WO2005051540A1 - Catalizadores ácidos híbridos orgánicos-inorgánicos, procedimiento de preparación y su uso - Google Patents
Catalizadores ácidos híbridos orgánicos-inorgánicos, procedimiento de preparación y su uso Download PDFInfo
- Publication number
- WO2005051540A1 WO2005051540A1 PCT/ES2004/070100 ES2004070100W WO2005051540A1 WO 2005051540 A1 WO2005051540 A1 WO 2005051540A1 ES 2004070100 W ES2004070100 W ES 2004070100W WO 2005051540 A1 WO2005051540 A1 WO 2005051540A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid catalyst
- catalyst according
- alkylation
- inorganic
- inorganic matrix
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 10
- 150000007524 organic acids Chemical class 0.000 title description 3
- 150000007522 mineralic acids Chemical class 0.000 title 1
- 239000011159 matrix material Substances 0.000 claims abstract description 45
- 239000003377 acid catalyst Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000005804 alkylation reaction Methods 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 25
- 230000029936 alkylation Effects 0.000 claims description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 17
- 239000010457 zeolite Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- -1 Ce0 Chemical compound 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- SNHPHIVOTMMDRF-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane-2-sulfonic acid Chemical compound OS(=O)(=O)C(F)(C(F)(F)F)C(F)(F)F SNHPHIVOTMMDRF-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- BEJNERDRQOWKJM-UHFFFAOYSA-N kojic acid Chemical compound OCC1=CC(=O)C(O)=CO1 BEJNERDRQOWKJM-UHFFFAOYSA-N 0.000 claims description 6
- 229960004705 kojic acid Drugs 0.000 claims description 6
- WZNJWVWKTVETCG-UHFFFAOYSA-N kojic acid Natural products OC(=O)C(N)CN1C=CC(=O)C(O)=C1 WZNJWVWKTVETCG-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 230000010933 acylation Effects 0.000 claims description 5
- 238000005917 acylation reaction Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002168 alkylating agent Substances 0.000 claims description 4
- 229940100198 alkylating agent Drugs 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001879 gelation Methods 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- 230000017105 transposition Effects 0.000 claims description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 230000021736 acetylation Effects 0.000 claims description 3
- 238000006640 acetylation reaction Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- 229940119170 jojoba wax Drugs 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 claims description 2
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000002314 glycerols Chemical class 0.000 claims description 2
- 238000005858 glycosidation reaction Methods 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims 2
- 150000001345 alkine derivatives Chemical class 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 229910052680 mordenite Inorganic materials 0.000 claims 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 claims 1
- 230000001131 transforming effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 37
- 229920000557 Nafion® Polymers 0.000 description 17
- 239000002253 acid Substances 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 239000011949 solid catalyst Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000010908 decantation Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 150000002923 oximes Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 150000008053 sultones Chemical class 0.000 description 3
- 239000003930 superacid Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical class CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 101150101537 Olah gene Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009838 combustion analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000006361 intramolecular Friedel-Crafts acylation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VTACLVUOTMPORB-UHFFFAOYSA-N n,n-bis(trimethylsilyl)acetamide Chemical compound CC(=O)N([Si](C)(C)C)[Si](C)(C)C VTACLVUOTMPORB-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions
- the present invention relates to hybrid acid solid catalysts containing perfluoroalkyl sulfonic groups, their preparation and their use as heterogeneous reusable catalysts for reactions in organic chemistry as well as active components in fuel cells.
- the alkylsulfonic group is a functionality that has a Bronsted acidity of slightly lower strength than H 2 S0 pure, and whose intrinsic acidity can be modulated by inductive effects, increasing it with the presence of electronegative groups that increase the acid strength of the sulfonic group.
- cogels formed by partially depolymerized Nafion are cogelified with a silica gel, obtaining an amorphous hybrid material with surface areas up to 200m 2 g -1 .
- the derivative of depolymerized Nafion deposited on silica is analogous to that indicated in scheme 1 for the polymeric Nafion, but * x "e" and "in the formula are small compared to the polymeric Nafion and may be between 10 and 20.
- organic-inorganic hybrid materials containing sulfonic groups of high surface area molecules that act as precursors of alkylsulfonic groups such as, for example, 3-mercaptopropyltriethoxysilane have been anchored in silica or structured meso silica of the MCM-41 type.
- These hybrid materials of large surface area show after the oxidation of the -SH group to sulfonic, the catalytic activity of the sulfonic groups (scheme 2).
- a material formed by an inorganic matrix containing silicon and / or one or more types of metal atoms is described, for example amorphous silica, silica-alumina, micro and / or mesoporous solids with molecular sieve structure or not, containing perfluoroalkyl sulfonic groups covalently anchored to the walls and which are responsible for the acidity and catalytic properties of the material.
- the substantial structural fact of the present invention is the existence of covalent bonds between the large surface area support (> 200 m 2 xg _1 ) and the perfluoroalkylsulfonic groups.
- the materials of this invention are different from Nafion since this does not contain an inorganic component that is the organizer of the surface and responsible for the area of the material and its high catalytic activity.
- the values of "x" e "and" of scheme 1 are typically 0 or very low but in no case can the polymeric perfluoroalkylsulfonic group be considered.
- the materials described herein differ from any other organic-inorganic hybrid that has been described with sulfonic groups in the existence of covalent bonds between the inorganic matrix and the organic part of the hybrid.
- the presence of perfluoroalkylsulfonic groups is essential and is responsible for greater intrinsic acidity of the acid sites and greater stability of the chains with respect to the non-perfluorinated alkylsulfonic groups.
- the present invention relates to an acid catalyst characterized in that it is an organic-inorganic hybrid solid comprising at least: - an inorganic matrix one or more perfluoroalkyl groups covalently bonded to said 'matrix through COT links, where C represents carbon, 0 represents oxygen and T represents atoms selected from silicon atoms, atoms of a metallic element, atoms of different metal elements, and mixtures from them.
- T is a metal atom
- said metal atom is preferably forming part of the corresponding oxide.
- T is silicon, it is also preferably in the form of silica.
- the inorganic matrix may be formed by inorganic oxides and may be selected from one or more amorphous inorganic oxides, one or more ordered inorganic oxides and mixtures thereof.
- said inorganic matrix is one or more structured mesoporous silicates.
- said structured mesoporous silicate is selected from MCM-41, MCM-48, SBA-15 and mixtures thereof.
- said inorganic matrix is one or more zeolite.
- Said zeolite may be a synthetic or suitably modified microporous zeolite, such as the zeolite Y, beta, order, ZSM5, or mixtures thereof.
- Said zeolite may be one or more delaminated zeolites.
- the ITQ-2 zeolite for example, the ITQ- ⁇ zeolite or a mixture of both are used.
- Other materials that may be constitutive of the inorganic matrix are an oxide selected from silica, alumina, silica-alumina, an oxide or metal oxides, and mixtures thereof.
- the oxide is silica, it can be colloidal or non-colloidal.
- the metal oxides there are examples of high-area oxides such as Ce0 2 , titania-TiO 2 - (anatase phase, rutile or mixture of both in any proportion), zirconia -Zr0 2 -, ZnO, Nb0 2 A1 2 0 3 (in any of its crystallographic phases or mixtures of them in any proportion), or mixtures thereof.
- the inorganic matrix may also be one or more types of clays. For example, it may consist of a laminar clay, a fibrous clay or a mixture of both.
- said clay is selected from montmorillonite, sepiolite, sepiolite in which all or part of the Mg has been extracted, and mixtures thereof.
- organic-inorganic hybrid acid catalyst is the material formed by the reaction of high surface silicas with the sultone.
- a second object of the present invention is a process for the preparation of a solid organic-inorganic hybrid catalyst comprising at least one inorganic matrix to which one or more perfluoroalkylsulfonic groups are covalently linked through COT bonds, where C represents carbon, O represents oxygen and T represents atoms selected from silicon atoms, atoms of a metallic element, atoms of different metallic elements, and mixtures thereof, characterized in that it comprises carrying out a reaction in which said inorganic matrix is contacted with a fluorinated reagent , which comprises at least one perfluoralkylsulfonic group and which may contain one or more non-fluorinated alkyl chains away from sulfur.
- Said fluorinated reagent comprises one or more functional groups -OS0 2 -.
- the reaction is preferably carried out at a temperature between room temperature and 60 ° C.
- the reaction is carried out with an inorganic matrix: fluorinated reagent ratio between 100: 1 and 2: 1.
- the fluorinated reagent is preferably trifluoromethylperfluorosultone.
- the contact reaction between the inorganic matrix and the partially or fully fluorinated reagent can be carried out by co-gelation of a soluble monomeric precursor of the inorganic matrix with the fluorinated reagent in which said precursor Soluble monomeric inorganic matrix undergoes hydrolysis.
- the fluorinated reagent is preferably 2- ⁇ triethoxy silyloxy) perfluoro-1-methylethylsulfonic acid.
- the soluble monomeric precursor of the inorganic matrix is preferably tetraethylorthosilicate.
- the oxide gel is formed in an aqueous solution or in another medium by hydrolysis at a determined pH in the presence of acid 2 - (triethoxysilyloxy) perfluoro-l-methylethylsulfonic acid which condenses during the process with the oxide precursor.
- acid 2 - (triethoxysilyloxy) perfluoro-l-methylethylsulfonic acid which condenses during the process with the oxide precursor.
- An illustrative example of this first embodiment of the process relates to the formation of a silica oxide containing perfluoroalkylsulfonic groups, by co-gelation of the monomeric tetraethylorthosilicate precursor with a perfluorinated reagent which is perfluoro-l-methylethylsulfonic acid 2- (triethoxysilyloxy) acid in which tetraethylorthosilicate undergoes hydrolysis in aqueous medium, and adding dodecylamine as a hydrolyzing agent.
- the proportion of tetraethylorthosilicate with respect to 2- (triethoxysilyloxy) perfluoro-l-methylethylsulfonic acid is 4: 1.
- the inorganic matrix is dehydrated, and said dehydrated inorganic matrix is contacted by heat treatment with the fluorinated reagent.
- Said inorganic matrix is preferably an inorganic oxide.
- the dehydrated inorganic matrix is contacted by heat treatment with the fluorinated reagent comprising at least one perfluoroalkylsulfonic group and which may or may not contain any alkyl group not bound to the sulfur atom, for a period of time between 5 minutes and 48 hours at a temperature between 20 ° C and 140 ° C.
- the fluorinated reagent is perfluorinated or partially fluorinated alpha-methyl-beta-sultone.
- a preferred example of this second embodiment is based on the reaction of an inorganic oxide conveniently dehydrated by heat treatment, with perfluorinated alpha-methyl-beta-sultone, obtaining a suspension.
- the suspension placed in a reactor, at a temperature between 20 and 140 ° C, is mechanically stirred for a time between 5 minutes and 48 hours, after which, the suspension is cooled and the solid containing the anchored perfluoroalkylsulfonic group is separated by decantation, filtration or centrifugation (scheme 3).
- the solid / sultone weight ratio can be varied between 100/1 and 2/1.
- the solid is thoroughly washed with distilled H 2 0 until the wash water has a neutral pH and the presence of sulfur in the wash is not detected.
- the content of perfluoroalkylsulfonic groups in the solid catalyst can be determined by acid-base titration, by chemical analysis of combustion C, S, by thermogravimetry, by quantitative spectroscopic methods and by combination of any of these methods.
- acid-base titration a certain amount of the solid catalyst is suspended in distilled water to which a few drops of phenolphthalein are added as an indicator, being titrated by a solution of NaOH of known normality.
- the IR spectra of these materials can be recorded in the transmission mode by preparing wafers of these solids that are transparent to infrared radiation by compression at pressures between 1 and 10 Tmxcm 2 for a time between 1 and 5 minutes. These self-consistent wafers are placed in a closed cell that allows their heating to a controlled temperature and reduced pressures (between 10 _1 and 10 "4 Pa).
- Erfluoroalkylsulfonic can be determined by gas adsorption isotherms (N 2 and Ar) applying BET and BJS algorithms, resulting in area measurements similar to the initial materials.
- the evacuation and pretreatment of the material should be carried out at temperatures below 380 ° C in order not to alter the perfluoroalkylsulfonic groups.
- Comparison of surface area and porosity measurements before and after anchoring of perfluorinated sulfonic groups, or cogel formation confirms that there is no substantial aggregation or modification of the surface during covalent anchoring treatment.
- a third object of the present invention is the use of the acid catalysts described in processes of transformation of organic or inorganic compounds.
- the solid catalysts described herein show a high catalytic activity as acids of a Bronsted nature for reactions of the types described in the chemical literature, and in specific references relating to Nafion, already inorganic-organic hybrids containing alkylsulfonic groups. .
- the transformations of organic compounds are: esterification, acylation, alkylation, glycosidation reactions (references cited in the background chapter: Synthesis (1986) 513-31; Recent Research Developments in Pur & Applied Chemistry 2 (1998) 297-310 ).
- An example of an esterification reaction is an esterification under stoichiometric conditions between a fatty acid and monoalcohols, diols or polyols.
- Products that can be obtained by said esterification reaction are an analogue of jojoba oil, a mixture of glycerin esters, one or more esters of kojic acid, and one or more esters of the sorbitan type.
- Another process of transforming organic compounds in which these catalysts can be used is a reaction selected from a transposition reaction of
- alkylations of benzene and its derivatives can be cited with electron donor substituents and using as alkylating agents alkenes or alcohols.
- alkylation of benzene with linear long-chain 1-alkenes such as the alkylation process of benzene with 1-dodecene.
- Friedel-Crafts acylation Friedel-Crafts acylations of aromatic compounds with carboxylic acids or anhydrides can be mentioned as acylating agents.
- a concrete example is an acetylation process of anisole or 2-methoxy naphthalene, as well as acetylation of 4-methoxybenzene.
- Beckmann transposition reaction mention may be made of obtaining ⁇ -caprolactam and dodecalactam by transposing the cyclodoxanone oxime and the cilododecanone oxime respectively.
- cyclohexanone to oxime and cyclododecanone to oxime can be carried out in a liquid phase and at temperatures around 170 ° C using a hybrid material where the perfluoroalkylsulfonic group is covalently anchored in the mesoporous silica MCM-41 (MCM-41 —PFS0 3 H) as catalyst at an oxime ratio: catalyst between 2 and 10%.
- MCM-41 mesoporous silica MCM-41
- PFS0 3 H mesoporous silica MCM-41
- a solvent a liquid such as benzonitrile can be used, dicyanobenzene, adipodinitrile or succinodinitrile at a solvent substrate ratio of 1:10.
- an alkylation reaction a process selected from an alkylation of isoparaffins, an alkylation of olefins and a mixture of both can be cited.
- a particular example is the alkylation of isobutene by isobutane at temperatures below 100 ° C.
- the alkylation of isobutene with isobutane can be carried out at a temperature of 50 ° C in order to obtain isooctane that serves to improve the octane number of the gasoline.
- an example is the alkylation of electron-rich alkenes by the addition of methanol and other alcohols.
- the methyl catalysts of isobutene and amylene which are used to improve the octane number of gasolines, can be obtained by using the solid catalysts described herein.
- These ethers can be obtained in a liquid phase at room temperature or below 50 ° C by reaction of the corresponding alkene in excess of methanol using MCM-41-PFSO 3 H as catalyst, in a catalyst alkene ratio between 2 and 10%.
- the reaction can also be catalyzed at atmospheric pressure and room temperature by passing an equimolar mixture of alkene and methanol over a fixed bed of MCM-41 — PFSO 3 H.
- the processes of transformation of organic compounds can be carried out in load processes (reactor discontinuous), as well as in continuous processes using for example a fixed bed reactor.
- the reactions are carried out by contacting the gas and / or liquid phase reagents with the solid catalyst containing the perfluoroalkylsulfonic groups anchored in the inorganic matrix.
- the temperature and reaction time will depend on the particular reaction to be studied and which are generally known from the knowledge existing in the chemical literature.
- Other applications of these materials are their use in ion permeable membranes, such as in fuel cells, since they combine high porosity and a high density of acid centers to the large surface area. In this case they are part of a porous electrode.
- the electrode can be constructed by deposition or immersion of the substrate in a suspension containing the hybrid material, by painting the substrate electrode, by the spin coating technique or any other method that allows a film of the solid to be arranged on the base support.
- FIGURES Figure 1 shows the X-ray powder diffractogram of MCM-41 (sample MCM-41-PFS0 3 H, solid line) and then (dashed line) of extracting the cetyltrimethylammonium used as the directing agent for structure, in which it is shown that the mesoporous structure of the material has been preserved during the perfluoroalkylation treatment.
- Figure 2 shows a thermogravimetric analysis and differential scanning calorimetry of the material MCM-41, (sample MCM-41-PFSO 3 H) where it is shown that the decomposition of the perfluoroalkylsulfonic group starts at temperatures above 380 ° C marking the limit of thermal stability of material; and the desorption of adsorption and protonated water in the sample is observed.
- Figure 3 shows a representative FT-IR spectrum of MCM-41 (self-consistent sample of MCM- 41 — PFSO 3 H), recorded at room temperature after heating the sample at 200 ° C for 1 h; the characteristic vibrations of the groups -S0 3 H and -S0 3 ⁇ have been highlighted.
- Example 1 Preparation of a material containing perfluoroalkylsulfonic groups anchored in mesostructured amorphous Si0 2 .
- Aerosil type silica (10 g) is suspended in 5 g. of perfluoro alfa-methyl-beta-sultone and the mixture is heated at 60 ° C for one day in autoclave under autogenous pressure.
- the autoclave allows mechanical agitation of the suspension that is regulated at 120 revolutions per minute.
- the solid is collected from the autoclave by decantation and washed thoroughly with distilled water until the pH of the wash waters is greater than 5 units.
- Example 2 Preparation of a material formed by a perfluoroalkylsulfonic anchor anchored in a long-distance mesoporous silica (MCM-41) 10 g of MCM-41 are added to 5 g. of the perfluorinated sultone and the suspension is heated at 60 ° C for one day in autoclave under autogenous pressure. The suspension is mechanically stirred at 120 revolutions per minute. After treatment, the autoclave is allowed to cool and the solid resulting from the reaction is collected by decantation and washed thoroughly with distilled water until the pH of the wash is greater than 5 units.
- MCM-411 long-distance mesoporous silica
- Example 3 Preparation of a material formed by a perfluoroalkylsulfonic anchor anchored in a mesoporous silica without long-distance order (SAM).
- SAM Long-distance order mesoporous silica
- 5 g. of perfluoro alfa-methyl-beta-sultone is suspended in 5 g. of perfluoro alfa-methyl-beta-sultone and the mixture is heated at 60 ° C for one day in autoclave under autogenous pressure.
- the autoclave allows mechanical agitation of the suspension that is regulated at 120 revolutions per minute. After time, the solid is collected from the autoclave by decantation and washed thoroughly with distilled water until the pH of the wash waters is greater than 5 units.
- Example 4 Preparation of a material formed by a perfluoroalkylsulfonic anchor anchored in a mesoporous silica without long-distance order (S
- Example 5 Esterification of fatty acids.
- the esterification of analogous fatty acids of jojoba oil used in cosmetics are achieved with selectivity greater than 95% and acid conversions greater than 90% by treating equivalent amounts of fatty acids and alcohols dissolved in toluene at 60 ° C in the presence of MCM-41 — PFS0H, the substrate catalyst ratio can be varied between 2% and 10%. Once the maximum conversion has been achieved, the catalyst is recovered by simple filtration and can be reused for the same reaction under the same conditions a minimum of times equal to 10.
- the reaction analysis is carried out following the standard method consisting in the extraction of an aliquot and addition thereof on pyridine followed by silylation using N, N-bis (trimethylsilyl) acetamide as the silylating agent.
- Example 6 Formation of glycerin onosters with fatty acids. These esters are formed by treating a mixture of fatty acid and glycerin in a ratio between 1: 1 and 1: 5, in the presence of the MCM-41-PFSO3H catalyst in a catalyst: fatty acid ratio between 2 and 10%.
- the reaction temperature can vary between ambient and 100 ° C, achieving a suitable speed when the reaction is carried out at 60 ° C.
- the analytical method used is analogous to that described in Example 5. In this case, mixtures of glycerin monoesters and diesters are obtained in which the monoester predominates in a percentage greater than 60% where a primary glycerin alcohol is esterified .
- Example 7 Esterification of kojic acid.
- the esters of fatty acid and kojic acid, particularly sterate and palmitate, are used in cosmetics as an active component of depigmenting and anti-aging formulations. These esters can be achieved by reaction of kojic acid and fatty acid in stoichiometric amounts and using a catalyst ratio MCM-41-PFSO3H to substrate between 2 and 10%.
- the reaction can be carried out at T between ambient and 100 ° C and in different solvents, achieving adequate speeds when the reaction is carried out at 60 ° C in CH 3 CN as solvent, conversions being achieved over 80%.
- the catalyst is recovered by filtration and can be reused in successive tests.
- Example 8 Esterification reaction to obtain esters of the sorbitan type. Sorbitol acetonides are prepared by dissolving this sorbitol in acetone by adding a few drops of HC1 as a catalyst. The solution is stirred at room temperature for a space exceeding two hours. To a crude mixture of these acetonides is added the desired fatty acid, in a sorbitol: stoichiometric fatty acid ratio, and MCM-41 — PFS0 3 H in a catalyst: substrate ratio between 2 and 10% is added as catalyst. The reaction is carried out at a temperature between room temperature and 100 ° C, with a suitable temperature being 60 ° C when the reaction is carried out in acetone.
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Application Number | Priority Date | Filing Date | Title |
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ES200302850A ES2233211B1 (es) | 2003-11-25 | 2003-11-25 | Catalizadores acidos hibridos organicos-inorganicos, procedimiento de preparacion y su uso. |
ESP200302850 | 2003-11-25 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2050755A1 (en) | 2007-10-19 | 2009-04-22 | Total Petrochemicals Research Feluy | Supported ionic liquids or activating supports |
EP2070953A1 (en) | 2007-12-11 | 2009-06-17 | Total Petrochemicals Research Feluy | Activating supports based on phosphonium complexes |
CN106040282A (zh) * | 2016-05-27 | 2016-10-26 | 南京工业大学 | 一种催化异丁烯与羧酸合成羧酸叔丁酯的so3h‑sba‑15分子筛催化剂及其制备方法与应用 |
CN108217684A (zh) * | 2018-02-11 | 2018-06-29 | 中国科学院大连化学物理研究所 | 一种促进Beta分子筛合成的方法 |
Families Citing this family (1)
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PT109991A (pt) * | 2017-03-24 | 2018-09-24 | Univ Do Porto | Catalisadores heterogéneos, processo de preparação e sua aplicação no processo de produção de ésteres alquílicos deácidos gordos. |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0034061A2 (en) * | 1980-02-07 | 1981-08-19 | Sumitomo Chemical Company, Limited | Method and apparatus for removal of heat from an olefin polymerization reactor |
US5922635A (en) * | 1997-05-07 | 1999-07-13 | Olah; George A. | Nanoscale solid superacid catalysts with pendant fluoroalkylsulfonic acid or fluoro, perfluoroalkylsulfonic acid groups |
-
2003
- 2003-11-25 ES ES200302850A patent/ES2233211B1/es not_active Expired - Fee Related
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2004
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0034061A2 (en) * | 1980-02-07 | 1981-08-19 | Sumitomo Chemical Company, Limited | Method and apparatus for removal of heat from an olefin polymerization reactor |
US5922635A (en) * | 1997-05-07 | 1999-07-13 | Olah; George A. | Nanoscale solid superacid catalysts with pendant fluoroalkylsulfonic acid or fluoro, perfluoroalkylsulfonic acid groups |
Non-Patent Citations (1)
Title |
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ALVARO M. ET AL: "Single-step and catalytic activity of mesoporous MCM-41 and SBA-15 silicas functionalized with perfluoroalkylsulfonic acid groups analogous to Nafion", CHEM. COMMUN., 11 March 2004 (2004-03-11), pages 956 - 957 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2050755A1 (en) | 2007-10-19 | 2009-04-22 | Total Petrochemicals Research Feluy | Supported ionic liquids or activating supports |
EP2070953A1 (en) | 2007-12-11 | 2009-06-17 | Total Petrochemicals Research Feluy | Activating supports based on phosphonium complexes |
CN106040282A (zh) * | 2016-05-27 | 2016-10-26 | 南京工业大学 | 一种催化异丁烯与羧酸合成羧酸叔丁酯的so3h‑sba‑15分子筛催化剂及其制备方法与应用 |
CN108217684A (zh) * | 2018-02-11 | 2018-06-29 | 中国科学院大连化学物理研究所 | 一种促进Beta分子筛合成的方法 |
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ES2233211B1 (es) | 2006-08-01 |
ES2233211A1 (es) | 2005-06-01 |
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