GB2529926A - Non-PGM ammonia slip catalyst - Google Patents

Non-PGM ammonia slip catalyst Download PDF

Info

Publication number
GB2529926A
GB2529926A GB1509439.4A GB201509439A GB2529926A GB 2529926 A GB2529926 A GB 2529926A GB 201509439 A GB201509439 A GB 201509439A GB 2529926 A GB2529926 A GB 2529926A
Authority
GB
United Kingdom
Prior art keywords
catalyst
layer
washcoat
oxidation
scr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB1509439.4A
Other versions
GB2529926B (en
GB201509439D0 (en
Inventor
Paul Joseph Andersen
Kevin Doura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Publication of GB201509439D0 publication Critical patent/GB201509439D0/en
Publication of GB2529926A publication Critical patent/GB2529926A/en
Application granted granted Critical
Publication of GB2529926B publication Critical patent/GB2529926B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/58—Ammonia
    • 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
    • B01D53/8634—Ammonia
    • 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
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9436—Ammonia
    • 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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • 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
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
    • B01D53/9468—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different layers
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • B01J29/24—Iron group metals or 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
    • B01J29/68—Iron group metals or 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7215—Zeolite Beta
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • B01J35/19—
    • B01J35/40—
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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
    • B01J37/08—Heat treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • 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
    • B01D2255/20715—Zirconium
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/65—Catalysts not containing noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/903—Multi-zoned catalysts
    • B01D2255/9032—Two zones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biomedical Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

A non-platinum group metal ammonia slip catalyst having an SCR catalyst, comprising a molecular sieve or a vanadium/titania SCR catalyst and an oxidation catalyst. The oxidation catalyst comprises a first metal selected from copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and a second metal selected from neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta) and strontium (Sr). Also disclosed, is a dual layer ammonia slip catalyst comprising the SCR catalyst and an oxidation catalyst layer positioned proximal to a substrate and methods of preparing and using the ammonia slip catalyst and the dual layer ammonia slip catalyst.

Description

NON-PGM AMMONTA SLIP CATALYST
FIELD OF THE INVENTION
The present invention is directed towards catalysts and methods for removal of ammonia from flue gases that have been subjected to selective catalytic reduction (5CR) of oxides of nitrogen (NOx) by ammonia injection. More specifically, the present invention is directed to a composite catalyst having a layer comprising an SCR catalyst and a layer comprising an oxidation catalyst, where the oxidation catalyst comprises at least two metals chosen from specific groups, and the layer comprising the oxidation catalyst does not contain a platinum group metal (PGM).
BACKGROUND OF TIlE INVENTION
Combustion of hydrocarbon-based ifiel in electrical power stations and in engines produces flue or exhaust gas that contains, in large part, relatively benign nitrogen (N2), water vapor (H70), and carbon dioxide (CO2). But the flue and exhaust gases also contains, in relatively small part, noxious and/or toxic substances, such as carbon monoxide (CO) from incomplete combustion, hydrocarbons (HC) from un-burnt fuel, nitrogen oxides (NO1) from excessive combustion temperatures, and particulate matter (mostly soot). To mitigate the environmental impact of flue and exhaust gas released into the atmosphere, it is desirable to eliminate or reduce the amount of the undesirable components, preferably by a process that, in turn, does not generate other noxious or toxic substances.
Typically, flue gases from electrical power stations and exhaust gases lean burn gas engines have a net oxidizing effect due to the high proportion of oxygen that is provided to ensure adequate combustion of the hydrocarbon fuel, In such gases, one of the most burdensome components to remove is NO1, which includes nitric oxide (NO), nitrogen dioxide (NO7), and nitrous oxide (N2O). The reduction of NO1 to N2 is particulady problematic because the exhaust gas contains enough oxygen to favor oxidative reactions instead of reduction. Notwithstanding, NO1 can be reduced by a process commonly known as Selective Catalytic Reduction (5CR). An SCR process involves the conversion of NO1, in the presence of a catalyst and with the aid of a nitrogenous reducing agent, such as ammonia, into elemental nitrogen (N2) and water. In an 5CR process, a gaseous reductant such as ammonia is added to an exhaust gas stream prior to contacting the exhaust gas with the SCR catalyst.
The reductant is absorbed onto the catalyst and the NO reduction reaction takes place as the gases pass through or over the catalyzed substrate. The chemical equation for stoichiometric SCR reactions using ammonia is: 4N0+4NH3+02 -÷4N2+6H20 2N0, + 4NH3 + 02 3N, + 61120 N0+N02+2NH3 -.2N7+31170 Most SCR processes utilize a stoichiometric excess of ammonia in order to maximize the conversion of NOx, Unreacted ammonia that passes through the SCR process (also referred to as "ammonia slip") is undesirable, because the released ammonia gas can negatively impact the atmosphere and can react with other combustion species. To reduce ammonia slip, SCR systems can include an ammonia oxidation catalyst (AIVIOX) (also known as an ammonia slip catalyst (ASC)) downstream of the SCR catalyst.
Catalysts for oxidizing excess ammonia in an exhaust gas are known. For example, US Pat. No. 7,393,511 describes an ammonia oxidation catalyst containing a precious metal, such as platinum, palladium, rhodium, or gold on a support of titania alumina, silica, zirconia, etc. Other ammonia oxidation catalyst contain a first layer of vanadium oxide, tungsten oxide, and molybdenum oxide on a titania support, and a second layer of platinum on a titania support (see, e.g., US Pat, Nos. 8,202,481 and US 7,410,626). However, these catalysts are not highly efficient at converting ammonia, particularly at relatively low temperatures. Most of the known systems for oxidizing excess ammonia rely of expensive precious metals as a component in the oxidation catalyst. Accordingly, there remains a need in the art for improved ammonia slip catalysts. The present invention satisfies this need among others.
SUMMARY OF THE iNVENTION
hone aspect of the invention, an ammonia slip catalyst comprises an SCR catalyst and an oxidation catalyst, where the oxidation catalyst comprises at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and the ammonia slip catalyst does not comprise a platinum group metal. The SCR catalyst and the oxidation catalyst can be present on a support as a mixture or in layers.
In another aspect of the invention, a dual layer ammonia slip catalyst can comprise a layer comprising an SCR catalyst and a layer comprising an oxidation catalyst, where the oxidation catalyst comprises at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and the ammonia slip catalyst does not comprise a platinum group metal. The layer comprising the SCR catalyst, also called the SCR layer, and the layer comprising the oxidation catalyst, also called the oxidation layer, can be provided in various configurations, either on the same substrate or on different substrates, In yet another aspect of the invention, a method for producing an ammonia slip catalyst comprises: (a) forming a washcoat comprising a mixture of the SCR catalyst and an oxidation catalyst comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and the ammonia slip catalyst does not comprise a platinum group metal; (b) applying the washcoat to a substrate; (c) drying the washcoat on the substrate; and (d) calcining the washcoat on the substrate, In still another aspect of the invention, a method for producing a dual layer ammonia slip catalyst comprises: (a) forming a oxidation layer on a substrate by applying onto a substrate a oxidation layer washcoat comprising an oxidation catalyst comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Tvlo), tin (Sn), tantalum (Ta), and strontium (Sr), where the ammonia slip catalyst does not comprise a platinum group metal, (b) drying the oxidation layer washcoat on the substrate, (c) calcining the oxidation layer washcoat on the substrate, (d) forming an SCR layer positioned over the oxidation layer by applying an SCR layer washcoat comprising an SCR catalyst over the calcined oxidation layer on a substrate formed in step (c), (e) drying the SCR layer washcoat on the calcined oxidation layer on a substrate and (f) calcining the SCR layer washcoat on the calcined oxidation layer washcoat on the substrate.
In yet another aspect of the invention, a method for producing a dual layer ammonia slip catalyst comprises (a) forming an oxidation layer on a substrate by placing on the substrate an oxidation layer washcoat comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and the ammonia slip catalyst does not comprise a platinum group metal, (b) drying the oxidation layer washcoat on the substrate, (c) forming an SCR layer positioned over the oxidation layer by applying an SCR washcoat comprising an SCR catalyst over the oxidation layer on a substrate formed in step (b), (d) drying the SCR layer washcoat on the calcined oxidation layer on the substrate and (e) calcining the oxidation layer washcoat and the SCR layer washcoat on the substrate.
In another aspect of the invention, a method for producing a dual layer ammonia slip catalyst comprises (a) forming an SCR layer of an SCR catalyst on a substrate by applying onto a portion of a substrate a washcoat comprising an SCR catalyst; (b) drying the SCR washcoat layer on the substrate; (c) optionally calcining the SCR washcoat layer on the substrate; (d) forming an oxidation layer of an oxidation catalyst comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and the ammonia slip catalyst does not comprise a platinum group metal, onto a portion of the substrate by applying onto a portion of a substrate a oxidation washcoat comprising the oxidation catalyst; (e) drying the oxidation layer on the substrate; and (0 calcining at least the oxidation catalyst on the substrate.
In still another aspect of the invention, methods for reducing the concentration of ammonia in a flue gas stream generated by a combustion source comprise contacting a flue gas stream containing ammonia with the ammonia slip catalyst or a dual layer ammonia slip cata'yst as described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may be understood from the following detailed description when read in connection with the accompanying drawing.
Figures 1A-IL are drawings of configurations of catalyst articles showing locations of the 5CR catalyst and the oxidations catalyst.
Figure 2 is a graph illustrating the percentage of NH3 conversion in the ammonia slip catalyst zone according to an embodiment of a catalyst of the present invention as compared NH3 conversions using two different platinum group metal based catalysts.
Figure 3 is a graph illustrating the percentage of NOx selectivity in the ammonia slip catalyst zone according to an embodiment of a catalyst of the present invention as compared NH3 conversions using two different platinum group metal based catalysts.
Figure 4 is a graph illustrating the total NH3 and NOx output (in ppm) in the ammonia slip catalyst zone according to an embodiment of a catalyst of the present invention as compared NH3 conversions using two different platinum group metal based catalysts.
DETAILED DESCRIPTION OF THE INVENTION
As used in this specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly indicates otherwise. Thus, for example, reference to "a catalyst" includes a mixture of two or more catalysts, and the like.
As used herein, the term "calcine", or "calcination", means heating the material in air or oxygen. This definition is consistent with the IUPAC definition of calcination. (IUPAC.
Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XIVIL on-line corrected version: http://goldbook.iupac.org (2006-) created by M, Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi: 10.1351/ goldbook.) Calcination is performed to decompose a metal salt and promote the exchange of metal ions within the catalyst and also to adhere the catalyst to a substrate. The temperatures used in calcination depend upon the components in the material to be calcined and generally are between about 400 °C to about 900 °C for approximately ito 8 hours. In some cases, calcination can be performed up to a temperature of about 1200 °C. In applications involving the processes described herein, calcinations are generally performed at temperatures from about 400 °C to about 700 °C for approximately 1 to 8 hours, preferably at temperatures from about 400 °C to about 650 °C for approximately 1 to 4 hours.
As used herein, the term "about" means approximately and refers to a range that is optionally + 25%, preferably + 10%, more preferably, + S?/o, or most preferably + 1% of the value with which the term is associated.
When a range, or ranges, for various numerical elements are provided, the range, or ranges, can include the values, unless otherwise specified.
The term "platinum group metal" or PGM, means ruthenium, rhodium, palladium, osmium, iridium, and platinum. The phrase "does not comprise a platinum group metal" means that a platinum group metal is not added in forming the catalyst but does not preclude one or more platinum group metals being present in trace amounts, which are levels that do not have measureable catalytic activity.
In one aspect of the invention, an ammonia slip catalyst comprises a mixture of an SCR catalyst and an oxidation catalyst, where the oxidation catalyst comprises at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and the ammonia slip catalyst does not comprise a platinum group metal.
In another aspect of the invention, a dual layer ammonia slip catalyst comprises an SCR layer comprising an 5CR catalyst and an oxidation layer an oxidation catalyst comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and the oxidation layer does not comprise a platinum group metal, The layer comprising the SCR catalyst, also called the SCR layer, and the layer comprising the oxidation catalyst, also called the oxidation layer, can be provided in various configurations, either on the same substrate or on different substrates.
SCR CATALYST
The 5CR catalyst can be an oxide of a base metal, a molecular sieve, a metal exchanged molecular sieve or a mixture thereof The base metal can be selected from the oup consisting of vanadium (V), molybdenum (Mo) and tungsten (W), chromium (Cr), cerium (Ce), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu), and mixtures thereof SCR compositions consisting of vanadium supported on a refractory metal oxide such as alumina, silica, zirconia, titania, ceria and combinations thereof are well known and widely used commercially in mobile applications. Typical compositions are described in U.S. Pat. Nos, 4,010,238 and 4,085,193, of which the entire contents are incorporated herein by reference. Compositions used commercially, especially in mobile applications, comprise Ti02 on to which W03 and V205 have been dispersed at concentrations ranging from 5 to 20 wt. % and 0,5 to 6 wt. %, respectively. These catalysts may contain other inorganic materials such as Si02 and Zr02 acting as binders and promoters.
When the SCR catalyst is a base metal, the catalyst article can further comprise at least one base metal promoter. As used herein, a "promoter" is understood to mean a substance that when added into a catalyst, increases the activity of the catalyst. The base metal promoter can be in the form of a metal, an oxide of the metal, or a mixture thereof The at least one base metal catalyst promoter may be selected from neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), strontium (Sr) and oxides thereof The at least one base metal catalyst promoter can preferably be Mn02, Mn203, Fe203, Sn02, CuO, CoO, CeO2 and mixtures thereof The at least one base metal catalyst promoter may be added to the catalyst in the form of a salt in an aqueous solution, such as a nitrate or an acetate. The at least one base metal catalyst promoter and at least one base metal catalyst, e.g., copper, maybe impregnated from an aqueous solution onto the oxide support material(s), may be added into a washcoat comprising the oxide support material(s), or may be impregnated into a support previously coated with the washcoat. The SCR catalyst can contain from at least about 0.1 weight percent, at least about 0.5 weight percent, at least about 1 weight percent, or at least about 2 weight percent to at most about 10 weight percent, about 7 weight percent, about 5 weight percent of a promoter m eta! based on the total weight of the promoter metal and support.
The 5CR catalyst can comprises a molecular sieve or a metal exchanged molecular sieve. As is used herein "molecular sieve" is understood to mean a metastable material containing tiny pores of a precise and uniform size that may be used as an adsorbent for gases or liquids. The molecules which are small enough to pass through the pores are adsorbed while the larger molecules are not. The molecular sieve can be a zeolitic molecular sieve, a non-zeolitic molecular sieve, or a mixture thereof A zeolitic molecular sieve is a microporous aluminosilicate having any one of the framework structures listed in the Database of Zeolite Structures published by the International Zeolite Association (IZA). The framework structures include, but are not limited to those of the CHA, FAU, BEA, MEl, MOR types. Non-limiting examples of zeolites having these structures include chabazite, faujasite, zeolite Y, ultrastable zeolite Y, beta zeolite, mordenite, silicalite, zeolite X, and ZSM-5. Aluminosilicate zeolites can have a silica/alumina molar ratio (SAR) defined as 5i02/A1203) from at least about 5, preferably at least about 20, with useful ranges of from about 10 to 200.
As used herein, the term "non zeolitic molecular sieve" refers to corner sharing tetrahedral frameworks where at least a portion of the tetrahedral sites are occupied by an element other than silicon or aluminum, Specific non-limiting examples of non-zeolitic molecular sieves include silicoaluminophosphates such as SAPO-34, SAPO-37 and SAPO- 44. The silicoaluminophosphates can have framework structures that contain framework elements that are found in zeolites, such as CHA, FAU, BEA, MFI, MOR and other types described below.
The SCR catalyst can comprise a small pore, a medium pore or a large pore molecular sieve, or combinations thereof The 5CR catalyst can comprise a small pore molecular sieve selected from the group consisting of aluminosilicate molecular sieves, metal-substituted aluminosilicate molecular sieves, aluminophosphate (AIPO) molecular sieves, metal-substituted aluminophosphate (MeAIPO) molecular sieves, silico-aluminophosphate (SAPO) molecular sieves, and metal substituted silico-aluminophosphate (MeAPSO) molecular sieves, and mixtures thereof The SCR catalyst can comprise a small pore molecular sieve selected from the group of Framework Types consisting of ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CT-TA, DDR, DFT, EAB, EDT, EPI, ERT, (iTS, (300,11-lw, ITE, TTW, LEV, KFT, MER, MON, NSI, OWE, PAIJ, PHI, RHO, RTH, SAT, SAy, Sly, THO, TSC, UEI, IJFI, VNI, YUG, and ZON, and mixtures and/or intergrowths thereof Preferably the small pore
B
molecular sieve is selected from the group of Framework Types consisting of CHA, LEV, AET, AFX, ERI, SFW, KFI, DDR and ITE.
The SCR catalyst comprises can comprise a medium pore molecular sieve selected from the group of Framework Types consisting of AEL, AFO, ART, BOF, BOZ, CGF, CGS, CHI, DAC, EUO, FER, HEU, IMF, ITH, TTR, JRY, JSR, 1ST, LAU, LOY, MEL, MEl, MIFS, MRE, MTT, MVY, IvIWW, NAB, NAT, NES, OBW, -PAR, PCR, PON, PUN, RRO, RSN, 5FF, SFG, STF, STI, STT, STW, -SVR, SZR, TER, TON, TUN, UOS, VSV, WET, and WEN, and mixtures and/or intergrowths thereof Preferably, the medium pore molecular sieve selected from the group of Framework Types consisting of MEL, FER and STT, The 5CR catalyst can comprise a large pore molecular sieve selected from the group of Framework Types consisting of AFt, AFR, AES, AFY, ASV, ATO, ATS, BEA, BEC, BOG, BPH, BSV, CAN, CON, CZP, DFO, EMT, EON, EZT, FM), GME, GUN, IFR, ISV, ITG, TWR, IWS, TWV, TWW, JSR, LTF, LTL, MAZ, MET, MOR, MOZ, MSE, MTW, NPO, OFF, OKO, OSI, -RON, RWY, SAF, SAO, SBE, SBS, SBT, SEW, SEE, SF0, SFS, SFV, SOF, SOS, STO, SSF, SSY, UST, UWY, and VET, and mixtures andlor intergrowths thereof Preferably, the large pore molecular sieve is selected from the group of Framework Types consisting of MOR, OFF and BEA.
A metal exchanged molecular sieve can have at least one metal from one of the groups VB, VIB, VIIB, VLILB, IB, or LIB of the periodic table deposited onto extra-framework sites on the external surface or within the channels, cavities, or cages of the molecular sieves.
Metals may be in one of several forms, including, but not limited to, zerovalent metal atoms or clusters, isolated cations, mononuclear or polynuclear oxycations, or as extended metal oxides. Preferably, the metals can be iron, copper, and mixtures or combinations thereof The metal can be combined with the zeolite using a mixture or a solution of the metal precursor in a suitable solvent. The term "metal precursor" means any compound or complex that can be dispersed on the zeolite to give a catalytically-active metal component. Preferably the solvent is water due to both economics and environmental aspects of using other solvents.
When copper, a preferred metal is used, suitable complexes or compounds include, but are not limited to, anhydrous and hydrated copper sulfate, copper nitrate, copper acetate, copper acetylacetonate, copper oxide, copper hydroxide, and salts of copper ammines (e.g. [Cu(NE13)412). This invention is not restricted to metal precursors of a particular type, composition, or purity, The molecular sieve can be added to the solution of the metal component to form a suspension, which is then allowed to react so that the metal component is distributed on the zeolite. The metal can be distributed in the pore channels as well as on the outer surface of the molecular sieve. The metal can be distributed in ionic form or as a metal oxide. For example, copper may be distributed as copper (II) ions, copper (I) ions, or as copper oxide. The molecular sieve containing the metal can be separated from the liquid phase of the suspension, washed, and dried, The resulting metal-containing molecular sieve can then be calcined to fix the metal in the molecular sieve.
A metal exchanged molecular sieve can contain in the range of about 0.10% and about 10% by weight ofa group VB, VIB, VIIB, VIIIB, IB, or IIB metal located on extra framework sites on the external surface or within the channels, cavities, or cages of the molecular sieve.
Preferably, the extra framework metal can be present in an amount of in the range of about 0,2% and about 5% by weight.
The metal exchanged molecular sieve can be a copper (Cu) supported small pore molecular sieve having from about 0,1 to about 20,0 wt, % copper of the total weight of the catalyst, Preferably copper is present from a about I wt. % to about 6 wt, % of the total weight of the catalyst, more preferably from about 1,8 wt, % to about 4,2 wt, % of the total weight of the catalyst.
The metal exchanged molecular sieve can be an iron (Fe) supported small pore molecular sieve having from about 0,1 to about 20,0 wt, % iron of the total weight of the catalyst, Preferably iron is present from about I wt, 94 to about 6 wt, 94 of the total weight of the catalyst, more preferably from about 1,8 wt, 94 to about 4,2 wt. 9/b of the total weight of the catalyst.
OXIDATION CATALYST
The oxidation catalyst comprises at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (IvIn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and ammonia slip catalyst does not comprise a platinum group metal, Each of the at least one first metal and second metal can be in the fomi of a salt, preferably a nitrate, sulfate, chloride or an acetate, an oxide, or a compound containing the metal where the compound containing the metal forms a oxide of the metal upon calcination. Preferably the first metal is Cu and the second metal is Mn.
A layer comprising an oxidation catalyst can further comprise an oxide support material comprising alumina (A1203), silica (Si02) zirconia (Zr02), ceria (CeO2) and titania (Ti02), or mixtures thereof The oxide support material can further comprise other oxide materials such as perovskites, nickel oxide (NiO), manganese dioxide (Mn02), praseodymium (III) oxide (Pr203). The oxide support material can include composite oxides or mixed oxides of two or more thereof (such as CeZrO2 mixed oxides, TiZrO2 mixed oxides, TiSiO2 mixed oxides, and TiAlO oxides where x is dependent on the ratio ofTiO2 to Al203.). The oxide support material, in addition for serving as a support may also serve as a binder. For example, alumina may act as both a support and a binder in an alumina and CeZrO2 mixed oxide. The second layer can comprise an oxide support material comprising one or more of a stabilized alumina, silica, zirconia, ceria, and titania. Stabilizers may be selected from zirconium (Zr), lanthanum (La), aluminum (Al), yttrium (Y), praseodymium (Pr), neodymium (Nd), an oxide thereof a composite oxide or mixed oxide of any two or more thereof or at least one alkaline earth metal, e.g., barium (Ba). if each oxide support material is stabilized, the stabilizers may be the same or different. The oxide support material can be A1203 and CeO2. Where the oxide support material is Al203, it maybe alpha-, gamma-, beta-, delta-, or theta-A1203, for example. The support material can be in the form of mixed oxides or stabilized mixed oxides, The metal oxides in mixed oxides are present in the form of a single phase, while stabilized mixed oxides are present in two phases.
Preferably a layer comprising the oxidation catalyst comprises Cu and Mn, as the first and second metals, alumina and either Ce02/Zr02 or a Zr-stabilized CeO2 mixed oxide. The Zr-stabilized CeO2 mixed oxide can comprise Ce and Zr in about a 1:] mole ratio. The oxide support material can be La-stabilized A1203 and Zr-stabilized CeO2. The oxide support material in the second layer can comprise about 20 mole ?/b La-stabilized A1203 and about 80 mole % Zr-stabilized CeO7.
SUBSTRATE
The term "substrate" refers to substantially inert substrate material, as generafly known in the art. The substrate maybe of any generaHy suitable form. For example, the substrate may comprise a flow through monolith, such as a ceramic or honeycomb structure, or the substrate may be in the form of foams, or the substrate may be in the form of pellets, fluidized bed particulates, or may comprise particles such as spheres or short extmded segments.
The solid substrate may be any of those materials typically used for preparing exhaust gas treatment catalysts and will preferably comprise a metal or refractory ceramic having a honeycomb structure, Any suitable substrate may be employed, such as a monolithic substrate of the type having a plurality of fine, parallel gas flow passages extending there through from an inlet or an outlet face of the carrier, such that passages are open to fluid flow there through. The passages that are essentially straight paths from their fluid inlet to their fluid outlet are defined by walls on which the ammonia oxidation catalyst is coated as a "washcoat" so that the gases flowing through the passages contact the catalytic material, The flow passages of the monolithic carrier are thin-walled channels which can be of any suitable cross-sectional shape and size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. Such structures may contain from about 60 to about 600 or more gas inlet openings (i.e., "cells") per square inch of cross section, Honeycomb substrates comprise multiple adjacent, parallel channels that generally extend from the inlet face to the outlet face of the substrate and are either open on both ends (flow-through substrates) or are capped on alternating ends in a checker-board type pattern (wall-flow filters), This geometry results in a high-surface area-to-volume ratio. Honeycomb configurations are more compact than plate types, but have higher pressure drops and plug more easily, However, for most mobile applications, preferred substrates are honeycombs.
For certain applications, the honeycomb flow though monolith has a high cell density, for example about 600 to 800 cells per square inch, and/or an average internal wall thickness of about 0.18-0.35 mm, preferably about 0.20-0.25 mm. For certain other applications, the honeycomb flow through monolith preferably has a low cell density of about 150-600 cells per square inch, more preferably about 200 -400 cells per square inch. Preferably, the honeycomb monoliths are porous. In addition to cordierite, silicon carbide, silicon nitride, ceramic, and metal, other materials that can be used for the substrate include aluminum nitride, silicon nitride, aluminum titanate, a-alumina, mullite e.g. acicular mullite, pollucite, a thermet such as AI2OsZFe, A1203/Ni orB4CZFe, or composites comprising segments of any two or more thereof Preferred materials include cordierite, silicon carbide, and alumina titanate. In certain embodiments, the substrate is inert.
The substrate wall of a honeycomb preferably has a porosity and pore size that is conducive for washcoating. Porosity is a measure of the percentage of void space in a porous substrate. Preferably, the porous substrate has a porosity of about 30 to about 80%, for example about 40 to about 75%, about 40 to about 65%, or from about 50 to about 60%. The pore interconnectivity, measured as a percentage of the substrate's total void volume, is the degree to which pores, void, and/or channels, arejoined to form continuous paths through a porous substrate, i.e., from the inlet face to the outlet face of a filter. Preferably, the porous substrate has a pore interconnectivity volume of at least about 30%, more preferably at least about 40%.
Mean pore size of the substrate wall can be determined by any acceptable means, including by mercury porosimetry. Preferred porous substrates have a mean pore size of about 10 to about 40 pm, for example about 20 to about 30!lm, about 10 to about 2SRm, about 10 to about 20gm, about 20 to about 25 tim, about 10 to about i5m, and about 15 to about 20 pm.
WASHCOAT
The term "washcoat" is a term widely recognized in the art and refers to mixture of one or more a catalyst or a catalysts precursor, support materials, and optionally other materials such as binders, promoters or stabilizers, The catalysts of the present invention can be utilized in heterogeneous catalytic reaction systems (i.e., solid catalyst in contact with a gas reactant). To improve contact surface area, mechanical stability, and fluid flow characteristics, the catalyst components can be disposed on and/or within a substrate, for example as a coating. h certain embodiments, a washcoat containing one or more of the catalyst components is applied as a coating to an inert substrate, such as conugated metal plate or a honeycomb cordierite brick. The washcoat is preferably a solution, suspension, or slurry. Suitable coatings include surface coatings that cover a portion or the entire substrate, coatings that penetrate a portion of the substrate, coatings that permeate the substrate, or some combination thereof In addition to the catalyst component, a washcoat can also include components, such as fillers, binders, stabilizers, rheology modifiers, and other additives, including one or more of alumina, silica, non-zeolite silica alumina, titania, zirconia, ceria, In certain embodiments, the washcoat comprises pore-forming agents such as graphite, cellulose, starch, polyacrylate, and polyethylene, and the like, These additional components do not necessarily catalyze the desired reaction, but instead improve the catalytic material's effectiveness, for example by increasing its operating temperature range, increasing contact surface area of the catalyst, increasing adherence of the catalyst to a substrate, modifying rheology for better processing, etc. Typically, metal oxide particles used as binders are distinguishable over metal oxide particles used as supports based on particle size, with the binder particles being significantly larger relative to support particles.
A variety of deposition methods are known in the art for depositing the catalyst on the substrate. Methods for depositing the catalyst on the substrate include, for example, disposing the catalyst in a liquid vehicle to form a slurry and wetting the substrate with the slurry by dipping the substrate into the slurry, spraying the slurry onto the substrate, etc. A washcoat is typically applied to a substrate as a water-based slurry. Typically, the slurry will contain a total water content of at least 20 wt, %, Water contents of at least 30 wt, %, at least wt. °/b, at least 50 wt, % or at least 60 wt. %, are also exemplified. The slurry coated substrate can be dried and calcined (thermally treated in presence of air or oxygen) prior to use. The temperatures and times used in calcination depend upon the components in the material to be calcined and generally are between about 400 °C to about 900 °C, k applications involving the processes described herein, calcinations are generally performed at temperatures from about 500 °C to about 550 °C for about 2 to about 6 hours.
The support for the oxidation catalyst can be kneaded along with other components such as fillers, binders, and reinforcing agents, into an extrudable paste which is then extruded through a die to form a honeycomb brick. Before or after the honeycomb brick is dried and/or calcined, the metal components of the oxidation catalyst are added to either one or more portions of the brick or to the entire brick in order to form the oxidation catalyst. k other embodiments, the oxidation catalyst containing the supported metals can be incorporated into the extrudable paste prior to extrusion. The SCR catalyst can then be applied as a coating on the extruded brick containing the oxidation catalyst. Two substrate designs useful in the present invention are plate and honeycomb. Plate-type catalysts have relative lower pressure drops and are tess susceptible to plugging and fouling than the honeycomb types, but plate configurations are much arger and more expensive. The plates are typicaHy constructed of metal or corrugated metal.
In certain embodiments, the washcoat or impregnation loading on and/or within the substrate for each layer or for the combination of two or more layers is 0. to 8 gun3, more preferably 0.5 to 6 s/in3, and even more preferably 1 to 4 gun3. In certain embodiments, the washcoat or impregnation loading on and/or within the substrate for each layer or for the combination of two or more layers is >1,00 gun3, such as >1,2 gin3, >1.5 gun3, >1,7 gun3 or >2.00 gun' or for example 1,5 to 2,5 g/int
CONFIGURATIONS OF SCR AND OXIDATION CATALYSTS
The SCR catalyst and the oxidation catalyst can be present in a variety of configurations, such as a mixture of the SCR catalyst and the oxidation catalyst, an overlayer of an SCR catalyst on an underlayer of the oxidation catalyst that is placed in, or on, a substrate, or a sequential placement along the flow of an exhaust gas of the SCR catalyst and the oxidation catalyst, where the oxidation catalyst is downstream of the SCR catalyst.
Figure IA shows a configuration in which the SCR catalyst and the oxidation catalyst are present in a single layer 8 on the substrate 14.
Figure lB shows a configuration in which the SCR layer 10 comprising the SCR catalyst is positioned over the oxidation layer 12 comprising the oxidation catalyst, and the oxidation layer 12 is positioned over the solid substrate, In Figure IB, both the SCR layer and the oxidation layer are positioned over the entire axial length of the substrate, The SCR layer and the oxidation layer can be positioned over a portion of the axial length of the substrate, as shown in Figures IC and ID. In placing the SCR layer over the oxidation layer, a portion of the SCR washcoat can occupy some or all of the space between adjacent oxidation layers, Figure IE shows where all of the space between adjacent oxidation layers comprises an SCR catalyst. The space between adjacent oxidation layers can be completely filed with an SCR overlay that also fills the space between the oxidation layers, as shown in Figure IF, Generally, a catalyst layer of the present invention permeates the substrate; penetrates a portion of the substrate, for example a ma] ority portion; coats the surface of the substrate; or a combination thereof Alternatively to being coated on a substrate wall, the oxidatiou catalyst cau be incorporated into a high porosity substrate, for example as au interior coating that permeates the wall or can be incorporated into extmdable paste which forms the substrate. Figure G shows a configuration in which the SCR catalyst is present in a layer over the substrate N and the oxidation catalyst is present in the substrate 14. One or more of the catalysts layers can cover only a portion of the substrate, For example a catalyst layer can be applied to about 10 percent of the length of the substrate, from the front of the substrate 46 or the rear of the substrate 48, relative to the overall direction of exhaust gas flow through the substrate. The oxidation catalyst layer can be coated on a portion at the rear of the substrate 48, The catalyst layers can cover about 25 percent, about 50 percent, or about percent of the substrate, preferably from the rear 48 or front 46 of the substrate, The catalyst coatings may be applied to the same or different portions of the substrate, but preferably the SCR catalyst layer completely covers the oxidation catalyst layer so that all exhaust gas being treated by the catalyst layers will first pass through the SCR layer before reaching the oxidation catalyst layer.
The SCR layer and the oxidation layer can be placed next to each other sequentially in the direction of exhaust gas flow. As used herein, the term "sequential" with respect to the layers means that each layer is contact with a substrate and that the layers as a whole are arranged next to one another on one or more substrates, Figure 1H shows a sequential positioning of an 8CR layer 10 comprising an SCR catalyst and an oxidation layer 12 comprising an oxidation catalyst on a solid support 14, The exhaust gas has a generalized flow in the direction of the arrow, from left to right. The support has a front end 46 and a back end 48, Figure 11 shows a sequential positioning of an 8CR layer 10 comprising an 8CR catalyst and an oxidation layer 12 comprising an oxidation catalyst on a solid support 14.
Part of the 8CR layer 10 also is an overlayer over the oxidation layer 12, The overlayer can be located over the entire oxidation layer, as shown in Figure II, or over a portion of the oxidation layer, as shown in Figure ii, The 8CR layer and the oxidation layer may be present on two different supports. An 8CR layer 10 comprising the SCR catalyst can be placed on a support 14 with an adjacent, downstream support 15 having an oxidation layer 12 comprising the oxidation catalyst on the support is shown in Figure 1K. An SCR layer 10 comprising the SCR catalyst can be placed on a support 14 with an opposite support 15 having an oxidation layer 12 comprising the oxidation catalyst on the support, as shown in Figure IL.
Preferably, the oxidation layer 12 and the SCR layer 10 are physically distinct and separate, but consecutive layers. The term "consecutive layers" is used to describe the relative positions of catalyst layers in the catalyst article with respect to the normal direction of exhaust gas flow through, past, and/or over the catalyst article, Under normal exhaust gas flow conditions, exhaust gas contacts and at least partially penetrates the second layer before contacting the first layer, arid subsequently returns through the second layer to exit the catalyst component.
Importantly, the 5CR catalyst is disposed over and/or upstream of the oxidation catalyst layer. The 5CR layer preferably covers the entire oxidation catalyst layer to prevent untreated secondary NOx formed via ammonia oxidation in the oxidation layer from exiting the system without contacting the SCR catalyst In another aspect of the invention, a method of manufacturing an ammonia slip catalyst comprises: (a) forming an layer on a substrate by applying onto the substrate a washcoat comprising an 5CR catalyst and an oxidation catalyst comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), where the washcoat does not comprise a platinum group metal, (b) drying the washcoat on the substrate, and (c) calcining the washcoat on the substrate. Each of the at least one first metal and second metal can may be present in the oxidation layer washcoat in the form of a salt, preferably a nitrate, sulfate, chloride or an acetate, an oxide, or a compound containing the metal where the compound containing the metal forms an oxide of the metal upon calcination. Preferably the first metal is Cu and the second metal is Mn, The washcoat can further comprise an oxide support material comprising alumina (Al203), silica (Si02) zirconia (Zr02), ceria (CeO2), and titania (Ti02), or mixtures thereof The washcoat can further comprise other oxide materials such as perovskites, nickel oxide (NiO), manganese dioxide (Mn02), praseodymium (Ill) oxide (Pr203). The oxide support material can include composite oxides or mixed oxides of two or more thereof (such as CeZrO, mixed oxides, TiZrO, mixed oxides, TiSiO2 mixed oxides, and TiAlO oxides where xis dependent on the ratio of Ti02 to A1203.). The oxide support material, in addition for serving as a support, may also serve as a binder. For example, alumina may act as both a support and a binder in an alumina and CeZrO2 mixed oxide. The oxidation layer washcoat can comprise an oxide support material comprising one or more of a stabilized alumina, silica, zirconia, ceria, and titania. Stabilizers may be selected from zirconium (Zr), lanthanum (La), aluminum (Al), yttrium (Y), praseodymium (Pr), neodymium (Nd), an oxide thereof, a composite oxide or mixed oxide of any two or more thereof, or at least one alkaline earth metal, e.g., barium (Ba). If each oxide support material is stabilized, the stabilizers may be the same or different. The oxide support material can be A1203 and CeO2. Where the oxide support material is A1203, it may be alpha-, gamma-, beta-, delta-, or theta-A1203, for example. The support material can be in the form of mixed oxides or stabilized mixed oxides. The metal oxides in mixed oxides are present in the form of a single phase, while stabilized mixed oxides are present in two phases. Preferably the washcoat comprises Cu and Mn, as the first and second metals, alumina and either Ce02/Zr02 or a Zr-stabilized CeO2 mixed oxide, The Zr-stabilized CeO2 mixed oxide can comprise Ce and Zr in about a 1: mole ratio, The oxide support material can be La-stabilized Al203 and Zr-stabilized CeO2. The oxide support material in the oxidation washcoat can comprise about 20 mole ?/ La-stabilized A1203 and about 80 mole % Zr-stabilized CeO2. The washcoat can comprise a molecular sieve selected from the group consisting of MOR (mordenite), FER (ferrierite), FATJ (zeolite Y), IVIFI (ZSM-5), BEA (beta zeolites), Fe-BRA, CHA (Chabazite), Cu-CHA and a silicoaluminophosphate comprising a structurally similar framework. The washcoat can preferably comprise a Fe-BEA or a Cu-CHA zeolite catalyst or a silicoaluminophosphate comprising a structurally similar framework, Preferably, the washcoat can comprise a Fe-BEA or a Cu-CHA zeolite catalyst or a silicoaluminophosphate comprising a stmcturally similar framework and further comprises Cu and Mn, The oxidation catalyst in the washcoat can be present at a concentration of 0.3 to 1,5 g per in3, based on the total weight of metal in the catalyst. The SCR catalyst in the washcoat can be present at a concentration of 0.5 to 2.5 g per in3, based on the total weight of metal in the catalyst. The ratio of the amount of SCR catalyst in the washcoat (in g per in3) to the amount of oxidation catalyst in the washcoat (in g per in3) can be between 0.3 and 8.3.
In another aspect of the invention, a method of manufacturing a dual layer ammonia slip catalyst comprises: (a) forming an oxidation layer on a substrate by applying onto a substrate an oxidation layer washcoat comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), where the washcoat does not comprise a platinum group metal, (b) drying the oxidation layer washcoat on the substrate, (c) calcining the oxidation layer washcoat on the substrate; (d) forming an 5CR layer positioned over the oxidation layer by applying an SCR layer washcoat comprising a molecular sieve, preferably having a substituted metal and/or an extra framework metal, or a vanadium/titania over the calcined oxidation layer formed in step (c), (e) drying the SCR layer washcoat on the calcined oxidation layer on a substrate, and (f) calcining the 5CR layer washcoat on the oxidation layer washcoat on the substrate. Each of the at least one first metal and second metal can may be present in the oxidation layer washcoat in the form of a salt, preferably a nitrate, sulfate, chloride or an acetate, an oxide, or a compound containing the metal where the compound containing the metal forms an oxide of the metal upon calcination, Preferably the first metal is Cu and the second metal is Mn, The oxidation layer washcoat can further comprise an oxide support material comprising alumina (A1203), silica (Si02) zirconia (Zr02), ceria (CeO2), and titania (Ti02), or mixtures thereof. The oxide support material can further comprise other oxide materials such as perovskites, nickel oxide (NiO), manganese dioxide (Mn02), praseodymium (III) oxide (Pr203). The oxide support material can include composite oxides or mixed oxides of two or more thereof (such as CeZrO2 mixed oxides, TiZrO2 mixed oxides, TiSiO2 mixed oxides, and TiAlO oxides where x is dependent on the ratio of TiO, to A1203.), The oxide support material, in addition for serving as a support may also serve as a binder. For example, alumina may act as both a support and a binder in an alumina and CeZrO2 mixed oxide. The oxidation layer washcoat can comprise an oxide support material comprising one or more of a stabilized alumina, silica, zirconia, ceria, and titania, Stabilizers may be selected from zirconium (Zr), lanthanum (La), aluminum (Al), yttrium (Y), praseodymium (Pr), neodymium (Nd), an oxide thereof, a composite oxide or mixed oxide of any two or more thereof or at least one alkaline earth metal, eg,, barium (Ba), If each oxide support material is stabilized, the stabilizers may be the same or different.
The oxide support material can be A1203 and CeO2, Where the oxide support material is A1203, it may be alpha-, gamma-, beta-, delta-, or theta-A1203, for example, The support material can be in the form of mixed oxides or stabilized mixed oxides. The metal oxides in mixed oxides are present in the form of a single phase, while stabilized mixed oxides are present in two phases. PreferaNy the oxidation layer washcoat comprises Cu and rvlli, as the first and second metals, alumina and either Ce02/Zr02 or a Zr-stabilized CeO2 mixed oxide, The Zr-stabilized CeO2 mixed oxide can comprise Ce and Zr in about a 1:1 mole ratio, The oxide support material can be La-stabilized A1203 and Zr-stabilized CeO2, The oxide support material in the oxidation washcoat can comprise about 20 mole % La-stabilized A1203 and about 80 mole % Zr-stabilized CeO2. The SCR layer washcoat can comprise a molecular sieve selected from the group consisting of MOR (mordenite), FER (ferrierite, FAU (zeolite Y), MFI (ZSM-5), BEA (beta zeolites), Fe-BEA, CHA (Chabazite), Cu-Cl-IA and a silicoaluminophosphate comprising a structurally similar framework. The 5CR layer washcoat can preferably comprise a Fe-BEA or a Cu-CHA zeolite catalyst or a silicoaluminophosphate comprising a structurally similar framework. Preferably, the 5CR layer washcoat can comprise a Fe-BEA or a Cu-CHA zeolite catalyst and the oxidation layer washcoat can comprise Cu and Mn, The catalyst in the oxidation layer washcoat can be present at a concentration ofo.3 to 1.5 g per in3, based on the total weight of metal in the catalyst. The catalyst in the 5CR layer washcoat can be present at a concentration of 0.5 to 2.5 g per in3, based on the total weight of metal in the catalyst. The ratio of the amount of catalyst in the SCR layer washcoat (in g per in3) to the amount of catalyst in the oxidation layer washcoat (in g per in3) can be between 0.3 and 8.3, based on the total weight of metal in each layer of the catalyst.
In yet another aspect of the invention, a method of manufacturing a dual layer ammonia slip catalyst comprises: (a) forming an oxidation layer on a substrate by applying onto a substrate an oxidation layer washcoat comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), is cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), where the washcoat does not comprise a platinum group metal, (b) forming a dried oxidation layer washcoat on the substrate, (c) forming an SCR layer positioned over the oxidation layer by applying an 5CR layer washcoat comprising a molecular sieve, preferably having a substituted metal and/or an extra framework metal, or a vanadium/titania over the dried oxidation layer formed in step (b), (d) drying the SCR layer washcoat on the calcined oxidation layer on a substrate, and (e) calcining the SCR layer washcoat on the calcined oxidation layer washcoat on the substrate. Each of the at least one first metal and second metal can may be present in the oxidation layer washcoat in the form of a salt, preferably a nitrate, sulfate, chloride or an acetate, an oxide, or a compound containing the metal where the compound containing the metal fonns an oxide of the metal upon calcination, Preferably the first metal is Cu and the second metal is Mn, The oxidation layer washcoat can frirther comprise an oxide support material comprising alumina (A1203), silica (Si02) zirconia (Zr02), ceria (CeO2), arid titania (Ti02), or mixtures thereof The oxide support material can further comprise other oxide materials such as perovskites, nickel oxide (NiO), manganese dioxide (Mn02), praseodymium (111) oxide (Pr203). The oxide support material can include composite oxides or mixed oxides of two or more thereof (such as CeZrO mixed oxides, TiZrO2 mixed oxides, TiSiO2 mixed oxides, and TiAlO oxides where xis dependent on the ratio of hO2 to A1203.). The oxide support material, in addition for serving as a support may also serve as a binder, For example, alumina may act as both a support and a binder in an alumina and CeZrO2 mixed oxide. The oxidation layer washcoat can comprise an oxide support material comprising one or more of a stabilized alumina, silica, zirconia, ceria, and titania, Stabilizers maybe selected from zirconium (Zr), lanthanum (La), aluminum (Al), yttrium (Y), praseodymium (Pr), neodymium (Nd), an oxide thereof, a composite oxide or mixed oxide of any two or more thereof, or at least one alkaline earth metal, e.g., barium (Ba). If each oxide support material is stabilized, the stabilizers may be the same or different. The oxide support material ca be A1203 and CeO2. Where the oxide support material is A1203, it may be alpha-, gamma-, beta-, delta-, or theta-A1203, for example. The support material can be in the form of mixed oxides or stabilized mixed oxides, The metal oxides in mixed oxides are present in the form of a single phase, while stabilized mixed oxides are present in two phases. Preferably the oxidation layer washcoat comprises Cu and Mn, as the first and second metals, alumina and either Ce02/ZrO or a Zr-stabilized CeO2 mixed oxide, The Zr-stabilized CeO2 mixed oxide can comprise Ce and Zr in about a 1:1 mole ratio, The oxide support material cai be La-stabilized A1203 and Zr-stabilized CeO2, The oxide support material in the oxidation layer washcoat can comprise about 20 mole % La-stabilized A1203 md about 80 mole ?7'b Zr-stabilized CeO2, The SCR layer washcoat ca comprise a molecular sieve selected from the group consisting of MOR (mordenite), FER (ferrierite), FAU (zeolite Y), MR (ZSM-5), BEA (beta zeolites), Fe-BEA, Cl-IA (Chabazite), Cu-CF-IA and a silicoaluminophosphate comprising a structurally similar framework. The SCR layer washcoat can preferably comprise a Fe-BEA or a Cu-CHA zeolite catalyst. Preferably, the SCR layer washcoat can comprise a Fe-BEA or a Cu-CHA zeolite catalyst and the oxidation layer washcoat can comprise Cu and Mn. The catalyst in the oxidation ayer washcoat can be present at a concentration of 0.3 to 1.5 g per in3, based on the total weight of metal in the catalyst. The cata'yst in the SCR layer washcoat can be present at a concentration ofO.5 to 2.5 g per in3, based on the total weight ofmeta in the catalyst. The ratio of the amount of catalyst in the SCR layer washcoat (in g per in3) to the amount of catalyst in the oxidation layer washcoat (in g per in3) can be between 0.3 and 83, based on the total weight of metal in each layer of the catalyst.
In still another aspect of the invention, a method for reducing the concentration of ammonia in a flue gas stream generated by a combustion source comprises contacting a flue gas stream comprising ammonia with either: (1) an ammonia slip catalyst comprising a mixture of an SCR catalyst, as described above, and an oxidation catalyst comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), is cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group con si sting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and the ammonia slip catalyst does not comprise a platinum group metal; or (2) a dual layer ammonia slip catalyst comprising an SCR layer comprising a molecular sieve, preferably having a substituted metal and/or an extra framework metal, or a vanadium/titania and the oxidation layer comprising an oxidation catalyst comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), is cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), and the second layer does not comprise a platinum group metal. Each of the at least one first metal and second metal can be in the form of a salt, preferably a nitrate, sulfate, chloride or an acetate, an oxide, or a compound containing the metal where the compound containing the metal forms an oxide of the metal upon calcination, Preferably the first metal is Cu and the second metal is Mn, The second layer can frirther comprise an oxide support material comprising alumina (A1203), silica (Si02) zirconia (Zr02), ceria (CeO2), and titania (Ti02), or mixtures thereof The oxide support material can further comprise other oxide materials such as perovskites, nickel oxide (NiO), manganese dioxide (Mn02), praseodymium (Ill) oxide (Pr203). The oxide support material can include composite oxides or mixed oxides of two or more thereof (such as CeZrO2 mixed oxides, TiZrO2 mixed oxides, TiSiO7 mixed oxides, and TiAIO oxides where x is dependent on the ratio of Ti02 to A1203,). The oxide support material, in addition for serving as a support may also serve as a binder. For example, alumina may act as both a support and a binder in an alumina and CeZrO2 mixed oxide. The second layer can comprise an oxide support material comprising one or more of a stabilized alumina, silica, zirconia, ceria, and titania. Stabilizers may be selected from zirconium (Zr), lanthanum (La), aluminum (Al), yttrium (Y), praseodymium (Pr), neodymium (Nd), an oxide thereof a composite oxide or mixed oxide of any two or more thereof or at least one alkaline earth metal, e.g., barium (Ba). if each oxide support material is stabilized, the stabilizers may be the same or different. The oxide support material can be A120, and CeO2. Where the oxide support material is A120,, it may be alpha-, gamma-, beta-, delta-, or theta-A120,, for example. The support material can be in the form of mixed oxides or stabilized mixed oxides, The metal oxides in mixed oxides are present in the form of a single phase, while stabilized mixed oxides are present in two phases.
Preferably the second layer comprises Cu and Mn, as the first and second metals, alumina and either Ce02/ZrO' or a Zr-stabilized CeO2 mixed oxide. The Zr-stabilized CeO2 mixed oxide can comprise Ce and Zr in about a 1:1 mole ratio, The oxide support material can be La-stabilized A120, and Zr-stabilized CeO2. The oxide support material in the second layer can comprise about 20 mole % La-stabilized A120, and about 80 mole ?/ Zr-stabilized CeO2, The first layer can comprise a zeolite selected from the group consisting of MOR (mordenite), FER (ferrierite), FAU (zeolite Y), MFI (ZSM-5), BEA (beta zeolites), Fe-BEA, CHA (Chabazite) and Cu-CHA, or a silicoaluminophosphate comprising a structurally similar framework. The first layer washcoat can preferably comprise a Fe-BEA or a Cu-CHA zeolite catalyst, Preferably, the first layer can comprise a Fe-BEA or a Cu-CHA zeolite catalyst and the second layer can comprise Cu and Mn, When the second layer comprises Cu and Mn, the conversion of NH3 to N2 can be more selective that when a PGM based second layer is used, The catalyst in the second layer can be present at a concentration of 0,3 to 1,5 g per in3, based on the total weight of metal in the catalyst. The catalyst in the first layer can be present at a concentration of 0,5 to 2.5 g per in', based on the total weight of metal in the catalyst. The ratio of the amount of catalyst in the first layer (in g per in') to the amount of catalyst in the second layer (in g per in') can be between 0,3 and 8,3, based on the total weight of metal in each layer of the catalyst.
The flue gas can contact the dual layer ammonia slip catalyst at temperatures from about 3000 to about 500°C, The use of the oxidation layer comprising the oxidation catalysts comprising at least one first metal and the at least one second metal from the groups of metal listed above eliminates the need for the use of platinum group metals (PGM) in the composition. This will significantly reduce the cost of the composite catalyst.
EXAIVIPLES
Although the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may be made in the details within the scope and range of equivalents of the claims and without departing from the invention.
Three catalysts, each having a first layer and a second layer, were prepared, Each of the catalysts had an 5CR layer comprising a Fe beta zeolite 5CR catalyst. Example 1 contained Cu, Mn, Ce02/Zr02, and alumina in an oxidation layer. Comparative Example 1 contained S gift3 Pt in an oxidation layer and Comparative Example 2 contained 20 gIft3 Pd in an oxidation layer. In prior art, layered ammonia slip catalysts with a zeolite overlayer contained an underlayer with precious metals components here used to oxidize the incoming ammonia.
Example 1: Base Metal Ammonia Slip Catalyst (ASC) The oxidation layer was prepared by mixing the required amount of unmilled CeO2IZrO2 and deionized water to form a slurry. The CeO2IZrO2 slurry was then milled to provide a dSO of i.5-2.5m. The milled CeO2IZrO2 was mixed with a slurry of alumina slurry, then the required amount of manganese acetate crystals were added and the mixture was mixed for 4 hours. The required amount of copper nitrate was added and the slurry was mixed for 30 minutes. Actigum was then added slowly to thicken the slurry. The slurry was coated onto a 230 cpsi cordierite substrate, dried then calcined at 500°C for about 3 hours.
This resulted in a Cu loading of 375 gIft3, a Mn loading of 600 gIft3, an alumina loading of 0.55 gun3, and a CeO2IZrO2 loading of 2.2 gun3.
The 5CR layer was prepared by adding a BRA zeolite to a solution of iron nitrate and mixing the slurry with a dispersion mixer, A slurry of milled alumina having a d50 of 3.4-4.2 pm and deionized water was added to the slurry containing the BRA zeolite and the resulting slurry was mixed, The required amount of binder, Disperal, was added to the slurry and the slurry was mixed before coating the oxidation layers.
The slurry was coated onto a 230 cpsi cordierite substrate, dried then calcined at 500°C for about 3 hours. This resulted in an iron loading of 190 g/&, a BEA zeolite loading of 1.90 gun3 and an alumina loading of 0.16 gun3.
Comparative Example 1: Pt ASC The first catalyst layer was prepared by mixing the required amount of an alumina washcoat having a d50 of about 3.4 -4.2 im and deionized water using a high shear mixer to for a slurry. Succinic acid was slowly added to the alumina slurry until the final concentration was about 100 gIft3, and then the admixture was continuously stirred for at least 30 minutes. The required amount of platinum nitrate was added and the resulting admixture was stirred for an additional 60 minutes, Hydroxyethyl cellulose (Natrasol) was added and the slurry was mixed for 24 hours. The slurry was coated onto a 230 cpsi cordierite substrate, dried then calcined at 500°C for about 3 hours. This resulted in aPt loading of S gIft3 and an alumina loading of 0.35g1in3.
The SCR layer was prepared and coated over the oxidation layers as described above
in Example 1.
Comparative Example 2: Pd ASC The first catalyst layer was prepared by mixing the required amount of an alumina washcoat having a d50 of about 3.4 -4.2 m and deionized water using a high shear mixer to for a slurry. Succinic acid was slowly added to the alumina slurry until the final concentration was about 100 gIft3, and then the admixture was continuously stirred for at least minutes. The required amount of palladium nitrate was added and the resulting admixture was stirred for an additional 60 minutes, Hydroxyethyl cellulose (Natrasol) was added and the slurry was mixed for 24 hours, The slurry was coated onto a 230 cpsi cordierite substrate, dried then calcined at 500°C for about 3 hours. This resulted in a Pd loading of 20 g/ft3 and an alumina loading of 0.35g/in3.
The SCR layer was prepared and coated over the oxidation layers as described above
in Example 1.
Evaluation of the catalytic activity of the catalysts used a two zone system with an SCR catalyst in the front zone followed by different ammonia slip catalysts in the rear zone.
The main constituents of the gas feed contained a mixture of 40 ppm NH3 and 3oppm NOx, with the remaining gas composition consisting of 02, H20, C02, propane, propene, and N2.
The steady state testing was done between 250°C-500°C at a system GHSV of 20,000 (40,000 through each zone), Fig. 2 shows that the catalyst of Example 1, a catalyst of the invention, was more effective than the catalyst of Comparative Example 2, which contained 20 gIft3 Pd, in the conversion of NH3 from 250 °C to 500 °C. The catalyst of Example 1 was especially more effective that the catalyst of Comparative Example 2 at temperatures from about 250 °C to about 350 °C. The catalyst of Example 1 was less effective in the conversion of NH3 than the catalyst of Comparative Example I, which contained 5 g/ft3 Pt, over this temperature range.
Fig. 3 shows that the catalyst of Example 1, a catalyst of the invention, was more effective than the catalyst of Comparative Example 2, which contained 20 gIft3 Pd, in converting CO in the range from about 250 °C to about 300 °C. The catalyst of Example 1, a catalyst of the invention, was slightly less effective in converting CO than the catalysts of Comparative Examples 1 and 2 at temperatures from about 350 °C to about 500 °C.
Fig. 4 shows that the catalyst of Example, a catalyst of the invention, was more effective than the catalysts of Comparative Examples 1 and 2, which contained S gIft3 Pt and gIft3 Pd, respectively, in lowering the total amounts of NH3 and NOx leaving the system at temperatures from about 300 °C to about 500 °C. At temperatures of about 400 °C to about 500 °C, the of Example I produced NH3 and NOx at levels that were about 60% to about 75% of those produced by Comparative Example I, which contained S g/ft3 Pt.

Claims (2)

  1. CLAIMS: 1, An ammonia slip catalyst comprising an SCR catalyst and an oxidation catalyst, the SCR catalyst comprising a molecular sieve or a vanadium/titania SCR catalyst and the oxidation catalyst comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), where the ammonia slip catalyst does not comprise a platinum group metal.
  2. 2. A dual layer ammonia slip catalyst comprising a SCR catalyst hyer, wherein the SCR cata'yst in the SCR catalyst layer is the SCR catalyst of claim 1 and an oxidation catalyst layer, wherein the oxidation catalyst in the oxidation catalyst layer is the oxidation catalyst of claim 1, wherein at least the oxidation layer is positioned proximal to a substrate.
    3, The dual layer ammonia slip catalyst according to claim 2, wherein the oxidation layer further comprises an oxide support material comprising one or more of alumina, silica, zirconia, ceria, and titania, 4, The dual layer ammonia slip catalyst according to claim 2 or 3, wherein the oxidation layer comprises a oxide support material comprising one or more of a stabilized a'umina, silica, zirconia, ceria, and titania.5. The dual layer ammonia slip catalyst according to claim 2, 3 or 4, wherein the oxidation layer comprises Cu and Mn.6. The dual layer ammonia slip catalyst according to any of claims 1 to 5, wherein the oxidation layer further comprises alumina and either a Ce02/Zr02 mixed oxide or a Zr-stabilized CeO2 mixed oxide.7. The dual layer ammonia slip catalyst according to claim 6, wherein the Zr-stabilized CeO7 mixed oxide comprises Ce and Zr present in about a 1: 1 mole ratio.8. The dual layer ammonia slip catalyst according to any of claims 1 to 7, wherein the oxide support material comprises about 20 mole % La-stabilized A1202 and about 80 mole % Zr-stabilized CeO,.9. The dual layer ammonia slip catalyst according to claim 2, wherein the molecular sieve is selected from the group consisting of MOR (mordenite), FER (ferrierite), FAU (zeolite Y), MFI (ZSM-5), BEA (beta zeolites), Fe-BEA, CHA (Chabazite), Cu-CHA and a silicoaluminophosphate comprising a structurally similar framework.10. The dual layer ammonia slip catalyst according to claim 9, wherein the SCR layer comprises a Fe-BEA or a Cu-CHA zeolite catalyst or a silicoaluminophosphate comprising a structurally similar framework.11. The dual layer ammonia slip catalyst according to claim 10, wherein the SCR layer comprises a Fe-BEA or a Cu-Cl-IA zeolite or a silicoaluminophosphate comprising a structurally similar framework catalyst and the oxidation layer comprises Cu and Mn.12. The dual layer ammonia slip catalyst according to claim 2, wherein, when the oxidation layer comprises Cu and Mn, the conversion of NH, to N2 is more selective that when a PGM based oxidation layer is used.13. The dual layer ammonia slip catalyst according to claim 2, wherein the catalyst in the oxidation layer is present at a concentration of 0.3 to 1.5 g per in3, based on the total weight of metal in the catalyst.14. The dual layer ammonia slip catalyst according to claim 2, wherein the catalyst in the SCR layer is present at a concentration of 0.5 to 2.5 g per in3, based on the total weight of metal in the catalyst.15. The dual layer ammonia slip catalyst according to claim 2, wherein the ratio of the amount of catalyst in the SCR layer (in g per in3) to the amount of catalyst in the oxidation layer (in g per in3) is between 0.3 and 8.3, based on the total weight of metal in each layer of the catalyst.16. The dual layer ammonia slip catalyst according to claim 2, wherein the 5CR layer is positioned as an overlayer over the oxidation catalyst or the oxidation layer is located sequential to the SCR layer.17. A method of preparing the ammonia slip catalyst according to claim 1, the method comprising: (a) forming an layer on a substrate by applying onto the substrate a washcoat comprising an SCR catalyst and an oxidation catalyst comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), where the washcoat does not comprise a platinum group metal, (b) drying the washcoat on the substrate, and (c) calcining the washcoat on the substrate.1 8. The method according to claim I 7, wherein the washcoat further comprises an oxide support material comprising one or more of alumina, silica, zirconia, ceria, and titania.19. The method according to claim 17 or 18, wherein the washcoat comprises an oxide support material comprising one or more of a stabilized alumina, silica, zirconia, ceria, and titania.20. The method according to claim 17, 18 or 19, wherein the washcoat comprises Cu and Mn.2!. The method according to claim 19, wherein the washcoat comprises alumina and either a Ce02/Zr02 mixed oxide or a Zr-stabilized CeO2 mixed oxide.22. The method according to claim 21, wherein the Zr-stabilized CeO2 mixed oxide comprises Ce and Zr present in about a 1: 1 mole ratio.23. The method according to claim 19, wherein the oxide support material comprises about 20 mole % La-stabilized A1203 and about 80 mole % Zr-stabilized CeO2, 24. The method according to any of claims 17 to 23, wherein the SCR catalyst comprises a molecular sieve selected from the group consisting of MOR (mordenite), FER (ferrierite), FAU (zeolite Y), MET (ZSM-5), BEA (beta zeolites), Fe-BEA, CHA (Chabazite), Cu-CHA and a silicoaluminophosphate comprising a structurally similar framework.25. The method according to any of claims 17 to 24, wherein the SCR layer washcoat comprises a Fe-BEA or a Cu-CHA zeolite catalyst or a silicoaluminophosphate comprising a structurally similar framework.26. The method according to any of claims 17 to 25, wherein the SCR layer washcoat comprises a Fe-BEA or a Cu-CHA zeolite or a silicoaluminophosphate comprising a structurally similar framework and the oxidation layer comprises Cu and Mn.27. The method according to any of claims 17 to 26, wherein the catalyst in the oxidation layer washcoat is present at a concentration of 0.3 to 1.5 g per in3, based on the total weight of metal in the catalyst.28. The method according to any of claims 17 to 26, wherein the catalyst in the SCR layer washcoat is present at a concentration of 0.5 to 2.5 g per in3, based on the total weight of metal in the catalyst.29. The method according to any of claims 17 to 26, wherein the ratio of the amount of catalyst in the SCR layer washcoat (in g per in3) to the amount of catalyst in the oxidation layer washcoat (in g per in3) is between 0.3 and 8.3, based on the total weight of metal in each layer of the catalyst.30. A method of preparing the dual layer ammonia slip catalyst according to any of claims 2 to 16, the method comprising: (a) forming an oxidation layer on a substrate by applying onto a substrate an oxidation layer washcoat comprising at least one first metal selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), and chromium (Cr) and at least one second metal selected from the group consisting of neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), and strontium (Sr), where the washcoat does not comprise a platinum group metal, (b) drying the oxidation layer washcoat on the substrate, (c) calcining the oxidation layer washcoat on the substrate; (d) forming an SCR layer positioned over the oxidation layer by applying an SCR layer washcoat comprising a molecular sieve or a vanadium/titania over the calcined oxidation layer formed in step (c), (e) drying the SCR layer washcoat on the calcined oxidation layer on a substrate, and (f) calcining the SCR layer washcoat on the oxidation layer washcoat on the substrate.3!. The method according to claim 30, wherein the oxidation layer washcoat further comprises an oxide support material comprising one or more of alumina, silica, zirconia, ceria, and titania.32. The method according to claim 30 or 31, wherein the oxidation layer washcoat comprises an oxide support material comprising one or more of a stabilized alumina, silica, zirconia, ceria, and titania.33. The method according to claim 30, 31 or 32, wherein the oxidation sayer washcoat comprises Cu and Mn.34. The method according to claim 30, 31, 32 or 33, wherein the oxidation layer washcoat further comprises alumina and either a Ce02/Zr02 mixed oxide or a Zr-stabilized CeO2 mixed oxide.35. The method according to claim 34, wherein the Zr-stabilized CeO2 mixed oxide comprises Ce and Zr present in about a 1: 1 mole ratio.36. The method according to claim 32, wherein the oxide support material comprises about 20 mole % La-stabilized A1201 and about 80 mole % Zr-stabilized CeO2.37. The method according to any of claims 30 to 36, wherein the molecular sieve is selected from the group consisting of MOR (mordenite), FER (ferrierite), FAU (zeolite Y), MFT (ZSM-5), BEA (beta zeolites), Fe-BEA, CHA (Chabazite), Cu-CHA and a silicoaluminophosphate comprising a structurally similar framework, 38. The method according to any of claims 30 to 37, wherein the SCR layer washcoat comprises a Fe-BEA or a Cu-CHA zeolite catalyst or a silicoaluminophosphate comprising a structurally similar framework.39. The method according to any of claims 30 to 38, wherein the SCR layer washcoat comprises a Fe-BEA or a Cu-CHA zeolite catalyst or a silicoaluminophosphate comprising a structurally similar framework and the oxidation layer comprises Cu and Mn.40. The method according to any of claims 30 to 39, wherein the catalyst in the oxidation layer washcoat is present at a concentration of 0.3 to 1 5 g per in3, based on the total weight of metal in the catalyst.4!. The method according to any of claims 30 to 40, wherein the catalyst in the SCR layer washcoat is present at a concentration of 0.5 to 2.5 g per in3, based on the total weight of metal in the catalyst.42. The method according to any of claims 30 to 41, wherein the ratio of the amount of catalyst in the SCR layer washcoat (in g per in3) to the amount of catalyst in the oxidation layer washcoat (in g per in3) is between 0.3 and 8.3, based on the total weight of metal in each layer of the catalyst.43. A method for reducing the concentration of ammonia in a flue gas stream generated by a combustion source, the method comprising contacting a flue gas stream containing ammonia with an ammonia slip catalyst according to any of claims I to 1 6, 44. The method according to claim 43, wherein the support is in the form of a honeycomb or plate configuration.45. The method according to claim 43 or 44, wherein the flue gas stream contacts the dual layer ammonia slip catalyst at temperatures from about 200° to about 450°C.46. The method according to claim 43, 44 or 45, wherein the flue gases are obtained from the combustion of coal, natural gas or oil.
GB1509439.4A 2014-06-04 2015-06-01 Non-PGM ammonia slip catalyst Active GB2529926B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US201462007608P 2014-06-04 2014-06-04

Publications (3)

Publication Number Publication Date
GB201509439D0 GB201509439D0 (en) 2015-07-15
GB2529926A true GB2529926A (en) 2016-03-09
GB2529926B GB2529926B (en) 2017-04-26

Family

ID=53677565

Family Applications (1)

Application Number Title Priority Date Filing Date
GB1509439.4A Active GB2529926B (en) 2014-06-04 2015-06-01 Non-PGM ammonia slip catalyst

Country Status (11)

Country Link
US (1) US11198094B2 (en)
EP (2) EP3151960B1 (en)
JP (2) JP7023046B2 (en)
KR (2) KR102458546B1 (en)
CN (2) CN106794420B (en)
BR (1) BR112016028146A8 (en)
DE (1) DE102015209987A1 (en)
DK (1) DK3151960T3 (en)
GB (1) GB2529926B (en)
RU (1) RU2715701C2 (en)
WO (1) WO2015187550A2 (en)

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015212356A1 (en) * 2014-07-02 2016-03-03 Johnson Matthey Public Limited Company Perovskite with a topcoat SCR component as an ammonia oxidation catalyst and exhaust gas purification system for diesel engines
EP3221032B1 (en) * 2014-11-19 2020-09-09 Johnson Matthey Public Limited Company Combining scr with pna for low temperature emission control
WO2016115451A1 (en) * 2015-01-16 2016-07-21 Basf Corporation Nano-sized functional binder
BR112018015842B1 (en) * 2016-02-03 2022-10-11 Basf Corporation CATALYST COMPOSITION, METHODS FOR PRODUCING A CATALYST AND FOR REDUCING THE NOX LEVEL IN AN EXHAUST GAS, CATALYST ARTICLE AND EMISSION TREATMENT SYSTEM
WO2018012566A1 (en) * 2016-07-14 2018-01-18 イビデン株式会社 Honeycomb structure and production method for said honeycomb structure
US10994267B2 (en) 2016-07-14 2021-05-04 Umicore Ag & Co. Kg Vanadium trapping SCR system
MX2019001500A (en) * 2016-08-05 2019-07-22 Basf Corp Selective catalytic reduction articles and systems.
US11065611B2 (en) 2016-10-05 2021-07-20 Monsanto Technology Llc Emission control during catalyst regeneration
US10047651B2 (en) * 2016-12-06 2018-08-14 GM Global Technology Operations LLC Soot oxidation catalyst materials and selective catalytic reduction filter devices incorporating the same
JP6693406B2 (en) * 2016-12-20 2020-05-13 三菱自動車工業株式会社 Exhaust gas purification device
CN106807390A (en) * 2017-03-27 2017-06-09 西安热工研究院有限公司 A kind of W types flame boiler NOxThe method and its SCO of ultra-clean discharge remove ammonia catalyst
GB201705158D0 (en) * 2017-03-30 2017-05-17 Johnson Matthey Plc Catalyst article for use in a emission treatment system
GB2561834A (en) * 2017-04-24 2018-10-31 Johnson Matthey Plc Passive NOx adsorber
DE102017006059A1 (en) * 2017-06-27 2018-12-27 Daimler Ag Exhaust system for a motor vehicle
JP2019035340A (en) * 2017-08-10 2019-03-07 いすゞ自動車株式会社 Exhaust emission control system
EP3727685A4 (en) * 2018-01-03 2021-08-25 BASF Corporation Surface-treated silicoaluminophosphate molecular sieve
JP6637643B1 (en) * 2018-03-28 2020-01-29 三井金属鉱業株式会社 Exhaust gas purification catalyst
CN108579730A (en) * 2018-03-29 2018-09-28 上海电力学院 A kind of catalyst and its preparation method and application for flue gas demercuration
GB201805312D0 (en) * 2018-03-29 2018-05-16 Johnson Matthey Plc Catalyst article for use in emission treatment system
CN108435161A (en) * 2018-03-29 2018-08-24 上海电力学院 A kind of catalyst and its preparation method and application for flue gas demercuration
JP7342031B2 (en) * 2018-04-23 2023-09-11 ビーエーエスエフ コーポレーション Selective catalytic reduction catalyst for diesel engine exhaust gas treatment
CN112638526B (en) * 2018-08-22 2024-01-05 巴斯夫公司 Advanced NOx reduction catalyst
JPWO2020149315A1 (en) * 2019-01-15 2021-12-02 日立造船株式会社 Manufacturing method of exhaust gas purification catalyst and exhaust gas purification catalyst
CN110479299B (en) * 2019-09-06 2021-09-28 山东科技大学 Low-temperature flue gas denitration catalyst and preparation method thereof
EP3957386A1 (en) * 2020-08-18 2022-02-23 UMICORE AG & Co. KG Catalyst for reducing ammonia emissions
CN114247450A (en) * 2020-12-28 2022-03-29 中化学科学技术研究有限公司 Catalytic composition, catalyst layer, catalytic device and gas treatment system
CN113069917B (en) * 2021-04-20 2021-12-28 南京科宜环保科技有限公司 Denitration catalyst module box with ammonia adsorption function and preparation method thereof
US11883805B2 (en) * 2021-05-12 2024-01-30 Johnson Matthey Public Limited Company Catalytic composition
CN113842921B (en) * 2021-10-27 2023-11-24 合肥神舟催化净化器股份有限公司 Ammonia oxidation catalyst for diesel engine based on ternary metal oxide, preparation method and application
KR20240021345A (en) * 2022-08-09 2024-02-19 주식회사 에코프로에이치엔 Emission treatment catalyst comprising zeolite and metal oxide
CN115555039B (en) * 2022-09-23 2023-12-19 无锡威孚环保催化剂有限公司 Non-noble metal DPF catalyst with good sulfur resistance and preparation method thereof
CN115920883A (en) * 2022-11-29 2023-04-07 东风商用车有限公司 Has regeneration performance and reduces N 2 O-forming SCR catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080112870A1 (en) * 2006-11-15 2008-05-15 Ahmad Moini Catalysts for dual oxidation of ammonia and carbon monoxide with low to no nox formation
US20080167178A1 (en) * 2007-01-09 2008-07-10 Rajashekharam Malyala High temperature ammonia SCR catalyst and method of using the catalyst
US20090209408A1 (en) * 2006-10-18 2009-08-20 Cataler Corporation Exhaust Gas-Purifying Catalyst
US20100111796A1 (en) * 2008-11-03 2010-05-06 Basf Catalysts Llc Integrated SCR and AMOX Catalyst Systems
WO2012160391A1 (en) * 2011-05-25 2012-11-29 Johnson Matthey Plc Exhaust gas oxidation catalyst

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US112870A (en) * 1871-03-21 Improvement in combined potato-planters and diggers
US209408A (en) * 1878-10-29 Improvement in stair-carpet fasteners
US111796A (en) * 1871-02-14 Improvement in machines for bundling wood
US167178A (en) * 1875-08-31 Improvement in fire-escapes
JPS5523086B2 (en) 1973-03-26 1980-06-20
US4085193A (en) 1973-12-12 1978-04-18 Mitsubishi Petrochemical Co. Ltd. Catalytic process for reducing nitrogen oxides to nitrogen
JPH06304447A (en) * 1993-02-24 1994-11-01 Nippon Kayaku Co Ltd Decomposition of organic compound containing halogen and catalyst therefor
GB9615123D0 (en) * 1996-07-18 1996-09-04 Johnson Matthey Plc Three-way conversion catalysts and methods for the preparation therof
FR2793163B1 (en) * 1999-05-07 2001-08-10 Ecia Equip Composants Ind Auto PURIFICATION COMPOSITION WITH TREATMENT OF NOX FROM EXHAUST GASES OF AN INTERNAL COMBUSTION ENGINE
ATE297805T1 (en) * 2000-03-28 2005-07-15 Umicore Ag & Co Kg SINGLE LAYER HIGH PERFORMANCE CATALYST
JP2003157332A (en) 2001-11-21 2003-05-30 Oki Electric Ind Co Ltd Personal identification device, personal identification system, card issuing device and card issuing system
US20040126286A1 (en) * 2002-06-19 2004-07-01 Deruyter John C. Method and apparatus for reducing a nitrogen oxide
US7410626B2 (en) 2003-09-10 2008-08-12 Basf Catalysts Llc Layered ammonia oxidation catalyst
KR100549778B1 (en) 2003-09-27 2006-02-08 한국전력기술 주식회사 Vanadium/titania-based catalyst for the removal of nitrogen oxide at low temperature, its uses and method of removing nitrogen oxide using the same
EP1743696A4 (en) 2004-03-30 2009-09-02 Cataler Corp Exhaust gas clarification catalyst
US7393511B2 (en) 2005-02-16 2008-07-01 Basf Catalysts Llc Ammonia oxidation catalyst for the coal fired utilities
JP2008119651A (en) * 2006-11-15 2008-05-29 Mitsubishi Heavy Ind Ltd Catalyst for nitrogen oxide removal, and exhaust gas treating method
US7767175B2 (en) * 2007-01-09 2010-08-03 Catalytic Solutions, Inc. Ammonia SCR catalyst and method of using the catalyst
DE502007003465D1 (en) 2007-02-23 2010-05-27 Umicore Ag & Co Kg Catalytically activated diesel particulate filter with ammonia barrier effect
CA2679599C (en) * 2007-02-27 2016-01-05 Basf Catalysts Llc Bifunctional catalysts for selective ammonia oxidation
JP5192754B2 (en) 2007-08-22 2013-05-08 三菱重工業株式会社 Exhaust gas treatment catalyst and exhaust gas treatment system
US7727499B2 (en) * 2007-09-28 2010-06-01 Basf Catalysts Llc Ammonia oxidation catalyst for power utilities
US10792647B2 (en) * 2009-04-21 2020-10-06 Johnson Matthey Public Limited Company Base metal catalysts for the oxidation of carbon monoxide and volatile organic compounds
US8745970B2 (en) 2010-04-27 2014-06-10 GM Global Technology Operations LLC Ammonia slip catalyst diagnostic methods and systems
US20120042631A1 (en) 2010-08-20 2012-02-23 Gm Global Technology Operations, Inc. Catalyst materials for ammonia oxidation in lean-burn engine exhaust
EP2612706B1 (en) 2010-08-31 2019-10-30 Hitachi Zosen Corporation Process for producing hydrogen
US8661788B2 (en) * 2010-12-29 2014-03-04 GM Global Technology Operations LLC Exhaust aftertreatment systems that include an ammonia-SCR catalyst promoted with an oxygen storage material
CN102716753B (en) * 2012-06-08 2015-06-17 华电电力科学研究院 Catalyst for low-temperature selective catalytic reduction of nitric oxide and preparation method of catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090209408A1 (en) * 2006-10-18 2009-08-20 Cataler Corporation Exhaust Gas-Purifying Catalyst
US20080112870A1 (en) * 2006-11-15 2008-05-15 Ahmad Moini Catalysts for dual oxidation of ammonia and carbon monoxide with low to no nox formation
US20080167178A1 (en) * 2007-01-09 2008-07-10 Rajashekharam Malyala High temperature ammonia SCR catalyst and method of using the catalyst
US20100111796A1 (en) * 2008-11-03 2010-05-06 Basf Catalysts Llc Integrated SCR and AMOX Catalyst Systems
WO2012160391A1 (en) * 2011-05-25 2012-11-29 Johnson Matthey Plc Exhaust gas oxidation catalyst

Also Published As

Publication number Publication date
KR20170016400A (en) 2017-02-13
DE102015209987A1 (en) 2015-12-10
BR112016028146A2 (en) 2017-08-22
RU2016151305A (en) 2018-07-17
DK3151960T3 (en) 2022-03-28
WO2015187550A3 (en) 2016-01-28
KR102458546B1 (en) 2022-10-25
CN113559877A (en) 2021-10-29
WO2015187550A2 (en) 2015-12-10
RU2016151305A3 (en) 2018-11-16
EP3981509A1 (en) 2022-04-13
EP3151960A2 (en) 2017-04-12
GB2529926B (en) 2017-04-26
EP3151960B1 (en) 2022-02-16
KR102634796B1 (en) 2024-02-08
JP2020073267A (en) 2020-05-14
BR112016028146A8 (en) 2020-10-20
CN113559877B (en) 2024-03-12
RU2715701C2 (en) 2020-03-03
JP2017518874A (en) 2017-07-13
KR20220146696A (en) 2022-11-01
CN106794420B (en) 2021-07-27
JP7023046B2 (en) 2022-02-21
US11198094B2 (en) 2021-12-14
US20150352492A1 (en) 2015-12-10
CN106794420A (en) 2017-05-31
GB201509439D0 (en) 2015-07-15

Similar Documents

Publication Publication Date Title
US11198094B2 (en) Non-PGM ammonia slip catalyst
US10589261B2 (en) Exhaust system without a DOC having an ASC acting as a DOC in a system with an SCR catalyst before the ASC
US9649596B2 (en) Perovskite with an ovlerlayer SCR component as an ammonia oxidation catalyst and a system for exhaust emission control on diesel engines
US10105692B2 (en) Zoned ammonia slip catalyst for use in combustion turbines
JP6871178B2 (en) Ammonia slip catalyst designed to be the first in the SCR system
US9757718B2 (en) Ammonia slip catalyst having platinum impregnated on high porosity substrates
GB2575371A (en) Zoned exhaust system
EP3221032A1 (en) Combining scr with pna for low temperature emission control
JP2023506375A (en) Compartmentalized Ammonia Slip Catalyst for Improved Selectivity, Activity and Toxicity