CN101209417A - Complex and car tail gas purifying catalyst containing the same - Google Patents
Complex and car tail gas purifying catalyst containing the same Download PDFInfo
- Publication number
- CN101209417A CN101209417A CNA2006101705984A CN200610170598A CN101209417A CN 101209417 A CN101209417 A CN 101209417A CN A2006101705984 A CNA2006101705984 A CN A2006101705984A CN 200610170598 A CN200610170598 A CN 200610170598A CN 101209417 A CN101209417 A CN 101209417A
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- Prior art keywords
- compound
- xrd diffraction
- diffraction maximum
- catalyst
- rare earth
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 150000001875 compounds Chemical class 0.000 claims abstract description 107
- 239000010970 precious metal Substances 0.000 claims abstract description 46
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 43
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 43
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims description 32
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 claims description 32
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 28
- 239000000969 carrier Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 25
- 229910000510 noble metal Inorganic materials 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 21
- 239000006104 solid solution Substances 0.000 claims description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 5
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- 230000001186 cumulative effect Effects 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 47
- 239000010948 rhodium Substances 0.000 description 47
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 41
- 238000002441 X-ray diffraction Methods 0.000 description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 description 27
- 239000000446 fuel Substances 0.000 description 26
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 25
- 238000001556 precipitation Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 239000002002 slurry Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 18
- 150000002430 hydrocarbons Chemical class 0.000 description 18
- 229910052763 palladium Inorganic materials 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000004215 Carbon black (E152) Substances 0.000 description 17
- 238000000498 ball milling Methods 0.000 description 17
- 229910052703 rhodium Inorganic materials 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- HLRPCWSWHIWFHM-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) zirconium(4+) Chemical class [O--].[O--].[O--].[O--].[O--].[Zr+4].[La+3].[Ce+3] HLRPCWSWHIWFHM-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- -1 rare-earth compound Chemical class 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 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 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 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 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 3
- 229910001630 radium chloride Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- QZVAOGVRRCUABO-UHFFFAOYSA-N cerium(3+) oxygen(2-) praseodymium(3+) zirconium(4+) Chemical compound [O-2].[Zr+4].[Ce+3].[Pr+3].[O-2].[O-2].[O-2].[O-2] QZVAOGVRRCUABO-UHFFFAOYSA-N 0.000 description 2
- WPQBNJRIWONKBL-UHFFFAOYSA-N cerium(3+);oxygen(2-);zirconium(4+) Chemical class [O-2].[Zr+4].[Ce+3] WPQBNJRIWONKBL-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Images
Abstract
The invention relates to a compound and an automobile exhaust purification catalyst containing the composite. The composite contains precious metal oxides and rare earth metal oxides; the position of characteristic XRD diffraction peak corresponds to the position of characteristic XRD diffraction peak of independently existing precious metal oxides and rare earth metal oxides, and the characteristic XRD diffraction peak of precious metal oxides and that of rare earth metal oxides in the characteristic XRD diffraction peak of the compound are respectively deviate from the characteristic XRD diffraction peak of independently existing precious metal oxides and rare earth metal oxides. The automobile exhaust purification catalyst has better heat proof and anti-aging capacities.
Description
Technical field
The present invention relates to a kind of compound and preparation method thereof, also relate to the cleaning catalyst for tail gases of automobiles that is used for that contains this compound.
Background technology
Along with developing of automobile industry, automobile pollution increases sharply, and motor vehicle exhaust emission has become the primary pollution source of atmosphere pollution, particularly urban atmospheric pollution, therefore the research of vehicle exhaust has been become an importance of environmental pollution improvement.Now, be extensive use of cleaning catalyst for tail gases of automobiles in the world and come purifying motor tail gas effectively, cleaning catalyst for tail gases of automobiles is mainly used in removes HC, NOx and three kinds of harmful substances of CO.Typical cleaning catalyst for tail gases of automobiles is made up of carrier, catalytic active component, hydrogen-storing material, and its catalytic active component is a noble metal, is in the noble metals such as Pt, Pd, Rh one or more, and they are scattered on the carrier with Large ratio surface.Because noble metal is Rh scarcity of resources and costing an arm and a leg especially, add that noble metal component runs off and sintering easily under hot conditions, thus need to reduce the consumption of noble metal, and keep good low temperature active and high high-temp stability and the ageing resistace of noble metal.
At present, although people are carrying out many research work aspect minimizing and the alternative noble metal, as US4738947, US6569803, US20050221979, CN98122041 and CN200510087450 etc., but because the non-precious metal catalyst low temperature active is poor, under excess oxygen easy shortcomings such as inactivation, reducing NOx ability, sulfur resistance difference, so main flow automobile in the market still is to select noble metal catalyst for use.
CN1251055A discloses a kind of carbon monoxide-olefin polymeric that contains the intimately mixed oxide of cerium and praseodymium, and said composition comprises the matrix that is distributed with following material on it: (a) include of catalytically effective amount
One catalytic metal component is disperseed the catalytic specie of refractory carrier material thereon, (b) with its on have the refractory carrier material of described first catalytic metal component to separate oxygen storage components, described oxygen storage components comprises the cerium that is selected from common shaping mixed oxide, sintered oxide and composition thereof and the immixture of praseodymium, the Pr:Ce atomic ratio is in about 2: 100 to 100: 100 scopes, and have the platinum component of catalytically effective amount to disperse thereon, wherein said oxygen storage components accounts at least 5% (weight) of the gross weight of described oxygen storage components and catalytic specie.Described first catalytic metal component comprises platinum group metal component.But the ageing resistace of this catalyst is relatively poor.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming of above-mentioned catalyst ageing resistace difference, a kind of ageing resistace that makes catalyst compound preferably is provided, the cleaning catalyst for tail gases of automobiles that contains this compound also is provided.
The invention provides a kind of compound, this compound contains metal oxide containing precious metals and rare-earth oxide, the feature XRD diffraction maximum of this compound is corresponding with the position of the feature XRD diffraction maximum of self-existent metal oxide containing precious metals and rare earth oxide, and the feature XRD diffraction maximum of metal oxide containing precious metals and the feature XRD diffraction maximum of rare-earth oxide depart from self-existent metal oxide containing precious metals and rare earth oxide feature XRD diffraction maximum respectively in the feature XRD diffraction maximum of this compound.
The present invention also provides cleaning catalyst for tail gases of automobiles, and this catalyst contains catalytic active component, hydrogen-storing material, heat-resistant carriers, and wherein, described catalytic active component is a compound provided by the invention.
Adopt the catalytic active component of compound provided by the invention, make the heat resistanceheat resistant ageing resistace of this catalyst good, improved the durability of catalyst as cleaning catalyst for tail gases of automobiles.Reduced the use amount of noble metal simultaneously, thereby can reduce cost.And in the air-fuel ratio scope of broad, good catalytic performance is arranged.
Description of drawings
Fig. 1 is Compound P dO, Pr
6O
11And compound PdO-Pr of the present invention
6O
11(Pd/Pr=1/2.5) X-ray diffractogram.
Fig. 2 is compound R h
2O
3, Pr
6O
11And compound Rh of the present invention
2O
3-Pr
6O
11(Rh/Pr=1/2) X-ray diffractogram.
Fig. 3 is that the catalyst of embodiment 1 and Comparative Examples 1-2 compares the air-fuel ratio characteristic that CO purifies.
Fig. 4 is that the catalyst of embodiment 1 and Comparative Examples 1-2 compares the air-fuel ratio characteristic that HC purifies.
Fig. 5 is that the catalyst of embodiment 1 and Comparative Examples 1-2 compares the air-fuel ratio characteristic that NO purifies.
The specific embodiment
Compound of the present invention contains metal oxide containing precious metals and rare-earth oxide, the feature XRD diffraction maximum of this compound is corresponding with the position of the feature XRD diffraction maximum of self-existent metal oxide containing precious metals and rare earth oxide, and the feature XRD diffraction maximum of metal oxide containing precious metals and the feature XRD diffraction maximum of rare-earth oxide depart from self-existent metal oxide containing precious metals and rare earth oxide feature XRD diffraction maximum respectively in the feature XRD diffraction maximum of this compound.
" self-existent " as herein described expression exists with pure form or physical mixed form.For example, self-existent metal oxide containing precious metals represents, pure metal oxide containing precious metals or with the metal oxide containing precious metals of other material physical mixed.
In compound provided by the invention, the angle of diffraction 2 θ of metal oxide containing precious metals feature XRD diffraction maximum are less than the angle of diffraction 2 θ of self-existent metal oxide containing precious metals feature XRD diffraction maximum, and the angle of diffraction 2 θ of the rare earth oxide feature XRD diffraction maximum in the described compound are greater than the angle of diffraction 2 θ of self-existent rare earth oxide feature XRD diffraction maximum.
According to compound provided by the invention, metal oxide containing precious metals is preferably palladium, rhodium and/or palladium oxide, rhodium oxide, rare earth oxide is preferably praseodymium oxide, the angle of diffraction 2 θ of the metal oxide containing precious metals feature XRD diffraction maximum in the described compound are less than the angle of diffraction 2 θ at least 0.07 degree of self-existent metal oxide containing precious metals feature XRD diffraction maximum, be preferably the 0.1-2.0 degree, the angle of diffraction 2 θ of the rare earth oxide feature XRD diffraction maximum in the described compound are greater than the angle of diffraction 2 θ at least 0.1 degree of self-existent rare earth oxide feature XRD diffraction maximum, be preferably the 0.2-1.0 degree, more preferably the 0.2-0.6 degree.
According to compound provided by the invention, metal oxide containing precious metals feature XRD diffraction maximum in the described compound refers to a diffraction maximum with the corresponding intensity maximum in position of self-existent metal oxide containing precious metals feature XRD diffraction maximum, and the rare earth oxide feature XRD diffraction maximum in the described compound refers to two diffraction maximums with the corresponding intensity maximum in position of the feature XRD diffraction maximum of self-existent rare earth oxide.These two characteristic diffraction peaks be on (111) (200) two crystal faces diffraction maximum.
In compound provided by the invention, under the preferable case, the atomic ratio of described noble metal and described rare earth element is 0.1-3, more preferably 0.3-1.
In compound provided by the invention, described noble metal is selected from one or more in Pt, Pd, Rh, Ru, Ir, Au, Ag and the Os element, and in the preferred case, Pt, Pd and Rh only select a kind of in the above-mentioned metal.In compound of the present invention, adopt the oxide of above-mentioned noble metal, suitable hydrocarbon adsorption potential is not only arranged, and a large amount of oxygen adsorption potentials is arranged,, the absorption of oxygen activation and hydrocarbon can take place fast with the carrying out of surface reaction, thereby reducing NOx rapidly, and oxidation CO and HC.
In compound provided by the invention, described rare earth element is selected from one or more among Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or the Lu.When rare earth element was praseodymium, the outer-shell electron of praseodymium was arranged and is 4f
36s
2, the praseodymium in the praseodymium oxide has Pr
4+, Pr
3+Two kinds of valence states, common praseodymium oxide are Pr
6O
11
In the compound of metal oxide containing precious metals and rare earth oxide, there is strong interaction between the oxide of metal oxide containing precious metals and rare earth element, this strong interaction makes the original structure of metal oxide containing precious metals and rare earth oxide that certain change take place, and the change of this structure has promoted concerted catalysis effect between metal oxide containing precious metals and the rare earth oxide just.For example, in the presence of praseodymium oxide, the oxide of platinum, palladium and/or platinum, palladium is easier being reduced in reducing atmosphere, and its catalytic activity is improved, and praseodymium oxide can keep the dispersiveness of noble metal under the hot conditions well, prevents that noble metal is because of the sintering inactivation.In addition, because appraising at the current rate of praseodymium element strengthened the storage oxygen function of catalyst, make noble metal in bigger air-fuel ratio scope, bring into play catalytic action.For example, the compound PdO-Pr of palladium oxide and praseodymium oxide
6O
11The catalytic performance of palladium is improved greatly, especially when oxidation CO, HC and the situation after the catalyst ageing.A major reason of this change is that the strong interaction between palladium oxide and the praseodymium oxide has suppressed precious metal palladium loss at high temperature, thereby has strengthened the stability and the durability of palladium.In compound provided by the invention, owing to there is this strong interaction, just can avoid forming alloy (as the Pd-Rh alloy) between the noble metal and the catalysqt deactivation that causes.
" air-fuel ratio " described here is the ratio of air and fuel mass.When air-fuel ratio hour does not have enough oxygen to burn down fuel, and cause the part of fuel imperfect combustion, hydrocarbon (HC), carbon monoxide (CO) growing amount are higher.Along with the increase of air-fuel ratio, CO is on a declining curve always; HC descended before this, gaseous mixture cross when rare can appearance point missing of ignition or flame propagation interrupt, HC discharges increase.Nitrogen oxide (NO
X) formation condition be high temperature in the combustion chamber, oxygen enrichment, when gaseous mixture is richer than theoretical value slightly, discharge.In catalyst, the conversion of HC and CO belongs to oxidation reaction, needs extra oxygen; NO
XConversion belong to reduction reaction, need deoxidation.Therefore, HC, CO transformation efficiency height during oxygen enrichment, NO during oxygen deprivation
XThe transformation efficiency height.In near the scope theoretical value, HC, CO and NO
XTransformation efficiency is called the air-fuel ratio window all than higher.The air-fuel ratio window is an important parameter selecting and mate catalyst.
The preparation method of compound provided by the invention is, precious metal chemical complex is mixed with the solution of rare-earth compound, the pH of regulator solution is 6-10, isolate the solid precipitation that obtains, with the dry and roasting of solid precipitation that obtains, the temperature of described roasting is 350-750 ℃, and roasting time is 1-8 hour.
In the preparation method of compound provided by the invention, the pH of regulator solution is 6-10, is preferably 7-8.The method of regulating the pH value is well known by persons skilled in the art, for example, and can be by adding acidity or alkaline matter is regulated.Acidic materials and alkaline matter can be any acidity well known by persons skilled in the art and alkaline matter, under the preferable case, acidic materials can be inorganic acids such as nitric acid, hydrochloric acid, carbonic acid, silicic acid, also can be solubility organic acids such as formic acid, acetate, can also be ackd salts such as ammonium chloride, ammonium nitrate; Alkaline matter can be an ammoniacal liquor, sodium acetate, potassium acetate, one or more in the sodium metasilicate etc.
In some cases, in two kinds of solution of precious metal chemical complex and rare-earth compound, when a kind of solution is acid, another kind of solution is alkalescence, and the scope of mixing back pH value reaches 6-10, preferably during 7-8, two kinds of solution mix can directly produce precipitation, for example uses Pd (NH
3)
2Cl
2The aqueous solution and the aqueous solution of praseodymium nitrate can directly produce precipitation.
In the preparation method of compound provided by the invention, described precious metal chemical complex and rare-earth compound all can be any soluble salt, are preferably nitrate, acetate, halide, oxyhalide or alkoxide.Solvent in described noble metal and the rare-earth compound solution can include but not limited to methyl alcohol, ethanol, polyalcohol etc. for water, alcohols or other polar organic solvent.Generally speaking, solvent is preferably water.As known to those skilled in the art, the aqueous solution of noble metal and rare-earth compound can be acidity, alkalescence or neutral, as long as guarantee to mix all dissolvings fully of compound of preceding noble metal and rare earth element.
In compound provided by the invention, in the preferred case, as long as do not hinder in the scope of effect of the present invention, other metallic element and/or metallic compound again can mix in compound, as Ni, V, Y, La, Ti, Co, Cu, Sc, Fe, Zr, Mo or Mn, the content of doping metals and/or metallic compound is the 0-10 weight % of described compound content, preferred 0.1-8 weight %.The metal and/or the metallic compound that mix can obviously suppress noble metal, especially platinosis, increase the adsorbance to NOx, improve the activity that purifies NOx.
The method that adds doping metals and/or metal oxide in described compound is any method well known by persons skilled in the art, for example physical mixed or closely mixing." closely mixing " as herein described, be meant the state of the tightness degree of each composition greater than the simple physical mixture, this term is got rid of simple physics and is mixed, but does not require the real chemical compound state between each composition.Closely mixing can be by immersing another with one of each composition, each composition is shaped altogether or each composition is evenly mixed after together sintering obtain." being shaped altogether " is meant that two or more compositions disperse on the whole fully, can be by co-precipitation or cogelled generation.
In the preferred case, the doping method of described doping metals and/or blended metal oxide is, in the solution that contains precious metal chemical complex and rare-earth compound, add the doping metals compound, come out with described mixture coprecipitation then, and separation, roasting.
According to cleaning catalyst for tail gases of automobiles provided by the invention, this catalyst contains catalytic active component, hydrogen-storing material, heat-resistant carriers, and wherein, described catalytic active component is a compound provided by the invention.
Catalyst provided by the invention preferred embodiment in, total amount with catalytic active component, hydrogen-storing material, heat-resistant carriers is a benchmark, the content of described catalytic active component is 0.01-5 weight %, preferred 0.02-3 weight %, the content of described hydrogen-storing material is 0-50 weight %, preferred 10-40 weight %, and the content of described heat-resistant carriers is 45-99.9 weight %, preferred 57-90 weight %.
Gross weight with catalyst is a benchmark, and the content of described noble metal is the 0.02-2 grams per liter, and wherein, the content of Rh is less than 0.1 grams per liter.
In catalyst of the present invention, described hydrogen-storing material is the solid solution of cerium Zirconium oxide, as co-catalyst.It act as, and can reduce noble metal dosage, changes catalyst electronic structure and surface nature, and catalyst activity and stability are provided, and has outstanding oxygen storage capacity.Utilize the oxygen uptake storage oxygen function of cerium Zirconium oxide, when lean-burn, absorb unnecessary oxygen in the tail gas, thereby guarantee NO
XReduction reaction; The oxygen that discharges storage when richness is fired is with too much HC and CO in the oxidized tail gas better.
The solid solution of described cerium Zirconium oxide can be by commercially available, and for example the trade mark is the cerium zirconium sosoloid of CZ-370.Also can obtain, for example coprecipitation, cogelled method, hydrothermal synthesis method, template, microemulsion method etc. by known any method.Described coprecipitation method is by the soluble-salt of cerium and zirconium, for example chloride, sulfate, nitrate, acetate, carry out co-precipitation,, in air, obtain the solid solution of cerium Zirconium oxide then at 500 ℃ or higher roasting temperature with this precipitate and separate, washing, drying.Described cogelled be exactly to utilize the colloidal sol of cerium and zirconium to prepare the sol-gel process of gel.Also can be by known any method with one of cerium oxide or zirconia dipping or be dispensed in another oxide, dry then, in air at 500 ℃ or higher roasting temperature, obtain the solid solution of cerium Zirconium oxide.Can also cerium oxide and zirconia thoroughly be mixed by known any method, then in air at 500 ℃ or higher roasting temperature, make cerium oxide and zirconic mixture generation chemistry and/or physical change, obtain the solid solution of cerium Zirconium oxide.
The cerium Zirconium oxide solid solution that uses which kind of method to obtain all should produce and contain cerium oxide and be dispersed in the zirconia, or zirconia is dispersed in the product in the cerium oxide.
Catalyst provided by the invention preferred embodiment in, also can add in the cerium Zirconium oxide and store up the cerium Zirconium oxide that the oxygen auxiliary agent becomes mixing, this storage oxygen auxiliary agent is selected from one or more rare earth elements among La, Pr, Nd, Sm, Y, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu.The present invention does not limit the shared ratio of each element of being mixed in the cerium Zirconium oxide, 0-100 weight % all can, as long as this material has storage oxygen function, be preferably 0.1-30 weight %.
In catalyst provided by the invention, described heat-resistant carriers is for it be known to those skilled in the art that generally speaking the preferred γ-Al of described heat-resistant carriers
2O
3, TiO
2, ZrO
2, SiO
2, in amorphous aluminum silicide or the molecular sieve one or more.The oxide that can also be added in an amount of one or more elements in the alkaline-earth metal, transition metal, rare earth metal of the 0-8 weight % of heat-resistant carriers gross weight in described heat-resistant carriers is as the carrier auxiliary agent.
Also contain matrix at catalyst provided by the invention.Generally speaking, the matrix that is adopted has low specific area usually, and aeration resistance is little, is used for catalyst-loaded.This matrix is for it be known to those skilled in the art that generally speaking one or more among the preferred cellular cordierite of described matrix, mullite, aluminum magnesium titanate and the Fe-Cr-Al.These matrixes have low thermal coefficient of expansion and outstanding thermal-shock resistance.
The preparation method of cleaning catalyst for tail gases of automobiles of the present invention can adopt any known preparation method preparation.In the preferred case, catalytic active component, hydrogen-storing material are mixed with heat-resistant carriers, obtain mixture, the gained mixture is added the water grinding make slurry, be coated on the matrix.
With in compound and the process that cerium Zirconium oxide and heat-resistant carriers are mixed, can adopt any known mode, method to mix, for example, mix with heat-resistant carriers again after can compound being carried on the cerium Zirconium oxide earlier, also compound can be carried on the mixture of cerium Zirconium oxide and refractory oxides.
Compound is carried on the cerium Zirconium oxide, the precipitation that noble metal compound solution and rare-earth compound solution generate directly can be mixed with the cerium Zirconium oxide, by wet grinding for example behind the wet ball grinding drying, roasting prepare the mixture of described compound and cerium Zirconium oxide.Roasting can be carried out in air atmosphere, also can carry out in a vacuum or in the inert gas atmosphere, can also carry out in reducing gas atmosphere.Described inert gas can be nitrogen, argon gas or its gaseous mixture.Described reducing gas can be H
2, CO or its gaseous mixture.Roasting is carried out at 350-750 ℃ usually, preferred 400-600 ℃.The time of carrying out roasting was generally 1-8 hour, preferred 2-4 hour.
Compound is carried on the cerium Zirconium oxide, also the precipitate and separate of noble metal compound solution and the generation of rare-earth compound solution can be come out, for example by separation method centrifugal or that filter, dry then, roasting, product after the roasting is mixed with the cerium Zirconium oxide, with dry grinding for example dry ball milling prepare the mixture of described compound and cerium Zirconium oxide.The condition of roasting can be identical with above-mentioned condition.
Compound is carried on after the cerium Zirconium oxide, mixes with heat-resistant carriers again, add water and grind, for example adopt ball grinding method, preparation coating paste, coated substrates.The method that applies slurry on matrix then is well-known to those skilled in the art, for example adopts the method for dipping or spraying that slurry is coated on the matrix, discharges unnecessary slurry then, and dry again, roasting coating promptly make the catalyst that is carried on the matrix.Also can adopt repeatedly applying coating on matrix of identical or different slurries, make the overbrushing layer and be carried on catalyst on the matrix.
The catalyst of making that is carried on the matrix activates and can use.The purpose of catalyst activation is to make the metal oxide containing precious metals in the catalyst be reduced to the simple substance form, and activation process is roasting in the atmosphere of reducing gas normally, and the temperature of roasting is generally 350-600 ℃.The example of described reducing gas comprise hydrogen,
Carbon monoxide and contain in the hydro carbons of 1-5 carbon atom one or more preferably includes in hydrogen, carbon monoxide, methane, ethane, interior alkane, butane, pentane and the various isomers thereof one or more.The gaseous mixture of hydrogen, carbon monoxide or hydrogen and carbon monoxide more preferably.
But, also can not need activate for cleaning catalyst for tail gases of automobiles, owing to contain in the vehicle exhaust
Carbon monoxide, therefore new catalyst vehicle exhaust by the time can be reduced and activate.
Below by non-limiting embodiment Catalysts and its preparation method of the present invention is described in further detail.Pd (the NH that is adopted
3)
2Cl
2, praseodymium nitrate, lanthanum nitrate, barium nitrate, zirconium nitrate, aluminum nitrate, radium chloride be analyze pure.The cerium Zirconium oxide solid solution that is adopted is that the trade mark of Zibo China celebrating powder body material technology company is the cerium Zirconium oxide solid solution of CZ-370, and cerium zirconium praseodymium oxide solid solution is that the trade mark of Zibo China celebrating powder body material technology company is the cerium zirconium praseodymium oxide solid solution of CZ-460.
Pd (the NH that will contain 1.58 gram palladiums
3)
2Cl
2Concentrated ammonia solution and the praseodymium nitrate aqueous solution that contains 5.23 gram praseodymiums produce during pH value to 7 left and right sides of mixed solution and precipitate.Precipitation and centrifugal separation is obtained solid precipitation, the solid that obtains is deposited in 90 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours make compound PdO-Pr
6O
11
The compound and the 200 gram cerium Zirconium oxides that make are mixed, and the particle diameter of dry ball milling to 90% particle obtains PdO-Pr less than 10 microns
6O
11The mixture of compound and cerium Zirconium oxide.
Again with 200 restrain PdO-Pr
6O
11The mixture of compound and cerium Zirconium oxide and 700 gram γ-Al
2O
3Mix, promptly obtain coating paste I after adding 1300 ml deionized water ball millings.
In the mixed aqueous solution of radium chloride that contains 0.37 gram rhodium and the praseodymium nitrate that contains 0.98 gram praseodymium, add ammonia spirit to pH value and be about 9.0, produce precipitation.Precipitation and centrifugal separation is obtained solid precipitation, the solid that obtains is deposited in 90 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours make compound Rh
2O
3-Pr
6O
11
With the compound Rh that makes
2O
3-Pr
6O
11Mix with 200 gram cerium Zirconium oxides, the particle diameter of dry ball milling to 90% particle makes compound Rh less than 10 microns
2O
3-Pr
6O
11Mixture with the cerium Zirconium oxide.
With 200 restrain Rh
2O
3-Pr
6O
11The mixture of compound and cerium Zirconium oxide and 700 gram γ-Al
2O
3Mix, add 1300 ml deionized water again after ball milling promptly obtain coating paste II.
To be of a size of 102 * 123 millimeters of Φ, porosity is 400 hole/inches
2Cordierite honeycomb ceramic matrix 435 gram immerse among the above-mentioned aquifer coating slurry I, the vacuumizing and adsorbing slurry blows down remaining slurry in the duct then, in 4 hours, 600 ℃ roastings of 90 ℃ of dryings 4 hours, has obtained applying the matrix of slurry I.The same operation then applies slurry II, has obtained applying the matrix of slurry I (load capacity is 91 grams per liters) and slurry II (load capacity is 108 grams per liters), and then activates 1.5 hours in 500 ℃ hydrogen atmosphere, promptly makes the catalyst that is carried on the matrix.At catalyst activity composition PdO-Pr
6O
11Middle palladium and praseodymium atomic ratio are 0.40, at Rh
2O
3-Pr
6O
11Middle rhodium and praseodymium atomic ratio are 0.50.In catalyst, each constituent content is respectively palladium 0.16 grams per liter, rhodium 0.04 grams per liter, and praseodymium 0.64 grams per liter, the total content of catalytic active component, hydrogen-storing material and heat-resistant carriers are 200 grams per liters.
With PdO-Pr among the embodiment 1
6O
11Solid composite do X-ray diffraction (XRD) test, and with pure PdO and Pr
6O
11XRD figure compare, the results are shown in Figure 1.Among Fig. 1, a
1, a
2Expression Pr
6O
11Characteristic diffraction peak, b represents the characteristic diffraction peak of PdO; a
1', a
2' expression and a
1, a
2Corresponding compound PdO-Pr
6O
11Middle Pr
6O
11(111) (200) two crystal faces on characteristic diffraction peak, b ' expression and the corresponding compound PdO-Pr of b
6O
11Characteristic diffraction peak on (101) crystal face of middle PdO.As can be seen from Figure 1, compound PdO-Pr
6O
11(Pd/Pr=1/2.5) PdO and Pr in
6O
11XRD characteristic diffraction peak value and pure PdO and Pr
6O
11XRD characteristic diffraction peak value compare, certain skew is all arranged.PdO, Pr
6O
11And Pd
6O-Pr
6O
11XRD characteristic diffraction peak value relatively see Table 1.
Table 1
"-" expression does not have this peak in the table.
The skew of compound characteristic diffraction peak value shows in the XRD test result, exists strong interaction (chemical bond) between palladium and the praseodymium, makes the configuration of palladium oxide that change take place, and variation has also taken place the configuration of simultaneous oxidation praseodymium.
With Rh among the embodiment 1
2O
3-Pr
6O
11Solid composite do X-ray diffraction (XRD) test, and with pure Rh
2O
3And Pr
6O
11XRD figure compare, the results are shown in Figure 2.Among Fig. 2, a
1, a
2Expression Pr
6O
11Characteristic diffraction peak, c represents Rh
2O
3Characteristic diffraction peak; a
1', a
2' expression and a
1, a
2Corresponding compound Rh
2O
3-Pr
6O
11Middle Pr
6O
11(111) (200) two crystal faces on characteristic diffraction peak, c ' expression and the corresponding compound Rh of c
2O
3-Pr
6O
11Middle Rh
2O
3(112) crystal face on characteristic diffraction peak.As can be seen from Figure 2, compound Rh
2O
3-Pr
6O
11(Rh/Pr=1/2) Rh in
2O
3And Pr
6O
11XRD characteristic diffraction peak value and pure Rh
2O
3And Pr
6O
11XRD characteristic diffraction peak value compare, certain skew is all arranged.Rh
2O
3, Pr
6O
11And Rh
2O
3-Pr
6O
11XRD characteristic diffraction peak value relatively see Table 2.
Table 2
"-" expression does not have this peak in the table.
The skew of compound characteristic diffraction peak value shows in the XRD test result, exists strong interaction (chemical bond) between rhodium and the praseodymium, makes the configuration of rhodium oxide that change take place, and variation has also taken place the configuration of simultaneous oxidation praseodymium.
Embodiment 2
In the mixed aqueous solution of rhodium nitrate that contains 0.58 gram rhodium and the praseodymium chloride that contains 0.80 gram praseodymium (atomic ratio that makes Rh and Pr is 1), add ammonia spirit to pH value and be about 8.0, produce precipitation.Precipitation and centrifugal separation is obtained solid precipitation, the solid that obtains is deposited in 90 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours make compound Rh
2O
3-Pr
6O
11
With the compound Rh that makes
2O
3-Pr
6O
11Mix with 200 gram cerium zirconium lanthanum-oxides (containing cerium 40 weight %, zirconium 50 weight %, lanthanum 10 weight %), the particle diameter of dry ball milling to 90% particle makes compound Rh less than 10 microns
2O
3-Pr
6O
11Mixture with cerium zirconium lanthanum-oxides.
Again with 200 restrain Rh
2O
3-Pr
6O
11The mixture of compound and cerium zirconium lanthanum-oxides, 80 gram lanthanum nitrates, 50 gram barium nitrates, 20 gram zirconium nitrates and 700 gram γ-Al
2O
3Mix, promptly obtain coating paste I after adding 1300 ml deionized water ball millings.
Use slurry I coated substrates twice respectively according to the method for embodiment 1, load capacity is 161 grams, and preparation is carried on the catalyst on the matrix.At catalyst activity composition Rh
2O
3-Pr
6O
11Middle rhodium and praseodymium atomic ratio are 1.In catalyst, each constituent content is respectively rhodium 0.10 grams per liter, and praseodymium 0.14 grams per liter, the total content of catalytic active component, hydrogen-storing material and heat-resistant carriers are 161 grams per liters.
Embodiment 3
In the mixed aqueous solution of palladium nitrate that contains 3.00 gram palladiums and the praseodymium chloride that contains 4.96 gram praseodymiums (atomic ratio that makes palladium and praseodymium is 0.8), add ammonia spirit to pH value and be about 10.0, produce precipitation.Precipitation and centrifugal separation is obtained solid precipitation, the solid that obtains is deposited in 90 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours make compound PdO-Pr
6O
11
The compound and the 200 gram cerium zirconium lanthanum-oxides solid solution (containing cerium 40 weight %, zirconium 50 weight %, lanthanum 10 weight %, down together) that make are mixed, and the particle diameter of dry ball milling to 90% particle makes compound PdO-Pr less than 10 microns
6O
11Mixture with cerium zirconium lanthanum-oxides.
Again with 200 restrain PdO-Pr
6O
11The mixture of compound and cerium zirconium lanthanum-oxides, 80 gram lanthanum nitrates, 50 gram barium nitrates, 20 gram zirconium nitrates and 700 gram γ-Al
2O
3Mix, promptly obtain coating paste I after adding 1300 ml deionized water ball millings.
Use slurry I coated substrates twice respectively according to the method for embodiment 1, load capacity is 190 grams, makes the catalyst that is carried on the matrix.At catalyst activity composition PdO-Pr
6O
11Middle palladium and praseodymium atomic ratio are 0.8, and in catalyst, each constituent content is respectively palladium 0.61 grams per liter, and praseodymium 1.01 grams per liters, the total content of catalytic active component, hydrogen-storing material and heat-resistant carriers are 192 grams per liters.
Embodiment 4
To the Pd (NH that contains 2.17 gram palladiums
3)
2Cl
2Add the cobalt nitrate aqueous solutions contain 0.32 gram cobalt in concentrated ammonia solution and the praseodymium nitrate aqueous solution (making Pd is 1.2 with the atomic ratio of Pr) that contains 2.39 gram praseodymiums and mixes, generation precipitates during pH value to 7 left and right sides of mixed solution.Precipitation and centrifugal separation is obtained the solid precipitation, the solid that obtains precipitation is directly mixed with cerium zirconium lanthanum-oxides solid solution, add 200 particle diameters that restrain deionized water ball milling to 90% particles again, 90 ℃ of dryings 4 hours less than 10 microns, 550 ℃ of roastings 4 hours make PdO-Pr
6O
11The mixture of the compound of doping cobalt and cerium zirconium lanthanum-oxides solid solution.
Again with 200 restrain PdO-Pr
6O
11The mixture of the compound of doping cobalt and cerium zirconium lanthanum-oxides, 80 gram lanthanum nitrates, 50 gram barium nitrates, 20 gram zirconium nitrates and 700 gram γ-Al
2O
3Mix, promptly obtain coating paste I after adding 1300 ml deionized water ball millings, load capacity is 76 grams per liters.
Add in the radium chloride that contains 0.31 gram rhodium and the praseodymium nitrate aqueous solution (making rhodium is 2 with the atomic ratio of praseodymium) that contains 0.21 gram praseodymium and contain 0.03 cobalt nitrate aqueous solution that restrains cobalt and mix, add ammonia spirit to pH value again and be about 9.0, generation precipitates.Precipitation and centrifugal separation is obtained solid precipitation, the solid precipitation that obtains is directly mixed with cerium zirconium lanthanum-oxides solid solution, add 200 particle diameters that restrain deionized water ball milling to 90% particles again less than 10 microns, 90 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours made Rh
2O
3-Pr
6O
11The mixture of the compound of doping cobalt and cerium zirconium lanthanum-oxides solid solution.
With 200 restrain Rh
2O
3-Pr
6O
11The mixture of the compound of doping cobalt and cerium Zirconium oxide, 80 gram lanthanum nitrates, 50 gram barium nitrates, 20 gram zirconium nitrates and 700 gram γ-Al
2O
3Mix, add 1300 ml deionized water again after ball milling promptly obtain coating paste II, load capacity is 128 grams per liters.
Method according to embodiment 1 is coated on coating paste I and coating paste II on the matrix respectively, makes the catalyst that is carried on the matrix.At catalyst activity composition PdO-Pr
6O
11Middle palladium and praseodymium atomic ratio are 1.2, at Rh
2O
3-Pr
6O
11Middle rhodium and praseodymium atomic ratio are 2, and in catalyst, each constituent content is respectively palladium 0.18 grams per liter, rhodium 0.04 grams per liter, and praseodymium 0.22 grams per liter, cobalt 0.03 grams per liter, the total content of catalytic active component, hydrogen-storing material and heat-resistant carriers are 203 grams per liters.
The clean-up effect test of embodiment
Performance evaluation to catalyst is carried out under the environment of laboratory simulation vehicle exhaust.Test condition: air speed is 6 * 10
4Hour
-1, temperature is 350 ℃, simulated exhaust gas consists of CO 2.4 volume %, C
3H
81800ppm, NO 1500ppm, CO
210.0 volume %, O
22.0 volume %, N
2Be balance gas.The test result that catalyst purifies sees Table 3.
Table 3
Purification test result from table 3 as can be seen, the catalyst of embodiments of the invention 1-4 is all fine to the clean-up effect of CO, HC, three kinds of tail gas of NO in the time of 350 ℃.
Comparative Examples 1
Do not prepare compound, but directly with 200 gram cerium Zirconium oxide solid solution and 700 gram γ-Al
2O
3Mix, add the 1300mL deionized water again after ball milling make slurry, in slurry, add the palladium chloride solution ball millings that contain 2.09 gram palladiums then and promptly obtain coating paste I, load capacity is 69 grams per liters.
Do not prepare compound, but directly with 200 gram cerium Zirconium oxide solid solution and 700 gram γ-Al
2O
3Mix, add the 1300mL deionized water again after ball milling make slurry, in slurry, add the rhodium chloride solution ball milling that contains 0.28 gram rhodium then and promptly obtain coating paste II, load capacity is 127 grams per liters.
Use slurry I and slurry II coated substrates respectively according to the method for embodiment 1, preparation is carried on the catalyst on the matrix.Each constituent content is identical with embodiment 1 in the final obtained catalyst activity composition, is respectively palladium 0.16 grams per liter, rhodium 0.04 grams per liter.
Performance evaluation to catalyst is carried out under the environment of laboratory simulation vehicle exhaust, and embodiment 1 and the clean-up effect of Comparative Examples 1 in aging front and back have been compared in experiment.Test condition: air speed is 6 * 10
4Hour
-1, temperature is 350 ℃, simulated exhaust gas consists of CO 2.4 volume %, C
3H
81800ppm, NO 1500ppm, CO
210.0 volume %, O
22.0 volume %, N
2Be balance gas.Aging condition is to calcine 20 hours in 1000 ℃ of following air atmosphere.Embodiment 1 sees Table 4 with the clean-up effect test result of Comparative Examples 1 aging front and back.
Table 4
Purification test result from table 4 as can be seen, the fresh catalyst of embodiments of the invention 1 and Comparative Examples 1 is all fine to the conversion ratio of three kinds of tail gas, does not have significant difference; And after wearing out, 1 couple of CO of embodiment and NO, especially the conversion ratio to HC is obviously high more a lot of than the conversion ratio of Comparative Examples 1-2.Even this shows catalyst of the present invention under the few situation of bullion content, ageing resistance also is better than the catalyst of prior art.
Test condition: air speed is 6 * 10
4Hour
-1, temperature is 500 ℃, simulated exhaust gas consists of CO volume 2.4%, C
3H
81800ppm, NO 1500ppm, CO
210.0 volume %, N
2Be balance gas, in addition, O
2Thereby amount can change redox rate R is changed.Wherein, redox rate R=([CO]+10[C
3H
8])/(2[O
2]+[NO]), R=1 represents that gaseous mixture is the situation of chemically correct fuel when (being equivalent to air-fuel ratio is 14.6).Air-fuel ratio characteristic test to embodiment 1 and Comparative Examples 1 the results are shown in Figure 3-5.
The purification test result of catalyst as can be seen from Fig. 3-5, the air-fuel ratio window of the catalyst of the embodiment of the invention 1 is wideer than the air-fuel ratio window of the catalyst of Comparative Examples 1, the catalyst that obviously shows embodiment 1 air-fuel ratio less than 1 o'clock to the clean-up effect of HC and air-fuel ratio greater than 1 o'clock to the NO clean-up effect all than the good purification of Comparative Examples 1, and in air-fuel ratio less than 1 o'clock to the clean-up effect of CO good purification than Comparative Examples 1.This air-fuel ratio window that shows catalyst of the present invention is wideer than the air-fuel ratio window of the catalyst of common methods preparation.
By the comparative descriptions of above-mentioned clean-up effect test and the test of air-fuel ratio window, the prepared catalyst ageing resistance of compound of the present invention obviously strengthens, and the durability of catalyst improves greatly, in the air-fuel ratio scope of broad good catalytic performance is arranged simultaneously.
Claims (16)
1. compound, this compound contains metal oxide containing precious metals and rare-earth oxide, wherein, the feature XRD diffraction maximum of this compound is corresponding with the position of the feature XRD diffraction maximum of self-existent metal oxide containing precious metals and rare earth oxide, and the feature XRD diffraction maximum of metal oxide containing precious metals and the feature XRD diffraction maximum of rare-earth oxide depart from self-existent metal oxide containing precious metals and rare earth oxide feature XRD diffraction maximum respectively in the feature XRD diffraction maximum of this compound.
2. compound according to claim 1, wherein, the angle of diffraction 2 θ of the metal oxide containing precious metals feature XRD diffraction maximum in the described compound are less than the angle of diffraction 2 θ of self-existent metal oxide containing precious metals feature XRD diffraction maximum, and the angle of diffraction 2 θ of the rare earth oxide feature XRD diffraction maximum in the described compound are greater than the angle of diffraction 2 θ of self-existent rare earth oxide feature XRD diffraction maximum.
3. compound according to claim 2, wherein, metal oxide containing precious metals is palladium oxide or rhodium oxide, rare earth oxide is a praseodymium oxide, the angle of diffraction 2 θ of the metal oxide containing precious metals feature XRD diffraction maximum in the described compound are less than the angle of diffraction 2 θ at least 0.07 degree of self-existent metal oxide containing precious metals feature XRD diffraction maximum, and the angle of diffraction 2 θ of the rare earth oxide feature XRD diffraction maximum in the described compound are greater than the angle of diffraction 2 θ at least 0.1 degree of self-existent rare earth oxide feature XRD diffraction maximum.
4. compound according to claim 3, wherein, the angle of diffraction 2 θ of the metal oxide containing precious metals feature XRD diffraction maximum in the described compound are less than the angle of diffraction 2 θ 0.1-2.0 degree of self-existent metal oxide containing precious metals feature XRD diffraction maximum, and the angle of diffraction 2 θ of the rare earth oxide feature XRD diffraction maximum in the described compound are greater than the angle of diffraction 2 θ 0.2-1.0 degree of self-existent rare earth oxide feature XRD diffraction maximum.
5. according to any described compound among the claim 1-4, wherein, metal oxide containing precious metals feature XRD diffraction maximum in the described compound refers to a diffraction maximum with the corresponding intensity maximum in position of self-existent metal oxide containing precious metals feature XRD diffraction maximum, and the rare earth oxide feature XRD diffraction maximum in the described compound refers to two diffraction maximums with the corresponding intensity maximum in position of the feature XRD diffraction maximum of self-existent rare earth oxide.
6. according to any described compound among the claim 1-4, wherein, in described compound, the atomic ratio of described noble metal and described rare earth element is 0.1-3.
7. according to any described compound among the claim 1-4, it is characterized in that, described compound also contains doping metals and/or the blended metal oxide of compound gross weight 0-10 weight %, and described doping metals is selected from one or more among Ni, V, Y, Ti, Co, Cu, Sc, Fe, Zr, Mo or the Mn.
8. cleaning catalyst for tail gases of automobiles, this catalyst contains catalytic active component, hydrogen-storing material, heat-resistant carriers, it is characterized in that, and described catalytic active component is each described compound among the claim 1-7.
9. catalyst according to claim 8, wherein, total amount with catalytic active component, hydrogen-storing material, heat-resistant carriers is a benchmark, the content of described catalytic active component is 0.01-5 weight %, the content of described hydrogen-storing material is 0-50 weight %, and the content of described heat-resistant carriers is 45-99.9 weight %.
10. catalyst according to claim 9, wherein, total amount with catalytic active component, hydrogen-storing material, heat-resistant carriers is a benchmark, the content of described catalytic active component is 0.02-3 weight %, the content of described hydrogen-storing material is 10-40 weight %, and the content of described heat-resistant carriers is 57-90 weight %.
11. according to Claim 8,9 or 10 described catalyst, wherein, described hydrogen-storing material is the solid solution of cerium Zirconium oxide.
12. catalyst according to claim 11, wherein, cerium Zirconium oxide solid solution also contains storage oxygen auxiliary agent, described storage oxygen auxiliary agent is selected from one or more in the oxide of La, Pr, Nd, Sm, Y, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, and the content of storage oxygen auxiliary agent is the 0.1-30 weight % of cerium Zirconium oxide solid solution gross weight.
13. according to Claim 8,9 or 10 described catalyst, wherein, described heat-resistant carriers is Al
2O
3, TiO
2, ZrO
2, SiO
2, in amorphous aluminum silicide or the molecular sieve one or more.
14. catalyst according to claim 13, wherein, described heat-resistant carriers also contains the carrier auxiliary agent that accounts for heat-resistant carriers gross weight 0-8 weight %, and described carrier auxiliary agent is the oxide of one or more elements among Mg, Ba, La, Ce, Pr, Zr, Ti, the Si.
15. catalyst according to claim 8, wherein, this catalyst also contains matrix, catalytic active component, hydrogen-storing material, heat-resistant carriers load on the surface of matrix and/or in the hole, cumulative volume with matrix is a benchmark, and the content of catalytic active component, hydrogen-storing material and heat-resistant carriers is the 50-300 grams per liter.
16. catalyst according to claim 14, wherein, described matrix is selected from one or more in cordierite, mullite, aluminum magnesium titanate and the Fe-Cr-Al alloy.
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