JP4835011B2 - Novel structure containing silica alumina and method for producing the same. - Google Patents
Novel structure containing silica alumina and method for producing the same. Download PDFInfo
- Publication number
- JP4835011B2 JP4835011B2 JP2005077163A JP2005077163A JP4835011B2 JP 4835011 B2 JP4835011 B2 JP 4835011B2 JP 2005077163 A JP2005077163 A JP 2005077163A JP 2005077163 A JP2005077163 A JP 2005077163A JP 4835011 B2 JP4835011 B2 JP 4835011B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- silica
- aluminum
- surface layer
- producing
- 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 - Fee Related
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 146
- 239000000377 silicon dioxide Substances 0.000 title claims description 73
- 239000002344 surface layer Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000010304 firing Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 claims description 4
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 4
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- FBOFHVFMPNNIKN-UHFFFAOYSA-N dimethylquinoline Natural products C1=CC=C2N=C(C)C(C)=CC2=C1 FBOFHVFMPNNIKN-UHFFFAOYSA-N 0.000 claims description 4
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 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 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229940118662 aluminum carbonate Drugs 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- YXZUDXLWSOZHFN-UHFFFAOYSA-N 2,3-diethylpyridine Chemical compound CCC1=CC=CN=C1CC YXZUDXLWSOZHFN-UHFFFAOYSA-N 0.000 claims description 2
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 claims description 2
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-UHFFFAOYSA-N 0.000 claims description 2
- FNRMMDCDHWCQTH-UHFFFAOYSA-N 2-chloropyridine;3-chloropyridine;4-chloropyridine Chemical compound ClC1=CC=NC=C1.ClC1=CC=CN=C1.ClC1=CC=CC=N1 FNRMMDCDHWCQTH-UHFFFAOYSA-N 0.000 claims description 2
- OFUFXTHGZWIDDB-UHFFFAOYSA-N 2-chloroquinoline Chemical compound C1=CC=CC2=NC(Cl)=CC=C21 OFUFXTHGZWIDDB-UHFFFAOYSA-N 0.000 claims description 2
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical compound C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 claims description 2
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 claims description 2
- ZTQNUTNKGQGWCM-UHFFFAOYSA-N 2-methoxyquinoline Chemical compound C1=CC=CC2=NC(OC)=CC=C21 ZTQNUTNKGQGWCM-UHFFFAOYSA-N 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- UDAIGHZFMLGNDQ-UHFFFAOYSA-N 2-nitroquinoline Chemical compound C1=CC=CC2=NC([N+](=O)[O-])=CC=C21 UDAIGHZFMLGNDQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003927 aminopyridines Chemical class 0.000 claims description 2
- 150000005010 aminoquinolines Chemical class 0.000 claims description 2
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 claims description 2
- HREHOXSRYOZKNT-UHFFFAOYSA-N quinolin-2-ylmethanol Chemical compound C1=CC=CC2=NC(CO)=CC=C21 HREHOXSRYOZKNT-UHFFFAOYSA-N 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- HLTDBMHJSBSAOM-UHFFFAOYSA-N 2-nitropyridine Chemical compound [O-][N+](=O)C1=CC=CC=N1 HLTDBMHJSBSAOM-UHFFFAOYSA-N 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 31
- 230000003197 catalytic effect Effects 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 22
- 239000010410 layer Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 21
- 229910052782 aluminium Inorganic materials 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- 229910052710 silicon Inorganic materials 0.000 description 21
- 239000010703 silicon Substances 0.000 description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 20
- 239000011324 bead Substances 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- -1 nitropyrine Chemical compound 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- 239000011973 solid acid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 150000003248 quinolines Chemical class 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
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- PVQAFBFZEZCAQR-UHFFFAOYSA-N [SiH3]CCCCCCC=C Chemical compound [SiH3]CCCCCCC=C PVQAFBFZEZCAQR-UHFFFAOYSA-N 0.000 description 1
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- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
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- 238000001833 catalytic reforming Methods 0.000 description 1
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- 239000011651 chromium Substances 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 1
- UBCPEZPOCJYHPM-UHFFFAOYSA-N dimethoxy-methyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(OC)OC UBCPEZPOCJYHPM-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
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- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
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- 239000010408 film Substances 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
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- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
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- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- BAXHQTUUOKMMGV-UHFFFAOYSA-N methoxy-dimethyl-octylsilane Chemical compound CCCCCCCC[Si](C)(C)OC BAXHQTUUOKMMGV-UHFFFAOYSA-N 0.000 description 1
- NCHMPORHGFKNSI-UHFFFAOYSA-N methoxy-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)OC NCHMPORHGFKNSI-UHFFFAOYSA-N 0.000 description 1
- XZVHZMFBMZYMTK-UHFFFAOYSA-N methyl 3-(dimethoxymethylsilyl)propanoate Chemical compound COC(OC)[SiH2]CCC(=O)OC XZVHZMFBMZYMTK-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- HIPXPABRMMYVQD-UHFFFAOYSA-N n-benzylbutan-1-amine Chemical compound CCCCNCC1=CC=CC=C1 HIPXPABRMMYVQD-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950006768 phenylethanolamine Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 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
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-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
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、シリカアルミナを含む新規な構造体、およびその製造方法に関する。さらに詳しくは、構造体表層部にシリカアルミナが存在し、表層部を除く構造体内部は実質的にシリカアルミナを含まない担体成分で構成される構造体、およびその製造方法に関する。 The present invention relates to a novel structure containing silica alumina and a method for producing the same. More specifically, the present invention relates to a structure composed of a carrier component in which silica alumina is present in the structure surface layer portion and the structure body excluding the surface layer portion is substantially free of silica alumina, and a method for producing the structure.
シリカアルミナは、固体酸性を持つ材料であることから、物質を化学的に変換させるための触媒として、数多くの反応に使用されている（非特許文献１参照。）。例えば、炭化水素の化学的変換反応であるクラッキング、アルキル化反応、エステル化反応、異性化反応等の触媒として利用される。 Since silica alumina is a material having solid acidity, it is used in many reactions as a catalyst for chemically converting a substance (see Non-Patent Document 1). For example, it is used as a catalyst for cracking, alkylation reaction, esterification reaction, isomerization reaction and the like, which are chemical conversion reactions of hydrocarbons.
酸触媒を用いる反応には、塩化アルミニウム、リン酸、硫酸、フッ化水素酸、パラトルエンスルホン酸等が使用される。しかしながら、これらの酸触媒は、極めて腐食性の高い物質であることから、反応装置に用いられる金属を腐食させる。そのために、腐食を防止するための高価な耐腐食材料を用いたり、腐食防止処理を施さなければならいという問題点があった。 For the reaction using an acid catalyst, aluminum chloride, phosphoric acid, sulfuric acid, hydrofluoric acid, paratoluenesulfonic acid, or the like is used. However, since these acid catalysts are extremely corrosive substances, they corrode the metals used in the reaction apparatus. For this reason, there is a problem that an expensive corrosion-resistant material for preventing corrosion must be used or a corrosion prevention treatment has to be performed.
また、硫酸等の均一系触媒では、触媒の蒸留分離等の分離工程が必要なため設備、分離エネルギーの面で経済的でなく、触媒の分離が困難な場合には、アルカリ洗浄などの煩雑な操作が必要になることに加え、廃水処理が必要となるために環境保全の面でも問題があった。そのために、塩化アルミニウムをアルミナ担体に担持した固体触媒が用いられるが、塩化アルミニウムは極めて不安定な物質で、水によって容易に分解し触媒活性が低下すると共に塩酸を生成する。そのために、反応原料から水を完全に除去する必要がある。また、一旦活性を失った触媒の活性を復活させることは困難なため、触媒を失活させないために塩酸等の塩素含有化合物を供給しなければならない等の問題があった。 In addition, a homogeneous catalyst such as sulfuric acid requires a separation step such as distillation separation of the catalyst, so that it is not economical in terms of equipment and separation energy, and when separation of the catalyst is difficult, complicated washing such as alkali washing is required. In addition to the need for operation, wastewater treatment is required, which has also caused problems in terms of environmental conservation. For this purpose, a solid catalyst in which aluminum chloride is supported on an alumina carrier is used, but aluminum chloride is an extremely unstable substance, which is easily decomposed by water to lower the catalytic activity and generate hydrochloric acid. Therefore, it is necessary to completely remove water from the reaction raw material. Further, since it is difficult to restore the activity of the catalyst once lost, there is a problem that a chlorine-containing compound such as hydrochloric acid has to be supplied in order not to deactivate the catalyst.
これらの欠点を克服する方法として、固体酸を触媒として使用する方法が提案されている。例えば、ヒドロキノンとメタノールをシリカアルミナ等の固体酸触媒層に連続して供給して、４−メトキシフェノールを製造する方法が提案されている。（特許文献１参照。）。また、フェノール類と１，３−ブタジエンを固体酸の存在下に反応させることによるＰ−ブテニルフェノール類の製造方法が提案されている（特許文献２参照。）。 As a method for overcoming these drawbacks, a method using a solid acid as a catalyst has been proposed. For example, a method for producing 4-methoxyphenol by continuously supplying hydroquinone and methanol to a solid acid catalyst layer such as silica alumina has been proposed. (See Patent Document 1). Further, a method for producing P-butenylphenols by reacting phenols with 1,3-butadiene in the presence of a solid acid has been proposed (see Patent Document 2).
このように多くの反応に固体酸触媒として用いられるシリカアルミナを製造する方法としては、例えば、シリカおよびアルミナヒドロゲルを混練し粗シリカアルミナヒドロゲルを調製し、これを精製した後に焼成して固体酸性を付与する方法が用いられる。また、工業的な反応器で固体触媒を使用する場合、例えば１ｍｍ〜６ｍｍ程度の大きさに成形することが望まれることから、シリカアルミナを成型する方法が考案されている。例えば、ケイ酸ナトリウム水溶液と硫酸アルミニウム水溶液を反応させて調製したシリカアルミナゾルを、溝付きコーンを通して細分化させ、これを加熱鉱物油中に沈降させることで球状とする方法が用いられている（非特許文献２参照。）。 As a method for producing silica alumina used as a solid acid catalyst in many reactions in this way, for example, silica and alumina hydrogel are kneaded to prepare a crude silica alumina hydrogel, which is purified and then baked to obtain solid acidity. The method of giving is used. Moreover, when using a solid catalyst with an industrial reactor, since it is desired to shape | mold to the magnitude | size of about 1 mm-6 mm, the method of shape | molding a silica alumina is devised. For example, a silica alumina sol prepared by reacting a sodium silicate aqueous solution and an aluminum sulfate aqueous solution is pulverized through a grooved cone and precipitated into heated mineral oil to form a sphere (non-contained). (See Patent Document 2).
シリカアルミナの形態や構造を規定した方法として、例えば、高い酸性度と大きな比表面積と大きな空孔容積を持つ無定形シリカアルミナを調製する方法が提案されている（特許文献３参照。）。この方法では、アルミニウム塩の溶液と沈殿剤を反応器中に並流で加えた後、ｐＨおよび温度を制御してアルミナコロイドを生成させ、その後、ケイ素化合物を添加することで大きな空孔をもつシリカアルミナを調製できる。また、基盤上に調製された両親媒性物質の多層二分子膜にシリカアルミナ化合物含有溶液を浸透させ、その後、両親媒性物質を除去することでシリカアルミナ薄膜を製造する方法が提案されている（特許文献４参照。）。この方法では、ナノメーターレベルの超薄膜からなる多層構造のシリカアルミナ薄膜を製造できることが示されている。 As a method for defining the form and structure of silica alumina, for example, a method of preparing amorphous silica alumina having high acidity, a large specific surface area, and a large pore volume has been proposed (see Patent Document 3). In this method, a solution of aluminum salt and a precipitating agent are added to the reactor in parallel flow, and then the pH and temperature are controlled to form an alumina colloid, and then a silicon compound is added to have large pores. Silica alumina can be prepared. In addition, a method for producing a silica alumina thin film by impregnating a solution containing a silica alumina compound into a multilayer bilayer film of an amphiphile prepared on a substrate and then removing the amphiphile is proposed. (See Patent Document 4). In this method, it has been shown that a silica-alumina thin film having a multilayer structure composed of an ultra-thin film at a nanometer level can be produced.
また、アルミナの表面をシリコン含有化合物で修飾し、これを焼成することでアルミナ表面をシリカアルミナに改質する方法が提案されている（特許文献５および特許文献６参照。）。この方法では、アルミナをシリカで修飾することにより酸性度等の触媒の性質を制御し、アルケン類の骨格異性化反応が効率的に進行することを示している。 Further, a method has been proposed in which the surface of alumina is modified with a silicon-containing compound and the alumina surface is modified to silica alumina by firing the compound (see Patent Document 5 and Patent Document 6). In this method, the properties of the catalyst such as acidity are controlled by modifying alumina with silica, and the skeletal isomerization reaction of alkenes proceeds efficiently.
固体触媒を用いた反応では、反応原料および反応生成物が成形剤あるいは担体を含む構造体全体の細孔を通り、構造体の内部まで進入する。そのために、構造体の構造、すなわち細孔分布や表面積が反応活性を左右する重要な因子になる。特許文献１および特許文献２の方法では、これらの構造体の構造が規定されておらず、シリカアルミナが適度な構造を有するように成形する必要がある。
In the reaction using the solid catalyst, the reaction raw material and the reaction product enter the inside of the structure through the pores of the entire structure including the forming agent or the support. Therefore, the structure of the structure, that is, the pore distribution and the surface area are important factors that influence the reaction activity. In the methods of
特許文献３および特許文献４では、薄膜状に成形したり細孔構造を制御したりして、構造体の構造の制御することを提案している。また、特許文献４および特許文献５では、成形されたアルミナを修飾することでアルミナの細孔構造を保ったまま触媒を調製することができる。しかし、その成形された構造体中のシリカアルミナ分布は制御されておらず、内部を含む構造体全体に触媒活性を持つシリカアルミナが存在することになる。 Patent Document 3 and Patent Document 4 propose controlling the structure of the structure by forming it into a thin film or controlling the pore structure. Moreover, in patent document 4 and patent document 5, a catalyst can be prepared, maintaining the pore structure of an alumina by modifying the shape | molded alumina. However, the distribution of silica alumina in the molded structure is not controlled, and silica alumina having catalytic activity exists in the entire structure including the inside.
固体触媒を用いた反応において、反応原料が触媒活性点に接触して生成した生成物が、触媒活性点に再度接触することなくそのまま触媒から脱離すれば、逐次反応を起こすことなく目的の生成物が得られる。しかし、担体を含む構造体の内部まで侵入した反応原料および反応生成物は、構造体内部で長い時間滞留することになるため、構造体内部の触媒活性点で逐次的な反応が進行し、目的とする生成物が更に別の物質に変化してしまい選択性が低下してしまう。また、目的生成物の逐次反応で生成した高沸点物質やコークが触媒の活性点および細孔部に析出し、活性点の被毒や細孔の閉塞を生じ、結果的に触媒活性を低下させ、さらに触媒寿命の低下を招く等の問題が発生する。 In a reaction using a solid catalyst, if the product produced when the reaction raw material comes into contact with the catalyst active site is detached from the catalyst without coming into contact with the catalyst active site again, the desired product can be generated without causing successive reactions. A thing is obtained. However, since the reaction raw materials and reaction products that have penetrated into the structure including the support stay in the structure for a long time, the sequential reaction proceeds at the catalytic activity point inside the structure, The product is further changed to another substance and the selectivity is lowered. In addition, high-boiling substances and coke produced by the sequential reaction of the target product precipitate on the active sites and pores of the catalyst, causing poisoning of the active sites and blockage of the pores, resulting in a decrease in catalytic activity. In addition, problems such as a reduction in catalyst life occur.
また、構造体内部の触媒活性点で副反応が進行しコーク等の炭素質が析出すると触媒を再生する際にも問題を生ずる。すなわち、炭素質の析出によって触媒活性が低下した触媒を再生させる際には酸化雰囲気で加熱処理を行い析出した炭素質を燃焼除去する必要があるが、担体を含む触媒の構造体の内部に生成した炭素質は燃焼しにくく、また、急激に炭素質の酸化を行うと燃焼で生成するガスや高温による構造体の破壊や触媒活性点の分解によって触媒活性が低下するという問題がある。そのため、例えば特許文献７に示されるように、酸素濃度を空気中の酸素濃度より極めて低い０．２〜５容量％まで低下させた雰囲気で再生処理をする必要があり、再生処理の操作が煩雑になると共に長い時間を要することになるという問題が発生する。 In addition, when a side reaction proceeds at a catalytic active point inside the structure and carbonaceous matter such as coke is deposited, a problem occurs when the catalyst is regenerated. In other words, when regenerating a catalyst whose catalytic activity has decreased due to the deposition of carbonaceous matter, it is necessary to perform heat treatment in an oxidizing atmosphere to burn and remove the deposited carbonaceous matter, but it is generated inside the catalyst structure including the support. The carbonaceous material is difficult to burn, and if the carbonaceous material is rapidly oxidized, there is a problem that the catalytic activity is lowered due to the destruction of the structure generated by the gas generated by the combustion or the high temperature or the decomposition of the catalytic activity point. Therefore, for example, as disclosed in Patent Document 7, it is necessary to perform the regeneration process in an atmosphere in which the oxygen concentration is reduced to 0.2 to 5% by volume, which is extremely lower than the oxygen concentration in the air, and the operation of the regeneration process is complicated. As a result, a problem arises that a long time is required.
これらの問題点を解決するためには、反応生成物が触媒活性点、すなわち、触媒活性を持つシリカアルミナがある場所から即座に離脱する触媒構造、および担体を含む構造体の内部でコーク生成等の副反応が進行しないことが必要となる。 In order to solve these problems, the reaction product is a catalyst active point, that is, a catalyst structure in which silica alumina having catalytic activity is immediately released from a place, and coke generation inside the structure including the support, etc. It is necessary that the side reaction does not proceed.
本発明は、上記の課題に鑑みてなされたものであり、その目的は触媒として有効な構造体表層部のみに触媒活性を持つシリカアルミナが存在し、構造体内部は実質的に触媒活性点が存在しない担体である構造体、およびその製造方法を提供することにある。 The present invention has been made in view of the above problems, and its purpose is that silica alumina having catalytic activity exists only in the surface layer portion of the structure effective as a catalyst, and the inside of the structure has substantially a catalytic activity point. The object is to provide a structure which is a non-existent carrier and a method for producing the structure.
本発明者らは、上記課題を解決するため鋭意検討した結果、シリカアルミナを含有する新規な構造体を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-described problems, the present inventors have found a novel structure containing silica alumina and have completed the present invention.
すなわち、本発明は構造体表層部のみにシリカアルミナが存在し、構造体表層部を除く内部は実質的に触媒活性を持つシリカアルミナが存在しない担体であり、担体が、シリカである構造体、およびその製造方法に関するものである。
That is, the present invention is silica-alumina is present only in the structure surface portion, internal excluding the structure surface portion is Ri carrier der the silica-alumina is not present with substantially the catalyst activity, carrier, structure is silica And a manufacturing method thereof.
本発明のシリカアルミナを含有する新規な構造体は、構造体表層部にシリカアルミナが存在し、構造体表層部を除く内部の層は実質的に触媒活性を持つシリカアルミナが存在しない担体である構造を有することを特徴とする。 The novel structure containing silica alumina of the present invention is a carrier in which silica alumina is present in the surface layer portion of the structure, and the inner layers other than the structure surface layer portion are substantially free of silica alumina having catalytic activity. It has a structure.
ここで、本発明における構造体とは、自重や外力などの荷重に抵抗できるように成形された物体のことをいう。 Here, the structure in the present invention refers to an object formed so as to resist a load such as its own weight or external force.
本発明の構造体では、構造体表層部のシリカアルミナが存在する層の厚さは、好ましくは構造体外表面から１〜１０００μｍ、さらに好ましくは１〜５００μｍである。また、構造体表層部を除く内部は、実質的に触媒活性を持つシリカアルミナを含まない担体である。 In the structure of the present invention, the thickness of the layer where silica alumina is present in the surface layer of the structure is preferably 1 to 1000 μm, more preferably 1 to 500 μm from the outer surface of the structure. Further, the inside excluding the surface layer of the structure is a carrier containing substantially no silica alumina having catalytic activity.
本発明の構造体の形状は、特に限定されるものではなく、例えば、図１〜４で示されるような球状、円柱状、中空円柱状、板状、楕円状、シート状、ハニカム状等が挙げられ、十分な反応活性があり、副反応、および、コーキングを抑制することができることから、好ましくは球状、楕円状、円柱状、中空円柱状、更に好ましくは球状が挙げられる。 The shape of the structure of the present invention is not particularly limited, and for example, a spherical shape, a cylindrical shape, a hollow cylindrical shape, a plate shape, an elliptical shape, a sheet shape, a honeycomb shape and the like as shown in FIGS. Preferably, it is spherical, elliptical, cylindrical, hollow cylindrical, more preferably spherical, because it has sufficient reaction activity and can suppress side reactions and coking.
また、本発明の構造体の大きさは、特に制限されるものではなく、例えば、副反応およびコーキングを抑制することができることから、好ましくは１０μｍ〜１０ｃｍの範囲、さらに好ましくは１００μｍ〜５ｃｍの範囲の構造体が挙げられる。 Further, the size of the structure of the present invention is not particularly limited. For example, since side reactions and coking can be suppressed, it is preferably in the range of 10 μm to 10 cm, more preferably in the range of 100 μm to 5 cm. The structure of this is mentioned.
本発明の構造体において、バインダーの有無に特に制限はない。 In the structure of the present invention, the presence or absence of a binder is not particularly limited.
本発明の構造体を製造する方法は特に規定されないが、例えば、（１）ケイ素及びアルミニウムの水酸化物及び／または酸化物を担体の表層部に担持させ、２００〜８００℃で焼成する方法、（２）シリカ及びアルミナの原料塩を担体に担持させた後に、加水分解を行うことでケイ素及びアルミニウムの水酸化物及び／または酸化物を担体の表層部に析出させ、２００〜８００℃で焼成する方法、（３）シリカ及びアルミナの原料塩を含む溶液を担体の表層に噴霧し、構造体の表層部に原料塩を担持させた後に加水分解することでケイ素及びアルミニウムの水酸化物及び／または酸化物を担体の表層に担持させた後に、２００〜８００℃で焼成する方法、（４）構造体の内部となる担体の外表面にシリカ及びアルミナの原料となるケイ素及びアルミニウムの水酸化物及び／または酸化物を塗布し、２００〜８００℃で焼成する方法により構造体を製造することができる。構造体の表層部に担持されるシリカアルミナが内部に拡散しにくいこと、および表層に存在する触媒活性を持つシリカアルミナが剥離することがないことから、（１）の方法が好ましく用いられる。 The method for producing the structure of the present invention is not particularly limited. For example, (1) a method in which a hydroxide and / or oxide of silicon and aluminum is supported on the surface layer portion of the support and fired at 200 to 800 ° C., (2) After supporting a raw material salt of silica and alumina on a carrier, hydrolysis is carried out to precipitate silicon and aluminum hydroxide and / or oxide on the surface layer of the carrier, and firing at 200 to 800 ° C. (3) A solution containing silica and alumina raw material salt is sprayed on the surface layer of the carrier, and the raw material salt is supported on the surface layer portion of the structure and then hydrolyzed, thereby hydrolyzing silicon and aluminum hydroxide and / or Alternatively, after the oxide is supported on the surface layer of the support, firing is performed at 200 to 800 ° C., (4) silicon that is a raw material for silica and alumina on the outer surface of the support that is the inside of the structure, and Hydroxides and / or oxides coated of aluminum, it is possible to produce a structure by a method of baking at 200 to 800 ° C.. The method (1) is preferably used because the silica alumina supported on the surface layer portion of the structure is difficult to diffuse inside and the silica alumina having catalytic activity present on the surface layer does not peel off.
本発明において、（１）の方法を詳しく説明する。まず、塩基性物質および／または水を担体に含浸担持させる。この担体を、シリカ及びアルミナの原料塩を溶解した溶液に浸すことで、溶液中の原料塩が担体に含浸されている塩基性物質および／または水と接触し、加水分解反応等によって水酸化物または酸化物になり担体の表層部に沈殿する。その後、乾燥、空気中２００〜８００℃での焼成を行い、表層部分にシリカアルミナが存在し、表層以外の内部は触媒活性を持つシリカアルミナが存在しない担体である構造体が製造できる。 In the present invention, the method (1) will be described in detail. First, a basic substance and / or water is impregnated and supported on a carrier. By immersing this carrier in a solution in which the raw material salt of silica and alumina is dissolved, the raw material salt in the solution comes into contact with the basic substance and / or water impregnated in the carrier, and a hydroxide is obtained by hydrolysis reaction or the like. Or it becomes an oxide and precipitates on the surface layer of the carrier. Thereafter, drying and baking at 200 to 800 ° C. in the air can be performed to produce a structure which is a carrier in which silica alumina is present in the surface layer portion and silica alumina having catalytic activity is not present inside the surface layer.
また、（１）の方法において、シリカまたはアルミナを担体とする場合について説明する。シリカを担体とする場合、まず、塩基性物質および／または水をシリカ担体に含浸担持させる。このシリカ担体をアルミナの原料塩を溶解した溶液に浸すことで、溶液中のアルミナの原料塩がシリカ担体に含浸されている塩基性物質および／または水と接触し、加水分解反応等によって水酸化物または酸化物になりシリカ担体の表層部に沈殿する。この際、シリカの原料塩は必要ない。その後、乾燥、空気中２００〜８００℃での焼成を行い、表層部分にシリカアルミナが存在し、表層以外の内部は触媒活性を持つシリカアルミナが存在しないシリカ担体である構造体が製造できる。 In the method (1), a case where silica or alumina is used as a carrier will be described. When silica is used as a support, first, a basic substance and / or water is impregnated and supported on the silica support. By immersing this silica support in a solution in which the alumina raw material salt is dissolved, the alumina raw material salt in the solution comes into contact with the basic substance and / or water impregnated in the silica support and is hydrolyzed by a hydrolysis reaction or the like. It becomes a product or an oxide and precipitates on the surface layer of the silica support. At this time, a raw material salt of silica is not necessary. Thereafter, drying and calcination in air at 200 to 800 ° C. can produce a structure which is a silica carrier in which silica alumina is present in the surface layer portion and silica alumina having catalytic activity is not present in the inside other than the surface layer.
また、アルミナを担体とする場合、まず、塩基性物質および／または水をアルミナ担体に含浸担持させる。このアルミナ担体をシリカの原料塩を溶解した溶液に浸すことで、溶液中のシリカの原料塩がアルミナ担体に含浸されている塩基性物質および／または水と接触し、加水分解反応等によって水酸化物または酸化物になりアルミナ担体の表層部に沈殿する。この際、アルミナの原料塩は必要ない。その後、乾燥、空気中２００〜８００℃での焼成を行い、表層部分にシリカアルミナが存在し、表層以外の内部は触媒活性を持つシリカアルミナが存在しないアルミナ担体である構造体が製造できる。 In the case of using alumina as a carrier, first, a basic substance and / or water is impregnated and supported on the alumina carrier. By immersing the alumina support in a solution in which the silica raw material salt is dissolved, the silica raw material salt in the solution comes into contact with the basic substance and / or water impregnated in the alumina support, and is hydroxylated by a hydrolysis reaction or the like. It becomes a product or an oxide and precipitates on the surface layer of the alumina support. At this time, a raw material salt of alumina is not necessary. Thereafter, drying and calcination at 200 to 800 ° C. in the air can be performed to produce a structure which is an alumina carrier in which silica alumina is present in the surface layer portion and silica alumina having catalytic activity is not present inside the surface layer.
本発明の方法で使用される塩基性物質は、特に限定されるものではなく無機物、有機物を問わず使用できるが、例えばリチウム、ナトリウム、カリウムセシウム等のアルカリ金属、マグネシウム、カルシウム、ストロンチウム、ストロンチウム、バリウム等のアルカリ度類金属、アンモニア、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ジブチルアミン、シクロブチルアミン、フェニルアミン、ベンジルアミン、ブチルベンジルアミン、フェニレンアミン、ジシクロヘキシルアミン、デシルアミン、エタノールアミン、プロパノールアミン、フェニルエタノールアミン等のアミン類、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム等のアンモニウム化合物、ピリジン、メチルピリジン、ジメチルピリジン、エチルピリジン、ジエチルピリジン、フェニルピリジン、アミノピリジン、ニトロピリン、ブロモピリジン、クロロピリジン等のピリジン類、キノリン、メチルキノリン、ジメチルキノリン、ヒドロキシメチルキノリン、ビニルキノリン、フェニルキノリン、ヒドロキシキノリン、テトラヒドロキノリン、アミノキノリン、クロロキノリン、ブロモキノリン、ニトロキノリン、メトキシキノリン等のキノリン類が使用できる。構造体の表層部に担持されるシリカアルミナ原料が内部に拡散しにくいことから、アルカリ金属、アルカリ度類金属、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム等のアンモニウム化合物、ピリジン類およびキノリン類が好ましい。さらに、焼成後に塩基性物質を残留させないことから、テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム等のアンモニウム化合物、ピリジン類およびキノリン類が好ましい。 The basic substance used in the method of the present invention is not particularly limited and can be used regardless of inorganic substance or organic substance. For example, alkali metals such as lithium, sodium and potassium cesium, magnesium, calcium, strontium, strontium, Alkalinity metals such as barium, ammonia, methylamine, ethylamine, propylamine, butylamine, dibutylamine, cyclobutylamine, phenylamine, benzylamine, butylbenzylamine, phenyleneamine, dicyclohexylamine, decylamine, ethanolamine, propanolamine, Amines such as phenylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide Pyridines such as pyridine, methylpyridine, dimethylpyridine, ethylpyridine, diethylpyridine, phenylpyridine, aminopyridine, nitropyrine, bromopyridine, chloropyridine, quinoline, methylquinoline, dimethylquinoline, hydroxymethylquinoline, Quinolines such as vinylquinoline, phenylquinoline, hydroxyquinoline, tetrahydroquinoline, aminoquinoline, chloroquinoline, bromoquinoline, nitroquinoline and methoxyquinoline can be used. Since the silica alumina raw material supported on the surface layer of the structure is difficult to diffuse inside, ammonium compounds such as alkali metals, alkalinity metals, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Pyridines and quinolines are preferred. Furthermore, ammonium compounds such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, pyridines, and quinolines are preferred because no basic substance remains after firing.
本発明で使用できるシリカの原料塩は、ケイ素を含有する化合物であれば、特に限定されるものではなく、例えば、テトラエトキシシラン、テトライソプロポキシシラン、テトラ−ｎ−ブトキシシラン、アミノプロピルトリエトキシシラン、トリエトキシビニルシラン、メチルトリエトキシシラン 、ジエトキシジメチルシラン、メチルトリメトキシシラン、アミノプロピルトリメトキシシラン、エトキシトリメチルシラン、ジヒドロキシジフェニルシラン、アミノプロピルジメチルメトキシシラン、カルボメトキシエチルジメトキシメチルシラン、ジメトキシメチル−ｎ−オクタデシルシラン、ジメチルメトキシ−ｎ−プロピルシラン、ジメチルメトキシ−ｎ−オクチルシラン、オクチルトリエトキシシラン、エチルトリエトキシシラン、トリメトキシ（７−オクテン−１−イル）シラン等のシラン化合物、ヘキサフルオロけい酸アンモニウム、けいふっ化アンモニウム、ヘキサフルオロけい酸、けいふっ化水素酸、けい酸、四塩化けい素、けい酸ナトリウム、水ガラス等のケイ素を含有する化合物を使用することができ、好ましくはテトラエトキシシラン、テトライソプロポキシシラン、テトラ−ｎ−ブトキシシラン、アミノプロピルトリエトキシシラン、トリエトキシビニルシラン、メチルトリエトキシシラン 、ジエトキシジメチルシランを使用することができる。 The raw material salt of silica that can be used in the present invention is not particularly limited as long as it is a compound containing silicon. For example, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, aminopropyltriethoxy Silane, triethoxyvinylsilane, methyltriethoxysilane, diethoxydimethylsilane, methyltrimethoxysilane, aminopropyltrimethoxysilane, ethoxytrimethylsilane, dihydroxydiphenylsilane, aminopropyldimethylmethoxysilane, carbomethoxyethyldimethoxymethylsilane, dimethoxymethyl -N-octadecylsilane, dimethylmethoxy-n-propylsilane, dimethylmethoxy-n-octylsilane, octyltriethoxysilane, ethyltriethoxysilane, Silane compounds such as limethoxy (7-octen-1-yl) silane, ammonium hexafluorosilicate, ammonium fluoride, hexafluorosilicic acid, hydrofluoric acid, silicic acid, silicon tetrachloride, sodium silicate, Silicon-containing compounds such as water glass can be used, preferably tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, aminopropyltriethoxysilane, triethoxyvinylsilane, methyltriethoxysilane, di- Ethoxydimethylsilane can be used.
本発明で使用できるアルミナの原料塩は、アルミニウムを含有する化合物であれば、特に限定されるものではなく、例えば、塩化アルミニウム、硝酸アルミニウム、硫酸アルミニウム、炭酸アルミニウム等のアルミニウム塩；アルミン酸リチウム、アルミン酸ナトリウム、アルミン酸カリウム、アルミン酸ルビジウム、アルミン酸セシウム等のアルミン酸塩；アルミニウムメトキシド、アルミニウムエトキシド、アルミニウムプロポキシド、アルミニウムブトキシド等のアルミニウムアルコキシド等が使用することができ、好ましくは、塩化アルミニウム、硝酸アルミニウム、硫酸アルミニウム、炭酸アルミニウム等のアルミニウム塩を使用することができる。 The raw material salt of alumina that can be used in the present invention is not particularly limited as long as it is a compound containing aluminum. For example, aluminum salts such as aluminum chloride, aluminum nitrate, aluminum sulfate, and aluminum carbonate; lithium aluminate, Aluminates such as sodium aluminate, potassium aluminate, rubidium aluminate, cesium aluminate; aluminum alkoxides such as aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, etc. can be used, preferably Aluminum salts such as aluminum chloride, aluminum nitrate, aluminum sulfate, and aluminum carbonate can be used.
本発明の方法では、使用する担体は特に限定されるものではなく、使用する触媒反応に対して実質的に触媒活性を持たない担体で、例えば、シリカ、アルミナ、チタニア、活性炭、アセチレンブラック、酸化亜鉛、炭酸カルシウム、硫酸バリウム、シリコンカーバイド、カーボンナノチューブ、カーボンナノホーン、ハイドロタルサイト、モンモリロナイト、サポナイト、マグネシア等、通常用いられる担体でよいが、好ましくはシリカ、アルミナがよい。 In the method of the present invention, the carrier to be used is not particularly limited, and is a carrier having substantially no catalytic activity for the catalytic reaction to be used. For example, silica, alumina, titania, activated carbon, acetylene black, oxidation Zinc, calcium carbonate, barium sulfate, silicon carbide, carbon nanotubes, carbon nanohorns, hydrotalcite, montmorillonite, saponite, magnesia and the like may be used, but silica and alumina are preferred.
本発明の方法で行われる焼成の温度は、２００〜８００℃でよく。触媒活性を持つシリカアルミナを表層部分に担持した際使用された塩基性の有機物が残存しないことから、好ましくは２５０〜７００℃がよい。焼成時間は０．５〜２０時間で良い。 The temperature of the baking performed by the method of the present invention may be 200 to 800 ° C. Since the basic organic substance used when the silica alumina having catalytic activity is supported on the surface layer portion does not remain, the temperature is preferably 250 to 700 ° C. The firing time may be 0.5 to 20 hours.
本発明の構造体は、固体酸触媒として使用することができる。例えば、軽油および重質油などの接触分解反応；重質油の水素化分解反応；シクロヘキサンの脱水素、シクロペンテンの異性化脱水素、パラフィンの環化脱水素、パラフィンの異性化、パラフィンの水素化分解などの石油ナフサの重質留分の接触改質反応；ブタン、ペンタン、ヘキサン、ブテン、ペンテン、ヘキセン、キシレンなどのアルカン、アルケンの骨格異性化反応およびアルケンの水素異性化反応；ベンゼン、アルキルベンゼン、ナフタレン、フェノール、チオフェン、ピリジン等とエチレン、プロピレン、ブテン、ペンテン、ヘキセン、メタノール、エタノール、プロパノール、ブタノール、エチルクロリド、プロピルプロリド、ブチルクロリド等のオレフィン、アルコールハロゲン化アルキル等の芳香族のアルキル化反応；トルエン、エチルベンゼン、プロピルベンゼン、ブチルベンゼン、キシレン、ジエチルベンゼン、ジプロピルベンゼン、ジブチルベンゼン、トリメチルベンゼン、トリエチルベンゼン、トリプロピルベンゼン、トリブチルベンゼン等のアルキル芳香族の異性化、不均化、トランスアルキル化、脱アルキル化反応、脱水素反応；エチレン、プロピレン、ブテン、ペンテン、ヘキセン等のオレフィンの重合やテトラヒドロフラン等の環状エーテルの開環重合反応、ＮＯＸの還元反応に使用することができる。 The structure of the present invention can be used as a solid acid catalyst. For example, catalytic cracking reaction of light oil and heavy oil; hydrocracking reaction of heavy oil; cyclohexane dehydrogenation, cyclopentene isomerization dehydrogenation, paraffin cyclization dehydrogenation, paraffin isomerization, paraffin hydrogenation Catalytic reforming reaction of heavy fraction of petroleum naphtha such as cracking; Alkane such as butane, pentane, hexane, butene, pentene, hexene, xylene, skeletal isomerization reaction of alkene and hydroisomerization reaction of alkene; benzene, alkylbenzene , Naphthalene, phenol, thiophene, pyridine and the like, ethylene, propylene, butene, pentene, hexene, methanol, ethanol, propanol, butanol, ethyl chloride, propyl prolide, butyl chloride and other olefins, and alcohols such as alkyl halides. Alkylation reaction; Isomerization, disproportionation, transalkylation of alkyl aromatics such as benzene, ethylbenzene, propylbenzene, butylbenzene, xylene, diethylbenzene, dipropylbenzene, dibutylbenzene, trimethylbenzene, triethylbenzene, tripropylbenzene, tributylbenzene, It can be used for dealkylation reaction, dehydrogenation reaction; polymerization of olefins such as ethylene, propylene, butene, pentene and hexene; ring-opening polymerization reaction of cyclic ethers such as tetrahydrofuran; and NO X reduction reaction.
また、本発明の構造体は、触媒の担体としても使用することができ、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウム等の１属元素；ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムなどの２属元素；スカンジウム、イットリウム、ランタノイド、アクチノイド等の３属元素；チタニウム、ジルコニウム等の４属元素；バナジウム、ニオブ、タンタル等の５属元素；クロム、モリブデン、タングステン等の６属元素；マンガン、レニウム等の７属元素；鉄、ルテニウム、オスニウム等の８属元素；コバルト、ロジウム、イリジウム等の９属元素；ニッケル、パラジウム、白金などの１０属元素；銅、銀、金等の１１属元素、亜鉛、カドミウムなどの１２属元素；ホウ素、アルミニウム、ガリウム、インジウム、タリウム等の１３属元素；ゲルマニウム、スズ、鉛等の１４属元素；アンチモン、ビスマス等の１５属元素、硫黄、テルル等の１６属元素に挙げられる一種類以上の元素を担持し触媒として使用できる。 The structure of the present invention can also be used as a catalyst support, for example, one group element such as lithium, sodium, potassium, rubidium and cesium; two groups such as beryllium, magnesium, calcium, strontium and barium. Elements; 3 group elements such as scandium, yttrium, lanthanoid and actinoid; 4 group elements such as titanium and zirconium; 5 group elements such as vanadium, niobium and tantalum; 6 group elements such as chromium, molybdenum and tungsten; manganese, rhenium and the like 7 group elements; 8 group elements such as iron, ruthenium and osmium; 9 group elements such as cobalt, rhodium and iridium; 10 group elements such as nickel, palladium and platinum; 11 group elements such as copper, silver and gold; , Cadmium and other 12 group elements; boron, aluminum, gallium, indigo Supports one or more kinds of elements such as 13 group elements such as sulfur and thallium; 14 group elements such as germanium, tin and lead; 15 group elements such as antimony and bismuth, and 16 group elements such as sulfur and tellurium. Can be used.
本発明の構造体は、構造体表層部にシリカアルミナが存在し、表層部以外の内部は実質的に触媒活性を持つシリカアルミナが存在しない担体である。したがって、反応原料および反応生成物が、副反応が起こりやすい構造体の内部で触媒と接触することがないので、目的物の選択性が高く、また活性点の被毒や細孔の閉塞を生じにくいため触媒活性が低下しにくく、さらに触媒寿命が長いという効果を有する。また、触媒活性点が構造体内部に存在しないため、構造体内部に炭素質が析出しないことから、炭素質の燃焼による触媒の再生が容易に行えるという効果を有する。 The structure of the present invention is a support in which silica alumina is present in the surface layer portion of the structure, and silica alumina having substantially catalytic activity is not present inside other than the surface layer portion. Therefore, since the reaction raw materials and reaction products do not come into contact with the catalyst inside the structure where side reactions are likely to occur, the selectivity of the target product is high, and poisoning of active sites and pore clogging occur. Since it is difficult to reduce the catalytic activity, it has the effect that the catalyst life is long. In addition, since there is no catalytic active site inside the structure, carbonaceous matter does not precipitate inside the structural body, so that the catalyst can be easily regenerated by burning carbonaceous matter.
以下、実施例により本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
以下の実施例に用いた測定法を示す。
（シリカアルミナの深さ方向の分布を求めるためのライン分析）
得られた構造体を樹脂に包埋し、ウルトラミクロトームで切削して得られた試料を、電子線プローブマイクロアナライザー（ＥＰＭＡ）（島津製作所製、商品名ＥＰＭ−８１０）を用い電圧２０ｋＶ、電流１０ｎＡにて粒子断面の深さ方向の線分析を行い、ケイ素およびアルミニウムの分布を測定した。
（酸性質を分析するためのアンモニア昇温脱離スペクトルの測定）
昇温脱離スペクトル装置（日本ベル製、商品名ＴＰＤ−１−ＡＴ）を用い、ヘリウム気流中５００℃で１時間前処理を行った後に１００℃でアンモニアを吸着させ、１００℃〜６００℃の測定温度で１０℃／分の昇温速度で測定した。
The measurement methods used in the following examples are shown.
(Line analysis to determine the distribution of silica alumina in the depth direction)
A sample obtained by embedding the obtained structure in a resin and cutting with an ultramicrotome was subjected to an electron beam probe microanalyzer (EPMA) (trade name EPM-810, manufactured by Shimadzu Corporation) with a voltage of 20 kV and a current of 10 nA. Was used to perform a line analysis in the depth direction of the particle cross section, and the distribution of silicon and aluminum was measured.
(Measurement of ammonia temperature-programmed desorption spectrum for analyzing acid properties)
Using a temperature-programmed desorption spectrometer (trade name TPD-1-AT, manufactured by Bell Japan), pretreatment was performed at 500 ° C. for 1 hour in a helium stream, and then ammonia was adsorbed at 100 ° C. The measurement was performed at a measurement temperature at a rate of temperature increase of 10 ° C./min.
実施例１
１．０モル／リッターのテトラ−ｎ−プロピルアンモニウムヒドロキシド水溶液１６．５ｇにシリカビーズ（富士シリシア化学社製 「キャリアクトＱ−５０」、粒子形状：球状、粒子径：１．７〜４．０ｍｍ、表面積：８０ｍ２／ｇ、平均細孔径５０ｎｍ）１０ｇを添加し、シリカビ−ズに水溶液を含浸した後、５０℃、２時間、２０ｈＰａで減圧乾燥した。
Example 1
16.5 g of 1.0 mol / liter tetra-n-propylammonium hydroxide aqueous solution was added to silica beads ("Caract Q-50" manufactured by Fuji Silysia Chemical Ltd., particle shape: spherical, particle diameter: 1.7-4. 10 g (0 mm, surface area: 80 m 2 / g, average pore diameter 50 nm) was added, and silica beads were impregnated with an aqueous solution, and then dried under reduced pressure at 50 ° C. for 2 hours at 20 hPa.
つぎに、硝酸アルミニウム・９水和物１．０２ｇをエタノール１０ｍｌに溶解させ、先のテトラプロピルアンモニウムヒドロキシドを含浸担持したシリカビーズを添加し、３０分攪拌した。撹拌後、５０℃、２０ｈＰａで２時間減圧乾燥した後、空気気流中６００℃で３時間焼成した。 Next, 1.02 g of aluminum nitrate nonahydrate was dissolved in 10 ml of ethanol, and the silica beads impregnated and supported with tetrapropylammonium hydroxide were added and stirred for 30 minutes. After stirring, it was dried under reduced pressure at 50 ° C. and 20 hPa for 2 hours, and then calcined at 600 ° C. for 3 hours in an air stream.
得られたシリカアルミナ構造体のアルミニウムおよびケイ素のライン分析を行った結果を図５に示す。担持されたアルミニウムはシリカビーズ外表面から４００μｍ以内に存在していることがわかった。アンモニア昇温脱離スペクトルを測定した結果を図６に示す。２００℃付近にアンモニアの脱離ピークが現れ、シリカアルミナの生成によって固体酸点が現れたことがわかった。 FIG. 5 shows the results of line analysis of aluminum and silicon of the obtained silica-alumina structure. It was found that the supported aluminum was present within 400 μm from the outer surface of the silica beads. The results of measuring the ammonia temperature programmed desorption spectrum are shown in FIG. It was found that an ammonia desorption peak appeared around 200 ° C., and solid acid sites appeared due to the formation of silica alumina.
比較例１
硝酸アルミニウム・９水和物１．０２ｇをエタノール１０ｍｌに溶解させた。得られた溶液に、シリカビーズ（富士シリシア化学社製「キャリアクトＱ−５０」、粒子形状：球状、粒子径：１．７〜４．０ｍｍ、表面積：８０ｍ２／ｇ、平均細孔径５０ｎｍ）１０ｇを添加し３０分攪拌した。撹拌後、５０℃、２０ｈＰａで２時間減圧乾燥した後、空気気流中６００℃で３時間焼成した。
Comparative Example 1
1.02 g of aluminum nitrate nonahydrate was dissolved in 10 ml of ethanol. In the resulting solution, silica beads ("Cartict Q-50" manufactured by Fuji Silysia Chemical Co., Ltd., particle shape: spherical, particle diameter: 1.7 to 4.0 mm, surface area: 80 m 2 / g, average pore diameter of 50 nm) 10 g was added and stirred for 30 minutes. After stirring, it was dried under reduced pressure at 50 ° C. and 20 hPa for 2 hours, and then calcined at 600 ° C. for 3 hours in an air stream.
得られたシリカアルミナ構造体のアルミニウムおよびケイ素のライン分析を行った結果を図７に示す。担持されたアルミニウムはシリカビーズの内部にも存在していた。 FIG. 7 shows the results of line analysis of aluminum and silicon of the obtained silica-alumina structure. The supported aluminum was also present inside the silica beads.
実施例２
アルミナビーズ（住友化学製「ＫＨＤ−２４」、粒子形状：球状、粒子径：２．４〜４．０ｍｍ、表面積：２７０ｍ２／ｇ、細孔容積０．３８ｍｌ／ｇ）を２００℃で３時間加熱乾燥した。このアルミナビーズ２０．０ｇに水１０ｍｌを添加し３０
分間攪拌した。攪拌後、５０℃、２０ｈＰａで３０分減圧乾燥した。水添加前を基準とした重量増加から、添加した水のうち３．１５ｇが残存していた。
Example 2
Alumina beads (“KHD-24” manufactured by Sumitomo Chemical Co., Ltd., particle shape: spherical, particle diameter: 2.4-4.0 mm, surface area: 270 m 2 / g, pore volume 0.38 ml / g) at 200 ° C. for 3 hours Heat-dried. Add 10 ml of water to 20.0 g of the alumina beads and add 30
Stir for minutes. After stirring, it was dried under reduced pressure at 50 ° C. and 20 hPa for 30 minutes. From the weight increase before the addition of water, 3.15 g of the added water remained.
つぎに、テトラエトキシシラン２．１４ｇをヘキサン７．５ｍｌに溶解させ、先に得られた水含浸アルミナビーズに添加し、３０分攪拌した。撹拌後、５０℃、２０ｈＰａで２時間減圧乾燥した後、空気気流中６００℃で３時間焼成した。 Next, 2.14 g of tetraethoxysilane was dissolved in 7.5 ml of hexane, added to the previously obtained water-impregnated alumina beads, and stirred for 30 minutes. After stirring, it was dried under reduced pressure at 50 ° C. and 20 hPa for 2 hours, and then calcined at 600 ° C. for 3 hours in an air stream.
得られたシリカアルミナ構造体のアルミニウムおよびケイ素のライン分析を行った結果を図８に示す。担持されたケイ素はアルミナビーズ外表面から５００μｍ以内に存在していることがわかった。 FIG. 8 shows the results of line analysis of aluminum and silicon of the obtained silica-alumina structure. It was found that the supported silicon was present within 500 μm from the outer surface of the alumina beads.
実施例３
ヘキサン７．５ｍｌの代わりにエタノール７．５ｍｌを用いたこと以外は、実施例２と同様にしてシリカアルミナ構造体を調製した。
Example 3
A silica alumina structure was prepared in the same manner as in Example 2 except that 7.5 ml of ethanol was used instead of 7.5 ml of hexane.
得られたシリカアルミナ構造体のアルミニウムおよびケイ素のライン分析を行った結果を図９に示す。担持されたアルミニウムはシリカビーズ外表面から５００μｍ以内に存在していることがわかった。 FIG. 9 shows the results of line analysis of aluminum and silicon of the obtained silica-alumina structure. It was found that the supported aluminum was present within 500 μm from the outer surface of the silica beads.
比較例２
アルミナビーズ（住友化学製「ＫＨＤ−２４」、粒子形状：球状、粒子径：２．４〜４．０ｍｍ、表面積：２７０ｍ２／ｇ、細孔容積０．３８ｍｌ／ｇ）を２００℃で３時間加熱乾燥した。
Comparative Example 2
Alumina beads (“KHD-24” manufactured by Sumitomo Chemical Co., Ltd., particle shape: spherical, particle diameter: 2.4-4.0 mm, surface area: 270 m 2 / g, pore volume 0.38 ml / g) at 200 ° C. for 3 hours Heat-dried.
つぎに、テトラエトキシシラン２．１４ｇをヘキサン７．５ｍｌに溶解させ、先に得られた水含浸アルミナビーズに添加し、３０分攪拌した。撹拌後、５０℃、２０ｈＰａで２時間減圧乾燥した後、空気気流中６００℃で３時間焼成した。 Next, 2.14 g of tetraethoxysilane was dissolved in 7.5 ml of hexane, added to the previously obtained water-impregnated alumina beads, and stirred for 30 minutes. After stirring, it was dried under reduced pressure at 50 ° C. and 20 hPa for 2 hours, and then calcined at 600 ° C. for 3 hours in an air stream.
得られたシリカアルミナ構造体のアルミニウムおよびケイ素のライン分析を行った結果を図１０に示す。担持されたケイ素はアルミナビーズの内部まで、ほぼ均一に存在していた。 FIG. 10 shows the results of line analysis of aluminum and silicon of the obtained silica-alumina structure. The supported silicon was present almost uniformly up to the inside of the alumina beads.
比較例３
ヘキサン７．５ｍｌの代わりにエタノール７．５ｍｌを用いたこと以外は、比較例２と同様にしてシリカアルミナ構造体を調製した。
Comparative Example 3
A silica-alumina structure was prepared in the same manner as in Comparative Example 2 except that 7.5 ml of ethanol was used instead of 7.5 ml of hexane.
得られたシリカアルミナ構造体のアルミニウムおよびケイ素のライン分析を行った結果を図１１に示す。担持されたケイ素はアルミナビーズの内部まで、ほぼ均一に存在していた。 FIG. 11 shows the results of line analysis of aluminum and silicon of the obtained silica-alumina structure. The supported silicon was present almost uniformly up to the inside of the alumina beads.
１ シリカアルミナ
２ 担体
1
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