JP2009255014A - Catalyst for producing olefin from methanol - Google Patents
Catalyst for producing olefin from methanol Download PDFInfo
- Publication number
- JP2009255014A JP2009255014A JP2008109966A JP2008109966A JP2009255014A JP 2009255014 A JP2009255014 A JP 2009255014A JP 2008109966 A JP2008109966 A JP 2008109966A JP 2008109966 A JP2008109966 A JP 2008109966A JP 2009255014 A JP2009255014 A JP 2009255014A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- catalyst
- methanol
- surfactant
- catalyst according
- 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.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 59
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000010457 zeolite Substances 0.000 claims abstract description 59
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 239000012452 mother liquor Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- -1 aluminum alkoxide Chemical class 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical class C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 4
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical compound C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 description 1
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- 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 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- WMLFGKCFDKMAKB-UHFFFAOYSA-M benzyl-diethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](CC)(CC)CC1=CC=CC=C1 WMLFGKCFDKMAKB-UHFFFAOYSA-M 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- SMQZZQFYHUDLSJ-UHFFFAOYSA-L disodium;1-dodecylnaphthalene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.C1=CC=C2C(CCCCCCCCCCCC)=CC=CC2=C1 SMQZZQFYHUDLSJ-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- HBRNMIYLJIXXEE-UHFFFAOYSA-N dodecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN HBRNMIYLJIXXEE-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- OKHRRIGNGQFVEE-UHFFFAOYSA-N methyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C)C1=CC=CC=C1 OKHRRIGNGQFVEE-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
Description
本発明はメタノールからオレフィンを製造するための触媒に関する。 The present invention relates to a catalyst for producing olefins from methanol.
本発明者らは、「ＺＳＭ−５ナノクリスタル積層触媒膜によるＭＴＯ反応」と題する研究報告を発表している（非特許文献１）。この報告においては、触媒としてＺＳＭ−５型ゼオライトが使用されているが、その結晶径は１５０〜３００μｍである。
本発明者らは、触媒活性に優れ、しかも、コーキングによる劣化を抑制することにより高い転化率を維持し得る触媒について研究を行った結果、ＺＳＭ−５型ゼオライトのナノサイズ化に成功し、また、このナノサイズＺＳＭ−５型ゼオライトを積層することにより触媒性能を一層高めることに成功し、本発明の完成に至った。 As a result of research on a catalyst having excellent catalytic activity and capable of maintaining a high conversion rate by suppressing deterioration due to coking, the inventors succeeded in nano-sizing ZSM-5 type zeolite, and The present inventors succeeded in further improving the catalyst performance by laminating this nano-sized ZSM-5 type zeolite, and completed the present invention.
すなわち、本発明の第１の要旨は、結晶径が１００ｎｍ以下のＺＳＭ−５型ゼオライトから成ることを特徴とするメタノールからオレフィンを製造するための触媒に存し、本発明の好ましい態様においては、上記のゼオライトはセラミックス多孔質支持体上に膜状に積層される。 That is, the first gist of the present invention resides in a catalyst for producing an olefin from methanol characterized by comprising a ZSM-5 type zeolite having a crystal diameter of 100 nm or less. In a preferred embodiment of the present invention, Said zeolite is laminated | stacked on a ceramic porous support body by the film form.
本発明の第２の要旨は、界面活性剤と有機溶媒とを含有し且つ界面活性剤の濃度が０．１〜０．７５ｍｏｌ／Ｌの溶液中に、少なくとも、アルミナ源、シリカ源およびテンプレートを含有し、アルミナ源の濃度が０．００４〜０．１２５ｍｏｌ／Ｌ、シリカ源の濃度が０．４〜２．５ｍｏｌ／Ｌ、Ｓｉ／Ａｌモル比が２０〜２００、Ｓｉ／テンプレートモル比が３〜１０である母液を添加し、この際、界面活性剤に対する母液の重量比を０．６７〜４０とし、母液のエマルジョンを形成した後、水熱合成を行うことを特徴とする上記の第１の要旨に係る触媒の製造方法に存する。 The second gist of the present invention is that at least an alumina source, a silica source and a template are contained in a solution containing a surfactant and an organic solvent and having a surfactant concentration of 0.1 to 0.75 mol / L. And the alumina source concentration is 0.004 to 0.125 mol / L, the silica source concentration is 0.4 to 2.5 mol / L, the Si / Al molar ratio is 20 to 200, and the Si / template molar ratio is 3. The mother liquor of 10 to 10 is added. At this time, the weight ratio of the mother liquor to the surfactant is 0.67 to 40, and the emulsion of the mother liquor is formed, followed by hydrothermal synthesis. A catalyst production method according to the gist of the present invention.
そして、本発明の第３の要旨は、上記の第１の要旨に係る触媒とメタノールとを接触させることを特徴とするオレフィンの製造方法に存する。 And the 3rd summary of this invention exists in the manufacturing method of the olefin characterized by making the catalyst which concerns on said 1st summary, and methanol contact.
本発明によれば、メタノールからオレフィンを製造するための触媒であって、触媒活性に優れ、しかも、コーキングによる劣化を抑制することにより高い転化率を維持し得る触媒が提供される。 ADVANTAGE OF THE INVENTION According to this invention, it is a catalyst for manufacturing an olefin from methanol, It is excellent in a catalyst activity, Furthermore, the catalyst which can maintain a high conversion rate by suppressing degradation by coking is provided.
先ず、説明の便宜上、本発明の触媒の製造方法について説明する。本発明の触媒はＺＳＭ−５型ゼオライトから成る。本発明においては、ＺＳＭ−５型ゼオライトは、基本的には、界面活性剤と有機溶媒の溶液に、少なくとも、アルミナ源、シリカ源およびテンプレートを含有する母液を添加し、母液のエマルジョンを形成した後、水熱合成を行う方法によって製造することが出来る。そして、本発明の好ましい態様においては、母液の調製の際、安定剤としてカチオン源が使用される。 First, for the convenience of explanation, the method for producing the catalyst of the present invention will be explained. The catalyst of the present invention comprises ZSM-5 type zeolite. In the present invention, the ZSM-5 type zeolite basically has a mother liquor containing at least an alumina source, a silica source and a template added to a surfactant and organic solvent solution to form an emulsion of the mother liquor. Thereafter, it can be produced by a method of hydrothermal synthesis. In a preferred embodiment of the present invention, a cation source is used as a stabilizer in preparing the mother liquor.
アルミナ源としては、特に限定されず、アルミニウムアルコキシド、塩化アルミニウム、硫酸アルミニウム、硝酸アルミニウム、酸化アルミニウム、水酸化アルミニウム、アルミン酸ナトリウム、アルミナホワイト、フッ化アルミニウム等が挙げられるが、これらの中ではアルミニウムアルコキシドが好ましい。アルミニウムアルコキシドの具体例としては、アルミニウムトリメトキシド、アルミニウムトリエトキシド、アルミニウムトリイソプロポキシド等が挙げられる。 The alumina source is not particularly limited, and examples thereof include aluminum alkoxide, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum oxide, aluminum hydroxide, sodium aluminate, alumina white, and aluminum fluoride. Among these, aluminum Alkoxides are preferred. Specific examples of the aluminum alkoxide include aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide and the like.
シリカ源としては、特に限定されず、ケイ素アルコキシド、コロイダルシリカ、湿式シリカ、無定形シリカ、ヒュームドシリカ、ケイ酸ナトリウム、シリカゾル、シリカゲル、カオリナイト、珪藻土、ケイ酸アルミニウム、ホワイトカーボン等が挙げれるが、これらの中ではケイ素アルコキシドが好ましい。ケイ素アルコキシドの具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等が挙げられる。 The silica source is not particularly limited, and examples include silicon alkoxide, colloidal silica, wet silica, amorphous silica, fumed silica, sodium silicate, silica sol, silica gel, kaolinite, diatomaceous earth, aluminum silicate, and white carbon. Of these, silicon alkoxide is preferred. Specific examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like.
テンプレートとしては、特に制限されず、水酸化テトラプロピルアンモニウム（ＴＰＡＯＨ）、臭化テトラプロピルアンモニウム（ＴＰＡＢｒ）、水酸化テトラブチルアンモニウム（ＴＢＡＯＨ）、水酸化テトラメチルアンモニウム（ＴＭＡＯＨ）、塩化テトラメチルアンモニウム（ＴＭＡＣｌ）等が挙げられる。 The template is not particularly limited, and tetrapropylammonium hydroxide (TPAOH), tetrapropylammonium bromide (TPABr), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), tetramethylammonium chloride ( TMACl) and the like.
カチオン源としては、特に限定されず、通常、アルカリ金属、アルカリ金属などの塩化物、硫酸塩などの各種金属の塩が使用され、その具体例としては、塩化ナトリウム、硫酸ナトリウム等が挙げられるが、通常は塩化ナトリウムが使用される。 The cation source is not particularly limited, and usually salts of various metals such as chlorides and sulfates of alkali metals and alkali metals are used, and specific examples thereof include sodium chloride and sodium sulfate. Usually, sodium chloride is used.
界面活性剤としては、特に限定されず、例えば、ドデシル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ドデシルナフタレン硫酸ナトリウム、ジアルキルベンゼンアルキル、サルフェート、スルホネ−トを含む陰イオン性界面活性剤；ジアルキルベンゼンアルキルアンモニウムクロライド、アルキルベンジルメチルアンモニウムクロライド、アルキルベンジルジメチルアンモニウムブロマイド、ベンズアルコニウムクロライド、セチルピリジニウムブロマイド、ドデシルベンジルトリエチルアンモニウムクロライド、ラウリルアミン酢酸、ステアリルアミンアセテート、及びラウリルトリメチルアンモニウムクロライドを含む陽イオン性界面活性剤；ラウリルジメチルアミンオキサイドを含む両性イオン性界面活性剤；ポリビニルアルコール、ポリアクリル酸、メタローズ、メチルセルロース、エチルセルロース、プロピルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、トリスチリルフェノールエトキシレートフォスフェートエステル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオクチルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンノニルフェニルエーテル、ジアルキルフェノキシポリ(エチレンオキシ)エタノールを含む非イオン性界面活性剤などが挙げられる。これらの中では、非イオン性界面活性剤、特にポリオキシエチレンオレイルエーテルが好ましい。 The surfactant is not particularly limited, and examples thereof include anionic surfactants including sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl naphthalene sulfate, dialkyl benzene alkyl, sulfate, sulfonate; dialkyl benzene alkyl ammonium. Cationic surfactants including chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, cetylpyridinium bromide, dodecylbenzyltriethylammonium chloride, laurylamine acetic acid, stearylamine acetate, and lauryltrimethylammonium chloride A zwitterionic surfactant containing lauryldimethylamine oxide; Alcohol, polyacrylic acid, metalrose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, tristyrylphenol ethoxylate phosphate ester, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxy Nonionic surfactants including ethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly (ethyleneoxy) ethanol, etc. Can be mentioned. In these, a nonionic surfactant, especially polyoxyethylene oleyl ether are preferable.
有機溶媒としては、例えば、非水溶性の有機溶媒、例えば、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素、エーテル、ハロゲン化炭化水素、エステル等が挙げられる。脂肪族炭化水素の具体例としては、ｎ−ヘキサン、イソヘキサン、ｎ−ヘプタン、イソヘプタン、流動パラフィン、ｎ−オクテン、イソオクテン、ガソリン、石油エーテル、灯油、ベンジン、ミネラルスピリット等が挙げられる。脂環式炭化水素の具体例としては、シクロペンタン、シクロヘキサン、シクロヘキセン、シクロノナン等が挙げられる。芳香族炭化水素の具体例としては、ベンゼン、トルエン、キシレン、エチルベンゼン、ｎ−プロピルベンゼン、クメン、メシチレン、テトラリン、スチレン等が挙げられる。エーテルの具体例としては、ジプロピルエーテル、ジイソプロピルエーテル等が挙げられる。ハロゲン化炭化水素の具体例としては、塩化メチレン、クロロホルム、塩化エチレン、トリクロロエタン、トリクロロエチレン等が挙げられる。エステルの具体例としては、酢酸エチル、酢酸ｎ−プロピル、酢酸イソプロピル、酢酸ｎ−ブチル、酢酸イソブチル、酢酸ｎ−アミル、酢酸イソアミル、乳酸ｎ−ブチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸ｎ−ブチル、酪酸メチル、酪酸エチル、酪酸ｎ−ブチル等が挙げられる。これらの中では、脂環式炭化水素が好ましく、特にシクロヘキサンが好ましい。これらの有機溶剤は２種以上を併用してもよい。 Examples of the organic solvent include water-insoluble organic solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers, halogenated hydrocarbons, esters, and the like. Specific examples of the aliphatic hydrocarbon include n-hexane, isohexane, n-heptane, isoheptane, liquid paraffin, n-octene, isooctene, gasoline, petroleum ether, kerosene, benzine, mineral spirit and the like. Specific examples of the alicyclic hydrocarbon include cyclopentane, cyclohexane, cyclohexene, cyclononane and the like. Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, cumene, mesitylene, tetralin, styrene and the like. Specific examples of the ether include dipropyl ether and diisopropyl ether. Specific examples of the halogenated hydrocarbon include methylene chloride, chloroform, ethylene chloride, trichloroethane, trichloroethylene and the like. Specific examples of the ester include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl lactate, methyl propionate, ethyl propionate, and n propionate. -Butyl, methyl butyrate, ethyl butyrate, n-butyl butyrate and the like. Among these, alicyclic hydrocarbons are preferable, and cyclohexane is particularly preferable. Two or more of these organic solvents may be used in combination.
界面活性剤と有機溶媒の溶液において、有機溶媒中の界面活性剤の濃度（ｍｏｌ／Ｌ）は、０．１〜０．７５ｍｏｌ／Ｌである。母液において、アルミナ源の濃度は０．００４〜０．１２５ｍｏｌ／Ｌ、シリカ源の濃度は０．４〜２．５ｍｏｌ／Ｌ、Ｓｉ／Ａｌモル比は２０〜２００、Ｓｉ／テンプレートモル比は３〜１０である。カチオン源の濃度は、通常０．０１２〜０．３７５ｍｏｌ／Ｌである。 In the solution of the surfactant and the organic solvent, the concentration (mol / L) of the surfactant in the organic solvent is 0.1 to 0.75 mol / L. In the mother liquor, the alumina source concentration is 0.004 to 0.125 mol / L, the silica source concentration is 0.4 to 2.5 mol / L, the Si / Al molar ratio is 20 to 200, and the Si / template molar ratio is 3. -10. The concentration of the cation source is usually 0.012 to 0.375 mol / L.
先ず、本発明においては、界面活性剤と有機溶媒の溶液に母液を添加し、母液のマイクロエマルジョン（Ｏ／Ｗ型）を形成する。マイクロエマルジョンの形成は、常法に従い、各種のホモジナイザーを含む各種の攪拌装置を使用して行うことが出来る。 First, in the present invention, a mother liquor is added to a solution of a surfactant and an organic solvent to form a microemulsion (O / W type) of the mother liquor. The formation of the microemulsion can be performed using various stirring devices including various homogenizers according to a conventional method.
本発明においては、界面活性剤と有機溶媒の溶液に母液を添加してマイクロエマルジョンを形成する際、界面活性剤に対する母液の重量比を０．６７〜４０の範囲にすることが重要である。界面活性剤に対する母液の重量比を上記の範囲に選定することにより、水熱合成によって得られるＺＳＭ−５型ゼオライトのナノサイズ化が達成され、その結晶径を１００ｎｍ以下にすることが出来る。 In the present invention, when a mother liquor is added to a solution of a surfactant and an organic solvent to form a microemulsion, it is important that the weight ratio of the mother liquor to the surfactant is in the range of 0.67 to 40. By selecting the weight ratio of the mother liquor to the surfactant within the above range, nano-sizing of the ZSM-5 type zeolite obtained by hydrothermal synthesis can be achieved, and the crystal diameter can be reduced to 100 nm or less.
次いで、本発明においては、水熱合成を行ってＺＳＭ−５型ゼオライトを得るが、水熱合成の条件としては、一般にＺＳＭ−５類を合成する条件を採用することが出来る。具体的には、オートクレーブを使用し、通常３７３〜４５３Ｋ、好ましくは３９３〜４４３Ｋの温度で、通常１０〜１００時間、好ましくは２４〜７２時間処理する。 Next, in the present invention, hydrothermal synthesis is performed to obtain a ZSM-5 type zeolite. Generally, conditions for synthesizing ZSM-5 compounds can be adopted as conditions for hydrothermal synthesis. Specifically, an autoclave is used, and the treatment is usually performed at a temperature of 373 to 453 K, preferably 393 to 443 K for 10 to 100 hours, preferably 24 to 72 hours.
水熱合成の後、焼成を行ってテンプレートを除去し、更に、焼成後のゼオライトがＮａ型であるため、必要に応じ、Ｈ型にイオン交換する。テンプレートを除去やイオン交換の条件は、特に制限されず、公知の条件を採用することが出来る。テンプレートの除去のため焼成には例えばマッフル炉を使用することか出来る。また、イオン交換は、ＮＨ４型を経由してＨ型へ変換する方法が好適である。 After hydrothermal synthesis, calcination is performed to remove the template. Furthermore, since the zeolite after calcination is Na type, ion exchange is performed to H type as necessary. The conditions for removing the template and ion exchange are not particularly limited, and known conditions can be adopted. For removal of the template, for example, a muffle furnace can be used for firing. Further, ion exchange is preferably performed by a method of converting to H type via NH 4 type.
次に、本発明の第１の要旨に係る触媒について説明する。本発明の触媒は、メタノールからオレフィンを製造するための触媒であり、結晶径が１００ｎｍ以下のＺＳＭ−５型ゼオライトから成ることを特徴とする。本発明の触媒は、前記の製造方法で得ることが出来る。結晶径は、ＳＥＭ写真（倍率５０，０００）により測定することが出来、ＺＳＭ−５型の構造確認はX線回折測定より行うことが出来る。本発明において、結晶径は６０ｎｍ以下であることが好ましい。結晶径の下限は、特に制限されないが、実際的には２０ｎｍである。また、粒径分布に関しては、結晶サイズ５０〜７０ｎｍの範囲に約９０％の粒子が存在し、非常に単分散である。 Next, the catalyst according to the first aspect of the present invention will be described. The catalyst of the present invention is a catalyst for producing an olefin from methanol, and is characterized by comprising a ZSM-5 type zeolite having a crystal diameter of 100 nm or less. The catalyst of the present invention can be obtained by the above production method. The crystal diameter can be measured by an SEM photograph (magnification 50,000), and the structure confirmation of the ZSM-5 type can be performed by X-ray diffraction measurement. In the present invention, the crystal diameter is preferably 60 nm or less. The lower limit of the crystal diameter is not particularly limited, but is actually 20 nm. As for the particle size distribution, about 90% of the particles are present in the crystal size range of 50 to 70 nm and are very monodispersed.
本発明の触媒は次のような利点を有する。すなわち、従来のマイクロサイズのゼオライト触媒では結晶内の酸点で反応が進行する際、拡散律速となり易く、コーキングによる活性劣化が起こる。これに対し、本発明のナノサイズのゼオライト触媒では活性劣化が起こり難い。これは、結晶の外表面積が増大し、原料・生成物の拡散抵抗が低減しているためと考えられる。 The catalyst of the present invention has the following advantages. That is, in the conventional micro-sized zeolite catalyst, when the reaction proceeds at an acid point in the crystal, it tends to be diffusion-controlled, and the activity deterioration due to coking occurs. In contrast, the nanosized zeolite catalyst of the present invention is unlikely to deteriorate in activity. This is presumably because the outer surface area of the crystal is increased and the diffusion resistance of the raw material / product is reduced.
本発明においては結晶の外表面の酸点を不活性化するのが好ましい。外表面の酸点の不活性化は、例えば、ゼオライトの細孔より大きなシラン化合物、例えば、ジフェニルメチルシラン等の各種のジフェニルシランによる表面処理が好適である。例えば、窒素雰囲気下、ＺＳＭ−５型ゼオライトの表面にジフェニルシランを吸着させた後に空気中で焼成する。これにより、ゼオライトの酸点に化学吸着したジフェニルシランは酸点上で酸化ケイ素（ＳｉＯ２）に変換される。 In the present invention, it is preferable to deactivate the acid sites on the outer surface of the crystal. For inactivation of acid sites on the outer surface, for example, surface treatment with various silane compounds larger than the pores of the zeolite, for example, various diphenylsilanes such as diphenylmethylsilane is suitable. For example, diphenylsilane is adsorbed on the surface of a ZSM-5 type zeolite in a nitrogen atmosphere and then calcined in air. Thereby, diphenylsilane chemically adsorbed on the acid sites of the zeolite is converted to silicon oxide (SiO 2 ) on the acid sites.
上記の方法は具体的には次のように行うことが出来る。Ｈ−ＺＳＭ−５型ゼオライト０．５〜２ｇを固定床型石英反応管に充填し、窒素雰囲気下、７７３Ｋ、１時間焼成した。その後、窒素気流中、３７３Ｋまで温度を下げ、ジフェニルシランを供給し、ゼオライトとジフェニルシラン蒸気とを接触させる。この際、窒素気流中におけるジフェニルシラン分圧は１〜１０％、接触時間は３０〜９０分で十分である。次いで、ジフェニルシランの供給を停止し、窒素気流中、７２３〜８７３Ｋまで昇温する。この際、昇温速度は１〜１０Ｋ／ｍｉｎが好ましい。そして、２０〜９０分間同雰囲気で焼成し、シラン化合物をゼオライトの外表面の酸点上へ固定化する。雰囲気ガスを窒素から空気に切り替え、同温度で３０〜１２０分間焼成し、炭素成分を除去する。上記の一連の操作は複数回（例えば２〜６回）繰り返えすのが好ましい。 Specifically, the above method can be performed as follows. 0.5-2 g of H-ZSM-5 type zeolite was charged in a fixed bed type quartz reaction tube and calcined at 773 K for 1 hour in a nitrogen atmosphere. Thereafter, the temperature is lowered to 373 K in a nitrogen stream, diphenylsilane is supplied, and the zeolite and diphenylsilane vapor are brought into contact with each other. At this time, a partial pressure of diphenylsilane in a nitrogen stream is 1 to 10%, and a contact time of 30 to 90 minutes is sufficient. Next, the supply of diphenylsilane is stopped and the temperature is raised to 723-873K in a nitrogen stream. At this time, the heating rate is preferably 1 to 10 K / min. Then, it is baked in the same atmosphere for 20 to 90 minutes to immobilize the silane compound on the acid sites on the outer surface of the zeolite. The atmosphere gas is switched from nitrogen to air and baked at the same temperature for 30 to 120 minutes to remove the carbon component. The above series of operations is preferably repeated a plurality of times (for example, 2 to 6 times).
外表面の酸点を不活性化した本発明の触媒は次のような利点を有する。すなわち、外表面の酸点が反応に利用される場合は、空間的な制限を受けないことから、芳香族炭化水素が生成し易い。これに対し、結晶の外表面の酸点を不活性化した場合は、結晶細孔内の酸点が反応に利用されるため、芳香族炭化水素の生成が抑制され、生成するオレフィン（特にプロピレン）の選択率が高められる。 The catalyst of the present invention in which the acid sites on the outer surface are deactivated has the following advantages. That is, when the acid sites on the outer surface are used for the reaction, there is no spatial restriction, and therefore aromatic hydrocarbons are easily generated. In contrast, when the acid sites on the outer surface of the crystal are deactivated, the acid sites in the crystal pores are used for the reaction, so that the production of aromatic hydrocarbons is suppressed and the olefins produced (particularly propylene) ) Is increased.
本発明においては上記のゼオライトをセラミックス多孔質支持体上に膜状に積層するのが好ましい。セラミックス多孔質支持体は、特に制限されないが、平均細孔孔１００ｎｍのものが好適に使用される。斯かる多孔質支持体は、例えば、アルミナ、シリカ、ムライト、炭化ケイ素、窒化ケイ素などの粉末に、結合材としてメチルセルロース系バインダーを５〜１０重量％混合し、これを押し出し成形などで所定の厚さ及び長さの円筒体や板状体とした後、１９７３〜２１２３Ｋで焼成することにより得ることが出来る。本発明においては、円筒状アルミナフィルタとして知られている日本ガイシ社製の商品「ｗｂｃ−０１１０−１０００ＢＧ」が好適である。 In the present invention, the above zeolite is preferably laminated in a film form on a ceramic porous support. The ceramic porous support is not particularly limited, but those having an average pore size of 100 nm are preferably used. Such a porous support is prepared, for example, by mixing 5 to 10% by weight of a methylcellulose binder as a binder with powders of alumina, silica, mullite, silicon carbide, silicon nitride and the like, and extruding the mixture to a predetermined thickness. After obtaining a cylindrical body or plate-like body having a length and length, it can be obtained by firing at 1974-2123K. In the present invention, a product “wbc-0110-1000BG” manufactured by NGK, known as a cylindrical alumina filter, is suitable.
セラミックス多孔質支持体上へのゼオライトの積層方法は、特に制限されないが、吸引力を利用して行うのが好ましい。例えば、円筒状アルミナフィルタを使用する場合は、一端を封止し、ゼオライトの分散液中に開放端が液面上に位置するように垂直に配置し、開放端から吸引することにより、円筒状アルミナフィルターの表面にゼオライトを積層することが出来る。ゼオライト積層膜の厚さは、通常５〜２００μｍ、好ましくは１０〜１００μｍであり、ゼオライトの積層割合は、通常１〜１００ｍｇ／ｃｍ２、好ましくは５〜５０ｍｇ／ｃｍ２である。なお、ゼオライト積層膜の厚さは、ＳＥＭ写真で測定することが出来る。 The method for laminating the zeolite on the ceramic porous support is not particularly limited, but it is preferable to use a suction force. For example, when using a cylindrical alumina filter, one end is sealed, placed vertically in the zeolite dispersion so that the open end is positioned on the liquid surface, and sucked from the open end. Zeolite can be laminated on the surface of the alumina filter. The thickness of the zeolite laminated film is usually 5 to 200 [mu] m, preferably 10 to 100 [mu] m, laminated ratio of zeolite is usually 1 to 100 mg / cm 2, preferably from 5 to 50 mg / cm 2. In addition, the thickness of a zeolite laminated film can be measured with a SEM photograph.
セラミックス多孔質支持体上にゼオライトが膜状に積層された触媒は次のような利点を有する。すなわち、ゼオライトの活性点を三次元的に利用することができるため、拡散の影響が少なくなって均一な接触時間が得られ、ゼオライトの結晶間メインルートとした大きな透過速度が得られる。その結果、芳香族炭化水素の生成が抑制され、生成するオレフィンの選択率が高められる。 A catalyst in which a zeolite is laminated in a film form on a ceramic porous support has the following advantages. That is, since the active sites of the zeolite can be used three-dimensionally, the influence of diffusion is reduced, a uniform contact time can be obtained, and a large permeation rate as a main route between zeolite crystals can be obtained. As a result, the production of aromatic hydrocarbons is suppressed, and the selectivity of the produced olefin is increased.
次に、本発明に係るオレフィンの製造方法について説明する。本発明の製造方法は触媒とメタノールとを接触させることを特徴とする。 Next, the manufacturing method of the olefin which concerns on this invention is demonstrated. The production method of the present invention is characterized in that a catalyst and methanol are brought into contact with each other.
オレフィンの製造反応は、触媒反応の常法に従って、例えば、固定層流通式反応器を使用し、ガス化したメタノールを流通させて触媒と接触させる方法を採用することが出来る。反応温度は、通常５２３〜８７３Ｋであり、原料ガスの供給速度（ＳＶ）は通常１０００〜１０００００ｈ−１である。原料ガスの濃度は通常０．１〜１００００ｐｐｍである。通常、濃度調節のためのガス（キャリヤーガス）としては窒素が使用される。 For the production reaction of olefins, for example, a method using a fixed bed flow reactor and allowing gasified methanol to flow and contact with the catalyst can be employed according to a conventional method of catalytic reaction. The reaction temperature is usually 523 to 873 K, and the feed rate (SV) of the raw material gas is usually 1000 to 100,000 h −1 . The concentration of the raw material gas is usually 0.1 to 10,000 ppm. Usually, nitrogen is used as a gas for adjusting the concentration (carrier gas).
以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を超えない限り以下の実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by a following example, unless the summary is exceeded.
実施例１：
［触媒の製造］
＜ナノクリスタルＺＳＭ−５型ゼオライトの製造＞
アルミニウムイソプロポキシド（アルミナ源：和光純薬工業（株）製、９５．０％）０．５１４５ｇ、塩化ナトリウム（カチオン源（安定剤）：和光純薬工業（株）製、９９．５％）０．４４２ｇ、テトラプロピルアンモニウムヒドロキシド（テンプレート：和光純薬工業（株）製、１０％水溶液）、蒸留水１２９．５ｇを混合した後、攪拌し、均一な水溶液となったのを確認した後、テトラエトキシシラン（シリカ源：和光純薬工業（株）製、９５．０％）４２ｇを添加し、室温で２４時間攪拌し、ＳｉＯ２−テンプレート複合体（母液）を得た。
Example 1:
[Manufacture of catalyst]
<Manufacture of nanocrystal ZSM-5 type zeolite>
Aluminum isopropoxide (alumina source: Wako Pure Chemical Industries, Ltd., 95.0%) 0.5145 g, sodium chloride (cation source (stabilizer): Wako Pure Chemical Industries, Ltd., 99.5%) 0.442 g, tetrapropylammonium hydroxide (template: Wako Pure Chemical Industries, Ltd., 10% aqueous solution) and 129.5 g of distilled water were mixed and then stirred to confirm that the aqueous solution was uniform. 42 g of tetraethoxysilane (silica source: 95.0%, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 24 hours to obtain a SiO 2 -template complex (mother liquor).
一方、ポリオキシエチレン（１５）オレイルエーテル（非イオン性界面活性剤：日本サーファクタント工業（株）製）とシクロヘキサン（有機溶媒：和光純薬工業（株）製、９９．５％）とを使用し、界面活性剤濃度が０．５ｍｏｌ／Ｌの界面活性剤／有機溶媒溶液１９６０ｍｌを調製した。 On the other hand, polyoxyethylene (15) oleyl ether (nonionic surfactant: manufactured by Nippon Surfactant Kogyo Co., Ltd.) and cyclohexane (organic solvent: manufactured by Wako Pure Chemical Industries, Ltd., 99.5%) were used. 1960 ml of a surfactant / organic solvent solution having a surfactant concentration of 0.5 mol / L was prepared.
次いで、上記の界面活性剤／有機溶媒溶液を３２３Ｋの水浴中に保持し、これに前記の母液２８０ｍｌを約１時間かけて少量づつ滴下した。そして、そのまま１時間攪拌することにより系を均一にした後、オートクレーブに移し、３９３Ｋで２４時間水熱合成を行った。 Next, the above surfactant / organic solvent solution was kept in a 323 K water bath, and 280 ml of the mother liquor was dropped in small portions over about 1 hour. Then, the system was made uniform by stirring for 1 hour as it was, and then transferred to an autoclave, and hydrothermal synthesis was performed at 393 K for 24 hours.
水熱合成後、室温まで冷却し、ビーカーに移し、収率を上げるために硝酸を使用してｐＨを７〜８に調節した。この際、粒状のものが析出した。その後、少量の２−プロパノールを加えて５分間攪拌洗浄した後、遠心分離（２５００ｒｐｍ、１０分間）により、ナノクリスタルＺＳＭ−５型ゼオライトを沈殿物として回収した。上記の攪拌洗浄・遠心分離操作を合計３回繰り返した。ＳＥＭ写真の結果上記のゼオライトの平均粒径は５０ｎｍであった。また、ＺＳＭ−５型の構造確認はX線回折測定によって行った。 After hydrothermal synthesis, it was cooled to room temperature, transferred to a beaker, and the pH was adjusted to 7-8 using nitric acid to increase the yield. At this time, a granular material was deposited. Thereafter, a small amount of 2-propanol was added and the mixture was stirred and washed for 5 minutes, and then the nanocrystal ZSM-5 type zeolite was recovered as a precipitate by centrifugation (2500 rpm, 10 minutes). The above stirring and washing / centrifugation operation was repeated three times in total. As a result of SEM photography, the average particle size of the zeolite was 50 nm. The structure of the ZSM-5 type was confirmed by X-ray diffraction measurement.
＜ゼオライト積層膜の製造＞
セラミックス多孔質支持体として、長さ５０ｍｍ、外径１０ｍｍ、内径８ｍｍ、多孔率５０〜６０％の円筒状アルミナフィルター（日本ガイシ社製の商品「ｗｂｃ−０１１０−１０００ＢＧ」）を使用した。予め、０．１Ｎ塩酸水溶液に一晩浸漬した後蒸留水で十分に洗浄し、空気中に一日放置として風乾し、一端を封止した。
<Manufacture of zeolite laminated film>
A cylindrical alumina filter having a length of 50 mm, an outer diameter of 10 mm, an inner diameter of 8 mm, and a porosity of 50 to 60% (commercial product “wbc-0110-1000BG” manufactured by NGK Co., Ltd.) was used as the ceramic porous support. In advance, it was immersed in a 0.1N aqueous hydrochloric acid solution overnight, washed thoroughly with distilled water, allowed to stand in the air for one day and air-dried, and one end was sealed.
ｐＨ９．５程度の苛性ソーダ水溶液を容器に収容し、上記のゼオライトを投入して分散させ、その中に、開放端が液面上に位置するように上記の円筒状アルミナフィルターを垂直に配置した。液中に浸漬された円筒状アルミナフィルターは全体の約１／４の長さである。そして、開放端を吸引装置に接続し、円筒状アルミナフィルターの表面にゼオライトを積層した。ゼオライトの全投入量は０．０６３９３ｇであり、投入は３回に分けて行った。最初の投入量は約０．０２ｇであり、２回目以降は残量を半分に分けて行った。また、苛性ソーダ水溶液中におけるゼオライトの分散は超音波を利用して行った。ゼオライト積層膜の厚さはＳＥＭ写真の結果４０μｍであった。また、ゼオライトの積層割合は１０ｍｇ／ｃｍ２であった。 A caustic soda aqueous solution having a pH of about 9.5 was placed in a container, and the above zeolite was added and dispersed therein, and the above cylindrical alumina filter was arranged vertically so that the open end was positioned on the liquid surface. The cylindrical alumina filter immersed in the liquid is about 1/4 of the total length. Then, the open end was connected to a suction device, and zeolite was laminated on the surface of the cylindrical alumina filter. The total amount of zeolite charged was 0.06393 g, and the charging was performed in three portions. The initial input amount was about 0.02 g, and the remaining amount was divided in half after the second time. Further, the dispersion of the zeolite in the aqueous caustic soda solution was performed using ultrasonic waves. The thickness of the zeolite laminated film was 40 μm as a result of SEM photography. Further, the lamination ratio of zeolite was 10 mg / cm 2 .
＜積層膜の安定化＞
次いで、ゼオライト積層膜が剥がれ落ちないようにするため、ドライヤーで温めながらテトラエトキシシラン１ｍｌをゆっくりと積層膜全体に滴下し、ケイ素の穏やかなネットワークを作成した。
<Stabilization of laminated film>
Next, in order to prevent the zeolite laminated film from peeling off, 1 ml of tetraethoxysilane was slowly dropped over the entire laminated film while warming with a drier to create a gentle network of silicon.
＜シリカライト保護層の形成＞
次いで、ゼオライト積層膜を固着するため、次の要領で上記のゼオライト積層膜の表面にシリカライト保護層を形成した。
<Formation of silicalite protective layer>
Next, in order to fix the zeolite laminated film, a silicalite protective layer was formed on the surface of the zeolite laminated film in the following manner.
先ず、Ａ液（蒸留水１３７．５ｇ、塩化ナトリウム３．５０ｇ）、Ｂ液（蒸留水５８．５ｇ、ケイ酸ナトリウム（Ｎａ２ＳｉＯ３）５．３８ｇ、水酸化ナトリウム０．２８ｇ）、Ｃ液（蒸留水８６．０ｇ、硫酸１．５５ｇ、臭化テトラプロピルアンモニウム（ＴＰＡＢｒ）１．１８ｇ）を調製した。そして、Ａ液に攪拌条件下でＢ液とＣ液とを滴下し２０分間攪拌を続行した後、硫酸によって混合液のｐＨを９．５に調節し、シリカライト母液を調製した。 First, liquid A (distilled water 137.5 g, sodium chloride 3.50 g), liquid B (distilled water 58.5 g, sodium silicate (Na 2 SiO 3 ) 5.38 g, sodium hydroxide 0.28 g), liquid C (86.0 g of distilled water, 1.55 g of sulfuric acid, 1.18 g of tetrapropylammonium bromide (TPABr)) was prepared. Then, the liquid B and the liquid C were dropped into the liquid A under stirring conditions, and stirring was continued for 20 minutes. Then, the pH of the mixed liquid was adjusted to 9.5 with sulfuric acid to prepare a silicalite mother liquid.
次いで、水熱合成用石英容器に炭素パッキンを入れ、その上に上記の円筒状アルミナフィルターを乗せた架台を置き、上記のシリカライト母液を注いだ。そして、水熱合成用石英容器をオートクレーブに投入し、水熱合成を行った。水熱合成は、２４時間で３９３Ｋに昇温し、２４時間保持し、１２時間で常温に戻す条件で行った。その後、円筒状アルミナフィルターの積層膜に残留している塩化ナトリウム等を除去するため、還流装置に蒸留水を入れ、円筒状アルミナフィルターの積層膜を浸し３７３Ｋで一昼夜煮沸した。 Next, carbon packing was placed in a quartz container for hydrothermal synthesis, a frame on which the cylindrical alumina filter was placed was placed, and the silicalite mother liquor was poured. And the quartz container for hydrothermal synthesis was put into the autoclave, and hydrothermal synthesis was performed. Hydrothermal synthesis was performed under the conditions that the temperature was raised to 393 K in 24 hours, held for 24 hours, and returned to room temperature in 12 hours. Thereafter, in order to remove sodium chloride and the like remaining in the laminated film of the cylindrical alumina filter, distilled water was put into a reflux apparatus, and the laminated film of the cylindrical alumina filter was immersed and boiled overnight at 373K.
次いで、残存するテンプレートを除去するため、マッフル炉で焼成し、Ｎａ型のゼオライトを得た。この際、昇温過程は、（１）室温から６２３Ｋまで３時間かけて昇温、（２）６２３Ｋで８時間保持、（３）６２３Ｋから７５３Ｋまで３時間かけて昇温、（４）７５３Ｋで６時間保持、となるように行った。 Next, in order to remove the remaining template, it was fired in a muffle furnace to obtain Na-type zeolite. At this time, the temperature raising process was (1) raising temperature from room temperature to 623K over 3 hours, (2) holding at 623K for 8 hours, (3) raising temperature from 623K to 753K over 3 hours, and (4) at 753K. It was carried out so as to hold for 6 hours.
＜イオン交換＞
次いで、次の要領に従ってＮａ型ゼオライトのＨ型ゼオライトに変換した。すなわち、Ｎａ型ゼオライトに５ｗｔ％硝酸アンモニウム水溶液を１０重量倍量添加し、３７３Ｋの温浴中で還流条件下に約８時間攪拌した後に遠心分離によって上澄み液とゼオライトとを分離した。この攪拌・遠心分離処理を合計３回繰り返した。この際、硝酸アンモニウム水溶液の濃度は、５ｗｔ％→８ｗｔ％→１０ｗｔ％となるように漸次高めた。次いで、十分な量の蒸留水で約１時間攪拌した後に遠心分離によって上澄み液とゼオライトとを分離する洗浄操作を合計３回繰り返した後、３７３Ｋの乾燥機中で約１２時間乾燥した。そして、マッフル炉で、７５３Ｋ、４時間焼成し、細孔内に残存する水分を十分に除去した。焼成時の昇温速度は０．５Ｋ／ｍｉｎとした。最終的に得られた膜厚さは、ゼオライト膜約５０μｍ、シリカライト膜約２〜４μｍであった。
<Ion exchange>
Next, it was converted into H-type zeolite of Na-type zeolite according to the following procedure. That is, 10 wt times of 5 wt% ammonium nitrate aqueous solution was added to Na-type zeolite, stirred for about 8 hours under reflux conditions in a 373 K hot bath, and then the supernatant and zeolite were separated by centrifugation. This stirring / centrifugation treatment was repeated a total of 3 times. At this time, the concentration of the ammonium nitrate aqueous solution was gradually increased so as to be 5 wt% → 8 wt% → 10 wt%. Next, after washing with a sufficient amount of distilled water for about 1 hour and washing the supernatant and zeolite by centrifugation for a total of 3 times, the mixture was dried in a 373 K drier for about 12 hours. Then, it was baked in a muffle furnace at 753 K for 4 hours to sufficiently remove moisture remaining in the pores. The heating rate during firing was 0.5 K / min. The final film thicknesses were about 50 μm zeolite membrane and about 2-4 μm silicalite membrane.
［オレフィンの製造］
＜反応装置＞
図１に示す固定層型流通反応器を使用した。この装置は、概略、円筒状に形成された多孔質構造の触媒エレメント（１）と、両端が封止され且つ触媒エレメント（１）を収容する外管（２）と、基端が触媒エレメント（１）の筒内に挿入されたオレフィン取出用の内管（３）と、外管（２）の外周側に配置され且つ当該外管内部を加熱するヒーター（４）とを備え、気化させたメタノールを外管（２）に供給し、且つ、内管（３）を通じて触媒エレメント（１）の筒内を減圧することにより、外管（２）内のメタノールを触媒エレメント（１）に透過させて当該触媒エレメントの筒内に得られたオレフィンを内管（３）から取り出す様に構成されている。
[Olefin production]
<Reactor>
The fixed bed flow reactor shown in FIG. 1 was used. This device is roughly composed of a cylindrical catalyst element (1) having a porous structure, an outer tube (2) sealed at both ends and containing the catalyst element (1), and a base end having a catalyst element ( The olefin extraction inner tube (3) inserted into the cylinder of 1) and a heater (4) disposed on the outer peripheral side of the outer tube (2) and heating the inside of the outer tube were vaporized. Methanol is supplied to the outer pipe (2) and the inside of the cylinder of the catalyst element (1) is depressurized through the inner pipe (3), thereby allowing the methanol in the outer pipe (2) to permeate the catalyst element (1). Thus, the olefin obtained in the cylinder of the catalyst element is taken out from the inner pipe (3).
具体的には、触媒エレメント（１）は、円筒状多孔質アルミナフィルター（１０）と、その外周面に順次に積層されたゼオライト積層膜および保護膜とから成り、且つ、両端が封止材（１２）及び（１３）で気密に封止されている。そして、触媒エレメント（１）の一端には、上記の内管（３）の基端部が封止材（１３）を貫通する状態で接続されている。 Specifically, the catalyst element (1) is composed of a cylindrical porous alumina filter (10), a zeolite laminated film and a protective film sequentially laminated on the outer peripheral surface, and both ends are sealed ( 12) and (13) are hermetically sealed. And the base end part of said inner pipe (3) is connected to the end of the catalyst element (1) in the state which penetrates the sealing material (13).
外管（２）は、有底円筒状の容器の開放された他端を蓋部材（２１）で封止して構成されており、蓋部材（２１）には、上記の内管（３）の先端側が挿通されている。また、外管（２）の他端側の外周部には、当該外管内へ原料としてのメタノールを供給する原料供給機構（６）の配管（６６）、および、容器内ガスのよどみを避けるためとメタノールの希釈・濃度調節の目的を兼ね備えたガスを供給する希釈ガス供給機構（７）の配管（７４）が接続されている。 The outer tube (2) is configured by sealing the other open end of a bottomed cylindrical container with a lid member (21), and the lid member (21) includes the inner tube (3) described above. The tip side of is inserted. Further, in order to avoid the stagnation of the pipe (66) of the raw material supply mechanism (6) for supplying methanol as a raw material into the outer pipe and the gas in the container at the outer peripheral portion on the other end side of the outer pipe (2). And a pipe (74) of a dilution gas supply mechanism (7) for supplying a gas having the purpose of dilution / concentration adjustment of methanol.
内管（３）は、上記の様に、その基端が触媒エレメント（１）の筒内に挿入され、その先端側が外管（２）の他端を貫通して当該外管の外側まで伸長されている。そして、内管（３）は、真空ポンプ等を含む減圧系に接続されることにより、触媒エレメント（１）の筒内を減圧し且つ当該触媒エレメントを透過して生成されたオレフィンを系外へ取り出す様になされている。 As described above, the inner tube (3) has its proximal end inserted into the cylinder of the catalyst element (1), and its distal end extends through the other end of the outer tube (2) to the outside of the outer tube. Has been. The inner pipe (3) is connected to a decompression system including a vacuum pump or the like, so that the inside of the cylinder of the catalyst element (1) is decompressed and the olefin generated through the catalyst element is removed from the system. It is made to take out.
ヒーター（４）としては、上記の外管（２）の少なくとも触媒エレメント（１）収容部分を収容可能な円筒状のブロックヒーター等が使用される。ヒーター（４）の筒内には、外管（２）の加熱温度を検出する温度センサー（５）が配置されており、ヒーター（４）は、別途設けられた温度調節器により、温度センサー（５）で検出された温度に基づき、外管（２）の温度が設定温度となる様に通電制御される。 As the heater (4), a cylindrical block heater or the like that can accommodate at least the catalyst element (1) accommodating portion of the outer pipe (2) is used. A temperature sensor (5) for detecting the heating temperature of the outer tube (2) is arranged in the cylinder of the heater (4). The heater (4) is connected to the temperature sensor (by a temperature controller provided separately). Based on the temperature detected in 5), the energization is controlled so that the temperature of the outer tube (2) becomes the set temperature.
原料供給機構（６）は、窒素などの不活性ガスの容器（図示省略）から蒸発器（６４）に接続された配管（６１）と、当該配管に介装されたマスフローコントローラー（６２）及び開閉弁（６３）と、メタノール供給用のマイクロフィーダー（図示省略）から蒸発器（６４）に接続された配管（６５）と、蒸発器（６４）から外管（２）に接続された前述の配管（６６）とから構成されている。そして、容器から蒸発器（６４）へ一定流量で窒素を供給し、且つ、マイクロフィーダーから定量供給したメタノールを蒸発器（６４）で気化させると共に、前記の窒素をキャリアガスとして、外管（２）へメタノールを送気する様になされている。 The raw material supply mechanism (6) includes a pipe (61) connected from an inert gas container (not shown) such as nitrogen to the evaporator (64), a mass flow controller (62) interposed in the pipe, and an open / close Valve (63), piping (65) connected to the evaporator (64) from a microfeeder for methanol supply (not shown), and the above-mentioned piping connected from the evaporator (64) to the outer tube (2) (66). Then, nitrogen is supplied from the container to the evaporator (64) at a constant flow rate, and methanol quantitatively supplied from the microfeeder is vaporized by the evaporator (64), and the nitrogen is used as a carrier gas and the outer tube (2 ) To feed methanol.
一方、希釈ガス供給機構（７）は、前述の配管（６１）の上流部で分岐された配管（７１）と、当該配管に介装されたマスフローコントローラー（７２）及び開閉弁（７３）と、配管（７１）から伸長され且つ外管（２）に接続された前述の配管（７４）とから構成されている。そして、容器から外管（２）へ一定流量で窒素を供給することにより、外管（２）内のメタノール濃度を制御する様になされている。 On the other hand, the dilution gas supply mechanism (7) includes a pipe (71) branched at the upstream portion of the pipe (61), a mass flow controller (72) and an on-off valve (73) interposed in the pipe, The pipe (71) extends from the pipe (71) and is connected to the outer pipe (2). Then, by supplying nitrogen from the container to the outer tube (2) at a constant flow rate, the methanol concentration in the outer tube (2) is controlled.
＜反応条件＞
上記の反応装置を使用し、表１に示す条件で反応を行った。反応ガスの分析はガスクロマトグラフィー（島津製作所製「ＧＣ８Ａ」：検出器ＦＩＤ）で行った。カラムには、ＧＬサイエンス社製のポラパック充填カラム「ポラパックＱ」（８０〜１００メッシュ：３ｍ）を使用した。分析条件は、カラム温度：３２３〜４９３Ｋ（３Ｋ／ｍｉｎ昇温）、試料気化室および検出器（ＩＮＪ／ＤＥＴ）温度：４２３Ｋとした。
<Reaction conditions>
The reaction was performed under the conditions shown in Table 1 using the above reaction apparatus. The analysis of the reaction gas was performed by gas chromatography (“GC8A” manufactured by Shimadzu Corporation: detector FID). As the column, a Polapack packed column “Polapack Q” (80 to 100 mesh: 3 m) manufactured by GL Sciences Inc. was used. The analysis conditions were column temperature: 323 to 493K (temperature increase of 3 K / min), sample vaporization chamber and detector (INJ / DET) temperature: 423K.
＜反応結果＞
反応結果は以下の表２に示す通りであった。
<Reaction result>
The reaction results were as shown in Table 2 below.
比較例１：
触媒として、結晶径２０００ｎｍのＨ−ＺＳＭ−５型ゼオライトの積層膜を実施例１と同様にして製造し、実施例１と同一条件でオレフィンの製造を行い、反応ガスの分析を行った。反応結果は以下の表３に示す通りであった。
Comparative Example 1:
As a catalyst, a laminated film of H-ZSM-5 type zeolite having a crystal diameter of 2000 nm was produced in the same manner as in Example 1, olefin was produced under the same conditions as in Example 1, and reaction gas was analyzed. The reaction results were as shown in Table 3 below.
１：触媒エレメント
１０：円筒状多孔質アルミナフィルター
１２：封止材
１３：封止材
２：外管
２１：蓋部材
３：内管
４：ヒーター
５：温度センサー
６：原料供給機構
６１：配管
６２：マスフローコントローラー
６３：開閉弁
６４：蒸発器
６５：配管
６６：配管
７：希釈ガス供給機構
７１：配管
７２：マスフローコントローラー
７３：開閉弁
７４：配管
1: Catalyst element 10: Cylindrical porous alumina filter 12: Sealing material 13: Sealing material 2: Outer tube 21: Lid member 3: Inner tube 4: Heater 5: Temperature sensor 6: Raw material supply mechanism 61: Pipe 62 : Mass flow controller 63: Open / close valve 64: Evaporator 65: Pipe 66: Pipe 7: Dilution gas supply mechanism 71: Pipe 72: Mass flow controller 73: Open / close valve 74: Pipe
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008109966A JP2009255014A (en) | 2008-04-21 | 2008-04-21 | Catalyst for producing olefin from methanol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008109966A JP2009255014A (en) | 2008-04-21 | 2008-04-21 | Catalyst for producing olefin from methanol |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012087079A (en) * | 2010-10-18 | 2012-05-10 | Toyota Motor Corp | Method of producing lower olefin |
| CN104069888A (en) * | 2013-03-29 | 2014-10-01 | 上海碧科清洁能源技术有限公司 | Modified ZSM-5 molecular sieve catalyst and preparation method and application thereof |
| JP2015506824A (en) * | 2011-12-19 | 2015-03-05 | 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Catalyst for producing ethylene and propylene from methanol and / or dimethyl ether, its production method and use |
| JP2015526401A (en) * | 2012-06-29 | 2015-09-10 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for the conversion of oxygen-containing materials to olefins |
| WO2018221706A1 (en) | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | Methanol reforming catalyst structure, methanol reforming device, production method for methanol reforming catalyst structure, and production method for at least one of olefins and aromatic hydrocarbons |
| US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
| US11547987B2 (en) | 2017-05-31 | 2023-01-10 | Furukawa Electric Co., Ltd. | Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method |
| US11648542B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11648543B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11648538B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11655157B2 (en) | 2017-05-31 | 2023-05-23 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11654422B2 (en) | 2017-05-31 | 2023-05-23 | Furukawa Electric Co., Ltd. | Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization |
| US11666894B2 (en) | 2017-05-31 | 2023-06-06 | Furukawa Electric Co., Ltd. | Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water |
| US11680211B2 (en) | 2017-05-31 | 2023-06-20 | Furukawa Electric Co., Ltd. | Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization |
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Cited By (18)
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| JP2012087079A (en) * | 2010-10-18 | 2012-05-10 | Toyota Motor Corp | Method of producing lower olefin |
| JP2015506824A (en) * | 2011-12-19 | 2015-03-05 | 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Catalyst for producing ethylene and propylene from methanol and / or dimethyl ether, its production method and use |
| KR101622496B1 (en) * | 2011-12-19 | 2016-05-18 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Catalyst used in the production of ethylene and propylene from methanol and/or dimethyl ether, method for preparing the same and method for using the same |
| US9844770B2 (en) | 2011-12-19 | 2017-12-19 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst used in the production of ethylene and propylene from methanol and/or dimethyl ether, method for preparing the same and method for using the same |
| JP2015526401A (en) * | 2012-06-29 | 2015-09-10 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for the conversion of oxygen-containing materials to olefins |
| CN104069888A (en) * | 2013-03-29 | 2014-10-01 | 上海碧科清洁能源技术有限公司 | Modified ZSM-5 molecular sieve catalyst and preparation method and application thereof |
| US11547987B2 (en) | 2017-05-31 | 2023-01-10 | Furukawa Electric Co., Ltd. | Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method |
| US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
| WO2018221706A1 (en) | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | Methanol reforming catalyst structure, methanol reforming device, production method for methanol reforming catalyst structure, and production method for at least one of olefins and aromatic hydrocarbons |
| US11648542B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11648543B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11648538B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11655157B2 (en) | 2017-05-31 | 2023-05-23 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11654422B2 (en) | 2017-05-31 | 2023-05-23 | Furukawa Electric Co., Ltd. | Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization |
| US11666894B2 (en) | 2017-05-31 | 2023-06-06 | Furukawa Electric Co., Ltd. | Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water |
| US11680211B2 (en) | 2017-05-31 | 2023-06-20 | Furukawa Electric Co., Ltd. | Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization |
| US11684909B2 (en) | 2017-05-31 | 2023-06-27 | Furukawa Electric Co., Ltd. | Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon |
| US11904306B2 (en) | 2017-05-31 | 2024-02-20 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
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