CN1245444A - 还原氮氧化物的方法 - Google Patents
还原氮氧化物的方法 Download PDFInfo
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- CN1245444A CN1245444A CN97181718A CN97181718A CN1245444A CN 1245444 A CN1245444 A CN 1245444A CN 97181718 A CN97181718 A CN 97181718A CN 97181718 A CN97181718 A CN 97181718A CN 1245444 A CN1245444 A CN 1245444A
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- 238000000034 method Methods 0.000 title claims description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title description 90
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 18
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 15
- 239000011029 spinel Substances 0.000 claims abstract description 14
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 3
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 238000002485 combustion reaction Methods 0.000 claims description 14
- 230000002902 bimodal effect Effects 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 230000003137 locomotive effect Effects 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 17
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 229910002706 AlOOH Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000640882 Condea Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- -1 magnesium aluminate Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229960001730 nitrous oxide Drugs 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000264877 Hippospongia communis Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000013842 nitrous oxide Nutrition 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 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
- 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
- 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
- 101710134784 Agnoprotein Proteins 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 241000282461 Canis lupus Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910052681 coesite 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
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 231100001143 noxa Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/202—Hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2251/20—Reductants
- B01D2251/204—Carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/00—Reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/207—Transition metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/524—Spinel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
一种催化剂用于还原NOx、特别是在燃烧废气中的NOx,所述催化剂含有:(a)20至97wt%的Al2O3,(b)1至40wt%的CuO,(c)1至50wt%的ZnO,(d)1至40wt%Ag,(e)0至2wt%Pt,(f)以组分(a)至(e)的总重量计0至20wt%的稀土金属、元素周期表第3副族元素或其混合物的氧化物,其中组分(a)至(e)的重量总和为100wt%,其中,在各种情况下,组分(a)重量的最高达一半可被Fe2O3、Cr2O3、Ga2O3或其混合物替代,组分(b)的最高达一半可被CoO替代,组分(c)的最高达一半可被MgO替代,组分(d)的最高达一半可被Au替代,组分(e)的最高达一半可被Pd、Ru、Os、Ir、Rh、Re或其混合物替代。所述组分(a)、(b)和(c)形成尖晶石,所述尖晶石中掺杂有组分(d)、(e)和(f)。
Description
本发明涉及使用催化剂还原氮氧化物(NOx)的用途及对应的方法。氮氧化物主要来自燃烧废气,特别是来自内燃机如柴油机。
烃与作为氧化剂的空气燃烧特别是与过量空气在高温下燃烧,通过在空气存在下氮的氧化产生氮氧化物。这类氮氧化物的实例有NO、NO2、NO3、N2O3、N2O4和N2O5。对于污染物氮氧化物应尽可能完全地从燃烧废气中除去,以避免环境污染。由于使用废气处理设备,发电厂和工业排放持续减少,降低在机动车废气中污染物数量变得日益重要,特别是考虑到机动车数目的增加。
已提出过许多降低机动车发动机NOx排放的解决方案。降低NOx排放的有效解决方案必须满足许多标准,特别是如使用催化剂时,例如:
-高转化率,即大量除去NOx,甚至是在高和低温下及在操作过程中载荷频繁变换的情况下
-避免使用辅助物质如氨或尿素
-生产和操作费用低
-使用时间长
-产生的N2O少
-催化剂机械稳定性高
也有人设计了一些还原氮氧化物的催化剂。
EP-A-0687499叙述了用于还原氮氧化物的由尖晶石制成的尖晶石催化剂,包含铜、锌、和铝。
US3974255叙述了涂覆有铂的铝酸镁尖晶石催化剂。该催化剂用来还原内燃机废气中的NOx。
EP-B-0494388叙述了从废气中除去氮氧化物的方法,其中使用的催化剂是多价金属磷酸盐。多价金属硫酸盐或元素周期表第4周期的过渡金属的尖晶石铝酸盐。特别叙述了铝酸钴催化剂,它是通过硝酸钴与硝酸铝共沉淀随后经干燥和焙烧制备的。
JP-A2-08024648叙述了从废气中除去氮氧化物的催化剂。该催化剂的组成例如是Ag0.01P0.01Pr0.01Cu0.2Zn0.5Al2.0,还可存在Fe0.02Co0.02或者0.01%的MgO。该催化剂通过将Ag和Pr的硝酸盐与磷酸混合、并将该混合物在存在氨或碳酸铵或硫酸铵水溶液的条件下引入到Cu、Zn和Al的氧化物混合物中来制备的。分别在500℃和800℃下进行焙烧。该催化剂的银含量为0.67wt%。
也公知有催化分解一氧化二氮的催化剂。DE-A-4224881叙述了由铝氧化物承载的含银催化剂及催化分解纯或在混合物中的一氧化二氮的方法,其中一氧化二氮以显著的程度选择性分解为元素,而其它氮氧化物不分解。所使用的催化剂可呈浸渍有银的铜/锌/铝尖晶石形态。这包括例如氧化铝载体用硝酸铜和硝酸锌溶液浸渍、干燥、焙烧,然后用硝酸银溶液浸渍,干燥并焙烧。
本发明的目的是提供与公知催化剂相比改进了的用于还原NOx的催化剂。此外,还提供用于还原特别来自内燃机废气中的NOx的方法。
通过使用包括如下组分的催化剂来还原NOx可实现这一目的,所述催化剂包括:
(a)20至97wt%的Al2O3,
(b)1至40wt%的CuO,
(c)1至50wt%的ZnO,
(d)1至40wt%Ag,
(e)0至2wt%Pt,
(f)以组分(a)至(e)的总重量计0至20wt%的稀土金属、元素周期表第3副族元素或其混合物的氧化物,其中组分(a)至(e)的重量总和为100wt%,
其中,在各种情况下,组分(a)重量的最高达一半可被Fe2O3、Cr2O3、Ga2O3或其混合物替代,组分(b)的最高达一半可被CoO替代,组分(c)的最高达一半可被MgO替代,组分(d)的最高达一半可被Au替代,组分(e)的最高达一半可被Pd、Ru、Os、Ir、Rh、Re或其混合物替代。
本发明还发现,在DE-A-4224881中所叙述的催化剂可用来还原NOx。
本发明所使用的催化剂优选包括30至80、特别优选40至75、特别是45至65wt%的Al2O3,优选3至35、特别优选5至30、特别是8至25wt%的CuO,优选2至40、特别优选5至30、特别是10至26wt%的ZnO,优选2至35、特别优选3至30特别是5至25wt%的Ag和优选0至1、特别优选0至0.5、特别是0至0.1wt%的Pt。如上所述,所标明的重量以组分(a)至(e)的总重量计,总和为100wt%。
在各种情况下,优选组分(a)、(b)、(c)、(d)和/或(e)的最多1/3、特别优选最多1/5、特别是1/10按上述替代。优选组分(a)、(b)、(c)、(d)和(e)的任一种都不被替代。
可用作组分(f)的是稀土金属和元素周期表第3副族元素的氧化物,优选三价稀土金属特别是La和/或Ce的氧化物。优选在催化剂中不存在Pr。
组分(f)的用量优选为0至15、特别优选0至10、特别是0至5wt%,以组分(a)至(e)的总重量计。优选不存在组分(f)。
特别优选催化剂由组分(a)至(e)组成,特别是仅由Al2O3、CuO、ZnO、Ag和可能有的Pt组成。
按照本发明,使用铜/锌/铝氧化物化合物,它可总体上由下式代表:CuaZnbAl2O3+a+b,其中a>0,b>0,a+b≤1。
优选组分(a)、(b)和(c)形成尖晶石。尖晶石例如在C.W.Correns,Einfuhrung in die Mineralogie[Introduction tomineralogy],Springer Verlag 1949,pp77-80,H.Remy,Lehrbuchder Anorganischen Chemie[Textbook of inorganicchemistry],Akademische Verlagsgesellschaft Geest&PortigK.-G.Leipzig 1950,pp.308-311,Romp,Chenielexikon,9th edition1995,p.4245中有叙述。尖晶石通常由MgAl2O4衍生,其中镁可被其它二价离子如锌、铜、铁置换。铝可被其它三价离子如铁或铬置换。在尖晶石晶格中氧原子构成对应于面心晶格的立方密堆积结构。其中的八面体间隙的一半被铝占据,别一半间隙为空缺。八分之一的四面体间隙被镁占据。
优选主要存在的是铜/锌尖晶石。对于a+b=1,在尖晶石晶格中不存在空缺位置。Al2O3可起基物作用,在其中存在其它氧化物。特别是在a+b≤1的情况下是这样。
本发明催化剂可含有少量的SiO2、TiO2、ZrO2滑石和/或水泥,只要这些物质不明显影响催化剂的性能。按照一种实施方案,催化剂不含磷,特别是如存在Pr时。
本发明催化剂的孔体积为0.01至1、优选0.01至0.8、特别优选0.1至0.7ml/g,孔尺寸分布是单一模式(monomodal)、双模式(bimodal)、或多模式(polymodal)的。双模式或多模式催化剂就此而论优选具有中孔和大孔。中孔的直径小于50nm,大孔的直径为50至10000nm。该催化剂优选为双模式或多模式孔尺寸分布,40至99%、优选50至98%、特别优选55至95%的孔体积呈中孔存在,1至60%、优选2至50%、特别优选5至45%的孔体积呈大孔存在。特别优选催化剂为双模式的。
较高模式催化剂还可含有直径大于10000nm的孔,这类孔优选占孔体积的0.1至20、特别优选1至15%,其中以上标明的中孔和大孔的数值涉及的是残余的孔体积。
在催化剂具有双模式或多模式孔尺寸分布的情况下,构成孔体积的大部分的孔尺寸范围为10到1000nm。
在催化剂中存在的银颗粒的尺寸优选为0.1至200、特别优选5至50nm。在此种情况下,高于300℃时,银呈金属存在,低于这一温度时也可呈氧化物存在。以上标明的重量是以金属计。
孔体积和孔体积分布优选通过Hg气孔测量法来确定。银颗粒的尺寸例如通过测量X-射线衍射图的线宽度来确定。
BET比表面积优选为1至200、特别优选20至150、特别是50至100m2/g。
本发明采用的催化剂可呈任何形态存在,例如为颗粒、片状,可是空心的或实心的;直径优选为0.5至3mm的颗粒,切片,蜂窝体等。本发明催化剂还可存在于其它载体物质上,如玻璃纤维垫、陶瓷或金属载体,且所述载体可呈各种形状,如波形或卷状。在本文以上标明的数量涉及的是催化剂本身,而无附加的载体。将要在机动车领域中采用的本发明所使用催化剂优选呈蜂窝体形,孔直径优选为0.1至10mm,特别为0.5至5mm,筋肋宽度优选为0.1至5mm,特别为0.3至3mm。
本发明所使用催化剂可通过任何适当的方法来制备。例如在DE-A-4224881中叙述了适当的方法。例如,AlOOH(勃姆石)、CuO、ZnO和任何其它需要的金属可与水在存在粘合剂的条件下捏合,挤压形成挤出物,干燥并焙烧。如此制备的催化剂基体可用硝酸银水溶液浸渍。然后将经浸渍的催化剂干燥并焙烧。
除金属氧化物外,还可使用对应的氢氧化物、氢氧化合物(oxyhydrates)、碳酸盐、有机酸盐、硝酸盐、氯化物、硫酸盐或磷酸盐。为制备双模式或多模式催化剂,除AlOOH外,还可使用AlOOH与Al2O3、优选γ-或δ-Al2O3的混合物,可采用不同孔尺寸分布的三氧化二铝(Al2O3)。
干燥优选在10至200℃下进行,特别优选20至150℃,特别是30至120℃。焙烧在低于1100℃下进行,优选为600至900℃。在浸渍硝酸银溶液后进行的焙烧优选在200至800℃下进行。
本发明所用的催化剂优选用来还原在燃烧废气中的NOx。NO的还原通过与还原剂的反应来实现。
本发明还涉及催化还原在含有NOx、O2和烃化合物的混合物中的NOx的方法,所述还原在存在以上定义的催化剂的条件下进行,且烃化合物用作还原剂。
所述混合物优选为燃烧废气,所述燃烧废气特别来自内燃机车或内燃机。
这类废气尤其含有氮氧化物(NOx)、氧(O2)、水蒸气及还可能有烃化合物。烃化合物例如为含氧烃化合物如醇、醚、醛、酮、环氧化物等。术语“烃化合物”还包括烃如烷烃、烯烃、炔烃或芳族化合物。除烃化合物外,还可使用CO或H2。优选使用附加烃化合物。例如,短链烃如丙烯可计量加入废气流中。另一种优选方案是例如在机动车的情况下将部分燃料添加到废气流中,使得在废气中存在烃化合物。以下反应方程式示出了以丙烯作为烃化合物所发生的反应的实例。
在柴油废气中特别还含有氧,因为燃烧是用过量空气进行的。这意味着会发生进一步的反应,其中形成含氧有机化合物。
因而,所存在的烃化合物一方面与所存在的氧反应,另一方面与存在的氮氧化物反应。与烃与氧的反应相对比,本发明所用的催化剂优先催化烃与NOx的反应。
废气特别是柴油机废气除NOx和烃外还含有CO、可能的烟灰、SO2和水蒸气、氧、氮(N2)和CO2。柴油废气具有如下组成:
NOx10至10000、平均为2000ppm
烃10至2000、平均为200ppm
CO10至4000、平均为100ppm
烟灰0至1、平均为0.3g/l
二氧化硫0至200、平均为40ppm
水蒸气1.5至8、平均为7vol%
氧3至18、平均为4vol%
CO22至15、平均为3vol%
典型的催化剂载荷为20000至30000,峰值载荷高达100000Nm3气体/m3催化剂/小时。以下参照实施例更详细地说明本发明。
催化剂的总的制备步骤
本发明所用催化剂可以与DE-A-4224881中叙述的相似步骤来制备。
例如,这包括,将400gAlOOH(Boehmite,PuralSB fromCondea)、50gCuO、154.5gZnO和25g甲基纤维素(WalocelfromWolff,Walsrode)与270g水捏合1小时,进行挤出操作以生成直径为3mm且长度为8mm的固体挤出物,干燥并在800℃下焙烧4小时。在焙烧后所得到的物质的比表面积为54m2/g。孔隙率为0.32ml/g。
无机成分具有如下组成:Cu:0.63mol(CuO:10wt%),Zn:1.90mol(ZnO:28wt%),Al:6.67mol(Al2O3:62wt%)。这对应于通式Cu0.2Zn0.6Al2O3.8。
将108g这种物质(尖晶石)用51ml含有30.2g硝酸银的水溶液浸渍,并放置1小时。将浸渍过的物质在120℃下干燥1小时至恒重,然后在600℃下焙烧。如此得到的催化剂颗粒含有19.2g金属银,对应于17.8wt%。
在以下的实施例中,除非另外指明,百分比以重量计。
实施例1
组成为20%CuO、20%ZnO、45%Al2O3、15%Ag的单模式催化剂
将400gAlOOH(Boehmite,Pural SB from Condea)、151gCuO和151gZnO以及30g甲基纤维素(Walocel from Wolff,Walsrode)与320g水捏合1小时,挤出形成直径为3mm且长度为8mm的固体挤出物,干燥并在800℃下焙烧4小时。
用178g硝酸银以50%的AgNO3水溶液形式浸渍640g该尖晶石,在120℃干燥1小时,然后在600℃熔烧4小时。
如此得到的颗粒含有15%的Ag、20%的CuO、20%的ZnO和45%的Al2O3。它们是单模式的且含有孔,其95%的直径为50-50000nm。总孔隙率为0.32ml/g。
实施例2
具有5%Ag、15%CuO、19%ZnO、61%Al2O3的双模式催化剂
使用AlOOH和Al2O3的混合物替代单独的AlOOH获得了双模式催化剂。
将611gCu(NO3)2×3H2O、581g PuraloxSCF-A 230(Al2O3,由Condea制备)和322g Pural SB(AlOOH,由Condea制备)充分混合3小时。然后将干燥的组合物与足够的水混合以生成可捏合的捏合组合物。然后引入45g甲酸。将该组合物捏合70分钟,成形为挤出物,在120℃下干燥16小时,并在800℃下焙烧4小时。
将800g如此获得的物体用溶于水并使总溶液体积达400升的373gZn(NO3)2×6H2O浸渍。经1.5小时浸渍后,在120℃下干燥16小时,随后在600℃下焙烧4小时。
如实施例1所述,所述催化剂用50%的AgNO3溶液浸渍,使得最终的催化剂含有5%的银。所述催化剂的组成为5%Ag、19%ZnO、15%CuO、61%Al2O3。BET表面积为约100m2/g。水摄取量为约0.5ml/g,这对应于相同数量级的总孔隙率。
实施例3
以与实施例2相似的方式制备催化剂,但该催化剂具有如下组成:15%Ag、17%ZnO、13.6%CuO、54.4%Al2O3。
实施例4
重复实施例2步骤,但所获得的催化剂具有如下组成:25%Ag、15%ZnO、12%CuO、46%Al2O3。
实施例5
重复实施例2步骤,但所获得的组成如下:15%Ag、17%ZnO、13.6%CuO、54.3%Al2O3、0.1%Pt。通过浸渍硝酸铂水溶液来实现Pt的掺入。
这一浸渍可与硝酸银的浸渍同时进行,但也可单独进行。
实施例6
以与实施例2中所述的步骤类似的方式来制备催化剂,但组成如下:15%Ag、25.5%ZnO、8.5%CuO、51%Al2O3。
对比例1
为进行对比,以与实施例2相似的方式制备催化剂,不同之处是不采用银。该催化剂的组成如下:15%ZnO、21.3CuO、63.7%Al2O3。
对比例2
以与实施例2相似的方式制备对比催化剂,不同之处是采用了很少量的铂来代替银。该催化剂具有如下组成:
20%ZnO、16%CuO、64%Al2O3、0.1%Pd。
对催化剂的试验
对所获得的催化剂进行如下试验:
对于对应的催化剂,将其1.6至2.0mm的切片份10g装入垂直设置的石英反应器(直径20mm,高度约500mm)中,在所述反应器的中心处设置有容纳催化剂的透气板。床高度为约15mm。围绕该石英反应器设置有加热炉,该炉可将长度在100mm以上的反应器中间段加热至高达550℃的温度。
使气体混合物以约10000(Nl气体)/(l催化剂×小时)的流速流经催化剂。所述气体混合物由1000ppm的NO、1000ppm的丙烯、10vol%的氧和氩(余量)作为载体气体组成。
在反应器的下游用气体检测器测量NO浓度,在检测器上游形成的任何NO2在一个转化器中被还原为NO。该反应在200至400℃的温度下进行。所获得的试验结果列于下表中,包括在反应器下游测量的NOx浓度和NOx最小浓度和测量到NOx最小浓度处的温度。此外,还列出了最大转化比,即,(上游NOx)减去(下游NOx)之差比(上游NOx)。
表
催化剂来源的实施例No. | 反应器上游NOx(ppm) | 反应器下游NOx(ppm) | 反应器下游NOx最小值(ppm) | 在NOx最小值处的 T(℃) | 最大转化比(%) | ||||
200℃ | 250℃ | 300℃ | 350℃ | 400℃ | |||||
1 | 1000 | 620 | 400 | 305 | 390 | 705 | 300 | 295 | 70.0 |
2 | 1000 | 810 | 300 | 280 | 600 | 840 | 235 | 280 | 76.5 |
3 | 1000 | 945 | 480 | 195 | 365 | 540 | 190 | 295 | 81.0 |
4 | 1000 | 980 | 520 | 345 | 820 | 910 | 345 | 300 | 65.5 |
5 | 1000 | 885 | 575 | 495 | 725 | 860 | 485 | 285 | 51.5 |
6 | 1000 | 610 | 385 | 220 | 415 | 595 | 215 | 290 | 78.5 |
对比例1 | 1000 | 800 | 605 | 580 | 615 | 685 | 575 | 280 | 42.5 |
对比例2 | 1000 | 935 | 660 | 635 | 815 | 895 | 605 | 285 | 39.5 |
表中结果证明本发明所使用的实施例1-6的催化剂与对比例1和2的对比催化剂相比较,取得了相当好的降低NOx的效果。
Claims (10)
1.一种用于还原NOx的催化剂的用途,所述催化剂包含
(a)20至97wt%的Al2O3,
(b)1至40wt%的CuO,
(c)1至50wt%的ZnO,
(d)1至40wt%Ag,
(e)0至2wt%Pt,
(f)以组分(a)至(e)的总重量计0至20wt%的稀土金属、元素周期表第3副族元素或其混合物的氧化物,其中组分(a)至(e)的重量总和为100wt%,
其中,在各种情况下,组分(a)重量的最高达一半可被Fe2O3、Cr2O3、Ga2O3或其混合物替代,组分(b)的最高达一半可被CoO替代,组分(c)的最高达一半可被MgO替代,组分(d)的最高达一半可被Au替代,组分(e)的最高达一半可被Pd、Ru、Os、Ir、Rh、Re或其混合物替代。
2.如权利要求1的用途,其中组分(a)、(b)和(c)形成尖晶石,所述尖晶石中掺杂有组分(d)、(e)和(f)。
3.如权利要求1或2的用途,其中所述催化剂的孔体积为0.01至1ml/g。
4.如权利要求1至3任一项的用途,其中所述催化剂具有单模式、双模式或多模式孔尺寸分布。
5.如权利要求4的用途,其中所述催化剂具有双模式或多模式孔尺寸分布,孔体积中40-99%呈中孔存在,孔体积的1-60%呈大孔存在。
6.如前述任一项权利要求的用途,用于还原在燃烧废气中的NOx。
7.一种催化还原在含有NOx、O2和烃化合物的混合物中的NOx的方法,所述还原在存在权利要求1至5任一项所限定的催化剂的条件下进行。
8.如权利要求7的方法,其中所述混合物是燃烧废气。
9.如权利要求6的用途或如权利要求8的方法,其中所述燃烧废气来自内燃机车或内燃机。
10.如权利要求1、6、或9的用途或如权利要求7、8或9的方法,其中烃化合物、CO、或H2用作还原剂。
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DE19653200A DE19653200A1 (de) | 1996-12-19 | 1996-12-19 | Verfahren zur Reduktion von Stickoxiden |
DE19653200.0 | 1996-12-19 |
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US (1) | US6153162A (zh) |
EP (1) | EP0951341B1 (zh) |
JP (1) | JP4270581B2 (zh) |
KR (1) | KR20000057669A (zh) |
CN (1) | CN1245444A (zh) |
BR (1) | BR9714044A (zh) |
DE (2) | DE19653200A1 (zh) |
ES (1) | ES2159896T3 (zh) |
WO (1) | WO1998026858A1 (zh) |
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Publication number | Priority date | Publication date | Assignee | Title |
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Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3974255A (en) * | 1973-03-12 | 1976-08-10 | Atlantic Richfield Company | Method for treatment of engine exhaust gases |
EP0362960A3 (en) * | 1988-10-05 | 1990-06-27 | Sakai Chemical Industry Co., Ltd., | Use of a catalyst composition for denitrization and denitrizing catalysts |
JP2691750B2 (ja) * | 1988-10-06 | 1997-12-17 | 堺化学工業株式会社 | 窒素酸化物分解触媒 |
JP2784444B2 (ja) * | 1988-10-05 | 1998-08-06 | 堺化学工業株式会社 | 窒素酸化物分解触媒 |
EP0494388B1 (en) * | 1991-01-08 | 1995-12-06 | Agency Of Industrial Science And Technology | Process for removing nitrogen oxides from exhaust gases |
DE4224881A1 (de) * | 1992-07-28 | 1994-02-03 | Basf Ag | Silberhaltiger Aluminiumoxid-Trägerkatalysator und Verfahren zur katalytischen Zersetzung von reinem oder in Gasgemischen enthaltenem Distickstoffmonoxid |
DE4419486C2 (de) * | 1994-06-03 | 1996-09-05 | Daimler Benz Ag | Katalysator, Verfahren zu dessen Herstellung sowie Verwendung des Katalysators |
DE4420932A1 (de) * | 1994-06-16 | 1996-01-11 | Basf Ag | Material zur katalytischen Reduktion von Stickoxiden |
JPH0824648A (ja) * | 1994-07-22 | 1996-01-30 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及びその製造方法 |
DE19606657C1 (de) * | 1996-02-23 | 1997-07-10 | Basf Ag | Verfahren und Vorrichtung zum Reinigen von Gasen |
-
1996
- 1996-12-19 DE DE19653200A patent/DE19653200A1/de not_active Withdrawn
-
1997
- 1997-12-17 EP EP97954415A patent/EP0951341B1/de not_active Expired - Lifetime
- 1997-12-17 DE DE59703453T patent/DE59703453D1/de not_active Expired - Lifetime
- 1997-12-17 US US09/331,059 patent/US6153162A/en not_active Expired - Lifetime
- 1997-12-17 KR KR1019990705498A patent/KR20000057669A/ko not_active Application Discontinuation
- 1997-12-17 WO PCT/EP1997/007091 patent/WO1998026858A1/de not_active Application Discontinuation
- 1997-12-17 JP JP52732698A patent/JP4270581B2/ja not_active Expired - Lifetime
- 1997-12-17 CN CN97181718A patent/CN1245444A/zh active Pending
- 1997-12-17 ES ES97954415T patent/ES2159896T3/es not_active Expired - Lifetime
- 1997-12-17 BR BR9714044-9A patent/BR9714044A/pt unknown
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Also Published As
Publication number | Publication date |
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WO1998026858A1 (de) | 1998-06-25 |
EP0951341A1 (de) | 1999-10-27 |
JP2001506180A (ja) | 2001-05-15 |
KR20000057669A (ko) | 2000-09-25 |
DE59703453D1 (de) | 2001-05-31 |
BR9714044A (pt) | 2000-05-09 |
JP4270581B2 (ja) | 2009-06-03 |
ES2159896T3 (es) | 2001-10-16 |
US6153162A (en) | 2000-11-28 |
EP0951341B1 (de) | 2001-04-25 |
DE19653200A1 (de) | 1998-06-25 |
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