JP5495763B2 - Method for producing metal-supported crystalline silica aluminophosphate catalyst and metal-supported crystalline silica aluminophosphate catalyst - Google Patents
Method for producing metal-supported crystalline silica aluminophosphate catalyst and metal-supported crystalline silica aluminophosphate catalyst Download PDFInfo
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- JP5495763B2 JP5495763B2 JP2009287187A JP2009287187A JP5495763B2 JP 5495763 B2 JP5495763 B2 JP 5495763B2 JP 2009287187 A JP2009287187 A JP 2009287187A JP 2009287187 A JP2009287187 A JP 2009287187A JP 5495763 B2 JP5495763 B2 JP 5495763B2
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- Prior art keywords
- crystalline silica
- metal
- silica aluminophosphate
- catalyst
- supported
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 175
- 229910002026 crystalline silica Inorganic materials 0.000 title claims description 165
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 165
- 239000003054 catalyst Substances 0.000 title claims description 132
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 239000006185 dispersion Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 34
- 150000002736 metal compounds Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000001694 spray drying Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 111
- 239000010949 copper Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 13
- 238000010335 hydrothermal treatment Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 241000264877 Hippospongia communis Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- SUOTZEJYYPISIE-UHFFFAOYSA-N iron(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SUOTZEJYYPISIE-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004541 SiN Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 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
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- GDRLAWYXAIXEGC-UHFFFAOYSA-N propan-2-amine;hydrate Chemical compound O.CC(C)N GDRLAWYXAIXEGC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 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
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
本発明は、内燃機関の排ガス処理に好適に用いることのできる金属担持触媒であって、排気ガスの処理効率を高めた金属担持触媒の製造方法、および該金属担持触媒に関する。 The present invention relates to a metal-supported catalyst that can be suitably used for exhaust gas treatment of an internal combustion engine, and relates to a method for producing a metal-supported catalyst with improved exhaust gas treatment efficiency, and the metal-supported catalyst.
ディーゼルエンジンから排出される排気ガスには、ＨＣ（炭化水素）、ＣＯ（一酸化炭素）、ＮＯｘ（窒素酸化物）およびＰＭ（Particulate Matter：パティキュレート）等の汚染物質が含まれる。これらの汚染物質の中でもＮＯｘは、酸化触媒やガソリン自動車で実用化されている三元触媒では浄化が難しく、ＮＯｘを浄化することができる有望な触媒として選択還元型ＮＯｘ触媒（以下、ＳＣＲ触媒という。）の開発が行われている。 Exhaust gas discharged from the diesel engine includes contaminants such as HC (hydrocarbon), CO (carbon monoxide), NOx (nitrogen oxide), and PM (Particulate Matter). Among these pollutants, NOx is difficult to purify with an oxidation catalyst or a three-way catalyst put to practical use in gasoline automobiles. As a promising catalyst capable of purifying NOx, a selective reduction type NOx catalyst (hereinafter referred to as SCR catalyst). .) Is being developed.
ＳＣＲ触媒としては、ＴｉＯ2あるいはＳｉＯ2−ＴｉＯ2、ＷＯ3−ＴｉＯ2、ＳｉＯ2−ＴｉＯ2などの二元系複合酸化物、または、ＷＯ3−ＳｉＯ2−ＴｉＯ2、ＭｏＯ3−ＳｉＯ2−ＴｉＯ2などの三元系複合酸化物などの担体に、Ｖ，Ｃｒ，Ｍｏ，Ｍｎ，Ｆｅ，Ｎｉ，Ｃｕ，Ａｇ，Ａｕ，Ｐｄ，Ｙ，Ｃｅ，Ｎｄ，Ｗ，Ｉｎ，Ｉｒなどの活性成分を担持してなるハニカム構造を有する触媒が知られている。これらの排ガス処理触媒は次式に示すように、アンモニアなどの還元剤の存在下でＮＯｘを還元して窒素ガスに変換して浄化するものである。 The SCR catalyst, TiO 2 or SiO 2 -TiO 2, WO 3 -TiO 2, binary composite oxide such as SiO 2 -TiO 2, or, WO 3 -SiO 2 -TiO 2, MoO 3 -SiO 2 -Supports such as ternary complex oxides such as TiO 2 , V, Cr, Mo, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, W, In, Ir, etc. A catalyst having a honeycomb structure on which components are supported is known. As shown in the following formula, these exhaust gas treatment catalysts reduce NOx in the presence of a reducing agent such as ammonia, convert it into nitrogen gas, and purify it.
４ＮＯ＋４ＮＨ3＋Ｏ2 → ４Ｎ2＋６Ｈ2Ｏ ・・・・（１）
ＮＯ＋ＮＯ2＋２ＮＨ3 → ２Ｎ2＋３Ｈ2Ｏ ・・・・（２）
６ＮＯ2 ＋ ８ＮＨ3 → ７Ｎ2＋１２Ｈ2Ｏ ・・・・（３）
4NO + 4NH 3 + O 2 → 4N 2 + 6H 2 O (1)
NO + NO 2 + 2NH 3 → 2N 2 + 3H 2 O (2)
6NO 2 + 8NH 3 → 7N 2 + 12H 2 O (3)
また、モノリシス担体にゼオライト等の触媒活性を有する微粒子の担持層を形成した触媒も知られている。 Also known is a catalyst in which a carrier layer of fine particles having catalytic activity such as zeolite is formed on a monolysis support.
さらに、特開２００３−３３６６４号公報（特許文献１）には、排ガス浄化用ハニカム触媒のセル隔壁の主要構成材料として、アルミナ、ジルコニア、チタニア、ゼオライト、ＳｉＣ、ＳｉＮ、ムライト、リチウムアルミニウムシリケート（ＬＡＳ）、リン酸チタン、ペロブスカイト、スピネル、シャモット、無配向コージェライト等が使用でき、なかでも酸化チタン、ゼオライト、アルミナが好適に使用できることが記載されている。 Furthermore, Japanese Patent Laid-Open No. 2003-33664 (Patent Document 1) discloses alumina, zirconia, titania, zeolite, SiC, SiN, mullite, lithium aluminum silicate (LAS) as main constituent materials of the cell partition walls of the honeycomb catalyst for exhaust gas purification. ), Titanium phosphate, perovskite, spinel, chamotte, non-oriented cordierite, etc., among which titanium oxide, zeolite, and alumina can be preferably used.
ゼオライトとしては、Ｘ型、Ｙ型、ＺＳＭ−５型、β型等のものを用いることができるが、耐熱性の観点から、アルカリ成分の含有量は極力押さえることが重要であり、ＳｉＯ2／Ａｌ2Ｏ3比を２５以上とすることが好まく、また、ＡｌＰＯやＳＡＰＯ、メタロシリケート、層状化合物も好適に用いることができ、前述の触媒活性成分をイオン交換担持したものも、好適に用いられることが記載されている。 The zeolite, X-type, Y-type, ZSM-5 type, but can be used as the β type or the like, from the viewpoint of heat resistance, the content of alkali components, it is important to suppress as much as possible, SiO 2 / The Al 2 O 3 ratio is preferably 25 or more, and AlPO, SAPO, metallosilicate, and layered compounds can also be preferably used, and those having the above-mentioned catalytic active components supported by ion exchange are also preferably used. It is described that
特表２００９−５１９８１７号公報（特許文献２）には、ゼオライトの金属イオン交換をｐＨ３付近で行い、その後、５４０℃以上の高温で水熱処理した、水熱的に安定な選択的ＮＯｘ還元用金属処理ゼオライト触媒が開示されている。 JP-T-2009-519817 (Patent Document 2) discloses a hydrothermally stable selective NOx reducing metal obtained by performing metal ion exchange of zeolite in the vicinity of pH 3, followed by hydrothermal treatment at a high temperature of 540 ° C. or higher. A treated zeolite catalyst is disclosed.
また、再表２００６−０１１５７５号公報（特許文献３）には鉄イオン交換したβ型ゼオライト担体に酸化第二鉄を担持した脱硝触媒が開示されている。 Further, RE-Table 2006-011575 (Patent Document 3) discloses a denitration catalyst in which ferric oxide is supported on a β-type zeolite carrier subjected to iron ion exchange.
しかしながら、前記したゼオライトなどの従来の結晶質多孔性物質触媒は、水分が生成する反応で、且つ７００℃以上の高温で使用すると結晶性、比表面積が低下し、これに伴い活性が低下することから、水熱的に安定で、高活性を長期にわたって維持することのできる触媒が求められている。 However, conventional crystalline porous material catalysts such as zeolite described above are reactions in which moisture is generated, and when used at a high temperature of 700 ° C. or higher, the crystallinity and specific surface area decrease, and the activity decreases accordingly. Therefore, there is a need for a catalyst that is hydrothermally stable and can maintain high activity over a long period of time.
従来、結晶性シリカアルミノフォスフェートは、触媒担体として高温で使用しても比較的結晶性、比表面積の低下が小さく、安定であることが知られている。
結晶性シリカアルミノフォスフェートを担体とし、これに金属を担持した触媒の製造方法としては、結晶性アルミノシリケートと同様に、イオン交換法、含浸法、沈着法が知られているが、（１）金属塩水溶液でイオン交換する方法では、充分な活性が得られる量の金属を担持することができず、（２）金属塩水溶液中に結晶性シリカアルミノフォスフェートを分散させ、金属塩を加水分解して金属水酸化物を沈着させる方法では、結晶性シリカアルミノフォスフェートの結晶性が損なわれ、また、（３）結晶性シリカアルミノフォスフェートに金属塩を含浸する方法では、金属が結晶性シリカアルミノフォスフェートの細孔表面に均一に分散しないためか充分な活性が得られないという問題が判明した。
Conventionally, it is known that crystalline silica aluminophosphate is stable even if it is used as a catalyst carrier at a high temperature, with relatively little crystallinity and a decrease in specific surface area.
As a method for producing a catalyst in which a crystalline silica aluminophosphate is used as a carrier and a metal is supported thereon, an ion exchange method, an impregnation method, and a deposition method are known as in the case of the crystalline aluminosilicate. In the method of ion exchange with an aqueous metal salt solution, sufficient amount of metal cannot be supported, and (2) crystalline silica aluminophosphate is dispersed in the aqueous metal salt solution to hydrolyze the metal salt. In the method of depositing the metal hydroxide, the crystallinity of the crystalline silica aluminophosphate is impaired, and in the method of (3) impregnating the crystalline silica aluminophosphate with a metal salt, the metal is crystalline silica. The problem was that sufficient activity could not be obtained because the aluminophosphate was not uniformly dispersed on the pore surface.
そこで、本発明者らはさらに検討した結果、結晶性シリカアルミノフォスフェートを活性金属化合物水溶液に分散させ、これを噴霧乾燥した後高温で焼成すると、金属担持量が増大し、しかもこの方法で金属を担持した触媒は高温で水熱処理しても結晶性が大きく低下することなく高い活性を発現することを見出して本発明を完成するに至った。 Therefore, as a result of further studies, the present inventors have found that when the crystalline silica aluminophosphate is dispersed in an active metal compound aqueous solution, and this is spray-dried and then fired at a high temperature, the amount of supported metal increases, and in this method, the metal loading is increased. It has been found that a catalyst supporting bismuth exhibits high activity without a significant decrease in crystallinity even when hydrothermally treated at a high temperature, thereby completing the present invention.
本発明は、水熱安定性に優れ、長期にわたって高活性を維持することのできる金属担持触媒の製造方法および金属担持触媒を提供することを目的としている。 An object of the present invention is to provide a method for producing a metal-supported catalyst that is excellent in hydrothermal stability and can maintain high activity over a long period of time, and a metal-supported catalyst.
本発明に係る金属担持結晶性シリカアルミノフォスフェート触媒の製造方法は、下記の工程（ａ）〜（ｃ）、（ｅ）からなることを特徴としている。
（ａ）結晶性シリカアルミノフォスフェート粒子分散液を調製する工程
（ｂ）活性成分金属化合物水溶液を混合する工程
（ｃ）噴霧乾燥する工程
（ｅ）４００〜９００℃で加熱処理（焼成）する工程
The method for producing a metal-supported crystalline silica aluminophosphate catalyst according to the present invention comprises the following steps (a) to (c) and (e).
(A) Step for preparing crystalline silica aluminophosphate particle dispersion (b) Step for mixing active component metal compound aqueous solution (c) Step for spray drying (e) Step for heat treatment (firing) at 400 to 900 ° C.
前記工程（ｃ）についで下記の工程（ｄ）を行うことが好ましい。
（ｄ）洗浄する工程
前記結晶性シリカアルミノフォスフェート粒子が、合成後、洗浄および／または焼成したものであることが好ましい。
前記結晶性シリカアルミノフォスフェートがＳＡＰＯ−５、ＳＡＰＯ−１１、ＳＡＰＯ−３４、ＳＡＰＯ−３７から選ばれる１種以上であることが好ましい。
前記結晶性シリカアルミノフォスフェートがＳＡＰＯ−３４であることが好ましい。
前記活性成分金属化合物が、周期律表第８族、第９族、第１０族、第１１族、第１２族から選ばれる元素の化合物またはこれらの混合物（合金を含む）であることが好ましい。
前記活性成分金属の担持量が金属として０．１〜１０重量％の範囲にあることが好ましい。
Following the step (c), the following step (d) is preferably performed.
(D) Step of washing The crystalline silica aluminophosphate particles are preferably washed and / or baked after synthesis.
The crystalline silica aluminophosphate is preferably at least one selected from SAPO-5, SAPO-11, SAPO-34, and SAPO-37.
The crystalline silica aluminophosphate is preferably SAPO-34.
The active component metal compound is preferably a compound of an element selected from Group 8, Group 9, Group 10, Group 11, Group 12 of the periodic table, or a mixture thereof (including an alloy).
The supported amount of the active component metal is preferably in the range of 0.1 to 10% by weight as a metal.
本発明に係る金属担持結晶性シリカアルミノフォスフェート触媒は、
活性金属成分が担持された結晶性シリカアルミノフォスフェートからなる金属担持結晶性シリカアルミノフォスフェート触媒であって、(1)水分１０Ｖｏｌ％含有空気中、(2)温度７００℃、かつ(3)２０時間の条件で水熱処理した後の、ＢＥＴ法で測定した比表面積の保持率が８０％以上、かつ結晶性の保持率が８０％以上であることを特徴としている。
The metal-supported crystalline silica aluminophosphate catalyst according to the present invention is:
A metal-supported crystalline silica aluminophosphate catalyst comprising a crystalline silica aluminophosphate supported with an active metal component, comprising: (1) 10 vol% moisture in air, (2) a temperature of 700 ° C., and (3) 20 It is characterized by having a specific surface area retention of 80% or more and a crystallinity retention of 80% or more measured by the BET method after hydrothermal treatment under time conditions.
前記結晶性シリカアルミノフォスフェートがＳＡＰＯ−５、ＳＡＰＯ−１１、ＳＡＰＯ−３４、ＳＡＰＯ−３７から選ばれる１種以上であることが好ましい。
前記結晶性シリカアルミノフォスフェートがＳＡＰＯ−３４であることが好ましい。
前記活性金属成分が、周期律表第８族、第９族、第１０族、第１１族、第１２族から選ばれる元素の金属またはこれらの混合物（合金を含む）であることが好ましい。
前記活性金属成分の担持量が金属として０．１〜１０重量％の範囲にあることが好ましい。
The crystalline silica aluminophosphate is preferably at least one selected from SAPO-5, SAPO-11, SAPO-34, and SAPO-37.
The crystalline silica aluminophosphate is preferably SAPO-34.
The active metal component is preferably a metal of an element selected from Group 8, Group 9, Group 10, Group 11, Group 12 of the periodic table, or a mixture thereof (including an alloy).
The amount of the active metal component supported is preferably in the range of 0.1 to 10% by weight as a metal.
請求項１〜７のいずれかに記載の金属担持結晶性シリカアルミノフォスフェート触媒の製造方法によって得られた金属担持結晶性シリカアルミノフォスフェート触媒であることが好ましい。 It is preferable that it is a metal carrying crystalline silica aluminophosphate catalyst obtained by the manufacturing method of the metal carrying crystalline silica aluminophosphate catalyst in any one of Claims 1-7.
本発明によれば、概ね７００℃以上と云う超高温における水熱安定性に優れる金属担持結晶性シリカアルミノフォスフェート触媒および排ガス処理用ＮＯｘ還元触媒を提供することができる。また、本発明の金属担持結晶性シリカアルミノフォスフェート触媒および排ガス処理用ＮＯｘ還元触媒は、長期にわたって高活性を維持することができる。
本発明の金属担持結晶性シリカアルミノフォスフェート触媒の製造方法は、工程が簡略であり、経済性に優れている。
According to the present invention, it is possible to provide a metal-supported crystalline silica aluminophosphate catalyst and an NOx reduction catalyst for exhaust gas treatment that are excellent in hydrothermal stability at an ultrahigh temperature of approximately 700 ° C. or higher. In addition, the metal-supported crystalline silica aluminophosphate catalyst and the NOx reduction catalyst for exhaust gas treatment of the present invention can maintain high activity over a long period of time.
The method for producing a metal-supported crystalline silica aluminophosphate catalyst of the present invention has a simple process and is excellent in economic efficiency.
［金属担持結晶性シリカアルミノフォスフェート触媒の製造方法］
本発明に係る金属担持結晶性シリカアルミノフォスフェート触媒の製造方法は、下記の工程（ａ）〜（ｃ）、（ｅ）からなり、好ましくは工程（ｃ）と工程（ｅ）の間に工程（ｄ）を含むものである。
（ａ）結晶性シリカアルミノフォスフェート粒子分散液を調製する工程
（ｂ）活性成分金属化合物水溶液を混合する工程
（ｃ）噴霧乾燥する工程
（ｄ）洗浄する工程
（ｅ）４００〜９００℃で加熱処理（焼成）する工程
[Method of producing metal-supported crystalline silica aluminophosphate catalyst]
The method for producing a metal-supported crystalline silica aluminophosphate catalyst according to the present invention comprises the following steps (a) to (c) and (e), preferably a step between step (c) and step (e). (D) is included.
(A) Step of preparing crystalline silica aluminophosphate particle dispersion (b) Step of mixing active component metal compound aqueous solution (c) Step of spray drying (d) Step of washing (e) Heating at 400-900 ° C Process (baking)
工程（ａ）
結晶性シリカアルミノフォスフェート粒子分散液を調製する。
本発明に用いる結晶性シリカアルミノフォスフェート粒子としては従来公知の結晶性シリカアルミノフォスフェート粒子を用いることができる（U.S.Patent4,440,871, April 3,1984. Microporous and Mesoporous Materials 53 (2002) 97-108 ）。
Step (a)
A crystalline silica aluminophosphate particle dispersion is prepared.
As the crystalline silica aluminophosphate particles used in the present invention, conventionally known crystalline silica aluminophosphate particles can be used (US Patent 4,440,871, April 3,1984. Microporous and Mesoporous Materials 53 (2002) 97-108). .
結晶性シリカアルミノフォスフェートとしては、ＳＡＰＯ−５、ＳＡＰＯ−１１、ＳＡＰＯ−３４、ＳＡＰＯ−３７から選ばれる１種以上であることが好ましい。
なかでも、ＳＡＰＯ−３４は高温での熱的安定性、特に水熱安定性に優れ、ＳＣＲ触媒等として用いる場合、高い活性と選択性を示し、これを長く維持することができるので好適に用いることができる。
The crystalline silica aluminophosphate is preferably at least one selected from SAPO-5, SAPO-11, SAPO-34, and SAPO-37.
Among these, SAPO-34 is excellent in thermal stability at high temperatures, particularly hydrothermal stability, and when used as an SCR catalyst or the like, it exhibits high activity and selectivity and can be suitably used because it can be maintained for a long time. be able to.
結晶性シリカアルミノフォスフェートは、シリカ、アルミナおよび酸化燐からなる多孔質の結晶性複合酸化物である。
ＳＡＰＯ−３４の場合、シリカの含有量がＳｉＯ2として概ね１〜１２重量％、アルミナの含有量がＡｌ2Ｏ3として概ね３５〜４５重量％、酸化燐がＰ2Ｏ5として概ね４５〜５５重量％の範囲にあり、比表面積が概ね５００〜７５０ｍ2／ｇの範囲にある。
Crystalline silica aluminophosphate is a porous crystalline composite oxide composed of silica, alumina and phosphorus oxide.
For SAPO-34, generally 1 to 12% by weight content as SiO 2 of silica, approximately 35 to 45% by weight content of Al 2 O 3 alumina, generally phosphorus oxide as the P 2 O 5 45 to 55 The specific surface area is in the range of about 500 to 750 m 2 / g.
結晶性シリカアルミノフォスフェート粒子は、触媒の形態にもよるが、平均粒子径が０．１〜７μｍ、さらには０．２〜３μｍの範囲に有ることが好ましい。
結晶性シリカアルミノフォスフェート粒子の平均粒子径が０．２μｍ未満の場合は、水熱安定性が不充分となる場合がある。
結晶性シリカアルミノフォスフェート粒子の平均粒子径が７μｍを超えると、成型体として用いる場合、充分な強度、耐摩耗性等が得られない場合がある。
本発明での平均粒子径は、結晶性シリカアルミノフォスフェート粒子の走査型電子顕微鏡写真（ＳＥＭ）を撮影し、任意の１００個の粒子について粒子径を測定し、その平均値として求める。
Although the crystalline silica aluminophosphate particles depend on the form of the catalyst, the average particle diameter is preferably in the range of 0.1 to 7 μm, more preferably 0.2 to 3 μm.
When the average particle diameter of the crystalline silica aluminophosphate particles is less than 0.2 μm, the hydrothermal stability may be insufficient.
When the average particle diameter of the crystalline silica aluminophosphate particles exceeds 7 μm, sufficient strength and wear resistance may not be obtained when used as a molded product.
The average particle diameter in the present invention is obtained as an average value obtained by taking a scanning electron micrograph (SEM) of crystalline silica aluminophosphate particles, measuring the particle diameter of 100 arbitrary particles, and measuring the particle diameter.
このような結晶性シリカアルミノフォスフェート粒子は、通常、シリカ源、アルミナ源、酸化燐源および有機結晶化剤（テンプレートということがある。）の混合物を水熱処理して合成され、合成後は通常、有機結晶化剤を含有している。
有機結晶化剤としては、テトラエチルアンモニウムハイドロオキサイド、イソプロピルアンミニウムハイドロオキサイド等が用いられる。
通常、この有機結晶化剤を５００〜６００℃で焼成して除去し、金属を担持する等して使用される。
Such crystalline silica aluminophosphate particles are usually synthesized by hydrothermal treatment of a mixture of a silica source, an alumina source, a phosphorus oxide source and an organic crystallization agent (sometimes referred to as a template), and after synthesis, Contains an organic crystallization agent.
As the organic crystallization agent, tetraethylammonium hydroxide, isopropylammonium hydroxide, or the like is used.
Usually, the organic crystallization agent is removed by baking at 500 to 600 ° C., and a metal is supported.
本発明では、焼成した結晶性シリカアルミノフォスフェート粒子を用いることができるが、合成後、洗浄し、必要に応じて乾燥した結晶性シリカアルミノフォスフェート粒子、即ち、有機結晶化剤を含有した結晶性シリカアルミノフォスフェート粒子をそのまま用いることができる。
有機結晶化剤を含有した結晶性シリカアルミノフォスフェート粒子をそのまま用いると、理由は明らかではないが高温での水熱安定性が向上し、活性、選択性が向上することに加えて、有機結晶化剤を除去するための焼成工程がなくなることから生産性、経済性が向上する利点がある。
In the present invention, calcined crystalline silica aluminophosphate particles can be used, but after the synthesis, the crystalline silica aluminophosphate particles that are washed and dried as necessary, that is, crystals containing an organic crystallization agent. Silica aluminophosphate particles can be used as they are.
If crystalline silica aluminophosphate particles containing an organic crystallization agent are used as they are, the reason is not clear, but hydrothermal stability at high temperature is improved, and activity and selectivity are improved. Since the firing step for removing the agent is eliminated, there is an advantage that productivity and economy are improved.
このような結晶性シリカアルミノフォスフェート粒子を水に分散させて分散液を調製する。
結晶性シリカアルミノフォスフェート粒子分散液の濃度は、後述する活性成分金属化合物水溶液と混合でき、後述する噴霧乾燥用混合分散液の濃度に調整できれば特に制限はない。
Such crystalline silica aluminophosphate particles are dispersed in water to prepare a dispersion.
The concentration of the crystalline silica aluminophosphate particle dispersion is not particularly limited as long as it can be mixed with an aqueous solution of an active ingredient metal compound described later and can be adjusted to the concentration of the mixed dispersion for spray drying described later.
工程（ｂ）
活性成分金属化合物水溶液を混合する。
本発明に用いる活性成分金属としては、周期律表第８族、第９族、第１０族、第１１族、第１２族から選ばれる元素の金属またはこれらの混合物（合金を含む）が用いられる。このため、活性成分金属としては、周期律表第８族の金属としてＦｅ、Ｒｕが挙げられ、金属化合物として具体的には硝酸鉄、酢酸鉄、塩化鉄、硫酸第一鉄、硫酸第二鉄、硝酸ルテニウム、塩化ルテニウム等が挙げられる。
Step (b)
The aqueous solution of the active ingredient metal compound is mixed.
As the active component metal used in the present invention, a metal of an element selected from Group 8, Group 9, Group 10, Group 11, Group 12 of the periodic table, or a mixture thereof (including an alloy) is used. . For this reason, examples of the active component metal include Fe and Ru as metals of Group 8 of the periodic table. Specific examples of metal compounds include iron nitrate, iron acetate, iron chloride, ferrous sulfate, and ferric sulfate. , ruthenium nitrate, ruthenium chloride and the like.
周期律表第９族の金属としてはＣｏ、Ｒｈ、Ｉｒが挙げられ、金属化合物として具体的には硝酸コバルト、塩化コバルト、蓚酸コバルト、硫酸コバルト、硝酸ロジウム、硝酸イリジウム等が挙げられる。
周期律表第１０族の金属としてはＮｉ、Ｐｄ、Ｐｔが挙げられ、金属化合物として具体的には硝酸ニッケル、酢酸ニッケル、炭酸ニッケル、塩化ニッケル、硝酸パラジウム、塩化白金酸等が挙げられる。
周期律表第１１族の金属としてはＣｕ、Ａｇ、Ａｕが挙げられ、金属化合物として具体的には硝酸第二銅、硝酸銀、塩化金酸等が挙げられる。
周期律表第１２族の金属としてはＺｎ、Ｃｄが挙げられ、金属化合物として具体的には硝酸亜鉛、硝酸カドミウム等が挙げられる。
Examples of metals in Group 9 of the periodic table include Co, Rh, and Ir. Specific examples of metal compounds include cobalt nitrate, cobalt chloride, cobalt oxalate, cobalt sulfate, rhodium nitrate, and iridium nitrate.
Examples of metals in Group 10 of the periodic table include Ni, Pd, and Pt. Specific examples of metal compounds include nickel nitrate, nickel acetate, nickel carbonate, nickel chloride, palladium nitrate, and chloroplatinic acid.
Examples of the metal belonging to Group 11 of the periodic table include Cu, Ag, and Au. Specific examples of the metal compound include cupric nitrate, silver nitrate, and chloroauric acid.
Examples of the metal of Group 12 of the periodic table include Zn and Cd, and specific examples of the metal compound include zinc nitrate and cadmium nitrate.
このような金属化合物の水溶液を調製し、工程（ａ）で調製した結晶性シリカアルミノフォスフェート粒子分散液と混合して、噴霧乾燥用の結晶性シリカアルミノフォスフェート粒子と金属化合物との混合分散液を調製する。 An aqueous solution of such a metal compound is prepared and mixed with the crystalline silica aluminophosphate particle dispersion prepared in step (a) to mix and disperse the crystalline silica aluminophosphate particles for spray drying and the metal compound. Prepare the solution.
本発明では、有機結晶化剤を含有した結晶性シリカアルミノフォスフェート粒子をそのまま用いた場合、分散液のｐＨが高くなり、後述する使用する金属化合物の種類によっては沈殿を生成し、結晶性シリカアルミノフォスフェートに活性金属を均一に担持できないために活性が不充分となる場合がある。
このため、金属化合物の種類によっても異なるが、混合分散液のｐＨを概ね１〜６に調整しておくことが好ましい。
In the present invention, when crystalline silica aluminophosphate particles containing an organic crystallization agent are used as they are, the pH of the dispersion becomes high, and depending on the type of metal compound to be used later, a precipitate is formed. The active metal may not be uniformly supported on the aluminophosphate, so that the activity may be insufficient.
For this reason, although it changes also with the kind of metal compound, it is preferable to adjust pH of a mixed dispersion to about 1-6.
結晶性シリカアルミノフォスフェート粒子と金属化合物の混合割合は、最終的に得られる金属担持結晶性シリカアルミノフォスフェート触媒中の金属の含有量が０．１〜１０重量％、さらには０．２〜８重量％の範囲となるように混合する。
金属担持結晶性シリカアルミノフォスフェート触媒中の金属の含有量が０．１重量％未満の場合は、ＮＯｘの還元反応に用いた場合、低温（１００〜２５０℃）での活性が不十分となる場合があり、また、本発明の方法によらずとも同様の性能を有する触媒を得ることができる。
金属担持結晶性シリカアルミノフォスフェート触媒中の金属の含有量が１０重量％を超えると、金属の分散担持が困難であり、できたとしてもさらに活性が向上することもなく、寧ろ活性が低下する場合がある。
The mixing ratio of the crystalline silica aluminophosphate particles and the metal compound is such that the metal content in the finally obtained metal-supported crystalline silica aluminophosphate catalyst is 0.1 to 10% by weight, more preferably 0.2 to Mix so as to be in the range of 8% by weight.
When the metal content in the metal-supported crystalline silica aluminophosphate catalyst is less than 0.1% by weight, the activity at low temperatures (100 to 250 ° C.) becomes insufficient when used for the reduction reaction of NOx. In some cases, a catalyst having the same performance can be obtained without using the method of the present invention.
If the metal content in the metal-supported crystalline silica aluminophosphate catalyst exceeds 10% by weight, it is difficult to disperse and support the metal, and even if it can, the activity will not be improved, but rather the activity will decrease. There is a case.
噴霧乾燥用混合分散液の濃度は、結晶性シリカアルミノフォスフェート粒子の固形分濃度として1〜３５重量％、さらには２〜２０重量％の範囲にあることが好ましい。
噴霧乾燥用混合分散液の濃度が、結晶性シリカアルミノフォスフェート粒子の固形分濃度として１重量％未満の場合は、生産性、経済性が低下し、３５重量％を超えると、理由は明らかではないが活性が不充分となる場合がある。
The concentration of the mixed dispersion for spray drying is preferably in the range of 1 to 35% by weight, more preferably 2 to 20% by weight, as the solid content concentration of the crystalline silica aluminophosphate particles.
When the concentration of the spray-dispersed mixed dispersion is less than 1% by weight as the solid content concentration of the crystalline silica aluminophosphate particles, the productivity and economy are reduced, and when it exceeds 35% by weight, the reason is not clear. Although there is no activity, the activity may be insufficient.
工程（ｃ）
ついで、噴霧乾燥する。
噴霧乾燥方法としては、所定量の金属を担持できれば特に制限はなく、従来公知の方法を採用することができる。
例えば、噴霧乾燥用混合分散液をノズル、アトマイザー等により熱風中に噴霧する。
熱風の温度は８０〜５００℃、さらには１２０〜４００℃の範囲にあることが好ましい。
Step (c)
Then spray dry.
The spray drying method is not particularly limited as long as a predetermined amount of metal can be supported, and a conventionally known method can be employed.
For example, the spray-dispersed mixed dispersion is sprayed into hot air using a nozzle, an atomizer, or the like.
The temperature of the hot air is preferably in the range of 80 to 500 ° C, more preferably 120 to 400 ° C.
熱風の温度が８０℃未満の場合は、乾燥が不充分となり、金属成分を固定できず、再度、他の方法による乾燥を必要とし、この場合、金属成分の担持が不均一になるためか活性が不充分となる場合がある。また、金属化合物の濃縮が起きないためか、所望の金属担持量とならない場合があり、このため活性が不充分となる場合がある。さらに、後述する工程（ｄ）で洗浄する場合、金属成分が除去される場合がある。
熱風の温度が５００℃を超えても、金属成分の固定効果、他の担持方法に比して金属担持量を増加させる効果、細孔内に均一に担持できる効果等がさらに向上することもない。
When the temperature of the hot air is less than 80 ° C., the drying becomes insufficient, the metal component cannot be fixed, and it is necessary to dry again by another method. In this case, the loading of the metal component is not uniform. May be insufficient. In addition, the concentration of the metal compound may not occur, or the desired metal loading may not be achieved, and thus the activity may be insufficient. Further, when washing is performed in step (d) described later, the metal component may be removed.
Even when the temperature of the hot air exceeds 500 ° C., the effect of fixing the metal component, the effect of increasing the amount of metal supported compared to other supporting methods, the effect of being uniformly supported in the pores, etc. are not further improved. .
工程（ｄ）
噴霧乾燥して得た粉末は、洗浄することができる。本工程（ｄ）は任意工程であるが、特に前記工程（ｂ）で金属化合物として硝酸塩以外の硫酸塩、塩酸塩等を用いた場合は、本工程（ｄ）で洗浄することが好ましい。噴霧乾燥後、洗浄することによって硫酸根、塩素等を選択的に除去することができ、除去しない場合に比して活性に優れた触媒を得ることができる。
Step (d)
The powder obtained by spray drying can be washed. Although this step (d) is an optional step, in particular, when a sulfate other than nitrate is used as the metal compound in step (b), a hydrochloride, etc., it is preferable to wash in this step (d). After spray drying, washing can selectively remove sulfate radicals, chlorine, and the like, and a catalyst excellent in activity can be obtained as compared with the case where it is not removed.
洗浄方法としては、特に金属化合物のアニオンを選択的に除去できれば特に制限はなく、例えば、噴霧乾燥して得た粉末を水、あるいは温水に懸濁し、攪拌後、濾過することにより洗浄することができる。
洗浄後、乾燥する。乾燥方法は乾燥後の水分が概ね２０重量％以下になれば特に制限はなく、従来公知の乾燥方法を採用することができる。例えば、乾燥機中、１００〜１５０℃で０．５〜２時間程度乾燥すればよい。
The washing method is not particularly limited as long as the anion of the metal compound can be selectively removed. For example, the powder obtained by spray drying can be washed by suspending in water or warm water, stirring, and filtering. it can.
Dry after washing. The drying method is not particularly limited as long as the moisture after drying is approximately 20% by weight or less, and a conventionally known drying method can be employed. For example, what is necessary is just to dry for about 0.5 to 2 hours at 100-150 degreeC in dryer.
工程（ｅ）
ついで、加熱処理（焼成）する。
加熱処理温度は４００〜９００℃、さらには５００〜８００℃の範囲にあることが好ましい。
加熱処理温度が４００℃未満の場合は、有機結晶化剤を除去できないために活性が不充分となる場合があり、加熱処理温度が９００℃を超えると活性が不充分となる場合がある。
Step (e)
Next, heat treatment (firing) is performed.
The heat treatment temperature is preferably 400 to 900 ° C, more preferably 500 to 800 ° C.
When the heat treatment temperature is less than 400 ° C., the activity may be insufficient because the organic crystallization agent cannot be removed, and when the heat treatment temperature exceeds 900 ° C., the activity may be insufficient.
加熱処理する際の雰囲気は、酸化雰囲気下、好ましくは空気中で行うことが経済的で好ましい。なお、本発明では、酸化雰囲気での加熱処理についで還元雰囲気下、例えば水素ガス雰囲気下で加熱処理しても良く、その場合は予め還元処理された金属担持結晶性シリカアルミノフォスフェート触媒を得ることができる。
還元処理は例えば、通常３００〜６００℃で０．５〜５時間、水素ガスを供給しながら処理する。
It is economical and preferable to perform the heat treatment in an oxidizing atmosphere, preferably in the air. In the present invention, the heat treatment in an oxidizing atmosphere may be followed by a heat treatment in a reducing atmosphere, for example, in a hydrogen gas atmosphere. In this case, a metal-supported crystalline silica aluminophosphate catalyst that has been previously reduced is obtained. be able to.
For example, the reduction treatment is usually performed at 300 to 600 ° C. for 0.5 to 5 hours while supplying hydrogen gas.
［金属担持結晶性シリカアルミノフォスフェート触媒］
上記製造方法によって得られた金属担持結晶性シリカアルミノフォスフェート触媒は、水熱安定性に優れている。
即ち、本発明の金属担持結晶性シリカアルミノフォスフェート触媒は、(1)水分１０Ｖｏｌ％含有空気中、(2)温度７００℃、かつ(3)２０時間の条件で水熱処理した後の、ＢＥＴ法で測定した比表面積の保持率が８０％以上、さらには８５％以上となる。
水熱処理後の、ＢＥＴ法で測定した比表面積の保持率が８０％未満の場合は、活性が不充分となる場合がある。なお、比表面積の保持率とは水熱処理前後の比表面積の割合である。さらに、粉体で対比してもよく、後述する成型体で対比してもよい。
[Metal-supported crystalline silica aluminophosphate catalyst]
The metal-supported crystalline silica aluminophosphate catalyst obtained by the above production method is excellent in hydrothermal stability.
That is, the metal-supported crystalline silica aluminophosphate catalyst of the present invention is obtained by the BET method after (1) hydrothermal treatment under the conditions of (2) temperature 700 ° C. and (3) 20 hours in air containing 10 vol% of water. The retention ratio of the specific surface area measured in (1) is 80% or more, and further 85% or more.
When the retention ratio of the specific surface area measured by the BET method after hydrothermal treatment is less than 80%, the activity may be insufficient. The specific surface area retention is the ratio of the specific surface area before and after hydrothermal treatment. Furthermore, it may be compared with powder, or may be compared with a molded body described later.
また、本発明の金属担持結晶性シリカアルミノフォスフェート触媒は、水熱処理後の結晶性の保持率が８０％以上であり、さらには８５％以上であることが好ましい。
水熱処理後の結晶性の保持率が８０％未満の場合は、活性が不充分となる場合がある。
なお、結晶性の保持率とは水熱処理前後の結晶性の割合である。さらに、粉体で対比してもよく、後述する成型体で対比してもよい。
The metal-supported crystalline silica aluminophosphate catalyst of the present invention has a crystallinity retention of 80% or more after hydrothermal treatment, and preferably 85% or more.
When the crystallinity retention after hydrothermal treatment is less than 80%, the activity may be insufficient.
The crystallinity retention is the ratio of crystallinity before and after hydrothermal treatment. Furthermore, it may be compared with powder, or may be compared with a molded body described later.
なお、水熱処理後の結晶性の保持率の基準は、６００℃で２時間焼成した金属担持結晶性シリカアルミノフォスフェート触媒のＸ線回折スペクトルの主ピーク（ＳＡＰＯ−５の場合は２θ＝７．５０°、ＳＡＰＯ−１１の場合は２θ＝２１．９５°、ＳＡＰＯ−３４の場合は、２θ＝９．５０°、ＳＡＰＯ−３７の場合は、２θ＝６．２０°）のピーク高さを基準とし、本発明の実施例では実施例１の金属担持結晶性シリカアルミノフォスフェート触媒を基準の１とした。 The standard of the crystallinity retention rate after hydrothermal treatment is the main peak of the X-ray diffraction spectrum of the metal-supported crystalline silica aluminophosphate catalyst calcined at 600 ° C. for 2 hours (2θ = 7.7 in the case of SAPO-5). 50 °, 2θ = 2.95 ° for SAPO-11, 2θ = 9.50 ° for SAPO-34, 2θ = 6.20 ° for SAPO-37) In the examples of the present invention, the metal-supported crystalline silica aluminophosphate catalyst of Example 1 was set to 1.
なお、本発明では、前記工程（ｃ）、工程（ｄ）、工程（ｅ）のいずれかの後、金属担持結晶性シリカアルミノフォスフェート粉末を所望の形状に成型して用いることができる。
例えば、ペレット、ビード、板状、ハニカム等に従来公知の成型方法で成型することができる。また、ハニカムの場合はハニカム状の金属基材、あるいはセラミックス基材表面にウオッシュコート法等で金属担持結晶性シリカアルミノフォスフェート触媒層を形成してもよい。成型体を得る際は、従来公知のバインダー、成型助剤等を使用することができる。
In the present invention, the metal-supported crystalline silica aluminophosphate powder can be molded into a desired shape after any of the steps (c), (d), and (e).
For example, it can be molded into pellets, beads, plates, honeycombs, etc. by a conventionally known molding method. In the case of a honeycomb, a metal-supported crystalline silica aluminophosphate catalyst layer may be formed on the surface of a honeycomb-shaped metal substrate or ceramic substrate by a wash coat method or the like. When obtaining a molded body, conventionally known binders, molding aids, and the like can be used.
［排ガス処理用ＮＯｘ還元触媒］
本発明に係る金属担持結晶性シリカアルミノフォスフェート触媒は、アンモニアなどの還元剤の存在下でＮＯｘを還元して窒素ガスに変換して排ガスを浄化する触媒として好適に用いることができる。
[NOx reduction catalyst for exhaust gas treatment]
The metal-supported crystalline silica aluminophosphate catalyst according to the present invention can be suitably used as a catalyst for purifying exhaust gas by reducing NOx in the presence of a reducing agent such as ammonia to convert it into nitrogen gas.
［参考例１］
金属担持結晶性シリカアルミノフォスフェート触媒(1)の調製
結晶性シリカアルミノフォスフェート(1)の調製
濃度７５重量％のリン酸水溶液８０７．３ｇと純水２０６０．７ｇとを混合して、濃度２１．１重量％のリン酸水溶液２８６８ｇを調製した。これに、濃度３５重量％のテトラエチルアンモニウムハイドロオキサイド（ＴＥＡＨ）９７４．９ｇを混合し、ついで、アルミナ源として擬ベーマイト粉末（Ａｌ２Ｏ３含有量７４重量％）４４０．５ｇを１０分程度で分散させ、分散液を１５分間攪拌した。
ついで、分散液にシリカ源としてシリカゾル（日揮触媒化成（株）製：ＳＩ−３０、ＳｉＯ２濃度３０重量％）２１６．５ｇを約１０分間で添加して、結晶性シリカアルミノフォスフェート合成用スラリー(1)を調製した。
[ Reference Example 1 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (1)
Preparation of crystalline silica aluminophosphate (1) 807.3 g of 75% by weight phosphoric acid aqueous solution and 2060.7 g of pure water were mixed to prepare 2868 g of 21.1% by weight phosphoric acid aqueous solution. This was mixed with 974.9 g of 35% by weight tetraethylammonium hydroxide (TEAH), and then 440.5 g of pseudoboehmite powder (Al 2 O 3 content 74 wt%) was dispersed in about 10 minutes as an alumina source. And the dispersion was stirred for 15 minutes.
Next, 216.5 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-30, SiO 2 concentration 30% by weight) as a silica source was added to the dispersion in about 10 minutes, and a slurry for synthesizing crystalline silica aluminophosphate. (1) was prepared.
ついで、結晶性シリカアルミノフォスフェート合成用スラリー(1)をオートクレーブに充填し、１時間攪拌後、１７０℃に昇温し４８時間水熱処理した。
その後、濾過分離し、６０℃の温水を十分掛け水して洗浄し、１３０℃で２４時間乾燥した。ついで、空気中６００℃で２時間焼成して結晶性シリカアルミノフォスフェート(1)を調製した。
結晶性シリカアルミノフォスフェート(1)の組成および平均粒粒子径を測定し、結果を表に示した。また、比表面積は６００ｍ2／ｇであった。
Next, the slurry for synthesizing crystalline silica aluminophosphate (1) was filled in an autoclave, stirred for 1 hour, heated to 170 ° C. and hydrothermally treated for 48 hours.
Thereafter, the mixture was separated by filtration, sufficiently washed with 60 ° C. warm water, and dried at 130 ° C. for 24 hours. Subsequently, it was calcined in air at 600 ° C. for 2 hours to prepare crystalline silica aluminophosphate (1).
The composition and average particle size of the crystalline silica aluminophosphate (1) were measured, and the results are shown in the table. The specific surface area was 600 m 2 / g.
得られた結晶性シリカアルミノフォスフェート(1)５００ｇを水２５００ｇに分散させ、コロイドミル処理して結晶性シリカアルミノフォスフェート(1)分散液を調製した。
別途、硝酸第二銅３水和物５８．８ｇを水２５００ｇに溶解して硝酸銅水溶液を調製した。
硝酸銅水溶液に結晶性シリカアルミノフォスフェート(1)分散液を混合して噴霧乾燥用混合分散液を調製した。この時、分散液のｐＨは３．５であった。
500 g of the obtained crystalline silica aluminophosphate (1) was dispersed in 2500 g of water and subjected to colloid mill treatment to prepare a crystalline silica aluminophosphate (1) dispersion.
Separately, 58.8 g of cupric nitrate trihydrate was dissolved in 2500 g of water to prepare an aqueous copper nitrate solution.
Crystalline silica aluminophosphate (1) dispersion was mixed with copper nitrate aqueous solution to prepare a mixed dispersion for spray drying. At this time, the pH of the dispersion was 3.5.
ついで、噴霧乾燥用混合分散液を熱風温度２３０℃の噴霧乾燥機中に回転数７０００ｒｐｍのアトマイザーにて噴霧し、得られた粉末を６００℃で２時間焼成して金属担持結晶性シリカアルミノフォスフェート触媒(1)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(1)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
Next, the spray-dispersed mixed dispersion was sprayed in a spray dryer having a hot air temperature of 230 ° C. with an atomizer having a rotation speed of 7000 rpm, and the obtained powder was fired at 600 ° C. for 2 hours to form a metal-supported crystalline silica aluminophosphate. Catalyst (1) was prepared.
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (1) were measured, and the results are shown in the table.
ＮＯｘ除去試験
金属担持結晶性シリカアルミノフォスフェート触媒(1)とバインダーとしてアルミナ粉末（日揮触媒化成（株）製：ＡＰ−１）を固形分重量比で８０/２０の割合で混合し、これに水を加え、充分に混練し、ついで押出成型器（ノズル径３ｍｍφ）にて成型した後、１３０℃で２４時間乾燥し、粉砕して径が３〜５ｍｍの粒子に調製、６００℃で２時間焼成して、試験用金属担持結晶性シリカアルミノフォスフェート触媒(1)を得た。
NOx removal test Metal-supported crystalline silica aluminophosphate catalyst (1) and alumina powder (manufactured by JGC Catalysts & Chemicals Co., Ltd .: AP-1) as a binder were mixed at a solid content weight ratio of 80/20. Add water, knead well, then mold with an extruder (nozzle diameter 3 mmφ), then dry at 130 ° C. for 24 hours, pulverize to prepare particles with a diameter of 3-5 mm, 600 ° C. for 2 hours Calcination gave a test metal-supported crystalline silica aluminophosphate catalyst (1).
試験用金属担持結晶性シリカアルミノフォスフェート触媒(1)１０ｃｃを常圧固定床流通式反応管に充填し、反応ガス（ＮＯ：５００ｐｐｍ、ＮＨ3：５００ｐｐｍ、Ｏ2：１０ｖｏｌ％、Ｎ2：バランス）を６０００ｃｃ／ｍｉｎで流通させながら、反応温度１５０℃、２００℃、３００℃、４００℃の各温度で定常状態になった時点でのＮＯｘ除去率を下記式によって求め、結果を表に示した。
Ｘ＝［({ＮＯｘ}in−{ＮＯｘ}out)／{ＮＯｘ}in］Ｘ１００
ここで、ＸはＮＯｘ除去率（％）、{ＮＯｘ}inは入り口の窒素酸化物ガス濃度、{ＮＯｘ}outは出口の窒素酸化物ガス濃度を示す。
A test metal-supported crystalline silica aluminophosphate catalyst (1) 10 cc was charged into a normal pressure fixed bed flow type reaction tube, and reaction gas (NO: 500 ppm, NH 3 : 500 ppm, O 2 : 10 vol%, N 2 : balance) ) At a reaction temperature of 150 ° C., 200 ° C., 300 ° C., and 400 ° C., the NOx removal rate was determined by the following formula, and the results are shown in the table. .
X = [({NOx} in− {NOx} out) / {NOx} in] X100
Here, X is the NOx removal rate (%), {NOx} in is the nitrogen oxide gas concentration at the inlet, and {NOx} out is the nitrogen oxide gas concentration at the outlet.
耐水熱性の測定
上記と同様にして調製した試験用金属担持結晶性シリカアルミノフォスフェート触媒(1)５０ｃｃを水熱処理反応官に充填し、７００℃に昇温した後、水分を１０ｖｏｌ％含む空気を５０ｃｃ／ｍｉｎで供給しながら２０時間水熱処理した。
水熱処理した試験用金属担持結晶性シリカアルミノフォスフェート触媒(1)の比表面積を測定し、６００℃で２時間焼成して得た試験用金属担持結晶性シリカアルミノフォスフェート触媒(1)の比表面積（表に示す）と対比し、比表面積保持率として結果を表に示した。
Hydrothermal resistance measurement 50cc of a test metal-supported crystalline silica aluminophosphate catalyst (1) prepared in the same manner as described above was charged in a hydrothermal treatment reactor, heated to 700 ° C, and then air containing 10 vol% of water was added. Hydrothermal treatment was performed for 20 hours while supplying at 50 cc / min.
The specific surface area of the hydrothermally-treated test metal-supported crystalline silica aluminophosphate catalyst (1) was measured, and the ratio of the test metal-supported crystalline silica aluminophosphate catalyst (1) obtained by calcining at 600 ° C. for 2 hours. The results are shown in the table as the specific surface area retention ratio in comparison with the surface area (shown in the table).
また、Ｘ線回折により、水熱処理した試験用金属担持結晶性シリカアルミノフォスフェート触媒(1)および６００℃で２時間焼成して得た試験用金属担持結晶性シリカアルミノフォスフェート触媒(1)の２θ＝９．５０°のピーク高さを測定し、ピーク高さを対比し、結晶性保持率として表に示した。
また、前記耐水熱性の測定で水熱処理した試験用金属担持結晶性シリカアルミノフォスフェート触媒(1)について、前記と同様にＮＯｘ除去試験を行い、結果を表に示した。
Further, by X-ray diffraction, a test metal-supported crystalline silica aluminophosphate catalyst (1) hydrothermally treated and a test metal-supported crystalline silica aluminophosphate catalyst (1) obtained by calcination at 600 ° C. for 2 hours were obtained. The peak height of 2θ = 9.50 ° was measured, the peak heights were compared, and the crystallinity retention was shown in the table.
The test metal-supported crystalline silica aluminophosphate catalyst (1) hydrothermally treated by the hydrothermal resistance measurement was subjected to a NOx removal test in the same manner as described above, and the results are shown in the table.
［参考例２］
金属担持結晶性シリカアルミノフォスフェート触媒(2)の調製
参考例１において、洗浄した後、乾燥および焼成しなかった以外は同様にして結晶性シリカアルミノフォスフェート(2)を調製した。
ついで、洗浄して得られた結晶性シリカアルミノフォスフェート(2)の固形分濃度１６．７重量％の分散液３０００ｇを調製し、コロイドミル処理して結晶性シリカアルミノフォスフェート(2)分散液を調製した。
別途、硝酸第二銅３水和物６８．６ｇを水２５００ｇに溶解して硝酸銅水溶液を調製した。
ついで、結晶性シリカアルミノフォスフェート(2)分散液に希硝酸を加えてｐＨを３．５に維持しながら硝酸銅水溶液を混合して噴霧乾燥用混合分散液を調製した。
[ Reference Example 2 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (2)
Crystalline silica aluminophosphate (2) was prepared in the same manner as in Reference Example 1 , except that it was not dried and fired after washing.
Next, 3000 g of a dispersion of crystalline silica aluminophosphate (2) having a solid content concentration of 16.7% by weight obtained by washing was prepared and subjected to colloid mill treatment to obtain a dispersion of crystalline silica aluminophosphate (2). Was prepared.
Separately, 68.6 g of cupric nitrate trihydrate was dissolved in 2500 g of water to prepare an aqueous copper nitrate solution.
Next, a dilute nitric acid was added to the crystalline silica aluminophosphate (2) dispersion, and the aqueous solution of copper nitrate was mixed while maintaining the pH at 3.5 to prepare a mixed dispersion for spray drying.
ついで、参考例１と同様に噴霧乾燥、焼成して金属担持結晶性シリカアルミノフォスフェート触媒(2)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(2)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(2)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
Next, spray-dried and calcined in the same manner as in Reference Example 1 to prepare a metal-supported crystalline silica aluminophosphate catalyst (2).
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (2) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (2) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［参考例３］
金属担持結晶性シリカアルミノフォスフェート触媒(3)の調製
参考例１において、硝酸第二銅３水和物２５．５ｇを用いた以外は同様にして金属担持結晶性シリカアルミノフォスフェート触媒(3)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(3)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(3)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
[ Reference Example 3 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (3)
A metal-supported crystalline silica aluminophosphate catalyst (3) was prepared in the same manner as in Reference Example 1 except that 25.5 g of cupric nitrate trihydrate was used.
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (3) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (3) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［参考例４］
金属担持結晶性シリカアルミノフォスフェート触媒(4)の調製
参考例１において、硝酸第二銅３水和物１３７ｇを用いた以外は同様にして金属担持結晶性シリカアルミノフォスフェート触媒(4)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(4)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(4)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
[ Reference Example 4 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (4)
A metal-supported crystalline silica aluminophosphate catalyst (4) was prepared in the same manner as in Reference Example 1 except that 137 g of cupric nitrate trihydrate was used.
The Cu content and specific surface area of copper in the resulting metal-supported crystalline silica aluminophosphate catalyst (4) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (4) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［参考例５］
金属担持結晶性シリカアルミノフォスフェート触媒(5)の調製
参考例１において、噴霧乾燥温度を１２０℃とした以外は同様にして金属担持結晶性シリカアルミノフォスフェート触媒(5)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(5)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(5)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
[ Reference Example 5 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (5)
A metal-supported crystalline silica aluminophosphate catalyst (5) was prepared in the same manner as in Reference Example 1 except that the spray drying temperature was 120 ° C.
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (5) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (5) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［参考例６］
金属担持結晶性シリカアルミノフォスフェート触媒(6)の調製
参考例１において、噴霧乾燥温度を２５０℃とした以外は同様にして金属担持結晶性シリカアルミノフォスフェート触媒(6)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(6)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(6)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
[ Reference Example 6 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (6)
A metal-supported crystalline silica aluminophosphate catalyst (6) was prepared in the same manner as in Reference Example 1 except that the spray drying temperature was 250 ° C.
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (6) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (6) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［参考例７］
金属担持結晶性シリカアルミノフォスフェート触媒(7)の調製
参考例１において、焼成温度を４００℃とした以外は同様にして金属担持結晶性シリカアルミノフォスフェート触媒(7)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(7)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(7)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
[ Reference Example 7 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (7)
A metal-supported crystalline silica aluminophosphate catalyst (7) was prepared in the same manner as in Reference Example 1 except that the calcination temperature was 400 ° C.
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (7) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (7) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［参考例８］
金属担持結晶性シリカアルミノフォスフェート触媒(8)の調製
参考例１において、焼成温度を７００℃とした以外は同様にして金属担持結晶性シリカアルミノフォスフェート触媒(8)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(8)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(8)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
[ Reference Example 8 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (8)
A metal-supported crystalline silica aluminophosphate catalyst (8) was prepared in the same manner as in Reference Example 1 except that the calcination temperature was 700 ° C.
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (8) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (8) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［参考例９］
金属担持結晶性シリカアルミノフォスフェート触媒(9)の調製
参考例１において、硝酸第二銅３水和物５８．８ｇの代わりに硝酸第一鉄６水和物８０ｇ用いた以外は同様にして金属担持結晶性シリカアルミノフォスフェート触媒(9)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(9)中の鉄のＦｅとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(9)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
[ Reference Example 9 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (9)
In Example 1 , a metal-supported crystalline silica aluminophosphate catalyst (9) was prepared in the same manner except that 80 g of ferrous nitrate hexahydrate was used instead of 58.8 g of cupric nitrate trihydrate. .
The content of iron as Fe and the specific surface area of the obtained metal-supported crystalline silica aluminophosphate catalyst (9) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (9) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［実施例１］
金属担持結晶性シリカアルミノフォスフェート触媒(10)の調製
参考例１と同様にして噴霧乾燥用混合分散液を調製した。ついで、噴霧乾燥用混合分散液を熱風温度２５０℃の噴霧乾燥機中に回転数７０００ｒｐｍのアトマイザーにて噴霧し、得られた粉末を５０℃の温水に分散させ、１０分間撹拌した後、濾過し、５０℃の温水を充分掛けて洗浄した後、１３０℃で２４時間乾燥し、ついで、６００℃で２時間焼成して金属担持結晶性シリカアルミノフォスフェート触媒(10)を調製した。
[ Example 1 ]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (10)
A mixed dispersion for spray drying was prepared in the same manner as in Reference Example 1 . Next, the spray-dispersed mixed dispersion is sprayed into a spray dryer having a hot air temperature of 250 ° C. with an atomizer having a rotational speed of 7000 rpm, and the obtained powder is dispersed in hot water at 50 ° C., stirred for 10 minutes, and then filtered. After sufficiently washing with hot water of 50 ° C., it was dried at 130 ° C. for 24 hours, and then calcined at 600 ° C. for 2 hours to prepare a metal-supported crystalline silica aluminophosphate catalyst (10).
得られた金属担持結晶性シリカアルミノフォスフェート触媒(10)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。なお、硫酸根は大きく減少していた。
また、金属担持結晶性シリカアルミノフォスフェート触媒(10)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (10) were measured, and the results are shown in the table. The sulfate radical was greatly reduced.
The metal-supported crystalline silica aluminophosphate catalyst (10) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［比較例１］
金属担持結晶性シリカアルミノフォスフェート触媒(R1)の調製
参考例１と同様にして結晶性シリカアルミノフォスフェート(1)を調製した。
得られた結晶性シリカアルミノフォスフェート(1)５００ｇを水２５００ｇに分散させ、コロイドミル処理して結晶性シリカアルミノフォスフェート(1)分散液を調製した。
別途、硝酸第二銅３水和物５８．８ｇを水２５００ｇに溶解して硝酸銅水溶液を調製した。
硝酸銅水溶液に結晶性シリカアルミノフォスフェート(1)分散液を混合し、分散液のｐＨを４．５に調製した後、５０℃で２時間撹拌してイオン交換を行い、ついで、濾過分離し、１３０℃で２４時間乾燥し、ついで、空気中６００℃で２時間焼成して金属担持結晶性シリカアルミノフォスフェート触媒(R1)を調製した。
[Comparative Example 1]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (R1)
Crystalline silica aluminophosphate (1) was prepared in the same manner as in Reference Example 1 .
500 g of the obtained crystalline silica aluminophosphate (1) was dispersed in 2500 g of water and subjected to colloid mill treatment to prepare a crystalline silica aluminophosphate (1) dispersion.
Separately, 58.8 g of cupric nitrate trihydrate was dissolved in 2500 g of water to prepare an aqueous copper nitrate solution.
After mixing crystalline silica aluminophosphate (1) dispersion with copper nitrate aqueous solution and adjusting the pH of the dispersion to 4.5, the mixture is stirred at 50 ° C for 2 hours for ion exchange, and then filtered and separated. Then, it was dried at 130 ° C. for 24 hours, and then calcined in air at 600 ° C. for 2 hours to prepare a metal-supported crystalline silica aluminophosphate catalyst (R1).
得られた金属担持結晶性シリカアルミノフォスフェート触媒(R1)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(R1)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (R1) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (R1) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［比較例２］
金属担持結晶性シリカアルミノフォスフェート触媒(R2)の調製
比較例１において、イオン交換した後、結晶性シリカアルミノフォスフェート(1)分散液のｐＨを７．０に調整して同成分を沈着させた以外は同様にして金属担持結晶性シリカアルミノフォスフェート触媒(R2)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(R2)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(R2)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
[Comparative Example 2]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (R2) In Comparative Example 1, after ion exchange, the pH of the crystalline silica aluminophosphate (1) dispersion was adjusted to 7.0 to deposit the same component. A metal-supported crystalline silica aluminophosphate catalyst (R2) was prepared in the same manner except for the above.
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (R2) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (R2) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［比較例３］
金属担持結晶性シリカアルミノフォスフェート触媒(R3)の調製
参考例２と同様にして、洗浄した結晶性シリカアルミノフォスフェート(2)を調製し、ついで、洗浄した結晶性シリカアルミノフォスフェート(2)の固形分濃度１６．７重量％の分散液３０００ｇを調製し、コロイドミル処理して結晶性シリカアルミノフォスフェート(2)分散液を調製した。
ついで、結晶性シリカアルミノフォスフェート(2)分散液を熱風温度２３０℃の噴霧乾燥機中に回転数７０００ｒｐｍのアトマイザーにて噴霧して結晶性シリカアルミノフォスフェート(R3)の粉末を得た。
[Comparative Example 3]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (R3)
In the same manner as in Reference Example 2 , a washed crystalline silica aluminophosphate (2) was prepared, and then 3000 g of a dispersion of the washed crystalline silica aluminophosphate (2) having a solid content concentration of 16.7% by weight was added. A crystalline silica aluminophosphate (2) dispersion was prepared by colloid milling.
Subsequently, the crystalline silica aluminophosphate (2) dispersion was sprayed in a spray dryer having a hot air temperature of 230 ° C. with an atomizer of 7000 rpm to obtain crystalline silica aluminophosphate (R3) powder.
別途、硝酸第二銅３水和物５８．８ｇを水２５００ｇに溶解して硝酸銅水溶液を調製した。
硝酸銅水溶液に結晶性シリカアルミノフォスフェート(R3)の粉末５００ｇと水２５００ｇを混合し、分散液のｐＨを４．５に調整した後、５０℃で２時間撹拌してイオン交換し、ついで、分散液のｐＨを７．０に調製して銅成分を沈着させ、ついで、濾過分離し、１３０℃で２４時間乾燥し、ついで、空気中６００℃で２時間焼成して金属担持結晶性シリカアルミノフォスフェート触媒(R3)を調製した。
Separately, 58.8 g of cupric nitrate trihydrate was dissolved in 2500 g of water to prepare an aqueous copper nitrate solution.
After mixing 500 g of crystalline silica aluminophosphate (R3) powder and 2500 g of water in an aqueous copper nitrate solution and adjusting the pH of the dispersion to 4.5, the mixture was stirred at 50 ° C. for 2 hours for ion exchange, The pH of the dispersion was adjusted to 7.0 to deposit the copper component, then filtered and separated, dried at 130 ° C. for 24 hours, and then calcined in air at 600 ° C. for 2 hours to obtain a metal-supported crystalline silica alumino. A phosphate catalyst (R3) was prepared.
得られた金属担持結晶性シリカアルミノフォスフェート触媒(R3)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(R3)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (R3) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (R3) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［比較例４］
金属担持結晶性シリカアルミノフォスフェート触媒(R4)の調製
参考例１と同様にして結晶性シリカアルミノフォスフェート(1)を調製した
別途、硝酸第二銅３水和物５８．８ｇを水２５００ｇに溶解して硝酸銅水溶液を調製した。
ついで、結晶性シリカアルミノフォスフェート(1)５００ｇを硝酸銅水溶液に分散させ、コロイドミル処理した後、１３０℃で２４時間、水分を蒸発させるとともに乾燥し、ついで、空気中６００℃で２時間焼成して金属担持結晶性シリカアルミノフォスフェート触媒(R4)を調製した。
[Comparative Example 4]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (R4)
Crystalline silica aluminophosphate (1) was prepared in the same manner as in Reference Example 1. Separately, 58.8 g of cupric nitrate trihydrate was dissolved in 2500 g of water to prepare an aqueous copper nitrate solution.
Next, 500 g of crystalline silica aluminophosphate (1) was dispersed in an aqueous copper nitrate solution, treated with a colloid mill, dried at 130 ° C for 24 hours, evaporated and then fired in air at 600 ° C for 2 hours. Thus, a metal-supported crystalline silica aluminophosphate catalyst (R4) was prepared.
得られた金属担持結晶性シリカアルミノフォスフェート触媒(R4)中の銅のＣｕとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(R4)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
The Cu content and specific surface area of copper in the obtained metal-supported crystalline silica aluminophosphate catalyst (R4) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (R4) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
［比較例５］
金属担持結晶性シリカアルミノフォスフェート触媒(R5)の調製
比較例４において、硝酸第二銅３水和物５８．８ｇの代わりに硝酸第一鉄６水和物８０ｇ用いた以外は同様にして金属担持結晶性シリカアルミノフォスフェート触媒(R5)を調製した。
得られた金属担持結晶性シリカアルミノフォスフェート触媒(R5)中の鉄のＦｅとしての含有量および比表面積を測定し、結果を表に示した。
また、金属担持結晶性シリカアルミノフォスフェート触媒(R5)について、参考例１と同様にＮＯｘ除去試験、耐水熱性の評価を行い、結果を表に示した。
[Comparative Example 5]
Preparation of metal-supported crystalline silica aluminophosphate catalyst (R5) In Comparative Example 4, the same procedure was performed except that 80 g of ferrous nitrate hexahydrate was used instead of 58.8 g of cupric nitrate trihydrate. A supported crystalline silica aluminophosphate catalyst (R5) was prepared.
The content of iron as Fe and the specific surface area of the obtained metal-supported crystalline silica aluminophosphate catalyst (R5) were measured, and the results are shown in the table.
The metal-supported crystalline silica aluminophosphate catalyst (R5) was evaluated for NOx removal test and hydrothermal resistance in the same manner as in Reference Example 1 , and the results are shown in the table.
Claims (7)
（ａ）結晶性シリカアルミノフォスフェート粒子分散液を調製する工程
（ｂ）活性成分金属化合物水溶液を混合する工程
（ｃ）噴霧乾燥する工程
（ｄ）洗浄する工程
（ｅ）４００〜９００℃で加熱処理（焼成）する工程 A method for producing a metal-supported crystalline silica aluminophosphate catalyst, comprising sequentially performing the following steps (a) to (e) :
(A) Step of preparing crystalline silica aluminophosphate particle dispersion (b) Step of mixing active component metal compound aqueous solution (c) Step of spray drying (d) Step of washing (e) Heating at 400-900 ° C Process (baking)
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| EP10194903.0A EP2377613B1 (en) | 2009-12-18 | 2010-12-14 | Metal-supported crystalline silica aluminophosphate catalyst and process for producing the same |
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| CN201010600998.0A CN102101058B (en) | 2009-12-18 | 2010-12-17 | Metal carrier band crystal silicoaluminophosphacatalyst catalyst and manufacture method thereof |
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