention, the selective calculation formula is as follows: selectivity (amount of raw material consumed for conversion into the objective product/amount of raw material converted) × 100%
Example 1
9g P123, 0.5g of diethanolamine and 360mL of 2mol/L hydrochloric acid are sequentially added into a three-neck flask, stirred for 1-3 h at 40 ℃ to completely dissolve P123 and diethanolamine, then 24.48g of tetraethyl orthosilicate (TEOS, the molar ratio of P123 to TEOS is 0.013:1 in the embodiment) is added, stirred for 30min at 40 ℃, then 12.25mL of 0.2g/mL silicotungstic acid aqueous solution (namely 2.45g silicotungstic acid) is slowly dropped, stirred for 24h at 40 ℃, the uniformly stirred mixed suspension is put into a stainless steel water thermal synthesis kettle with a polytetrafluoroethylene lining, crystallized for 2 days (48h) at 100 ℃, cooled to room temperature, the crystallized solid-liquid two-phase mixture is filtered and washed, the filter cake is put into an oven to be dried for 8-12 h at 50 ℃, the dried article is roasted for 6h at 300 ℃ under nitrogen atmosphere. Obtaining the required alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst, recorded as 0.1HSiW-0.2DEA @ C/SiO2(TEOS) -300-P123 (wherein 0.1 refers to the mass ratio of silicotungstic acid to tetraethyl orthosilicate, 0.2 refers to the mass ratio of diethanolamine to silicotungstic acid, and 300 is the calcination temperature). As can be seen from the small-angle X-ray diffraction spectrum (shown in figure 1) of the catalyst, a characteristic peak of the ordered pore channel appears at 0.7, which indicates that the pore channel of the catalyst is of an ordered structure. By using N2Analyzing the pore structure of the catalyst by physical absorption and desorption means (see figure 2), and finding out the synthesized catalyst N2The adsorption and desorption isothermal curve is a type of IV-type nitrogen adsorption and desorption curve with an H1 type hysteresis loop, which indicates that the catalyst has a mesoporous pore channel structure with uniform pore size. TEM visually reflects the order of the channels (see figure 4).
Example 2
Adding 9g of P123, 1g of diethanolamine and 360mL of 2mol/L hydrochloric acid into a three-neck flask in sequence, stirring for 1-3 h at 40 ℃ to completely dissolve the P123 and the diethanolamine, adding 24.48g of tetraethyl orthosilicate (TEOS, the molar ratio of P123 to TEOS is 0.013:1 in the embodiment), stirring for 30min at 40 ℃, then slowly dropwise adding 24.5mL of 0.2g/mL phosphotungstic acid aqueous solution (namely 4.90g of phosphotungstic acid), uniformly stirring for 24h at 40 ℃, putting the uniformly stirred mixed suspension into a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene lining, crystallizing for 2 days at 100 DEG C(48h) And then cooling to room temperature, filtering and washing the crystallized solid-liquid two-phase mixture, placing the filter cake in an oven for drying at 50 ℃ for 8-12 h, placing the dried product in a muffle furnace in a nitrogen atmosphere, and roasting at 300 ℃ for 6 h. Obtaining the required alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst, noted as 0.2HPW-0.2DEA @ C/SiO2(TEOS) -300-P123 (wherein 0.2 refers to the mass ratio of phosphotungstic acid to tetraethyl orthosilicate, 0.2 refers to the mass ratio of diethanolamine to phosphotungstic acid, and 300 is the calcination temperature). Pyridine infrared surface alcohol amine group modified ordered mesoporous C/SiO2The supported heteropolyacid catalyst has
And Lewis acidic. (FIG. 3)
Example 3
21g F127, 4.52g of diethanolamine and 360mL of 2mol/L hydrochloric acid are added into a three-neck flask in turn, stirring at 40 ℃ for 1-3 h to completely dissolve P123 and diethanolamine, adding 37.66g of butyl silicate (TBOS, the molar ratio of F127 to TBOS in this example is 0.014:1), stirring at 40 deg.C for 30min, slowly adding 37.65mL of 0.2g/mL aqueous solution of phosphotungstic acid (i.e. 7.53g of phosphotungstic acid) dropwise, uniformly stirring for 24h at 40 ℃, putting the uniformly stirred mixed suspension into a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene lining, crystallizing at 100 ℃ for 2 days (48h), cooling to room temperature, filtering and washing the crystallized solid-liquid two-phase mixture, drying the filter cake in an oven at 50 ℃ for 8-12 h, placing the dried product in a muffle furnace in nitrogen atmosphere, and roasting at 300 ℃ for 6 h. Obtaining the required alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst, noted as 0.2HPW-0.6DEA @ C/SiO2A TEM representation of the catalyst obtained from (TBOS) -300-F127 (wherein 0.2 means the mass ratio of phosphotungstic acid to tetraethyl orthosilicate, 0.6 means the mass ratio of diethanolamine to phosphotungstic acid, and 300 is the calcination temperature) is shown in FIG. 4.
Example 4
9g P123, 6g of monoethanolamine and 360mL of 2mol/L hydrochloric acid are sequentially added into a three-neck flask, stirred for 1-3 h at 40 ℃ to completely dissolve P123 and monoethanolamine, and then 37.6 is added6g of butyl silicate (TBOS, the molar ratio of P123 to TBOS in this example is 0.013:1), stirring at 40 ℃ for 30min, then slowly dropwise adding 75mL of a 0.2g/mL phosphotungstic acid aqueous solution (i.e. 15g of phosphotungstic acid), uniformly stirring at 40 ℃ for 24h, putting the uniformly stirred mixed suspension into a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene lining, crystallizing at 100 ℃ for 2 days (48h), cooling to room temperature, filtering and washing the crystallized solid-liquid two-phase mixture, drying the filter cake in an oven at 50 ℃ for 8-12 h, placing the dried product in a muffle furnace under a nitrogen atmosphere, and roasting at 400 ℃ for 6 h. Obtaining the required alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst, noted as 0.4HPW-0.4MEA @ C/SiO2(TBOS) -400-P123 (wherein 0.4 refers to the mass ratio of phosphotungstic acid to butyl silicate, 0.6 refers to the mass ratio of monoethanolamine to phosphotungstic acid, and 400 is the calcination temperature).
Example 5
21g F127, 4.90g of triethanolamine and 360mL of 2mol/L hydrochloric acid are sequentially added into a three-neck flask, stirred for 1-3 hours at 40 ℃ to completely dissolve P123 and the triethanolamine, then 24.48g of tetraethyl orthosilicate (TEOS, the molar ratio of F127 to TEOS is 0.014:1 in the embodiment) is added, stirred for 30 minutes at 40 ℃, then 24.5mL of 0.2g/mL phosphotungstic acid aqueous solution (namely 4.90g of phosphotungstic acid) is slowly dropped, stirred for 24 hours at 40 ℃, the uniformly stirred mixed suspension is put into a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene lining, crystallized for 2 days (48 hours) at 100 ℃, cooled to room temperature, the crystallized solid-liquid two-phase mixture is filtered and washed, the filter cake is put into a baking oven to be dried for 8-12 hours at 50 ℃, and the dried product is put into a muffle baking oven to be baked for 6 hours at 300 ℃. Obtaining the required alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst, noted as 0.2HPW-1TEA @ C/SiO2(TEOS) -300-F127 (wherein 0.2 refers to the mass ratio of phosphotungstic acid to tetraethyl orthosilicate, 1 refers to the mass ratio of triethanolamine to phosphotungstic acid, and 300 is the calcination temperature).
Example 6
74g of propionic acid, 0.74g of 0.1HSiW-0.2DEA @ C/SiO of example 12(TEOS) -300-P123 was charged into a 300mL batch titanium autoclave, followed by 112g of isobutylene (isobutylene)The mol ratio of the acid to the propionic acid is 2:1), the reaction temperature is 30 ℃, nitrogen is introduced to increase the pressure in the kettle to 1MPa, and the reaction is carried out for 10 hours under the condition that the stirring speed is 600 r/min. Reaction liquid is collected through a sampling pipe, then a catalyst is removed through centrifugation, then a gas chromatograph is used for analysis, and the analysis result is calculated to obtain that the propionic acid conversion rate is 90%, the tert-butyl propionate selectivity is 96% and the diisobutylene selectivity is 1.4%.
Example 7
60g of acetic acid, 0.6g of 0.2HPW-0.2DEA @ C/SiO of example 2 were mixed2(TEOS) -300-P123 was added into a 300mL batch titanium autoclave, followed by addition of 82g of cyclohexene (the molar ratio of cyclohexene to acetic acid was 1:1), and the reaction was carried out at 80 ℃ and 600r/min of stirring speed for 10 h. Reaction liquid is collected through a sampling pipe, then a catalyst is removed through centrifugation, then a gas chromatograph is used for analysis, and the analysis result is calculated to obtain that the acetic acid conversion rate is 92% and the cyclohexyl acetate selectivity is 99%.
Example 8
60g of acetic acid, 0.6g of 0.2HPW-0.2DEA @ C/SiO of example 2 were mixed2(TEOS) -300-P123 was added into a 300mL batch titanium autoclave, 112g of isobutylene (molar ratio of isobutylene to acetic acid: 2:1) was introduced, and the reaction was carried out at 30 ℃ under conditions of nitrogen introduction to raise the pressure in the autoclave to 1MPa and stirring speed of 600r/min for 10 hours. Reaction liquid is collected through a sampling pipe, then the catalyst is removed through centrifugation, and then a gas chromatograph is used for analysis, and the analysis result is calculated to obtain that the acetic acid conversion rate is 92%, the tert-butyl acetate selectivity is 96%, and the diisobutylene selectivity is 1.7%.
Example 9
60g of acetic acid, 0.6g of 0.2HPW-0.6DEA @ C/SiO of example 3 were mixed2(TBOS) -300-F127 was added into a 300mL batch titanium autoclave, 112g of isobutylene (molar ratio of isobutylene to acetic acid: 2:1) was introduced thereinto, and the reaction was carried out at a reaction temperature of 40 ℃ under a condition that the pressure in the autoclave was increased to 1MPa by introducing nitrogen and the stirring rate was 600r/min for 10 hours. Collecting reaction liquid through a sampling pipe, removing a catalyst through centrifugation, analyzing by using a gas chromatograph, and calculating an analysis result to obtain the acetic acid conversion rate of 95 percent and tertiary acetateThe selectivity to butyl ester was 95% and the selectivity to diisobutylene was 2.9%.
Example 10
46g of formic acid, 0.46g of 0.2HPW-0.6DEA @ C/SiO of example 32(TBOS) -300-F127 is added into a 300mL batch titanium material autoclave, then 82g of cyclohexene (the molar ratio of the cyclohexene to the formic acid is 1:1) is introduced, and the reaction is carried out for 10h at the reaction temperature of 70 ℃ and the stirring speed of 600 r/min. Reaction liquid is collected through a sampling pipe, then a catalyst is removed through centrifugation, then a gas chromatograph is used for analysis, and the analysis result is calculated to obtain that the formic acid conversion rate is 86% and the cyclohexyl formate selectivity is 99%.
Example 11
72g of acrylic acid, 0.72g of 0.4HPW-0.4MEA @ C/SiO of example 42(TBOS) -400-P123 was charged into a 300mL batch titanium autoclave, followed by charging 112g of isobutylene (molar ratio of isobutylene to acrylic acid: 2:1), and reacting at 40 ℃ under a condition of increasing the pressure in the autoclave to 1MPa with nitrogen gas introduction and a stirring speed of 600r/min for 10 hours. Reaction liquid is collected through a sampling pipe, then the catalyst is removed through centrifugation, and then the analysis is carried out through a gas chromatograph, and the analysis result is calculated to obtain that the conversion rate of acrylic acid is 91%, the selectivity of tert-butyl acrylate is 94%, and the selectivity of diisobutylene is 3.1%.
Example 12
72g of acrylic acid, 0.72g of 0.4HPW-0.4MEA @ C/SiO of example 42(TBOS) -400-P123 was added into a 300mL batch titanium autoclave, followed by addition of 82g of cyclohexene (cyclohexene to acrylic acid molar ratio 1:1) and reaction was carried out at 80 ℃ and 600r/min of stirring speed for 10 h. Reaction liquid is collected through a sampling pipe, then a catalyst is removed through centrifugation, then a gas chromatograph is used for analysis, and the conversion rate of acrylic acid is 95% and the selectivity of cyclohexyl acrylate is 99% are calculated according to the analysis result.
Example 13
60g of acetic acid, 0.6g of 0.2HPW-1TEA @ C/SiO of example 52(TEOS) -300-F127 was charged into a 300mL batch titanium autoclave, followed by 112g of isobutylene (isobutylene to acetic acid molar ratio of 2:1) at a reaction temperature of 30 deg.CAnd introducing nitrogen to increase the pressure in the kettle to 1MPa, and reacting for 10 hours under the condition that the stirring speed is 600 r/min. Reaction liquid is collected through a sampling pipe, then a catalyst is removed through centrifugation, then a gas chromatograph is used for analysis, and the analysis result is calculated to obtain that the acetic acid conversion rate is 92% and the tert-butyl acetate selectivity is 95%.
Example 14
74g of propionic acid, 0.74g of 0.2HPW-1TEA @ C/SiO of example 52(TEOS) -300-F127 was charged into a 300mL batch titanium autoclave, followed by 112g of isobutylene (molar ratio of isobutylene to propionic acid was 2:1), and the reaction was carried out at 30 ℃ under conditions of increasing the pressure in the autoclave to 1MPa by introducing nitrogen and stirring at 600r/min for 10 hours. Reaction liquid is collected through a sampling pipe, then a catalyst is removed through centrifugation, then a gas chromatograph is used for analysis, and the analysis result is calculated to obtain that the acetic acid conversion rate is 89% and the tert-butyl acetate selectivity is 97%.
Example 15
This example was divided into 7 groups and examined the catalytic effect of different catalyst samples of the present invention on the reaction of carboxylic acid and olefin under different conditions. The specific operation is as follows:
1. alcohol amine group modified ordered mesoporous C/SiO2Preparation of the supported heteropolyacid catalyst:
adding 9g P123, alcohol amine with different mass and 360mL of 2mol/L hydrochloric acid into a three-neck flask in sequence, stirring for 1-3 h at 40 ℃, adding 24.48g of tetraethyl orthosilicate (TEOS) after P123 and the alcohol amine are completely dissolved, stirring for 30min at 40 ℃, then respectively adding phosphotungstic acid with different mass (slowly dropwise adding a phosphotungstic acid aqueous solution), uniformly stirring for 24h at 40 ℃, putting the uniformly stirred mixed suspension into a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene lining, cooling to room temperature after 2 days (48h) at 100 ℃, filtering and washing the crystallized solid-liquid two-phase mixture, putting the filter cake into a drying oven, drying for 8-12 h at 50 ℃, putting the dried product into a muffle furnace, and roasting for 6h at 300 ℃. Respectively obtain 7 kinds of ordered mesoporous C/SiO modified by needed alcohol amine groups2Supported heteropolyacid catalyst, recorded as 0.1HPW-0.8DEA @ C/SiO2(TEOS)-300-P123、0.2HPW-0.4DEA@C/SiO2(TEOS)-300-P123、 0.3HPW-0.6MEA@C/SiO2(TEOS)-300-P123、0.3HPW-0.2TEA@C/SiO2(TEOS)-300-P123、 0.4HPW-0.8DEA@C/SiO2(TEOS)-300-P123、0.4HPW-0.8MEA@C/SiO2(TEOS)-300-P123、 0.2HPW-0.6MEA@C/SiO2The (TEOS) -300-P123, according to the naming rules of examples 1-5, can clarify the raw materials and proportions of each catalyst of this example.
2. Catalyzing carboxylic acid with olefin to produce carboxylic ester:
respectively adding carboxylic acid with different mass and the catalyst with 1 wt% of the mass of the carboxylic acid into a 300mL batch titanium material autoclave, then adding olefin with different mass (when the reactant is isobutene, nitrogen is introduced to increase the pressure in the autoclave to 1Mpa, when the reactant is cyclohexene, the pressure is normal pressure), and reacting for 10 hours under the condition that the stirring speed is 600 r/min. The reaction solution was collected through a sampling tube, followed by removing the catalyst by centrifugation and analysis with a gas chromatograph.
Catalyst preparation, carboxylic acid, olefin reaction conditions and analytical results are calculated as shown in table 1.
Table 1:
example 16
60g of acetic acid, 0.6g of 0.2HPW-0.2DEA @ C/SiO of example 2 were mixed2(TEOS) -300-P123 was added into a 300mL batch titanium autoclave, 112g of isobutylene (molar ratio of isobutylene to acetic acid: 2:1) was introduced, and the reaction was carried out at 30 ℃ under conditions of nitrogen introduction to raise the pressure in the autoclave to 1MPa and stirring speed of 600r/min for 10 hours. The reaction solution was collected through a sampling tube, followed by removal of the catalyst by centrifugation, followed by analysis with a gas chromatograph. The catalyst after reaction is recovered, washed by ethanol, filtered and dried, and then the reaction is repeated under the conditions. Can be repeatedly usedThe results are given in the following table:
the result shows that the alcohol amine group modified ordered mesoporous C/SiO prepared by the invention2The supported heteropoly acid catalyst is easy to separate, solves the problem of solubility of heteropoly acid, still maintains better catalytic activity after separation, and realizes repeated use.
Comparative example 1
9g P123 and 360mL of 2mol/L hydrochloric acid are sequentially added into a three-neck flask, stirred for 1-3 h at 40 ℃ to completely dissolve P123, then 24.48g of tetraethyl orthosilicate (TEOS, the molar ratio of P123 to TEOS is 0.013:1 in the embodiment) is added, stirred for 30min at 40 ℃, then 24.5mL of 0.2g/mL phosphotungstic acid aqueous solution (4.90 g of phosphotungstic acid) is slowly dropped, stirred for 24h at 40 ℃, the uniformly stirred mixed liquid is put into a stainless steel thermal synthesis kettle with a polytetrafluoroethylene lining, crystallized for 2 days (48h) at 100 ℃, cooled to room temperature, the crystallized solid-liquid two-phase mixture is filtered and washed, the filter cake is put into an oven to be dried for 8-12 h at 50 ℃, the dried article is put into a muffle furnace to be calcined for 6h at 300 ℃ in a pure oxygen atmosphere. Obtaining the needed heteropoly acid loaded mesoporous silicon oxide catalyst which is recorded as 0.2HPW @/SiO2(TEOS) -300-P123 (wherein 0.2 refers to the mass ratio of phosphotungstic acid to tetraethyl orthosilicate, and 300 is the calcination temperature).
60g of acetic acid, 0.6g of 0.2HPW @ SiO prepared in this comparative example were added2(TEOS) -300-P123 was added into a 300mL batch titanium autoclave, 112g of isobutylene (molar ratio of isobutylene to acetic acid: 2:1) was introduced, and the reaction was carried out at 30 ℃ under conditions of nitrogen introduction to raise the pressure in the autoclave to 1MPa and stirring speed of 600r/min for 10 hours. Reaction liquid is collected through a sampling pipe, then the catalyst is removed through centrifugation, and then the analysis is carried out by using a gas chromatograph, and the analysis result is calculated to obtain that the acetic acid conversion rate is 79%, the tert-butyl acetate selectivity is 91%, and the diisobutylene selectivity is 5.7%.
Comparison with example 8 shows thatUnder the same conditions of dosage and the like, the alcohol amine group modified ordered mesoporous C/SiO2The supported heteropolyacid catalyst effectively improves the conversion rate of carboxylic acid and the selectivity of carboxylic ester.
Comparative example 2
9g P123 and 360mL of 2mol/L hydrochloric acid are sequentially added into a three-neck flask, stirred at 40 ℃ to completely dissolve P123, then 24.48g of tetraethyl orthosilicate (TEOS) is added, stirred uniformly at 40 ℃ for 24 hours, the uniformly stirred mixed liquid is put into a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene lining, crystallized at 100 ℃ for 1 day, cooled to room temperature, the crystallized solid-liquid two-phase mixture is filtered and washed, the filter cake is dried in an oven at 50 ℃, the dried product is put into a muffle furnace in a nitrogen atmosphere and is roasted at 300 ℃ for 6 hours. The catalyst was obtained, recorded as C/SiO2(TEOS) -300-P123 (where 300 is the firing temperature).
60g of acetic acid and 1.2g of catalyst C/SiO were added to a 300mL batch titanium autoclave2(TEOS) -300-P123, introducing 112g of isobutene (the molar ratio of isobutene to acetic acid is 2:1), heating to 40 ℃, pressurizing to 1MPa, and reacting for 10 hours under the condition that the stirring speed is 600 r/min. Collecting liquid phase reaction liquid, centrifugally separating to remove the catalyst, and analyzing by using a gas chromatograph, wherein the analysis result shows that acetic acid and isobutene are not reacted.
I.e. C/SiO without heteropoly acid loading2The catalyst has no catalytic activity to the addition reaction of acetic acid and isobutene.
Claims (45)
1. Alcohol amine group modified ordered mesoporous C/SiO2The supported heteropolyacid catalyst is characterized in that the catalyst is prepared by dissolving an organic template agent and an alcohol amine substance in an acidic aqueous solution, adding a silicon source for hydrolysis, slowly dropwise adding an aqueous solution of heteropolyacid, fully stirring, carrying out hydrothermal crystallization, filtering, washing and drying the crystallized solution, and roasting;
the heteropoly acid is selected from phosphotungstic acid, silicotungstic acid and phosphomolybdic acid; the roasting condition is roasting for 4-6 h at 200-400 ℃ in an inert atmosphere.
2. The alcohol amine group-modified ordered mesoporous C/SiO of claim 12A supported heteropolyacid catalyst, characterised in that the catalyst is prepared by:
(1) adding organic template and alcohol amine substance into H+Stirring for 1-3 h at 20-50 ℃ in 0.5-2.5 mol/L acidic aqueous solution, adding a silicon source after the template agent and the alcohol amine substance are completely dissolved, and stirring for 0.5-2 h at the temperature;
(2) dropwise adding 0.1-0.5 g/mL of heteropoly acid aqueous solution into the mixed solution in the step (1); stirring at 20-50 ℃ for 20-24 h, and placing the mixed suspension obtained after stirring in a hydrothermal synthesis kettle to crystallize at 80-130 ℃ for 24-96 h; cooling to room temperature and taking out the crystallized mixed solution;
(3) filtering or centrifugally washing the mixed solution obtained by crystallization in the step (2), placing the obtained filter cake or solid in an oven, drying at 50-100 ℃ for 8-12 h, and roasting the obtained solid powder at 200-400 ℃ for 4-6 h in an inert atmosphere, wherein the inert atmosphere can be vacuum or N2Ar, He; obtaining the alcohol amine group modified ordered mesoporous C/SiO2A supported heteropolyacid catalyst.
3. The alcohol amine group-modified ordered mesoporous C/SiO of claim 22The supported heteropolyacid catalyst is characterized in that 0.2g/mL of heteropolyacid aqueous solution is dropwise added into the mixed solution in the step (2).
4. The alcohol amine group-modified ordered mesoporous C/SiO of claim 22The supported heteropolyacid catalyst is characterized in that the mixed suspension obtained after stirring in the step (2) is placed in a hydrothermal synthesis kettle and crystallized at 100-120 ℃ for 48-72 hours.
5. The alcohol amine group-modified ordered mesoporous C/SiO of claim 22The supported heteropoly acid catalyst is characterized in that the inert atmosphere in the step (3) is N2。
6. The alcohol amine group-modified ordered mesoporous C/SiO of claim 22The supported heteropolyacid catalyst is characterized in that the roasting temperature in the step (3) is 300-350 ℃.
7. The alcohol amine group-modified ordered mesoporous C/SiO of claim 1 or 22A supported heteropolyacid catalyst, characterized in that,
the organic template agent is selected from nonionic surfactants;
the alcohol amine substance is selected from monoethanolamine, diethanolamine and triethanolamine;
the silicon source is selected from sodium silicate, tetraethyl orthosilicate, butyl silicate, silica sol, water glass and methyl silicate.
8. The alcohol amine group-modified ordered mesoporous C/SiO of claim 72The supported heteropolyacid catalyst is characterized in that the organic template is selected from P123, F127 and F108.
9. The alcohol amine group-modified ordered mesoporous C/SiO of claim 82The supported heteropolyacid catalyst is characterized in that the organic template agent is P123.
10. The alcohol amine group-modified ordered mesoporous C/SiO of claim 72The supported heteropolyacid catalyst is characterized in that the alcohol amine substance is diethanolamine.
11. The alcohol amine group-modified ordered mesoporous C/SiO of claim 72The supported heteropolyacid catalyst is characterized in that the silicon source is tetraethyl orthosilicate.
12. The alcohol amine group-modified ordered mesoporous C/SiO of claim 12The supported heteropolyacid catalyst is characterized in that the heteropolyacid is phosphotungstic acid.
13. The alcohol amine group-modified ordered mesoporous C/SiO of claim 1 or 22A supported heteropolyacid catalyst, characterized in that,
h of the acidic aqueous solution+The concentration is 1-2 mol/L;
the acid source of the acidic aqueous solution is hydrochloric acid, nitric acid and phosphoric acid;
h of the organic template agent and the acidic aqueous solution+The molar ratio is 0.001: 1-0.01: 1;
the molar ratio of the organic template to the silicon source is 0.01-0.05: 1;
the mass ratio of the heteropoly acid to the silicon source is 0.05-0.5: 1;
the mass ratio of the alcohol amine substance to the heteropoly acid is 0.1-1.2: 1.
14. the alcohol amine group-modified ordered mesoporous C/SiO of claim 132The supported heteropolyacid catalyst is characterized in that the acid source of the acidic aqueous solution is hydrochloric acid.
15. The alcohol amine group-modified ordered mesoporous C/SiO of claim 132A supported heteropolyacid catalyst, characterized in that the organic template is reacted with H of an acidic aqueous solution+The molar ratio is 0.001:1 to 0.005: 1.
16. The alcohol amine group-modified ordered mesoporous C/SiO of claim 132The supported heteropolyacid catalyst is characterized in that the molar ratio of the organic template to a silicon source is 0.01-0.025: 1.
17. the alcohol amine group-modified ordered mesoporous C/SiO of claim 132The supported heteropolyacid catalyst is characterized in that the mass ratio of the heteropolyacid to the silicon source is 0.1-0.4: 1.
18. the alcohol amine group-modified ordered mesoporous C/SiO of claim 132Load(s)The heteropoly acid catalyst is characterized in that the mass ratio of the alcohol amine substance to the heteropoly acid is 0.2-0.8: 1.
19. the alcohol amine group-modified ordered mesoporous C/SiO of any of claims 1 to 182The application of the supported heteropolyacid catalyst in catalyzing carboxylic acid and olefin to synthesize carboxylic ester.
20. Alcohol amine group modified ordered mesoporous C/SiO2A process for the preparation of a supported heteropolyacid catalyst, characterised in that the process comprises the steps of:
(1) adding organic template and alcohol amine substance into H+Stirring for 1-3 h at 20-50 ℃ in an acidic aqueous solution with the concentration of 0.5-2.5 mol/L, adding a silicon source after a template agent and an alcohol amine substance are completely dissolved, and stirring for 0.5-2 h at the temperature;
(2) dropwise adding 0.1-0.5 g/mL of heteropoly acid aqueous solution into the mixed solution in the step (1); stirring at 20-50 ℃ for 20-24 h, and placing the mixed suspension obtained after stirring in a hydrothermal synthesis kettle to crystallize at 80-130 ℃ for 24-96 h; cooling to room temperature and taking out the crystallized mixed solution;
(3) filtering or centrifugally washing the mixed solution obtained by crystallization in the step (2), placing the obtained filter cake or solid in an oven, drying at 50-100 ℃ for 8-12 h, and roasting the obtained solid powder at 200-400 ℃ for 4-6 h in an inert atmosphere, wherein the inert atmosphere can be vacuum or N2Ar, He; obtaining the alcohol amine group modified ordered mesoporous C/SiO2A supported heteropolyacid catalyst.
21. The alcohol amine group-modified ordered mesoporous C/SiO of claim 202The preparation method of the supported heteropolyacid catalyst is characterized in that 0.2g/mL of heteropolyacid aqueous solution is dropwise added into the mixed solution in the step (2).
22. The alcohol amine group-modified ordered mesoporous C/SiO of claim 202Preparation method of supported heteropolyacid catalystThe method is characterized in that the mixed suspension obtained after stirring is placed in a hydrothermal synthesis kettle and crystallized at 100-120 ℃ for 48-72 h in the step (2).
23. The alcohol amine group-modified ordered mesoporous C/SiO of claim 202The preparation method of the supported heteropoly acid catalyst is characterized in that the inert atmosphere in the step (3) is N2。
24. The alcohol amine group-modified ordered mesoporous C/SiO of claim 202The preparation method of the supported heteropolyacid catalyst is characterized in that the roasting temperature in the step (3) is 300-350 ℃.
25. The alcohol amine group-modified ordered mesoporous C/SiO of claim 202A process for preparing a supported heteropolyacid catalyst, which comprises,
the organic template agent is selected from nonionic surfactants;
the alcohol amine substance is selected from monoethanolamine, diethanolamine and triethanolamine;
the silicon source is selected from sodium silicate, tetraethyl orthosilicate, butyl silicate, silica sol, water glass and methyl silicate;
the heteropoly acid is selected from phosphotungstic acid, silicotungstic acid and phosphomolybdic acid.
26. The alkanolamine group-modified ordered mesoporous C/SiO of claim 252The preparation method of the supported heteropolyacid catalyst is characterized in that the organic template is selected from P123, F127 and F108.
27. The alkanolamine group-modified ordered mesoporous C/SiO of claim 252The preparation method of the supported heteropolyacid catalyst is characterized in that the organic template agent is P123.
28. The alkanolamine group-modified ordered mesoporous C/SiO of claim 252The preparation method of the supported heteropolyacid catalyst is characterized in that the alcohol amine substance is diethanolamine.
29. The alkanolamine group-modified ordered mesoporous C/SiO of claim 252The preparation method of the supported heteropolyacid catalyst is characterized in that the silicon source is tetraethyl orthosilicate.
30. The alkanolamine group-modified ordered mesoporous C/SiO of claim 252The preparation method of the supported heteropolyacid catalyst is characterized in that the heteropolyacid is phosphotungstic acid.
31. The alcohol amine group-modified ordered mesoporous C/SiO of claim 202A process for preparing a supported heteropolyacid catalyst, which comprises,
h of the acidic aqueous solution+The concentration is 1-2 mol/L;
the acid source is hydrochloric acid, nitric acid and phosphoric acid;
h of the organic template agent and the acidic aqueous solution+The molar ratio is 0.001: 1-0.01: 1;
the molar ratio of the organic template to the silicon source is 0.01-0.05: 1;
the mass ratio of the heteropoly acid to the silicon source is 0.05-0.5: 1;
the mass ratio of the alcohol amine substance to the heteropoly acid is 0.1-1.2: 1.
32. the alkanolamine group-modified ordered mesoporous C/SiO of claim 312The preparation method of the supported heteropolyacid catalyst is characterized in that the acid source of the acidic aqueous solution is hydrochloric acid.
33. The alkanolamine group-modified ordered mesoporous C/SiO of claim 312The preparation method of the supported heteropolyacid catalyst is characterized in that the organic template agent and H of acidic aqueous solution+The molar ratio is 0.001:1 to 0.005: 1.
34. The alkanolamine group-modified ordered mesoporous C/SiO of claim 312The preparation method of the supported heteropolyacid catalyst is characterized in that the molar ratio of the organic template to the silicon source is 0.01-0.025: 1.
35. the alkanolamine group-modified ordered mesoporous C/SiO of claim 312The preparation method of the supported heteropolyacid catalyst is characterized in that the mass ratio of the heteropolyacid to the silicon source is 0.1-0.4: 1.
36. the alkanolamine group-modified ordered mesoporous C/SiO of claim 312The preparation method of the supported heteropolyacid catalyst is characterized in that the mass ratio of the alcohol amine substance to the heteropolyacid is 0.2-0.8: 1.
37. an ordered mesoporous C/SiO modified with the alcohol amine group of any one of claims 1 to 182The method for synthesizing carboxylic ester by catalyzing carboxylic acid and olefin through supported heteropolyacid is characterized in that the alcohol amine group modified ordered mesoporous C/SiO2The dosage of the supported heteropolyacid catalyst is 0.05wt.% to 10wt.% of the mass of the carboxylic acid.
38. The alkanolamine group-modified ordered mesoporous C/SiO of claim 372A method for synthesizing carboxylic ester by catalyzing carboxylic acid and olefin with supported heteropoly acid is characterized in that,
the carboxylic acid is one of straight-chain carboxylic acid, alicyclic carboxylic acid and aromatic carboxylic acid, and the straight-chain carboxylic acid can be selected from formic acid, acetic acid, acrylic acid and propionic acid;
the molar ratio of the olefin to the carboxylic acid is 6: 1-1: 1;
the alcohol amine group modified ordered mesoporous C/SiO2The dosage of the supported heteropolyacid catalyst is 1-5 wt% of the mass of the carboxylic acid;
the reaction temperature is 30-80 ℃;
the reaction pressure is 0.5-1.5 MPa;
the stirring speed is 300-1000 r/min;
the reaction time is 2-12 h.
39. The alkanolamine group-modified ordered mesoporous C/SiO of claim 382The method for synthesizing carboxylic ester by catalyzing carboxylic acid and olefin through supported heteropolyacid is characterized in that the molar ratio of the olefin to the carboxylic acid is 4: 1-1: 1.
40. The alkanolamine group-modified ordered mesoporous C/SiO of claim 382The method for synthesizing carboxylic ester by catalyzing carboxylic acid and olefin through supported heteropoly acid is characterized in that the reaction temperature is 30-50 ℃.
41. The alkanolamine group-modified ordered mesoporous C/SiO of claim 382The method for synthesizing carboxylic ester by catalyzing carboxylic acid and olefin through the supported heteropolyacid is characterized in that the reaction pressure is 0.7-1.2 MPa.
42. The alkanolamine group-modified ordered mesoporous C/SiO of claim 382The method for synthesizing carboxylic ester by catalyzing carboxylic acid and olefin through the supported heteropolyacid is characterized in that the stirring speed is 400-1000 r/min.
43. The alcohol amine group-modified ordered mesoporous C/SiO of claim 422The method for synthesizing carboxylic ester by catalyzing carboxylic acid and olefin through the supported heteropolyacid is characterized in that the stirring speed is 600-800 r/min.
44. The alkanolamine group-modified ordered mesoporous C/SiO of claim 382The method for synthesizing carboxylic ester by catalyzing carboxylic acid and olefin through the supported heteropolyacid is characterized in that the reaction time is 8-12 hours.
45. The alcohol amine group-modified ordered mesoporous C/SiO of claim 442A process for synthesizing carboxylic ester from carboxylic acid and olefin by catalytic reaction of carried heteropoly acidThe reaction time is 8-10 h.
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