EP2451573A2 - Catalyseur de h2-scr contenant du platine supporté par un oxyde mixte promu de magnésium et cérium - Google Patents
Catalyseur de h2-scr contenant du platine supporté par un oxyde mixte promu de magnésium et cériumInfo
- Publication number
- EP2451573A2 EP2451573A2 EP10722966A EP10722966A EP2451573A2 EP 2451573 A2 EP2451573 A2 EP 2451573A2 EP 10722966 A EP10722966 A EP 10722966A EP 10722966 A EP10722966 A EP 10722966A EP 2451573 A2 EP2451573 A2 EP 2451573A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- ceo
- promoted
- mgo
- platinum
- 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.)
- Withdrawn
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 137
- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 86
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 62
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims description 101
- 239000000395 magnesium oxide Substances 0.000 title claims description 60
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 48
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000007790 solid phase Substances 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 182
- 238000006243 chemical reaction Methods 0.000 claims description 101
- 239000000203 mixture Substances 0.000 claims description 75
- 239000007789 gas Substances 0.000 claims description 64
- 239000013078 crystal Substances 0.000 claims description 36
- 229910001868 water Inorganic materials 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 34
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- 230000004913 activation Effects 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 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 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000012696 Pd precursors Substances 0.000 claims description 5
- 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 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 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 claims 2
- 230000000694 effects Effects 0.000 abstract description 28
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 38
- 229910002089 NOx Inorganic materials 0.000 description 29
- 230000003197 catalytic effect Effects 0.000 description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 description 24
- 229910052720 vanadium Inorganic materials 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 239000003546 flue gas Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 241000894007 species Species 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910018879 Pt—Pd Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007792 gaseous phase Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052905 tridymite 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/202—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/202—Alkali metals
- B01D2255/2022—Potassium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/202—Alkali metals
- B01D2255/2027—Sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2047—Magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20769—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
-
- 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
- B01D53/26—Drying gases or vapours
- B01D53/261—Drying gases or vapours by adsorption
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
- B01J35/45—Nanoparticles
Definitions
- Catalyst consisting of Platinum supported on chemically promoted Magnesium Oxide and Cerium Dioxide towards H?-SCR
- This invention refers to a catalyst comprising platinum on a support, a process for the preparation of such a catalyst, and a use of such a catalyst.
- This catalyst can be used in the selective conversion of nitric oxide (NO) or nitric dioxide (NO 2 ) produced in many industrial combustion processes, in the manufacture of nitric acid, etc., to N 2 gas using hydrogen (H 2 ) as a reducing agent (H 2 -SCR). It is known that hydrogen is available in numerous industrial installations. Using the said catalyst, only a very small percentage of the available hydrogen is necessary for the reduction of NO x to N 2 under strongly oxidizing conditions (H 2 -SCR) in the low- temperature range of 100-200 0 C.
- H 2 -SCR strongly oxidizing conditions
- Selective catalytic reduction (SCR) of NO x from an industrial flue gas stream at low- temperatures has many advantages over that at higher temperatures (e.g., T>250°C).
- placement of the catalyst after the electrostatic dust precipitator unit implies that the partially cleaned flue gas from dust requires less soot blowing and catalyst cleaning, thus providing longer catalyst lifetime.
- low- temperature SCR process can reduce both the investment and operating costs since the SCR unit can be installed at the end of the stack gas train, thus minimising the need to run ductwork from a high-temperature region and then return the flue gas to the stack gas train.
- less reheating of the flue gas from the de-SO x to the SCR unit is required [4,5].
- New low-temperature NO x control SCR catalysts are also capable of retrofitting existing large utility boilers and installations (e.g. industrial furnaces) firing natural gas or refinery fuel gas, where better heat economy of the whole flue gas after- treatment process is achieved.
- a low-temperature H 2 -SCR of NO x technology can be considered as breakthrough green and clean industrial NO x control technology compared to the existing NH 3 -SCR technology.
- Supported-palladium catalysts have also been investigated towards H 2 -SCR [57-63] but to a significantly less extent than supported-platinum catalysts.
- low- temperature NO x control has been also studied with H 2 /CO [64-67] and H 2 /CO/CH 4 [68] reducing gas mixtures over supported-palladium catalysts. It appears from these reports that N 2 -selctivity of H 2 -SCR might be lower or higher than that obtained over supported-platinum catalysts at the same temperature in a non-obvious way, while NO conversion appears in general to be lower on supported-palladium compared to supported-platinum catalysts for the same experimental conditions.
- EP 1 475 149 (2008) discloses a catalyst for NO x control comprising platinum in an amount between 0.1 and 2.0 wt% dispersed on a pre-nitrated and pre-sulphated mixed metal oxide support of magnesium and cerium [55, 56].
- the latter supported platinum catalyst provides a high activity (NO conversion larger than 90%) and N 2 -selectivity (up to 82%) at low reaction temperatures (e.g. 140-160 0 C) when hydrogen is used as reducing agent at reaction temperatures between 100 0 C and 200 0 C.
- the object of the present invention is the development of an alternative catalyst for the selective conversion of NO x to N 2 by hydrogen (H 2 ) to that reported [55,56] with significantly better performance in the 110-180 0 C range and in the presence of large concentrations of water (ca. 20 vol%) and carbon dioxide (ca. 10 vol%) in the simulated flue gas stream to be purified.
- catalyst comprising platinum as noble metal, which is dispersed on a mixed metal oxide support of magnesium and cerium, charaterized in that the mixed metal oxide support of magnesium and cerium is chemically promoted by one of the following elements or compound of the following elements: vanadium, sodium, potassium, molybdenum or tungsten.
- the inventive idea is the use of specific "chemical promoters" in combination with magnesia, ceria, and platinum in an appropriate composition (wt%) along with the application of an appropriate activation step to the final catalyst formed in a non- obvious way for achieving its effective H 2 -SCR of NO x performance.
- chemical promoter here implies the addition of a chemical compound in the final catalyst composition that would enhance the chemical function of the catalyst [69].
- chemical function is meant the selective conversion of NO x (NO/NO 2 ) into N 2 gas by the use of hydrogen from a gas mixture containing NO x , oxygen, carbon dioxide, and water, and especially in the low-temperature range of 110-180 0 C.
- the role of "chemical promoter” is to enhance the rate of conversion of NO x into N 2 than any other by-product (e.g. N 2 O, NH 3 ).
- the "chemical promoter" in the mixed metal oxide support of magnesium oxide and cerium dioxide could provide other centers for NO x adsorption, thus changing the concentration and reactivity of the active surface absorbed NO x species formed, which are then reduced by hydrogen into N 2 and H 2 O [71 ,72].
- the "chemical promoter” could interact directly with the platinum, since some platinum is expected to be found on the surface of oxides or compounds of the “chemical promoter”. Thus, different catalytic active components could have been expected to be formed.
- the "chemical promoter” may change the electronic structure of the catalytic surface which in turn could affect the catalysis at hand through alterations in the binding strength of adsorbed species or surface concentrations or energy barriers for hydrogen diffusion on the catalyst surface [71]. Therefore, very high conversion rates of NO x into nitrogen (N 2 -selectivity) by hydrogen in the temperature range of 110 - 180 0 C could be achieved.
- the mean primary crystal size of the mixed metal oxide support phases is between 5 and 10 nm.
- the mean primary crystal size is determined by X-ray diffraction and using the Scherrer relationship [73].
- the support is a mixture of vanadium-promoted magnesium oxide and vanadium-promoted cerium dioxide, whereby vanadium (V) oxide (V 2 O 5 ) in an amount between 0.1 wt% and 12 wt%, preferably between 2 wt% and 8 wt%, most preferred between 3.0 wt% and 5 wt%, is used as chemical promoter.
- vanadium (V) oxide V 2 O 5
- platinum is dispersed in an amount between 0.01 and 2.0 wt% on the promoted mixed metal oxide support (MgO-CeO 2 ).
- palladium (Pd) in an amount between 0.01 and 2.0 wt% as a second noble metal is dispersed on the mixed metal oxide support.
- 0.1 wt% of platinum and 0.05 wt% of palladium are dispersed on the promoted mixed metal oxide support.
- High N 2 -selectivity values could be obtained by using a catalyst comprising of platinum and palladium between 0.01 and 2.0 wt%, wherein the platinum and palladium noble metal are dispersed on a preferably vanadium-promoted MgO and CeO 2 mixed metal oxide.
- the use of primary crystals with a mean crystal size larger than 40 nm is also advantageous.
- the promoted mixed metal oxide support consists of magnesium oxide and cerium dioxide solid phases in the ratio between 50:50 and 70:30 (w/w), respectively, depending on the primary crystal size of MgO and CeO 2 used.
- the present invention refers also to a process for obtaining catalyst comprising platinum dispersed on a mixture of promoted magnesium oxide and promoted cerium dioxide comprising the steps:
- the promoter is one of the following elements or a compound of the following elements: vanadium (V), sodium (Na) 1 potassium (K), molybdenum (Mo) or tungsten (W),
- 35O 0 C range for at least 1 h.
- the present invention refers to a process for obtaining a catalyst comprising platinum and palladium dispersed on a mixture of promoted magnesium oxide and promoted cerium dioxide comprising the steps:
- the promoter is one of the following elements or a compound of the following elements: vanadium (V), sodium (Na), potassium (K), molybdenum (Mo) or tungsten (W) 1
- 35O 0 C range for at least 1 h.
- the activation of the said catalyst compositions is crucial for the catalyst performance (activity, N 2 -selectivity and stability) towards H 2 -SCR, where optimum calcination and reduction conditions (gas compostion, temperature, time on stream) depend on Pt, Pd, and chemical promoter loading (wt%).
- the temperature at which activation of the catalyst as prepared is conducted in a flow of O 2 /He gas mixture (calcination step) followed by a flow of H 2 /He gas mixture (reduction step), and the time on stream allowed for each activation step are crucial parameters that strongly influence the activity (NO conversion) and N 2 -selectivity of the H 2 -SCR process.
- the catalyst should be used for the NO x reduction in gas streams containing SO x , an additional step for the pre-nitration and pre-sulphatation of the catalyst is advantageous.
- the presence of sulphates on the MgO-CeO 2 support of the present invented catalyst does not exhibit any chemical promoting effect.
- the "chemical promoter” is one of the elements of vanadium, sodium, potassium, molybdenum and tungsten.
- a surface compound of magnesium is formed by interaction between NO x (NO and NO 2 ) species present in the gaseous phase under reaction conditions and the oxide of magnesium present.
- a surface compound of cerium is formed by interaction between NO x (NO and NO 2 ) species present in the gaseous phase under reaction conditions and the oxide of cerium present.
- a surface compound of vanadium is formed by interaction between NO x (NO and NO 2 ) species present in the gaseous phase under reaction conditions and the oxide of vanadium present.
- surface compounds of platinum and palladium are formed by interaction between species present in the gaseous phase under reaction conditions (NO, NO 2 , O 2 ) and metallic platinum and palladium present.
- the present invention also refers to the selective reduction of nitric oxide, nitrogen dioxide and/or mixture of nitric oxide and nitrogen dioxide to N 2 gas using hydrogen as reducing agent in the presence of the catalysts described herein.
- the inventive catalyst is used for the reduction of a chemical compound selected from the group consiting of nitrogen oxide, nitrogen dioxide or a mixture of both to nitrogen using hydrogen as reducing agent in the presence or absence of oxygen.
- One embodiment of the invention also refers to a method of reducing a chemical compound selected from the group consisting of NO, NO 2 and/or a mixture of NO and NO 2 to N 2 gas using hydrogen as reducing agent in the presence of oxygen, and also in the presence of other gases, for example H 2 O and CO 2 , by a catalyst comprising Pt in an amount between 0.01 and 2.0 wt% and Pd in an amount between 0.01 and 2.0 wt%, dispersed on a vanadium-promoted MgO and CeO 2 .
- a reactor selected from the group consisting of a fixed-bed and a monolithic-type reactor can be used.
- the present invention provides a variety of advantages.
- the N 2 -selectivity of a catalyst comprising platinum and palladium dispersed on a vanadium-promoted MgO and vanadium- promoted CeO 2 mixed metal oxide was remarkably increased by 10-30 percentage units in the H 2 -SCR of NO at temperatures in the 120-160 0 C low-temperature range compared to platinum dispersed on a mixed metal oxide of MgO and CeO 2 according to prior art.
- Pt/MgO-CeO 2 , PW-MgO-CeO 2 , and Pt-Pd/V-MgO-CeO 2 catalysts were prepared by means of the wet impregnation method as follows:
- 0.5 g of commercial nano-crystalline MgO (Aldrich, product no. 549649, mean primary crystal size 9.0 nm) or MgO with larger mean primary crystal size (Aldrich, product no. 288667, mean primary crystal size 44 nm) were mechanically mixed with 0.5 g of commercial nano-crystalline CeO 2 (Aldrich, product no. 544841 , mean primary crystal size 5 nm) or CeO 2 with larger mean primary crystal size (Aldrich, product no. 211575, mean primary crystal size 41 nm), and the resulting solid (1.0 g) was impregnated with 200 ml of an aqueous solution containing the desired quantity of hexachloroplatinic acid solution (Aldrich, product no.
- the catalyst is activated first in a flow of air or 10 vol% O 2 /He gas mixture in the 500-650 0 C range for 1-2 h, and then reduced in a flow of 10-15 vol% H 2 /He gas mixture in the 200-350 0 C range for at least 1 h.
- the content of metallic platinum varied in the 0.01-2.0 wt% range.
- the catalyst is activated first in a flow of air or 10 vol% O 2 /He gas mixture in the 500-650 0 C range for 1-2 h, and then reduced in a flow of 10-15 vol% H 2 /He gas mixture in the 200- 350 0 C range for at least 1 h.
- the content of metallic platinum varied in the 0.01-2.0 wt% range.
- V-MgO-CeO 2 prepared according to the same procedure as in the case of PW-MgO-CeO 2 solid, was impregnated with 200 ml of an aqueous solution containing the desired quantity of hexachloroplatinic acid (Aldrich, product no. 262587). The excess of water was evaporated with continuous stirring at 60-70 0 C and the residue was dried at 120 0 C for ⁇ 12 h. The dry residue was sieved and heated at 500 0 C in a flow of air or 20%O 2 /He gas mixture for at least 2 h.
- the solid material was again impregnated with 200 ml of an aqueous solution containing the desired quantity of palladium(ll) nitrate solution (Aldrich, product no. 380040).
- the excess of water was evaporated with continuous stirring at 60-70 0 C and the residue was dried at 120 0 C for ⁇ 12 h.
- the dry residue was sieved and heated at 500 0 C in a flow of 20%O 2 /He for at least 2 h in order to remove chlorine and nitrates from the solid surface and convert Pt and Pd into their respective metal oxides, cooled to room temperature and stored for further use.
- the catalyst is activated first in a flow of air or 10 vol% O 2 /He gas mixture in the 500-650 0 C range for 1-2 h, and then reduced in a flow of 10-15 vol% H 2 /He gas mixture in the 200-350 0 C range for at least 1 h.
- the content of metallic platinum (Pt) and palladium (Pd) was varied in the 0.01-2.0 wt% and 0.01-2.0 wt% range, respectively.
- Example 9 the combination of Pt, Pd, V, MgO and CeO 2 , the latter two solids having a primary crystal size larger than 40 nm, with the said chemical composition in a non-obvious way, resulted in remarkable improvements of N 2 - selectivity (10-30 percentage units) in the low-temperature range of 120-180 0 C for the H 2 -SCR process at the said feed gas composition as compared to the Pt/MgO-CeO 2 catalyst chemical composition previously reported by us [55,56].
- a catalyst sample of 0.62 g was placed in a fixed-bed quartz micro-reactor, and it was first activated in a flow of 10%O 2 /He gas mixture (100 NmL/min) at 500 0 C for 1 h, followed by H 2 reduction (12.5%H 2 /He, 100 NmL/min) at 250 0 C for 1 h before a reaction feed gas mixture of 325 ppm NO, 0.8 vol% H 2 , 2.5 vol% O 2 , 10 vol% CO 2 , 20 vol% H 2 O and 66.67 vol% He at a GHSV of 40,000 h 1 (Lgas/Lca t .b e d /h) was used.
- Figure 1 clearly demonstrates that the use of 3.5 wt% V 2 O 5 -MgO-CeO 2 (magnesium oxide and cerium dioxide chemically promoted with vanadia) as a carrier to deposit 0.2 wt% Pt resulted in a remarkable improvement of both the NO conversion and N 2 - selectivity, especially at the lowest temperatures (130-150 0 C) investigated, compared to the case of use of MgO-CeO 2 carrier alone.
- the NO conversion (X NO , %) was increased from 20.5% to 72.5% (an increase by a factor of ⁇ 3.5), whereas at 18O 0 C from 60.0 to 96.0% (an increase by a factor of 1.6).
- the high NO conversions (73.5 - 97.0%) obtained in the 130-180 0 C range under the given experimental conditions is noted which are representative of many industrial flue gas compositions and space velocities encountered.
- N 2 -selectivity of H 2 -SCR reaction the effect of vanadia was to siginificantly enhance N 2 -selectivities (S N2 , %) to values of 90% in the 160-180 0 C range, and 72-87% in the 130-150 0 C range.
- Example 2 The experimental conditions were the same as those presented in Example 2, except that now a feed flue gas composition of 175 ppm NO, 0.8 vol% H 2 , 2.5 vol% O 2 , 10 vol% CO 2 , 20 vol% H 2 O and 66.69 vol% He was used.
- the beneficial effect of vanadia promoter on the X NO (%) and S N2 (%) is now larger compared to the previous Example 2 (use of 325 ppm NO in the feed stream).
- Very high NO conversions (85.0 - 98.7%) were seen in the 130-180 0 C range, and N 2 - selectivities of 80-90% in the same temperature range were obtained.
- the NO conversion (X N0 , %) was increased from 11.0 to 85.0% (increase by a factor of 7.7), whereas the N 2 -selectivity (S N2 , %) from 14.0 to 80.0% (increase by a factor of 5.7).
- vanadia loadings in the 0.1 - 12.0 wt% V 2 O 5 range were investigated over various MgO-CeO 2 support compositions (0-100 wt% MgO) and using 0.1-2.0 wt% Pt loadings.
- vanadia loading by increasing the vanadia loading from 3.5 to 5 wt% V 2 O 5 , an increase of NO conversion by 10-20 percentage units was seen at the lowest temperatures of 120-130 0 C for the 0.2 wt% Pt-supported catalyst with the MgO-CeO 2 support composition and feed gas compositions mentioned previously (Examples 2 and 3). Improvements up to 10-15 percentage units were seen in the N 2 -selectivity for the given catalyst composition.
- the optimum vanadia loading for catalyst performance (X NO (%) and S N2 (%)) was found to depend on the BET area of support composition, the primary crystal size of MgO and CeO 2 support, and the Pt loading (wt%) used.
- a pre-sulphated MgO-CeO 2 support used to deposit 0.2 wt% Pt was also not able to prevent catalytic activity loss. However, in this case the activity loss was less than that observed with the 0.2 wt% Pt/MgO-CeO 2 (Fig. 3) catalyst and larger than that observed with the 0.2 wt% Pt/3.5wt%V 2 O 5 -MgO-CeO 2 catalyst (Fig. 3).
- a very important parameter that determines the catalytic performance of the PW 2 O 5 - MgO-CeO 2 solid towards its effective low-temperature H 2 -SCR performance (NO conversion and N 2 -selectivity) is the way the as prepared catalyst is activated before reaction (contact with the flue gas for NO x purification).
- Catalyst activation includes calcination (use of O 2 /He or air gas flow) and reduction (use of H 2 /He gas mixture or pure hydrogen flow) steps at a given temperature and for a given time on stream. This parameter is illustrated by experimental data obtained and presented in Table 1 for the 0.2 wt% Pt/3.5wt%V 2 O 5 -MgO-CeO 2 catalyst, the same used in Examples 2-4.
- the NO-conversion and N 2 -selectivity versus reaction temperature (T, 0 C) profile is strongly influenced by the activation steps performed on the given catalytic system before H 2 -SCR reaction.
- catalyst activation by H 2 reduction only performed at 300 0 C for 14 h results in high NO conversion values (88.5-97.0%) in the whole 125-18O 0 C range, but with N 2 -selectivity values in the 66-80% range.
- both the NO conversion and N 2 -selectivity values obtained become significantly lower in the whole temperature range of 125-18O 0 C, when compared to the case of 500 0 C calcination.
- N 2 -selectivities larger in the 160-180 0 C range but lower in the 125-15O 0 C range are obtained.
- lower NO conversion values are obtained in the whole 125-18O 0 C range.
- Pt loading (wt%) is a very important parameter that determines not only the catalytic performance (NO conversion and N 2 -selectivity) of Pt/MgO-CeO 2 solid towards H 2 -SCR [53-56] but also the economics of the associated technology for industrial applications.
- Figure 4 illustrates that using only 0.1 wt% R supported on the MgO-CeO 2 carrier, the latter promoted with 3.5 wt% V 2 O 5 , results in an excellent H 2 -SCR performance in the 140-18O 0 C range, where both NO conversion and N 2 -selectivity exchibit values larger than 90%.
- Examples 2-7 where smaller primary crystals for the MgO-CeO 2 support were used.
- a catalyst sample of 0.3-g was placed in a fixed-bed quartz micro-reactor, and it was first calcined in 20%O 2 /He gas flow (50 NmL/min) at 600 0 C for 2 h, followed by H 2 reduction (1 bar H 2 , 50 NmLJmin) before a reaction feed gas mixture consisting of 500 ppm NO, 0.8 vol% H 2 , 5 vol% O 2 and 94.15 vol% He or 500 ppm NO, 0.8 vol% H 2 , 5 vol% O 2 , 10 vol% CO 2 , and 84.15 vol% He at a GHSV of 40,000 h 1 was used.
- Figure 6 clearly demonstrates that the use of 3.5 wt% V 2 O 5 -MgO-CeO 2 (magnesium oxide and cerium dioxide promoted with vanadia) as carrier to deposit 0.1 wt% Pt resulted in a remarkable improvement of NO conversion when 10 vol% CO 2 was also present in the reaction feed stream, compared to the case of use of MgO-CeO 2 carrier alone.
- the NO conversion (%) was increased from 15% to 57% (an increase by a factor of 3.8), whereas at 140 and 16O 0 C an increase by a factor of 2.3 and 1.7, respectively, was obtained.
- Similar results to those depicted in Fig. 6 were obtained when 20 vol% H 2 O was also present in the 500 ppm NO, 0.8 vol% H 2 , 5 vol% O 2 , 10 vol% CO 2 , He reaction feed gas composition.
- Vanadium (V) loadings in the 0.1-12 wt% range were investigated, where it was found that the optimum loading for the 0.1 wt% Pt/x wt% V-MgO-CeO 2 catalytic system strongly depends not only on the reaction feed gas composition in NO, O 2 and H 2 gases but also on the primary crystal size of MgO and CeO 2 support used, as it is illustrated in the following Example 9.
- Figure 6 presents also the effect of 2 wt% vanadium (V) loading on the N 2 -selectivity (S N2 , %) of the H 2 -SCR of NO under the same reaction conditions described for the NO-conversion versus T profile (500 ppm NO, 0.8 vol% H 2 , 5 vol% O 2 , 10 vol% CO 2 , and 84.15 vol% He). It is seen that in the lowest reaction temperature range of 110- 13O 0 C, an increase in S N2 (%) between 6 and 15 percentage units was observed, whereas at higher temperatures S N2 (%) was practically the same. Siginificantly larger N 2 -selectivity values were obtained at another V loading (wt%) and feed gas composition, as illustrated in the following Example 9, and also after using smaller primary crystals for MgO and CeO 2 support phases (see Examples 2 and 3).
- V vanadium
- Pt loadings in the 0.01 - 2.0 wt% range were investigated, where an optimum Pt loading in the 0.1-0.3 wt% range was found, depending on vanadia loading, feed gas composition, and primary crystal size of MgO-CeO 2 support.
- Pt and Pd loadings lower than 0.05 wt% or larger than 2.0 wt% did not result in better catalytic performance (S N2 , %) as that presented in Fig. 7.
- An optimum Pt and Pd loading was found to depend on the loading (wt%) of V, the mean primary crystal size of MgO and CeO 2 , and also on their wheight ratio (w/w) used to deposit V, Pt and Pd.
- Example 10 This example illustrates the effect of using nano-crystalline MgO and CeO 2 support phases (mean primary crystal size lower than 10 nm) to deposit the combination of Pt and V catalytic and chemical promoter components, respectively, on the low- temperature H 2 -SCR of NO in terms of NO conversion, X N o(%) and N 2 -selectivity, S N2 (%) at a feed containing larger NO concentrations (e.g. 500 ppm) as compared to the cases presented in Examples 2 and 3.
- a catalyst sample of 0.3 g and a feed gas composition of 500 ppm NO, 0.7 vol% H 2 , 3 vol% O 2 and 96.25 vol% He at a GHSV of 40,000 h "1 were used.
- Figure 1 illustrates the strong chemical promoting effect of vanadia when deposited on MgO and CeO 2 support solid phases (70 wt% MgO-30 wt% CeO 2 ) on the NO conversion, X N o(%), and N 2 -selectivity, S N2 (%) of H 2 -SCR in the low-temperature range of 130-18O 0 C for the 0.2 wt%Pt/3.5wt% V 2 O 5 -MgO-CeO 2 catalyst.
- Figure 3 illustrates the strong chemical and likely structural promoting effect of vanadia when deposited on MgO and CeO 2 support solid phases (70 wt% MgO-30 wt% CeO 2 ) on the stability with time on stream (up to 70 h) of NO conversion, X NO (%), and N 2 - selectivity, S N2 (%) of H 2 -SCR at 16O 0 C for the 0.2 wt%Pt/3.5wt% V 2 O 5 -MgO-CeO 2 catalyst.
- Figure 4 illustrates the catalytic performance in terms of NO conversion, X NO (%), and N 2 -selectivity, S N2 (%) of H 2 -SCR in the low-temperature range of 120-180 0 C over a low- loading 0.1 wt%Pt supported on vanadia-promoted support (3.5wt% V 2 O 5 -MgO-CeO 2 ).
- Figure 5 illustrates the effect of increasing the vanadia loading from 3.5 to 5.0 wt% on the catalytic activity in terms of NO conversion, X NO (%) of H 2 -SCR in the low- temperature range of 120-180 0 C for the 0.2 wt%Pt supported on vanadia- promoted support (3.5 or 5.0 wt% V 2 O 5 -MgO-CeO 2 ).
- Figure 6 illustrates the effect of 2 wt% vanadium deposited on MgO and CeO 2 support solid phases (50 wt% MgO-50 wt% CeO 2 ) on the NO conversion, X N o(%) and N 2 - selectivity, S N2 (%) of H 2 -SCR in the low-temperature range of 110-180 0 C for the 0.1 wt%Pt/2 wt% V-MgO-CeO 2 catalyst.
- X N o(%) versus reaction temperature, T( 0 C) behaviour over the 0.1 wt% Pt/MgO-CeO 2 (absence of 2 wt% V) is also presented.
- the mean primary crystal size of MgO and CeO 2 support phases used was 44 and 41 nm, respectively.
- Figure 7 compares the N 2 -selectivity, S N2 (%) of H 2 -SCR obtained in the low- temperature range of 120-18O 0 C over 0.1 wt% Pt supported on MgO-CeO 2 ( ⁇ ) or 8 wt% V-MgO-CeO 2 (•), and 0.1 wt% Pt - 0.05 wt% Pd supported on 8 wt% V-MgO-
- Figure 8 illustrates the effect of 8 wt% vanadium deposited on MgO and CeO 2 support solid phases (50 wt% MgO-50 wt% CeO 2 ) on the NO conversion, X N o(%) and N 2 - selectivity, S N2 (%) of H 2 -SCR in the low-temperature range of 120-180 0 C over 0.1 wt% Pt/8 wt% V-MgO-CeO 2 catalyst.
- Figure 9 illustrates the effect of catalyst (0.2wt%Pt/3.5wt%V 2 O 5 -MgO-CeO 2 ) activation conditions on its performance in terms of NO conversion (X N0 , %), N 2 -selectivity (S N2 , %), and H 2 conversion (X H2 , %).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
Cette invention porte sur un nouveau catalyseur d'activité et sélectivité excellentes destiné à la réduction d'oxydes nitriques (NO/NO2) en azote gazeux (N2), de l'hydrogène (H2) étant utilisé comme agent réducteur dans des conditions fortement oxydantes (par exemple 2 à 10 % en volume d'O2) (RCS par H2) dans la plage de 100 à 400°C, mais en particulier dans la plage de basses températures de 110 à 180°C. Le catalyseur de l'invention est constitué de nanoparticules de platine et de palladium ayant une morphologie et une structure de surface appropriées qui sont en contact avec des phases solides d'un milieu de MgO et CeO2 mélangés activés par exemple par de l'oxyde de vanadium (par exemple V2O5).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10722966A EP2451573A2 (fr) | 2009-06-16 | 2010-06-10 | Catalyseur de h2-scr contenant du platine supporté par un oxyde mixte promu de magnésium et cérium |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09007863A EP2269729A1 (fr) | 2009-06-16 | 2009-06-16 | Catalyseur pour H2-SCR contenant du platine supporté par un oxyde mixte promu de magnésium et cérium |
PCT/EP2010/003494 WO2010145777A2 (fr) | 2009-06-16 | 2010-06-10 | Catalyseur constitué de platine supporté sur de l'oxyde de magnésium et du dioxyde de cérium chimiquement activés destiné à la rcs par h2 |
EP10722966A EP2451573A2 (fr) | 2009-06-16 | 2010-06-10 | Catalyseur de h2-scr contenant du platine supporté par un oxyde mixte promu de magnésium et cérium |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2451573A2 true EP2451573A2 (fr) | 2012-05-16 |
Family
ID=41210477
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09007863A Withdrawn EP2269729A1 (fr) | 2009-06-16 | 2009-06-16 | Catalyseur pour H2-SCR contenant du platine supporté par un oxyde mixte promu de magnésium et cérium |
EP10722966A Withdrawn EP2451573A2 (fr) | 2009-06-16 | 2010-06-10 | Catalyseur de h2-scr contenant du platine supporté par un oxyde mixte promu de magnésium et cérium |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09007863A Withdrawn EP2269729A1 (fr) | 2009-06-16 | 2009-06-16 | Catalyseur pour H2-SCR contenant du platine supporté par un oxyde mixte promu de magnésium et cérium |
Country Status (2)
Country | Link |
---|---|
EP (2) | EP2269729A1 (fr) |
WO (1) | WO2010145777A2 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4252891A3 (fr) | 2016-10-18 | 2023-12-20 | BASF Corporation | Réduction des nox à basse température à l'aide de h2-scr pour véhicules diesel |
CN110801849B (zh) * | 2019-10-10 | 2022-07-15 | 北京华电光大环境股份有限公司 | 平板式宽温抗硫抗碱金属scr脱硝催化剂及其制备方法 |
CN110801848B (zh) * | 2019-10-10 | 2022-07-15 | 北京华电光大环境股份有限公司 | 平板式宽温抗硫scr脱硝催化剂及其制备方法 |
CN113786828B (zh) * | 2021-09-16 | 2023-12-29 | 清华大学 | 一种用于NOx和CVOCs的协同脱除的催化剂及其制备方法和用途 |
EP4282513A1 (fr) * | 2022-05-23 | 2023-11-29 | Basf Corporation | Catalyseurs améliorés pour la réduction sélective de nox à l'aide d'hydrogène |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3965711B2 (ja) * | 1996-10-25 | 2007-08-29 | 株式会社日立製作所 | 窒素酸化物の浄化触媒及び浄化方法 |
EP1358933A4 (fr) * | 2001-02-02 | 2005-08-10 | Hitachi Ltd | Catalyseur de traitement des gaz d' mission et moteur combustion interne pourvu d'un tel catalyseur |
US7138358B2 (en) * | 2001-11-13 | 2006-11-21 | Sud-Chemie Inc. | Catalyzed diesel particulate matter filter with improved thermal stability |
ES2192985B1 (es) | 2002-02-15 | 2005-02-16 | Consejo Sup. Investig. Cientificas | Nuevo catalizador para la reduccion de no a n2 con hidrogeno en condiciones de nox oxidantes. |
-
2009
- 2009-06-16 EP EP09007863A patent/EP2269729A1/fr not_active Withdrawn
-
2010
- 2010-06-10 EP EP10722966A patent/EP2451573A2/fr not_active Withdrawn
- 2010-06-10 WO PCT/EP2010/003494 patent/WO2010145777A2/fr active Application Filing
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2010145777A2 * |
Also Published As
Publication number | Publication date |
---|---|
WO2010145777A2 (fr) | 2010-12-23 |
WO2010145777A3 (fr) | 2011-05-19 |
EP2269729A1 (fr) | 2011-01-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Gholami et al. | Recent advances in selective catalytic reduction of NOx by carbon monoxide for flue gas cleaning process: a review | |
US8193114B2 (en) | Catalysts for dual oxidation of ammonia and carbon monoxide with low to no NOx formation | |
US5741468A (en) | Exhaust gas cleaner and method for cleaning exhaust gas | |
Pérez-Ramı́rez et al. | Ex-framework FeZSM-5 for control of N2O in tail-gases | |
EP1475149B1 (fr) | CATALYSEUR CONTENANT DU PLATINE SUR UN SUPPORT A BASE D'OXYDE DE MAGNESIUM DE D'OXYDE DE CERIUM POUR LA REDUCTION DE NO A N2 AVEC DE L'HYDROGENE DANS DES CONDITIONS D'OXYDATION NOx | |
US5714130A (en) | Exhaust gas cleaner and method for cleaning exhaust gas | |
US8673809B2 (en) | Low level noble metal-supporting three-way catalyst | |
US4585632A (en) | Process for the removal of nitrogen oxides from exhaust gases | |
US8114369B2 (en) | Catalyst containing platinum and palladium for the selective reduction of NOx with hydrogen (H2-SCR) | |
Ai et al. | Effect of surface and bulk palladium doping on the catalytic activity of La 2 Sn 2 O 7 pyrochlore oxides for diesel soot oxidation | |
US20100284875A1 (en) | Treatment of power utilities exhaust | |
EP2451573A2 (fr) | Catalyseur de h2-scr contenant du platine supporté par un oxyde mixte promu de magnésium et cérium | |
US20210101111A1 (en) | Process for the removal of sulphur oxides and nitrogen oxides contained in off-gas from an industrial plant | |
JP2021517508A (ja) | 排出処理システムにおいて使用するための触媒物品 | |
Qi et al. | Low-temperature SCR of NO with NH 3 over noble metal promoted Fe-ZSM-5 catalysts | |
CN103028400A (zh) | 选择氧化催化剂及其制备方法 | |
WO1992004967A1 (fr) | Reduction de la teneur en oxyde azote et en monoxyde de carbone dans des gaz effluents | |
EP2177257A1 (fr) | Catalyseur contenant de la platine sur un support comportant un oxyde de magnésium de nano-cristaL et dioxyde de cérium vers H2-SRC | |
WO2018158184A1 (fr) | Processus d'élimination d'oxydes de soufre et d'oxydes d'azote contenus dans un effluent gazeux d'une installation industrielle | |
KR101799022B1 (ko) | 암모니아 환원제에 의한 배가스 내 일산화질소 및 아산화질소의 동시 저감 방법 및 일산화질소와 아산화질소를 동시 저감하기 위한 촉매 반응기 | |
WO2003053545A1 (fr) | Systeme de filtration et de traitement des gaz d'echappement pour piles a combustible a carbonate fondu | |
US6217838B1 (en) | Process for reducing emissions of oxides of nitrogen in a medium which is super-stoichiometric in oxidizing agents | |
JP5285459B2 (ja) | 排ガス浄化用触媒および排ガス浄化方法 | |
강태훈 | Physical mixing of V2O5-WO3/TiO2 with inorganic compounds for selective catalytic reduction of nitrogen oxides with ammonia | |
Guo et al. | Against catalyst deactivation during toluene oxidation on CuCeOx in flue gas: High oxidation efficiency and rapid oxidation pathway |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20120116 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20151215 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Effective date: 20170403 |