AU2012327482A1 - Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides - Google Patents
Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides Download PDFInfo
- Publication number
- AU2012327482A1 AU2012327482A1 AU2012327482A AU2012327482A AU2012327482A1 AU 2012327482 A1 AU2012327482 A1 AU 2012327482A1 AU 2012327482 A AU2012327482 A AU 2012327482A AU 2012327482 A AU2012327482 A AU 2012327482A AU 2012327482 A1 AU2012327482 A1 AU 2012327482A1
- Authority
- AU
- Australia
- Prior art keywords
- zeolite
- catalyst composition
- catalyst
- beta
- zro
- 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.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000010531 catalytic reduction reaction Methods 0.000 title description 2
- 239000010457 zeolite Substances 0.000 claims abstract description 80
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 74
- 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 69
- 239000004071 soot Substances 0.000 claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 11
- 239000000306 component Substances 0.000 claims description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229960005419 nitrogen Drugs 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 4
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000006069 physical mixture Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 22
- 239000002131 composite material Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 21
- 239000000523 sample Substances 0.000 description 21
- 239000010949 copper Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 235000019391 nitrogen oxide Nutrition 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000013074 reference sample Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910003465 moissanite Inorganic materials 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000001256 tonic effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910020203 CeO Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000286904 Leptothecata Species 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007775 late Effects 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
- B01D2255/2073—Manganese
-
- 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
- B01D2255/20738—Iron
-
- 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
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
- B01D2255/407—Zr-Ce mixed oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
- B01D2255/502—Beta zeolites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Catalyst composition for selective reduction of nitrogen oxides and soot oxidation comprising a physical mixture of one or more acidic zeolite or zeotype components with one ore more redox active metal compounds and a method for selective reduction of nitrogen oxides and soot oxidation by use of the catalyst composition.
Description
WO 2013/060487 PCT/EP2012/058003 1 Title: Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides 5 The present invention relates to catalyst composition for use in selective reduction of nitrogen oxides in off-gases by reaction with ammonia or a precursor thereof. Catalysts for NH3-SCR, i.e. selective reduction of nitrogen 10 oxides (NOx) by use of ammonia as reductant are well known in the art. Those catalysts include zeolitic material, op tionally promoted with copper or iron The problem to be solved by this invention is to provide a 15 catalyst composition and method for the reduction of nitro gen oxides with a DeNOx activity at reaction temperatures between 150 and 5500C. Off-gases from lean combustion engines contain in addition 20 to NOx, hydrocarbons, CO and soot particles which can be reduced or removed by catalytic oxidation. Consequently, the catalyst composition and method of this invention shall further include soot and hydrocarbon oxidation activity si multaneously with the DeNOx activity. 25 Our recent studies revealed several examples of a pro nounced synergistic effect in composite catalysts prepared by mechanical mixing of acidic zeolite or zeotype powder and redox active metal compounds. 30 We have found that catalyst composition comprising a one or more acidic zeolite or zeotype components physically ad- WO 2013/060487 PCT/EP2012/058003 2 mixed with one ore more redox active metal compounds shown an improved activity in the selective reduction of nitrogen oxides and oxidation of hydrocarbons, CO and soot contained in off-gas. 5 The term "redox active metal compounds" as used herein re lates to metal compounds which reversibly can be oxidized and reduced in terms of changes in oxidation number, or oxidation state, of the metal atom or compound. 10 Pursuant to the above findings, the present invention pro vides a catalyst composition for selective reduction of ni trogen oxides and soot oxidation comprising one or more acidic zeolite or zeotype components selected from the 15 group consisting of BEA, MFI, FAU, FER, CHA, MOR or mix tures thereof physically admixed with one ore more redox active metal compounds selected from the group consisting of Cu/A1 2 0 3 , Mn/A1 2 0 3 , CeO 2 -ZrO 2 , Ce-Mn/A1 2 0 3 and mixtures thereof. 20 Catalyst compositions prepared by mechanical mixing of the above mentioned zeolites or zeotype materials and redox metal components mixing according to the invention exhibit a pronounced synergistic effect. DeNOx activity of such 25 composite catalysts significantly exceeds activity of their individual components. The acidic zeolite or zeotype component can be used in pro tonic form or promoted with Fe. 30 Preferably, the weight ratio between the zeolite components and the redox components is between 1:1 to 1:50 WO 2013/060487 PCT/EP2012/058003 3 In an embodiment of the invention, the redox components are dispersed on a support selected from the group consisting of of A1 2 0 3 , TiO 2 , SiO 2 , CeO 2 , ZrO 2 or mixtures thereof. 5 It is generally preferred that the mean molar ratio Si/Al of the zeolite components according to the invention is from 5 to 100. 10 The above described catalyst composition according to the invention can be utilised as coating material or as coat on structured bodies of metallic, ceramic, metal oxide, SiC or silica materials or fibres. 15 Thus, the invention provides furthermore a monolithic structured body being coated with a catalyst composition according to anyone of the above disclosed embodiments of the invention. 20 The monolithic structured body is preferably made from me tallic, ceramic, metal oxide, SiC or silica fiber materi als. The monolithic structured body may be in form of a particle 25 filter, e.g. a honeycomb structured filter or a wall flow filter. In further an embodiment, the catalyst composition is coated on the body in of two or several separate catalyst 30 layers in series or as two or several catalyst layers in parallel and wherein the layers have different compositions or layer thicknesses.
WO 2013/060487 PCT/EP2012/058003 4 Specific advantages resulting from the invention are 1) Addition of Ce0 2 -ZrO 2 , Cu/A1 2 0 3 , Mn/A1 2 0 3 or Ce 5 Mn/A1 2 0 3 to acidic zeolite or zeotype in protonic form or promoted with iron markedly enhances DeNOx activity at Treact < 2500C without increasing amount of zeolite component. In this case, overall volume of the catalyst is increased by the volume of redox component added. 10 2) Alternatively, amount of expensive zeolite/zeotype com ponent in the composite catalyst can be significantly re duced by its replacement with equivalent volume of redox component. In this case overall volume of the catalyst re 15 mains constant, but the amount of zeolite component can be decreased by 2-5 times, without notable sacrificing DeNOx performance. When Ce-Mn/A1 2 0 3 component is used for the catalyst preparation, notable improvement of NOx conversion at Treact < 2500C is observed despite decreased amount of 20 zeolite component. 3) In addition to favourable DeNOx activity, [CeO 2 -ZrO 2 + zeolites/zeotypes] or [Ce-Mn/A1 2 0 3 + zeolites/zeotypes] compositions demonstrate significant soot oxidation activ 25 ity, which makes them promising candidates for development of integrated DeNOx-DeSoot catalytic systems. 4) In addition to favorable DeNOx activity, [Ce0 2 -ZrO 2 + zeolites/zeotypes] or [Ce-Mn/A1 2 0 3 + zeolites/zeotypes] 30 compositions demonstrate significantly lower ammonium slip at high temperature due to selective oxidation of excess ammonia.
WO 2013/060487 PCT/EP2012/058003 5 The invention provides additionally a method for the selec tive reduction of nitrogen oxides and oxidation of soot contained in an off-gas comprising the step of contacting 5 the off-gas in presence of ammonia with a catalyst composi tion comprising one or more acidic zeolite or zeotype com ponents selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or mixtures thereof physically admixed with one ore more redox active metal compounds selected 10 from the group consisting of Cu/A1 2 0 3 , Mn/A1 2 0 3 , CeO 2 -ZrO 2 , Ce-Mn/A1 2 0 3 and mixtures thereof. The acidic zeolite or zeotype component can be used in pro tonic form or promoted with Fe 15 In an embodiment of the inventive method, the one or more redox active metal compounds are dispersed on a support se lected from the group consisting of A1 2 0 3 , TiO 2 , SiO 2 , ZrO 2 or mixtures thereof. 20 In still an embodiment of the inventive method, the cata lyst composition is contacted with the off-gas at a tem perature below 2500C. 25 In a further embodiment of the inventive method excess of ammonia is selectively oxidized to nitrogen by contact with the catalyst composition.
WO 2013/060487 PCT/EP2012/058003 6 Examples Example 1 5 Synergistic effect in NH 3 -DeNOx over CeO2-ZrO2 + H-Beta zeolite catalyst compositions. [CeO 2 -ZrO 2 + H-Beta zeolite] composite catalyst was pre pared by thorough mixing 74wt%CeO 2 -26wt%ZrO 2 powder with H 10 Beta powder at a weight ratio of 10. This weight ratio re sults in volume ratio of components CeO 2 -ZrO 2 /H-Beta = 3/1 due to difference in densities of these materials. The pow ders were thoroughly grinded in agate mortar for 10-15 min, followed by pelletization. The pellets were crushed and 15 sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized 74wt%CeO 2 -26wt%ZrO 2 , H-Beta, and Fe Beta zeolite were used as reference samples. The catalysts were tested in the NH 3 -DeNOx in the tempera 20 ture range of 150-550 0C. The test was performed under fol lowing conditions: decreasing reaction temperature with a rate of 2 0 C/min, feed gas composition: 500 ppm NO, 540 ppm NH3, 10 vol % 02, 6 vol% H 2 0, balanced with N 2 to obtain a total flow of 300 mL/min. 25 Catalyst loading and resulted GHSV: 0.197g with 74wt%CeO 2 -ZrO 2 + 0.02g H-Beta zeolite, catalyst volume 0.134 ml, GHSV = 135 000 h-' 30 Under these conditions CeO 2 -ZrO 2 + H-Beta zeolite composite catalyst showed DeNOx activity, which substantially WO 2013/060487 PCT/EP2012/058003 7 exceeded activities of individual 74wt%CeO 2 -ZrO 2 (0.131g Ce0 2 -ZrO2, catalyst volume 0.067 ml, GHSV = 270,000 h1) and H-Beta zeolite (0.04g, catalyst volume 0.067 ml, GHSV = 270 000 h-1), indicating pronounced synergistic effect be 5 tween components of composite catalyst as shown in Fig. 1. NOx conversion over composite catalyst is similar to NOx conversion over commercial Fe-Beta zeolite (Fe-Beta) at 230-550'C, and exceeds NOx conversion over Fe-Beta zeolite 10 at 150-2000C. Example 2 Enhanced DeNOx performance of [Ce0 2 -ZrO 2 + Fe-Beta] compos 15 ite catalyst at Treact < 2500C Two samples of [Ce0 2 -ZrO 2 + Fe-Beta zeolite] composite catalyst were prepared by thorough grinding of 74wt%CeO 2 26wt%ZrO 2 and Fe-Beta zeolite powders. 20 A first sample was prepared by mixing 74wt%CeO 2 -26wt%ZrO 2 and Fe-Beta zeolite powders at a weight ratio of 3.3. This weight ratio results in a volume ratio of 74wt%CeO 2 26wt%ZrO 2 /Fe-Beta components in composite catalyst = 1/1. 25 A second sample was prepared by mixing 74wt%CeO 2 -26wt%ZrO 2 and Fe-Beta powders at a weight ratio of 10. For the second sample volume ratio of 74wt%CeO 2 -26wt%ZrO 2 /Fe-Beta zeolite equals 3/1. 30 After grinding in agate mortar for 10-15 min, the resulted mixtures were pelletized. The pellets were crushed and WO 2013/060487 PCT/EP2012/058003 8 sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized Fe-Beta zeolite was used as reference. Activities of the prepared samples were tested using the 5 following catalyst loading which kept constant amount of Fe-Beta zeolite component in the reactor: The first sample with 1/1 volume component ratio: [0.065g 74%CeO 2 -ZrO 2 + 0.02g Fe-Beta zeolite] 10 The second sample with 3/1 volume component ratio: [0.197g 74%CeO 2 -ZrO 2 + 0.02g Fe-Beta zeolite]. Reference sample: 0.02 g Fe-Beta zeolite. 15 The catalysts were tested in NH3-DeNOx within the tempera ture range of 150-550 0C. The test was performed under fol lowing conditions: decreasing reaction temperature with a rate of 2 0 C/min, feed gas composition: 500 ppm NO, 540 ppm 20 NH3, 10 vol % 02, 6 vol% H 2 0, balanced with N 2 to obtain a total flow of 300 mL/min. Catalyst loading and resulted GHSV: [0.197g 74%CeO 2 -ZrO2 + 0.02g Fe-Beta zeolite], catalyst 25 vol. = 0.134 ml, GHSV = 135 000 h-'; [0.065g 74%CeO 2 -ZrO2 + 0.02g Fe-Beta zeolite], catalyst vol. = 0.067 ml, GHSV = 270 000 h'; 0.02 Fe-Beta zeolite, catalyst vol. = 0.034 ml, GHSV = 540 000 h-'. 30 Under these test conditions [CeO 2 -ZrO 2 + Fe-Beta zeolite] composite catalysts showed enhanced DeNOx activity within WO 2013/060487 PCT/EP2012/058003 9 low-temperature range (150-300'C), which significantly ex ceeded activity of individual Fe-Beta zeolite, as shown in Fig. 2. It is important to note that the activity of [CeO 2 ZrO 2 + Fe-Beta zeolite] is improved when the amount of 5 CeO 2 -ZrO 2 component was increased. Example3 Catalyst with reduced amount of zeolite component. 10 Three samples of [CeO 2 -ZrO 2 + Fe-Beta zeolite] composite catalyst were prepared by thorough grinding of 74wt%CeO 2 26wt%ZrO 2 powder with Fe-Beta zeolite powder: 15 A first sample was prepared by mixing 74wt%CeO 2 -26wt%ZrO 2 and Fe-Beta powders at a weight ratio of 3.3. In this case volume ratio of 74wt% CeO 2 - 26wt% ZrO 2 /Fe-Beta zeolite equals 1/1. 20 A second sample was prepared by mixing 74wt%CeO 2 -26wt%ZrO 2 and Fe-Beta zeolite powders at a weight ratio of 15.5. For the second sample volume ratio of 74wt%CeO 2 -26wt%ZrO 2 and Fe-Beta zeolite components equals 5/1. 25 A third sample was prepared by was prepared by mixing 74wt%CeO 2 -26wt%ZrO 2 and Fe-Beta zeolite powders at a weight ratio of 30. For the second sample volume ratio of 74wt%CeO 2 -26wt%ZrO 2 and Fe-Beta zeolite components equals 10/1. 30 After grinding in agate mortar for 10-15 min, the resulted mixtures were pelletized. The pellets were crushed and WO 2013/060487 PCT/EP2012/058003 10 sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized Fe-Beta zeolite was used as reference. Activities of the prepared samples were tested using the 5 following catalyst loading which kept constant volume of the catalyst in the reactor. In all experiments described below overall volume on the catalyst loaded was 0.067 ml, which results in GHSW ~ 270 000 h': 10 First sample (1/1 vol component ratio): [0.065g 74wt%CeO 2 ZrO 2 + 0.02g Fe-Beta zeolite]. Second sample (5/1 vol component ratio): [0.109g 74wt%CeO 2 ZrO 2 + 0.007g Fe-Beta zeolite] 15 Third sample (10/1 vol component ratio): [0.119g 74wt%CeO 2 ZrO 2 + 0.0035g Fe-Beta zeolite]. Reference sample: 0.02 g Fe beta-zeolite. 20 Feed gas composition: 540 ppm NH3, 500 ppm NO, 10 % 02, 6 %
H
2 0 balance with N 2 . Under these conditions [CeO 2 -ZrO 2 + Fe-Beta zeolite] com 25 posite catalysts showed DeNOx performances, which were es sentially identical to the performance of reference Fe-Beta zeolite sample, despite significantly reduced amount of zeolite catalyst (Fe-Beta zeolite) loaded into the reactor as a part of composite [CeO 2 -ZrO 2 + Fe-Beta zeolite] 30 The data in Fig. 3 show that amount of zeolite can be re duced at least 10 times without sacrificing DeNOx perform- WO 2013/060487 PCT/EP2012/058003 11 ance of [Ce0 2 -ZrO 2 + Fe-Beta zeolite] by its replacement with corresponding volume of Ce0 2 -ZrO 2 . Example 4 5 Enhanced DeNOx performance of [Ce-Mn/Al 2 0 3 + Fe-Beta zeo lite] composite catalyst at Treact < 250'C. [Ce-Mn/Al 2 0 3 + Fe-Beta] composite catalysts were prepared 10 by thorough mixing 15wt%Ce-15wt%Mn/Al 2 0 3 powder with Fe Beta powder at a weight ratio of 0,8:1; 1,7:1 and 3,4:1 keeping the same total volume of the catalyst constant. These weight ratios result in volume ratio of components Ce-Mn/Al 2 0 3 /Fe-Beta = 2/1; 1/1 and 1/2 due to difference in 15 densities of these materials. The powders were thoroughly grinded in agate mortar for 10-15 min, followed by pelleti zation. The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized Fe-Beta was used as reference. 20 The catalysts were tested in the NH 3 -DeNOx in the tempera ture range of 150-550 0C. The test was performed under fol lowing conditions: decreasing reaction temperature with a rate of 2 0 C/min, feed gas composition: 500 ppm NO, 540 ppm 25 NH3, 10 vol % 02, 6 vol% H 2 0, balanced with N 2 to obtain a total flow of 300 mL/min. Catalyst load: 0.04g Fe-Beta and [0.045g Ce-Mn/A1 2 0 3 + 0.013g Fe-Beta] (2/1 ratio), [0.034g 30 Ce-Mn/A1 2 0 3 + 0.02g Fe-Beta] (1/1 ratio), [0.022g Ce Mn/A1 2 0 3 + 0.027g Fe-Beta] (1/2 ratio).
WO 2013/060487 PCT/EP2012/058003 12 Under these conditions all [Ce-Mn/Al 2 0 3 + Fe-Beta] composite catalysts showed DeNOx activity, which radically exceeded activities of individual Ce-Mn/A1 2 0 3 and Fe-Beta at tem peratures below 3500C, indicating pronounced synergistic 5 effect between components of composite catalyst (Fig. 4). Besides that, ammonia slip on composite catalysts was sig nificantly lower than for a reference Fe-Beta catalyst in dicating that those composite systems can be used as inte grated DeNOx-ASC. 10 Example 5 Enhanced DeNOx performance of [10wt%Cu/Al 2 0 3 + H-zeolite] composite catalysts. 15 Three samples of [10wt%Cu/Al 2 0 3 + H-zeolite] composite catalyst were prepared by thorough grinding of lOwt%Cu/A1 2 0 3 and H-Beta, H-ZSM-5, or H-ferrierite powder. 20 A first sample was prepared by mixing lOwt%Cu/Al 2 0 3 and H Beta (Si/Al = 20) powders at a weight ratio of 1/1. A second sample was prepared by mixing lOwt%Cu/Al 2 0 3 and H ZSM-5 powders (Si/Al = 20) at a weight ratio of 1/1. 25 A third sample was prepared by mixing lOwt%Cu/Al 2 0 3 and H ferrierite powders (Si/Al = 32) at a weight ratio of 1/1. After grinding in agate mortar for 10-15 min, the resulted 30 mixtures were pelletized. The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test.
WO 2013/060487 PCT/EP2012/058003 13 Similarly corresponding pelletized zeolites (H-Beta, H-ZSM 5, and H-ferrierite) were used as reference. Activities of the prepared samples were tested using the 5 following catalyst loading which kept constant amount of zeolite component in the reactor: The first sample with 1/1 weight component ratio: [0.040g l0wtCu/A1 2 0 3 + 0.040g H-Beta] 10 The second sample with 1/1 weight component ratio: [0.040g l0wtCu/A1 2 0 3 + 0.040g H-ZSM-5]. The third sample with 1/1 weight component ratio: [0.040g 15 10wtCu/A1 2 0 3 + 0.040g H-ferrierite]. Reference samples: 0.040 g H-Beta; 0.040g H-ZSM-5, or H ferrierite, or 0.040 g 10wt%Cu/Al 2 0 3 . 20 The catalysts were tested in NH3-DeNOx within the tempera ture range of 150-550 0C. The test was performed under fol lowing conditions: decreasing reaction temperature with a rate of 2 0 C/min, feed gas composition: 500 ppm NO, 540 ppm NH3, 10 vol % 02, 6 vol% H 2 0, balanced with N 2 to obtain a 25 total flow of 300 mL/min. Catalyst loading and resulted GHSV: [0.040g 10wt%Cu/Al 2 0 3 + 0.040g H-Beta], catalyst vol. = 0.134 ml, GHSV = 135 000 h-1; 30 [0.040g lOwt%Cu/Al 2 0 3 + 0.040g H-ZSM-5], catalyst vol. = 0.134 ml, GHSV = 135 000 h-1; WO 2013/060487 PCT/EP2012/058003 14 [0.040g l0wtCu/A1 2 0 3 + 0.040g H-ferrierite], catalyst vol. = 0.134 ml, GHSV = 135 000 h-'; Reference catalysts 0.040g H-Beta, catalyst vol. = 0.067 ml, 5 GHSV = 270,000 h'; 0.040g H-ZSM-5, catalyst vol. = 0.067 ml, GHSV = 270,000 h'; 0.040g H-ferrierite, catalyst vol. = 0.067 ml, GHSV = 270,000 h'; 10 0.040g Cu/A1 2 0 3 , catalyst vol. = 0.067 ml, GHSV = 270,000 h'. Under these test conditions [10wt%Cu/Al 2 0 3 + H-zeolite] composite catalysts showed enhanced DeNOx within the whole 15 temperature range (150-550'C), which significantly exceeded activity of individual components, as shown by comparing Fig. 5 and Fig. 6. Example 6 20 Catalyst with enhanced soot oxidation activity. [CeO 2 -ZrO 2 + Fe-Beta] with 3/1 vol. component ratio was prepared as described in Example 2. For testing soot oxida 25 tion activity of [CeO 2 -ZrO 2 + Fe-Beta] a part of pelletized sample was crushed, and the catalyst powder was mixed with soot ("Printex U", Degussa) at a weight ratio catalyst/soot = 1/10. Soot and catalyst were mixed by shaking in a glass bottle for 5 min, thus establishing loose contact between 30 soot and the catalyst. Reference sample was prepared in a similar manner using Fe-Beta powder.
WO 2013/060487 PCT/EP2012/058003 15 Soot oxidation was carried out at temperature ramp = 10'C/min in a flow of dried air. Profiles of soot oxidation over [CeO 2 -ZrO 2 + Fe-Beta] and Fe-Beta are displayed in Fig. 7. [CeO 2 -ZrO 2 + Fe-Beta] significantly higher activity 5 in soot oxidation then individual Fe-Beta, as evidenced by a shift of soot oxidation maximum from ~ 6000C for (Fe-Beta + soot) to ~ 4200C for ([Ce0 2 -ZrO 2 + Fe-Beta] + soot).
Claims (16)
1. Catalyst composition for selective reduction of nitrogen oxides and soot oxidation comprising of one or more acidic 5 zeolite or zeotype components selected from the group con sisting of BEA, MFI, FAU, FER, CHA, MOR or mixtures thereof physically admixed with one ore more redox active metal compounds selected from the group consisting of Cu/A1 2 0 3 , Mn/A1 2 0 3 , CeO 2 -ZrO 2 , Ce-Mn/A1 2 0 3 and mixtures thereof. 10
2. The catalyst composition of claim 1, wherein weight ratio between the zeolite components and the redox compo nents is between 1:1 and 1:50. 15
3. The catalyst composition of claim 1 or 2, wherein the one or more redox active metal compounds are dispersed on a support selected from the group consisting of of A1 2 0 3 , TiO 2 , SiO 2 , ZrO 2 or mixtures thereof. 20
4. The catalyst composition according to anyone of claims 1 to 3, wherein the one or more acidic zeolite or zeotype components are in protonic form or promoted with Fe.
5. The catalyst composition according to anyone of claims 25 1 to 4, wherein mean molar ratio of Si/Al of the one or more acidic zeolite or zeotype components is from 5 to 100.
6. The catalyst composition according to anyone of the preceding claims, wherein the one or more acidic zeolite or 30 zeotype components are selected from the group consisting of beta-zeolite, ZSM-5 and ferrierite. WO 2013/060487 PCT/EP2012/058003 17
7. A monolithic structured body being coated with a cata lyst composition according to anyone of the preceding claims. 5
8. The monolithic structured body of claim 7, wherein the monolithic structured body is in a form of a particle fil ter.
9. The monolithic structured body of claims 7 or 8, 10 wherein the catalyst composition is coated on the body in two or several separate catalyst layers in series or as two or several catalyst layers in parallel and wherein the lay ers have different compositions or layer thicknesses. 15
10. Method for the selective reduction of nitrogen oxides and oxidation of soot contained in an off-gas comprising the step of contacting the off-gas in presence of ammonia with a catalyst composition comprising one or more acidic zeolite or zeotype components selected from the group con 20 sisting of BEA, MFI, FAU, FER, CHA, MOR or mixtures thereof physically admixed with one ore more redox active metal compounds selected from the group consisting of Cu/A1 2 0 3 , Mn/A1 2 0 3 , CeO 2 -ZrO 2 , Ce-Mn/A1 2 0 3 and mixtures thereof. 25
11. The method according claim 10, wherein the one ore more redox active metal components dispersed on the surface of the one or more zeolite components contain Ce, Mn, Zr, Cr or mixtures thereof. 30
12. The method of according to claim 10 or 11, wherein the catalyst composition is contacted with the off-gas at a temperature below 2500C. WO 2013/060487 PCT/EP2012/058003 18
13. The method according to anyone of claim 10 to 12, wherein excess of ammonia is selectively oxidized to nitro gen by contact with the catalyst composition. 5
14. The method according to anyone of claims 10 to 13, wherein the one or more acidic zeolite or zeotype compo nents are in protonic form or promoted with Fe. 10
15. The method according to anyone of claims 10 to 14, wherein mean molar ratio of Si/Al of the one or more acidic zeolite or zeotype components is from 5 to 100.
16. The method according to anyone of claims 10 to 15, 15 wherein the one or more acidic zeolite or zeotype compo nents are selected from the group consisting of beta zeolite, ZSM-5 and ferrierite.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPCT/EP2011/005344 | 2011-10-24 | ||
| PCT/EP2011/005344 WO2013060341A1 (en) | 2011-10-24 | 2011-10-24 | Catalyst composition for use in selective catalytic reduction of nitrogen oxides |
| PCT/EP2012/058003 WO2013060487A1 (en) | 2011-10-24 | 2012-05-02 | Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2012327482A1 true AU2012327482A1 (en) | 2014-05-15 |
Family
ID=46085901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2012327482A Abandoned AU2012327482A1 (en) | 2011-10-24 | 2012-05-02 | Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JP6112734B2 (en) |
| KR (1) | KR101789114B1 (en) |
| CN (1) | CN103889569B (en) |
| AU (1) | AU2012327482A1 (en) |
| BR (1) | BR112014008669B1 (en) |
| CA (1) | CA2853154C (en) |
| CL (1) | CL2014000993A1 (en) |
| IN (1) | IN2014CN02950A (en) |
| MX (1) | MX2014004494A (en) |
| RU (1) | RU2608616C2 (en) |
| WO (2) | WO2013060341A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014324B (en) * | 2014-05-14 | 2016-08-17 | 华东理工大学 | Cerium oxide base support type catalyst for denitrating flue gas and preparation method thereof |
| CN105435789A (en) * | 2014-09-09 | 2016-03-30 | 中国石油化工股份有限公司 | Preparation method for Cu-base methanol-synthesizing catalyst large-specific-surface-area carrier |
| CN104525216B (en) * | 2014-12-11 | 2017-01-04 | 清华大学 | Denitrating catalyst under the conditions of wide temperature window high-sulfur and preparation method thereof |
| CN104437540A (en) * | 2014-12-31 | 2015-03-25 | 安徽省元琛环保科技有限公司 | Phosphorus-resistant low-temperature SCR denitration catalyst and preparation method thereof |
| CN108472636B (en) * | 2015-08-21 | 2021-08-06 | 巴斯夫公司 | Exhaust gas treatment catalyst |
| EP3356019A1 (en) * | 2015-09-29 | 2018-08-08 | Johnson Matthey Public Limited Company | Catalytic filter having a soot catalyst and an scr catalyst |
| CA3182231A1 (en) | 2015-10-30 | 2017-05-04 | Blueshift Materials, Inc. | Highly branched non-crosslinked aerogel, methods of making, and uses thereof |
| WO2017212424A1 (en) | 2016-06-08 | 2017-12-14 | Blueshift International Materials, Inc. | Polymer aerogel with improved mechanical and thermal properties |
| EP3281698A1 (en) | 2016-08-11 | 2018-02-14 | Umicore AG & Co. KG | Scr active material |
| EP3496854A1 (en) | 2016-08-11 | 2019-06-19 | Umicore AG & Co. KG | Scr-active material having enhanced thermal stability |
| TW201838708A (en) * | 2017-03-02 | 2018-11-01 | 丹麥商托普索公司 | Process for the removal of sulphur oxides and nitrogen oxides contained in off-gas from an industrial plant |
| JP7383628B2 (en) | 2017-12-05 | 2023-11-20 | ブルーシフト マテリアルズ インコーポレイテッド | Heat treated polyamic acid amide airgel |
| DE102018100833A1 (en) | 2018-01-16 | 2019-07-18 | Umicore Ag & Co. Kg | Process for producing an SCR catalyst |
| DE102018100834A1 (en) | 2018-01-16 | 2019-07-18 | Umicore Ag & Co. Kg | Process for producing an SCR catalyst |
| CN111742121B (en) * | 2018-02-19 | 2022-08-16 | 巴斯夫公司 | Exhaust treatment system with upstream SCR catalyst |
| CN109126817B (en) * | 2018-11-07 | 2021-07-16 | 东北大学 | Iron, tungsten and zinc modified cerium oxide/manganese oxide SCR denitration catalyst and preparation method thereof |
| EP3791955A1 (en) | 2019-09-10 | 2021-03-17 | Umicore Ag & Co. Kg | Scr-catalytic material containing copper-zeolite and copper/alumina, exhaust gas treatment process with said material and method for producing said material |
| CN110586176B (en) * | 2019-09-27 | 2020-11-17 | 中国环境科学研究院 | Electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and preparation method thereof |
| CN110917829A (en) * | 2019-12-13 | 2020-03-27 | 西安润川环保科技有限公司 | Desulfurization and denitrification flue gas advanced treatment method |
| CN111111429A (en) * | 2019-12-16 | 2020-05-08 | 山东金城柯瑞化学有限公司 | Method for treating acetylfuran oxidized tail gas by using single-active-center heterogeneous catalyst technology |
| CN111389454B (en) * | 2020-04-29 | 2022-09-20 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing p-tolualdehyde from synthesis gas and toluene |
| US11989661B1 (en) * | 2023-07-24 | 2024-05-21 | Morgan Stanley Services Group Inc. | Dynamic rules for rules engines |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0557196A (en) * | 1991-08-29 | 1993-03-09 | Toyota Motor Corp | Production of catalyst for purifying exhaust gas |
| AU1461201A (en) * | 1999-12-28 | 2001-07-09 | Corning Incorporated | Zeolite/alumina catalyst support compositions and method of making the same |
| DE60122243T2 (en) * | 2000-06-28 | 2007-06-28 | Ict Co. Ltd. | purifying catalyst |
| JP3917541B2 (en) * | 2003-03-20 | 2007-05-23 | 日産ディーゼル工業株式会社 | Diesel engine exhaust purification system |
| JP2006136776A (en) * | 2004-11-10 | 2006-06-01 | Toyota Central Res & Dev Lab Inc | Nox selection reduction catalyst |
| FR2898887B1 (en) * | 2006-03-21 | 2008-05-02 | Rhodia Recherches & Tech | COMPOSITION BASED ON ZIRCONIUM OXIDE AND CERIUM OXIDE WITH HIGH REDUCIBILITY AND STABLE SPECIFIC SURFACE PROCESS FOR THE PREPARATION AND USE IN THE TREATMENT OF EXHAUST GASES |
| JP2008100152A (en) * | 2006-10-18 | 2008-05-01 | Cataler Corp | Catalyst for cleaning exhaust gas |
| US7527776B2 (en) * | 2007-01-09 | 2009-05-05 | Catalytic Solutions, Inc. | Ammonia SCR catalyst and method of using the catalyst |
| US8802582B2 (en) * | 2007-01-09 | 2014-08-12 | Catalytic Solutions, Inc. | High temperature ammonia SCR catalyst and method of using the catalyst |
| US7767175B2 (en) * | 2007-01-09 | 2010-08-03 | Catalytic Solutions, Inc. | Ammonia SCR catalyst and method of using the catalyst |
| US20100290963A1 (en) * | 2007-04-26 | 2010-11-18 | Johnson Matthey Public Limited Company | Transition metal / zeolite scr catalysts |
| US20090263297A1 (en) * | 2007-09-19 | 2009-10-22 | General Electric Company | Catalyst and method of manufacture |
| WO2009141894A1 (en) * | 2008-05-20 | 2009-11-26 | イビデン株式会社 | Honeycomb structure |
| CN101722059B (en) * | 2008-10-31 | 2011-12-21 | 中国石油化工股份有限公司 | Regeneration method of absorbent composite capable of removing sulphur and/or nitrogen oxides in fume |
| EP2335810B1 (en) * | 2009-12-11 | 2012-08-01 | Umicore AG & Co. KG | Selective catalytic reduction of nitrogen oxides in the exhaust gas of diesel engines |
-
2011
- 2011-10-24 WO PCT/EP2011/005344 patent/WO2013060341A1/en active Application Filing
- 2011-10-24 MX MX2014004494A patent/MX2014004494A/en not_active Application Discontinuation
-
2012
- 2012-05-02 IN IN2950CHN2014 patent/IN2014CN02950A/en unknown
- 2012-05-02 WO PCT/EP2012/058003 patent/WO2013060487A1/en active Application Filing
- 2012-05-02 BR BR112014008669-9A patent/BR112014008669B1/en not_active IP Right Cessation
- 2012-05-02 CA CA2853154A patent/CA2853154C/en not_active Expired - Fee Related
- 2012-05-02 CN CN201280052240.5A patent/CN103889569B/en active Active
- 2012-05-02 AU AU2012327482A patent/AU2012327482A1/en not_active Abandoned
- 2012-05-02 RU RU2014120917A patent/RU2608616C2/en not_active IP Right Cessation
- 2012-05-02 KR KR1020147013999A patent/KR101789114B1/en active IP Right Grant
- 2012-05-02 JP JP2014537523A patent/JP6112734B2/en not_active Expired - Fee Related
-
2014
- 2014-04-17 CL CL2014000993A patent/CL2014000993A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR112014008669A2 (en) | 2017-04-18 |
| KR20140095512A (en) | 2014-08-01 |
| CN103889569A (en) | 2014-06-25 |
| JP6112734B2 (en) | 2017-04-12 |
| IN2014CN02950A (en) | 2015-07-03 |
| KR101789114B1 (en) | 2017-10-23 |
| MX2014004494A (en) | 2014-07-11 |
| RU2014120917A (en) | 2015-12-10 |
| CN103889569B (en) | 2017-02-15 |
| WO2013060487A1 (en) | 2013-05-02 |
| CA2853154C (en) | 2018-04-03 |
| WO2013060341A1 (en) | 2013-05-02 |
| CL2014000993A1 (en) | 2014-08-22 |
| CA2853154A1 (en) | 2013-05-02 |
| RU2608616C2 (en) | 2017-01-23 |
| JP2015501210A (en) | 2015-01-15 |
| BR112014008669B1 (en) | 2019-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2012327482A1 (en) | Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides | |
| EP3096875B1 (en) | Exhaust system comprisng a diesel oxidation catalyst | |
| EP2908947B1 (en) | Mixed metal 8-ring small pore molecular sieve catalytic articles and methods | |
| EP2908946B1 (en) | 8-ring small pore molecular sieve as high temperature scr catalyst | |
| US20170341026A1 (en) | Vanadium Catalysts for High Engine-Out NO2 Systems | |
| US11365660B2 (en) | NOx adsorber catalyst | |
| JP7152401B2 (en) | SCR catalyst containing vanadium oxide and molecular sieve containing iron | |
| US11229901B2 (en) | SCR catalyst device containing vanadium oxide and molecular sieve containing iron | |
| EP2593212B2 (en) | Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox | |
| US9168517B2 (en) | Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides | |
| US20150231620A1 (en) | IRON-ZEOLITE CHABAZITE CATALYST FOR USE IN NOx REDUCTION AND METHOD OF MAKING | |
| US20240167410A1 (en) | Catalytic article comprising vanadium-based catalyst and molecular sieve-based catalyst | |
| KR20170063596A (en) | Thermally stable nh3-scr catalyst compositions | |
| EP3775510B1 (en) | Exhaust system including scrf catalyst with oxidation zone | |
| KR20240149386A (en) | SCR catalyst with blended oxide and H-zeolite | |
| KR20240110562A (en) | Catalyst system comprising antimony-containing catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK4 | Application lapsed section 142(2)(d) - no continuation fee paid for the application |