JP2558566B2 - Catalyst for catalytic reduction of nitrogen oxides - Google Patents
Catalyst for catalytic reduction of nitrogen oxidesInfo
- Publication number
- JP2558566B2 JP2558566B2 JP4020305A JP2030592A JP2558566B2 JP 2558566 B2 JP2558566 B2 JP 2558566B2 JP 4020305 A JP4020305 A JP 4020305A JP 2030592 A JP2030592 A JP 2030592A JP 2558566 B2 JP2558566 B2 JP 2558566B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- perovskite compound
- honeycomb
- zeolite
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 81
- 239000003054 catalyst Substances 0.000 title claims description 54
- 238000010531 catalytic reduction reaction Methods 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 62
- 229930195733 hydrocarbon Natural products 0.000 claims description 26
- 150000002430 hydrocarbons Chemical class 0.000 claims description 26
- 239000010457 zeolite Substances 0.000 claims description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 20
- 239000011973 solid acid Substances 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001603 reducing effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 ammonium ions Chemical class 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 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 5
- 239000011734 sodium Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910017090 AlO 2 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010571 fourier transform-infrared absorption spectrum Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002617 Gd(NO3)3·6H2O Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001072332 Monia Species 0.000 description 1
- 229910017498 Nd(NO3)3.6H2O Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 240000001987 Pyrus communis Species 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- CWDUIOHBERXKIX-UHFFFAOYSA-K lanthanum(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] CWDUIOHBERXKIX-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- VQVDTKCSDUNYBO-UHFFFAOYSA-N neodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VQVDTKCSDUNYBO-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 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
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- RQHUQJCIAFYPAI-UHFFFAOYSA-K praseodymium(3+);trichloride;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Pr+3] RQHUQJCIAFYPAI-UHFFFAOYSA-K 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XRKAJAPEZSHSLG-UHFFFAOYSA-N yttrium(3+);trinitrate;tetrahydrate Chemical compound O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XRKAJAPEZSHSLG-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は窒素酸化物接触還元用触
媒に関し、詳しくは、工場、自動車等から排出される排
ガスの中に含まれる有害な窒素酸化物を還元除去する際
に用いて好適な炭化水素及び／又は含酸素化合物を還元
剤として使用する窒素酸化接触還元用触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for catalytic reduction of nitrogen oxides. More specifically, it is suitable for use in reducing and removing harmful nitrogen oxides contained in exhaust gas discharged from factories, automobiles and the like. The present invention relates to a catalyst for catalytic reduction of nitrogen oxides using various hydrocarbons and / or oxygen-containing compounds as a reducing agent.
【０００２】[0002]
【従来の技術】従来、排ガス中に含まれる窒素酸化物
は、窒素酸化物を酸化した後、アルカリに吸収させる方
法や、アンモニア、水素、一酸化炭素、炭化水素等の還
元剤を用いて、窒素に変換する方法等によつて除去され
ている。しかしながら、前者の方法によれば、生成する
アルカリ廃液を処理して、公害の発生を防止する方策が
必要である。他方、後者の方法によれば、還元剤として
アンモニアを用いるときは、これが排ガス中のイオウ酸
化物と反応して塩類を生成し、その結果、触媒の還元活
性が低下する問題がある。また、水素、一酸化炭素、炭
化水素等を還元剤として用いる場合でも、これらが低濃
度に存在する窒素酸化物よりも高濃度に存在する酸素と
反応するため、窒素酸化物を低減するためには多量の還
元剤を必要とするという問題がある。2. Description of the Related Art Conventionally, nitrogen oxides contained in exhaust gas are obtained by oxidizing the nitrogen oxides and then absorbing them into an alkali, or by using a reducing agent such as ammonia, hydrogen, carbon monoxide, or a hydrocarbon. It has been removed by a method of converting to nitrogen. However, according to the former method, it is necessary to take measures for treating the generated alkaline waste liquid to prevent the occurrence of pollution. On the other hand, according to the latter method, when ammonia is used as the reducing agent, it reacts with the sulfur oxide in the exhaust gas to form salts, and as a result, the reducing activity of the catalyst is lowered. Even when hydrogen, carbon monoxide, hydrocarbon, etc. are used as a reducing agent, they react with oxygen present in a higher concentration than nitrogen oxide present in a low concentration, and therefore, in order to reduce nitrogen oxides. Has a problem that it requires a large amount of reducing agent.
【０００３】このため、最近では、還元剤の不存在下に
窒素酸化物を触媒にて直接分解する方法も提案されてい
るが、しかし、従来知られているそのような触媒は、窒
素酸化物分解活性が低いために実用に供し得ないという
問題がある。また、炭化水素や含酸素化合物を還元剤と
して用いる新たな窒素酸化物接触還元用触媒として、Ｈ
型ゼオライトやＣｕイオン交換ＺＳＭ−５等が提案され
ている。特に、Ｈ型ＺＳＭ−５（ＳｉＯ2 ／Ａｌ2 Ｏ3
モル比＝３０〜４０）が最適であるとされている。しか
しながら、このようなＨ型ＺＳＭ−５でも、未だ十分な
還元活性を有するものとはいい難く、より高い還元活性
を有する窒素酸化物接触還元用触媒が望まれている。For this reason, recently, a method of directly decomposing a nitrogen oxide with a catalyst in the absence of a reducing agent has been proposed. However, such a conventionally known catalyst has been proposed as a nitrogen oxide. There is a problem that it cannot be put to practical use because of its low decomposition activity. Further, as a new catalyst for catalytic reduction of nitrogen oxides using a hydrocarbon or an oxygen-containing compound as a reducing agent, H
Type zeolite and Cu ion exchange ZSM-5 have been proposed. In particular, H type ZSM-5 (SiO 2 / Al 2 O 3
(Molar ratio = 30 to 40) is considered to be optimal. However, even with such H-type ZSM-5, it is hard to say that it has sufficient reducing activity, and a catalyst for catalytic reduction of nitrogen oxides having higher reducing activity is desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上述したよ
うな事情に鑑みてなされたものであつて、その目的とす
るところは、炭化水素や含酸素化合物を還元剤として用
いる場合に、酸素の共存下において窒素酸化物が炭化水
素や含酸素化合物と選択的に反応するため、多量の還元
剤を用いることなく、排ガス中の窒素酸化物を効率よく
還元することができる窒素酸化物接触還元用触媒を提供
するにある。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to use oxygen when a hydrocarbon or an oxygen-containing compound is used as a reducing agent. Nitrogen oxide reacts selectively with hydrocarbons and oxygen-containing compounds in the coexistence of nitrogen, so nitrogen oxide catalytic reduction can efficiently reduce nitrogen oxide in exhaust gas without using a large amount of reducing agent. To provide a catalyst for use.
【０００５】[0005]
【課題を解決するための手段】請求項１記載の発明によ
る炭化水素及び／又は含酸素化合物を還元剤として用い
る窒素酸化物接触還元用触媒は、一般式（Ｉ）A catalyst for catalytic reduction of nitrogen oxides using a hydrocarbon and / or an oxygen-containing compound as a reducing agent according to the invention of claim 1 is represented by the general formula (I).
【０００６】[0006]
【化３】 ＡＸＢ３−ＸＣ３Ｏ７ Embedded image A X B 3-X C 3 O 7
【０００７】（式中、ＡはＬａ、Ｙ、Ｃｅ、Ｐｒ、Ｎ
ｄ、Ｓｍ、Ｅｕ、Ｇｄ及びＢｉよりなる群から選ばれる
少なくとも１種の元素を示し、ＢはＢａ、Ｓｒ、Ｃａ、
Ｍｇ、Ｐｂ、Ｚｎ及びＡｇよりなる群から選ばれる少な
くとも１種の元素を示し、ＣはＭｎ、Ｃｏ、Ｆｅ、Ｎ
ｉ、Ｃｒ、Ｃｕ、Ｖ、Ｍｏ、Ｗ、Ｔｉ、Ｚｒ、Ｎｂ、Ｐ
ｄ、Ｒｈ、Ｒｕ及びＰｔよりなる群から選ばれる少なく
とも１種の元素を示し、０≦Ｘ≦１である。）で表わさ
れるペロブスカイト型複合酸化物がゼオライト系固体酸
担体に担持されてなることを特徴とする。(In the formula, A is La, Y, Ce, Pr, N
d represents at least one element selected from the group consisting of Sm, Eu, Gd and Bi, and B represents Ba, Sr, Ca,
At least one element selected from the group consisting of Mg, Pb, Zn, and Ag is shown, and C is Mn, Co, Fe, N.
i, Cr, Cu, V, Mo, W, Ti, Zr, Nb, P
It represents at least one element selected from the group consisting of d, Rh, Ru, and Pt, and 0 ≦ X ≦ 1. ) Is a zeolite-based solid acid
It is characterized in that it is supported on a carrier .
【０００８】請求項２記載の発明による炭化水素及び／
又は含酸素化合物を還元剤として用いる窒素酸化物接触
還元用触媒は、一般式（Ｉ）Hydrocarbons according to the second aspect of the invention and /
Alternatively, a catalyst for catalytic reduction of nitrogen oxides using an oxygen-containing compound as a reducing agent has a general formula ( I )
【０００９】[0009]
【化４】 ＡＸＢ３−ＸＣ３Ｏ７ Embedded image A X B 3-X C 3 O 7
【００１０】（式中、ＡはＬａ、Ｙ及びＣｅよりなる群
から選ばれる少なくとも１種の元素を示し、ＢはＢａ、
Ｓｒ、Ｃａ、Ｍｇ、Ｐｂ、Ｚｎ及びＡｇよりなる群から
選ばれる少なくとも１種の元素を示し、ＣはＭｎ、Ｃ
ｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｃｕ、Ｖ、Ｍｏ、Ｗ、Ｔｉ、Ｚ
ｒ、Ｎｂ、Ｐｄ、Ｒｈ、Ｒｕ及びＰｔよりなる群から選
ばれる少なくとも１種の元素を示し、０≦Ｘ≦１であ
る。）で表わされるペロブスカイト型複合酸化物がゼオ
ライト系固体酸担体に担持されてなることを特徴とす
る。(In the formula, A represents at least one element selected from the group consisting of La, Y and Ce, B represents Ba,
At least one element selected from the group consisting of Sr, Ca, Mg, Pb, Zn, and Ag is shown, and C is Mn, C
o, Fe, Ni, Cr, Cu, V, Mo, W, Ti, Z
It represents at least one element selected from the group consisting of r, Nb, Pd, Rh, Ru and Pt, and 0 ≦ X ≦ 1. ) Perovskite-type composite oxide represented by the Zeo
It is characterized in that it is supported on a light type solid acid carrier .
【００１１】本発明において、ゼオライト系固体酸担体
とは、触媒が使用される温度領域において固体酸性を示
すゼオライト系担体をいう。固体酸性の確認は、アンモ
ニアを用いた昇温脱離法や、アンモニア又はピリジンを
用いる in situ ＦＴＩＲ（フーリエ変換赤外線吸収ス
ペクトル）法によりなされる。ゼオライト系固体酸担体
は、Ｎａ−モルデナイト、Ｎａ−ＺＳＭ−５、Ｎａ−Ｕ
ＳＹ（ＵＳＹ：ウルトラステイブル又は超安定Ｙ型ゼオ
ライト）等の耐熱性にすぐれるゼオライトを硫酸アンモ
ニウム等のアンモニウム塩の水溶液又は硫酸等の酸で処
理して、ゼオライト中のアルカリ金属の一部又は全部を
アンモニウムイオン又は水素イオンにてイオン交換する
ことによつて得ることができる。アンモニウムイオンに
てイオン交換する方法による場合は、最後に焼成処理を
必要とする。[0011] In There Contact with the invention, the zeolite type solid acid carrier, refers to a zeolite carrier showing solid acidity in a temperature range where the catalyst is used. The solid acidity is confirmed by a temperature programmed desorption method using ammonia or an in situ FTIR (Fourier transform infrared absorption spectrum) method using ammonia or pyridine. Zeolitic solid acid carriers include Na-mordenite, Na-ZSM-5, Na-U.
Zeolites such as SY (USY: Ultra Stable or Ultra Stable Y-type Zeolite) having excellent heat resistance are treated with an aqueous solution of ammonium salt such as ammonium sulfate or an acid such as sulfuric acid to partially or completely remove the alkali metal in the zeolite. It can be obtained by ion exchange with ammonium ion or hydrogen ion. In the case of the method of performing ion exchange with ammonium ions, a calcination treatment is finally required.
【００１２】ゼオライト系固体酸担体の一例として、例
えば、次式As an example of the zeolite-based solid acid carrier, for example, the following formula
【００１３】[0013]
【化５】 Ｍ２（（ＡｌＯ２）２±ｒ（ＳｉＯ２）１０）・ＺＨ２
ＯEmbedded image M 2 ((AlO 2 ) 2 ± r (SiO 2 ) 10 ) .ZH 2
O
【００１４】で表わされるモルデナイト型ゼオライトを
酸処理して得られる酸型モルデナイトであつて、ＳｉＯ
2 ／Ａｌ2 Ｏ3 モル比が１３〜２０であり、且つ、Ｓｉ
Ｏ2 ／Ｎａ2 Ｏモル比が２５〜２００である酸型モルデ
ナイトを挙げることができる。但し、上式中、Ｍはアル
カリ金属イオンを示し、ｒはゼオライトの合成条件によ
り変動する値である。Acid-type mordenite obtained by acid-treating the mordenite-type zeolite represented by
2 / Al 2 O 3 molar ratio is 13 to 20, and Si
O 2 / Na 2 O molar ratio can be exemplified acid type mordenite is 25 to 200. However, in the above formula, M represents an alkali metal ion, and r is a value that varies depending on the synthesis conditions of zeolite.
【００１５】また、ゼオライト系固体酸担体の他の一例
として、例えば、次式Another example of the zeolite-based solid acid carrier is, for example, the following formula
【００１６】[0016]
【化６】 Ｍ´Ａ（（ＡｌＯ２）ｐ（ＳｉＯ２）ｑ｝・Ｚ´Ｈ２ＯEmbedded image M ′ A ((AlO 2 ) p (SiO 2 ) q} · Z′H 2 O
【００１７】で表わされるゼオライト中のイオンＭの一
部又は全部をチタンイオン（Ｔｉ4+）、ジルコニウムイ
オン（Ｚｒ4+）又はスズイオン（Ｓｎ4+）にて交換して
得られるゼオライトを挙げることができる。但し、上式
中、Ｍ’はアルカリ金属イオン、アルカリ土類金属イオ
ン又は水素イオンを示し、ｎＡ＝ｐ（ｎはイオンＭの価
数である。）、ｑ／ｐ≧５である。The zeolite obtained by exchanging a part or all of the ions M in the zeolite represented by the formula with titanium ions (Ti 4+ ), zirconium ions (Zr 4+ ) or tin ions (Sn 4+ ). You can However, in the above formula, M ′ represents an alkali metal ion, an alkaline earth metal ion, or a hydrogen ion, and nA = p (n is the valence of the ion M) and q / p ≧ 5.
【００１８】本発明による触媒は、例えば、次に示す
（１）、（２）又は（３）の方法によつて調製すること
ができる。 （１）ゼオライト系固体酸担体を分散させたスラリー中
に、Ｌａ、Ｙ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、
Ｂｉ、Ｂａ、Ｓｒ、Ｃａ、Ｍｇ、Ｐｂ、Ｚｎ、Ａｇ、Ｍ
ｎ、Ｃｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｃｕ、Ｖ、Ｍｏ、Ｗ、Ｔ
ｉ、Ｚｒ、Ｎｂ、Ｐｄ、Ｒｈ、Ｒｕ又はＰｔの硝酸塩等
の水溶性塩や、これらのアルコキシドのアルコール溶液
を投入し、これらを中和或いは加水分解させる方法等に
よつて、ゼオライト系固体酸担体にこれらの複合金属種
の水酸化物等のペロブスカイト化合物の前駆体を担持さ
せ、次いで、濾過、水洗、リパルプを繰り返し行なつた
後、乾燥し、焼成する。The catalyst according to the present invention can be prepared, for example, by the method (1), (2) or (3) shown below. (1) In a slurry in which a zeolite-based solid acid carrier is dispersed, La, Y, Ce, Pr, Nd, Sm, Eu, Gd,
Bi, Ba, Sr, Ca, Mg, Pb, Zn, Ag, M
n, Co, Fe, Ni, Cr, Cu, V, Mo, W, T
A zeolite-based solid acid is prepared by adding a water-soluble salt such as i, Zr, Nb, Pd, Rh, Ru, or Pt nitrate, or an alcohol solution of these alkoxides to neutralize or hydrolyze them. The carrier is made to carry a precursor of a perovskite compound such as a hydroxide of these composite metal species, and then filtration, washing with water and repulping are repeatedly carried out, followed by drying and firing.
【００１９】（２）ゼオライト系固体酸担体と別途調製
したペロブスカイト化合物とを遊星ミル等によつて十分
に湿式粉砕混合する。 （３）ゼオライト系固体酸担体の水溶性塩又は水酸化物
等の前駆体と、Ｌａ、Ｙ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅ
ｕ、Ｇｄ、Ｂｉ、Ｂａ、Ｓｒ、Ｃａ、Ｍｇ、Ｐｂ、Ｚ
ｎ、Ａｇ、Ｍｎ、Ｃｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｃｕ、Ｖ、
Ｍｏ、Ｗ、Ｔｉ、Ｚｒ、Ｎｂ、Ｐｄ、Ｒｈ、Ｒｕ又はＰ
ｔの硝酸塩等の水溶性塩やアルコキシドのアルコール溶
液とを均質に混合した溶液を中和又は加水分解させる方
法等によつて沈殿物を生成させ、次いで、この沈澱物を
濾過、水洗、リパルプを繰り返し行なつた後、乾燥し、
焼成する。(2) The zeolite-based solid acid carrier and the separately prepared perovskite compound are thoroughly wet-milled and mixed by a planetary mill or the like. (3) A precursor such as a water-soluble salt or hydroxide of a zeolite-based solid acid carrier, and La, Y, Ce, Pr, Nd, Sm, E
u, Gd, Bi, Ba, Sr, Ca, Mg, Pb, Z
n, Ag, Mn, Co, Fe, Ni, Cr, Cu, V,
Mo, W, Ti, Zr, Nb, Pd, Rh, Ru or P
A precipitate is formed by a method of neutralizing or hydrolyzing a solution in which a water-soluble salt such as a nitrate of t and an alcohol solution of an alkoxide are homogeneously mixed, and then the precipitate is filtered, washed with water, and repulped. After repeating the process, dry
Bake.
【００２０】以上の方法において、ペロブスカイト化合
物の生成温度は低い方が好ましい。その理由は、その生
成温度が低い程、大きな比表面積を有するペロブスカイ
ト化合物が得られ、ゼオライト系固体酸担体とペロブス
カイト化合物を構成する元素との反応によりゼオライト
系固体酸担体の固体酸性が変質したり、ペロブスカイト
化合物の生成量の低下により触媒の活性が低下したりす
ることを回避することができるからである。In the above method, it is preferable that the production temperature of the perovskite compound is low. The reason is that the lower the production temperature, the more perovskite compound having a large specific surface area is obtained, and the zeolite-based solid acid carrier reacts with the elements constituting the perovskite compound to form a zeolite.
This is because it is possible to avoid the deterioration of the solid acidity of the system solid acid carrier and the decrease in the activity of the catalyst due to the decrease in the production amount of the perovskite compound.
【００２１】ペロブスカイト化合物の好適な担持量は、
このペロブスカイト化合物と固体酸担体との総重量に対
して、0.１〜６０重量％である。ペロブスカイト化合物
の担持量が６０重量％を越えても、そのような増量に応
じた添加効果が得られないばかりでなく、酸素が共存す
る反応系においては、酸素による炭化水素や含酸素化合
物の消耗が多くなる。一方、担持量が0.１重量％よりも
少ないときは、触媒の還元活性を十分に向上させること
ができない。The preferable loading amount of the perovskite compound is
The amount is 0.1 to 60% by weight based on the total weight of the perovskite compound and the solid acid carrier. Even if the supported amount of the perovskite compound exceeds 60% by weight, not only the effect of addition corresponding to such increase cannot be obtained, but also in the reaction system in which oxygen coexists, the consumption of hydrocarbons and oxygen-containing compounds by oxygen Will increase. On the other hand, when the supported amount is less than 0.1% by weight, the reducing activity of the catalyst cannot be sufficiently improved.
【００２２】本発明による触媒は、従来、知られている
成形方法によつて、ハニカム状、球状等の種々の形状に
成形することができる。この成形の際に、成形助剤、成
形体補強体、無機繊維、有機バインダー等を適宜配合し
てもよい。また、予め成形された基材上にウオツシユコ
ート法等によつて被覆担持させることもできる。更に、
従来、知られているその他の触媒の調製法によることも
できる。The catalyst according to the present invention can be molded into various shapes such as a honeycomb shape and a spherical shape by a conventionally known molding method. At the time of this molding, a molding aid, a molded body reinforcing material, an inorganic fiber, an organic binder and the like may be appropriately mixed. It is also possible to carry the coating on a preformed substrate by a washcoat method or the like. Furthermore,
It is also possible to use other conventionally known catalyst preparation methods.
【００２３】本発明の実施において、還元剤として使用
する炭化水素の具体例としては、気体状のものとして、
メタン、エタン、ブチレン等の炭化水素ガスが、液体状
のものとして、ペンタン、ヘキサン、オクタン、ヘプタ
ン、ベンゼン、トルエン、キシレン等の単一成分系の炭
化水素や、ガソリン、灯油、軽油、重油等の鉱油系炭化
水素等が挙げられる。特に好適な炭化水素としては、ア
セチレン、メチルアセチレン、１−ブチン等の低級アル
キン、エチレン、プロピレン、イソブチレン、１−ブテ
ン、２−ブテン等の低級アルケン、ブタジエン、イソプ
レン等の低級ジエン、プロパン、ブタン等の低級アルカ
ン等が挙げられる。In the practice of the present invention, a specific example of the hydrocarbon used as the reducing agent is a gaseous one,
Hydrocarbon gas such as methane, ethane, butylene, etc. in liquid form, such as pentane, hexane, octane, heptane, benzene, toluene, xylene, etc., single component hydrocarbons, gasoline, kerosene, light oil, heavy oil, etc. Mineral oil-based hydrocarbons and the like. Particularly preferred hydrocarbons include lower alkynes such as acetylene, methylacetylene and 1-butyne, lower alkenes such as ethylene, propylene, isobutylene, 1-butene and 2-butene, lower dienes such as butadiene and isoprene, propane and butane. And lower alkanes and the like.
【００２４】炭化水素の好適な添加量は、その種類によ
つて異なるが、窒素酸化物に対するモル比にて0.１〜２
程度である。0.１未満であるときは、十分な還元活性を
得ることができず、他方、モル比が２を越えるときは、
未反応の炭化水素の排出量が多くなるために、これを回
収するための後処理が必要となる。また、本発明の実施
において還元剤として使用する含酸素化合物とは、酸素
元素を分子内に有する有機化合物のことである。その具
体例としては、メチルアルコール、エチルアルコール、
プロピルアルコール、オクチルアルコール等のアルコー
ル類、ジメチルエーテル、ジエチルエーテル、ジプロピ
ルエーテル等のエーテル類、酢酸メチル、酢酸エチル、
油脂類等のエステル類、アセトン、メチルエチルケトン
等のケトン類等が挙げられる。好適な含酸素化合物とし
ては、メチルアルコール、エチルアルコール等の低級ア
ルコールが挙げられる。The suitable amount of the hydrocarbon added varies depending on the kind, but is 0.1 to 2 in terms of molar ratio to nitrogen oxide.
It is a degree. When it is less than 0.1, sufficient reducing activity cannot be obtained, while when the molar ratio exceeds 2,
Since the amount of unreacted hydrocarbons emitted is large, a post-treatment is required to recover the unreacted hydrocarbons. Further, the oxygen-containing compound used as a reducing agent in the practice of the present invention is an organic compound having an oxygen element in a molecule. Specific examples include methyl alcohol, ethyl alcohol,
Propyl alcohol, alcohols such as octyl alcohol, dimethyl ether, diethyl ether, ethers such as dipropyl ether, methyl acetate, ethyl acetate,
Esters such as oils and fats, and ketones such as acetone and methyl ethyl ketone are exemplified. Suitable oxygen-containing compounds include lower alcohols such as methyl alcohol and ethyl alcohol.
【００２５】上記炭化水素及び含酸素化合物は、それぞ
れ一種を単独で用いてもよく、必要に応じて二種以上併
用してもよい。また、炭化水素と含酸素化合物とを一種
又は二種以上併用するようにしてもよい。尚、排ガス中
に存在する燃料等の未燃焼物乃至不完全燃焼生成物、即
ち、炭化水素類やパテイキユレート類等も還元剤として
有効であり、これらも本発明における炭化水素に含まれ
る。このことから、見方を変えれば、本発明による触媒
は、排ガス中の炭化水素類やパテイキユレート類等の減
少或いは除去触媒としても有用であるということができ
る。The above hydrocarbons and oxygen-containing compounds may be used alone or in combination of two or more as required. Further, the hydrocarbon and the oxygen-containing compound may be used alone or in combination of two or more. Unburned or incomplete combustion products such as fuel present in the exhaust gas, that is, hydrocarbons and paticular ureates are also effective as reducing agents, and these are also included in the hydrocarbon of the present invention. From this point of view, it can be said that the catalyst according to the present invention is also useful as a catalyst for reducing or removing hydrocarbons, patty chelates and the like in exhaust gas.
【００２６】上記還元剤が窒素酸化物に対して選択的還
元反応を示す温度は、含酸素化合物＜アルキン＜アルケ
ン＜芳香族系炭化水素＜アルカンの順に高くなる。ま
た、同系の炭化水素においては、炭素数が大きくなるに
従つて、その温度は低くなる。本発明による触媒が窒素
酸化物に対して還元活性を示す最適な温度は、使用する
還元剤や触媒種により異なるが、通常、１００〜８００
℃である。この温度領域においては、空間速度（ＳＶ）
５００〜１０００００程度で排ガスを流通させることが
好ましい。本発明において特に好適な温度領域は２００
〜６００℃である。The temperature at which the reducing agent shows a selective reduction reaction with respect to nitrogen oxides increases in the order of oxygen-containing compound <alkyne <alkene <aromatic hydrocarbon <alkane. Further, in the hydrocarbons of the same system, the temperature becomes lower as the carbon number becomes larger. The optimum temperature at which the catalyst according to the present invention exhibits reduction activity for nitrogen oxides varies depending on the reducing agent and the catalyst species used, but is usually 100 to 800.
° C. In this temperature range, space velocity (SV)
It is preferable to circulate the exhaust gas at about 500 to 100,000. In the present invention, a particularly suitable temperature range is 200
~ 600 ° C.
【００２７】[0027]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれら実施例により何ら限定されるものではな
い。 （１）触媒の調製The present invention will be described below with reference to examples.
The present invention is not limited to these examples. (1) Preparation of catalyst
【００２８】実施例１ 硝酸イツトリウム（Ｙ（ＮＯ3 ）3 ・４Ｈ2 Ｏ）１７3.
４９ｇ、硝酸バリウム（Ｂａ（ＮＯ3 ）2 ）２６1.３４
ｇ及び硝酸第二銅３水和物（Ｃｕ（ＮＯ3 ）2・３Ｈ2
Ｏ）３６2.４ｇを水１０００mlに溶解させて、水溶液を
調製した。 この水溶液に更に過酸化水素水１００ｇを加
え、十分に攪拌しながら、濃度１２１ｇ／１の炭酸ナト
リウム水溶液を加えてpHを１０とした。中和反応終了
後、１８時間攪拌を続けて、熟成を行なつた。その後、
濾過、水洗、リパルプを濾液の導電率がリパルプ用水と
ほぼ同じになるまで繰り返した。得られた濾過ケーキを
１２０℃で１８時間乾燥し、次いで、７００℃で３時間
焼成して、ペロブスカイト化合物（ＹＢａ 2 Ｃｕ
3 Ｏ 7 ）を得た。このペロブスカイト化合物の比表面積
は２4.５m 2 ／ｇであつた。 [0028]Example 1 Yttrium nitrate (Y (NO3)3・ 4H2O) 173.
49 g, barium nitrate (Ba (NO3)2) 261.34
g and cupric nitrate trihydrate (Cu (NO3)2・ 3H2
O) 362.4 gDissolve in 1000 ml of water,
Prepared. 100 g of hydrogen peroxide solution was added to this aqueous solution.
Well, with sufficient stirring, the concentration of sodium carbonate of 121g / 1
The pH was adjusted to 10 by adding an aqueous solution of lithium. Neutralization reaction completed
After that, stirring was continued for 18 hours for aging. afterwards,
Filtration, washing with water, and repulp with the filtrate conductivity as repulp water
Repeated until it was almost the same. The obtained filter cake
Dry at 120 ° C for 18 hours, then 700 ° C for 3 hours
After firing, the perovskite compound (YBa 2 Cu
3 O 7 ) Got. Specific surface area of this perovskite compound
Is 24.5m 2 / G.
【００２９】得られた焼成物がペロブスカイト型化合物
であることは、Ｘ線回折によって確認した。また、ペロ
ブスカイト型化合物の比表面積は、ＢＥＴ法にて測定し
た。以下の比表面積の測定も同じ方法法によった。この
ようにして得たペロブスカイト化合物３０ｇと日本化学
社製Ｈ型モルデナイト（ＨＭ−２３）１００ｇとの混合
物に水を１００ｇ加えてスラリーを得、これをハニカム
に塗布し、触媒を担持させて、試作サンプル（Ａ−１）
を得た。このときの触媒の担持量は、ハニカム１cc当た
り0.０９４ｇであつた。The obtained fired product is a perovskite-type compound
It was confirmed by X-ray diffraction. Also, Pero
The specific surface area of the buskite type compound is measured by the BET method.
It was The following specific surface area measurements were made by the same method. To a mixture of 30 g of the perovskite compound thus obtained and 100 g of H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd., 100 g of water was added to obtain a slurry, which was coated on a honeycomb and supported with a catalyst to make a prototype. Sample ( A-1 )
I got The amount of the catalyst loaded at this time was 0.094 g per 1 cc of the honeycomb.
【００３０】実施例２ 硝酸ランタン６水和物７1.６０ｇ、硝酸鉛（Ｐｂ（ＮＯ
3 ）2 ）１２7.７９ｇ及び酢酸マンガン４水和物４5.０
３ｇを混合し、８００℃で３時間焼成した以外は、実施
例１と同様の方法にによつて、ペロブスカイト化合物
（Ｌａ0.9 Ｐｂ2.1 Ｍｎ3 Ｏ7 ）を得た。このペロブス
カイト化合物の比表面積は２3.７m2／ｇであつた。この
ようにして得たペロブスカイト化合物３０ｇと日本化学
社製Ｈ型モルデナイト（ＨＭ−２３）１００ｇとの混合
物に水１００ｇ加えてスラリーを得、これをハニカムに
塗布し、触媒を担持させて、試作サンプル（Ａ−２）を
得た。このときの触媒の担持量は、ハニカム１cc当たり
0.１１７ｇであつた。 Example 2 71.60 g of lanthanum nitrate hexahydrate, lead nitrate (Pb (NO
3 ) 2 ) 127.79 g and manganese acetate tetrahydrate 45.0
A perovskite compound (La 0.9 Pb 2.1 Mn 3 O 7 ) was obtained by the same method as in Example 1 except that 3 g was mixed and baked at 800 ° C. for 3 hours. The specific surface area of this perovskite compound was 23.7 m 2 / g. A mixture of 30 g of the perovskite compound thus obtained and 100 g of H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd. was added with 100 g of water to obtain a slurry, which was coated on a honeycomb and supported with a catalyst to prepare a trial sample. ( A-2 ) was obtained. The amount of catalyst loaded at this time was 1 cc of honeycomb.
It was 0.117 g.
【００３１】実施例３ 硝酸ランタン６水和物２１6.５１ｇ、硝酸ストロンチウ
ム１０5.８２ｇ、硝酸バリウム１３0.６７ｇ及び硝酸コ
バルト６水和物４３6.５５ｇを混合し、８００℃で３時
間焼成した以外は、実施例１と同様の方法にて、ペロブ
スカイト化合物（ＬａＳｒＢａＣｏ3 Ｏ7 ）を得た。こ
のペロブスカイト化合物の比表面積は１9.９m2／ｇであ
つた。このようにして得たペロブスカイト化合物３０ｇ
と日本化学社製Ｈ型モルデナイト（ＨＭ−２３）１００
ｇとの混合物に水１００ｇを加えてスラリーを得、これ
をハニカムに塗布し、触媒を担持させて、試作サンプル
（Ａ−３）を得た。このときの触媒の担持量は、ハニカ
ム１cc当たり0.０９３ｇであつた。 Example 3 Lanthanum nitrate hexahydrate 216.51 g, strontium nitrate 105.82 g, barium nitrate 130.67 g and cobalt nitrate hexahydrate 436.55 g were mixed and calcined at 800 ° C. for 3 hours. A perovskite compound (LaSrBaCo 3 O 7 ) was obtained in the same manner as in Example 1. The specific surface area of this perovskite compound was 19.9 m 2 / g. 30 g of the perovskite compound thus obtained
And Nippon Kagaku H-type mordenite (HM-23) 100
100 g of water was added to the mixture with g to obtain a slurry, which was applied on a honeycomb to support a catalyst, and a trial sample ( A-3 ) was obtained. The amount of the catalyst carried at this time was 0.093 g per 1 cc of the honeycomb.
【００３２】実施例４ 硝酸セリウム６水和物（Ｃｅ（ＮＯ3 ）2 ・６Ｈ2 Ｏ）
７0.６５ｇ、硝酸バリウム８5.０４ｇ、硝酸ニツケル６
水和物（Ｎｉ（ＮＯ3 ）2 ・６Ｈ2 Ｏ）７0.９７ｇ及び
硝酸クロム（Ｃｒ（ＮＯ3 ）3 ）５8.１２ｇを用い、実
施例１と同様の方法にて、ペロブスカイト化合物（Ｃｅ
Ｂａ2 Ｎｉ1.5 Ｃｒ1.5 Ｏ7 ）を得た。このペロブスカ
イト化合物の比表面積は２1.７m2／ｇであつた。このよ
うにして得たペロブスカイト化合物３０ｇと日本化学社
製Ｈ型モルデナイト（ＨＭ−２３）との混合物に水１０
０ｇを加えてスラリーを得、これをハニカムに塗布し、
触媒を担持させて、試作サンプル（Ａ−４）を得た。こ
のときの触媒の担持量は、ハニカム１cc当たり0.０９８
ｇであつた。 Example 4 Cerium Nitrate Hexahydrate (Ce (NO 3 ) 2 .6H 2 O)
70.65g, barium nitrate 85.04g, nickel nitrate 6
Hydrate (Ni (NO 3) 2 · 6H 2 O) 70.97g and chromium nitrate (Cr (NO 3) 3) using 58.12G, in the same manner as in Example 1, a perovskite compound (Ce
Ba 2 Ni 1.5 Cr 1.5 O 7 ) was obtained. The specific surface area of this perovskite compound was 21.7 m 2 / g. A mixture of 30 g of the perovskite compound thus obtained and H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd. was added to water 10
0 g was added to obtain a slurry, which was applied to a honeycomb,
A catalyst was supported to obtain a trial sample ( A-4 ). The loading amount of the catalyst at this time was 0.098 per 1 cc of honeycomb.
It was g.
【００３３】実施例５ （ペロブスカイト化合物の調製）硝酸イツトリウム４水和物８8.２１ｇ、硝酸ストロンチ
ウム１０7.６４ｇ及び酢酸コバルト４水和物１５1.９８
ｇを５００mlの水に溶解させて水溶液を調製した。この
水溶液に十分に攪拌しながら、濃度１２１ｇ／１の水酸
化ナトリウム水溶液を滴下して、液のpHを１０とした。
中和反応終了後、１８時間攪拌を続け、熟成を行なつ
た。その後、濾過、水洗、リパルプを濾液の導電率がリ
パルプ用水 とほぼ同じになるまで繰り返した後、得られ
た濾過ケーキを１２０℃で１８時間乾燥させた。 この乾
燥物を粉砕し、これにモリブデン酸アンモニウムのアン
モニア性水溶液（ＭｏＯ 2 として２５ｇ／１濃度の水溶
液）７８0.６６mlを加え、十分に混練した後、蒸発乾固
させ、１２０℃で１８時間乾燥させ、次いで、８５０℃
で３時間焼成して、 ペロブスカイト化合物（ＹＳｒ2.0
Ｃｏ2.4 Ｍｏ0.6 Ｏ7 ）を得た。このペロブスカイト化
合物の比表面積は１0.９m2／ｇであつた。 Example 5 (Preparation of perovskite compound) Yttrium nitrate tetrahydrate 88.21 g, strontium nitrate
Um 107.64 g and cobalt acetate tetrahydrate 151.98
g was dissolved in 500 ml of water to prepare an aqueous solution. this
Hydrolyzed with a concentration of 121 g / 1 while thoroughly stirring in an aqueous solution
The pH of the solution was adjusted to 10 by dropping an aqueous sodium chloride solution.
After completion of the neutralization reaction, continue stirring for 18 hours to mature the mixture.
It was After that, filtration, washing with water, and repulping are performed to reduce the conductivity of the filtrate.
Obtained after repeated until it is almost the same as pulp water
The filtered cake was dried at 120 ° C. for 18 hours. This dry
The dried product is crushed and ammonium molybdate
Monia aqueous solution ( 25g / 1 concentration water solution as MoO 2
Liquid) 780.66 ml was added, and the mixture was thoroughly kneaded and then evaporated to dryness.
Dried at 120 ° C for 18 hours, then at 850 ° C
After firing for 3 hours, the perovskite compound (YSr 2.0
To obtain a Co 2.4 Mo 0.6 O 7). The specific surface area of this perovskite compound was 10.9 m 2 / g.
【００３４】（Ｚｒ−モルデナイトの調製） 日本化学社製のＮａモルデナイト（ＮＭ−１００Ｐ）１
００ｇを硝酸ジルコニル水溶液（ＺｒＯ2 として１００
ｇ／１濃度の水溶液）に浸漬し、攪拌しながら７０℃に
１時間保持し、ＮａをＺｒとイオン交換させた。濾過、
水洗して得たゼオライトケーキを乾燥させた後、６５０
℃で４時間焼成した。このゼオライト（Ｚｒ−モルデナ
イト）のＺｒ含有量は3.３重量％であり、また、比表面
積は３９１m2／ｇであつた。(Preparation of Zr-mordenite) Na mordenite (NM-100P) 1 manufactured by Nippon Kagaku Co., Ltd.
00 g of zirconyl nitrate aqueous solution (100 as ZrO 2
g / concentration aqueous solution) and kept at 70 ° C. for 1 hour with stirring to exchange Na with Zr. filtration,
After drying the zeolite cake obtained by washing with water, 650
Calcination was performed for 4 hours. The zeolite (Zr-mordenite) had a Zr content of 3.3% by weight and a specific surface area of 391 m 2 / g.
【００３５】前述したようにして得たペロブスカイト化
合物３０ｇと上記Ｚｒ−モルデナイト１００ｇとの混合
物に水を１００ｇを加え、遊星ミルにて３０分間粉砕混
合し、皿に、水で粘度調整して、ウオツシユコート用ス
ラリーを得た。このスラリーをハニカムに塗布し、触媒
を担持させて、試作サンプル（Ａ−５）を得た。このと
きの触媒の担持量は、ハニカム１cc当たり0.１０３ｇで
あつた。[0035] Water to 100g added to a mixture of perovskite compound 30g and the Zr- mordenite 100g obtained as described above, were pulverized and mixed for 30 minutes with a planetary mill, a dish, and the viscosity adjusted with water, Walsh A slurry for a wash coat was obtained. This slurry was applied to a honeycomb to support a catalyst, and a trial sample ( A-5 ) was obtained. At this time, the supported amount of the catalyst was 0.103 g per 1 cc of honeycomb.
【００３６】実施例６ 実施例１ において、ペロブスカイト化合物（ＹＢａ2 Ｃ
ｕ3 Ｏ7 ）１ｇと日本化学社製Ｈ型モルデナイト（ＨＭ
−２３）１００ｇとを用いた以外は、実施例１と同様に
して、試作サンプル（Ａ−６）を得た。このときの触媒
の担持量は、ハニカム１cc当たり0.０７９ｇであつた。 Example 6 In Example 1 , the perovskite compound (YBa 2 C
u 3 O 7 ) 1g and H-type mordenite (HM
-23) A trial sample ( A-6 ) was obtained in the same manner as in Example 1 except that 100 g was used. The amount of the catalyst loaded at this time was 0.079 g per 1 cc of the honeycomb.
【００３７】実施例７ 実施例１ において、ペロブスカイト化合物（ＹＢａ2 Ｃ
ｕ3 Ｏ7 ）１０ｇと日本化学社製Ｈ型モルデナイト（Ｈ
Ｍ−２３）１００ｇとを用いた以外は、実施例１と同様
にして、試作サンプル（Ａ−７）を得た。このときの触
媒の担持量は、ハニカム１cc当たり0.０８３ｇであつ
た。 Example 7 In Example 1 , the perovskite compound (YBa 2 C
u 3 O 7 ) 10 g and H-type mordenite (H
A prototype sample ( A-7 ) was obtained in the same manner as in Example 1 except that 100 g of M-23) was used. The amount of the catalyst loaded at this time was 0.083 g per 1 cc of the honeycomb.
【００３８】実施例８ 実施例１ において、ペロブスカイト化合物（ＹＢａ2 Ｃ
ｕ3 Ｏ7 ）５０ｇと日本化学社製Ｈ型モルデナイト（Ｈ
Ｍ−２３）１００ｇとを用いた以外は、実施例１と同様
にして、試作サンプル（Ａ−８）を得た。このときの触
媒の担持量は、ハニカム１cc当たり0.１０７ｇであつ
た。 Example 8 In Example 1 , the perovskite compound (YBa 2 C
u 3 O 7 ) 50 g and H-type mordenite (H
A prototype sample ( A-8 ) was obtained in the same manner as in Example 1 except that 100 g of M-23) was used. The amount of the catalyst loaded at this time was 0.107 g per 1 cc of the honeycomb.
【００３９】実施例９ 実施例１ において、ペロブスカイト化合物（ＹＢａ2 Ｃ
ｕ3 Ｏ7 ）５０ｇと日本化学社製Ｈ型モルデナイト（Ｈ
Ｍ−２３）５０ｇとを用いた以外は、実施例１と同様に
して、試作サンプル（Ａ−９）を得た。このときの触媒
の担持量は、ハニカム１cc当たり0.１２５ｇであつた。 Example 9 In Example 1 , the perovskite compound (YBa 2 C
u 3 O 7 ) 50 g and H-type mordenite (H
A prototype sample ( A-9 ) was obtained in the same manner as in Example 1 except that 50 g of M-23) was used. The amount of the catalyst loaded at this time was 0.125 g per 1 cc of the honeycomb.
【００４０】実施例１０ 組成式Ｎａｘ〔（ＡｌＯ2 ）X ・（ＳｉＯ2 ）Y 〕・Ｚ
Ｈ2 Ｏで表わされるナトリウム型ＺＳＭ−５（日本モー
ビル社製ＺＳＭ−５、Ｙ／Ｘ＝３５）１００ｇを0.０２
５モル／１のＴｉＯＳＯ4 水溶液１リットル中に浸漬
し、十分に攪拌した。これをオートクレーブ中にて攪拌
しながら、１００℃／時の昇温速度で昇温し、１２５℃
に１時間保持し、ＴｉＯＳＯ4 を加水分解させて、Ｎａ
をＴｉでイオン交換した後、濾別、水洗して、ゼオライ
トのケーキを得た。次いで、このケーキを乾燥した後、
６５０℃で４時間焼成して、ゼオライトを得た。このゼ
オライト中のＴｉ含有量は、ＴｉＯ2 として2.４重量％
であつた。このようにして得たＴｉ−ＺＳＭ−５をＨ型
モルデナイトに代えて用いた以外は、実施例１と同様に
して、試作サンプル（Ａ−１０）を得た。このときの触
媒の担持量は、ハニカム１cc当たり0.０９９ｇであつ
た。 Example 10 Compositional formula Nax [(AlO 2 ) X. (SiO 2 ) Y ] .Z
0.02 of 100 g of sodium type ZSM-5 (ZSM-5 manufactured by Nippon Mobile Co., Ltd., Y / X = 35) represented by H 2 O was used.
It was dipped in 1 liter of a 5 mol / 1 TiOSO 4 aqueous solution and sufficiently stirred. While stirring this in an autoclave, the temperature was raised at a heating rate of 100 ° C / hour to 125 ° C.
The mixture is kept at room temperature for 1 hour to hydrolyze TiOSO 4 ,
Was ion-exchanged with Ti, then filtered and washed with water to obtain a cake of zeolite. Then, after drying this cake,
It was calcined at 650 ° C. for 4 hours to obtain zeolite. The Ti content in this zeolite is 2.4% by weight as TiO 2.
It was. A prototype sample ( A-10 ) was obtained in the same manner as in Example 1 except that the Ti-ZSM-5 thus obtained was used instead of the H-type mordenite. The amount of the catalyst carried at this time was 0.099 g per 1 cc of the honeycomb.
【００４１】実施例１１ 硝酸ランタン６水和物８9.５０ｇ、硝酸鉛（Ｐｂ（ＮＯ
3 ）2 ）１３6.９３ｇ及び硝酸コバルト６水和物１５4.
４５ｇを用いて、実施例１と同様にして、ペロブスカイ
ト化合物（ＬａＰｂ2 Ｃｏ3 Ｏ7 ）を得た。このペロブ
スカイト化合物の比表面積は、１2.６m2／ｇであつた。
このようにして得たペロブスカイト化合物６０ｇと日本
化学社製Ｈ型モルデナイト（ＨＭ−２３）１００ｇとの
混合物に水を１００ｇ加えてスラリーを得、これをハニ
カムに塗布し、触媒を担持させて、試作サンプル（Ａ−
１１）を得た。このときの触媒の担持量は、ハニカム１
cc当たり0.１３７ｇであつた。 Example 11 89.50 g of lanthanum nitrate hexahydrate, lead nitrate (Pb (NO
3 ) 2 ) 136.93 g and cobalt nitrate hexahydrate 154.
Using 45 g, a perovskite compound (LaPb 2 Co 3 O 7 ) was obtained in the same manner as in Example 1. The specific surface area of this perovskite compound was 12.6 m 2 / g.
To a mixture of 60 g of the perovskite compound thus obtained and 100 g of H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd., 100 g of water was added to obtain a slurry, which was coated on a honeycomb and supported with a catalyst to make a prototype. Sample ( A-
11 ) was obtained. The loading amount of the catalyst at this time is the same as that of the honeycomb 1.
It was 0.137 g per cc.
【００４２】実施例１２ 硝酸ネオジム６水和物（Ｎｄ（ＮＯ3 ）3 ・６Ｈ2 Ｏ）
１２4.８２ｇ、硝酸バリウム１４8.８３ｇ、硝酸第二銅
３水和物３７1.４８ｇ及び硝酸ニツケル６水和物４9.６
８ｇを用いて、実施例１と同にして、ペロブスカイト化
合物（ＮｄＢａ2 Ｃｕ2.7 Ｎｉ0.3 Ｏ7 ）を得た。この
ペロブスカイト化合物の比表面積は、１0.３m2／ｇであ
つた。このようにして得たペロブスカイト化合物６０ｇ
と日本化学社製Ｈ型モルデナイト（ＨＭ−２３）との混
合物に水を１００ｇ加えてスラリーを得、これをハニカ
ムに塗布し、触媒を担持させて、試作サンプル（Ａ−１
２）を得た。このときの触媒の担持量は、ハニカム１cc
当たり0.１４１ｇであつた。 Example 12 Neodymium nitrate hexahydrate (Nd (NO 3 ) 3 .6H 2 O)
124.82 g, barium nitrate 148.83 g, cupric nitrate trihydrate 371.48 g and nickel nitrate hexahydrate 49.6
A perovskite compound (NdBa 2 Cu 2.7 Ni 0.3 O 7 ) was obtained in the same manner as in Example 1 except that 8 g was used. The specific surface area of this perovskite compound was 10.3 m 2 / g. 60 g of the perovskite compound thus obtained
To a mixture of H-type mordenite manufactured by Nippon Kagaku Co., Ltd. (HM-23) to obtain 100 g of water to obtain a slurry, which is applied to a honeycomb to support a catalyst, and a prototype sample ( A-1
2 ) was obtained. The amount of catalyst loaded at this time was 1 cc of honeycomb.
The amount was 0.141 g.
【００４３】実施例１３ 塩化プラセオジム７水和物（ＰｒＣｌ3 ・７Ｈ2 Ｏ）２
７3.２ｇ、硝酸ストロンチウム３０9.７１ｇ、硝酸第二
銅３水和物２６5.１７ｇ及び酢酸マンガン４水和物２６
9.００ｇを混合し、次いで、実施例１と同様にして、ペ
ロブスカイト化合物（ＰｒＳｒ2 Ｃｕ1.5 Ｍｎ
1.5 Ｏ7 ）を得た。このペロブスカイト化合物の比表面
積は、9.８m2／ｇであつた。このようにして得たペロブ
スカイト化合物６０ｇと日本化学社製Ｈ型モルデナイト
（ＨＭ−２３）１００ｇとの混合物に水を１００ｇ加え
てスラリーを得、これをハニカムに塗布し、触媒を担持
させて、試作サンプル（Ａ−１３）を得た。このときの
触媒の担持量は、ハニカム１cc当たり0.１３３ｇであつ
た。 Example 13 Praseodymium chloride heptahydrate (PrCl 3 .7H 2 O) 2
73.2 g, strontium nitrate 309.71 g, cupric nitrate trihydrate 265.17 g and manganese acetate tetrahydrate 26
9.00 g were mixed, and then, in the same manner as in Example 1, the perovskite compound (PrSr 2 Cu 1.5 Mn) was mixed.
1.5 O 7 ) was obtained. The specific surface area of this perovskite compound was 9.8 m 2 / g. To a mixture of 60 g of the perovskite compound thus obtained and 100 g of H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd., 100 g of water was added to obtain a slurry, which was coated on a honeycomb and supported with a catalyst to make a prototype. A sample ( A-13 ) was obtained. The amount of catalyst supported at this time was 0.133 g per 1 cc of honeycomb.
【００４４】実施例１４ 塩化ランタン６水和物２０2.０５ｇ、硝酸ガドリウム６
水和物（Ｇｄ（ＮＯ3）3 ・６Ｈ2 Ｏ）５2.６６ｇ、硝
酸バリウム２２8.６５ｇ、硝酸ストロンチウム６1.７２
ｇ、硝酸第二銅３水和物１２6.８３ｇ、硝酸コバルト６
水和物４０7.４０ｇ及び硝酸第二鉄６水和物１０0.７７
ｇを用いて、実施例１と同様にして、ペロブスカイト化
合物（Ｌａ0.8 Ｇｄ0.2 Ｃｏ2.4 Ｆｅ0.6 Ｏ7 ）を得
た。このペロブスカイト化合物の比表面積は、8.８m2／
ｇであつた。このようにして得たペロブスカイト化合物
６０ｇと日本化学社製Ｈ型モルデナイト（ＨＭ−２３）
１００ｇとの混合物に水を１００ｇ加えてスラリーを
得、これをハニカムに塗布し、触媒を担持させて、試作
サンプル（Ａ−１４）を得た。このときの触媒の担持量
は、ハニカム１cc当たり0.１２９ｇであつた。 Example 14 202.05 g of lanthanum chloride hexahydrate, gadolinium nitrate 6
Hydrate (Gd (NO 3) 3 · 6H 2 O) 52.66g, barium nitrate 228.65G, strontium nitrate 61.72
g, cupric nitrate trihydrate 126.83 g, cobalt nitrate 6
Hydrate 407.40 g and ferric nitrate hexahydrate 100.77
Using g, a perovskite compound (La 0.8 Gd 0.2 Co 2.4 Fe 0.6 O 7 ) was obtained in the same manner as in Example 1. The specific surface area of this perovskite compound is 8.8 m 2 /
It was g. 60 g of the perovskite compound thus obtained and H-type mordenite manufactured by Nippon Kagaku Co. (HM-23)
100 g of water was added to a mixture with 100 g to obtain a slurry, which was applied on a honeycomb to support a catalyst, and a trial sample ( A-14 ) was obtained. At this time, the supported amount of the catalyst was 0.129 g per 1 cc of the honeycomb.
【００４５】実施例１５ 硝酸ランタン６水和物２０2.０５ｇ、塩化プラセオジム
４3.５６ｇ、硝酸ストロンチウム２４6.８８ｇ及び硝酸
第二銅３水和物４２2.７６ｇを用いて、実施例１と同様
にして、ペロブスカイト化合物（Ｌａ0.8 Ｐｒ0.2 Ｓｒ
2.0 Ｃｕ3.0 Ｏ7 ）を得た。このペロブスカイト化合物
の比表面積は、9.２m2／ｇであつた。このようにして得
たペロブスカイト化合物６０ｇと日本化学社製Ｈ型モル
デナイト（ＨＭ−２３）１００ｇとの混合物に水を１０
０ｇ加えてスラリーを得、これをハニカムに塗布し、触
媒を担持させて、試作サンプル（Ａ−１５）を得た。こ
のときの触媒の担持量は、ハニカム１cc当たり0.１３５
ｇであつた。 Example 15 The same procedure as in Example 1 was carried out using 202.05 g of lanthanum nitrate hexahydrate, 43.56 g of praseodymium chloride, 246.88 g of strontium nitrate and 422.76 g of cupric nitrate trihydrate. , Perovskite compounds (La 0.8 Pr 0.2 Sr
2.0 Cu 3.0 O 7 ) was obtained. The specific surface area of this perovskite compound was 9.2 m 2 / g. Water was added to a mixture of 60 g of the perovskite compound thus obtained and 100 g of H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd.
0 g was added to obtain a slurry, which was applied to a honeycomb to carry a catalyst, and a trial sample ( A-15 ) was obtained. The loading amount of catalyst at this time was 0.135 per 1 cc of honeycomb.
It was g.
【００４６】比較例１実施例３ において、Ｈ型モルデナイトを用いず、ペロブ
スカイト化合物（ＬａＳｒＢａＣｏ3 Ｏ7 ）のみを用い
てウオツシユコート用スラリーを得、その他は実施例１
と同様にして、1.２５mmピツチのハニカム形状の比較サ
ンプル（Ｂ−１）を得た。このときの触媒の担持量はハ
ニカム１cc当たり0.１３３ｇであつた。Comparative Example 1 In Example 3 , a slurry for washcoat was obtained by using only the perovskite compound (LaSrBaCo 3 O 7 ) without using the H-type mordenite.
In the same manner as above, a honeycomb-shaped comparative sample (B-1) having a pitch of 1.25 mm was obtained. The amount of catalyst supported at this time was 0.133 g per 1 cc of honeycomb.
【００４７】比較例２ 日本モービル社製のナトリウム型モルデナイト（ＳｉＯ
2 ／Ａｌ2 Ｏ3 のモル比＝３４）を実施例１と同様の方
法により処理して、1.２５mmピツチのハニカム形状の比
較サンプル（Ｂ−２）を得た（Ｈ型ＺＳＭ−５）。この
ときの触媒の担持量は、ハニカム１cc当たり0.１２８ｇ
であつた。Comparative Example 2 Sodium type mordenite (SiO
2 / Al 2 O 3 molar ratio = 34) was treated in the same manner as in Example 1 to obtain a 1.25 mm pitch honeycomb-shaped comparative sample (B-2) (H-type ZSM-5). . The amount of catalyst loaded at this time was 0.128 g per 1 cc of honeycomb.
It was.
【００４８】（２）評価試験 上記サンプル（Ａ−１）〜（Ａ−１５）並びに比較サン
プル（Ｂ−１）及び（Ｂ−２）について、下記の試験条
件により窒素酸化物含有ガスの窒素酸化物接触還元を行
い、窒素酸化物のＮ2 への転化率を、ガスクロマトグラ
フ法によりＮ2を定量して算出した。 （試験条件） （１）ガス組成 ＮＯ １容量％ Ｏ2 １０容量％ 還元剤 １容量％ Ｈｅ 残部 （２）空間速度 ２００００（１／Ｈｒ） （３）反応温度 ３００℃、４００℃、５００℃又は６００℃ 結果を表１に示す。(2) Evaluation test With respect to the samples (A-1) to ( A-15 ) and the comparative samples (B-1) and (B-2), the nitrogen oxidation of the nitrogen oxide-containing gas was carried out under the following test conditions. carried things catalytic reduction, the conversion to N 2 of nitrogen oxides was calculated to quantify the N 2 by gas chromatography. (Test conditions) (1) Gas composition NO 1% by volume O 2 10% by volume Reducing agent 1% by volume He balance (2) Space velocity 20000 (1 / Hr) (3) Reaction temperature 300 ° C, 400 ° C, 500 ° C or The results at 600 ° C. are shown in Table 1 .
【００４９】[0049]
【表１】 [Table 1]
【００５０】表１に示す結果から明らかなように、本発
明による触媒（試作サンプル（Ａ−１）〜（Ａ−１
５））は、いずれも窒素酸化物の窒素への転化率が高い
のに対して、比較触媒（比較サンプル（Ｂ−１）及び
（Ｂ−２））は、総じて、その窒素への転化率が低い。As is clear from the results shown in Table 1 , the catalysts of the present invention (prototype samples (A-1) to (A-1)
5)) has a high conversion rate of nitrogen oxides to nitrogen, whereas the comparative catalysts (comparative samples (B-1) and (B-2)) generally have a higher conversion rate to nitrogen. Is low.
【００５１】[0051]
【発明の効果】以上に詳細に説明したように、本発明に
よる炭化水素や含酸素化合物を還元剤として使用する窒
素酸化物接触還元用触媒は、酸素の共存下において、排
ガス中の窒素酸化物を効率よく接触還元することができ
る。As described above in detail, the catalyst for catalytic reduction of nitrogen oxides using the hydrocarbon or the oxygen-containing compound according to the present invention as a reducing agent is a nitrogen oxide in exhaust gas in the presence of oxygen. Can be efficiently catalytically reduced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 29/46 Ｂ０１Ｊ 29/48 Ａ 29/48 Ｂ０１Ｄ 53/36 １０２Ｃ (72)発明者 仲辻 忠夫 大阪府堺市戎島町５丁１番地 堺化学工 業株式会社内 (72)発明者 清水 宏益 大阪府堺市戎島町５丁１番地 堺化学工 業株式会社内 (72)発明者 安川 律 大阪府堺市戎島町５丁１番地 堺化学工 業株式会社内 (72)発明者 菅沼 藤夫 埼玉県北葛飾郡庄和町新宿新田228−16 (72)発明者 宮本 勝見 埼玉県北葛飾郡鷺宮町鷺宮１−11−17 (72)発明者 川付 正明 埼玉県越谷市大沢2856−１ センチュリ ーマンション嵯峨103号 (72)発明者 金田一 嘉昭 茨城県つくば市東１−１ 工業技術院化 学技術研究所内 (72)発明者 佐々木 基 茨城県つくば市東１−１ 工業技術院化 学技術研究所内 審査官 野田 直人 (56)参考文献 特開 昭64−30641（ＪＰ，Ａ)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication location B01J 29/46 B01J 29/48 A 29/48 B01D 53/36 102C (72) Inventor Tadao Nakatsuji Sakai Chemical Industry Co., Ltd. 5-1, Ebishimacho, Sakai City, Osaka Prefecture (72) Inventor Hiromasu Shimizu 5-1, Ebisucho, Sakai City, Osaka Prefecture (72) Inventor Ritsu Yaskawa Osaka Sakai Chemical Industry Co., Ltd., 5-1, Ebishima-cho, Sakai-shi, Japan (72) Inventor Fujio Suganuma 228-16 Shinjuku Shinden, Showa-cho, Kitakatsushika-gun, Saitama Prefecture (72) Inventor Katsumi Miyamoto 1 Saginomiya-cho, Kitatsukashi-gun, Saitama Prefecture −11−17 (72) Inventor Masaaki Kawatsuki 2856-1 Osawa, Koshigaya City, Saitama Century Condominium No. 103 Saga (72) Inventor Kazuaki Kaneda 1-1 Tsukuba City, Ibaraki Prefecture Industrial Technology Institute Chemical Technology Research house (72) inventor Sasaki based on Higashi, Tsukuba, Ibaraki, 1-1 Agency of Industrial Science and Technology Chemical Technology Institute in the examiner Naoto Noda (56) Reference Patent Sho 64-30641 (JP, A)
Claims (2)
ｕ、Ｇｄ及びＢｉよりなる群から選ばれる少なくとも１
種の元素を示し、ＢはＢａ、Ｓｒ、Ｃａ、Ｍｇ、Ｐｂ、
Ｚｎ及びＡｇよりなる群から選ばれる少なくとも１種の
元素を示し、ＣはＭｎ、Ｃｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｃ
ｕ、Ｖ、Ｍｏ、Ｗ、Ｔｉ、Ｚｒ、Ｎｂ、Ｐｄ、Ｒｈ、Ｒ
ｕ及びＰｔよりなる群から選ばれる少なくとも１種の元
素を示し、０≦Ｘ≦１である。）で表わされるペロブス
カイト型複合酸化物がゼオライト系固体酸担体に担持さ
れてなることを特徴とする炭化水素及び／又は含酸素化
合物を還元剤として用いる窒素酸化物接触還元用触媒。1. General formula (I) embedded image A X B 3-X C 3 O 7 (wherein A is La, Y, Ce, Pr, Nd, Sm, E).
at least 1 selected from the group consisting of u, Gd and Bi
Represents the elements of the species, B is Ba, Sr, Ca, Mg, Pb,
At least one element selected from the group consisting of Zn and Ag is shown, and C is Mn, Co, Fe, Ni, Cr, C.
u, V, Mo, W, Ti, Zr, Nb, Pd, Rh, R
It represents at least one element selected from the group consisting of u and Pt, and 0 ≦ X ≦ 1. ) A catalyst for catalytic reduction of nitrogen oxides using a hydrocarbon and / or oxygen-containing compound as a reducing agent, characterized in that the perovskite-type composite oxide represented by the formula (3) is supported on a zeolite-based solid acid carrier.
少なくとも１種の元素を示し、ＢはＢａ、Ｓｒ、Ｃａ、
Ｍｇ、Ｐｂ、Ｚｎ及びＡｇよりなる群から選ばれる少な
くとも１種の元素を示し、ＣはＭｎ、Ｃｏ、Ｆｅ、Ｎ
ｉ、Ｃｒ、Ｃｕ、Ｖ、Ｍｏ、Ｗ、Ｔｉ、Ｚｒ、Ｎｂ、Ｐ
ｄ、Ｒｈ、Ｒｕ及びＰｔよりなる群から選ばれる少なく
とも１種の元素を示し、０≦Ｘ≦１である。）で表わさ
れるペロブスカイト型複合酸化物がゼオライト系固体酸
担体に担持されてなることを特徴とする炭化水素及び／
又は含酸素化合物を還元剤として用いる窒素酸化物接触
還元用触媒。Wherein in the general formula (I) ## STR2 ## A X B 3-X C 3 O 7 ( wherein, A is La, represents at least one element selected from the group consisting of Y and Ce, B Is Ba, Sr, Ca,
At least one element selected from the group consisting of Mg, Pb, Zn, and Ag is shown, and C is Mn, Co, Fe, N.
i, Cr, Cu, V, Mo, W, Ti, Zr, Nb, P
It represents at least one element selected from the group consisting of d, Rh, Ru, and Pt, and 0 ≦ X ≦ 1. ) Perovskite-type composite oxide represented by is characterized by comprising supported on a zeolite type solid acid carrier hydrocarbons and /
Alternatively, a catalyst for nitrogen oxide catalytic reduction using an oxygen-containing compound as a reducing agent.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4020305A JP2558566B2 (en) | 1991-11-13 | 1992-02-05 | Catalyst for catalytic reduction of nitrogen oxides |
| DE69226581T DE69226581T2 (en) | 1991-09-12 | 1992-09-11 | Catalyst for the reduction of nitrogen oxides |
| US07/944,106 US5380692A (en) | 1991-09-12 | 1992-09-11 | Catalyst for catalytic reduction of nitrogen oxide |
| EP92115572A EP0532024B1 (en) | 1991-09-12 | 1992-09-11 | Catalyst for catalytic reduction of nitrogen oxide |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32637291 | 1991-11-13 | ||
| JP3-326372 | 1991-11-13 | ||
| JP4020305A JP2558566B2 (en) | 1991-11-13 | 1992-02-05 | Catalyst for catalytic reduction of nitrogen oxides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05184930A JPH05184930A (en) | 1993-07-27 |
| JP2558566B2 true JP2558566B2 (en) | 1996-11-27 |
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|---|---|---|---|
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| JP (1) | JP2558566B2 (en) |
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| WO2003033431A1 (en) * | 2001-10-15 | 2003-04-24 | Nippon Steel Corporation | Porcelain composition, composite material comprising catalyst and ceramic, film reactor, method for producing synthetic gas, apparatus for producing synthetic gas and method for activating catalyst |
| JP2006036558A (en) * | 2004-07-23 | 2006-02-09 | Dowa Mining Co Ltd | Perovskite complex oxide and catalyst |
| JP4848554B2 (en) * | 2004-07-30 | 2011-12-28 | Ｄｏｗａエレクトロニクス株式会社 | Production method of perovskite complex oxide with pore distribution with high catalytic activity |
| JP5388052B2 (en) | 2008-10-31 | 2014-01-15 | 独立行政法人産業技術総合研究所 | Exhaust gas treatment catalyst |
| JP5680973B2 (en) * | 2011-01-05 | 2015-03-04 | 三井金属鉱業株式会社 | Method for producing yttrium manganate YMnO3 |
| JP5822682B2 (en) * | 2011-11-25 | 2015-11-24 | ダイハツ工業株式会社 | Exhaust gas purification catalyst |
| CN104741142A (en) * | 2015-03-15 | 2015-07-01 | 北京工业大学 | Preparation method and application of Fe-ZSM-5 Zr and Sr doped compound catalyst |
| CN104741143A (en) * | 2015-03-15 | 2015-07-01 | 北京工业大学 | Preparation method and application of Cu-ZSM-5 doped Zr and Sr composite catalyst |
| CN113307303B (en) * | 2021-04-24 | 2023-11-28 | 苏州大学 | High-stability all-inorganic perovskite/aluminum phosphate composite nano material and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| JPH05184930A (en) | 1993-07-27 |
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