CN104364003A - 基本金属催化剂及其使用方法 - Google Patents
基本金属催化剂及其使用方法 Download PDFInfo
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- CN104364003A CN104364003A CN201380024714.XA CN201380024714A CN104364003A CN 104364003 A CN104364003 A CN 104364003A CN 201380024714 A CN201380024714 A CN 201380024714A CN 104364003 A CN104364003 A CN 104364003A
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- Prior art keywords
- carbon monoxide
- weight
- base metal
- oxide
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 239000010953 base metal Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 21
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 125
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 47
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 47
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001868 water Inorganic materials 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 19
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 15
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 15
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 15
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 229910052788 barium Inorganic materials 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 238000000629 steam reforming Methods 0.000 claims abstract description 7
- 239000000446 fuel Substances 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 238000002485 combustion reaction Methods 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 4
- 229910052676 chabazite Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 239000011572 manganese Substances 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000012071 phase Substances 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 18
- 239000010949 copper Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 238000004088 simulation Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- WPQBNJRIWONKBL-UHFFFAOYSA-N cerium(3+);oxygen(2-);zirconium(4+) Chemical compound [O-2].[Zr+4].[Ce+3] WPQBNJRIWONKBL-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- -1 NOx compound Chemical class 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- JGKRELFHRXXOLR-UHFFFAOYSA-N [Fe].[Pr].[Co] Chemical compound [Fe].[Pr].[Co] JGKRELFHRXXOLR-UHFFFAOYSA-N 0.000 description 3
- LFYMLMKKOJHYFY-UHFFFAOYSA-N [O-2].[Al+3].[Ni+2] Chemical compound [O-2].[Al+3].[Ni+2] LFYMLMKKOJHYFY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 3
- 230000010412 perfusion Effects 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- XBAOPMPPZXHFEX-UHFFFAOYSA-N [Ni]=O.[Pr] Chemical compound [Ni]=O.[Pr] XBAOPMPPZXHFEX-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 229910017163 MnFe2O4 Inorganic materials 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- 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
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- B01D—SEPARATION
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- 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
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7065—CHA-type, e.g. Chabazite, LZ-218
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/783—CHA-type, e.g. Chabazite, LZ-218
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Abstract
本发明的诸多方面涉及一种在富燃和贫燃发动机操作条件下都能有效地催化烃类、一氧化碳和氮氧化物的减少的基本金属催化剂组合物,其包含:包括至少10重量%的可还原铈土的载体,所述可还原铈土掺杂有多达约60重量%的选自Al、Pr、Sm、Zr、Y、Si、Ti和La中的一种或多种的氧化物;和处于所述可还原铈土载体上的基本金属氧化物,所述基本金属选自Ni、Fe、Mn、Cu、Co、Ba、Mg、Ga、Ca、Sr、V、W、Bi和Mo中的一种或多种,所述基本金属催化剂组合物能有效地促进烃类的蒸汽重整反应和水气变换反应以提供H2作为还原剂减少NOx。本发明的其它方面涉及使用和制造此类催化剂的方法。
Description
技术领域
本发明的实施方案总体上涉及一种用于减少排气流中的烃类、一氧化碳和氮氧化物的基本金属催化剂。更确切地说,本发明提供了用于处理由内燃发动机,包括汽化器式摩托车发动机产生的排气的催化剂制品和方法。
发明背景
发动机排气往往含有不完全燃烧化合物,诸如烃类、一氧化碳(CO)和氮氧化物(NOx)。出于空气污染控制的目的和为了满足各种政府规定,必须从发动机排气中除去这些化合物。已经针对不同的发动机类型和燃料配置建立了不同的系统,以解决具有挑战性的排放控制问题。这些系统包括三效催化剂、密偶催化剂,以及过滤器或催化过滤器。这些催化剂或组合催化剂系统中大部分是基于贵金属,包括Pt、Pd和Rh。虽然这些贵金属催化剂对于汽车排放控制是有效的并且在工业上已经实现了产业化,但贵金属非常昂贵。这种高成本对于这些催化剂的广泛应用来说仍然是一个重要因素。持续需要更便宜的替代催化剂用于从汽车排放源中有效去除HC、CO和NOx化合物,以便满足日益严格的规定。
一个可能的替代方案是使用基本金属。基本金属较为丰富,且成本比贵金属低得多。已经若干次尝试开发基于基本金属的催化剂用于排放控制。然而,这些尝试每一次都充满了问题。举例来说,已经制造出的一些整体催化剂导致了AB2O4和钙钛矿型晶体ABO3的形成。然而,钙钛矿结构的形成显著减少了催化剂表面积。在其它尝试中,使用了Cr。然而,Cr是高毒性的。含有Zn和Cr两者的基本金属制剂很可能由于Zn损失而导致催化剂失活和由于Cr的毒性而不符合规定。其它基本金属催化剂根本不能够实现可接受程度的污染物减少。
在汽化器式摩托车发动机中,往往由于汽化器的宽松控制而遇到空气对燃料比范围较宽的问题。因此,排放控制催化剂被要求在这样较宽范围的环境中起作用,且在富燃老化条件下往往会丧失CO转化活性。汽化器式摩托车发动机排放物以不同的驾驶循环期间的波动的气体组成和流速(体积)为特征。在所谓的“富燃条件”下,排气的空气-燃料比低于烃和CO完全氧化和NOx还原所需的化学计量比。类似地,在本领域中已知的“贫燃条件”下,供应了过量空气,这为CO和烃氧化提供了绰绰有余的氧气。然而在贫燃条件下,所存在的还原剂对于NOx还原来说是不充分的。
另外,发动机排放物的温度可以取决于驾驶循环的阶段、燃料的类型和发动机技术而变化。排放气体还含有呈燃烧副产物形式的蒸汽,含量为约10%。因而,为了在富燃和贫燃条件下同时转化HC、CO和NOx,水活化非常重要。在富燃条件下,烃类的蒸汽重整和水气变换反应可以弥补氧化剂(O2)的缺乏。类似地,在贫燃条件下,重整和水气变换反应可以产生比烃类和CO更有效的还原剂(H2)用于进行NOx转化。
因而,需要一种在热水老化之后,特别是在富燃发动机操作条件下具有改良的CO转化性能和稳定性的含TWC的催化剂制品。还需要一种实惠又有效的催化剂。确切地说,需要这样的催化剂以用于汽化器式摩托车发动机应用。
发明概要
本发明的一个方面涉及一种在富燃和贫燃发动机操作条件下都能有效地催化烃类、一氧化碳和氮氧化物的减少的基本金属催化剂组合物。所述催化剂组合物包含:包括至少10重量%可还原铈土的载体,所述可还原铈土掺杂有多达约60重量%的选自Al、Pr、Sm、Zr、Y、Si、Ti和La中的一种或多种的氧化物;和处于所述可还原铈土载体上的基本金属氧化物,所述基本金属选自Ni、Fe、Mn、Cu、Co、Ba、Mg、Ga、Ca、Sr、V、W、Bi和Mo中的一种或多种,所述基本金属催化剂组合物能有效地促进烃类的蒸汽重整反应和水气变换反应以提供H2作为还原剂以减少NOx。在一个实施方案中,各反应的动力学匹配发动机操作动力学的富燃-贫燃循环。在第二实施方案中,所述催化剂提供富燃操作期间的热力学限制性氧化剂和贫燃操作期间的还原剂和为接近完全转化HC、CO和NOx所需的反应动力学。
可以改变所选组分和组分的量。举例来说,在一个实施方案中,所述载体包括至少35重量%可还原铈土,而在另一个实施方案中,包括多达约99重量%可还原铈土。在另一个实施方案中,所述可还原铈土掺杂有多达约90重量%的Al、Pr、Sm、Zr、Y和La中一种或多种的氧化物。在另一个实施方案中,Al、Pr、Sm、Zr、Y、Si、Ti和La中一种或多种的氧化物的存在量在约1重量%至约50重量%范围内。在另一个实施方案中,所述催化剂载体包含Zr和Pr的氧化物、Al的氧化物或Zr、La和Y的氧化物。在另一个实施方案中,所述载体还包含具有菱沸石晶体结构的沸石。
还可以改变所选的基本金属和相对量。因而,在一个实施方案中,所述基本金属是选自Ni、Mn、Co、Mo、Ga、Fe、Cu、Mg和Ba中的一种或多种。在另一个实施方案中,所述基本金属是选自Ni、Mn、Co、Fe和Cu中的一种或多种。在另一个实施方案中,所述基本金属氧化物的存在量在约1重量%至约30重量%、约2重量%至约30重量%、约5重量%至约25重量%或约10重量%至约20重量%范围内。在一个或多个实施方案中,所述催化剂包含一种以上基本金属。举例来说,所述催化剂可以包含两种或三种基本金属。
本发明的第二方面涉及一种使用上述催化剂处理由摩托车产生的气流的方法。因而,所述方法包括使由摩托车产生并且含有烃类、一氧化碳和氮氧化物的气流在富燃和贫燃发动机操作条件下与基本金属催化剂组合物接触,所述基本金属催化剂组合物包含:包括至少10重量%可还原铈土的载体,所述可还原铈土掺杂有多达约60重量%的选自Al、Pr、Sm、Zr、Y、Si、Ti和La中的一种或多种的氧化物;和处于所述可还原铈土载体上的基本金属氧化物,所述基本金属选自Ni、Fe、Mn、Cu、Co、Ba、Mg、Ga、Ca、Sr、V、W、Bi和Mo中的一种或多种,所述基本金属催化剂组合物能有效地促进烃类的蒸汽重整反应和水气变换反应以提供H2作为还原剂以减少NOx,从而除去气流中的至少一部分烃类、一氧化碳和氮氧化物。在一个实施方案中,所述催化剂提供富燃操作期间的热力学限制性氧化剂和贫燃操作期间的还原剂和为接近完全转化HC、CO和NOx所需的反应动力学。
附图简述
所以,可以理解本发明的上述特征的实现方式的细节,并且参考附图中所说明的本发明的实施方案,可以获得上文简要总结的本发明的更确切描述。然而,应注意,附图仅说明本发明的典型实施方案,且因此不应被视为限制其范围,因为本发明可能承认其它同样有效的实施方案。
图1示出了来自于实施例1的催化剂在450℃下的模拟富燃-贫燃循环测试下的性能;
图2是XRD图案,它示出了在500℃和950℃下焙烧过的来自于实施例1的催化剂的相结构;
图3示出了来自于实施例2的催化剂在450℃下的模拟富燃-贫燃循环测试下的性能;
图4是XRD图案,它示出了在500℃和950℃下焙烧过的来自于实施例2的催化剂的相结构;
图5示出了来自于实施例3的催化剂在450℃)下的模拟富燃-贫燃循环测试下的性能;
图6是XRD图案,它示出了在500℃和950℃下焙烧过的来自于实施例3的催化剂的相结构;
图7示出了来自于实施例4的催化剂在450℃下的模拟富燃-贫燃循环测试下的性能;
图8是XRD图案,它示出了在500℃和950℃下焙烧过的来自于实施例4的催化剂的相结构;
图9示出了来自于实施例5的催化剂在450℃下的模拟富燃-贫燃循环测试下的性能;
图10是XRD图案,它示出了在500℃和950℃下焙烧过的来自于实施例5的催化剂的相结构;
图11示出了来自于实施例6的催化剂在450℃下的模拟富燃-贫燃循环测试下的性能;
图12是XRD图案,它示出了在500℃和950℃下焙烧过的来自于实施例6的催化剂的相结构;
图13示出了来自于实施例10的催化剂在450℃下的模拟富燃-贫燃循环测试下的性能;
图14是XRD图案,它示出了在500℃和950℃下焙烧过的来自于实施例10的催化剂的相结构;
图15示出了来自于实施例11的催化剂在450℃下的模拟富燃-贫燃循环测试下的性能;
图16是XRD图案,它示出了在500℃和950℃下焙烧过的来自于实施例11的催化剂的相结构;
图17示出了来自于实施例12的催化剂在450℃下的模拟富燃-贫燃循环测试下的性能;
图18是XRD图案,它示出了在500℃和950℃下焙烧过的来自于实施例12的催化剂的相结构;和
发明详述
在描述本发明的若干个示例性实施方案之前,应理解本发明不限于以下描述中所阐述的构建细节或方法步骤。本发明能够具有其它实施方案而且能够用不同的方式实施或进行。
本文中提供了基本金属催化剂制剂及其制造和使用方法。根据本发明的不同的实施方案,所述基本金属催化剂适合于用作三效催化剂,用于在典型发动机操作循环下同时除去烃类(HC)、CO和NOx。
因而,本发明的一个方面涉及一种在富燃和贫燃发动机操作条件下都能有效地催化烃类、一氧化碳和氮氧化物的减少的基本金属催化剂组合物。所述基本金属催化剂组合物包含:包括至少10重量%可还原铈土的载体,所述可还原铈土掺杂有多达约60重量%的选自Al、Pr、Sm、Zr、Y、Si、Ti和La中的一种或多种的氧化物;和处于所述可还原铈土载体上的基本金属氧化物,所述基本金属选自Ni、Fe、Mn、Cu、Co、Ba、Mg、Ga、Ca、Sr、V、W、Bi和Mo中的一种或多种,所述基本金属催化剂组合物能有效地促进烃类的蒸汽重整反应和水气变换反应以提供H2作为还原剂以减少NOx。
尽管不希望受任何特定理论束缚,但认为根据本发明的一个或多个实施方案的基本金属催化剂能催化与烃类、CO和NOx减少相关的各种反应,使得各反应的动力学匹配发动机操作的富燃-贫燃循环动态。
汽化器式摩托车发动机排放物以不同的驾驶循环期间的波动的气体组成和流速(体积)为特征。在所谓的“富燃条件”下,排气的空气-燃料比低于烃和CO完全氧化和NOx还原所需的化学计量比。类似地,在本领域中已知的“贫燃条件”下,供应了过量空气,这为CO和烃氧化提供了绰绰有余的氧气。然而在贫燃条件下,所存在的还原剂对于NOx还原来说是不充分的。
另外,发动机排放物的温度可以取决于驾驶循环的阶段、燃料的类型和发动机技术而变化。排放气体还含有呈燃烧副产物形式的蒸汽,含量为约10%。因而,为了在富燃和贫燃条件下同时转化HC、CO和NOx,水活化非常重要。在富燃条件下,烃类的蒸汽重整和水气变换反应可以弥补氧化剂(O2)的缺乏。类似地,在贫燃条件下,重整和水气变换反应可以产生比烃和CO更有效的还原剂(H2)用于进行NOx转化。以下列出了这些催化反应:
CO:水气变换/氧化:
CO+H2O→CO2+H2
CO+O2→CO2
烃类:重整/氧化:
HC+O2→CO2+H2O
HC+H2O→CO2+H2+CO
NOx:选择性催化还原(HC、CO和H2作为还原剂):
NOx+CO/HC→N2+CO2
NOx+H2→N2+H2O
其它反应:
H2+O2→H2O
储氧组分(OSC)氧化还原反应,
即,Ce2O3+O2→CeO2
因而,通过水活化,本发明的一个或多个实施方案提供了在富燃和贫燃操作循环下接近完全转化HC、CO和NOx所需的热力学限制性氧化剂/还原剂和动力学。这些制剂含有呈固体混合相或负载型混合相的混合基本金属氧化物。因此,在本发明的一个或多个实施方案中,各反应的动力学匹配发动机操作动力学的富燃-贫燃循环。在另一个实施方案中,所述催化剂提供了富燃操作期间的热力学限制性氧化剂和贫燃操作期间的还原剂和为接近完全转化HC、CO和NOx所需的反应动力学。
在一个或多个实施方案中,催化剂载体含有储氧组分(OSC),其价态在排放条件下可能变化。在一个实施方案中,所述OSC是铈土。在其它实施方案中,所述载体包括至少35重量%可还原铈土。在其它实施方案中,所述载体包括多达约99重量%可还原铈土。
在某些实施方案中,所述OSC还含有其它元素/组分以改良OSC组分的可还原性和稳定OSC组分,以防在高温热水老化条件下损失表面积和结构完整性。这样的组分可以包括Al、Pr、Sm、Zr、Y、Si、Ti和La,其存在量可以多达约60重量%。因而,在其它实施方案中,所述可还原铈土掺杂有多达约90重量%的Al、Pr、Sm、Zr、Y和La中一种或多种的氧化物。在其它实施方案中,所述可还原铈土掺杂有这些元素中一种或多种的氧化物,其量小于或等于约60重量%,或为约1重量%到约50重量%。在一个具体实施方案中,所述载体包含铝的氧化物。
在本发明的一个或多个实施方案中,可以使用一种以上这些组分来掺杂所述可还原铈土。合适的组合的非限制性例子包括以下组合的氧化物:锆和镨;锆、镧和钇;和锆、镨和铝。注意,掺杂剂的上述重量百分比是相对于总量。因而,举例来说,对于包含50重量%氧化物和两种掺杂剂的催化剂载体,则所组合的两种掺杂剂的氧化物将合计达50重量%。
在其它实施方案中,所述载体还可以包含其它组分。举例来说,在一个实施方案中,所述载体还可以沸石,且在更具体的实施方案中,包含具有菱沸石晶体结构的沸石。与含有沸石的载体有关的实施方案还可以含有上述种类的其它掺杂剂。因而,在一个示例性实施方案中,所述载体包含铈土、氧化锆、氧化镧、氧化钇和具有菱沸石晶体结构的沸石。
如上文所论述,所述基本金属是选自Ni、Fe、Mn、Cu、Co、Ba、Mg、Ga、Ca、Sr、V、W、Bi和Mo中的一种或多种的金属,并且能有效地促进烃类的蒸汽重整反应和水气变换反应以提供H2作为还原剂以减少NOx。在另一个实施方案中,所述基本金属是选自Ni、Mn、Co、Mo、Ga、Fe、Cu、Mg和Ba中的一种或多种。在一个更具体的实施方案中,所述基本金属是选自Ni、Mn、Co、Fe和Cu中的一种或多种。在其它实施方案中,所述基本金属氧化物的存在量在约1重量%至约30重量%,或约2重量%至约30重量%,或约5重量%至约25重量%,或约10重量%至约20重量%范围内。
在一些实施方案中,可以使用一种以上基本金属。因而,在某些实施方案中,所述催化剂包含两种、三种或甚至更多种基本金属。基本金属组合的非限制性实例包括但不限于:铜和锰;钴、铁、锰、铜、铁和锰;钴、镍和铁;钴、镍和锰;镍、铁和锰;铜、钴和铁;铁和锰;和镍、铁和锰。注意,基本金属氧化物的上述重量百分比是相对于基本金属总量。因而,举例来说,对于包含15重量%基本金属氧化物和两种基本金属的催化剂,则所组合的两种基本金属氧化物将合计达15重量%。
制备
本发明的另一个方面涉及制备本文中所描述的催化剂的方法。在一个或多个实施方案中,OSC和助催化剂可以通过诸如共同沉淀、老化、干燥和焙烧等湿式化学方法或化学气相沉积(CVD)、气溶胶喷雾干燥/焙烧、等离子或其它方法等干式方法制备成固相混合物。还可以在催化剂制备期间在不使用预形成的氧化物作为载体的情况下将这些成分与活性基本金属组分添加在一起。
在一个或多个实施方案中,基本金属催化剂的使用模式是作为整体载体负载型催化剂。本文中所描述的催化剂制造有许多合适的变化方案。可以将活性基本金属催化剂制剂涂布在用于汽车排放应用的整体结构的表面上。整体结构提供较高的几何表面积,优良的热强度和机械强度,并且因而特别适合用于汽车排放控制。可以使用任何整体结构,包括陶瓷、金属(诸如不锈钢和其它金属),或合金。所述整体可以具有直通道或图案状通道,或者呈泡沫或其它结构形式。
可以使用任何合适的方法将活性催化剂涂覆于整体表面,包括浆液涂布、喷雾涂布等等。活性基本金属是选自Ni、Fe、Mn、Cu、Co、Ba、Mg、Ga、Ca、Sr、V、W、Bi和Mo。在具体实施方案中,基本金属是选自Ni、Mn、Co、Mo、Ga、Fe、Cu、Mg和Ba中的一种或多种。这些基本金属的合适的前驱物可能是纯盐或混合盐、氧化物或混合氧化物。可以使用本领域技术人员众所周知的化学前驱物和涂布技术来涂覆基本金属。举例来说,通过湿式灌注和浆液涂布方法,可以使用Co(NO3)2·6H2O来涂覆钴,可以使用Fe(NO3)2·9H2O来涂覆铁,且可以使用Mn(NO3)2·4H2O来涂覆锰。
在与负载型基本金属制剂有关的实施方案中,可以使用预制载体来灌注活性基本金属或基本金属组合的溶液。这样的预制载体的例子包括但不限于铈土-氧化铝。然后可以将所得催化剂与合适的粘合剂混合。或者,可以首先焙烧所得催化剂,然后与粘合剂混合以制造适合用于整体涂布的浆液。在其它实施方案中,可以将沉积在一个载体中的一种或多种活性基本金属与沉积在另一个载体中的其它基底金属催化剂混合以制造用于整体洗覆的浆液。
然后可以在120℃下将最终经过涂布的整体催化剂干燥2小时且在约300℃至约1000℃范围内的温度下焙烧。在其它实施方案中,在约400℃至约950℃范围内的温度下焙烧催化剂。在另一个实施方案中,在约450℃至约500℃范围内的温度下焙烧催化剂。
如果在催化剂制备中未使用预制载体,则可以将所需基本金属与OSC和OSC助催化剂混合以形成均质溶液。然后,可以通过加入例如NH4OH、氨络物或其它结构引导剂(诸如聚合物或表面活性剂)以进行共同沉淀来调节溶液pH值。然后可以使母液老化以获得适合用于整体涂布的粒度。还可以通过使用过滤来分离沉淀物以便进行干燥和焙烧。然后将经过焙烧的基底金属固相混合物用于制造浆液和整体涂布。
使用方法
本文中所描述的催化剂的一个或多个实施方案适合于处理摩托车的排气流。因此,本发明的另一个方面涉及一种处理由摩托车产生的气流的方法。所述方法包括使由摩托车产生并且含有烃类、一氧化碳和氮氧化物的气流在富燃和贫燃发动机操作条件下与基本金属催化剂组合物接触,所述基本金属催化剂组合物包含:包括至少10重量%可还原铈土的载体,所述可还原铈土掺杂有多达约60重量%的选自Al、Pr、Sm、Zr、Y、Si、Ti和La中的一种或多种的氧化物;和处于所述可还原铈土载体上的基本金属氧化物,所述基本金属选自Ni、Fe、Mn、Cu、Co、Ba、Mg、Ga、Ca、Sr、V、W、Bi和Mo中的一种或多种,所述基本金属催化剂组合物能有效地促进烃类的蒸汽重整反应和水气变换反应以提供H2作为还原剂以减少NOx,从而除去气流中的至少一部分烃类、一氧化碳和氮氧化物。总体来说,这个方面所使用的催化剂的变化方案可以选自上述催化剂实施方案。
然而,在具体实施方案中,所述催化剂提供富燃操作期间的热力学限制性氧化剂和贫燃操作期间的还原剂和为接近完全转化HC、CO和NOx所需的反应动力学。在其它实施方案中,所述基本金属氧化物的存在量在约1重量%至约30重量%范围内。在其它实施方案中,所述基本金属氧化物的存在量在约2重量%至约25重量%范围内。在其它实施方案中,所述载体包括至少35重量%可还原铈土。
实施例
可以在不偏离本公开的精神的情况下基于本公开进行许多变更和组合以制造用于汽车排放控制的基本金属催化剂。给出以下实施例和实施方案仅用作说明目的,而不应被用作对本发明的限制。
实施例1
将17.546g Co(NO3)2·6H2O、25.299g Fe(NO3)2·9H2O和14.436g Mn(NO3)2·4H2O与20g去离子水混合以制造溶液。使用35g含有55%铈土、15%氧化锆和30%氧化镨的预制载体进行灌注。将所述溶液逐滴加入到载体上,直到饱和为止。然后在120℃下将经过灌注的载体干燥2小时,之后加入其余溶液。重复灌注-干燥-灌注循环,直到没有溶液剩余为止。然后将水加入到经过灌注的样品,以制造具有40%固体含量的浆液。继续研磨所述浆液,直到所要求的粒度达到D90<10微米。
使用孔密度为300cpsi的1"OD×1"高度的整体。在对催化剂浆液进行洗覆之前,将所述整体涂有氧化铝薄层,以确保催化剂制剂的良好粘附。使用浸涂法涂覆催化剂涂层,其中洗覆层负载为2g/in3。然后在120℃下将经过涂布的整体干燥2小时,并且在500℃下在空气中焙烧2小时。将所得催化剂组成示于以下表1中。
图2是来自于实施例1的催化剂的XRD图案,其示出了相结构。下面的光谱示出了在500℃下焙烧的催化剂,而上面的光谱示出了在950℃下焙烧的催化剂。如由图中可见,本实施例并入了锆铈氧化物、镨铁钴氧化物、磁铁矿、方锰矿、氧化钴和氧化锰的混合氧化物。如本实施例中所公开的金属氧化物组合被证明是活性三效催化剂。这些金属氧化物或其组合可以用本领域技术人员已知的不同的方法按照本公开制备。
实施例2-6
使用与实施例1中相同的预制载体并且按照与实施例1中所给出的程序完全相同的程序但利用不同的制剂来进行这些实施例。实施例2-6的制剂的总结可见于以下表1中。
图4是来自于实施例2的催化剂的XRD图案,其示出了相结构。下面的光谱示出了在500℃下焙烧的催化剂,而上面的光谱示出了在950℃下焙烧的催化剂。如由图中可见,本实施例的催化剂并入了锆铈氧化物、镨锰氧化物、CuO、Fe2O3、Fe3O4和ZrO2的混合氧化物。。
图6是来自于实施例3的催化剂的XRD图案,其示出了相结构。下面的光谱示出了在500℃下焙烧的催化剂,而上面的光谱示出了在950℃下焙烧的催化剂。如由图中可见,本实施例的催化剂并入了锆铈氧化物、镨铁钴氧化物、NiO、Fe2O3、Fe3O4和Co3O4的混合氧化物。
图8是来自于实施例4的催化剂的XRD图案,其示出了相结构。下面的光谱示出了在500℃下焙烧的催化剂,而上面的光谱示出了在950℃下焙烧的催化剂。如由图中可见,本实施例的催化剂并入了锆铈氧化物、镨镍氧化物、NiO和Co3O4的混合氧化物。
图10是来自于实施例5的催化剂的XRD图案,其示出了相结构。下面的光谱示出了在500℃下焙烧的催化剂,而上面的光谱示出了在950℃下焙烧的催化剂。如由图中可见,本实施例的催化剂并入了锆铈氧化物(Ce0.7Zr0.3O2)、镨镍氧化物(PrNiO3)、FeNi2O4和MnNi6O8的混合氧化物。
图12是来自于实施例6的催化剂的XRD图案,其示出了相结构。下面的光谱示出了在500℃下焙烧的催化剂,而上面的光谱示出了在950℃下焙烧的催化剂。如由图中可见,本实施例的催化剂并入了锆铈氧化物(Ce0.7Zr0.3O2)、镨铁钴氧化物(PrFe0.9Co0.1O3)、铁钴氧化物、铜钴氧化物和CuO的混合氧化物。
实施例7
使用含有50%铈土和50%氧化铝的预制载体进行灌注。使用与实施例1中所给出的程序相同的灌注程序制造这种仅含Ni的制剂。所得制剂可见于以下表1中。
实施例8
利用与实施例1中所使用的载体相同的载体,按照实施例7中所给出的程序但利用不同的制剂来制造样品。所得制剂可见于以下表1中。
实施例9
利用含有40.5%CeO2、5%La2O3、49.6%ZrO2和4.8%Y2O3的载体,按照实施例7中给出的程序,但利用不同的制剂来制造样品。所得制剂可见于以下表1中。
实施例10
将12g铜菱沸石(预制,含有3.23重量%CuO)和12g实施例9中所描述的催化剂混合,以制造浆液。按照实施例1中给出的相同浆液和洗覆程序制备整体样品。所得制剂可见于以下表1中。
图14是来自于实施例10的催化剂的XRD图案,其示出了相结构。下面的光谱示出了在500℃下焙烧的催化剂,而上面的光谱示出了在950℃下焙烧的催化剂。本实施例的催化剂并入了锆铈氧化物(Ce0.5Zr0.5O1.75)、锰铁矿(Cu0.5MnFe1.5O4)、氧化铁(Fe2O3)和沸石的混合氧化物。
实施例11
按照实施例10中给出的程序制造样品,但使用实施例7中制造的催化剂和实施例9中的催化剂进行共同研磨。所得制剂可见于以下表1中。
图16是来自于实施例11的催化剂的XRD图案,其示出了相结构。下面的光谱示出了在500℃下焙烧的催化剂,而上面的光谱示出了在950℃下焙烧的催化剂。本实施例的催化剂并入了锆铈氧化物(Ce0.5Zr0.5O1.75)、方铈矿(CeO2)、镍铝氧化物[(Ni0.141Al0.859)(Al1.141Ni0.859)O4]、氧化铝、磁铁矿(Fe3O4)和氧化铁(Fe2O3)的混合氧化物。
实施例12
按照实施例10中给出的程序制造样品,但使用实施例7中制造的催化剂和实施例8中的催化剂进行共同研磨。所得制剂可见于以下表1中。
图18是来自于实施例12的催化剂的XRD图案,其示出了相结构。下面的光谱示出了在500℃下焙烧的催化剂,而上面的光谱示出了在950℃下焙烧的催化剂。本实施例的催化剂并入了锆铈氧化物(Ce0.2Zr0.8O2)、方铈矿(CeO2)、镍铝氧化物[(Ni0.141Al0.859)(Al1.141Ni0.859)O4]、氧化铝、氧化锆(ZrO2)、镨铁氧化物(PrFeO3)、氧化铁(Fe2O3)、氧化镍、锰铁矿(MnFe2O4)和镍铝氧化物的混合氧化物。
实施例13
使用纯铈土作为载体。按照实施例1中给出的程序制造样品,但利用不同的制剂。所得制剂可见于以下表1中。
表1:实施例1-13中所描述的催化剂的组成(重量%)
CuO | Co2O3 | NiO | Fe2O3 | MnO2 | CeO2 | ZrO2 | Pr2O3 | Al2O3 | La2O3 | Y2O3 | 菱沸石 | |
实施例1 | 10 | 10 | 10 | 38.5 | 10.5 | 21 | ||||||
实施例2 | 15 | 10 | 10 | 35.75 | 9.75 | 19.5 | ||||||
实施例3 | 10 | 10 | 10 | 38.5 | 10.5 | 21 | ||||||
实施例4 | 10 | 10 | 10 | 38.5 | 10.5 | 21 | ||||||
实施例5 | 10 | 10 | 10 | 38.5 | 10.5 | 21 | ||||||
实施例6 | 15 | 10 | 10 | 35.75 | 9.75 | 19.5 | ||||||
实施例7 | 15 | 42.5 | 42.5 | |||||||||
实施例8 | 10 | 10 | 44 | 12 | 24 | |||||||
实施例9 | 10 | 10 | 32.4 | 39.7 | 4.08 | 3.84 | ||||||
实施例10 | 1.6 | 5 | 5 | 16.2 | 19.8 | 2.04 | 1.92 | 48.4 | ||||
实施例11 | 7.5 | 5 | 5 | 37.45 | 19.8 | 21.25 | 2.04 | 1.92 | ||||
实施例12 | 7.5 | 5 | 5 | 43.25 | 6 | 12 | 21.25 | |||||
实施例13 | 10 | 90 |
性能测试
使用实验室测试方案来测试以上实施例中所描述的催化剂的性能,以模拟富燃-贫燃循环发动机操作。
在固定床反应器中,在表3中所示的条件下进行实验室模拟测试。通过改变CO流量而保持空气流量恒定来改变λ。
表2:固定床反应器的条件
结果:
图1、3、5、7、9、11、13、15、17和19分别示出了实施例1-6和10-12的催化剂的性能。数据示出了在450℃下的模拟富燃-贫燃循环测试下的性能(表2)。结果示出了在λ变化时的CO、NOx和总烃(THC)转化百分比。如由这些图可见,所制备的所有催化剂都能在富燃条件(例如,当λ较小时)下有效地进行NOx转化和在贫燃条件(例如,当λ较大时)下有效地进行CO和烃转化。图1示出了实施例1的催化剂在富燃和贫燃条件下的良好CO转化率和优良的富燃NOx活性和一定的贫燃Nox活性。图3、5和11中显示了在利用实施例2、3和6中所描述的催化剂的情况下大大提高了富燃烃转化率。类似地,图13中显示在利用实施例10的催化剂的情况下大大提高了贫燃NOx活性。通过组合和优化所公开的金属氧化物、空间速度和优化基于本公开的整体结构上的催化剂涂层的孔隙度和构造,可以在富燃和贫燃条件下都实现高CO、烃和NOx转化率。
在本说明书全文中,提到“一个实施方案”、“某些实施方案”、“一个或多个实施方案”或“实施方案”意指结合所述实施方案加以描述的特定特征、结构、材料或特性被包括在本发明的至少一个实施方案中。因而,在本说明书全文中不同位置出现的诸如“在一个或多个实施方案中”、“在某些实施方案中”、“在一个实施方案中”或“在实施方案中”等短语未必是指本发明的同一实施方案。此外,在一个或多个实施方案中,特定的特征、结构、材料或特性可以用任何合适的方式组合。
尽管本文中已经参考特定实施方案描述了本发明,但应理解这些实施方案仅说明本发明的原则和应用。本领域技术人员应显而易见,可在不背离本发明的精神和范围的情况下对本发明的方法和设备进行各种修改和变化。因而,希望本发明包括所附权利要求书及其相等物范围内的修改和变更。
Claims (15)
1.一种在富燃和贫燃发动机操作条件下都能有效地催化烃类、一氧化碳和氮氧化物的减少的基本金属催化剂组合物,其包含
包括至少10重量%的可还原铈土的载体,所述可还原铈土掺杂有多达约60重量%的选自Al、Pr、Sm、Zr、Y、Si、Ti和La中一种或多种的氧化物;和
处于所述可还原铈土载体上的基本金属氧化物,所述基本金属选自Ni、Fe、Mn、Cu、Co、Ba、Mg、Ga、Ca、Sr、V、W、Bi和Mo中的一种或多种,所述基本金属催化剂组合物能有效地促进烃类的蒸汽重整反应和水气变换反应以提供H2作为还原剂减少NOx。
2.如权利要求1所述的催化剂组合物,其中各反应的动力学匹配发动机操作动力学的富燃-贫燃循环。
3.如权利要求1或2所述的催化剂组合物,其中所述催化剂提供富燃操作期间的热力学限制性氧化剂和贫燃操作期间的还原剂及为接近完全转化HC、CO和NOx所需的反应动力学。
4.如权利要求1-3中任一项所述的催化剂组合物,其中所述载体包括至少35重量%的可还原铈土。
5.如权利要求1-4中任一项所述的催化剂组合物,其中所述载体包括多达约99重量%的可还原铈土。
6.如权利要求1-5中任一项所述的催化剂组合物,其中所述可还原铈土掺杂有多达约90重量%的Al、Pr、Sm、Zr、Y和La中一种或多种的氧化物。
7.如权利要求1-6中任一项所述的催化剂组合物,其中所述基本金属选自Ni、Mn、Co、Mo、Ga、Fe、Cu、Mg和B中的一种或多种,或更优选地选自Ni、Mn、Co、Fe和Cu。
8.如权利要求1-7中任一项所述的催化剂组合物,其中所述基本金属氧化物的存在量在约1重量%至约30重量%范围内,或更优选地在约2重量%至约30重量%范围内,或更优选地在约5重量%至约25重量%范围内,或更优选地在约10重量%至约20重量%范围内。
9.如权利要求1-8中任一项所述的催化剂组合物,其中所述催化剂包含两种或三种基本金属。
10.如权利要求1-9中任一项所述的催化剂组合物,其中Al、Pr、Sm、Zr、Y、Si、Ti和La中一种或多种的氧化物的存在量在约1重量%至约50重量%范围内。
11.如权利要求1-10中任一项所述的催化剂组合物,其中所述载体包含Zr和Pr的氧化物。
12.如权利要求1-11中任一项所述的催化剂组合物,其中所述载体包含Al的氧化物。
13.如权利要求1-12中任一项所述的催化剂组合物,其中所述载体包含Zr、La和Y的氧化物。
14.如权利要求1-13中任一项所述的催化剂组合物,其中所述载体还包含具有菱沸石晶体结构的沸石。
15.一种处理由摩托车产生的气流的方法,所述方法包括:使含有烃类、一氧化碳和氮氧化物并且由摩托车产生的气流在富燃和贫燃发动机操作条件下与如权利要求1-14中任一项所述的基本金属催化剂组合物接触,从而除去气流中的至少一部分烃类、一氧化碳和氮氧化物。
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US8765085B2 (en) | 2014-07-01 |
WO2013163523A1 (en) | 2013-10-31 |
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US20130330258A1 (en) | 2013-12-12 |
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