JP3905948B2 - High silica zeolite catalyst - Google Patents
High silica zeolite catalyst Download PDFInfo
- Publication number
- JP3905948B2 JP3905948B2 JP11418597A JP11418597A JP3905948B2 JP 3905948 B2 JP3905948 B2 JP 3905948B2 JP 11418597 A JP11418597 A JP 11418597A JP 11418597 A JP11418597 A JP 11418597A JP 3905948 B2 JP3905948 B2 JP 3905948B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zeolite
- hours
- zinc
- reaction
- 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 145
- 239000010457 zeolite Substances 0.000 title claims description 114
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 113
- 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 111
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 59
- 239000000377 silicon dioxide Substances 0.000 title claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 68
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 62
- 239000011701 zinc Substances 0.000 claims description 59
- 229910052725 zinc Inorganic materials 0.000 claims description 58
- 239000002253 acid Substances 0.000 claims description 56
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 42
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 34
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 31
- 238000003795 desorption Methods 0.000 claims description 31
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 28
- -1 zinc aluminate Chemical class 0.000 claims description 21
- 239000011787 zinc oxide Substances 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000011164 primary particle Substances 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 36
- 230000000694 effects Effects 0.000 description 34
- 239000002002 slurry Substances 0.000 description 34
- 230000006866 deterioration Effects 0.000 description 31
- 229910001868 water Inorganic materials 0.000 description 29
- 230000008929 regeneration Effects 0.000 description 27
- 238000011069 regeneration method Methods 0.000 description 27
- 239000000126 substance Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 24
- 239000002245 particle Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 238000004939 coking Methods 0.000 description 20
- 150000001412 amines Chemical class 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 238000010025 steaming Methods 0.000 description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 15
- 239000004115 Sodium Silicate Substances 0.000 description 14
- 229910052911 sodium silicate Inorganic materials 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- MUDSDYNRBDKLGK-UHFFFAOYSA-N 4-methylquinoline Chemical compound C1=CC=C2C(C)=CC=NC2=C1 MUDSDYNRBDKLGK-UHFFFAOYSA-N 0.000 description 10
- 235000010724 Wisteria floribunda Nutrition 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 238000007363 ring formation reaction Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229940057054 1,3-dimethylurea Drugs 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012494 Quartz wool Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- HMJBXEZHJUYJQY-UHFFFAOYSA-N 4-(aminomethyl)octane-1,8-diamine Chemical compound NCCCCC(CN)CCCN HMJBXEZHJUYJQY-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、原料または生成物中に芳香族炭化水素を含む反応に使用する高シリカゼオライト系触媒に関する。更に詳しくは、原料または生成物中に芳香族炭化水素を含む反応の間に該触媒上に蓄積する炭素質の蓄積量を低減し、かつ、該炭素質による活性の一時的な低下を抑え、更に、該炭素質を酸素含有イナートガスで燃焼除去する際に起こる如き、水分の存在する高温雰囲気下での脱アルミニウムによる永久活性劣化を抑える、耐コーキング性および耐再生劣化性に優れた高シリカゼオライト系触媒に関する。
【０００２】
【従来の技術】
従来より高シリカ含有量ゼオライトを合成する方法、および、その方法にて製造された高シリカゼオライトは知られている。例えば、特公昭４６−１００６４号公報や特公昭５６−４９８５０号公報には、シリカ，アルミナ，アルカリ金属，水および有機窒素陽イオン先駆物の供給物質を含む反応混合物を水熱処理する方法が開示されている。
【０００３】
また、高耐熱水性高シリカゼオライトを製造する方法、および、その方法にて製造された高シリカゼオライトも公知である。例えば、特開平７−２９１６２０号公報には、アルミナ分当たり７．５モル倍以上の中性塩水溶液中にシリカ成分とアルミナ成分を同時注加して得られるｐＨ１１乃至１３のアルミノケイ酸ゲルを水熱処理して、長軸／短軸の比が２乃至１５、長軸／厚みの比が４乃至５０である長六角板状結晶粒子を７５個数％以上を含み且つ９００℃で５時間のスチーミング処理をしたときの結晶保持率が８５％以上である、従来の高シリカゼオライトに比べイオン交換率が高く、耐熱水性に優れた高シリカゼオライトおよびその製造方法が開示されている。
【０００４】
更に、特開平３−２９３０３１号公報は、酸化物のモル組成で表して、ａＫ2 Ｏ，ｂＮａ2 Ｏ，Ａｌ2 Ｏ3 ，ｃＳｉＯ2 ，ｄＨ2 Ｏである高耐熱性ゼオライトであって、水分１０％以上を含む水蒸気下、９００℃で５時間熱水処理した後の結晶化度が、熱水処理前の９０％以上である高耐熱性ゼオライト及びその製造方法について開示している。
【０００５】
また、特開平３−１９３６２２号公報は、シリカ源、アルミナ源、アルカリ金属源、水を含む原料混合物を水熱合成条件下に結晶化させる際に、種スラリーとして、スラリー中の固形物の乾燥後のＸ線回折パターンがＺＳＭ−５であり、窒素吸着ＢＥＴ表面積が１００〜２５０ｍ3 ／ｇである結晶化途中の水熱合成スラリーを、全体の１０〜４０重量％結晶化前に加えることを特徴とする、ＺＳＭ−５微粒子体の製造法について開示している。
【０００６】
更にまた、特公平７−３５３４３号公報および特公平７−９４３９６号公報には、亜鉛を含むＺＳＭ−５型ゼオライトを触媒として軽質炭化水素より芳香族炭化水素を製造する方法において、該触媒が特定のケイ素／アルミニウム原子比と亜鉛／ケイ素原子比をもち、昇温脱離法による５００〜９００℃における該ＺＳＭ−５型ゼオライト１ｇあたりのピリジンの脱離量が４０〜１２０μｍｏｌであることを特徴とする、芳香族炭化水素の製造方法が開示されている。
【０００７】
しかし、特公昭４６−１００６４号公報や特公昭５６−４９８５０号公報に記載されている方法で合成した高シリカ含有量ゼオライトでは、結晶性が不十分で結晶自体の耐熱性が悪くなり、該反応の間に蓄積した炭素質を燃焼除去する際に起こる如き、水分の存在する高温雰囲気下での脱アルミニウムによりゼオライト触媒が永久劣化する問題があり、更に、該反応の間に蓄積する炭素質の量が多いため、これを燃焼除去する設備が大きくなるという課題があった。
【０００８】
特開平７−２９１６２０号公報や特開平３−２９３０３１号公報の方法で合成されたゼオライトは、耐熱水性の高いゼオライトではあるが、原料または生成物中に芳香族炭化水素を含む反応系での使用については記載がなく、該反応の間にゼオライト触媒上に蓄積する炭素質による活性低下という問題点自体認識されていなかった。
【０００９】
また、一般に、耐熱水性の高いゼオライトは、その結晶化度を高める必要があるため、結果的に粒子径が大きくなる傾向があるが、粒子径が大きすぎると表面酸点の全酸点に対する割合が少ないため、原料または生成物中に芳香族炭化水素を含む反応において、該反応の間にゼオライト触媒上に蓄積する炭素質による活性低下が速く、実用に耐えないという問題があった。
【００１０】
特開平３−１９３６２２号公報で合成されるゼオライトは、その実施例にも記載されているように、シクロヘキセンからシクロヘキサノールを生成する反応に使用される微粒子ゼオライトであって、粒子径を微粒化することで炭素質の蓄積による触媒寿命を延長させることを目的としている。
【００１１】
本願のゼオライトは、例えば、特開平３−１９３６２２号公報の方法で合成することも可能であるが、その方法で合成されたゼオライトの粒径が小さすぎたり、表面酸点の全酸点に対する割合が大きすぎると、オレフィンや芳香族炭化水素、特にスチレン等の、反応中に蓄積する炭素質を多くする原因となる成分を原料中もしくは生成物中に含む反応においては、該反応の間に蓄積する炭素質の量が多くなる。
【００１２】
炭素質の量が多くなると、これを燃焼除去する設備が同一であれば、炭素質の量が少ない場合に比較して燃焼除去する時間が長くなり、同一燃焼時間で燃焼除去させる場合は、燃焼除去の設備が大きくなるとともに、単位時間当たりに発生する水分が多くなり、脱アルミニウムによる永久劣化が速いという課題があった。
【００１３】
また、特開平３−１９３６２２号公報の実施例に記載されているＺＳＭ−５では、結晶化度が小さく、該反応の間に蓄積した炭素質を燃焼除去する際に起こる如き、水分の存在する高温雰囲気下での脱アルミニウムによりゼオライト触媒が永久劣化する問題があった。
【００１４】
特公平７−３５３４３号公報および特公平７−９４３９６号公報では、軽質炭化水素より芳香族炭化水素を製造する方法において、該反応の間に蓄積する炭素質による経時活性低下を減少させるため、特定のケイ素／アルミニウム原子比と亜鉛／ケイ素原子比をもつ触媒であって、昇温脱離法による５００〜９００℃におけるＺＳＭ−５型ゼオライト１ｇあたりのピリジンの脱離量が４０〜１２０μｍｏｌであるＺＳＭ−５型ゼオライトを含む触媒を使用する製造方法を開示している。ピリジンの脱離量を上記範囲とすることで、軽質炭化水素から芳香族炭化水素を製造するための必要活性は保持しながら、蓄積する炭素質による経時活性低下を少なくしている。
【００１５】
しかしながら、これらの公報では、該反応の間に蓄積した炭素質を燃焼除去する際に起こる如き、水分の存在する高温雰囲気下での脱アルミニウムによりゼオライト触媒が永久劣化する問題については解決されていない。どちらの公報でもその実施例から明らかなように、該触媒をＨ2 Ｏ分圧０．８ａｔｍ，６５０℃で５時間水蒸気処理をした後での、Ｈ型にしたときの昇温脱離法による５００〜９００℃におけるピリジンの脱離量（Ｂ）と該水蒸気処理前のＨ型にしたときの昇温脱離法による５００〜９００℃におけるピリジンの脱離量（Ａ）とで表されるパラメータαが１．６より大きく、各反応毎の炭素質の析出による劣化は小さいが、永久劣化が速く、反応と該反応の間に蓄積した炭素質を燃焼除去する再生とを繰り返して数ヶ月あるいは数年使用するには実用に耐えない。
【００１６】
以上列挙したように、ゼオライトの合成方法は前期記載の如く種々提唱されているが、原料もしくは生成物に芳香族炭化水素が含まれる反応での、該反応の間に該触媒上に蓄積する炭素質の量が少なく、かつ、該炭素質による活性の一時的な低下を抑え、更に、該炭素質を酸素含有イナートガスで燃焼除去する際に起こる、水分の存在する高温雰囲気下での脱アルミニウムによる永久活性劣化を抑えることができる、耐コーキング性にも耐再生劣化性にも同時に優れる高シリカゼオライト系触媒は見いだされていなかった。
【００１７】
【発明が解決しようとする課題】
本発明の課題は、上記の従来技術の問題点を解決し、原料もしくは生成物に芳香族炭化水素が含まれる反応に用いられる高シリカゼオライト系触媒であって、該反応の間に該触媒上に蓄積する炭素質の量を低減し、かつ、該炭素質による活性の一時的な低下を抑え、更に、該炭素質を酸素含有イナートガスで燃焼除去する際に起こるような、水分の存在する高温雰囲気下での脱アルミニウムによる永久活性劣化を抑えることができる耐コーキング性及び耐再生劣化性に優れた高シリカゼオライト系触媒を提供することにある。
【００１８】
【課題を解決するための手段】
本発明者は鋭意研究を重ねた結果、原料もしくは生成物に芳香族炭化水素が含まれる反応に用いられる高シリカゼオライトとして、特定のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比を持ち、特定の粒子径と特定の酸点の割合および特定の酸点を有するゼオライトを用いれば、上記の課題を一挙に解決できることを見いだし、本発明を完成した。
【００１９】
すなわち、本発明は、オレフィンおよび／またはパラフィンを含む軽質炭化水素から芳香族炭化水素を製造する反応に用いられる高シリカゼオライト系触媒であって、下記の要件（１），（２），（３），（４）を満足する高シリカゼオライト系触媒を提供するものである。
（１）該ゼオライト系触媒を構成するゼオライトのＳｉＯ２／Ａｌ２Ｏ４モル比が２０から２００。
（２）該ゼオライト系触媒を構成するゼオライトの一次粒子の粒子径が０．３から３μｍ。
（３）該ゼオライト系触媒をＨ型にしたときの全酸点に対する表面酸点の割合が０．０３〜０．１５。
（４）該ゼオライト系触媒をＨ２Ｏ分圧０．８ａｔｍ，６５０℃で５時間水蒸気処理した後での、Ｈ型にしたときの昇温脱離法による５００〜９００℃におけるピリジンの脱離量（Ｂ）と該水蒸気処理前のＨ型にしたときの昇温脱離法による５００〜９００℃におけるピリジン脱離量（Ａ）とが以下を満足する。
【００２０】
【数２】
本発明における、原料もしくは生成物に芳香族炭化水素が含まれる反応とは、該反応の原料中に５重量％以上の芳香族炭化水素が含まれるか、もしくは、該反応の生成物中に５重量％以上の芳香族炭化水素が含まれる反応をいう。芳香族炭化水素特にスチレンなどの炭素数が８以上の芳香族炭化水素が原料もしくは生成物中に含まれると、該反応中に蓄積する炭素質が多い。原料もしくは生成物に芳香族炭化水素が含まれる反応としては、例えば、オレフィンおよび／またはパラフィンを含む軽質炭化水素から芳香族炭化水素を製造する環化反応や、ナフサやＨ−ＮＧＬ等の炭化水素を含む原料から低級オレフィン類および芳香族炭化水素類を効率よく、かつエチレンを主成分とする低級オレフィン類を芳香族炭化水素類より高収率に得る接触分解反応、トルエンの不均化反応、キシレンの異性化反応、エチルベンゼン合成反応等が挙げられる。
【００２２】
以下、これらの反応のうち、オレフィンおよび／またはパラフィンを含む軽質炭化水素から芳香族炭化水素を製造する環化反応について、詳細に説明する。 本発明におけるオレフィンおよび／またはパラフィンを含む軽質炭化水素とは、炭素数２以上、９０％留出温度１９０℃以下の炭化水素である。たとえば、パラフィンとしてはエタン，プロパン，ブタン，ペンタン，ヘキサン，ヘプタン，オクタン，ノナンであり、オレフィンとしてはエチレン，プロピレン，ブテン，ペンテン，ヘキセン，ヘプテン，オクテン，ノネンがあげられる。上記以外にシクロペンタン，シクロペンテン，メチルシクロペンタン，シクロヘキサン，メチルシクロペンテン，シクロヘキセン，シクロヘキサジエンなどのナフタン，ナフテンを含んでもよく、ブタジエン，ペンタジエン，シクロペンタジエンなどのジエン類を含んでいてもよい。
【００２３】
上記のそれぞれの混合物を原料として用いてもよく、該混合物には希釈剤としてＮ2 ，ＣＯ2 ，ＣＯ等のイナートガスや、反応にともない触媒上に蓄積する炭素質（コーク）の生成を抑えるためにＨ2 ，ＣＨ4 を含んでいてもよい。さらに該混合物中の飽和炭化水素と不飽和炭化水素の重量比が０．４３〜２．３３であると特によい。ここでいう飽和炭化水素と不飽和炭化水素の重量比とは、供給される混合物中の重量比を意味する。
【００２４】
混合物としては、上記のそれぞれの混合物、あるいはナフサなどの石油系炭化水素の高温熱分解生成物のＣ4 留分、前記Ｃ4 留分よりブタジエンまたはブタジエンとｉ−ブテンを除いた留分、高温熱分解生成物のＣ5 留分、前記Ｃ5 留分からジエン類を除いた留分、熱分解ガソリン、熱分解ガソリンより芳香族炭化水素抽出を行ったラフィネート、ＦＣＣ−ＬＰＧ、ＦＣＣ分解ガソリン、リフォーメートより芳香族炭化水素を抽出したラフィネート、コーカーのＬＰＧ、直留ナフサがあげられるが、この内、ナフサなどの石油系炭化水素の高温熱分解生成物のＣ4 留分、Ｃ5 留分、該Ｃ4 ，Ｃ5 留分からブタジエン，ｉ−ブテン，イソプレン，シクロペンタジエンの一部もしくは全部を除いた留分が特に好適に利用でき、該Ｃ4 留分、Ｃ5 留分の重量比が３／７〜７／３である原料が特に好ましい。ここでいうＣ4 留分とＣ5 留分の重量比とは供給される混合物中の重量比を意味する。本発明の方法においては、該原料中に不純物としてＴＢＡ，メタノール等の含酸素化合物が含まれていてもよい。
【００２５】
本発明における高シリカゼオライト系触媒を構成するゼオライトは、そのゼオライトのＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が２０〜２００であり、例えば、β−ゼオライト、Ω−ゼオライト、Ｙ−ゼオライト、Ｌ−ゼオライト、エリオナイト、オフレタイト、モルデナイト、フェリエライト、ＺＳＭ−５、ＺＳＭ−８、ＺＳＭ−１１、ＺＳＭ−１２、ＺＳＭ−３５、ＺＳＭ−３８等があげられるが、ＺＳＭ−５、ＺＳＭ−８、ＺＳＭ−１１等のＺＳＭ−５型の結晶性アルミノシリケートまたはメタロシリケートが好ましい。ＺＳＭ−５のゼオライトについては、例えば、米国特許第５，２６８，１６２号明細書を参照することができる。
【００２６】
本発明に用いるゼオライトは、いずれもＨ型あるいは金属置換型として用いることができ、該金属置換型の金属はＶＩＩＩ族，Ｉｂ族，ＩＩｂ族、またはＩＩＩｂ族に属する金属であることが好ましい。ＶＩＩＩ族，Ｉｂ族，ＩＩｂ族，ＩＩＩｂ族に属する金属としては、Ｚｎ，Ｃｕ，Ａｇ，Ｎｉ，Ｐｔ，Ｐｄ，Ｇａが更に好ましく、それらのうちでもＺｎ，Ａｇ，Ｎｉ，Ｇａがより好適に用いられる。この時、該金属は、ゼオライト骨格内に含まれていてもよく、イオン交換されていてもよい。
また、更に、後述するように、アルミナ等のバインダーおよび／または酸化亜鉛等の脱水素を促進する金属酸化物と併用することもできる。
【００２７】
本発明において、ゼオライトの合成方法は特に限定されないが、特開平３−１９３６２２号公報に記載されている、種スラリーを用いて合成する方法が特に好ましい。また、本発明の方法においては、国際出願番号ＰＣＴ／ＪＰ９５／０２０４０記載の如き、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が２０以上で、１種または２種以上の周期律表第Ｉｂ族に属する金属を有する、実質的にプロトンを含まない中間細孔径ゼオライトを用いることもできる。いずれの場合でも、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比、ゼオライトの一次粒子の粒径、Ｈ型にしたときの全酸点に対する表面酸点の割合、パラメータαが本発明の範囲内にあることが重要である。
【００２８】
仕込み原料のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比、攪拌速度、合成温度等の合成条件、テンプレートの使用有無、使用テンプレートの種類等を調整することによって、ゼオライトのＳｉＯ2 ／Ａｌ2 Ｏ3 モル比、ゼオライトの一次粒子の粒径、Ｈ型にしたときの全酸点に対する表面酸点の割合、パラメータαを本願発明の範囲内にすることができる。
【００２９】
本発明の触媒を構成するゼオライトは、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が２０から２００であり、３０から１００が好ましく、３０から８０が更に好ましい。ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が２０より小さいと、原料もしくは生成物に芳香族炭化水素が含まれる反応の間に該触媒上に蓄積する炭素質を酸素含有イナートガスで燃焼除去する際に起こる如き、水分の存在する高温雰囲気下での脱アルミニウムによる永久活性劣化が速くなる。
【００３０】
脱アルミニウムによる永久活性劣化は、Ｘ線回折法による結晶化度の相対値が高いほど抑制されると考えられるが、該結晶化度の相対値はＳｉＯ2 ／Ａｌ2 Ｏ3 モル比に影響され、該ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が２０より小さい、あるいは２００より大きいと、結晶化度の相対値が小さくなり、脱アルミニウムによる永久劣化が速く、好ましくない。また、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が２００より大きいと、充分な活性が得られず、原料もしくは生成物に芳香族炭化水素が含まれる反応に充分なだけの活性がない触媒となる場合がある。
【００３１】
本発明の触媒を構成するゼオライトのＳｉＯ2 ／Ａｌ2 Ｏ3 モル比とは、バインダーとしてのアルミナやシリカを含んでいない、水熱合成したゼオライトであって、水蒸気処理等の脱アルミニウム処理や、軽質炭化水素から芳香族炭化水素を生成する如き反応に供していない新鮮なゼオライトを蛍光Ｘ線装置またはＥＰＭＡ（Ｘ線マクロアナライザー）で測定することによって求められるモル比である。
【００３２】
本発明におけるゼオライト系触媒としては、前記記載のＨ型あるいは金属置換型の実質的にゼオライトからなるものを用いることができるが、上記したゼオライトと、周期律表ＶＩＩＩ族，Ｉｂ族，ＩＩｂ族およびＩＩＩｂ族に属する金属類から選ばれた少なくとも一種の金属およびそれらの化合物（例えば、酸化亜鉛等の脱水素を促進する金属酸化物）からなる群から選ばれる少なくとも一種との混合物を含む、あるいは化合物として担持されていてるものが好ましい。
【００３３】
ＶＩＩＩ族，Ｉｂ族，ＩＩｂ族，ＩＩＩｂ族に属する金属としては、Ｚｎ，Ｃｕ，Ａｇ，Ｎｉ，Ｐｔ，Ｐｄ，Ｇａが更に好ましく、それらのうちでもＺｎ，Ａｇ，Ｎｉ，Ｇａがより好適に用いられる。例えば、ゼオライトと、亜鉛およびその化合物から選ばれる少なくとも一種との混合物を含むことが好ましい。更に、バインダーとしてアルミナ、シリカを併用すると、より好ましい。
【００３４】
本発明において、亜鉛成分は、例えば、亜鉛、酸化亜鉛、水酸化亜鉛、あるいは硝酸亜鉛、炭酸亜鉛、硫酸亜鉛、塩化亜鉛、酢酸亜鉛、シュウ酸亜鉛などの塩、あるいはアルキル亜鉛などの有機亜鉛化合物が挙げられる。
【００３５】
本発明においては、ゼオライト系触媒は、ゼオライトと、亜鉛成分、およびアルミナの混合物を含むことが好ましい。また、亜鉛成分およびアルミナの混合物を水蒸気中で熱処理したものとゼオライトの混合物であることも好ましい。いずれの触媒も、水蒸気処理すると、亜鉛成分とアルミナが反応しアルミン酸亜鉛に変化するため亜鉛が安定化され、オレフィンおよび／またはパラフィンを含む軽質炭化水素から高収率で芳香族炭化水素を製造する反応等において、亜鉛の飛散損失を大幅に低減することができる。ここでいうアルミン酸亜鉛とは、島津製作所のＸＤ−６１０等のＸ線回折装置で観察した場合にＪＣＰＤＳ ５−０６６９ＮＢＳ Ｃｉｒｃ．，５３９，Ｖｏｌ．ＩＩ，３８（１９５３）に示されるパターンと同一のＸ線回折パターンを持つものを意味する。
【００３６】
アルミナのアルミナ源としては、無水アルミナまたはアルミナの水和物があるが、そのほかにたとえば、アルミニウム塩のように加水分解または加熱分解、酸化などにより、無水アルミナまたはアルミナ水和物を生成する原料を使用する事もできる。
【００３７】
本発明において、アルミナ源としてアルミナゾルを使用することも好ましい。アルミナ源としてアルミナゾルを使用すると、上記水蒸気処理を実施せずとも亜鉛成分とアルミナが反応しアルミン酸亜鉛が生成するため、亜鉛が安定化する。
【００３８】
上記したゼオライト系触媒においては、亜鉛およびその化合物から選ばれる少なくとも一種の含有量が、亜鉛として５〜２５重量％であることが好ましい。 本発明において、アルミナを含む場合のアルミナ含有率は、Ａｌ2 Ｏ3 として全触媒に対し５〜５０重量％、好ましくは１５〜４０重量％であり、かつ、アルミナと亜鉛を含む場合は、アルミナと亜鉛のモル比（Ａｌ2 Ｏ3 ／Ｚｎ）が１以上である。
【００３９】
また、本発明においては、反応に供される時点において、該ゼオライト触媒に酸化亜鉛とアルミン酸亜鉛とが共存することが好ましい。アルミン酸亜鉛はスピネル構造を持つため該ゼオライト系触媒中からの亜鉛の飛散は抑制されるものの亜鉛担持の本来の目的である芳香族選択率の向上効果が小さくなってしまうため、芳香族選択率の向上効果を発揮する酸化亜鉛を共存させておくことが好ましい。酸化亜鉛とアルミン酸亜鉛の好ましい存在量は、原料もしくは生成物に芳香族炭化水素が含まれる反応に供される時点で酸化亜鉛１．２〜２０重量％、アルミン酸亜鉛８．２〜５０重量％であり、更に好ましくは酸化亜鉛が１．０〜５．０重量％、アルミン酸亜鉛が１４〜４０重量％である。
【００４０】
アルミン酸亜鉛自体の芳香族選択性向上効果は小さいが、酸化亜鉛の補給源となり、酸化亜鉛の減少を抑制し、その結果として芳香族選択率向上効果を長時間持続させることが出来る。さらにアルミン酸亜鉛が存在することで、酸化亜鉛の、原料もしくは生成物に芳香族炭化水素が含まれる反応時の、還元による飛散速度を抑制する効果もある。故に触媒に酸化亜鉛とともにアルミン酸亜鉛を共存させることは芳香族選択率向上効果維持に有効である。
【００４１】
本発明でいう酸化亜鉛とは下記分析方法で測定されたものをいう。すなわち、触媒１ｇを乳鉢で数百ミクロン程度にすり潰し、１２０℃で１時間乾燥後約０．５ｇを正確に計りとり２００ｃｃビーカーに入れる。そこに３％塩酸水溶液１５０ｃｃを加え電熱ヒーター上で８０℃で２時間加熱する。その後０．２μｍメンブランフィルターで濾過し、濾液を原子吸光分析計（島津製作所製 島津原子吸光／フレーム分光光度計 ＡＡ−６４０−１２型）でフレーム分析、標準添加法で酸化亜鉛の定量分析を行なう。
【００４２】
本発明におけるアルミン酸亜鉛重量は、全亜鉛重量から上記方法にて定量分析した酸化亜鉛の重量を減算したものである。ここで言う全亜鉛重量とは、蛍光Ｘ線分析装置（理学ＲＩＸ１０００）で標準物質の検量線より求めたものをいう。
【００４３】
本発明におけるゼオライトの一次粒子の粒径とは、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比と同様に、実質的に新鮮な状態のゼオライトを走査型電子顕微鏡で見た時の一次粒子の粒径である。本願発明では、該粒径が０．３から３μｍ、更には０．５から２μｍであると好ましい。これら一次粒子の形状は種々のものがあるが、ここで言う粒径とは、それぞれの粒子の最も幅の広いところの平均径を示している。これらの一次粒子は、単独で存在しても、二次凝集していてもかまわない。
【００４４】
粒径が０．３μｍより小さいと、原料もしくは生成物に芳香族炭化水素が含まれる反応の間に該触媒上に蓄積する炭素質の量が多くなるとともに、該炭素質を酸素含有イナートガスで燃焼除去する際に起こる如き、水分の存在する高温雰囲気下での脱アルミニウムによる永久活性劣化が速くなり、逆に粒径が３μｍより大きいと原料もしくは生成物に芳香族炭化水素が含まれる反応の間に該触媒上に蓄積する炭素質による、活性の一時的な低下が速くなるため、実用に耐えない。
【００４５】
本発明においては、該ゼオライト系触媒を該反応に供する時点において、Ｈ型にした時の全酸点に対する表面酸点の割合が０．０３から０．１５であり、０．０５から０．１がより好適である。全酸点に対する表面酸点の割合が０．０３より小さいと、原料もしくは生成物に芳香族炭化水素が含まれる反応の間に該触媒上に蓄積する炭軽質による、活性の一時的な低下が速くなり、逆に該割合が０．１５より大きいと原料もしくは生成物に芳香族炭化水素が含まれる反応の間に該触媒上に蓄積する炭軽質の量が多くなるとともに、該炭素質を酸素含有イナートガスで燃焼除去する際に起こる如き、水分の存在する高温雰囲気下での脱アルミニウムによる永久活性劣化が速くなる。
【００４６】
本発明における、触媒のＨ2 Ｏ分圧０．８ａｔｍ，６５０℃での５時間水蒸気処理は、第２図に示す装置において、１０ｍｍφの石英反応管１０中に下から石英ウール１１、触媒１２、ラシヒリング１３の順で充填し、温度計１４で測定した触媒１２の温度が６５０℃の等温になるように温度調節用熱電対１５で温度が調節できる電気炉１６にて石英反応管１０を加熱し、大気圧、Ｈ2 Ｏ分圧０．８ａｔｍの条件で、実質的に新鮮な触媒に水または水蒸気を、原料流入口１７より５時間供給することで実施される。
【００４７】
本発明においては、該触媒を上記方法によりＨ2 Ｏ分圧０．８ａｔｍ，６５０℃で５時間水蒸気処理をした後での、Ｈ型にしたときの昇温脱離法による５００〜９００℃におけるピリジンの脱離量（Ｂ）と該水蒸気処理前のＨ型にしたときの昇温脱離法による５００〜９００℃におけるピリジン脱離量（Ａ）とで表される以下のパラメータαが１．６以下であり、特に好ましくは１．４以下である。
【００４８】
【数３】
パラメータαが１．６より大きいと原料もしくは生成物に芳香族炭化水素が含まれる反応の間に該触媒上に蓄積する炭素質を酸素含有イナートガスで燃焼除去する際に起こる如き、水分の存在する高温雰囲気下での脱アルミニウムによる永久活性劣化が速く、耐再生劣化性が悪い。
【００５０】
該パラメータαはＸ線回折法により求められる結晶化度に依存する。すなわち、後述の比較例に示すとおり、比較例１の如くゼオライトの粒径が小さい場合や、比較例３の如くＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が小さい場合、更に比較例４の如くＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が大きい場合は、Ｘ線回折法による結晶化度の相対値が小さく、パラメータαが大きくなり、耐再生劣化性が悪くなる。
【００５１】
また、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比、粒径が本発明の範囲にあっても、比較例５の如く、パラメータαが１．６より大きくなり、耐再生劣化性が悪くなる場合もある。比較例５も、結晶化度の相対値が小さいことから、合成されたゼオライトに非晶質のアモルファスが共存していると推定される。従って、水分の存在する高温雰囲気下での脱アルミニウムによる永久活性劣化が少ない、数年の反応/再生繰り返しに耐えうる触媒とするには、本発明の（１）〜（４）全ての要件を満たしている必要がある。
ここで、結晶化度の相対値とは、該ゼオライト系触媒のゼオライトのＸ線回折パターンの２θ＝２３．１゜、２４．０゜、２４．４゜それぞれのピーク高さの和の相対値をいう。
【００５２】
また、脱離量および全酸点に対する表面酸点の割合を測定する方法は、以下の方法による。
（酸点測定方法）
まず、酸点を測定する前に、該ゼオライト系触媒がＨ型でない場合は、以下の方法に従ってＨ型にする必要がある。ゼオライトをＨ型にするには、該ゼオライトに１規定の硝酸を加えて１０重量％スラリーとして、６０℃で４時間イオン交換を行い、そのスラリーを濾過し、更に５倍量の水で水洗した後、１２０℃で１０時間乾燥しする。このようにして得られたＨ型のゼオライトの酸点を以下の方法で測定する。
【００５３】
酸点の測定装置としては、島津製作所製ガスクロマトグラフィーＧＣ−１４Ａおよびデータ処理装置ＣＲ−４Ａを用いた。本発明に用いる酸点測定装置を第１図に示す。すなわち、内径６ｍｍ、全長２２０ｍｍのＳＵＳ製短カラム３へ試料４を０．１〜１ｇ充填する。該試料４は、ペレット状に成形されていれば１〜５ｍｍの長さで、粉末であれば２０〜３０メッシュに圧縮成型して充填する。キャリアガスとして窒素を６０ｃｃ／分の流量でガス流量計１を調節しながら流し、同時に炉芯管内径２０ｍｍφ、長さ１５０ｍｍの管状電気炉２の温度を、使用するアミンがピリジンの場合は１８０℃に、４−メチルキノリンの場合は２８０℃に設定する。次に、アミン（ピリジン、４−メチルキノリン）の一定量（１μｃｃ）をオートサンプラーマイクロシリンジ（ＡＯＣ）を用いて、注入口５より一定期間（２〜５分）をおいて断続的に注入し続ける。
【００５４】
一方、充填カラム３を通ったキャリアガスは、ＦＩＤ型検出器６を用いて分析し、周期的にピークが現れる経時的なアミン濃度変化のクロマトグラムを得る。注入回数の増加とともに試料に対するアミン吸着量が飽和に近づき、それに伴って注入で得られる非吸着アミン量が増加する。従って、前記クロマトグラムにおいて、アミンの注入に対応する非吸着ピーク面積Ｓi は次第に注入したアミンの量に対応する面積Ｓo に近づく。すなわち、データ処理装置で確認される、ピーク面積Ｓi に対応するトータルカウント数が、面積Ｓo に対応するトータルカウント数に近づく。得られた非吸着アミン量に対応するトータルカウント数Ｎi と、その直前の注入時に得られた非吸着アミン量に対応するトータルカウント数Ｎi-1 とが、以下の条件を満たした場合に、アミン吸着量が飽和になったと判断する。
【００５５】
【数４】
上記条件で、アミンの触媒への飽和吸着が完了したと判断された後、管状電気炉２で１５℃／分の速度で昇温する。ここで、アミン注入口５の周りからＦＩＤ型検出器６間でのガス流路は、電気炉内の部分を除き、リボンヒータ８等で加温し、外側を保温材９で覆ってアミンがピリジンの場合は２００℃に、アミンが４−メチルキノリンの場合は３００℃に保温する。温度検出は試料管外部に密着設置した温度検出端の位置で行う。温度検出端７が９００℃に達するまでの間に試料４から脱離するアミンをＦＩＤ型検出器６で検出し、アミンの検量線を用いてその脱離量を換算する。
【００５７】
本発明における全酸点とは、アミンとしてピリジンを用いて測定した場合のピリジン脱離量で表し、表面酸点とは、アミンとして４−メチルキノリンを用いて測定した場合の４−メチルキノリン脱離量で表される。また、昇温脱離法による５００〜９００℃におけるピリジンの脱離量とは、温度検出端７が５００℃になった時点から、更に昇温して９００℃に達するまでの間に得られる脱離量である。いずれの脱離量もゼオライトを含む触媒１ｇ当たりの脱離量として表す。
【００５８】
（ｎ−ヘキサン分解１次反応速度定数測定法）
本発明における触媒のｎ−ヘキサン分解の１次反応速度定数とは、第２図に示す装置を用いて、１０ｍｍφの石英反応管１０中に下から石英ウール１１、炭素質（コーク）が実質的に存在しない触媒１２、ラシヒリング１３の順で充填し、温度計１４で測定した触媒１２の温度が５００℃の等温になるように温度調節用熱電対１５で温度が調節できる電気炉１６にて石英反応管１０を加熱し、大気圧、重量時間空間速度（ＷＨＳＶ）４ｈｒ-1の条件で、ｎ−ヘキサンを原料流入口１７より供給し、ｎ−ヘキサン供給後０．７５時間から１時間後の反応生成物をコンデンサー１８にて冷却した後、オイルトラップ１９にて更にドライアイス・エタノール冷媒で冷却し、オイルトラップ１９中に分離したオイル成分および発生ガス捕集用バッグ２０中に分離したガス成分をそれぞれ全量採取する。
【００５９】
そして、ヒューレット・パッカード社製のＦＩＤ−ＴＣＤガスクロマトグラフィー（ＨＰ−５８９０ シリーズＩＩ）にてガス組成を、島津製作所社製のＦＩＤガスクロマトグラフィー（ＧＣ−１７Ａ）にてオイル組成を分析して得られる反応生成物中のｎ−ヘキサン転化率を、下式に代入して求めた、上記ガス・オイル採取時間０．２５時間の平均のゼオライト基準のｎ−ヘキサン分解１次反応速度定数をいう。
【００６０】
【数５】
上記１次反応速度定数は、該触媒の活性を代表するものであって、本発明におけるゼオライト触媒のｎ−ヘキサン分解の１次反応速度定数は、反応に供される時点において、０．２以上であることが好ましく、０．３以上であれば更に好ましい。該ｎ−ヘキサン分解の１次反応速度定数が０．２を下回る触媒は、活性が低く原料もしくは生成物に芳香族炭化水素が含まれる反応で得られる目的生成物が少なくなる。
【００６２】
【発明の実施の形態】
次に、実施例および比較例によって本発明をさらに詳細に説明する。
【００６３】
【実施例】
実施例１
珪酸ナトリウム水溶液（ＳｉＯ2 ：２６重量％、Ｎａ2 Ｏ：７．０重量％）８．０ｋｇにＮａＯＨ０．０５ｋｇとＨ2 Ｏ４ｋｇを加えた溶液に、Ａｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ０．６１ｋｇと１，３−ジメチル尿素０．１ｋｇをＨ2 Ｏ１５ｋｇに溶かした溶液を攪拌しながら加え、５重量％の硫酸１０ｋｇを加えて均質なゲルを得た。このゲルを５０リットルのオートクレーブに仕込み、攪拌動力０．５〜１ＫＷ／ｍ2 で攪拌しながら１６０℃で１０時間合成反応を行い、種スラリーを得た。
【００６４】
次に、特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）６．４４ｋｇにＨ2 Ｏ１７．４７ｋｇとＡｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ（和光純薬Ｋ．Ｋ．社製）０．２４８ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）０．３５３ｋｇを加え、種スラリーとして上記で得られたスラリーを１０．４９ｋｇ添加して、均質なゲルを得た。このゲルを５０リットルオートクレーブに入れ、１５０℃で４５時間、回転数１１０ｒｐｍで攪拌させながら結晶化させた。
【００６５】
得られたスラリーを濾過した後、５倍量の水で水洗し、１２０℃で５時間乾燥させた。その乾燥物の走査型電子顕微鏡写真を第３図に示す。図から明らかなように生成したＺＳＭ−５は、最も幅の広い部分の厚さが１．５〜２μｍ、平均１．２μｍであることがわかる。
【００６６】
続いて、得られた乾燥物のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比を蛍光Ｘ線装置を用いて測定したところ、３６であった。
さらに、この乾燥物を１規定の硝酸中１０重量％スラリーで室温で、３時間イオン交換した後、濾過して５倍量の水で水洗し、更に１２０℃で１０時間乾燥した。
【００６７】
硝酸亜鉛六水和物１４４ｇを水４００ｇに溶かし、アルミナゾル４００ｇ（日産化学工業社製アルミナゾル５２０）と、上記Ｈ−ＺＳＭ−５を２００ｇ加え５０℃で加熱し２時間混合した。水分が減少し粘土状になった上記混合物を直径１．６ｍｍ、長さ４〜６ｍｍの円柱状に成型後、１２０℃で２時間乾燥した後、電気炉で空気雰囲気中５００℃で３時間焼成し、亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト触媒を成形した。
【００６８】
更に、得られた成形触媒を第２図に示す装置の石英反応管に充填し、前記記載の方法で６５０℃、Ｈ2 Ｏ分圧０．８ａｔｍの条件で５時間水蒸気処理を実施した。次いで、上記水蒸気処理をする前後でのＨ型にしたときの昇温脱離法による５００〜９００℃におけるピリジンの脱離量を前記方法にて求めた。
【００６９】
続いて、後述の実施例，比較例の触媒と初期活性をそろえるために、前記記載の方法で６５０℃、Ｈ2 Ｏ分圧０．８ａｔｍの条件で１．２時間追加水蒸気処理を実施した。該水蒸気処理をした後の触媒のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を前記記載の方法でもとめた。
【００７０】
次に、この触媒の耐再生劣化性を評価するために、モデル的な再生劣化試験を実施した。すなわち、上記の合計６．２時間水蒸気処理をした触媒を第２図に示す装置に充填し、５３０℃、Ｈ2 Ｏ分圧０．１５ａｔｍの条件で１００時間追加水蒸気処理を実施し、その前後の触媒のｎ−ヘキサンの１次反応速度定数を上記と同様の方法にてもとめた。結果を表１に示す。
【００７１】
更に、耐コーキング性を評価するために、水蒸気処理をしていない成形したＨ−ＺＳＭ−５ゼオライト触媒を、第４図に示す反応装置を用いて、表２に示すＣ5 留分と表３に示すＣ4 留分を６：４（重量比）で供給する、環化反応試験を行った。すなわち、該成形触媒を内径２７．２ｍｍφのＳＵＳ製の反応管２１に１００ｇ充填し、温度計２２で測定した触媒２３の平均温度が６５０℃の等温になるように温度調節用熱電対２４で温度が調節できる電気炉２５にてＳＵＳ製反応管２１を加熱し、１Ｋｇ／ｃｍ2 ・Ｇ、Ｈ2 Ｏ分圧０．８ａｔｍの条件で、実質的に新鮮な触媒に水または水蒸気を、原料流入口２６より６．２時間供給することで、水蒸気処理を実施した。
【００７２】
その後、触媒２３の平均温度が５２０℃の等温になるように温度調節用熱電対２４を用いて調節し、原料タンク２７中の表２に示す組成を持つＣ5 留分と原料タンク２８中の表３に示すＣ4 留分とをポンプ２９および３０にて重量比６：４、圧力５Ｋｇ／ｃｍ2 ・Ｇ、温度５２０℃、ＷＨＳＶ（重量時間空間速度）２．８ｈｒ-1の条件で、ＳＵＳ製反応管２１内の触媒２３に４８時間供給した。供給開始後５時間後および４０時間後の芳香族収率を求めるとともに、４８時間の反応の間に触媒上に蓄積したコークの量も求めた。結果を表１に示す。
【００７３】
実施例２
特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）６．７５ｋｇにＨ2 Ｏ２３．０ｋｇとＡｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ（和光純薬Ｋ．Ｋ．社製）０．１８６ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）０．１９８ｋｇを加え、種結晶としてＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が既知の市販ＺＳＭ−５（ＮＥ−ケムキャット社製，ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）を０．１６７ｋｇ添加して、均質なゲルを得た。
【００７４】
このゲルを５０リットルオートクレーブに入れ、１５０℃で２５時間、回転数２００ｒｐｍで攪拌させながら結晶化させた。得られたスラリーを濾過した後、５倍量の水で水洗し、１２０℃で５時間乾燥させた。このゼオライトの走査型電子顕微鏡写真を第５図に示す。図から明らかなように生成したＺＳＭ−５は、最も幅の広い部分の厚さが０．５〜１μｍ、平均０．７μｍであることがわかる。
【００７５】
次に、得られた触媒のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比を実施例１と同じ方法にて求めた。
また、実施例１と同じ方法で亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト成形触媒を得た。この成形触媒の、６５０℃で５時間水蒸気処理した前後の５００℃〜９００℃のピリジン脱離量と、６５０℃で１１時間水蒸気処理した後のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を実施例１と同じ方法でもとめた。結果を表１に示す。
【００７６】
更に、６５０℃で１１時間水蒸気処理した触媒を用いて、実施例１と同じ耐再生劣化性を評価する試験と、耐コーキング性を評価する試験を実施した。結果を表１に示す。
【００７７】
実施例３
珪酸ナトリウム水溶液（ＳｉＯ2 ：２６重量％、Ｎａ2 Ｏ：７．０重量％）８．０ｋｇにＮａＯＨ０．０５ｋｇとＨ2 Ｏ４kgを加えた溶液に、Ａｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ０．６１ｋｇと１，３−ジメチル尿素０．１ｋｇをＨ2 Ｏ１５ｋｇに溶かした溶液を攪拌しながら加え、５重量％の硫酸１０ｋｇを加えて均質なゲルを得た。このゲルを５０リットルのオートクレーブに仕込み、攪拌動力０．５〜１ＫＷ／ｍ2 で攪拌しながら１６０℃で１０時間合成反応を行い、種スラリーを得た。
【００７８】
次に、特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）５．４５ｋｇにＨ2 Ｏ１１．０ｋｇとＡｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ（和光純薬Ｋ．Ｋ．社製）３．０５ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）３．１５ｋｇを加え、種スラリーとして上記で得られたスラリーを１１．６７ｋｇ添加して、均質なゲルを得た。このゲルを５０リットルオートクレーブに入れ、１５０℃で３９．５時間、回転数１１０ｒｐｍで攪拌させながら結晶化させた。
【００７９】
得られたスラリーを濾過した後、５倍量の水で水洗し、１２０℃で５時間乾燥させ、このゼオライトの粒径を走査型電子顕微鏡により測定した。
次に、得られた触媒のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比を実施例１と同じ方法にて求めた。
【００８０】
また、実施例１と同じ方法で亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト成形触媒を得た。この成形触媒の、６５０℃で５時間水蒸気処理した前後の５００℃〜９００℃のピリジン脱離量と、６５０℃で９．５時間水蒸気処理した後のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を実施例１と同じ方法でもとめた。結果を表１に示す。
【００８１】
更に、６５０℃で９．５時間水蒸気処理した触媒を用いて、実施例１と同じ耐再生劣化性を評価する試験と、耐コーキング性を評価する試験を実施した。結果を表１に示す。
【００８２】
実施例４
特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）９２ｋｇにＨ2 Ｏ９５ｋｇとＡｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ（和光純薬Ｋ．Ｋ．社製）７．３ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）３．８ｋｇと１，３−ジメチル尿素１．１５ｋｇをＨ2 Ｏ１５０ｋｇに溶かした溶液を攪拌しながら加えて均質なゲルを得た。このゲルを６００リットルのオートクレーブに仕込み、攪拌しながら１６０℃で３０時間合成反応を行い、Ｎａ型ＺＳＭ−５を合成した。この合成後のスラリーを濾過、水洗を濾液ＰＨが８以下になるまで繰り返し、１２０℃で２０時間乾燥し、その後５５０℃で３時間空気中で焼成してＮａ型ＺＳＭ−５の粉末２０ｋｇを得た。
【００８３】
特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）９２ｋｇにＨ2 Ｏ２４５ｋｇとＡｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ（和光純薬Ｋ．Ｋ．社製）７．３ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）３．８ｋｇ、そして、先に得たＮａ型ＺＳＭ−５の粉末３ｋｇを加えて均質なゲルを得た。このゲルを６００リットルのオートクレーブに仕込み、攪拌しながら１５０℃で１０時間合成反応を行い、種スラリーを得た。
【００８４】
次に、特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）９２ｋｇにＨ2 Ｏ２４５ｋｇとＡｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ（和光純薬Ｋ．Ｋ．社製）４．８ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）４．９ｋｇを加え、種スラリーとして上記で得られたスラリーを１６７ｋｇ添加して、均質なゲルを得た。このゲルを６００リットルオートクレーブに入れ、１６０℃で４５時間、回転数１３０ｒｐｍで攪拌させながら結晶化させた。
【００８５】
得られたスラリーを遠心濾過しながらＰＨが９以下になるまで水洗し、そのあと１２０℃で５時間乾燥させた。その乾燥物の走査型電子顕微鏡写真を第６図に示す。図から明らかなように生成したＮａ型ＺＳＭ−５は、最も幅の広い部分の長さが２〜３μｍ、平均２．５μｍであることがわかる。
続いて、得られた乾燥物のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比を蛍光Ｘ線装置を用いて測定したところ、３９であった。
【００８６】
更に、この乾燥物を１規定の硝酸中１０重量％スラリーで室温で、３時間イオン交換した後、遠心濾過しながらＰＨが４．５以上になるまで水洗し、更に１２０℃で１０時間乾燥し、Ｈ−ＺＳＭ−５を得た。硝酸亜鉛六水和物１４４ｇを水２００ｇに溶かし酢酸５ｇを添加し、アルミナゾル２００ｇ（日産化学工業社製アルミナゾル５２０）と、ベーマイト２０ｇ、そして上記Ｈ−ＺＳＭ−５を２００ｇ加え２時間混合した。粘土状になった上記混合物を直径１．６ｍｍ、長さ４〜６ｍｍの円柱状に成型後、１２０℃で２時間乾燥した後、電気炉で空気雰囲気中５００℃で３時間焼成し、亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト触媒を成形した。
【００８７】
更に、実施例１と同様に、得られた成形触媒の、６５０℃、Ｈ2 Ｏ分圧０．８ａｔｍの条件で５時間水蒸気処理をする前後のＨ型にしたときの昇温脱離法による５００〜９００℃におけるピリジンの脱離量を前記方法にて求めた。
続いて、前記記載の方法で６５０℃、Ｈ2 Ｏ分圧０．８ａｔｍの条件で８時間水蒸気処理を実施した触媒のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合をもとめ、耐再生劣化性と耐コーキング性のテストを実施例１と同様に実施した。結果を表１に示す。
【００８８】
実施例５
特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）２３００ｋｇにＨ2 Ｏ２３７５ｋｇとＡｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ（和光純薬Ｋ．Ｋ．社製）１８３ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）９５ｋｇと１，３−ジメチル尿素３０ｋｇをＨ2 Ｏ３７５０ｋｇに溶かした溶液を攪拌しながら加えて均質なゲルを得た。このゲルを１８ｍ3 のオートクレーブに仕込み、攪拌しながら１６０℃で３０時間合成反応を行い、Ｎａ型ＺＳＭ−５を合成した。この合成後のスラリーを濾過、水洗を濾液ＰＨが８以下になるまで繰り返し、１２０℃で３０時間乾燥し、その後５５０℃で３時間空気中で焼成してＮａ型ＺＳＭ−５の粉末５２０ｋｇを得た。
【００８９】
特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）１９３０ｋｇにＨ2 Ｏ５７８０ｋｇと硫酸バンド（住友化学工業製液体硫酸バンド、酸化アルミニウム８．１重量％、ｐＨ＝３．７）／水＝１３７ｋｇ／６５０ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）／水＝８１ｋｇ／８００ｋｇ、そして、先に得たＮａ型ＺＳＭ−５の粉末７５ｋｇを加えて均質なゲルを得た。このゲルを１８ｍ3 のオートクレーブに仕込み、攪拌しながら１５０℃で１０時間合成反応を行い、種スラリーを得た。
【００９０】
次に、特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）１９１０ｋｇにＨ2 Ｏ５０５０ｋｇと硫酸バンド（住友化学工業製液体硫酸バンド、酸化アルミニウム８．１重量％、ｐＨ＝３．７）／水＝１９６ｋｇ／９３０ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）／水＝７０ｋｇ／８００ｋｇを加え、種スラリーとして上記で得られた種スラリーを４４８０ｋｇ添加して、均質なゲルを得た。このゲルを１８ｍ3 オートクレーブに入れ、１６０℃で２０時間、回転数４０ｒｐｍで攪拌させながら結晶化させた。
【００９１】
得られたスラリーを遠心濾過しながらＰＨが９以下になるまで水洗し、更に、１規定の硝酸中１０重量％スラリーで７０℃で、５時間イオン交換した後、遠心濾過しながらＰＨが４．５以上になるまで水洗し、１２０℃で３０時間乾燥した。その乾燥物の走査型電子顕微鏡写真を第７図に示す。図から明らかなように生成したＨ−ＺＳＭ−５は、最も幅の広い部分の長さが２〜３μｍ、平均２．５μｍであることがわかる。
続いて、得られた乾燥物のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比を蛍光Ｘ線装置を用いて測定したところ、４１であった。
【００９２】
硝酸亜鉛六水和物１４４ｇを水２００ｇに溶かし酢酸５ｇを添加し、アルミナゾル２００ｇ（日産化学工業社製アルミナゾル５２０）と、ベーマイト２０ｇ、そして上記Ｈ−ＺＳＭ−５を２００ｇ加え２時間混合した。粘土状になった上記混合物を直径１．６ｍｍ、長さ４〜６ｍｍの円柱状に成型後、１２０℃で２時間乾燥した後、電気炉で空気雰囲気中５００℃で３時間焼成し、亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト触媒を成形した。
【００９３】
更に、実施例１と同様に、得られた成形触媒の、６５０℃、Ｈ2 Ｏ分圧０．８ａｔｍの条件で５時間水蒸気処理をする前後でのＨ型にしたときの昇温脱離法による５００〜９００℃におけるピリジンの脱離量を前記方法にて求めた。
続いて、前記記載の方法で６５０℃、Ｈ2 Ｏ分圧０．８ａｔｍの条件で８．５時間水蒸気処理を実施した触媒のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を求め、耐再生劣化性と耐コーキング性のテストを実施例１と同様に実施した。結果を表１に示す。
【００９４】
比較例１
（１）種スラリー合成
珪酸ナトリウム水溶液（ＳｉＯ2 ：２５．２重量％、Ｎａ2 Ｏ：７．３５重量％）１２９ｇにＮａＯＨ０．６４ｇとＨ2 Ｏ１３３ｇを加えた溶液に、Ａｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ０．９．７ｇと１，３−ジメチル尿素０．２ｇをＨ2 Ｏ２３０ｇに溶かした溶液を攪拌しながら加え、４．６重量％の硫酸１４０ｇを加えて均質なゲルを得た。このゲルのＰＨは１０．８であった。このゲルを１リットルのオートクレーブに仕込み、１８０℃で４０時間合成反応を行った。
得られたスラリーを３０℃まで冷却して、一部を濾過して１２０℃で８時間乾燥した。このもののＸ線回折パターンは、ＺＳＭ−５と一致した。
【００９５】
（２）本合成
（１）と同じ組成のゲル４００ｇに（１）で得られた種スラリー２５０ｇを加えよく混合した後、１リットルのオートクレーブに入れ、１６０℃で１５時間結晶化させた。
得られたスラリーを濾過した後、５倍量の水で水洗した後、１２０℃で８時間乾燥したもののＸ線回折パターンはＺＳＭ−５と一致した。
このゼオライトの走査型電子顕微鏡写真を第８図に示す。図から明らかなように生成したＺＳＭ−５は、微粒体が凝集したもので、凝集体はその最も幅の広い部分の厚さが０．２μｍ程度の表面に凹凸のある粒子であることがわかる。
次に、得られた触媒のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比を実施例１と同じ方法にて求めた。
【００９６】
また、実施例１と同じ方法で亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト成形触媒を得た。この成形触媒の、６５０℃で５時間水蒸気処理した前後の５００℃〜９００℃のピリジン脱離量と、６５０℃で３．８時間水蒸気処理した後のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を実施例１と同じ方法でもとめた。結果を表１に示す。
【００９７】
更に、６５０℃で３．８時間水蒸気処理した触媒を用いて、実施例１と同じ耐再生劣化性を評価する試験と、耐コーキング性を評価する試験を実施した。結果を表１に示す。
粒径が小さく、全酸点に対する表面酸点の割合が大きく、また、ピリジン脱離量のパラメータαも大きいため、耐再生劣化性が悪く、また、耐コーキング性試験におけるコーク蓄積量も多いことがわかる。
【００９８】
比較例２
１，８−ジアミノ−４−アミノメチルオクタン１００ｇ、硫酸アルミニウム４ｇ、水酸化ナトリウム５ｇを２００ｇに溶かし、さらにシリカゾル（３０％ＳｉＯ2 ）２５０ｇを加えて均質な溶液を得た。この溶液にかき混ぜながら２０％硫酸を滴下してｐＨ１２．５に調整して均質なゲルを得た。さらに、このゲルをミキサーに入れ２０００ｒｐｍ、２０分間高速攪拌した。このゲルをオートクレーブに仕込み、５０ｒｐｍでかき混ぜながら、１５０℃で２４時間結晶化させた。得られたスラリーを濾過した後、５倍量の水で洗浄し、１２０℃で８時間乾燥させ、この触媒の粒径を走査型電子顕微鏡で測定したところ、５μｍ以上であった。
【００９９】
また、実施例１と同じ方法で亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト成形触媒を得た。この成形触媒の、６５０℃で５時間水蒸気処理した前後の５００℃〜９００℃のピリジン脱離量と、６５０℃で１６時間水蒸気処理した後のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を実施例１と同じ方法でもとめた。結果を表１に示す。
【０１００】
更に、６５０℃で１６時間水蒸気処理した触媒を用いて、実施例１と同じ耐再生劣化性を評価する試験と、耐コーキング性を評価する試験を実施した。結果を表１に示す。
表１から、本触媒は粒径が大きく、表面酸点と全酸点の割合が小さいため、耐再生劣化性は良いが、コーキングによる劣化が速いことがわかる。
【０１０１】
比較例３
特３号ケイ酸ソーダ（富士化学(株)社製，ＳｉＯ2 ２５重量％，Ｎａ2 Ｏ ８重量％）６．７５ｋｇにＨ2 Ｏ２３．０ｋｇとＡｌ2 （ＳＯ4 ）3 ・１６Ｈ2 Ｏ（和光純薬Ｋ．Ｋ．社製）０．４１ｋｇおよび硫酸（和光純薬Ｋ．Ｋ．社製、純度９７％）０．１９８ｋｇを加え、種結晶としてＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が既知の市販ＺＳＭ−５（ＮＥ−ケムキャット社製，ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２５）を０．１６７ｋｇ添加して、均質なゲルを得た。このゲルを５０リットルオートクレーブに入れ、１５０℃で２５時間、回転数２００ｒｐｍで攪拌させながら結晶化させた。
得られたスラリーを濾過した後、５倍量の水で水洗し、１２０℃で５時間乾燥させた。このゼオライトのＳｉＯ2 ／Ａｌ2 Ｏ3 モル比を実施例１と同じ方法にて求めたところ１８であった。
【０１０２】
また、実施例１と同じ方法で亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト成形触媒を得た。この成形触媒の、６５０℃で５時間水蒸気処理した前後の５００℃〜９００℃のピリジン脱離量と、６５０℃で３時間水蒸気処理した後のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を実施例１と同じ方法でもとめた。結果を表１に示す。
【０１０３】
更に、６５０℃で３時間水蒸気処理した触媒を用いて、実施例１と同じ耐再生劣化性を評価する試験と、耐コーキング性を評価する試験を実施した。結果を表１に示す。
ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が小さいため耐再生劣化性が悪い。
【０１０４】
比較例４
市販のＨ−ＺＳＭ−５ゼオライト（ＮＥ−ケムキャット社製，ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２５０）を用いて、一次粒子径を測定した後、実施例１と同じ方法で亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト成形触媒を得た。この成形触媒の、６５０℃で５時間水蒸気処理した前後の５００℃〜９００℃のピリジン脱離量と、６５０℃で１時間水蒸気処理した後のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を実施例１と同じ方法でもとめた。結果を表１に示す。
【０１０５】
更に、６５０℃で１時間水蒸気処理した触媒を用いて、実施例１と同じ耐再生劣化性を評価する試験と、耐コーキング性を評価する試験を実施した。結果を表１に示す。
ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が大きすぎ、結晶化度が低いため、水蒸気処理前後のピリジン脱離量のパラメータαが大きくなり、耐再生劣化性が悪い。
【０１０６】
比較例５
ケイ酸ソーダ（水ガラス３号）２９０ｇを蒸留水２３０ｇに溶解させたＡ液、別に硫酸アルミニウム１６水塩１１．４ｇおよび１，３−ジメチル尿素２３．４ｇ、硫酸１３ｇを蒸留水３００ｇに溶解させたＢ液を調合した。ついでホモジナイザーを用い、Ａ液を強攪拌下にＢ液を添加し、ゲル状組成物が均一になるまで約３時間攪拌した。このゲル組成物を１リットルオートクレーブに仕込み、１５０℃、１０００ｒｐｍでの攪拌下、３５時間反応結晶化させた。反応後、固形物を濾過、水洗、脱水、乾燥し、これを５５０℃で３時間空気中で焼成した。得られたＨ−ＺＳＭ−５型ゼオライトのＳｉＯ2 ／Ａｌ2 Ｏ3 モル比を実施例１と同じ方法にて求めたところ４６であった。また、このゼオライトの粒径を走査型電子顕微鏡により測定した。
【０１０７】
また、実施例１と同じ方法で亜鉛を１０重量％含むＺＳＭ−５ゼオライト成形触媒を得た。この成形触媒の、６５０℃で５時間水蒸気処理した前後の５００℃〜９００℃のピリジン脱離量を求めた。６５０℃で３時間水蒸気処理した後のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を実施例１と同じ方法でもとめた。結果を表１に示す。
更に、６５０℃で３時間水蒸気処理した触媒を用いて、実施例１と同じ耐再生劣化性を評価する試験と、耐コーキング性を評価する試験を実施した。結果を表１に示す。
水蒸気処理前後のピリジン脱離量のパラメータαが１．８と大きいため、耐再生劣化性が悪い。
【０１０８】
比較例６
市販のＨ−ＺＳＭ−５ゼオライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝４００）を用いて、一次粒子径を測定した後、実施例１と同じ方法で亜鉛を１０重量％含むＨ−ＺＳＭ−５ゼオライト成形触媒を得た。この成形触媒の、６５０℃で５時間水蒸気処理した前後の５００℃〜９００℃のピリジン脱離量と、水蒸気処理をする前のｎ−ヘキサンの１次反応速度定数および表面酸点と全酸点の割合を実施例１と同じ方法でもとめた。結果を表１に示す。
更に、水蒸気処理をしない触媒を用いて、実施例１と同じ耐再生劣化性を評価する試験と、耐コーキング性を評価する試験を実施した。結果を表１に示す。 ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が大きすぎるため、活性が低く芳香族収率も少ない。
【０１０９】
実施例６
実施例４と同じ方法で合成・成形したゼオライト触媒を、一段断熱型反応器に充填し、圧力５Ｋｇ／ｃｍ2 ・Ｇ、６５０℃で８時間水蒸気処理を行った。さらに、表２に示すＣ5 留分と表３に示すＣ4 留分を６：４の重量比で、圧力５Ｋｇ／ｃｍ2 ・Ｇ、入り口温度５３０℃、ＷＨＳＶ（重量時間空間速度）２．８ｈｒ-1の条件下で４８時間供給する環化反応を実施した。４８時間の間に蓄積した炭素質を圧力５Ｋｇ／ｃｍ2 ・Ｇ、４８０〜５３０℃の雰囲気で、酸素濃度１〜１．５ｖｏｌ％の窒素ガスを５０００Ｎｍ３／ｈｒの流量で４０〜４３時間循環させることで燃焼除去（再生）させた。上記環化反応と再生とを７５回（３００日）繰り返した。１回目と７５回目の環化反応結果を表４に示す。
【０１１０】
比較例７
比較例１と同じ方法で合成・成形したゼオライト触媒を、一段断熱型反応器に充填し、圧力５Ｋｇ／ｃｍ2 ・Ｇ、６５０℃で３．８時間水蒸気処理を行った。さらに、表２に示すＣ5 留分と表３に示すＣ4 留分を６：４の重量比で、圧力５Ｋｇ／ｃｍ2 ・Ｇ、入り口温度５３０℃、ＷＨＳＶ（重量時間空間速度）２．８ｈｒ-1の条件下で４８時間供給する環化反応を実施した。４８時間の間に蓄積した炭素質を圧力５Ｋｇ／ｃｍ2 ・Ｇ、４８０〜５３０℃の雰囲気で、酸素濃度１〜１．５ｖｏｌ％の窒素ガスを５０００Ｎｍ３／ｈｒの流量で４０〜４３時間循環させることで燃焼除去（再生）させた。上記環化反応と再生とを７５回（３００日）繰り返した。１回目と７５回目の環化反応結果を表４に示す。表面酸点と全酸点の割合が大きいため、耐再生劣化性が悪く、永久活性劣化が速いことがわかる。
【０１１１】
実施例７
実施例４で得られた、水蒸気処理を６５０℃で８時間施した触媒を、蛍光Ｘ線にて全亜鉛量を求め、塩酸で触媒を処理した後に原子吸光分析法にて酸化亜鉛を求めた。触媒重量に対し酸化亜鉛２．９重量％、アルミン酸亜鉛２２．４重量％であった。この触媒１０ｇを反応管に充填し、水素を２０［Ｌ／Ｈｒ］流し５００℃で２０Ｈｒ還元する。この水素還元前後の酸化亜鉛量、アルミン酸亜鉛量の測定結果を表５に示した。また、水素還元前後の触媒をもちいて、前期記載の方法にてＣ4 留分とＣ5 留分を用いた耐コーキング性を評価する試験を実施した。結果を表５に示す。
【０１１２】
比較例８
実施例４で得られた、亜鉛を含まないＨ−ＺＳＭ−５を１００ｇ、７重量％硝酸亜鉛水溶液中に浸し、蒸発乾固後、１２０℃、４時間乾燥、５００℃３時間焼成し、亜鉛２．０重量％を含有する触媒を調整した。ついで、この触媒を圧縮成型後、粉砕し、９〜２０メッシュにそろえたもの２０ｇを、内径１２ｍｍの石英ガラス製反応器に充填し、水蒸気を８０重量％含む水蒸気−窒素混合ガス中で、大気圧下６５０℃で１時間熱処理した。蛍光Ｘ線と原子吸光法にて酸化亜鉛とアルミン酸亜鉛を求め、実施例８と同様の方法で水素還元した。さらに、水素還元前後でのＣ4 留分とＣ5 留分を用いた耐コーキング性を評価する試験を実施した。結果を表５に示す。
【０１１３】
比較例９
実施例１で得られた、亜鉛を含まないＨ−ＺＳＭ−５を６５０℃で５時間水蒸気処理をし、高純度化学研究所製アルミン酸亜鉛を、亜鉛としての全触媒に対する濃度が１０重量％となるように混合した。Ｃ4 留分とＣ5 留分を用いた耐コーキング性を評価する試験を実施した。結果を表５に示す。
【０１１４】
【表１】
【表２】
【表３】
【表４】
【表５】
【発明の効果】
以上の如き本発明の方法に従えば、原料もしくは生成物に芳香族炭化水素が含まれる反応の間に該触媒上に蓄積する炭素質の量を低減し、かつ、該炭素質による活性の一時的な低下を抑え、更に、該炭素質を酸素含有イナートガスで燃焼除去する際に起こる如き、水分の存在する高温雰囲気下での脱アルミニウムによる永久活性劣化を抑え得る、すなわち、耐再生劣化性と耐コーキング性に優れた触媒が得られる。従って本発明の方法は、石油化学工業、石油精製に広く利用することができ、特に芳香族化合物や高オクタン価ガソリンの製造に有効に利用できる。
【図面の簡単な説明】
【図１】本発明の方法における酸点測定装置の概略図。
【図２】本発明の方法における等温型反応装置の概略図。
【図３】本発明の方法における触媒の走査型顕微鏡写真。
【図４】本発明の方法における等温型反応装置の概略図。
【図５】本発明の方法における触媒の走査型顕微鏡写真。
【図６】本発明の方法における触媒の走査型顕微鏡写真。
【図７】本発明の方法における触媒の走査型顕微鏡写真。
【図８】本発明の方法における触媒の走査型顕微鏡写真。
【符号の説明】
１ ガス流量計
２ 管状電気炉
３ ＳＵＳ製短管カラム
４ 試料
５ 注入口
６ ＦＩＤ型検出器
７ 温度検出端
８ リボンヒーター
９ 保温材
１０ 石英反応管
１１ 石英ウール
１２ 触媒
１３ ラシヒリング
１４ 温度計
１５ 温度調整用熱電対
１６ 電気炉
１７ 原料流入口
１８ コンデンサー
１９ オイルトラップ
２０ 発生ガス補修用バック
２１ ＳＵＳ製反応管
２２ 温度計
２３ 触媒
２４ 温度調節用熱電対
２５ 電気炉
２６ 原料流入口
２７ Ｃ5 留分用原料タンク
２８ Ｃ4 留分用原料タンク
２９ ポンプ
３０ ポンプ[0001]
[Industrial application fields]
The present invention relates to a high silica zeolite-based catalyst used for a reaction in which an aromatic hydrocarbon is contained in a raw material or a product. More specifically, the amount of carbonaceous material accumulated on the catalyst during the reaction containing aromatic hydrocarbons in the raw material or product is reduced, and the temporary decrease in activity due to the carbonaceous material is suppressed, Furthermore, high silica zeolite excellent in coking resistance and regeneration deterioration resistance, which suppresses permanent activity deterioration due to dealumination in a high temperature atmosphere where moisture exists, such as occurs when the carbonaceous material is burned and removed with an oxygen-containing inert gas. The present invention relates to a system catalyst.
[0002]
[Prior art]
Conventionally, a method for synthesizing a zeolite having a high silica content and a high silica zeolite produced by the method are known. For example, Japanese Patent Publication No. Sho 46-10063 and Japanese Patent Publication No. Sho 56-49850 disclose a method of hydrothermally treating a reaction mixture containing silica, alumina, alkali metal, water and an organic nitrogen cation precursor precursor. ing.
[0003]
Further, a method for producing a highly heat-resistant and high-silica zeolite and a high-silica zeolite produced by the method are also known. For example, JP-A-7-291620 discloses an aluminosilicate gel having a pH of 11 to 13 obtained by simultaneously adding a silica component and an alumina component in a neutral salt aqueous solution of 7.5 mole times or more per alumina content. Steaming for 5 hours at 900 ° C. containing 75% by number or more of long hexagonal plate-like crystal grains having a major axis / minor axis ratio of 2 to 15 and a major axis / thickness ratio of 4 to 50 after heat treatment A high-silica zeolite having a high ion exchange rate compared to conventional high-silica zeolite, having a crystal retention rate of 85% or more when treated, and excellent in hot water resistance, and a method for producing the same are disclosed.
[0004]
Furthermore, Japanese Patent Application Laid-Open No. 3-293301 discloses an aK expressed by a molar composition of an oxide. 2 O, bNa 2 O, Al 2 O Three , CSiO 2 , DH 2 A high heat-resistant zeolite which is O and has a crystallinity of 90% or more before hydrothermal treatment after hydrothermal treatment at 900 ° C. for 5 hours under water vapor containing 10% or more of water And a manufacturing method thereof.
[0005]
JP-A-3-193622 discloses drying a solid in a slurry as a seed slurry when a raw material mixture containing a silica source, an alumina source, an alkali metal source, and water is crystallized under hydrothermal synthesis conditions. The later X-ray diffraction pattern is ZSM-5, and the nitrogen adsorption BET surface area is 100 to 250 m. Three It discloses a method for producing ZSM-5 fine particles, characterized in that a hydrothermal synthesis slurry in the middle of crystallization of / g is added before crystallization of 10 to 40% by weight of the whole.
[0006]
Furthermore, in Japanese Patent Publication No. 7-35343 and Japanese Patent Publication No. 7-94396, in a method for producing aromatic hydrocarbons from light hydrocarbons using ZSM-5 type zeolite containing zinc as a catalyst, the catalyst is specified. Characterized by having a silicon / aluminum atomic ratio and a zinc / silicon atomic ratio of 40 to 120 μmol of pyridine per 1 g of the ZSM-5 type zeolite at 500 to 900 ° C. by a temperature programmed desorption method. A method for producing aromatic hydrocarbons is disclosed.
[0007]
However, the high silica content zeolite synthesized by the method described in Japanese Patent Publication No. 46-10063 and Japanese Patent Publication No. 56-49850 has insufficient crystallinity and the heat resistance of the crystal itself deteriorates. There is a problem that the zeolite catalyst is permanently deteriorated by dealumination in a high-temperature atmosphere where moisture exists, as occurs when the carbonaceous matter accumulated during the combustion is removed by combustion, and the carbonaceous matter accumulated during the reaction is further deteriorated. Since there is much quantity, the subject that the equipment which carries out combustion removal of this became large occurred.
[0008]
Zeolite synthesized by the methods of JP-A-7-291620 and JP-A-3-29331 is a zeolite with high hot water resistance, but is used in a reaction system containing aromatic hydrocarbons in the raw material or product. There was no description about the above, and the problem of reduced activity due to carbonaceous matter accumulated on the zeolite catalyst during the reaction was not recognized.
[0009]
In general, zeolite with high hot water resistance needs to increase its crystallinity, and as a result, the particle size tends to increase. However, if the particle size is too large, the ratio of the surface acid point to the total acid point Therefore, in the reaction containing aromatic hydrocarbon in the raw material or product, there is a problem that the activity is rapidly lowered due to carbonaceous matter accumulated on the zeolite catalyst during the reaction, and it cannot be put into practical use.
[0010]
The zeolite synthesized in Japanese Patent Laid-Open No. 3-193622 is a fine particle zeolite used in a reaction for producing cyclohexanol from cyclohexene as described in the examples, and the particle diameter is atomized. The purpose is to extend the catalyst life due to the accumulation of carbonaceous matter.
[0011]
The zeolite of the present application can be synthesized, for example, by the method disclosed in JP-A-3-193622, but the particle size of the zeolite synthesized by the method is too small or the ratio of the surface acid points to the total acid points. Is too large, it accumulates during the reaction in a raw material or product containing a component that causes more carbonaceous matter to accumulate during the reaction, such as olefin and aromatic hydrocarbon, especially styrene. Increases the amount of carbon.
[0012]
When the amount of carbon is increased, if the equipment for burning and removing this is the same, the time for burning and removing is longer than when the amount of carbon is small. As removal equipment becomes larger, moisture generated per unit time increases and permanent deterioration due to dealumination is quick.
[0013]
In addition, in ZSM-5 described in the examples of JP-A-3-193622, the crystallinity is small, and moisture is present as occurs when the carbonaceous matter accumulated during the reaction is removed by combustion. There was a problem that the zeolite catalyst was permanently deteriorated by dealumination under a high temperature atmosphere.
[0014]
In Japanese Patent Publication No. 7-35343 and Japanese Patent Publication No. 7-94396, in the method for producing aromatic hydrocarbons from light hydrocarbons, in order to reduce the decrease in activity over time due to carbonaceous matter accumulated during the reaction, specific ZSM having a silicon / aluminum atomic ratio and a zinc / silicon atomic ratio of 40 to 120 μmol of pyridine per 1 g of ZSM-5 type zeolite at 500 to 900 ° C. by a temperature programmed desorption method A production method using a catalyst containing −5 type zeolite is disclosed. By setting the amount of desorption of pyridine within the above range, while maintaining the necessary activity for producing aromatic hydrocarbons from light hydrocarbons, the decrease in activity over time due to accumulated carbonaceous matter is reduced.
[0015]
However, these publications do not solve the problem that the zeolite catalyst is permanently deteriorated by dealumination in a high-temperature atmosphere in the presence of moisture, such as occurs when the carbonaceous matter accumulated during the reaction is burned and removed. . As is apparent from the examples in both publications, the catalyst is H 2 Desorption amount (B) of pyridine at 500 to 900 ° C. by the temperature-programmed desorption method in the H type after steam treatment at O partial pressure 0.8 atm and 650 ° C. for 5 hours and before the steam treatment The parameter α represented by the amount of pyridine desorbed (A) at 500 to 900 ° C. by the temperature-programmed desorption method when the H type is used is greater than 1.6, and deterioration due to carbonaceous precipitation for each reaction Although it is small, its permanent deterioration is fast, and it is not practical to use for several months or years by repeating the reaction and regeneration for burning and removing carbonaceous matter accumulated during the reaction.
[0016]
As enumerated above, various methods for synthesizing zeolite have been proposed as described above, but carbon that accumulates on the catalyst during the reaction in a reaction in which an aromatic hydrocarbon is contained in the raw material or product. The amount of quality is small, and the temporary decrease in the activity due to the carbonaceous matter is suppressed, and furthermore, due to dealumination in a high-temperature atmosphere where moisture exists when the carbonaceous matter is burned and removed with an oxygen-containing inert gas. A high silica zeolite-based catalyst that can suppress permanent activity deterioration and is excellent in coking resistance and regeneration deterioration resistance at the same time has not been found.
[0017]
[Problems to be solved by the invention]
An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a high silica zeolite catalyst used in a reaction in which an aromatic hydrocarbon is contained in a raw material or a product, and on the catalyst during the reaction. This reduces the amount of carbonaceous matter that accumulates at the same time, suppresses a temporary decrease in activity due to the carbonaceous matter, and further, when the carbonaceous matter is burned and removed with an oxygen-containing inert gas. It is an object of the present invention to provide a high silica zeolite catalyst excellent in coking resistance and regeneration deterioration resistance that can suppress permanent activity deterioration due to dealumination in an atmosphere.
[0018]
[Means for Solving the Problems]
As a result of extensive research, the present inventor has developed a specific SiO as a high silica zeolite used in a reaction in which an aromatic hydrocarbon is contained in a raw material or product. 2 / Al 2 O Three The inventors have found that the above problems can be solved at once by using a zeolite having a molar ratio, a specific particle size, a specific acid point ratio, and a specific acid point, and completed the present invention.
[0019]
That is, the present invention Production of aromatic hydrocarbons from light hydrocarbons containing olefins and / or paraffins The present invention provides a high silica zeolite catalyst that is used in the reaction and satisfies the following requirements (1), (2), (3), and (4).
(1) Zeolite SiO constituting the zeolitic catalyst 2 / Al 2 O 4 The molar ratio is 20 to 200.
(2) The particle diameter of the primary particles of the zeolite constituting the zeolite catalyst is 0.3 to 3 μm.
(3) The ratio of the surface acid point to the total acid point when the zeolite catalyst is made to be H-type is 0.03 to 0.15.
(4) The zeolite catalyst is H 2 Oxygen partial pressure of 0.8 atm, steam treatment at 650 ° C. for 5 hours, pyridine desorption amount (B) at 500 to 900 ° C. by the temperature-programmed desorption method when using H type, and before the steam treatment The amount of pyridine desorption (A) at 500 to 900 ° C. by the temperature programmed desorption method when the H type is satisfied satisfies the following.
[0020]
[Expression 2]
In the present invention, the reaction in which an aromatic hydrocarbon is contained in the raw material or the product means that 5% by weight or more of the aromatic hydrocarbon is contained in the raw material of the reaction, or 5 in the product of the reaction. This refers to a reaction containing aromatic hydrocarbons by weight percent or more. When an aromatic hydrocarbon, particularly an aromatic hydrocarbon having 8 or more carbon atoms such as styrene, is contained in the raw material or product, a large amount of carbon is accumulated during the reaction. Examples of reactions in which aromatic hydrocarbons are contained in the raw material or product include, for example, cyclization reactions for producing aromatic hydrocarbons from light hydrocarbons containing olefins and / or paraffins, hydrocarbons such as naphtha and H-NGL A catalytic cracking reaction to obtain lower olefins and aromatic hydrocarbons efficiently from raw materials containing ethylene and lower olefins mainly composed of ethylene in higher yield than aromatic hydrocarbons, disproportionation reaction of toluene, Examples include xylene isomerization reaction and ethylbenzene synthesis reaction.
[0022]
Hereinafter, among these reactions, a cyclization reaction for producing an aromatic hydrocarbon from a light hydrocarbon containing olefin and / or paraffin will be described in detail. The light hydrocarbon containing olefin and / or paraffin in the present invention is a hydrocarbon having 2 or more carbon atoms and 90% distillation temperature of 190 ° C. or less. For example, ethane, propane, butane, pentane, hexane, heptane, octane and nonane are listed as paraffin, and ethylene, propylene, butene, pentene, hexene, heptene, octene and nonene are listed as olefins. In addition to the above, naphthane and naphthene such as cyclopentane, cyclopentene, methylcyclopentane, cyclohexane, methylcyclopentene, cyclohexene and cyclohexadiene may be included, and dienes such as butadiene, pentadiene and cyclopentadiene may be included.
[0023]
Each of the above mixtures may be used as a raw material, and the mixture contains N as a diluent. 2 , CO 2 In order to suppress the generation of inert gases such as CO and CO, and carbonaceous matter (coke) that accumulates on the catalyst during the reaction. 2 , CH Four May be included. Further, the weight ratio of saturated hydrocarbon to unsaturated hydrocarbon in the mixture is particularly preferably 0.43 to 2.33. The weight ratio of saturated hydrocarbon and unsaturated hydrocarbon here means the weight ratio in the supplied mixture.
[0024]
As the mixture, each of the above-mentioned mixtures or C of high-temperature pyrolysis products of petroleum hydrocarbons such as naphtha is used. Four Fraction, C Four A fraction obtained by removing butadiene or butadiene and i-butene from the fraction, C of the high-temperature pyrolysis product Five Fraction, C Five Dienes from fractions, pyrolysis gasoline, raffinate from which aromatic hydrocarbons were extracted from pyrolysis gasoline, FCC-LPG, FCC cracked gasoline, raffinate from which aromatic hydrocarbons were extracted from reformate, coker Examples include LPG and straight-run naphtha. Among these, C is a high-temperature pyrolysis product of petroleum hydrocarbons such as naphtha. Four Fraction, C Five Fraction, C Four , C Five A fraction obtained by removing part or all of butadiene, i-butene, isoprene, and cyclopentadiene from the fraction can be particularly preferably used. Four Fraction, C Five The raw material whose weight ratio of a fraction is 3/7-7/3 is especially preferable. C here Four Fraction and C Five The weight ratio of the fraction means the weight ratio in the supplied mixture. In the method of the present invention, the raw material may contain oxygen-containing compounds such as TBA and methanol as impurities.
[0025]
The zeolite constituting the high silica zeolite catalyst in the present invention is the SiO of the zeolite. 2 / Al 2 O Three Molar ratio is 20-200, for example, β-zeolite, Ω-zeolite, Y-zeolite, L-zeolite, erionite, offretite, mordenite, ferrierite, ZSM-5, ZSM-8, ZSM-11, ZSM -12, ZSM-35, ZSM-38, etc., ZSM-5 type crystalline aluminosilicates or metallosilicates such as ZSM-5, ZSM-8, and ZSM-11 are preferred. Regarding the ZSM-5 zeolite, reference can be made, for example, to US Pat. No. 5,268,162.
[0026]
Any of the zeolites used in the present invention can be used as an H-type or a metal-substituted type, and the metal-substituted metal is preferably a metal belonging to Group VIII, Group Ib, Group IIb, or Group IIIb. As metals belonging to Group VIII, Group Ib, Group IIb, Group IIIb, Zn, Cu, Ag, Ni, Pt, Pd, and Ga are more preferable, and among these, Zn, Ag, Ni, and Ga are more preferably used. It is done. At this time, the metal may be contained in the zeolite skeleton or may be ion-exchanged.
Furthermore, as described later, a binder such as alumina and / or a metal oxide that promotes dehydrogenation such as zinc oxide can be used in combination.
[0027]
In the present invention, the method for synthesizing the zeolite is not particularly limited, but the method for synthesizing using the seed slurry described in JP-A-3-193622 is particularly preferable. Further, in the method of the present invention, as described in International Application No. PCT / JP95 / 02040, SiO 2 / Al 2 O Three It is also possible to use an intermediate pore diameter zeolite having a molar ratio of 20 or more and having one or more metals belonging to Group Ib of the periodic table and substantially free of protons. In either case, SiO 2 / Al 2 O Three It is important that the molar ratio, the particle size of the primary particles of the zeolite, the ratio of the surface acid points to the total acid points when in the H-type, and the parameter α are within the scope of the present invention.
[0028]
Raw material SiO 2 / Al 2 O Three By adjusting the synthesis conditions such as molar ratio, stirring speed, synthesis temperature, use / nonuse of template, type of template used, etc. 2 / Al 2 O Three The molar ratio, the particle size of the primary particles of the zeolite, the ratio of the surface acid points to the total acid points in the H-type, and the parameter α can be within the scope of the present invention.
[0029]
The zeolite constituting the catalyst of the present invention is SiO. 2 / Al 2 O Three The molar ratio is 20 to 200, preferably 30 to 100, and more preferably 30 to 80. SiO 2 / Al 2 O Three If the molar ratio is less than 20, high temperature in the presence of moisture, such as occurs when the carbonaceous material accumulated on the catalyst during the reaction in which the raw material or product contains aromatic hydrocarbons is burned off with an oxygen-containing inert gas. Deterioration of permanent activity due to dealumination under atmosphere is accelerated.
[0030]
Permanent activity degradation due to dealumination is considered to be suppressed as the relative value of crystallinity by X-ray diffraction increases, but the relative value of crystallinity is SiO 2. 2 / Al 2 O Three Affected by the molar ratio, the SiO 2 / Al 2 O Three When the molar ratio is smaller than 20 or larger than 200, the relative value of crystallinity becomes small, and permanent deterioration due to dealumination is fast, which is not preferable. In addition, SiO 2 / Al 2 O Three If the molar ratio is greater than 200, sufficient activity may not be obtained, and the catalyst may not have sufficient activity for a reaction in which an aromatic hydrocarbon is contained in the raw material or product.
[0031]
SiO of zeolite constituting the catalyst of the present invention 2 / Al 2 O Three The molar ratio is a hydrothermally synthesized zeolite that does not contain alumina or silica as a binder, and is subjected to a dealumination treatment such as steam treatment or a reaction that generates aromatic hydrocarbons from light hydrocarbons. This is the molar ratio determined by measuring fresh fresh zeolite with a fluorescent X-ray apparatus or EPMA (X-ray macroanalyzer).
[0032]
As the zeolitic catalyst in the present invention, the above-described H-type or metal-substituted type substantially consisting of zeolite can be used, and the above-mentioned zeolite, periodic table groups VIII, Ib, IIb and A mixture of at least one metal selected from metals belonging to Group IIIb and a compound thereof (for example, a metal oxide that promotes dehydrogenation such as zinc oxide) or a compound thereof. Those supported as are preferable.
[0033]
As metals belonging to Group VIII, Group Ib, Group IIb, Group IIIb, Zn, Cu, Ag, Ni, Pt, Pd, and Ga are more preferable, and among these, Zn, Ag, Ni, and Ga are more preferably used. It is done. For example, it is preferable to include a mixture of zeolite and at least one selected from zinc and a compound thereof. Furthermore, it is more preferable to use alumina and silica as a binder.
[0034]
In the present invention, the zinc component is, for example, zinc, zinc oxide, zinc hydroxide, or a salt such as zinc nitrate, zinc carbonate, zinc sulfate, zinc chloride, zinc acetate, zinc oxalate, or an organic zinc compound such as alkyl zinc. Is mentioned.
[0035]
In the present invention, the zeolitic catalyst preferably contains a mixture of zeolite, a zinc component, and alumina. Moreover, it is also preferable that the mixture of a zinc component and alumina is heat-treated in water vapor and a zeolite. When both catalysts are treated with steam, the zinc component reacts with alumina and changes to zinc aluminate, which stabilizes zinc and produces aromatic hydrocarbons in high yield from light hydrocarbons containing olefins and / or paraffins. In such a reaction, the scattering loss of zinc can be greatly reduced. Zinc aluminate as used herein refers to JCPDS 5-0669NBS Circ. When observed with an X-ray diffractometer such as XD-610 manufactured by Shimadzu Corporation. 539, Vol. II, 38 (1953) means the same X-ray diffraction pattern as that shown in FIG.
[0036]
As an alumina source of alumina, there is anhydrous alumina or hydrated alumina. In addition, for example, a raw material that produces anhydrous alumina or hydrated alumina by hydrolysis, thermal decomposition, oxidation, etc. like an aluminum salt. It can also be used.
[0037]
In the present invention, it is also preferable to use alumina sol as the alumina source. When alumina sol is used as the alumina source, the zinc component reacts with alumina to produce zinc aluminate without performing the steam treatment, so that zinc is stabilized.
[0038]
In the above zeolitic catalyst, the content of at least one selected from zinc and its compound is preferably 5 to 25% by weight as zinc. In the present invention, when alumina is included, the alumina content is Al 2 O Three 5 to 50% by weight, preferably 15 to 40% by weight with respect to the total catalyst, and when alumina and zinc are included, the molar ratio of alumina to zinc (Al 2 O Three / Zn) is 1 or more.
[0039]
In the present invention, it is preferable that zinc oxide and zinc aluminate coexist in the zeolite catalyst at the time of being subjected to the reaction. Since zinc aluminate has a spinel structure, it is possible to suppress the scattering of zinc from the zeolite-based catalyst, but the effect of improving the aromatic selectivity, which is the original purpose of zinc loading, is reduced. It is preferable to coexist zinc oxide which exhibits the improvement effect of the above. The preferred abundance of zinc oxide and zinc aluminate is 1.2 to 20% by weight of zinc oxide and 8.2 to 50% by weight of zinc aluminate when the raw material or product contains an aromatic hydrocarbon. More preferably, zinc oxide is 1.0 to 5.0% by weight and zinc aluminate is 14 to 40% by weight.
[0040]
Although the effect of improving the aromatic selectivity of zinc aluminate itself is small, it becomes a supply source of zinc oxide and suppresses the decrease of zinc oxide. As a result, the effect of improving the aromatic selectivity can be sustained for a long time. Further, the presence of zinc aluminate also has an effect of suppressing the scattering rate due to reduction during the reaction in which the raw material or product of zinc oxide contains aromatic hydrocarbons. Therefore, the presence of zinc aluminate together with zinc oxide in the catalyst is effective for maintaining the effect of improving the aromatic selectivity.
[0041]
The zinc oxide as used in the field of this invention means what was measured with the following analysis method. That is, 1 g of the catalyst is ground to about several hundreds of microns in a mortar, dried at 120 ° C. for 1 hour, and about 0.5 g is accurately measured and placed in a 200 cc beaker. Thereto, 150 cc of 3% hydrochloric acid aqueous solution is added and heated at 80 ° C. for 2 hours on an electric heater. Thereafter, the solution is filtered through a 0.2 μm membrane filter, and the filtrate is subjected to flame analysis with an atomic absorption spectrometer (Shimadzu atomic absorption / flame spectrophotometer AA-640-12 type manufactured by Shimadzu Corporation), and zinc oxide is quantitatively analyzed by a standard addition method. .
[0042]
The zinc aluminate weight in the present invention is obtained by subtracting the weight of zinc oxide quantitatively analyzed by the above method from the total zinc weight. The total weight of zinc here refers to that obtained from a calibration curve of a standard substance with a fluorescent X-ray analyzer (Science RIX1000).
[0043]
In the present invention, the primary particle size of zeolite is SiO. 2 / Al 2 O Three Similar to the molar ratio, it is the particle size of the primary particles when the substantially fresh zeolite is viewed with a scanning electron microscope. In the present invention, the particle size is preferably 0.3 to 3 μm, more preferably 0.5 to 2 μm. These primary particles have various shapes, and the particle size referred to here indicates the average diameter of the widest portion of each particle. These primary particles may be present alone or may be secondary agglomerated.
[0044]
When the particle size is smaller than 0.3 μm, the amount of carbonaceous matter accumulated on the catalyst during the reaction in which the raw material or product contains aromatic hydrocarbons increases, and the carbonaceous matter is combusted with an oxygen-containing inert gas. Permanent activity deterioration due to dealumination in a high-temperature atmosphere in the presence of moisture is accelerated as occurs during removal, and conversely, if the particle size is larger than 3 μm, during the reaction in which the raw material or product contains aromatic hydrocarbons In addition, since the temporary decrease in activity due to the carbonaceous matter accumulated on the catalyst is accelerated, it is not practical.
[0045]
In the present invention, at the time when the zeolitic catalyst is subjected to the reaction, the ratio of the surface acid points to the total acid points when the H-type catalyst is made is 0.03 to 0.15, and 0.05 to 0.1 Is more preferred. If the ratio of the surface acid point to the total acid point is less than 0.03, there is a temporary decrease in activity due to light carbon accumulated on the catalyst during the reaction in which the raw material or product contains aromatic hydrocarbons. Conversely, if the ratio is greater than 0.15, the amount of light carbon that accumulates on the catalyst during the reaction in which the raw material or product contains aromatic hydrocarbons increases, and the carbonaceous matter is oxygenated. The permanent activity deterioration due to dealumination in a high-temperature atmosphere in which moisture exists is accelerated as occurs when burning and removing with the contained inert gas.
[0046]
In the present invention, the catalyst H 2 In the apparatus shown in FIG. 2, the steam treatment at O partial pressure of 0.8 atm and 650 ° C. for 5 hours was carried out by filling quartz wool 11,
[0047]
In the present invention, the catalyst is converted to H by the above method. 2 Desorption amount (B) of pyridine at 500 to 900 ° C. by the temperature-programmed desorption method in the H type after steam treatment at O partial pressure 0.8 atm and 650 ° C. for 5 hours and before the steam treatment The following parameter α represented by the amount of pyridine desorption (A) at 500 to 900 ° C. by the temperature-programmed desorption method when the H type is used is 1.6 or less, particularly preferably 1.4 or less. is there.
[0048]
[Equation 3]
If the parameter α is larger than 1.6, moisture is present as occurs when the carbonaceous material accumulated on the catalyst is burned and removed with an oxygen-containing inert gas during the reaction in which the raw material or product contains aromatic hydrocarbons. Permanent activity deterioration due to dealumination under a high temperature atmosphere is fast, and regeneration resistance is poor.
[0050]
The parameter α depends on the crystallinity obtained by the X-ray diffraction method. That is, as shown in the comparative example described later, when the particle size of the zeolite is small as in comparative example 1, or as in comparative example 3, 2 / Al 2 O Three When the molar ratio is small, SiO 2 is further added as in Comparative Example 4. 2 / Al 2 O Three When the molar ratio is large, the relative value of the crystallinity by the X-ray diffraction method is small, the parameter α is large, and the reproduction deterioration resistance is deteriorated.
[0051]
In addition, SiO 2 / Al 2 O Three Even if the molar ratio and the particle diameter are within the range of the present invention, as in Comparative Example 5, the parameter α is larger than 1.6, and the regeneration deterioration resistance may be deteriorated. In Comparative Example 5 as well, since the relative value of crystallinity is small, it is presumed that amorphous amorphous coexists in the synthesized zeolite. Therefore, in order to make a catalyst that can withstand repeated reaction / regeneration for several years with little deterioration in permanent activity due to dealumination in a high temperature atmosphere in the presence of moisture, all the requirements (1) to (4) of the present invention are satisfied. Must meet.
Here, the relative value of crystallinity is the relative value of the sum of the peak heights of 2θ = 23.1 °, 24.0 °, and 24.4 ° of the X-ray diffraction pattern of the zeolite catalyst. Say.
[0052]
The method for measuring the amount of desorption and the ratio of the surface acid points to the total acid points is as follows.
(Acid point measurement method)
First, before the acid point is measured, if the zeolitic catalyst is not H-type, it must be converted to H-type according to the following method. In order to change the zeolite into the H type, 1N nitric acid was added to the zeolite to make a 10 wt% slurry, which was subjected to ion exchange at 60 ° C. for 4 hours, the slurry was filtered, and further washed with 5 times the amount of water. Then, it is dried at 120 ° C. for 10 hours. The acid point of the H-type zeolite thus obtained is measured by the following method.
[0053]
As the acid point measuring device, Shimadzu Gas Chromatography GC-14A and Data Processing Unit CR-4A were used. FIG. 1 shows an acid point measuring apparatus used in the present invention. That is, 0.1 to 1 g of the
[0054]
On the other hand, the carrier gas that has passed through the packed column 3 is analyzed using the FID-type detector 6 to obtain a chromatogram of changes in amine concentration over time in which peaks periodically appear. As the number of injections increases, the amount of amine adsorbed on the sample approaches saturation, and the amount of non-adsorbed amine obtained by injection increases accordingly. Therefore, in the chromatogram, the non-adsorption peak area S corresponding to the injection of amine. i Is the area S corresponding to the amount of amine injected gradually. o Get closer to. That is, the peak area S confirmed by the data processing device i The total count corresponding to the area S o It approaches the total count corresponding to. Total count N corresponding to the amount of non-adsorbed amine obtained i And a total count N corresponding to the amount of non-adsorbed amine obtained at the time of injection immediately before i-1 However, when the following conditions are satisfied, it is determined that the amine adsorption amount is saturated.
[0055]
[Expression 4]
Under the above conditions, it is determined that the saturated adsorption of the amine to the catalyst is completed, and then the temperature is raised in the tubular electric furnace 2 at a rate of 15 ° C./min. Here, the gas flow path from around the amine inlet 5 to the FID-type detector 6 is heated by a
[0057]
The total acid point in the present invention is represented by the amount of pyridine desorption when measured using pyridine as an amine, and the surface acid point is 4-methylquinoline desorption when measured using 4-methylquinoline as an amine. Expressed as a separation. The desorption amount of pyridine at 500 to 900 ° C. by the temperature programmed desorption method is the desorption obtained from the time when the temperature detection end 7 reaches 500 ° C. until the temperature is further raised to 900 ° C. The amount of separation. Any desorption amount is expressed as a desorption amount per 1 g of the catalyst containing zeolite.
[0058]
(Measurement method of n-hexane decomposition primary reaction rate constant)
In the present invention, the first-order reaction rate constant of n-hexane decomposition of the catalyst means that quartz wool 11 and carbonaceous matter (coke) are substantially from the bottom in a 10 mmφ
[0059]
Then, the gas composition is obtained by FID-TCD gas chromatography (HP-5890 series II) manufactured by Hewlett-Packard Co., and the oil composition is analyzed by FID gas chromatography (GC-17A) manufactured by Shimadzu Corporation. The average conversion rate constant of n-hexane decomposition based on zeolite with the above gas / oil sampling time of 0.25 hours, obtained by substituting the conversion rate of n-hexane in the obtained reaction product into the following equation.
[0060]
[Equation 5]
The first-order reaction rate constant represents the activity of the catalyst, and the first-order reaction rate constant of n-hexane decomposition of the zeolite catalyst in the present invention is 0.2 or more at the time of being subjected to the reaction. Preferably, it is more preferably 0.3 or more. A catalyst having a primary reaction rate constant of less than 0.2 for the decomposition of n-hexane has a low activity, and the target product obtained by a reaction in which an aromatic hydrocarbon is contained in the raw material or product decreases.
[0062]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail with reference to examples and comparative examples.
[0063]
【Example】
Example 1
Sodium silicate aqueous solution (SiO 2 : 26% by weight, Na 2 (O: 7.0% by weight) NaOH of 0.05 kg and H of 8.0 kg 2 To a solution with O4 kg added, add Al 2 (SO Four ) Three ・ 16H 2 0.61 kg of O and 0.1 kg of 1,3-dimethylurea 2 A solution dissolved in 15 kg of O was added with stirring, and 10 kg of 5 wt% sulfuric acid was added to obtain a homogeneous gel. This gel was charged into a 50 liter autoclave and the stirring power was 0.5 to 1 KW / m. 2 A synthetic reaction was carried out at 160 ° C. for 10 hours with stirring to obtain a seed slurry.
[0064]
Next, No. 3 sodium silicate (Fuji Chemical Co., Ltd.,
[0065]
The obtained slurry was filtered, washed with 5 times the amount of water, and dried at 120 ° C. for 5 hours. A scanning electron micrograph of the dried product is shown in FIG. As is clear from the figure, it can be seen that the ZSM-5 produced has a widest portion with a thickness of 1.5 to 2 μm and an average of 1.2 μm.
[0066]
Subsequently, SiO of the obtained dried product 2 / Al 2 O Three When the molar ratio was measured using a fluorescent X-ray apparatus, it was 36.
Further, this dried product was ion-exchanged with a 10 wt% slurry in 1N nitric acid at room temperature for 3 hours, filtered, washed with 5 times the amount of water, and further dried at 120 ° C. for 10 hours.
[0067]
144 g of zinc nitrate hexahydrate was dissolved in 400 g of water, 400 g of alumina sol (alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.) and 200 g of H-ZSM-5 were added and heated at 50 ° C. and mixed for 2 hours. After the moisture-reduced clay-like mixture was formed into a cylindrical shape having a diameter of 1.6 mm and a length of 4 to 6 mm, it was dried at 120 ° C. for 2 hours and then baked in an electric atmosphere at 500 ° C. for 3 hours. Then, an H-ZSM-5 zeolite catalyst containing 10% by weight of zinc was formed.
[0068]
Further, the obtained molded catalyst was filled into a quartz reaction tube of the apparatus shown in FIG. 2, and 650 ° C., H 2 Steam treatment was performed for 5 hours under the condition of O partial pressure of 0.8 atm. Next, the amount of pyridine desorbed at 500 to 900 ° C. by the temperature-programmed desorption method before and after the steam treatment was determined by the above method.
[0069]
Subsequently, in order to align the initial activity with the catalysts of Examples and Comparative Examples described later, 650 ° C., H 2 The additional steam treatment was performed for 1.2 hours under the condition of O partial pressure of 0.8 atm. The primary reaction rate constant of n-hexane and the ratio of the surface acid point to the total acid point of the catalyst after the steam treatment were determined by the method described above.
[0070]
Next, in order to evaluate the regeneration degradation resistance of this catalyst, a model regeneration degradation test was conducted. That is, the above-mentioned catalyst subjected to steam treatment for a total of 6.2 hours is filled in the apparatus shown in FIG. 2 An additional steam treatment was carried out for 100 hours under the condition of O partial pressure of 0.15 atm, and the first-order reaction rate constant of n-hexane of the catalyst before and after that was determined by the same method as described above. The results are shown in Table 1.
[0071]
Further, in order to evaluate the coking resistance, a molded H-ZSM-5 zeolite catalyst which has not been subjected to a steam treatment is subjected to the C shown in Table 2 using the reactor shown in FIG. Five Fraction and C shown in Table 3 Four A cyclization reaction test was conducted in which the fraction was fed at 6: 4 (weight ratio). That is, 100 g of the formed catalyst was filled in a
[0072]
Thereafter, the temperature of the
[0073]
Example 2
Special 3 sodium silicate (Fuji Chemical Co., Ltd.,
[0074]
This gel was put into a 50 liter autoclave and crystallized while being stirred at 150 ° C. for 25 hours at a rotation speed of 200 rpm. The obtained slurry was filtered, washed with 5 times the amount of water, and dried at 120 ° C. for 5 hours. A scanning electron micrograph of this zeolite is shown in FIG. As is clear from the figure, it can be seen that the ZSM-5 produced has a thickness of 0.5-1 μm at the widest portion and an average of 0.7 μm.
[0075]
Next, SiO of the obtained catalyst 2 / Al 2 O Three The molar ratio was determined by the same method as in Example 1.
Moreover, the H-ZSM-5 zeolite shaping | molding catalyst which contains zinc 10weight% by the same method as Example 1 was obtained. The amount of pyridine desorbed from 500 ° C. to 900 ° C. before and after steaming at 650 ° C. for 5 hours, and the primary reaction rate constant and surface acid point of n-hexane after steaming at 650 ° C. for 11 hours. The ratio of total acid points was also determined by the same method as in Example 1. The results are shown in Table 1.
[0076]
Furthermore, using the catalyst steam-treated at 650 ° C. for 11 hours, the same test for evaluating the deterioration resistance against regeneration as in Example 1 and the test for evaluating the coking resistance were performed. The results are shown in Table 1.
[0077]
Example 3
Sodium silicate aqueous solution (SiO 2 : 26% by weight, Na 2 (O: 7.0% by weight) NaOH of 0.05 kg and H of 8.0 kg 2 To a solution with O4 kg added, add Al 2 (SO Four ) Three ・ 16H 2 0.61 kg of O and 0.1 kg of 1,3-dimethylurea 2 A solution dissolved in 15 kg of O was added with stirring, and 10 kg of 5 wt% sulfuric acid was added to obtain a homogeneous gel. This gel was charged into a 50 liter autoclave and the stirring power was 0.5 to 1 KW / m. 2 A synthetic reaction was carried out at 160 ° C. for 10 hours with stirring to obtain a seed slurry.
[0078]
Next, No. 3 sodium silicate (Fuji Chemical Co., Ltd.,
[0079]
The obtained slurry was filtered, washed with 5 times the amount of water, dried at 120 ° C. for 5 hours, and the particle size of the zeolite was measured with a scanning electron microscope.
Next, SiO of the obtained catalyst 2 / Al 2 O Three The molar ratio was determined by the same method as in Example 1.
[0080]
Moreover, the H-ZSM-5 zeolite shaping | molding catalyst which contains zinc 10weight% by the same method as Example 1 was obtained. The amount of pyridine desorbed between 500 ° C. and 900 ° C. before and after steaming at 650 ° C. for 5 hours, and the primary reaction rate constant and surface of n-hexane after steaming at 650 ° C. for 9.5 hours The ratio between the acid points and the total acid points was determined in the same manner as in Example 1. The results are shown in Table 1.
[0081]
Furthermore, using the catalyst steam-treated at 650 ° C. for 9.5 hours, the same test for evaluating the deterioration resistance against regeneration as in Example 1 and the test for evaluating the coking resistance were performed. The results are shown in Table 1.
[0082]
Example 4
Special 3 sodium silicate (Fuji Chemical Co., Ltd.,
[0083]
Special 3 sodium silicate (Fuji Chemical Co., Ltd.,
[0084]
Next, No. 3 sodium silicate (Fuji Chemical Co., Ltd.,
[0085]
The obtained slurry was washed with centrifugal filtration until the pH was 9 or less, and then dried at 120 ° C. for 5 hours. A scanning electron micrograph of the dried product is shown in FIG. As is apparent from the figure, the produced Na-type ZSM-5 has a widest portion having a length of 2 to 3 μm and an average of 2.5 μm.
Subsequently, SiO of the obtained dried product 2 / Al 2 O Three When the molar ratio was measured using a fluorescent X-ray apparatus, it was 39.
[0086]
Further, this dried product was ion-exchanged with a 10% by weight slurry in 1N nitric acid at room temperature for 3 hours, washed with water until pH became 4.5 or more while centrifugal filtration, and further dried at 120 ° C. for 10 hours. , H-ZSM-5 was obtained. 144 g of zinc nitrate hexahydrate was dissolved in 200 g of water, 5 g of acetic acid was added, 200 g of alumina sol (alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.), 20 g of boehmite, and 200 g of the H-ZSM-5 were added and mixed for 2 hours. The mixture in the form of clay is molded into a cylindrical shape having a diameter of 1.6 mm and a length of 4 to 6 mm, dried at 120 ° C. for 2 hours, and then baked in an electric furnace at 500 ° C. for 3 hours in an air furnace. An H-ZSM-5 zeolite catalyst containing 10% by weight was molded.
[0087]
Further, in the same manner as in Example 1, the obtained molded catalyst was obtained at 650 ° C., H 2 The amount of pyridine desorbed at 500 to 900 ° C. determined by the temperature-programmed desorption method when the H type was formed before and after steaming for 5 hours under the condition of O partial pressure of 0.8 atm was determined by the above method.
Subsequently, 650 ° C., H 2 Test of resistance to regeneration degradation and coking resistance by determining the primary reaction rate constant of n-hexane and the ratio of surface acid points to total acid points of the catalyst that was steamed for 8 hours under the condition of O partial pressure 0.8atm. Was carried out in the same manner as in Example 1. The results are shown in Table 1.
[0088]
Example 5
Special 3 sodium silicate (Fuji Chemical Co., Ltd.,
[0089]
Special 3 sodium silicate (Fuji Chemical Co., Ltd.,
[0090]
Next, No. 3 sodium silicate (Fuji Chemical Co., Ltd.,
[0091]
The resulting slurry was washed with centrifugal water until the pH was 9 or less, and further ion-exchanged at 10 ° C. with a 10 wt% slurry in 1N nitric acid at 70 ° C. for 5 hours. It washed with water until it became 5 or more, and it dried at 120 degreeC for 30 hours. FIG. 7 shows a scanning electron micrograph of the dried product. As can be seen from the figure, the generated H-ZSM-5 has a widest portion having a length of 2 to 3 μm and an average of 2.5 μm.
Subsequently, SiO of the obtained dried product 2 / Al 2 O Three The molar ratio was 41 as measured using a fluorescent X-ray apparatus.
[0092]
144 g of zinc nitrate hexahydrate was dissolved in 200 g of water, 5 g of acetic acid was added, 200 g of alumina sol (alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.), 20 g of boehmite, and 200 g of the H-ZSM-5 were added and mixed for 2 hours. The mixture in the form of clay is molded into a cylindrical shape having a diameter of 1.6 mm and a length of 4 to 6 mm, dried at 120 ° C. for 2 hours, and then baked in an electric furnace at 500 ° C. for 3 hours in an air furnace. An H-ZSM-5 zeolite catalyst containing 10% by weight was molded.
[0093]
Further, in the same manner as in Example 1, the obtained molded catalyst was obtained at 650 ° C., H 2 The amount of pyridine desorbed at 500 to 900 ° C. by the temperature-programmed desorption method when the H type was formed before and after steaming for 5 hours under the condition of O partial pressure of 0.8 atm was determined by the above method.
Subsequently, 650 ° C., H 2 The primary reaction rate constant of n-hexane and the ratio of the surface acid point to the total acid point of the catalyst subjected to the steam treatment for 8.5 hours under the condition of O partial pressure of 0.8 atm were obtained, and the regeneration deterioration resistance and coking resistance were obtained. The test was conducted in the same manner as in Example 1. The results are shown in Table 1.
[0094]
Comparative Example 1
(1) Seed slurry synthesis
Sodium silicate aqueous solution (SiO 2 : 25.2% by weight, Na 2 O: 7.35 wt%) 129 g with NaOH 0.64 g and H 2 To a solution with 133 g of O added, 2 (SO Four ) Three ・ 16H 2 0.9.7 g of O and 0.2 g of 1,3-dimethylurea 2 A solution dissolved in 230 g of O was added with stirring, and 140 g of 4.6% by weight sulfuric acid was added to obtain a homogeneous gel. The pH of this gel was 10.8. This gel was charged into a 1 liter autoclave and subjected to a synthesis reaction at 180 ° C. for 40 hours.
The resulting slurry was cooled to 30 ° C., partly filtered and dried at 120 ° C. for 8 hours. The X-ray diffraction pattern of this product was consistent with ZSM-5.
[0095]
(2) This synthesis
After adding 250 g of the seed slurry obtained in (1) to 400 g of the gel having the same composition as in (1) and mixing well, the mixture was placed in a 1 liter autoclave and crystallized at 160 ° C. for 15 hours.
The obtained slurry was filtered, washed with 5 times the amount of water, and then dried at 120 ° C. for 8 hours, the X-ray diffraction pattern of which coincided with ZSM-5.
A scanning electron micrograph of this zeolite is shown in FIG. As is apparent from the figure, the produced ZSM-5 is an agglomeration of fine particles, and the agglomerates are particles having irregularities on the surface where the thickness of the widest portion is about 0.2 μm. .
Next, SiO of the obtained catalyst 2 / Al 2 O Three The molar ratio was determined by the same method as in Example 1.
[0096]
Moreover, the H-ZSM-5 zeolite shaping | molding catalyst which contains zinc 10weight% by the same method as Example 1 was obtained. The amount of pyridine desorbed from 500 ° C. to 900 ° C. before and after steaming at 650 ° C. for 5 hours, and the primary reaction rate constant and surface of n-hexane after steaming at 650 ° C. for 3.8 hours. The ratio between the acid points and the total acid points was determined in the same manner as in Example 1. The results are shown in Table 1.
[0097]
Further, using the catalyst steam-treated at 650 ° C. for 3.8 hours, the same test for evaluating the deterioration resistance against regeneration as in Example 1 and the test for evaluating the coking resistance were performed. The results are shown in Table 1.
The particle size is small, the ratio of the surface acid points to the total acid points is large, and the parameter α for the amount of pyridine elimination is large, so the regeneration resistance is poor, and the amount of coke accumulated in the coking resistance test is large. I understand.
[0098]
Comparative Example 2
100 g of 1,8-diamino-4-aminomethyloctane, 4 g of aluminum sulfate and 5 g of sodium hydroxide are dissolved in 200 g, and silica sol (30% SiO 2 ) 250 g was added to obtain a homogeneous solution. While stirring the solution, 20% sulfuric acid was added dropwise to adjust the pH to 12.5 to obtain a homogeneous gel. Furthermore, this gel was put into a mixer and stirred at 2000 rpm for 20 minutes at high speed. This gel was charged into an autoclave and crystallized at 150 ° C. for 24 hours while stirring at 50 rpm. The obtained slurry was filtered, washed with 5 times the amount of water, dried at 120 ° C. for 8 hours, and the particle size of the catalyst was measured with a scanning electron microscope and found to be 5 μm or more.
[0099]
Moreover, the H-ZSM-5 zeolite shaping | molding catalyst which contains zinc 10weight% by the same method as Example 1 was obtained. The amount of pyridine desorbed between 500 ° C. and 900 ° C. before and after steaming at 650 ° C. for 5 hours, and the primary reaction rate constant and surface acid point of n-hexane after steaming at 650 ° C. for 16 hours. The ratio of total acid points was also determined by the same method as in Example 1. The results are shown in Table 1.
[0100]
Furthermore, using the catalyst steam-treated at 650 ° C. for 16 hours, the same test for evaluating the deterioration resistance against regeneration as in Example 1 and the test for evaluating the coking resistance were performed. The results are shown in Table 1.
From Table 1, it can be seen that the present catalyst has a large particle size and a small ratio between the surface acid points and the total acid points, so that the regeneration deterioration resistance is good, but the deterioration due to coking is fast.
[0101]
Comparative Example 3
Special 3 sodium silicate (Fuji Chemical Co., Ltd.,
The obtained slurry was filtered, washed with 5 times the amount of water, and dried at 120 ° C. for 5 hours. SiO of this zeolite 2 / Al 2 O Three The molar ratio determined by the same method as in Example 1 was 18.
[0102]
Moreover, the H-ZSM-5 zeolite shaping | molding catalyst which contains zinc 10weight% by the same method as Example 1 was obtained. The amount of pyridine desorbed between 500 ° C. and 900 ° C. before and after steaming at 650 ° C. for 5 hours, and the primary reaction rate constant and surface acid point of n-hexane after steaming at 650 ° C. for 3 hours. The ratio of total acid points was also determined by the same method as in Example 1. The results are shown in Table 1.
[0103]
Furthermore, using the catalyst steam-treated for 3 hours at 650 ° C., the same test for evaluating the deterioration resistance against regeneration as in Example 1 and the test for evaluating the resistance to coking were performed. The results are shown in Table 1.
SiO 2 / Al 2 O Three Since the molar ratio is small, the regeneration resistance is poor.
[0104]
Comparative Example 4
Commercially available H-ZSM-5 zeolite (NE-Chemcat, SiO 2 / Al 2 O Three = 250), the H-ZSM-5 zeolite shaped catalyst containing 10% by weight of zinc was obtained in the same manner as in Example 1. The amount of pyridine desorbed between 500 ° C. and 900 ° C. before and after steaming at 650 ° C. for 5 hours, and the primary reaction rate constant and surface acid point of n-hexane after steaming at 650 ° C. for 1 hour. The ratio of total acid points was also determined by the same method as in Example 1. The results are shown in Table 1.
[0105]
Furthermore, using the catalyst steam-treated at 650 ° C. for 1 hour, the same test for evaluating the regeneration resistance as in Example 1 and the test for evaluating the coking resistance were performed. The results are shown in Table 1.
SiO 2 / Al 2 O Three Since the molar ratio is too large and the degree of crystallinity is low, the parameter α of the amount of pyridine desorption before and after the steam treatment becomes large, and the regeneration deterioration resistance is poor.
[0106]
Comparative Example 5
Solution A in which 290 g of sodium silicate (water glass No. 3) was dissolved in 230 g of distilled water, 11.4 g of aluminum sulfate 16-hydrate, 23.4 g of 1,3-dimethylurea, and 13 g of sulfuric acid were dissolved in 300 g of distilled water. B liquid was prepared. Next, using a homogenizer, solution B was added to solution A with strong stirring, and stirred for about 3 hours until the gel composition became uniform. This gel composition was charged into a 1 liter autoclave and subjected to reaction crystallization for 35 hours under stirring at 150 ° C. and 1000 rpm. After the reaction, the solid was filtered, washed with water, dehydrated and dried, and calcined in air at 550 ° C. for 3 hours. SiO of obtained H-ZSM-5 type zeolite 2 / Al 2 O Three The molar ratio determined by the same method as in Example 1 was 46. Further, the particle size of the zeolite was measured with a scanning electron microscope.
[0107]
Moreover, the ZSM-5 zeolite shaping | molding catalyst which contains zinc 10weight% by the same method as Example 1 was obtained. The amount of pyridine desorbed between 500 ° C. and 900 ° C. before and after steaming at 650 ° C. for 5 hours of this shaped catalyst was determined. The first-order rate constant of n-hexane after steaming at 650 ° C. for 3 hours and the ratio of surface acid points to total acid points were determined in the same manner as in Example 1. The results are shown in Table 1.
Furthermore, using the catalyst steam-treated for 3 hours at 650 ° C., the same test for evaluating the deterioration resistance against regeneration as in Example 1 and the test for evaluating the resistance to coking were performed. The results are shown in Table 1.
Since the parameter α of the amount of pyridine desorption before and after the steam treatment is as large as 1.8, the regeneration deterioration resistance is poor.
[0108]
Comparative Example 6
Commercially available H-ZSM-5 zeolite (SiO 2 / Al 2 O Three = 400), the H-ZSM-5 zeolite shaped catalyst containing 10% by weight of zinc was obtained by the same method as in Example 1. The amount of pyridine desorbed from 500 ° C. to 900 ° C. before and after steam treatment at 650 ° C. for 5 hours, the primary reaction rate constant of n-hexane, the surface acid point, and the total acid point of this molded catalyst before steam treatment. The ratio was also determined by the same method as in Example 1. The results are shown in Table 1.
Furthermore, using the catalyst not subjected to steam treatment, the same test for evaluating the regeneration resistance as in Example 1 and the test for evaluating the coking resistance were performed. The results are shown in Table 1. SiO 2 / Al 2 O Three Since the molar ratio is too large, the activity is low and the aromatic yield is low.
[0109]
Example 6
The zeolite catalyst synthesized and molded by the same method as in Example 4 was charged into a one-stage adiabatic reactor, and the pressure was 5 kg / cm. 2 G was steamed at 650 ° C. for 8 hours. Furthermore, C shown in Table 2 Five Fraction and C shown in Table 3 Four The fraction is 6: 4 by weight and the pressure is 5 kg / cm. 2 G, inlet temperature 530 ° C., WHSV (weight hourly space velocity) 2.8 hr -1 A cyclization reaction was carried out for 48 hours under the above conditions. The carbonaceous material accumulated during 48 hours is pressure 5 kg / cm. 2 G was burned and removed (regenerated) by circulating nitrogen gas having an oxygen concentration of 1 to 1.5 vol% at a flow rate of 5000 Nm3 / hr for 40 to 43 hours in an atmosphere of 480 to 530 ° C. The cyclization reaction and regeneration were repeated 75 times (300 days). Table 4 shows the results of the first and 75th cyclization reactions.
[0110]
Comparative Example 7
A zeolite catalyst synthesized and molded in the same manner as in Comparative Example 1 was charged into a one-stage adiabatic reactor, and the pressure was 5 kg / cm. 2 G was steamed at 650 ° C. for 3.8 hours. Furthermore, C shown in Table 2 Five Fraction and C shown in Table 3 Four The fraction is 6: 4 by weight and the pressure is 5 kg / cm. 2 G, inlet temperature 530 ° C., WHSV (weight hourly space velocity) 2.8 hr -1 A cyclization reaction was carried out for 48 hours under the above conditions. The carbonaceous material accumulated during 48 hours is pressure 5 kg / cm. 2 G was burned and removed (regenerated) by circulating nitrogen gas having an oxygen concentration of 1 to 1.5 vol% at a flow rate of 5000 Nm3 / hr for 40 to 43 hours in an atmosphere of 480 to 530 ° C. The cyclization reaction and regeneration were repeated 75 times (300 days). Table 4 shows the results of the first and 75th cyclization reactions. It can be seen that since the ratio of the surface acid points to the total acid points is large, the deterioration resistance against regeneration is poor and the permanent activity deterioration is fast.
[0111]
Example 7
The total amount of zinc obtained from the catalyst obtained in Example 4 subjected to steam treatment at 650 ° C. for 8 hours was determined by fluorescent X-ray, and the catalyst was treated with hydrochloric acid, and then zinc oxide was determined by atomic absorption spectrometry. . They were 2.9% by weight of zinc oxide and 22.4% by weight of zinc aluminate based on the catalyst weight. 10 g of this catalyst is filled in a reaction tube, hydrogen is supplied at 20 [L / Hr], and reduced at 500 ° C. for 20 Hr. Table 5 shows the measurement results of the amount of zinc oxide and the amount of zinc aluminate before and after the hydrogen reduction. In addition, using the catalyst before and after hydrogen reduction, C Four Fraction and C Five The test which evaluates the coking resistance using a fraction was implemented. The results are shown in Table 5.
[0112]
Comparative Example 8
The zinc-free H-ZSM-5 obtained in Example 4 was immersed in 100 g of a 7 wt% zinc nitrate aqueous solution, evaporated to dryness, dried at 120 ° C. for 4 hours, and calcined at 500 ° C. for 3 hours. A catalyst containing 2.0% by weight was prepared. Next, 20 g of this catalyst after compression molding, pulverized, and aligned to 9 to 20 mesh was charged into a quartz glass reactor having an inner diameter of 12 mm, and a large amount of steam in a steam-nitrogen mixed gas containing 80% by weight of steam was used. Heat treatment was performed at 650 ° C. for 1 hour under atmospheric pressure. Zinc oxide and zinc aluminate were determined by X-ray fluorescence and atomic absorption, and reduced by hydrogen in the same manner as in Example 8. Furthermore, C before and after hydrogen reduction Four Fraction and C Five The test which evaluates the coking resistance using a fraction was implemented. The results are shown in Table 5.
[0113]
Comparative Example 9
Zinc-free H-ZSM-5 obtained in Example 1 was steam treated at 650 ° C. for 5 hours, and zinc aluminate manufactured by High-Purity Chemical Laboratory was 10% by weight based on the total catalyst as zinc. It mixed so that it might become. C Four Fraction and C Five The test which evaluates the coking resistance using a fraction was implemented. The results are shown in Table 5.
[0114]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
【The invention's effect】
According to the method of the present invention as described above, the amount of carbonaceous material accumulated on the catalyst during the reaction in which the raw material or product contains aromatic hydrocarbons is reduced, and the activity of carbonaceous material is temporarily reduced. Further, it is possible to suppress permanent activity deterioration due to dealumination in a high-temperature atmosphere where moisture exists, such as occurs when the carbonaceous material is burned and removed with an oxygen-containing inert gas. A catalyst having excellent coking resistance can be obtained. Therefore, the method of the present invention can be widely used in the petrochemical industry and petroleum refining, and can be effectively used particularly for the production of aromatic compounds and high octane gasoline.
[Brief description of the drawings]
FIG. 1 is a schematic view of an acid point measuring apparatus in the method of the present invention.
FIG. 2 is a schematic view of an isothermal reactor in the method of the present invention.
FIG. 3 is a scanning photomicrograph of a catalyst in the method of the present invention.
FIG. 4 is a schematic view of an isothermal reactor in the method of the present invention.
FIG. 5 is a scanning photomicrograph of a catalyst in the method of the present invention.
FIG. 6 is a scanning photomicrograph of a catalyst in the method of the present invention.
FIG. 7 is a scanning photomicrograph of a catalyst in the method of the present invention.
FIG. 8 is a scanning photomicrograph of a catalyst in the method of the present invention.
[Explanation of symbols]
1 Gas flow meter
2 Tubular electric furnace
3 SUS short tube column
4 samples
5 Inlet
6 FID type detector
7 Temperature detection end
8 Ribbon heater
9 Insulation material
10 Quartz reaction tube
11 Quartz wool
12 Catalyst
13 Raschig rings
14 Thermometer
15 Thermocouple for temperature adjustment
16 Electric furnace
17 Raw material inlet
18 condenser
19 Oil trap
20 Back for generating gas repair
21 SUS reaction tube
22 Thermometer
23 Catalyst
24 Thermocouple for temperature control
25 Electric furnace
26 Raw material inlet
27 C Five Raw material tank for fractions
28 C Four Raw material tank for fractions
29 Pump
30 pumps
Claims (9)
（１）該ゼオライト系触媒を構成するゼオライトのＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が２０から２００。
（２）該ゼオライト系触媒を構成するゼオライトの一次粒子の粒径が０．３から３μｍ。
（３）該ゼオライト系触媒をＨ型にしたときの全酸点に対する表面酸点の割合が０．０３〜０．１５。
（４）該ゼオライト系触媒をＨ2 Ｏ分圧０．８ａｔｍ，６５０℃で５時間水蒸気処理をした後での、Ｈ型にしたときの昇温脱離法による５００〜９００℃におけるピリジンの脱離量（Ｂ）と該水蒸気処理前のＨ型にしたときの昇温脱離法による５００〜９００℃におけるピリジン脱離量（Ａ）とが以下を満足する。
(1) The SiO 2 / Al 2 O 3 molar ratio of the zeolite constituting the zeolite catalyst is 20 to 200.
(2) The primary particle diameter of the zeolite constituting the zeolitic catalyst is 0.3 to 3 μm.
(3) The ratio of the surface acid point to the total acid point when the zeolite catalyst is made to be H-type is 0.03 to 0.15.
(4) Dehydration of pyridine at 500 to 900 ° C. by the temperature-programmed desorption method when the zeolite-based catalyst is steamed for 5 hours at H 2 O partial pressure of 0.8 atm and 650 ° C. The amount of separation (B) and the amount of pyridine desorption (A) at 500 to 900 ° C. by the temperature programmed desorption method when the H-type before the steam treatment is satisfied satisfy the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11418597A JP3905948B2 (en) | 1996-04-18 | 1997-04-17 | High silica zeolite catalyst |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11953996 | 1996-04-18 | ||
| JP8-119539 | 1996-04-18 | ||
| JP11418597A JP3905948B2 (en) | 1996-04-18 | 1997-04-17 | High silica zeolite catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1052646A JPH1052646A (en) | 1998-02-24 |
| JP3905948B2 true JP3905948B2 (en) | 2007-04-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11418597A Expired - Lifetime JP3905948B2 (en) | 1996-04-18 | 1997-04-17 | High silica zeolite catalyst |
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| JP (1) | JP3905948B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010016338A1 (en) | 2008-08-06 | 2010-02-11 | 旭化成ケミカルズ株式会社 | Zeolite-containing catalyst, process for producing the zeolite-containing catalyst, and process for producing propylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BRPI0707115B1 (en) | 2006-01-16 | 2017-03-28 | Asahi Kasei Chemical Corp | process to produce propylene and aromatic hydrocarbons |
| TW200918486A (en) | 2007-09-18 | 2009-05-01 | Asahi Kasei Chemicals Corp | Process for production of propylene |
| BRPI1009564B1 (en) * | 2009-03-02 | 2017-12-26 | Asahi Kasei Chemicals Corporation | METHOD FOR PRODUCING PROPYLENE. |
| CN107469857B (en) * | 2016-06-07 | 2020-12-01 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing aromatic hydrocarbon by directly converting synthesis gas |
| US10821425B2 (en) | 2016-06-09 | 2020-11-03 | Exxonmobil Chemical Patents Inc. | Treatment of aromatic alkylation catalysts |
| JP2019026571A (en) * | 2017-07-27 | 2019-02-21 | 東ソー株式会社 | Method for producing aromatic compound |
| CN111499094B (en) * | 2020-04-13 | 2023-03-17 | 南京卓越环保科技有限公司 | Harmless treatment method of high-concentration pyridinol sodium acid water |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010016338A1 (en) | 2008-08-06 | 2010-02-11 | 旭化成ケミカルズ株式会社 | Zeolite-containing catalyst, process for producing the zeolite-containing catalyst, and process for producing propylene |
| US8993469B2 (en) | 2008-08-06 | 2015-03-31 | Asahi Kasei Chemicals Corporation | Zeolite-containing catalyst and method for producing the same, and method for producing propylene |
| US9643167B2 (en) | 2008-08-06 | 2017-05-09 | Asahi Kasei Chemicals Corporation | Zeolite-containing catalyst and method for producing the same, and method for producing propylene |
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| Publication number | Publication date |
|---|---|
| JPH1052646A (en) | 1998-02-24 |
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