JP4974468B2 - Y型ゼオライトアルキル化触媒 - Google Patents
Y型ゼオライトアルキル化触媒 Download PDFInfo
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- JP4974468B2 JP4974468B2 JP2005071799A JP2005071799A JP4974468B2 JP 4974468 B2 JP4974468 B2 JP 4974468B2 JP 2005071799 A JP2005071799 A JP 2005071799A JP 2005071799 A JP2005071799 A JP 2005071799A JP 4974468 B2 JP4974468 B2 JP 4974468B2
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- JP
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- Prior art keywords
- catalyst
- angstroms
- olefin
- type zeolite
- pore size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims description 214
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 114
- 239000010457 zeolite Substances 0.000 title claims description 112
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 108
- 238000005804 alkylation reaction Methods 0.000 title claims description 78
- 230000029936 alkylation Effects 0.000 title claims description 45
- 239000011148 porous material Substances 0.000 claims description 148
- 150000001336 alkenes Chemical class 0.000 claims description 96
- 238000000034 method Methods 0.000 claims description 81
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 67
- 239000002131 composite material Substances 0.000 claims description 64
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 55
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 44
- 238000004519 manufacturing process Methods 0.000 claims description 41
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000004711 α-olefin Substances 0.000 claims description 33
- 230000001186 cumulative effect Effects 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 24
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 239000003039 volatile agent Substances 0.000 claims description 10
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 description 44
- 230000009849 deactivation Effects 0.000 description 36
- 239000000047 product Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000002459 porosimetry Methods 0.000 description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 15
- 229910052753 mercury Inorganic materials 0.000 description 15
- -1 aluminum halide Chemical class 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 13
- 229910017604 nitric acid Inorganic materials 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 150000004996 alkyl benzenes Chemical class 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 238000006317 isomerization reaction Methods 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000006277 sulfonation reaction Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 230000002152 alkylating effect Effects 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 3
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PMPBFICDXLLSRM-UHFFFAOYSA-N 1-propan-2-ylnaphthalene Chemical compound C1=CC=C2C(C(C)C)=CC=CC2=C1 PMPBFICDXLLSRM-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
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Description
(a)上記本発明のY型ゼオライト触媒、および(b)結合剤。
(a)Y型ゼオライトを揮発物の存在下で結合剤と接触させて、Y型ゼオライトの重量%が得られる触媒複合体の全乾量に基づき約40乃至約99%の範囲にあり、そして混合物の揮発分が混合物の約30重量%乃至約70重量%の範囲にある混合物を形成する工程、
(b)混合物を成形して複合体を形成する工程、
(c)複合体を乾燥する工程、そして
(d)複合体を実質的に乾燥した環境下で焼成する工程。
「アルキレート」は、アルキル化芳香族炭化水素を意味する。
異性化工程は、バッチ式または連続式で実施することができる。工程温度は50℃乃至250℃の範囲であってよい。バッチ式では、一般的な方法は撹拌下にあるオートクレーブまたはガラス製フラスコを使用することであり、所望の反応温度に加熱してもよい。連続法は、固定床法で最も効率良く行われる。固定床法の空間速度は、0.1乃至10またはもっと高い時間当り重量の空間速度範囲とすることができる。
ノルマルアルファオレフィン、部分分枝鎖異性化オレフィンおよび分枝鎖オレフィンによる芳香族炭化水素のアルキル化は、当該分野の熟練者には知られている任意の方法で実施することができる。
アルキル化炭化水素のスルホン化は、当該分野の熟練者には公知の任意の方法により実施することができる。
アルキル芳香族スルホン酸の炭酸塩化・過塩基性化は、当該分野の熟練者には公知の任意の方法により実施することができ、アルキル芳香族スルホネートが生成する。
[実施例1] 触媒複合体1の製造
Y型ゼオライトアルキル化触媒複合体を下記の方法により製造した。
次のようにしたことを除いては、上記実施例1で使用した操作に従ってY型ゼオライト触媒を製造した。
次のようにしたことを除いては、上記実施例2に記載した操作によりこの触媒を製造した。
次のようにしたことを除いては、実施例2に記載した操作によりこの触媒を製造した。
ゼオリスト・インターナショナル社より入手したY型ゼオライト、CBV760(商品名)の試料を用いて、受注触媒製造業者の手によりタブレット状Y型ゼオライト触媒を製造した。タブレットは、円筒状で直径1/8インチ、長さおよそ1/8インチであった。水銀圧入式ポロシメトリは、ピーク孔径が815オングストロームで、300オングストローム未満の孔径の細孔の累積孔容積が0.0844mL/グラムであることを示した。
次のようにしたことを除いては、実施例2に記載した操作によりこの触媒を製造した。
次のようにしたことを除いては、実施例2に記載した操作によりこの触媒を製造した。
────────────────────────────────────
水銀圧入式ポロシメトリ特性
触媒 全PV* PV<300オングスト 細孔ピーク孔径
複合体 (mL/グラム) ローム**(mL/グラム) (オングストローム)
────────────────────────────────────
1 0.4612 0.140 1167
2 0.4207 0.142 878
3 0.4208 0.140 1006
4 0.4492 0.149 1486
5*** 0.3914 0.084 815
10 0.403 0.155 941
12 0.399 0.144 900
────────────────────────────────────
*全孔容積
**300オングストローム以下の孔径の細孔の全孔容積
***触媒5は複合体ではない。触媒5は、上記実施例5に記載したようにして
製造したタブレット状のY型ゼオライト粉末である。
一般に、ノルマルアルファオレフィンの異性化は以下に記載するようにして実施する。
アルファオレフィン 89.1%
ベータオレフィン 0.5%
内部オレフィン 1.4%
三置換オレフィン 0.2%
ビニリデンオレフィン 9.5%(炭素核磁気共鳴分光法により測定)
分枝鎖オレフィン 11%(赤外分光法により測定)
ノルマルアルファオレフィン、部分分枝鎖異性化オレフィンおよび分枝鎖オレフィンによる芳香族炭化水素のアルキル化を以下のようにして実施した。
上記実施例9のようにして製造したアルキルベンゼンアルキレートを、下記の条件を用いて、チューブ状反応器(長さ2メートル、内径1センチメートル)内に三酸化硫黄(SO3)と空気を順流で同時に流すことによりスルホン化した。
加熱及び冷却能力を備え、300から350rpmの間で回転するステンレス鋼製機械撹拌器、撹拌翼の真上に位置するCO2添加用のガス導入管(内径2ミリメートル)、窒素ガス下にある蒸留カラムと冷却器を備えた5リットル四つ口反応器に、収集物123.7グラムを入れた。
上記実施例9のアルキル化反応と同様のアルキル化反応において、アルキル化触媒の失活速度を測定した。
如何なる理論にも結び付かないが、本発明の触媒複合体に関して相対失活速度を大きく低減させるには、触媒のシリカ対アルミナ比とパーセントゼオライトが高いことが重要であると思われる。表3において、触媒6及び8は同じような細孔のピーク孔径と累積孔容積を有するものの、シリカ対アルミナ比は非常に違っている。シリカ対アルミナ比が6.7から60に増加し、パーセントゼオライトが70%から80%に増加することによって、触媒8では100の相対失活速度が触媒6では67に低減する。
如何なる理論にも結び付かないが、ピーク孔径が本発明の触媒複合体の失活速度に影響を及ぼすと思われる。ピーク孔径が大きいほど相対失活速度は速くなる。表4において、触媒複合体9及び10の比較を行う、というのは、両者は累積孔容積が174対155で僅かしか違わないのに、触媒複合体10のピーク孔径941、相対失活速度35に比べて、触媒複合体9はピーク孔径が1513でずっと大きく、そして相対失活速度が73でずっと速いからである。
如何なる理論にも結び付かないが、300オングストローム以下の孔径の細孔の累積孔容積を減らすことが失活速度の低減をもたらすと思われる。表5において、触媒複合体16及び18は累積孔容積だけが違っていてそれぞれ162と136であるが、触媒複合体18の相対失活速度38に比べて、触媒複合体16は相対失活速度が54で速い。
Claims (43)
- Y型ゼオライトからなり、ピーク孔径がASTM試験第D4284−03による測定値として2000オングストローム未満であり、そして500オングストローム以下の孔径の細孔の累積孔容積が、ASTM試験第D4284−03による測定値としてグラム当り0.30ミリリットル以下である大細孔構造を持つ芳香族炭化水素のアルキル化のための触媒。
- 400オングストローム以下の孔径の細孔の累積孔容積が、グラム当り0.30ミリリットル未満である請求項1に記載の触媒。
- 300オングストローム以下の孔径の細孔の累積孔容積が、グラム当り0.25ミリリットル未満である請求項2に記載の触媒。
- 300オングストローム以下の孔径の細孔の累積孔容積が、グラム当り0.20ミリリットル未満である請求項3に記載の触媒。
- 400オングストローム以下の孔径の細孔の累積孔容積が、グラム当り0.05ミリリットル乃至0.18ミリリットルの範囲にある請求項4に記載の触媒。
- 300オングストローム以下の孔径の細孔の累積孔容積が、グラム当り0.08ミリリットル乃至0.16ミリリットルの範囲にある請求項5に記載の触媒。
- ピーク孔径が、700オングストローム乃至1800オングストロームの範囲にある請求項1に記載の触媒。
- ピーク孔径が、750オングストローム乃至1600オングストロームの範囲にある請求項7に記載の触媒。
- 触媒のピーク孔径が、900オングストローム乃至1400オングストロームの範囲にある請求項8に記載の触媒。
- Y型ゼオライトのシリカとアルミナとの比が、5:1乃至100:1の範囲にある請求項1に記載の触媒。
- Y型ゼオライトのシリカとアルミナとの比が、30:1乃至80:1の範囲にある請求項10に記載の触媒。
- Y型ゼオライトのシリカとアルミナとの比が、50:1乃至70:1の範囲にある請求項11に記載の触媒。
- 触媒がタブレットの形状にある請求項1に記載の触媒。
- ピーク孔径が500オングストローム乃至1500オングストロームの範囲にあり、そして500オングストローム以下の孔径の細孔の累積孔容積が、グラム当り0.05ミリリットル乃至0.15ミリリットルの範囲にある請求項13に記載の触媒。
- 下記の成分からなる芳香族炭化水素のアルキル化のための触媒複合体:
(a)請求項1に記載の触媒、および(b)結合剤。 - 結合剤が無機物質である請求項15に記載の触媒複合体。
- 結合剤がアルミナである請求項16に記載の触媒複合体。
- Y型ゼオライトが、触媒複合体の全乾量に基づき40重量%乃至99重量%の範囲の量で存在する請求項15に記載の触媒複合体。
- Y型ゼオライトが、触媒複合体の全乾量に基づき50重量%乃至85重量%の範囲の量で存在する請求項18に記載の触媒複合体。
- 下記の工程からなる芳香族炭化水素のアルキル化のための触媒複合体の製造方法:
(a)Y型ゼオライトを揮発物の存在下で結合剤と接触させて、得られる触媒複合体の全乾量に基づいてY型ゼオライトの重量%が40乃至99%の範囲にあり、そして混合物の揮発分が混合物の30重量%乃至70重量%の範囲にある混合物を形成する工程、
(b)混合物を成形して複合体を形成する工程、
(c)複合体を乾燥する工程、そして
(d)複合体を実質的に乾燥した環境下で焼成する工程。 - (b)工程において成形が押出し成形である請求項20に記載の方法。
- (a)工程においてY型ゼオライトの重量%が、50乃至85の範囲にある請求項20に記載の方法。
- (a)工程において結合剤が無機物質である請求項20に記載の方法。
- 結合剤がアルミナである請求項23に記載の方法。
- (a)工程において混合物の揮発分が混合物の40重量%乃至60重量%の範囲にある請求項20に記載の方法。
- 揮発分が水と酸とからなる請求項25に記載の方法。
- 請求項20に記載の方法により製造された芳香族炭化水素のアルキル化のための触媒複合体。
- Y型ゼオライトからなり、ピーク孔径がASTM試験第D4284−03による測定値として2000オングストローム未満であり、そして500オングストローム以下の孔径の細孔の累積孔容積が、ASTM試験第D4284−03による測定値としてグラム当り0.30ミリリットル以下である大細孔構造を持つ触媒の存在下に、少なくとも一種の芳香族炭化水素を、アルキル化条件下で少なくとも一種のオレフィンと接触させることからなるアルキル化芳香族組成物の製造方法。
- さらに、アルキル化芳香族組成物をスルホン化してアルキル化芳香族スルホン酸を生成させることを含む請求項28に記載の方法。
- さらに、アルキル化芳香族スルホン酸をアルカリ土類金属および二酸化炭素と反応させて、炭酸塩化した過塩基性アルキル化芳香族スルホネートを生成させることを含む請求項29に記載の方法。
- 少なくとも一種の芳香族炭化水素を、請求項20に記載の方法により製造された触媒複合体の存在下に、アルキル化条件下で少なくとも一種のオレフィンと接触させることからなるアルキル化芳香族組成物の製造方法。
- 芳香族炭化水素がベンゼンまたはトルエンである請求項31に記載の方法。
- オレフィンが、アルファオレフィン、異性化オレフィン、分枝鎖オレフィンまたはそれらの混合物である請求項31に記載の方法。
- オレフィンが炭素原子4個乃至80個を有する請求項33に記載の方法。
- アルファオレフィンまたは異性化オレフィンが炭素原子6個乃至40個を有する請求項33に記載の方法。
- アルファオレフィンまたは異性化オレフィンが炭素原子20個乃至40個を有する請求項35に記載の方法。
- 分枝鎖オレフィンが炭素原子6個乃至70個を有する請求項33に記載の方法。
- 分枝鎖オレフィンが炭素原子8個乃至50個を有する請求項37に記載の方法。
- 分枝鎖オレフィンが炭素原子12個乃至18個を有する請求項38に記載の方法。
- オレフィンが、炭素原子6個乃至40個を持つ部分分枝鎖異性化オレフィンである請求項33に記載の方法。
- 部分分枝鎖異性化オレフィンが炭素原子20個乃至40個を有する請求項40に記載の方法。
- さらに、アルキル化芳香族組成物をスルホン化してアルキル化芳香族スルホン酸を生成させることを含む請求項31に記載の方法。
- さらに、アルキル化芳香族スルホン酸をアルカリ土類金属および二酸化炭素と反応させて、炭酸塩化した過塩基性アルキル化芳香族スルホネートを生成させることを含む請求項42に記載の方法。
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JP2012012404A (ja) * | 2004-03-12 | 2012-01-19 | Chevron Oronite Co Llc | アルキル化芳香族組成物、ゼオライト触媒組成物及びその製造方法 |
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JP2005254237A (ja) | 2005-09-22 |
EP1584373A3 (en) | 2006-02-01 |
JP2012024766A (ja) | 2012-02-09 |
CA2497958A1 (en) | 2005-09-12 |
US20050250970A1 (en) | 2005-11-10 |
US7563937B2 (en) | 2009-07-21 |
EP2095874A3 (en) | 2009-10-21 |
EP2095874A2 (en) | 2009-09-02 |
EP2295392A2 (en) | 2011-03-16 |
CA2497958C (en) | 2013-09-24 |
EP1584373A2 (en) | 2005-10-12 |
US7041863B2 (en) | 2006-05-09 |
US6974788B2 (en) | 2005-12-13 |
US20050203322A1 (en) | 2005-09-15 |
SG115751A1 (en) | 2005-10-28 |
EP2295392A3 (en) | 2012-10-17 |
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