JPH04298235A - Catalyst for contact reduction of nox - Google Patents
Catalyst for contact reduction of noxInfo
- Publication number
- JPH04298235A JPH04298235A JP3089700A JP8970091A JPH04298235A JP H04298235 A JPH04298235 A JP H04298235A JP 3089700 A JP3089700 A JP 3089700A JP 8970091 A JP8970091 A JP 8970091A JP H04298235 A JPH04298235 A JP H04298235A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- nitrogen oxides
- nitrate
- nox
- al2o3
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 150000004645 aluminates Chemical class 0.000 claims abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 81
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910018404 Al2 O3 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 13
- 150000001298 alcohols Chemical class 0.000 abstract description 10
- 239000002244 precipitate Substances 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 5
- 229910006587 β-Al2O3 Inorganic materials 0.000 abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000011575 calcium Substances 0.000 description 9
- -1 etc. Substances 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 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
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 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
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007493 shaping process Methods 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 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
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 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
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 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
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 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
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、炭化水素やアルコール
類を還元剤として用いる窒素酸化物接触還元用触媒に係
わり、詳しくは工場、自動車などから排出される排気ガ
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
用いて好適な窒素酸化物接触還元用触媒に関する。[Industrial Application Field] The present invention relates to a catalyst for catalytic reduction of nitrogen oxides using hydrocarbons or alcohols as reducing agents, and more specifically, the present invention relates to a catalyst for catalytic reduction of nitrogen oxides using hydrocarbons or alcohols as reducing agents. The present invention relates to a catalyst for catalytic reduction of nitrogen oxides suitable for use in reducing and removing nitrogen oxides.
【０００２】0002
【従来の技術及び発明が解決しようとする課題】従来、
排気ガス中に含まれる窒素酸化物は、■該窒素酸化物を
酸化した後、アルカリに吸収させる方法、■ＮＨ３ 、
Ｈ２ 、ＣＯ等の還元剤を用いてＮ２ に変える方法な
どによって除去されてきた。[Prior art and problems to be solved by the invention] Conventionally,
Nitrogen oxides contained in exhaust gas can be treated by: (1) oxidizing the nitrogen oxides and then absorbing them into alkali; (2) NH3;
It has been removed by methods such as converting it into N2 using reducing agents such as H2 and CO.
【０００３】しかしながら、■の方法による場合は、公
害防止のためのアルカリの排液処理が必要となり、また
■の方法において還元剤としてＮＨ３ 等のアルカリ剤
を用いる場合においては、これが排ガス中のＳＯｘと反
応して塩類を生成し、その結果還元剤の還元活性が低下
してしまうという問題があった。また、Ｈ２ 、ＣＯ、
炭化水素を還元剤として用いる場合、これらが低濃度に
存在するＮＯＸ より高濃度に存在するＯ２ と反応し
てしまうため、ＮＯＸ を低減するためには多量の還元
剤を必要とした。However, when method (2) is used, it is necessary to treat alkaline waste liquid to prevent pollution, and when an alkaline agent such as NH3 is used as a reducing agent in method (2), this removes SOx in the exhaust gas. There is a problem in that the reducing agent reacts with salts to produce salts, resulting in a decrease in the reducing activity of the reducing agent. Also, H2, CO,
When hydrocarbons are used as reducing agents, they react with O2, which is present in high concentrations, rather than with NOX, which is present in low concentrations, so a large amount of the reducing agent is required to reduce NOX.
【０００４】このため、最近では、還元剤を用いること
なく窒素酸化物を触媒により直接分解する方法も提案さ
れているが、窒素酸化物分解活性が低いため、実用に供
し得ないという問題があった。[0004] For this reason, a method has recently been proposed in which nitrogen oxides are directly decomposed by a catalyst without using a reducing agent, but this method has the problem of being impractical due to its low nitrogen oxide decomposition activity. Ta.
【０００５】本発明は、以上の事情に鑑みなされたもの
であって、その目的とするところは、例えば炭化水素や
アルコール類を還元剤として用いたときに、酸素の共存
下においても窒素酸化物がこれらの還元剤と選択的に反
応するため、多量の炭化水素を用いることなく排気ガス
中の窒素酸化物を効率良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。The present invention was made in view of the above circumstances, and its object is to reduce nitrogen oxides even in the coexistence of oxygen when hydrocarbons or alcohols are used as reducing agents. An object of the present invention is to provide a catalyst for catalytic reduction of nitrogen oxides, which can efficiently reduce nitrogen oxides in exhaust gas without using a large amount of hydrocarbons, since the catalyst selectively reacts with these reducing agents.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の請求項１記載の発明に係る窒素酸化物の選択的還元触
媒（接触還元触媒）は、Ｋ、Ｎａ、Ｃａ、Ｍｇ、Ｂａ、
Ｌａ、ＣｅおよびＰｒからなる群より選ばれた少なくと
も一種の金属のアルミン酸塩を触媒成分として含有する
ものであり、また請求項２記載の発明に係る触媒は、組
成式Ｘ・β−Ａｌ２ Ｏ３ で表される物質を触媒成分
として含有するものである。ただし、式中のＸは、Ｋ、
Ｎａ、Ｃａ、Ｍｇ、Ｂａ、Ｌａ、ＣｅおよびＰｒからな
る群より選ばれた少なくとも一種の元素である。なお、
β−Ａｌ２ Ｏ３ はベータアルミナを示す。また、請
求項３記載の発明に係る触媒は、請求項１または２記載
の触媒成分のほかに、さらにＶ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、Ｍｏ、Ｗ、Ｒｕ、Ｒｈ、
Ｐｄ、ＡｇおよびＰｔからなる群より選ばれた少なくと
も一種の金属、その酸化物および／またはその硫酸塩を
触媒成分として含有するものである。本発明に係る窒素
酸化物選択的還元触媒は、例えば次に示す（１）、（２
）または（３）の各製法により製造される。[Means for Solving the Problems] A selective reduction catalyst (catalytic reduction catalyst) for nitrogen oxides according to the invention according to claim 1 for achieving the above object includes K, Na, Ca, Mg, Ba, K, Na, Ca, Mg, Ba,
The catalyst according to the invention according to claim 2 contains an aluminate of at least one metal selected from the group consisting of La, Ce, and Pr as a catalyst component, and has a compositional formula of X.β-Al2O3. It contains a substance represented by as a catalyst component. However, X in the formula is K,
It is at least one element selected from the group consisting of Na, Ca, Mg, Ba, La, Ce, and Pr. In addition,
β-Al2O3 indicates beta alumina. Further, the catalyst according to the invention according to claim 3 further includes V, Cr, Mn, Fe, C, in addition to the catalyst components according to claim 1 or 2.
o, Ni, Cu, Zn, Nb, Mo, W, Ru, Rh,
It contains at least one metal selected from the group consisting of Pd, Ag and Pt, its oxide and/or its sulfate as a catalyst component. The nitrogen oxide selective reduction catalyst according to the present invention can be used, for example, as shown below (1) or (2).
) or (3).
【０００７】（１） Ｋ、Ｎａ、Ｃａ、Ｍｇ、Ｂａ、
Ｌａ、ＣｅおよびＰｒからなる群より選ばれた少なくと
も一種の金属の酸化物とＡｌ２ Ｏ３とを予め湿式また
は乾式混合し、必要に応じて適宜の成形方法（押出成形
、打錠成形、球状成形等）により成形した後、８００〜
１４００°Ｃで焼成して焼成物を得る。要すれば、さら
にこの焼成物を、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、
Ｃｕ、Ｚｎ、Ｎｂ、Ｍｏ、Ｗ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ
およびＰｔからなる群より選ばれた少なくとも一種の金
属、または、それらの酸化物や硫酸塩の水溶液に浸漬し
、乾燥した後、３００〜６００°Ｃで焼成する。(1) K, Na, Ca, Mg, Ba,
An oxide of at least one metal selected from the group consisting of La, Ce, and Pr is wet or dry mixed in advance with Al2O3, and if necessary, an appropriate molding method (extrusion molding, tablet molding, spherical molding, etc.) is used. ) After molding, 800 ~
A fired product is obtained by firing at 1400°C. If necessary, this fired product may be further treated with V, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Nb, Mo, W, Ru, Rh, Pd, Ag
It is immersed in an aqueous solution of at least one metal selected from the group consisting of Pt and Pt, or an oxide or sulfate thereof, dried, and then fired at 300 to 600°C.
【０００８】（２） Ｃａ塩、Ｍｇ塩、Ｂａ塩、Ｌａ
塩、Ｃｅ塩およびＰｒ塩からなる群より選ばれた少なく
とも一種の可溶性塩とＡｌ塩とを水などに溶解し、これ
にアンモニア、水酸化ナトリウム等のアルカリや、炭酸
ナトリウム、炭酸アンモニウム等の塩基性炭酸塩を沈澱
剤として加えて加水分解して沈澱物を生成せしめ、該沈
澱物を乾燥した後、８００〜１４００°Ｃで焼成して焼
成物を得る。この焼成物を粉砕し、必要に応じて適宜の
成形方法（押出成形、打錠成形、球状成形等）により賦
形する。要すれば、この成形物をさらに３００〜１４０
０°Ｃで焼成する。要すれば、さらにこの成形物を、Ｖ
、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、
Ｍｏ、Ｗ、Ｒｕ、Ｒｈ、Ｐｄ、ＡｇおよびＰｔからなる
群より選ばれた少なくとも一種の金属、または、それら
の酸化物や硫酸塩の水溶液に浸漬し、乾燥した後、３０
０〜６００°Ｃで焼成する。(2) Ca salt, Mg salt, Ba salt, La
At least one soluble salt selected from the group consisting of salts, Ce salts, and Pr salts and Al salts are dissolved in water, etc., and an alkali such as ammonia or sodium hydroxide, or a base such as sodium carbonate or ammonium carbonate is added to the solution. A carbonate is added as a precipitant and hydrolyzed to form a precipitate. After drying the precipitate, the precipitate is fired at 800 to 1400°C to obtain a fired product. This fired product is pulverized and shaped as necessary by an appropriate shaping method (extrusion molding, tablet molding, spherical molding, etc.). If necessary, this molded product may be further heated by 300 to 140
Bake at 0°C. If necessary, this molded product may be further added to V
, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb,
After immersing in an aqueous solution of at least one metal selected from the group consisting of Mo, W, Ru, Rh, Pd, Ag and Pt, or an oxide or sulfate thereof, and drying,
Bake at 0-600°C.
【０００９】（３） Ｃａ塩、Ｍｇ塩、Ｂａ塩、Ｌａ
塩、Ｃｅ塩およびＰｒ塩からなる群より選ばれた少なく
とも一種の可溶性塩とＡｌ塩とを水などに溶解し、これ
にアンモニア、水酸化ナトリウム等のアルカリや、炭酸
ナトリウム、炭酸アンモニウム等の塩基性炭酸塩を沈澱
剤として加えて加水分解して沈澱物を生成せしめ、該沈
澱物を乾燥した後、８００〜１４００°Ｃで焼成して焼
成物を得る。この焼成物を粉砕し、Ｖ、Ｃｒ、Ｍｎ、Ｆ
ｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、Ｍｏ、Ｗ、Ｒｕ、
Ｒｈ、Ｐｄ、ＡｇおよびＰｔからなる群より選ばれた少
なくとも一種の金属、または、それらの酸化物や硫酸塩
の水溶液に浸漬し、アルカリまたは酸を沈澱剤として加
えて加水分解して沈澱物を生成せしめ、該沈澱物を乾燥
した後、３００〜６００°Ｃで焼成してＶ、Ｃｒ等の各
金属を担持させる。このようにして得た焼成物を適宜の
成形方法（押出成形、打錠成形、球状成形等）により賦
形する。要すれば、この成形物をさらに３００〜８００
°Ｃで焼成する。(3) Ca salt, Mg salt, Ba salt, La
At least one soluble salt selected from the group consisting of salts, Ce salts, and Pr salts and Al salts are dissolved in water, etc., and an alkali such as ammonia or sodium hydroxide, or a base such as sodium carbonate or ammonium carbonate is added to the solution. A carbonate is added as a precipitant and hydrolyzed to form a precipitate. After drying the precipitate, the precipitate is fired at 800 to 1400°C to obtain a fired product. This fired product is crushed and V, Cr, Mn, F
e, Co, Ni, Cu, Zn, Nb, Mo, W, Ru,
It is immersed in an aqueous solution of at least one metal selected from the group consisting of Rh, Pd, Ag and Pt, or its oxide or sulfate, and hydrolyzed by adding an alkali or acid as a precipitant to form a precipitate. After drying the precipitate, it is fired at 300 to 600°C to support various metals such as V and Cr. The baked product thus obtained is shaped by an appropriate shaping method (extrusion molding, tablet molding, spherical molding, etc.). If necessary, this molded product may be further heated by 300 to 800
Bake at °C.
【００１０】上記（１）〜（３）の方法の中では、触媒
成分の均一性が高い点で、（１）または（２）の方法が
好ましい。Among the methods (1) to (3) above, method (1) or (2) is preferred because the catalyst components are highly homogeneous.
【００１１】上記（１）〜（３）の方法は、本発明に係
る触媒の調製方法の例示に過ぎず、本発明に係る触媒は
、上記調製方法以外の方法によって調製することが可能
であることは勿論であり、触媒成分が実質的に同じもの
であれば、同等の効果を有するものが得られる。[0011] The above methods (1) to (3) are merely examples of methods for preparing the catalyst according to the present invention, and the catalyst according to the present invention can be prepared by methods other than the above-mentioned preparation methods. Of course, if the catalyst components are substantially the same, products with equivalent effects can be obtained.
【００１２】本発明におけるＡｌ２ Ｏ３ は、γ形、
α形、θ形、η形等、その結晶系を問われないが、比表
面積の大きいものの方がＮａ、Ｋ、Ｃａ、Ｍｇ、Ｂａ、
Ｌａ、Ｐｒ等との反応性が高く、比較的低温で反応させ
ることができるので好ましい。Ａｌ２ Ｏ３ に代えて
、より比表面積の大きいＡｌ２ Ｏ３ −ＳｉＯ２ を
用いてもよい。上記Ａｌ２ Ｏ３ の前駆体としては、
水酸化アルミニウム、硝酸アルミニウム、酢酸アルミニ
ウム、塩化アルミニウム等の水溶性塩、アルミニウムイ
ソプロポキシド等のアルコキシド類が例示される。[0012] Al2O3 in the present invention is in the γ form,
The crystal system does not matter, such as α type, θ type, η type, etc., but those with a larger specific surface area are Na, K, Ca, Mg, Ba, etc.
It is preferable because it has high reactivity with La, Pr, etc. and can be reacted at a relatively low temperature. Al2 O3 --SiO2, which has a larger specific surface area, may be used instead of Al2 O3. As the precursor of Al2O3,
Examples include water-soluble salts such as aluminum hydroxide, aluminum nitrate, aluminum acetate, and aluminum chloride, and alkoxides such as aluminum isopropoxide.
【００１３】本発明におけるＫ、Ｎａ、Ｃａ、Ｍｇ、Ｂ
ａ、Ｌａ、ＣｅおよびＰｒの原料としては、これらの酸
化物、水酸化物、炭酸塩等の粉末状物、硝酸塩、酢酸塩
等の水溶性塩が例示される。なお、水酸化物、炭酸塩、
硝酸塩、酢酸塩は焼成により最終的には酸化物となる。
これらの原料のうち、触媒成分の均一性の高い上記（２
）および（３）の方法に使用することができる点で、可
溶性塩類が好ましい。これらＫ、Ｎａ等の金属（ただし
Ｃｅを除く）とＡｌとの組成比の値が小さいと、Ｘ・β
−Ａｌ２ Ｏ３ が生成し易く、その値が大きいとアル
ミン酸塩を生成し易い傾向がある。一般に、２０／８０
以下ではＸ・β−Ａｌ２ Ｏ３ が主に生成する。Ｘ・
β−Ａｌ２ Ｏ３ を生成させる上での好適な組成比は
５／９５〜１０／９０である。K, Na, Ca, Mg, B in the present invention
Examples of raw materials for a, La, Ce, and Pr include powders such as their oxides, hydroxides, and carbonates, and water-soluble salts such as nitrates and acetates. In addition, hydroxide, carbonate,
Nitrate and acetate eventually become oxides through calcination. Among these raw materials, the above (2) with high homogeneity of catalyst components is used.
Soluble salts are preferred in that they can be used in the methods of ) and (3). If the composition ratio of these metals such as K and Na (excluding Ce) and Al is small,
-Al2O3 is likely to be produced, and when the value is large, aluminate tends to be easily produced. Generally 20/80
Below, X·β-Al2O3 is mainly produced. X・
The preferred composition ratio for producing β-Al2O3 is 5/95 to 10/90.
【００１４】本発明におけるＶ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、Ｍｏ、Ｗ、Ｒｕ、Ｒｈ、
Ｐｄ、ＡｇおよびＰｔの原料としては、これら各金属の
単体、酸化物、水酸化物、炭酸塩等の粉末状物、硝酸塩
、硫酸塩、酢酸塩等の水溶性塩が例示される。これらの
出発原料のうち、上記（２）または（３）の方法に使用
することができる点で、可溶性塩類が好ましい。V, Cr, Mn, Fe, C in the present invention
o, Ni, Cu, Zn, Nb, Mo, W, Ru, Rh,
Examples of raw materials for Pd, Ag, and Pt include simple substances of these metals, powders such as oxides, hydroxides, and carbonates, and water-soluble salts such as nitrates, sulfates, and acetates. Among these starting materials, soluble salts are preferred since they can be used in the method (2) or (3) above.
【００１５】本発明において、上記触媒成分にさらにＶ
、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、
Ｍｏ、Ｗ、Ｒｕ、Ｒｈ、Ｐｄ、ＡｇおよびＰｔからなる
群より選ばれた少なくとも一種の金属またはその酸化物
を担持させる場合は、これらの金属の単体、酸化物およ
び／または硫酸塩を用いればよい。これらＶ、Ｃｒ等の
金属の単体、その酸化物またはその硫酸塩の好適な触媒
中の含有割合は、重量比で上記触媒成分９９．９〜１０
に対して０．１〜９０、より好ましくは、９９．９〜５
０に対して０．１〜５０である。各成分の反応速度への
寄与は定かではないが、上記範囲の重量比において、最
も大きな還元性を示す。In the present invention, V is further added to the above catalyst component.
, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb,
When at least one metal selected from the group consisting of Mo, W, Ru, Rh, Pd, Ag and Pt or its oxide is supported, if the simple substance, oxide and/or sulfate of these metals is used. good. The content ratio of these metals such as V and Cr, their oxides, or their sulfates in a suitable catalyst is 99.9 to 10% by weight of the above catalyst components.
0.1 to 90, more preferably 99.9 to 5
0.1 to 50. Although the contribution of each component to the reaction rate is not certain, it exhibits the greatest reducing ability in the weight ratio within the above range.
【００１６】上記成分以外に、必要に応じて粘土、メチ
ルセルロース、カルボキシメチルセルロース、カルボキ
シエチルセルロース、ポリエチレンオキサイド等の成形
助剤や、ガラス繊維等の補強剤を配合してもよい。但し
、これらの任意成分の総量は５０％以下におさえること
が好ましい。また、本発明に係る触媒をアルミナ、シリ
カ、チタニア、シリカ−アルミナ等の従来公知の担体に
担持させてもよい。本発明に係る触媒は、用途に応じて
、粉末状、タブレット状、球状、ハニカム状等、適宜の
形状に賦形することが可能である。In addition to the above-mentioned components, molding aids such as clay, methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, polyethylene oxide, etc., and reinforcing agents such as glass fiber may be blended as required. However, it is preferable that the total amount of these optional components is kept to 50% or less. Further, the catalyst according to the present invention may be supported on a conventionally known carrier such as alumina, silica, titania, silica-alumina, or the like. The catalyst according to the present invention can be shaped into an appropriate shape, such as powder, tablet, spherical, or honeycomb shape, depending on the intended use.
【００１７】還元剤として炭化水素を使用する場合の炭
化水素としては、アルカン、アルケン、アルキン等の脂
肪族系炭化水素、芳香族系炭化水素などが挙げられる。
この場合、選択的還元反応を示す温度は、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
にしたがって、その温度は低くなる。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が例示される。When a hydrocarbon is used as a reducing agent, examples of the hydrocarbon include aliphatic hydrocarbons such as alkanes, alkenes, and alkynes, and aromatic hydrocarbons. In this case, the temperature at which the selective reduction reaction occurs increases in the order of alkyne<alkene<aromatic hydrocarbon<alkane. Furthermore, in similar hydrocarbons, the temperature decreases as the number of carbon atoms increases. Suitable hydrocarbons include lower alkynes such as acetylene, methylacetylene and 1-butyne, lower alkenes such as ethylene, propylene, isobutylene, 1-butene and 2-butene, and lower dienes such as butadiene and isoprene.
【００１８】還元剤としてアルコール類を使用する場合
のアルコール類としては、脂肪族系アルコール、芳香族
系アルコールなどが挙げられる。好適なアルコール類と
しては、エタノール、プロパノール、イソプロパノール
、ｎ−ブチルアルコール、イソブチルアルコール、ｔｅ
ｒｔ−ブチルアルコール、アリルアルコール等の低級ア
ルコールが例示される。When alcohols are used as reducing agents, examples of the alcohols include aliphatic alcohols and aromatic alcohols. Suitable alcohols include ethanol, propanol, isopropanol, n-butyl alcohol, isobutyl alcohol, te
Examples include lower alcohols such as rt-butyl alcohol and allyl alcohol.
【００１９】上記炭化水素またはアルコール類の好適な
添加量は、その種類によって異なるが、窒素酸化物１モ
ルに対して０．１〜２モルの割合である。０．１モル未
満であると、充分な活性を得ることができず、また２モ
ルを越えると、未反応物や部分酸化生成物の排出量が多
くなるため、これを処理するための後処理が必要となる
。The preferred amount of the hydrocarbon or alcohol added varies depending on the type, but is in the range of 0.1 to 2 moles per mole of nitrogen oxide. If it is less than 0.1 mol, sufficient activity cannot be obtained, and if it exceeds 2 mol, a large amount of unreacted substances and partial oxidation products will be discharged, so post-treatment is required to deal with this. Is required.
【００２０】本発明に係る触媒が窒素酸化物に対して良
好な還元活性を示す温度は、使用する還元剤、触媒種に
より異なるが、通常１００〜１０００°Ｃの範囲であり
、この温度領域においては、５００〜５００００程度の
空間速度（ＳＶ）で排気ガスを通流させることが好まし
い。なお、より良好な還元活性を示す温度は、２００〜
８００°Ｃである。The temperature at which the catalyst of the present invention exhibits good reducing activity against nitrogen oxides varies depending on the reducing agent and catalyst type used, but is usually in the range of 100 to 1000°C; Preferably, the exhaust gas is passed through at a space velocity (SV) of about 500 to 50,000. In addition, the temperature showing better reduction activity is 200~
It is 800°C.
【００２１】上述したように、本発明に係る触媒は、排
気ガス温度１００〜１０００°Ｃの範囲において炭化水
素やアルコール類を還元剤として窒素酸化物を効率良く
接触還元することを可能ならしめる。As described above, the catalyst according to the present invention makes it possible to efficiently catalytically reduce nitrogen oxides using hydrocarbons or alcohols as reducing agents at exhaust gas temperatures in the range of 100 to 1000°C.
【００２２】[0022]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。
（１）触媒の調製[Examples] The present invention will be explained in more detail based on Examples below, but the present invention is not limited to the following Examples in any way, and may be practiced with appropriate modifications within the scope of the gist thereof. is possible. (1) Preparation of catalyst
【００２３】（実施例１）硝酸アルミニウム（Ａｌ（Ｎ
Ｏ３ ）３・９Ｈ２ Ｏ）と硝酸ランタン（Ｌａ（ＮＯ
３ ）３ ・６Ｈ２ Ｏ）との混合物の１００ｇ／リッ
トル濃度（酸化物換算）の水溶液に、１２．５重量％濃
度のアンモニア水を約１時間かけて滴下して加水分解し
、ＡｌとＬａとの水酸化物を共沈せしめ、約１時間熟成
した後、生成した沈澱物を、濾別、水洗した後、１２０
°Ｃで１８時間乾燥した。次いで、５００°Ｃで２時間
仮焼した後、８００°Ｃ、１０００°Ｃまたは１２００
°Ｃで３時間焼成して表１に示す１５種の触媒（以下、
順にＮｏ．１、２、３、４、５、６、７、８、９、１０
、１１、１２、１３、１４、１５と称す）を作製した。
表１に、各触媒の焼成温度および使用した出発原料のモ
ル比（硝酸アルミニウム：硝酸ランタン）を示す。Ｎｏ
．１〜１５の結晶構造をＸ線回折により調べた結果、Ｎ
ｏ．１〜５、Ｎｏ．８〜１０、および、Ｎｏ．１３〜１
５の触媒の結晶相は主にＬａＡｌＯ３ （ランタンアル
ミネート）であり、他の触媒の結晶相は主にＬａ−βＡ
ｌ２ Ｏ３ であった。(Example 1) Aluminum nitrate (Al(N)
O3 )3.9H2 O) and lanthanum nitrate (La(NO
3) Ammonia water with a concentration of 12.5% by weight was added dropwise to an aqueous solution of a mixture with 3.6H2O) at a concentration of 100g/liter (in terms of oxide) over about 1 hour to hydrolyze it, and the mixture was dissolved into Al and La. After co-precipitating the hydroxide of
Dry at °C for 18 hours. Next, after calcination at 500°C for 2 hours, 800°C, 1000°C or 1200°C
The 15 types of catalysts shown in Table 1 (hereinafter referred to as
In order No. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10
, 11, 12, 13, 14, and 15) were prepared. Table 1 shows the firing temperature of each catalyst and the molar ratio of the starting materials used (aluminum nitrate:lanthanum nitrate). No
．． As a result of examining the crystal structures of Nos. 1 to 15 by X-ray diffraction, N
o. 1 to 5, No. 8 to 10, and No. 13-1
The crystalline phase of the catalyst No. 5 is mainly LaAlO3 (lanthanum aluminate), and the crystalline phase of the other catalysts is mainly La-βA.
It was l2 O3.
【００２４】[0024]
【表１】[Table 1]
【００２５】（実施例２）実施例１で作製したＮｏ．７
を、シュウ酸バナジウム、硝酸クロム、硝酸マンガン、
硝酸鉄、硝酸コバルト、硝酸ニッケル、硝酸銅、硝酸亜
鉛、シュウ酸ニオブ、モリブデン酸アンモニウムおよび
メタタングステン酸アンモニウムの各水溶液にそれぞれ
浸漬し、１２０°Ｃで１８時間乾燥し、さらに５００°
Ｃで３時間焼成して、各金属を３重量％（酸化物換算）
担持せる１１種の触媒（以下、順にＮｏ．１６、１７、
１８、１９、２０、２１、２２、２３、２４、２５、２
６と称す）を作製した。(Example 2) No. 2 prepared in Example 1. 7
, vanadium oxalate, chromium nitrate, manganese nitrate,
It was immersed in each aqueous solution of iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, niobium oxalate, ammonium molybdate, and ammonium metatungstate, dried at 120°C for 18 hours, and further heated at 500°C.
Calcinate at C for 3 hours to reduce each metal to 3% by weight (calculated as oxide)
11 types of catalysts that can be supported (hereinafter, in order No. 16, 17,
18, 19, 20, 21, 22, 23, 24, 25, 2
6) was produced.
【００２６】（実施例３）γ−Ａｌ２ Ｏ３ （住友化
学社製、商品名「ガンマーアルミナＡ−１１」）と、硝
酸カリウム、硝酸ナトリウム、硝酸カルシウム、硝酸マ
グネシウムの各水溶液とを１：１２のモル比で混合し、
さらに遊星ミルにて充分磨砕混合した。次いで、１２０
°Ｃで１８時間乾燥し、５００°Ｃで２時間仮焼し、さ
らに１０００°Ｃで３時間焼成して４種の触媒（以下、
順にＮｏ．２７、２８、２９、３０と称す）を作製した
。また、焼成温度を１２００°Ｃに代えたこと以外は同
様にして４種の触媒（以下、順にＮｏ．３１、３２、３
３、３４と称す）を作製した。Ｎｏ．２７〜３０の結晶
相は主に各原子のアルミネートであり、Ｎｏ．３１〜３
４の結晶相は主にＡ・βＡｌ２Ｏ３ （ただし、ＡはＫ
、Ｎａ、Ｃａ、Ｍｇ）形の結晶系であった。(Example 3) γ-Al2O3 (manufactured by Sumitomo Chemical Co., Ltd., trade name "Gamma Alumina A-11") and aqueous solutions of potassium nitrate, sodium nitrate, calcium nitrate, and magnesium nitrate were mixed in a molar ratio of 1:12. Mix in ratio,
Further, the mixture was sufficiently ground and mixed using a planetary mill. Then 120
It was dried at °C for 18 hours, calcined at 500 °C for 2 hours, and further fired at 1000 °C for 3 hours to produce four types of catalysts (hereinafter referred to as
In order No. 27, 28, 29, and 30) were produced. In addition, four types of catalysts (hereinafter, No. 31, 32, 3 in order) were prepared in the same manner except that the calcination temperature was changed to 1200
3, 34) was prepared. No. The crystal phases of Nos. 27 to 30 are mainly aluminates of each atom; 31-3
The crystal phase of 4 is mainly A・βAl2O3 (However, A is K
, Na, Ca, Mg) type crystal system.
【００２７】（実施例４）２０ｇ／リットル濃度（Ａｌ
２ Ｏ３ 換算）の市販のアルミニウムイソプロポキシ
ド（関東化学社製）のエタノール溶液を、コンデンサー
を備えた４ツ口フラスコ内に入れ、この溶液に硝酸セリ
ウム水溶液を約１時間かけて滴下して加水分解し、Ａｌ
／Ｃｅモル比９：１の共沈物を得た。次いで、この共沈
物を１２０°Ｃで１８時間乾燥し、５００°Ｃで２時間
仮焼し、さらに８００°Ｃで３時間焼成して触媒（Ｎｏ
．３５）を作製した。Ｎｏ．３５の結晶相は主にＣｅＡ
ｌＯ３ （アルミネート）であった。(Example 4) 20g/liter concentration (Al
An ethanol solution of commercially available aluminum isopropoxide (manufactured by Kanto Kagaku Co., Ltd.) with an amount of Decompose, Al
A coprecipitate with a /Ce molar ratio of 9:1 was obtained. Next, this coprecipitate was dried at 120°C for 18 hours, calcined at 500°C for 2 hours, and further calcined at 800°C for 3 hours to form the catalyst (No.
．． 35) was prepared. No. The crystal phase of 35 is mainly CeA
It was lO3 (aluminate).
【００２８】（実施例５）Ｎｏ．３５を、硫酸ニッケル
の水溶液に浸漬し、１２０°Ｃで１８時間乾燥し、５０
０°Ｃで３時間焼成して、硫酸ニッケルを６重量％担持
せる触媒（Ｎｏ．３６）を作製した。(Example 5) No. 35 was immersed in an aqueous solution of nickel sulfate and dried at 120°C for 18 hours.
A catalyst (No. 36) capable of supporting 6% by weight of nickel sulfate was produced by firing at 0°C for 3 hours.
【００２９】（実施例６）実施例４において、硝酸セリ
ウム水溶液に代えて硝酸プラセオジム水溶液を用いると
ともに、焼成温度を８００°Ｃに代えて１０００°Ｃと
したこと以外は実施例４と同様にして触媒（Ｎｏ．３７
）を作製した。Ｎｏ．３７の結晶相は主にＰｒ・βＡｌ
２ Ｏ３ であった。(Example 6) Example 4 was carried out in the same manner as in Example 4, except that a praseodymium nitrate aqueous solution was used in place of the cerium nitrate aqueous solution, and the firing temperature was changed to 1000°C instead of 800°C. Catalyst (No. 37
) was created. No. The crystal phase of 37 is mainly Pr/βAl
It was 2 O3.
【００３０】（実施例７）Ｎｏ．３７を、塩化ルテニウ
ム、硝酸ルジウム、塩化パラジウム、硝酸銀または塩化
白金酸の各水溶液にそれぞれ浸漬し、１２０°Ｃで１８
時間乾燥し、さらに５００°Ｃで３時間焼成して、各金
属を０．５重量％担持せる５種の触媒（以下、順にＮｏ
．３８、３９、４０、４１、４２と称す）を作製した。(Example 7) No. 37 was immersed in each aqueous solution of ruthenium chloride, rudium nitrate, palladium chloride, silver nitrate or chloroplatinic acid, and heated at 120°C for 18
After drying for 3 hours and then calcining at 500°C for 3 hours, 5 types of catalysts (hereinafter No.
．． 38, 39, 40, 41, and 42) were produced.
【００３１】（比較例１）ＳｉＯ２ １００ｇを水４０
０ミリリットルに投入し 遊星ミルにて３０分間湿式
粉砕してスラリーを得た。このスラリーを、ろ別、乾燥
した後、５００°Ｃで３時間焼成して触媒（Ｎｏ．４３
）を得た。(Comparative Example 1) 100g of SiO2 was mixed with 40g of water.
0 ml and wet milled in a planetary mill for 30 minutes to obtain a slurry. This slurry was filtered, dried, and then calcined at 500°C for 3 hours to produce a catalyst (No. 43).
) was obtained.
【００３２】（比較例２）Ｎｏ．４３をＰｔ担持後の触
媒中のＰｔの重量分率が１％になるべき量のＰｔを含有
するＨ２ ＰｔＣｌ６ 水溶液５００ミリリットルに浸
漬し、攪拌しながら、理論量の１．２倍のヒドラジンを
加えてＨ２ ＰｔＣｌ６ を還元した後、ろ別、水洗、
１００°Ｃで１８時間乾燥して触媒（Ｎｏ．４４）を得
た。(Comparative Example 2) No. 43 was immersed in 500 ml of H2PtCl6 aqueous solution containing Pt in an amount that would make the weight fraction of Pt in the catalyst after Pt support 1%, and while stirring, 1.2 times the theoretical amount of hydrazine was added. After reducing H2PtCl6, filtration, washing with water,
The catalyst (No. 44) was obtained by drying at 100°C for 18 hours.
【００３３】（２）評価試験
Ｎｏ．１〜４４について、下記の試験条件により窒素酸
化物含有ガス中の窒素酸化物の接触還元を行い、窒素酸
化物のＮ２ への転換率を、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）
（２）空間速度 １０００ １
／Ｈｒ（３）反応温度 ３００°Ｃ、４００°Ｃ
、５００°Ｃまたは６００°Ｃ
結果を表２〜４に示す。(2) Evaluation test No. For Nos. 1 to 44, catalytic reduction of nitrogen oxides in nitrogen oxide-containing gases was carried out under the following test conditions, and the conversion rate of nitrogen oxides to N2 was calculated by quantifying N2 by gas chromatography. (Test conditions) (2) Space velocity 1000 1
/Hr (3) Reaction temperature 300°C, 400°C
, 500°C or 600°C The results are shown in Tables 2-4.
【００３４】[0034]
【表２】[Table 2]
【００３５】[0035]
【表３】[Table 3]
【００３６】[0036]
【表４】[Table 4]
【００３７】表２〜４より、本発明に係る窒素酸化物接
触還元用触媒（Ｎｏ．１〜４２）は、いずれも窒素酸化
物のＮ２ への転化率が高いのに対して、従来の一成分
または二成分系の触媒（Ｎｏ．４３および４４）は、い
ずれの反応温度においても総じて転化率が低いことが分
かる。Tables 2 to 4 show that the catalysts for catalytic reduction of nitrogen oxides (Nos. 1 to 42) according to the present invention all have a high conversion rate of nitrogen oxides to N2, whereas the conventional catalysts have a high conversion rate of nitrogen oxides to N2. It can be seen that the component or two-component catalysts (Nos. 43 and 44) generally have low conversion rates at any reaction temperature.
【００３８】[0038]
【発明の効果】以上、詳細に説明したように、本発明に
係る窒素酸化物接触還元用触媒は、酸素の存在下におい
て排気ガス中の窒素酸化物を効率良く接触還元すること
ができるなど、本発明は優れた特有の効果を奏する。Effects of the Invention As described above in detail, the catalyst for catalytic reduction of nitrogen oxides according to the present invention can efficiently catalytically reduce nitrogen oxides in exhaust gas in the presence of oxygen, etc. The present invention has excellent unique effects.
Claims (3)
およびＰｒからなる群より選ばれた少なくとも一種の金
属のアルミン酸塩を触媒成分として含有することを特徴
とする窒素酸化物接触還元用触媒。Claim 1: K, Na, Ca, Mg, Ba, La, Ce
A catalyst for catalytic reduction of nitrogen oxides, comprising as a catalyst component an aluminate of at least one metal selected from the group consisting of Pr and Pr.
物質を触媒成分として含有することを特徴とする窒素酸
化物接触還元触媒。〔ただし、式中、ＸはＫ、Ｎａ、Ｃ
ａ、Ｍｇ、Ｂａ、Ｌａ、ＣｅおよびＰｒからなる群より
選ばれた少なくとも一種の元素である。〕2. A nitrogen oxide catalytic reduction catalyst characterized by containing a substance represented by the compositional formula X.β-Al2 O3 as a catalyst component. [However, in the formula, X is K, Na, C
At least one element selected from the group consisting of a, Mg, Ba, La, Ce, and Pr. ]
、Ｚｎ、Ｎｂ、Ｍｏ、Ｗ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇおよ
びＰｔからなる群より選ばれた少なくとも一種の金属、
その酸化物および／またはその硫酸塩を含有する請求項
１または２記載の窒素酸化物接触還元用触媒。Claim 3: V, Cr, Mn, Fe, Co, Ni, Cu
, at least one metal selected from the group consisting of Zn, Nb, Mo, W, Ru, Rh, Pd, Ag and Pt,
The catalyst for catalytic reduction of nitrogen oxides according to claim 1 or 2, comprising an oxide thereof and/or a sulfate thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3089700A JPH04298235A (en) | 1991-03-27 | 1991-03-27 | Catalyst for contact reduction of nox |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3089700A JPH04298235A (en) | 1991-03-27 | 1991-03-27 | Catalyst for contact reduction of nox |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04298235A true JPH04298235A (en) | 1992-10-22 |
Family
ID=13978051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3089700A Pending JPH04298235A (en) | 1991-03-27 | 1991-03-27 | Catalyst for contact reduction of nox |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04298235A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0667182A2 (en) * | 1994-02-10 | 1995-08-16 | Kabushiki Kaisha Riken | Exhaust gas cleaner and method for cleaning exhaust gas |
| EP0788829A1 (en) * | 1996-02-08 | 1997-08-13 | Sakai Chemical Industry Co., Ltd., | Catalyst and method for catalytic reduction of nitrogen oxides |
| WO2007049778A1 (en) * | 2005-10-24 | 2007-05-03 | Toyota Jidosha Kabushiki Kaisha | Catalyst support and catalyst for exhaust-gas purification |
| JP2007117852A (en) * | 2005-10-26 | 2007-05-17 | Mitsui Mining & Smelting Co Ltd | Catalyst for purification of exhaust gas and its manufacturing method |
| JP2012139631A (en) * | 2010-12-28 | 2012-07-26 | Jgc Catalysts & Chemicals Ltd | Exhaust gas purifying catalyst and method of manufacturing exhaust gas purifying catalyst |
| JP2013013834A (en) * | 2011-06-30 | 2013-01-24 | Daihatsu Motor Co Ltd | Exhaust gas purifying catalyst |
| US9492814B2 (en) | 2013-04-08 | 2016-11-15 | Saudi Basic Industries Corporation | Catalyst for conversion of propylene to product comprising a carboxylic acid moiety |
-
1991
- 1991-03-27 JP JP3089700A patent/JPH04298235A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0667182A2 (en) * | 1994-02-10 | 1995-08-16 | Kabushiki Kaisha Riken | Exhaust gas cleaner and method for cleaning exhaust gas |
| EP0667182A3 (en) * | 1994-02-10 | 1995-10-18 | Riken Kk | Exhaust gas cleaner and method for cleaning exhaust gas. |
| EP0788829A1 (en) * | 1996-02-08 | 1997-08-13 | Sakai Chemical Industry Co., Ltd., | Catalyst and method for catalytic reduction of nitrogen oxides |
| WO2007049778A1 (en) * | 2005-10-24 | 2007-05-03 | Toyota Jidosha Kabushiki Kaisha | Catalyst support and catalyst for exhaust-gas purification |
| US7776783B2 (en) | 2005-10-24 | 2010-08-17 | Toyota Jidosha Kabushiki Kaisha | Catalyst carrier and exhaust gas purification catalyst |
| JP2007117852A (en) * | 2005-10-26 | 2007-05-17 | Mitsui Mining & Smelting Co Ltd | Catalyst for purification of exhaust gas and its manufacturing method |
| JP2012139631A (en) * | 2010-12-28 | 2012-07-26 | Jgc Catalysts & Chemicals Ltd | Exhaust gas purifying catalyst and method of manufacturing exhaust gas purifying catalyst |
| JP2013013834A (en) * | 2011-06-30 | 2013-01-24 | Daihatsu Motor Co Ltd | Exhaust gas purifying catalyst |
| US9492814B2 (en) | 2013-04-08 | 2016-11-15 | Saudi Basic Industries Corporation | Catalyst for conversion of propylene to product comprising a carboxylic acid moiety |
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