CN110461469A - 选择性催化还原催化剂 - Google Patents
选择性催化还原催化剂 Download PDFInfo
- Publication number
- CN110461469A CN110461469A CN201880021313.1A CN201880021313A CN110461469A CN 110461469 A CN110461469 A CN 110461469A CN 201880021313 A CN201880021313 A CN 201880021313A CN 110461469 A CN110461469 A CN 110461469A
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- CN
- China
- Prior art keywords
- catalyst
- carbon monoxide
- olefin polymeric
- component
- titanium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract 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 abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 27
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 239000011159 matrix material Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 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 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002912 waste gas Substances 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 229910000628 Ferrovanadium Inorganic materials 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 description 12
- 241000264877 Hippospongia communis Species 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910002089 NOx Inorganic materials 0.000 description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- -1 nitrogenous Nitrogen oxides Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000009992 mercerising Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- GMVPRGQOIOIIMI-DODZYUBVSA-N 7-[(1R,2R,3R)-3-hydroxy-2-[(3S)-3-hydroxyoct-1-enyl]-5-oxocyclopentyl]heptanoic acid Chemical compound CCCCC[C@H](O)C=C[C@H]1[C@H](O)CC(=O)[C@@H]1CCCCCCC(O)=O GMVPRGQOIOIIMI-DODZYUBVSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- RMKJAAPVONZTMN-UHFFFAOYSA-N aluminum;dihydroxy(oxo)silane;sodium Chemical compound [Na].[Al].O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O RMKJAAPVONZTMN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- OQRWAMBQGTYSRD-UHFFFAOYSA-N dipotassium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[K+].[K+].[Ti+4].[Ti+4].[Ti+4].[Ti+4] OQRWAMBQGTYSRD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
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Abstract
用于应用含氮还原剂转化废气中氮氧化物(NOx)的选择性催化还原催化剂组合物,包含第一组分和第二组分的混合物,其中所述第一组分为H型铝硅酸盐丝光沸石(MOR)与铁促进的铝硅酸盐MFI沸石的混合物;和所述第二组分为在金属氧化物载体上载带的钒氧化物,所述载体为二氧化钛、二氧化硅稳定的二氧化钛或二氧化钛与二氧化硅稳定的二氧化钛的混合物,其中第一组分与第二组分的重量比为10:90至25:75。
Description
本发明涉及用于应用含氮还原剂转化废气中氮氧化物(NOx)的选择性催化还原催化剂组合物。
本申请人的WO 2014/027207 A1公开了用于处理由燃烧过程获得的废气中氮氧化物的催化剂组合物,例如来自内燃机(移动或固定的)、燃气透平或燃煤或燃油电站的废气,所述催化剂包含第一组分和第二组分的掺混物,其中所述第一组分为铝硅酸盐或铁硅酸盐分子筛组分,和其中所述分子筛或者为H+型或者用一种或多种过渡金属进行了离子交换,和所述第二组分为在选自氧化铝、二氧化钛、氧化锆、二氧化铈、二氧化硅及其组合上载带的钒氧化物。
EP 255121A2公开了包含如下的催化剂:(A)’钛的氧化物、(B)’选自钨和钼的至少一种金属的氧化物、(C)’钒的氧化物和(D)’选自钇、镧、铈、钕、铜、钴、锰和铁的至少一种金属,组分(D)’沉积于沸石上,这种催化剂用于脱除固定产生源如燃烧炉或锅炉产生的含氮氧化物和砷化合物的废气中的氮氧化物。
US 4798813公开了用于脱除燃烧炉废气中氮氧化物的催化剂,所述废气包含可挥发性催化剂毒物如砷、硒和碲。所述催化剂包含表面积为20m2/g或更低的二氧化钛和在其上载带0.01-20wt%铜的沸石,所述沸石平均孔径为或更小和二氧化硅/氧化铝的摩尔比为10或更大。
US 4735927A1公开了用于在氨的存在下选择性还原氮氧化物为氮的催化剂,其对于废气中包含的硫氧化物中毒具有耐受性,所述催化剂为由如下物质的混合物形成的复合体形式:锐钛矿(5-40wt%)、沸石(50-90%)、粘结材料(0-30%)和任选至少为0.1wt%的选自钒、钼和铜的氧化物的促进剂。
WO 88/02659公开了用于脱除电站或工业炉排出的烟气中的氮氧化物的催化剂,所述催化剂包含孔径为和处于其酸形式(H型)的耐酸沸石。催化剂的组分可以包括作为附加试剂的少量过渡金属元素铁、钒、钼、钨、镍、钴、铜、铬和/或铀。另外,以催化剂的质量计,所述催化剂可以包含至多40wt%的氧化钛。
US 2002/0004446A1公开了用于在还原剂的存在下在400-750℃的温度下分解氮氧化物的催化剂体,所述催化剂体包含:包含氢离子交换的酸沸石和活性组分的活性材料,所述活性材料包含40-60wt%的所述沸石和40-60wt%的所述活性组分,所述活性组分包含70-95wt%的二氧化钛、2-30wt%的三氧化钨、0.1-10wt%的氧化铝和0.1-10wt%的二氧化硅。
WO 2008/089957 A1公开了用于还原柴油机废气中氮氧化物的催化剂组合物,所述催化剂包含选自V2O5、WO3、TiO2的至少两种氧化物和金属交换的不含贵金属的沸石。所述交换金属优选为Co、Cu、Fe或Ni,特别是Fe。催化剂组合物中金属交换的沸石的含量限制为小于10wt%,5-8wt%最为优选。
US 4663300A公开了用于还原烟气中氮氧化物为氮的催化剂组合物和方法。所述催化剂包含二氧化钛、丝光沸石和金属组分。优选的金属组分包括钒氧化物和钨氧化物。至少存在15wt%的丝光沸石,优选的是高二氧化硅H-丝光沸石。
EP 2614886 A1公开了一种NOx还原催化剂,其用于对燃烧高含硫煤、来自PowderRiver Basin(USA)的煤、生物质等的锅炉废气用氨进行氮氧化物的催化还原,废气中也包含催化剂毒物如砷、磷和钾。这种催化剂需要较低比率的SO2氧化,以避免SO3排放和形成所谓的“酸雨”,和要求氧化废气中存在汞的高活性。所述催化剂由催化剂组合物组成,其包含钛(Ti)、磷的氧化物、钼(Mo)和/或钨(W)、钒(V)的氧化物、和高二氧化硅沸石(其SiO2/Al2O3比不小于20)。
随着对WO 2014/027207 A1中公开的催化剂配制物的继续研究,本发明人发现H型铝硅酸盐丝光沸石和铁促进的铝硅酸盐MFI沸石作为第一组分与第二载带的钒氧化物组分的组合物(掺混物)具有更好的NOx转化率和更低或可对比的N2O选择性(即选择性地转化NOx为N2,而不是N2O),无论与US 4663300A中公开的只包含H型丝光沸石的组合物相比还是与WO2014/027207 A1中公开的只包含铁促进的铝硅酸盐MFI沸石的组合物相比都如此,特别是当温度至多400℃时。这种协同作用按所附权利要求和下文描述进行定义。
按照第一方面,本发明提供用于转化废气中氮氧化物(NOx)的催化剂组合物,所述催化剂组合物包含第一组分和第二组分的混合物,其中所述第一组分为H型铝硅酸盐丝光沸石与铁促进的铝硅酸盐MFI沸石的混合物;和所述第二组分为在金属氧化物载体上载带的钒氧化物,所述载体为二氧化钛、二氧化硅稳定的二氧化钛或二氧化钛与二氧化硅稳定的二氧化钛的混合物,其中第一组分与第二组分的重量比为10:90至25:75。
下面将进一步描述本发明。在下文中,将更为详细地描述本发明的不同方面/实施方案。如果没有明显地相反说明,这样定义的每一方面/实施方案可以与任意的其它方面/实施方案组合。具体地,作为优选或有利指出的任何特征均可以与作为优选或有利指出的任何其它特征组合。打算的是与产品相关所公开的特征可以与方法相关所公开的那些特征组合,或者相反。
另外,这里所应用的术语“包含”可以与定义“主要包含…”或“由…组成”互换。术语“包含”用于指所提到的元素是主要的,但可以加入其它元素,和仍在权利要求范围内。“主要包含…”限制权利要求的范围至指定的材料或步骤及不实质影响所要求发明基础和新颖性特性的特征。术语“由…组成”封闭了权利要求,其包括除通常与之相关的杂质以外引述的那些不同的材料。
H型铝硅酸盐丝光沸石(MOR)与铁促进的铝硅酸盐MFI沸石的重量比优选为3:1至3:5,最优选为1:1至3:5。这些参数的优点在下文的实施例中示出。
任选地,第一组分与第二组分的重量比为15:85至20:80。
当按本发明的第一方面的催化剂组合物为用于挤出为基质时,所述催化剂组合物优选包含一种或多种粘结剂组分,其中第一和第二组分的组合重量与一种或多种粘结剂组分的组合重量的重量比为80:20至95:5,优选为90:10至85:15。所述一种多种粘结剂组分可以为粘土如氧化铝和/或玻璃纤维。
MFI骨架型号(由国际沸石协会定义)指共有相同结构的一类合成分子筛。MFI定义为具有十个四面体原子的最大孔开口,和具有该特征的分子筛在文献中称为“中孔”分子筛。铝硅酸盐分子筛通常称作沸石。优选的MFI骨架型号的铝硅酸盐沸石为ZSM-5。ZSM-5是已知的,和已进行过广泛研究和表征。例如参见G.T.Kokotailo等人的“Structure ofsynthetic zeolite ZSM-5”,Nature 272,437-438(1978)。使ZSM-5与铁离子交换的方法也是已知的(例如参见US20100172828A1)。在用于本发明的铁促进的铝硅酸盐MFI沸石中优选的铁含量为2-7wt%,例如3-6wt%。
铝硅酸盐MFI的二氧化硅-氧化铝比(SAR)优选为20-50。如果SAR太高,沸石的表面积减少,则存在太少的酸位来有效地存贮氨和/或提供NOx转化活性。如果SAR太低,沸石易于结构损坏和因此在应用中通过水热老化造成骨架和表面坍塌。
MOR骨架型号丝光沸石最初被认为是天然矿物,但其随后被合成生产(参见Meier,W.M.的The crystal structure of mordenite(ptilolite)Z.Kristallogr.,115,439-450(1961);和美国专利US 4503023)。虽然在本发明中可以应用天然丝光沸石,但要采取合适步骤例如通过洗涤和氨离子交换脱除天然材料中存在的杂质和反离子如钠和/或钾(例如参见DE102005010221),我们倾向于应用合成的铝硅酸盐丝光沸石。向用于制备本发明产品的混合物中添加的丝光沸石(参见实施例1)可为预制的H型丝光沸石或氨型,后者在煅烧后从中脱除氨转化为H型。
与上文针对Fe-MFI讨论的原因相同,用于本发明的合成铝硅酸盐丝光沸石的丝光沸石的SAR可以为10-30。天然丝光沸石的SAR通常为8-12。
合适的粘土包括富勒土、海泡石、锂蒙脱石、蒙脱石、高岭土及其任意两种或更多种的混合物,其中高岭土可选自亚膨润土、蠕陶土、埃洛石、高岭石、地开石、珍珠陶土及其任意两种或更多种的混合物;蒙脱石可选自蒙脱土、绿脱石、蛭石、皂石及其任何两种或更多种的混合物;富勒土可以是蒙脱土或坡缕石(绿坡缕石)。
无机纤维可以选自碳纤维、玻璃纤维、金属纤维、硼纤维、氧化铝纤维、二氧化硅纤维、二氧化硅-氧化铝纤维、碳化硅纤维、钛酸钾纤维、硼酸铝纤维和陶瓷纤维。无机纤维可以改进在优选的汽车用途中应用的煅烧产品的机械强度,和在汽车废气系统中应用的煅烧产品“罐封”期间的机械强度。
氧化铝优选为γ氧化铝。当应用氧化铝时,为了确保与氧化铝粘结,有利的是向氧化铝或氧化铝的前体物质中加入水溶性金属盐的水溶液,随后加入其它初始物质。替代地,可以应用任意的其它过渡氧化铝,即α氧化铝、β氧化铝、χ氧化铝、η氧化铝、ρ氧化铝、κ氧化铝、θ氧化铝、δ氧化铝、镧β氧化铝和这些过渡氧化铝中任意两种或更多种的混合物。也可以将氧化铝作为溶胶加入到可挤出混合物中,好处是所得的煅烧产品机械性更强。
优选地,为了改进催化剂的热稳定性和新鲜催化剂的NOx转化活性,第二组分的金属氧化物载体包含钨氧化物、钼氧化物、钨氧化物和钼氧化物两者,但更优选为钨氧化物。
第二组分的钒氧化物可以包含铁钒酸盐,因为其可以提供某些优点,包括改进低温(180-350℃)活性和比钒氧化物更高的温度稳定性,正如WO 2011/127505中所公开。
以催化剂组合物整体的总重量计,包括任何粘结剂的催化剂组合物可以包含0.5-5.0wt%按V2O5计算的钒,优选为1.0-3.0wt%。这种计算方法也适用于当钒组分为铁钒酸盐(FeVO4)时。
按照第二方面,提供一种催化载体涂层,所述载体涂层包含本发明第一方面的催化剂组合物,其包含一种或多种填料、粘结剂、处理助剂、水和掺杂剂。处理助剂可以包括在这种方法中应用的流变改性剂,例如在WO 99/047260 A1、WO 2011/080525 A1、WO 2014/195685 A1或WO 2015/145122 A2的涂覆方法中所公开的。
按照第三方面,本发明提供一种催化剂制品,其包含用本发明第二方面的催化载体涂层涂覆的整块基质。所述基质可为金属流通式基质、陶瓷流通式基质、壁流式过滤器、烧结金属过滤器或部分过滤器。
按照第四方面,优选的催化剂制品包含为挤出基质形式、优选为蜂窝整块形式的本发明第一方面的催化剂组合物。在这种情况中,催化剂组合物优选包含钨酸盐而不是钼酸盐。
将会理解的是无论催化剂组合物作为惰性基质上涂覆的载体涂层存在或作为挤出基质存在,均可以获得本发明的好处,即改进的NOx转化活性和产生更少的N2O。
制备本发明第四方面的挤出催化剂制品的方法例如由WO 2014/027207 A1和WO2011/092521 A1或这里作为背景技术认可的那些文献的任意一个已知。可以添加合适的有机助剂如粘结剂、填料、孔改性剂、挤出润滑剂和增塑剂以促进混合,从而形成均匀的可挤出物。所述有机助剂可以包括纤维素、水溶性树脂如聚环氧乙烷或聚乙二醇,并在煅烧过程中从最终基质中烧掉。
本发明第三或第四方面的催化剂制品可以包含为载体涂层形式的第二催化剂组合物,用于应用含氮还原剂选择性还原NOx和/或用于氧化NH3,其中第二催化剂组合物为:(a)本发明第一方面的催化剂混合物;(b)过渡金属促进的分子筛;(c)在金属氧化物上载带的铂族金属;或(d)在二氧化钛上载带的包含钒氧化物的催化剂。将会理解的是选项(a)已经由本发明的第三方面所定义,和因此可以由从属于本发明第三方面的任何权利要求中删除。
本发明第三或第四方面的催化剂制品可以包含氨滑流催化剂(ASC),其包含用于氧化氨的第一层(c)和包含本发明第一方面催化剂的第二层,其中第一层直接放置于基质上,而第二层覆盖第一层上。这种设置由于可以促进如下反应而有利。在第一层中:2NH3+1.5O2→N2+3H2O(+NO和/或NO2);和在第二层中:NO+NH3+1/4O2→N2+3/2H2O;或NO+NO2+2NH3→2N2+3H2O;或NO2+4/3NH3→7/6N2+2H2O。在第二层的反应中NO和NO2源可以为废气本身和/或第一层中产生NO或NO2的副反应。在第二层的反应中氨源可以为废气本身和/或由废气吸附到第二层组分中的氨。
按照第五方面,提供用于处理废气的废气系统,包含位于氨滑流催化剂(ASC)上游的选择性催化还原(SCR)催化剂,其中SCR和ASC催化剂的至少一个包含本发明第一方面的催化剂。
本发明第五方面的废气系统可以包含氧化催化剂,所述氧化催化剂包含在整块基质上涂覆的在金属氧化物中载带的铂族金属,和放置于SCR催化剂组合物的上游。这会促进废气中存在的氮氧化物以接近4NO:NO2至约NO:3NO2的体积比氧化为二氧化氮。如此操作以比单独的NO或NO2在动力学上更快速地转化NOx(例如参见S.Kasaoka等人的Nippon KagakuKaishi,1978,No.6,pp.874-881)。
本发明的SCR催化剂组合物可以用于处理来自静态来源的NOx排放的废气,如燃气透平或燃煤或燃油电站。在这种情况中,可以将所述催化剂组合物涂覆于所谓的波纹打孔金属片的板型基质上。用于这类用途的催化剂组合物优选包括钼酸盐而不是钨酸盐。但优选的和按照本发明的第六方面,本发明提供机动车辆的贫燃内燃机,其包含本发明第五方面的废气系统。
按照第七方面,本发明提供包含本发明第六方面的发动机的机动车辆。
按照第八方面,本发明提供一种处理废气的方法,其任选地包含约4:1至约1:3体积比的NO与NO2比,该比率例如可以通过合适设计的氧化催化剂被动地促进,所述方法包括如下步骤:使含NOx和NH3的废气物流与本发明第一方面的催化剂或本发明第三或第四方面的催化剂制品接触;和按上文针对第一层和第二层所述的反应,转化至少一部分NOx为N2和/或转化至少一部分NH3为N2、NO和NO2中的至少一种,其中所述第一层为(c),即金属氧化物上载带的铂族金属。
为了可以更全面地理解本发明,通过描述方式提供如下实施例。
实施例
实施例1:制备挤出的蜂窝状基质
通过首先使已用>1wt%铁离子交换的商购的粉末状MFI铝硅酸盐沸石、商购的粉末状H型丝光沸石或粉末状>1wt%铁/MFI铝硅酸盐沸石和粉末状H型丝光沸石两者的混合物与2wt%的V2O5-10 wt%WO3/TiO2以及余量的改变挤出物流变性和增加挤出物机械强度的无机助剂混合,以制备WO 2014/027207 A1的挤出蜂窝状基质催化剂。加入合适的有机助剂以利于混合从而形成均匀的可挤出物。将所述可挤出物挤出,以形成具有流通结构(即在两端均有开口的蜂窝)的1-英寸直径x 70mm长的圆柱状蜂窝体,其蜂窝密度为每平方英寸400个蜂窝和蜂窝壁厚为11/1000英寸(mil)。然后干燥和煅烧如此形成的挤出蜂窝基质,以形成最终产品。
选择沸石、V2O5-WO3/TiO2、无机助剂的合适比例,从而通过煅烧脱除有机助剂后,所述挤出基质具有如下表1所示的wt%组成。
表1
实施例2:挤出的蜂窝状基质老化
使实施例1获得的挤出催化剂蜂窝基质在加速老化步骤中热老化(不加入水),所述热老化在烘箱中在大于600℃下在空气中将它们加热2小时(在这里称作“新鲜的”),或者在650℃下加热100小时(在这里称作“老化的”)进行,以模拟按欧洲排放标准法规在汽车寿命终端时蜂窝基质预期暴露于机动车辆废气中。
实施例3:催化剂性能
将所述新鲜和老化的基质分别暴露于空速约120,000/h的模拟柴油发动机废气中。所述的模拟废气包含约9.3wt%的O2、约7.0wt%的H2O、约300ppm的NOx(仅NO)、约300ppm的NH3,余量为N2。在180、215、250、300和400℃的温度下确定新鲜和老化催化剂基质转化NOx的活性。在表2和表3中给出了以%NOx转化率数据表示的结果(数值越大越好)。
在表3中给出了在500℃下“老化的”催化剂基质样品的N2O选择性。N2O选择性按下式确定:
SN2O=2*(N2O出口-N2O进口)/(NOx进口-NOx出口)*100
表2-新鲜催化剂基质样品的NOx转化率%
表3-老化的催化剂基质样品的NOx转化率%
表4-“老化的”催化剂基质在500℃下的N2O选择性
对比例1 | 实施例1 | 实施例2 | 实施例3 | 对比例2 | |
N<sub>2</sub>O选择性 | 26.8 | - | 13.0 | - | 10.4 |
由表2、3和4所示的数据可以看出,实施例2和3的新鲜NOx转化活性与对比例2类似,而实施例1好于对比例2和类似于对比例1。所有实施例的老化NOx转化活性好于对比例1和好于实施例2(特别是≤400℃时)或类似于对比例2。表4中的N2O选择性数据表明实施例2的N2O选择性类似于对比例2和N2O选择性好于对比例1。
总之,这些数据表明优选顺序为实施例2>实施例1>实施例3。
通过解释和描述方式提供了前述详细描述,但不限制所附权利要求的范围。这里描述的优选实施方案的许多改变对本领域普通技术人员来说是很明显的,并且保留在所附权利要求及其等价物的范围内。
为避免怀疑,已知现有技术的全部内容在这里作为参考引入。
Claims (18)
1.用于应用含氮还原剂转化废气中氮氧化物(NOx)的选择性催化还原催化剂组合物,所述催化剂组合物包含第一组分和第二组分的混合物,其中所述第一组分为H型铝硅酸盐丝光沸石(MOR)与铁促进的铝硅酸盐MFI沸石的混合物;和所述第二组分为在金属氧化物载体上载带的钒氧化物,所述载体为二氧化钛、二氧化硅稳定的二氧化钛或二氧化钛与二氧化硅稳定的二氧化钛的混合物,其中第一组分与第二组分的重量比为10:90至25:75。
2.权利要求1的催化剂组合物,其中H型铝硅酸盐丝光沸石(MOR)与铁促进的铝硅酸盐MFI沸石的重量比为3:1-3:5,优选为1:1-3:5。
3.权利要求1或2的催化剂组合物,其中第一组分与第二组分的重量比为15:85-20:80。
4.权利要求1、2或3的催化剂组合物,包含一种或多种粘结剂组分,其中第一和第二组分的组合重量与一种或多种粘结剂组分的组合重量的重量比为80:20-95:5,优选90:10-85:15。
5.权利要求4的催化剂组合物,其中所述一种或多种粘结剂组分为粘土、氧化铝和/或玻璃纤维。
6.前述权利要求任一项的催化剂组合物,其中第二组分的金属氧化物载体包括钨氧化物。
7.前述权利要求任一项的催化剂组合物,其中第二组分的钒氧化物包括铁钒酸盐。
8.前述权利要求任一项的催化剂组合物,其中以催化剂组合物整体的总重量计,所述混合物包含0.5-5.0wt%按V2O5计算的钒,优选为1.0-3.0wt%。
9.包含前述权利要求任一项催化剂组合物的催化载体涂层,包含一种或多种填料、粘结剂、处理助剂、水和掺杂剂。
10.包含用权利要求9的催化载体涂层涂覆的整块基质的催化剂制品,其中所述基质为金属流通式基质、陶瓷流通式基质、壁流式过滤器、烧结金属过滤器或部分过滤器。
11.为挤出基质形式的权利要求1-9任一项的催化剂制品,优选为蜂窝状整块。
12.权利要求10或11的催化剂制品,包含用于应用含氮还原剂选择性还原NOx和/或氧化NH3的为载体涂层形式的第二催化剂组合物,所述第二催化剂组合物为:(a)权利要求1-9任一项的催化剂混合物;(b)过渡金属促进的分子筛;(c)在金属氧化物上载带的铂族金属;或(d)包含在二氧化钛上载带的钒氧化物的催化剂。
13.权利要求12的催化剂制品,其中所述基质包含氨滑流催化剂(ASC),所述氨滑流催化剂包括用于氧化氨的第一层(c)和包含权利要求1-8任一项的催化剂的第二层,其中第一层直接放置于基质上,和第二层覆盖在第一层上。
14.用于处理废气的废气系统,包含放置于氨滑流催化剂(ASC)上游的选择性催化还原(SCR)催化剂,其中SCR和ASC催化剂中的至少一个包含权利要求1-9任一项的催化剂。
15.权利要求14的废气系统,其包含氧化催化剂,所述氧化催化剂包含在整块基质上涂覆的在金属氧化物上载带的铂族金属,并放置于SCR催化剂组合物的上游。
16.一种机动车辆贫燃内燃机,其包含权利要求14或15的废气系统。
17.包含权利要求16的发动机的机动车辆。
18.一种处理废气的方法,其任选包含约4:1至约1:3体积比的NO与NO2比,所述方法包括如下步骤:
(i)使含NOx和NH3的废气物流与权利要求1-9任一项的催化剂或权利要求11、12或13的催化剂制品接触;和
(ii)转化至少一部分NOx为N2和/或转化至少一部分NH3为N2和NO2中的至少一种。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1320475A (zh) * | 2000-04-22 | 2001-11-07 | dmc2德古萨金属催化剂塞尔德克股份公司 | 还原氮氧化物的方法及催化剂 |
US20100111791A1 (en) * | 2008-11-03 | 2010-05-06 | Basf Catalysts Llc | Bimetallic Catalysts for Selective Ammonia Oxidation |
DE102008055890A1 (de) * | 2008-11-05 | 2010-05-12 | Süd-Chemie AG | Partikelminderung mit kombiniertem SCR- und NH3-Schlupf-Katalysator |
US20100196221A1 (en) * | 2007-05-09 | 2010-08-05 | N.E. Chemcat Corporation | Selective catalytic reduction type catalyst, and exhaust gas purification equipment and purifying process of exhaust gas using the same |
CN102834165A (zh) * | 2010-02-01 | 2012-12-19 | 约翰逊马西有限公司 | NOx吸收催化剂 |
CN103097006A (zh) * | 2010-08-27 | 2013-05-08 | 丹麦科技大学 | 具有铁或铜的丝光沸石型沸石scr催化剂 |
CN104582845A (zh) * | 2012-08-17 | 2015-04-29 | 庄信万丰股份有限公司 | 沸石助催化的V/Ti/W催化剂 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1558598A (en) * | 1918-04-26 | 1925-10-27 | Ellis Foster Co | Oxidation of ammonia |
US4503023A (en) | 1979-08-14 | 1985-03-05 | Union Carbide Corporation | Silicon substituted zeolite compositions and process for preparing same |
US4735927A (en) | 1985-10-22 | 1988-04-05 | Norton Company | Catalyst for the reduction of oxides of nitrogen |
US4663300A (en) * | 1985-12-23 | 1987-05-05 | Uop Inc. | Pollution control catalyst |
US4798813A (en) | 1986-07-04 | 1989-01-17 | Babcock-Hitachi Kabushiki Kaisha | Catalyst for removing nitrogen oxide and process for producing the catalyst |
CA1295598C (en) | 1986-07-29 | 1992-02-11 | Makoto Imanari | Process for removing nitrogen oxides from exhaust gases |
DE3635284A1 (de) | 1986-10-16 | 1988-04-28 | Steuler Industriewerke Gmbh | Katalysator zur entfernung von stickoxiden aus abgasen |
GB9805815D0 (en) | 1998-03-19 | 1998-05-13 | Johnson Matthey Plc | Manufacturing process |
DE19854502A1 (de) | 1998-11-25 | 2000-05-31 | Siemens Ag | Katalysatorkörper und Verfahren zum Abbau von Stickoxiden |
DE102005010221A1 (de) | 2005-03-05 | 2006-09-07 | S&B Industrial Minerals Gmbh | Verfahren zum Herstellen eines katalytisch wirkenden Minerals auf Basis eines Gerüstsilikates |
DE102007003155A1 (de) | 2007-01-22 | 2008-07-24 | Süd-Chemie AG | Katalysatorzusammensetzung zur Reduktion von Stickoxiden |
DE102007063604A1 (de) | 2007-05-24 | 2008-12-04 | Süd-Chemie AG | Metalldotierter Zeolith und Verfahren zu dessen Herstellung |
US7727499B2 (en) * | 2007-09-28 | 2010-06-01 | Basf Catalysts Llc | Ammonia oxidation catalyst for power utilities |
US8524185B2 (en) * | 2008-11-03 | 2013-09-03 | Basf Corporation | Integrated SCR and AMOx catalyst systems |
GB201000019D0 (en) | 2010-01-04 | 2010-02-17 | Johnson Matthey Plc | Coating a monolith substrate with catalyst component |
CN102821845B (zh) | 2010-04-16 | 2016-01-13 | 特莱巴赫工业有限公司 | 用于废气的选择性催化还原的催化剂组合物 |
JP5604235B2 (ja) * | 2010-09-07 | 2014-10-08 | バブコック日立株式会社 | 排ガス脱硝触媒およびその製造方法 |
GB201311615D0 (en) | 2013-06-03 | 2013-08-14 | Johnson Matthey Plc | Method of coating a substrate with a catalyst component |
CN105473230A (zh) * | 2013-08-14 | 2016-04-06 | 迪耐斯公司 | 涂覆的颗粒过滤器 |
DE102014201263A1 (de) * | 2014-01-23 | 2015-07-23 | Johnson Matthey Catalysts (Germany) Gmbh | Katalysator |
GB201405277D0 (en) | 2014-03-25 | 2014-05-07 | Johnson Matthey Plc | Method for coating a filter substrate |
US20170128881A1 (en) * | 2015-11-06 | 2017-05-11 | Paccar Inc | Diesel oxidation catalyst with minimal platinum group metal content |
-
2017
- 2017-03-31 GB GBGB1705289.5A patent/GB201705289D0/en not_active Ceased
-
2018
- 2018-03-23 CN CN201880021313.1A patent/CN110461469B/zh active Active
- 2018-03-23 WO PCT/GB2018/050777 patent/WO2018178643A1/en active Application Filing
- 2018-03-23 EP EP18715101.4A patent/EP3600659B8/en active Active
- 2018-03-23 BR BR112019019508A patent/BR112019019508A2/pt not_active Application Discontinuation
- 2018-03-23 GB GB1804747.2A patent/GB2561084B/en active Active
- 2018-03-26 US US15/935,082 patent/US10500575B2/en active Active
- 2018-03-27 DE DE102018204688.3A patent/DE102018204688A1/de not_active Ceased
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1320475A (zh) * | 2000-04-22 | 2001-11-07 | dmc2德古萨金属催化剂塞尔德克股份公司 | 还原氮氧化物的方法及催化剂 |
US20100196221A1 (en) * | 2007-05-09 | 2010-08-05 | N.E. Chemcat Corporation | Selective catalytic reduction type catalyst, and exhaust gas purification equipment and purifying process of exhaust gas using the same |
US20100111791A1 (en) * | 2008-11-03 | 2010-05-06 | Basf Catalysts Llc | Bimetallic Catalysts for Selective Ammonia Oxidation |
DE102008055890A1 (de) * | 2008-11-05 | 2010-05-12 | Süd-Chemie AG | Partikelminderung mit kombiniertem SCR- und NH3-Schlupf-Katalysator |
CN102834165A (zh) * | 2010-02-01 | 2012-12-19 | 约翰逊马西有限公司 | NOx吸收催化剂 |
CN103097006A (zh) * | 2010-08-27 | 2013-05-08 | 丹麦科技大学 | 具有铁或铜的丝光沸石型沸石scr催化剂 |
CN104582845A (zh) * | 2012-08-17 | 2015-04-29 | 庄信万丰股份有限公司 | 沸石助催化的V/Ti/W催化剂 |
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