JP6148665B2 - 有機化合物のアルキル化法 - Google Patents
有機化合物のアルキル化法 Download PDFInfo
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- JP6148665B2 JP6148665B2 JP2014503254A JP2014503254A JP6148665B2 JP 6148665 B2 JP6148665 B2 JP 6148665B2 JP 2014503254 A JP2014503254 A JP 2014503254A JP 2014503254 A JP2014503254 A JP 2014503254A JP 6148665 B2 JP6148665 B2 JP 6148665B2
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- Prior art keywords
- preferred
- alkylation
- zeolitic materials
- catalyst
- mixture
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 145
- 150000002894 organic compounds Chemical class 0.000 title claims description 74
- 230000002152 alkylating effect Effects 0.000 title claims description 5
- 239000000463 material Substances 0.000 claims description 162
- 238000005804 alkylation reaction Methods 0.000 claims description 89
- 239000000203 mixture Substances 0.000 claims description 88
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 85
- 239000003054 catalyst Substances 0.000 claims description 84
- 239000010457 zeolite Substances 0.000 claims description 69
- 239000002168 alkylating agent Substances 0.000 claims description 59
- 229940100198 alkylating agent Drugs 0.000 claims description 59
- 238000001308 synthesis method Methods 0.000 claims description 55
- 230000029936 alkylation Effects 0.000 claims description 54
- 229910021536 Zeolite Inorganic materials 0.000 claims description 53
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 47
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 37
- 150000001336 alkenes Chemical class 0.000 claims description 36
- 229910052783 alkali metal Inorganic materials 0.000 claims description 32
- 150000001340 alkali metals Chemical class 0.000 claims description 29
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 23
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 17
- 150000001768 cations Chemical class 0.000 claims description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 150000001555 benzenes Chemical class 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 43
- 230000015572 biosynthetic process Effects 0.000 description 41
- 125000000217 alkyl group Chemical group 0.000 description 39
- 238000001354 calcination Methods 0.000 description 39
- 238000003786 synthesis reaction Methods 0.000 description 39
- 239000000047 product Substances 0.000 description 34
- 150000001491 aromatic compounds Chemical class 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 238000001035 drying Methods 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 125000003118 aryl group Chemical group 0.000 description 27
- 125000000524 functional group Chemical group 0.000 description 27
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 22
- 239000011230 binding agent Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000011148 porous material Substances 0.000 description 17
- -1 dibenzylmethyl Chemical group 0.000 description 16
- 239000011734 sodium Substances 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 238000011282 treatment Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 238000002955 isolation Methods 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 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 7
- 150000007513 acids Chemical class 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 5
- BFIMMTCNYPIMRN-UHFFFAOYSA-N 1,2,3,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1 BFIMMTCNYPIMRN-UHFFFAOYSA-N 0.000 description 4
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 4
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 4
- HILAULICMJUOLK-UHFFFAOYSA-N 1,3-diethyl-5-methylbenzene Chemical compound CCC1=CC(C)=CC(CC)=C1 HILAULICMJUOLK-UHFFFAOYSA-N 0.000 description 4
- AFZZYIJIWUTJFO-UHFFFAOYSA-N 1,3-diethylbenzene Chemical compound CCC1=CC=CC(CC)=C1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 4
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 4
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- QUEBYVKXYIKVSO-UHFFFAOYSA-N m-propyltoluene Chemical compound CCCC1=CC=CC(C)=C1 QUEBYVKXYIKVSO-UHFFFAOYSA-N 0.000 description 4
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 4
- BWYYVSNVUCFQQN-UHFFFAOYSA-N 1,3-diphenylpropan-2-amine Chemical class C=1C=CC=CC=1CC(N)CC1=CC=CC=C1 BWYYVSNVUCFQQN-UHFFFAOYSA-N 0.000 description 3
- XNXIYYFOYIUJIW-UHFFFAOYSA-N 3-methylbutylbenzene Chemical compound CC(C)CCC1=CC=CC=C1 XNXIYYFOYIUJIW-UHFFFAOYSA-N 0.000 description 3
- SUMOGCZUNXXYRP-UHFFFAOYSA-N 4-methylpentylbenzene Chemical compound CC(C)CCCC1=CC=CC=C1 SUMOGCZUNXXYRP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 238000005469 granulation Methods 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
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- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
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- MEMBJMDZWKVOTB-UHFFFAOYSA-N 1-ethyl-2,4-dimethylbenzene Chemical group CCC1=CC=C(C)C=C1C MEMBJMDZWKVOTB-UHFFFAOYSA-N 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 2
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- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- OGVRJXPGSVLDRD-UHFFFAOYSA-N 2,3-dimethylanthracene Chemical compound C1=CC=C2C=C(C=C(C(C)=C3)C)C3=CC2=C1 OGVRJXPGSVLDRD-UHFFFAOYSA-N 0.000 description 2
- GYMFBYTZOGMSQJ-UHFFFAOYSA-N 2-methylanthracene Chemical compound C1=CC=CC2=CC3=CC(C)=CC=C3C=C21 GYMFBYTZOGMSQJ-UHFFFAOYSA-N 0.000 description 2
- XDWURHFOCYSDBT-UHFFFAOYSA-N 3,3-dibenzyl-1,4-diazabicyclo[2.2.2]octane Chemical compound C1N(CC2)CCN2C1(CC=1C=CC=CC=1)CC1=CC=CC=C1 XDWURHFOCYSDBT-UHFFFAOYSA-N 0.000 description 2
- GKYWZUBZZBHZKU-UHFFFAOYSA-N 3-methylphenanthrene Chemical compound C1=CC=C2C3=CC(C)=CC=C3C=CC2=C1 GKYWZUBZZBHZKU-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 229930192474 thiophene Natural products 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(a)BEA骨格構造を有する1種以上のゼオライト材料を含む触媒を供給する工程、
ここで、前記BEA骨格構造はYO2、および任意にX2O3を含み、
式中、Yは四価元素であり、Xは三価元素である前記工程、
(b)1種以上のアルキル化有機化合物を得るために、1基以上の反応器において、1種以上のアルキル化剤の存在下で、触媒と、1種以上のアルキル化可能な有機化合物とを接触させる工程を含み、
前記1種以上のゼオライト材料が、構造規定剤として有機テンプレートを採用しない合成プロセスにより得ることができる、前記プロセスに関する。
ここで、より好ましくは、X線回折パターンは少なくとも以下の反応を含む:
(1)種晶および1種以上のYO2供給源を含む混合物を調製する工程;ならびに
(2)前記混合物を結晶化する工程
を含み、BEA骨格構造が好ましくはX2O3を含むとき、工程(1)に記載の混合物は1種以上のX2O3供給源をさらに含む。
(3)BEA骨格構造を有するゼオライト材料を、好ましくは、濾過によって単離する工程、および/または
(4)BEA骨格構造を有するゼオライト材料を洗浄する工程、および/または
(5)BEA骨格構造を有するゼオライト材料を乾燥する工程、および/または
(6)BEA骨格構造を有するゼオライト材料をイオン交換処理に供する工程
を含み、ここで、工程(3)および/または(4)および/または(5)および/または(6)は、任意の順序で行うことができ、前記工程の1以上は、好ましくは、少なくとも1回繰り返される。
より好ましくはトルエン、ノルマルプロピルベンゼン、エチルベンゼン、クメン、ブチルベンゼン、イソアミルベンゼンおよびイソヘキシルベンゼンからなる群、より好ましくはトルエン、ノルマルプロピルベンゼン、エチルベンゼンおよびクメンからなる群より選択される1種以上の化合物を包含し、さらに好ましくは、1種以上のアルキル化可能な有機化合物は、トルエンおよび/またはエチルベンゼン、特に好ましくはトルエンを含む。
(I)1以上のゼオライト材料、および任意に少なくとも1種のバインダーを含むアルキル化触媒を含有する混合物を調製する工程;
(II)任意に、前記混合物を混練する工程;
(III)混練された混合物を成形して少なくとも1つの成形体を与える工程;
(IV)任意に、少なくとも1つの成形体を乾燥する工程;および/または
(V)任意に、少なくとも1つの乾燥された成形体をか焼する工程。
室温で0.5時間に亘ってエテン(5bar)で予め飽和した後、実施例2により得られたゼオライトベータ125mgを反応容器に置いた。撹拌(1350rpm)しながら、容器を170℃で24時間加熱した後、ベンゼン20mlを反応容器に添加した。
ベンゼンに代えてトルエンを用い、実施例3の手順を繰り返した。さらに、実施例1のゼオライトを用いて追加でこの手順を行った。そのようにして得られた各反応混合物の解析結果を表2に示す。
Claims (19)
- (a)BEA骨格構造を有する1種以上のゼオライト材料を含む触媒を供給する工程、
を含み、ここで前記BEA骨格構造がYO2、および任意にX2O3を含み、式中、Yは四価元素であり、Xは三価元素であり、更に、
(b)1基以上の反応器において、1種以上のアルキル化剤の存在下で、前記触媒と、1種以上のアルキル化可能な有機化合物とを接触させて1種以上のアルキル化有機化合物を得る工程
を含む有機化合物のアルキル化法であって、
前記1種以上のアルキル化可能な有機化合物が、置換または非置換のベンゼン、トルエン、およびそれらのヘテロ芳香族誘導体からなる群より選択される1以上の有機化合物を含み、
前記1種以上のアルキル化剤が、エテン、プロペン、ブテン、およびそれらの誘導体からなる群より選択される1種以上のオレフィンを含み、
工程(a)で触媒に使用される前記1種以上のゼオライト材料が、構造規定剤として有機テンプレートを用いない合成法により得られ、及び該合成方法は、
(1)種晶および1種以上のYO 2 供給源を含む混合物を調製する工程、及び
(2)前記混合物を結晶化する工程、
を含み、BEA骨格構造がX 2 O 3 を含むとき、工程(1)に記載の混合物は1種以上のX 2 O 3 供給源をさらに含むことを特徴とするアルキル化法。 - 1種以上のゼオライト材料がか焼されていない、請求項1に記載のアルキル化法。
- Yが、Si、Sn、Ti、Zr、Geおよびそれらの2種以上の組み合わせからなる群より選択される、請求項1または2に記載のアルキル化法。
- Xが、Al、B、In、Gaおよびそれらの2種以上の組み合わせからなる群より選択される、請求項1〜3のいずれか一項に記載のアルキル化法。
- 前記1種以上のゼオライト材料の1種以上のY:Xのモル比が1〜50の範囲である、請求項1〜4のいずれか一項に記載のアルキル化法。
- 前記1種以上のゼオライト材料の1種以上が、1種以上のアルカリ金属Mを含む、請求項1〜5のいずれか一項に記載のアルキル化法。
- M:Xのモル比が0.01〜20の範囲である、請求項6に記載のアルキル化法。
- 前記アルカリ金属原子Mの少なくとも一部が1種以上の陽イオンおよび/または陽イオン元素によって置換されている、請求項6または7に記載のアルキル化法。
- 前記1種以上のゼオライト材料の1種以上のDIN66135に従って測定されたBET表面積が、150〜650m2/gの範囲である、請求項1〜10のいずれか一項に記載のアルキル化法。
- 前記1種以上のゼオライト材料がゼオライトベータを含む、請求項1〜11のいずれか一項に記載のアルキル化法。
- 前記1種以上のアルキル化剤に対する、前記1種以上のアルキル化可能な有機化合物のモル比が、0.1:1〜50:1の範囲である、請求項1〜12のいずれか一項に記載のアルキル化法。
- 工程(b)が、100〜350℃の範囲の温度で行われる、請求項1〜13のいずれか一項に記載のアルキル化法。
- 工程(b)が、0.2〜250barの範囲に含まれる圧力で行われる、請求項1〜14のいずれか一項に記載のアルキル化法。
- 工程(b)が、0.5〜100時間の継続時間に亘って行われる、請求項1〜15のいずれか一項に記載のアルキル化法。
- 前記アルキル化法が連続アルキル化法である、請求項1〜16のいずれか一項に記載のアルキル化法。
- 前記1基以上の反応器が、固定床および/または流動床の形態で前記触媒を含有する、請求項1〜17のいずれか一項に記載のアルキル化法。
- BEA骨格構造を有する1種以上のゼオライト材料を含む前記触媒が、成形品の形態で供給される、請求項1〜18のいずれか一項に記載のアルキル化法。
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