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WO2013060341A1 - Catalyst composition for use in selective catalytic reduction of nitrogen oxides - Google Patents

Catalyst composition for use in selective catalytic reduction of nitrogen oxides Download PDF

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Publication number
WO2013060341A1
WO2013060341A1 PCT/EP2011/005344 EP2011005344W WO2013060341A1 WO 2013060341 A1 WO2013060341 A1 WO 2013060341A1 EP 2011005344 W EP2011005344 W EP 2011005344W WO 2013060341 A1 WO2013060341 A1 WO 2013060341A1
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Prior art keywords
components
zeolite
catalyst composition
catalyst
zeotype
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PCT/EP2011/005344
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French (fr)
Inventor
Alexandr STAKHEEV
Marie GRILL
Arkady Kustov
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Topsoe AS
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Haldor Topsoe AS
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Priority to MX2014004494A priority Critical patent/MX2014004494A/en
Priority to PCT/EP2011/005344 priority patent/WO2013060341A1/en
Priority to AU2012327482A priority patent/AU2012327482A1/en
Priority to KR1020147013999A priority patent/KR101789114B1/en
Priority to CA2853154A priority patent/CA2853154C/en
Priority to IN2950CHN2014 priority patent/IN2014CN02950A/en
Priority to BR112014008669-9A priority patent/BR112014008669B1/en
Priority to US14/353,620 priority patent/US9168517B2/en
Priority to JP2014537523A priority patent/JP6112734B2/en
Priority to PCT/EP2012/058003 priority patent/WO2013060487A1/en
Priority to RU2014120917A priority patent/RU2608616C2/en
Priority to CN201280052240.5A priority patent/CN103889569B/en
Priority to EP12721442.7A priority patent/EP2771111A1/en
Publication of WO2013060341A1 publication Critical patent/WO2013060341A1/en
Priority to CL2014000993A priority patent/CL2014000993A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/502—Beta zeolites

Definitions

  • the present invention relates to catalyst composition for use in selective reduction of nitrogen oxides in off-gases by reaction with ammonia or a precursor thereof.
  • Catalysts for NH 3 -SCR i.e. selective reduction of nitrogen oxides (NOx) by use of ammonia as reductant are well known in the art.
  • Those catalysts include zeolitic material, optionally promoted with copper or iron
  • the problem to be solved by this invention is to provide a catalyst composition and method for the reduction of nitrogen oxides with a DeNO x activity at reaction temperatures between 150 and 550°C.
  • the catalyst composition and method of this invention shall further include soot and hydrocarbon oxidation activity simultaneously with the DeNOx activity.
  • the invention provides in its broadest embodiment a catalyst composition for selective reduction of nitrogen
  • the catalyst composition comprises a physical mixture of one or more acidic zeolite or zeotype components and one ore more redox active metal compounds.
  • catalyst compositions comprising one or more zeolite or zeotype components from the group of BEA, MFI , FAU, FER, CHA, MOR in protonic form or promoted with Fe and redox metal component (Cu/Al 2 0 3( ⁇ / ⁇ 2 0 3 , Ce0 2 -Zr0 2 , Ce- n/Al 2 0 3 ) exhibit a pronounced synergistic effect.
  • DeNO x activity of such composite catalysts significantly exceeds activity of their individual components.
  • the redox component can additionally provide good soot oxidation function which can be used in combined SCR/DPF systems.
  • a preferred catalyst composition for selective reduction of nitrogen oxides and soot oxidation comprises one or more acidic zeolite or zeotype components and one or more redox active metal compounds wherein the one or more acidic zeolite or zeotype components are selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or mixtures thereof.
  • the acidic zeolite or zeotype component can be used in protonic form or promoted with Fe and one or more redox active metal components are selected form the group consisting of Cu/Al203, Mn/Al203, Ce02-Zr02, Ce- Mn/Al203 and mixtures thereof.
  • redox active metal compounds as used herein relates to metal compounds which reversibly can be oxidized and reduced in terms of changes in oxidation number, or oxidation state, of the metal atom or compound.
  • the weight ratio between the zeolite components and the redox components is between 1:1 to 1:50
  • the redox components are dispersed on a support selected from the group consisting of A1 2 0 3 , Ti0 2 , Si0 2 , Ce0 2 , Zr0 2 or mixtures thereof.
  • the mean molar ratio Si/Al of the zeolite components according to the invention is from 5 to 100.
  • Catalyst compositions prepared by mechanical mixing of the above mentioned zeolite and redox metal components exhibit a pronounced synergistic effect. DeNO x activity of such composite catalysts significantly exceeds activity of their individual components.
  • the one or more redox active metal components are physically mixed with the one or more zeolite components or dispersed on surface of the zeolite components.
  • the one or more redox active metal components dispersed on the surface of the one or more zeolite or zeotype components contain Ce, Mn, and Zr, Cr or mixtures thereof.
  • the above described catalyst composition according to the invention can be utilised as coating material or being coated on structured bodies of metallic, ceramic, metal oxide, SiC or silica materials or fibres.
  • the invention further provides a monolithic structured body being coated with a catalyst composition according to anyone of the above disclosed embodiments of the invention .
  • the monolithic structured body is preferably made from metallic, ceramic, metal oxide, SiC or silica fiber materials .
  • the monolithic structured body may be in form of a particle filter, e.g. a honeycomb structured filter or a wall flow filter .
  • the catalyst composition is coated on the body in of two or several separate catalyst layers in series or as two or several catalyst layers in parallel and wherein the layers have different compositions or layer thicknesses.
  • amount of expensive zeolite/ zeotype component in the composite catalyst can be significantly re- prised by its replacement with equivalent volume of redox component.
  • overall volume of the catalyst remains constant, but the amount of zeolite component can be decreased by 2-5 times, without notable sacrificing DeNO x performance.
  • Ce-Mn/Al 2 03 component is used for the catalyst preparation, notable improvement of NOx conversion at r eact ⁇ 250°C is observed despite decreased amount of zeolite component.
  • the invention provides additionally a method for the selective reduction of nitrogen oxides and oxidation of soot contained in an off-gas comprising the step of contacting the off-gas in presence of ammonia with a catalyst composition comprising a physical mixture of one or more acidic zeolite or zeotype components and one ore more redox active metal compounds .
  • the acidic zeolite or zeotype components are selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or mix- tures thereof and the one or more redox active metal components are selected form the group consisting of Cu/Al 2 0 3( Mn/Al 2 0 3 , Ce0 2 -Zr0 2 , Ce-Mn/Al 2 0 3 and mixtures thereof.
  • the acidic zeolite or zeotype component can be used in pro- tonic form or promoted with Fe
  • the one or more redox active metal compounds are dispersed on a support se- lected from the group consisting of Al 2 0 3/ Ti0 2 , Si0 2/ Zr0 2 or mixtures thereof.
  • the one or more redox active metal components are physically mixed with the one or more zeolite components or dispersed on surface of the zeolite components.
  • the one ore more redox active metal components are dispersed on the surface of the one or more zeolite components contain Ce, Mn, and Zr, Cr or mixtures thereof.
  • the catalyst composition is contacted with the off-gas at a tem- perature below 250°C.
  • the powders were thoroughly grinded in agate mortar for 10-15 min, followed by pelletization . The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized 74wt%Ce0 2 -26wt%Zr0 2 , H-Beta, and Fe- Beta zeolite were used as reference samples.
  • the catalysts were tested in the NH 3 -DeN0x in the temperature range of 150-550 °C.
  • the test was performed under fol- lowing conditions: decreasing reaction temperature with a rate of 2°C/min, feed gas composition: 500 ppm NO, 540 ppm NH 3 , 10 vol% 0 2 , 6 vol% H 2 0, balanced with N 2 to obtain a total flow of 300 mL/min.
  • ⁇ conversion over composite catalyst is similar to NO x conversion over commercial Fe-Beta zeolite (Fe-Beta) at 230-550°C, and exceeds NO x conversion over Fe-Beta zeolite at 150-200°C.
  • Fe-Beta Fe-Beta zeolite
  • a second sample was prepared by mixing 74wt%Ce0 2 -26wt%Zr0 2 and Fe-Beta powders at a weight ratio of 10. For the second sample volume ratio of 74wt%Ce0 2 -26wt%Zr0 2 /Fe-Beta zeolite equals 3/1.
  • the second sample with 3/1 volume component ratio [0.197g 74%Ce0 2 -Zr0 2 + 0.02g Fe-Beta zeolite];
  • Reference sample 0.02 g Fe-Beta zeolite
  • the catalysts were tested in NH 3 -DeNO x within the temperature range of 150-550 °C. The test was performed under following conditions: decreasing reaction temperature with a rate of 2°C/min, feed gas composition: 500 ppm NO, 540 ppm NH 3 , 10 vol% 0 2 , 6 vol% H 2 0, balanced with N 2 to obtain a total flow of 300 mL/min.
  • a first sample was prepared by mixing 74wt%Ce0 2 -26wt%ZrC>2 and Fe-Beta powders at a weight ratio of 3.3. In this case volume ratio of 74wt% Ce0 2 - 26wt% Zr0 2 /Fe-Beta zeolite equals 1/1.
  • a second sample was prepared by mixing 74wt%Ce0 2 -26wt%Zr0 2 and Fe-Beta zeolite powders at a weight ratio of 15.5.
  • For the second sample volume ratio of 74wt%Ce0 2 -26wt%Zr0 2 and Fe-Beta zeolite components equals 5/1.
  • a third sample was prepared by was prepared by mixing 74wt%Ce0 2 -26wt%Zr0 2 and Fe-Beta zeolite powders at a weight ratio of 30.
  • For the second sample volume ratio of 74wt%Ce0 2 -26wt%Zr0 2 and Fe-Beta zeolite components equals 10/1. After grinding in agate mortar for 10-15 min, the resulted mixtures were pelletized. The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized Fe-Beta zeolite was used as reference. Activities of the prepared samples were tested using the following catalyst loading which kept constant volume of the catalyst in the reactor. In all experiments described below overall volume on the catalyst loaded was 0.067 ml, which results in GHSW ⁇ 270 000 h "1 :
  • Second sample [0.109g 74wt%Ce0 2 - Zr0 2 + 0.007g Fe-Beta zeolite];
  • Reference sample 0.02 g Fe beta-zeolite.
  • Feed gas composition 540 ppm NH 3 , 500 ppm NO, 10 % 0 2 , 6 % H 2 0 balance with N 2
  • the powders were thoroughly grinded in agate mortar for 10-15 min, followed by pelleti- zation. The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized Fe-Beta was used as reference.
  • the catalysts were tested in the NH 3 -DeNOx in the temperature range of 150-550 °C . The test was performed under following conditions: decreasing reaction temperature with a rate of 2°C/min, feed gas composition: 500 ppm NO, 540 ppm NH 3 , 10 vol% 0 2 , 6 vol% H 2 0, balanced with N 2 to obtain a total flow of 300 mL/min.
  • Catalyst load 0.04g Fe-Beta and
  • Three samples of [10wt%Cu/Al 2 O 3 + H-zeolite] composite catalyst were prepared by thorough grinding of 10wt%Cu/Al 2 O 3 and H-Beta, H-ZSM-5, or H-ferrierite powder.
  • the first sample with 1/1 weight component ratio [0.040g 10wt%Cu/Al 2 O 3 + 0.040g H-Beta];
  • the second sample with 1/1 weight component ratio [0.040g 10wt%Cu/Al 2 O 3 + 0.040g H-ZSM-5];
  • the catalysts were tested in NH 3 -DeNO x within the temperature range of 150-550 °C. The test was performed under following conditions: decreasing reaction temperature with a rate of 2°C/min, feed gas composition: 500 ppm NO, 540 ppm NH 3 , 10 vol% 0 2 , 6 vol% H 2 0, balanced with N 2 to obtain a total flow of 300 mL/min.
  • Profiles of soot oxidation over [Ce0 2 -Zr0 2 + Fe-Beta] and Fe-Beta are displayed in Figure 7.
  • [Ce0 2 -Zr0 2 + Fe-Beta] significantly higher activity in soot oxidation then individual Fe-Beta, as evidenced by a shift of soot oxidation maximum from ⁇ 600°C for (Fe- Beta + soot) to ⁇ 420°C for ( [Ce0 2 -Zr0 2 + Fe-Beta] + soot)

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Abstract

Catalyst composition and method for selective reduction of nitrogen oxides and soot oxidation. An exhaust gas to be cleaned is passed together with ammonia or a compound decomposable to ammonia over a catalyst which comprises a mixture of acidic zeolite and redox component.

Description

Title : Catalyst composition for use in selective catalytic reduction of nitrogen oxides
The present invention relates to catalyst composition for use in selective reduction of nitrogen oxides in off-gases by reaction with ammonia or a precursor thereof.
Catalysts for NH3-SCR, i.e. selective reduction of nitrogen oxides (NOx) by use of ammonia as reductant are well known in the art. Those catalysts include zeolitic material, optionally promoted with copper or iron
The problem to be solved by this invention is to provide a catalyst composition and method for the reduction of nitrogen oxides with a DeNOx activity at reaction temperatures between 150 and 550°C.
Off-gases from lean combustion engines contain in addition to NOx, hydrocarbons, CO and soot particles which can be reduced or removed by catalytic oxidation. Consequently, the catalyst composition and method of this invention shall further include soot and hydrocarbon oxidation activity simultaneously with the DeNOx activity.
Our recent studies revealed several examples of a pronounced synergistic effect in composite catalysts prepared by mechanical mixing of acidic zeolite or zeotype powder and redox active metal compounds.
Thus, the invention provides in its broadest embodiment a catalyst composition for selective reduction of nitrogen
CONFUTATION COPY oxides and oxidation of hydrocarbons, CO and soot contained in off-gas. The catalyst composition comprises a physical mixture of one or more acidic zeolite or zeotype components and one ore more redox active metal compounds.
We have found that catalyst compositions comprising one or more zeolite or zeotype components from the group of BEA, MFI , FAU, FER, CHA, MOR in protonic form or promoted with Fe and redox metal component (Cu/Al203( Μη/Αΐ203, Ce02-Zr02, Ce- n/Al203) exhibit a pronounced synergistic effect. DeNOx activity of such composite catalysts significantly exceeds activity of their individual components. The redox component can additionally provide good soot oxidation function which can be used in combined SCR/DPF systems.
Thus, a preferred catalyst composition for selective reduction of nitrogen oxides and soot oxidation comprises one or more acidic zeolite or zeotype components and one or more redox active metal compounds wherein the one or more acidic zeolite or zeotype components are selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or mixtures thereof. The acidic zeolite or zeotype component can be used in protonic form or promoted with Fe and one or more redox active metal components are selected form the group consisting of Cu/Al203, Mn/Al203, Ce02-Zr02, Ce- Mn/Al203 and mixtures thereof.
The term "redox active metal compounds" as used herein relates to metal compounds which reversibly can be oxidized and reduced in terms of changes in oxidation number, or oxidation state, of the metal atom or compound. Preferably, the weight ratio between the zeolite components and the redox components is between 1:1 to 1:50
In an embodiment of the invention, the redox components are dispersed on a support selected from the group consisting of A1203, Ti02, Si02, Ce02, Zr02 or mixtures thereof.
It is generally preferred that the mean molar ratio Si/Al of the zeolite components according to the invention is from 5 to 100.
Catalyst compositions prepared by mechanical mixing of the above mentioned zeolite and redox metal components exhibit a pronounced synergistic effect. DeNOx activity of such composite catalysts significantly exceeds activity of their individual components.
Thus, in further an embodiment of the invention the one or more redox active metal components are physically mixed with the one or more zeolite components or dispersed on surface of the zeolite components.
In an embodiment, the one or more redox active metal components dispersed on the surface of the one or more zeolite or zeotype components contain Ce, Mn, and Zr, Cr or mixtures thereof.
The above described catalyst composition according to the invention can be utilised as coating material or being coated on structured bodies of metallic, ceramic, metal oxide, SiC or silica materials or fibres. Thus, the invention further provides a monolithic structured body being coated with a catalyst composition according to anyone of the above disclosed embodiments of the invention .
The monolithic structured body is preferably made from metallic, ceramic, metal oxide, SiC or silica fiber materials . The monolithic structured body may be in form of a particle filter, e.g. a honeycomb structured filter or a wall flow filter .
In further an embodiment, the catalyst composition is coated on the body in of two or several separate catalyst layers in series or as two or several catalyst layers in parallel and wherein the layers have different compositions or layer thicknesses. The pronounced synergistic effect in composite catalysts according to the invention can be utilized as described below
1) Addition of Ce02-Zr02, Cu/Al203, Mn/Al203 or Ce- Mn/Al203 to acidic zeolite or zeotype in protonic form or promoted with iron markedly enhances DeNOx activity at Treact < 250°C without increasing amount of zeolite component. In this case, overall volume of the catalyst is increased by the volume of redox component added.
2) Alternatively, amount of expensive zeolite/ zeotype component in the composite catalyst can be significantly re- duced by its replacement with equivalent volume of redox component. In this case overall volume of the catalyst remains constant, but the amount of zeolite component can be decreased by 2-5 times, without notable sacrificing DeNOx performance. When Ce-Mn/Al203 component is used for the catalyst preparation, notable improvement of NOx conversion at react < 250°C is observed despite decreased amount of zeolite component. 3) In addition to favourable DeNOx activity, [Ce02-Zr02 + zeolites/zeotypes] or [Ce-Mn/Al2C>3 + zeolites/zeotypes] compositions demonstrate significant soot oxidation activity, which makes them promising candidates for development of integrated DeNOx-DeSoot catalytic systems.
4) In addition to favorable DeNOx activity, [Ce02-ZrC>2 + zeolites/zeotypes] or [Ce-Mn/Al203 + zeolites/zeotypes] compositions demonstrate significantly lower ammonium slip at high temperature due to selective oxidation of excess ammonia.
The invention provides additionally a method for the selective reduction of nitrogen oxides and oxidation of soot contained in an off-gas comprising the step of contacting the off-gas in presence of ammonia with a catalyst composition comprising a physical mixture of one or more acidic zeolite or zeotype components and one ore more redox active metal compounds . In a preferred embodiment of the inventive method, the acidic zeolite or zeotype components are selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or mix- tures thereof and the one or more redox active metal components are selected form the group consisting of Cu/Al203( Mn/Al203, Ce02-Zr02, Ce-Mn/Al203 and mixtures thereof. The acidic zeolite or zeotype component can be used in pro- tonic form or promoted with Fe
In an embodiment of the inventive method, the one or more redox active metal compounds are dispersed on a support se- lected from the group consisting of Al203/ Ti02, Si02/ Zr02 or mixtures thereof.
In a further embodiment of the inventive method, the one or more redox active metal components are physically mixed with the one or more zeolite components or dispersed on surface of the zeolite components.
In a further embodiment, the one ore more redox active metal components are dispersed on the surface of the one or more zeolite components contain Ce, Mn, and Zr, Cr or mixtures thereof.
In still an embodiment of the inventive method, the catalyst composition is contacted with the off-gas at a tem- perature below 250°C.
In a further embodiment of the inventive method excess of ammonia is selectively oxidized to nitrogen by contact with the catalyst composition. EXAMPLES Example 1
Synergistic effect in NH3-DeNOx over Ce02-Zr02 + H-Beta zeolite catalyst compositions
[Ce02-Zr02 + H-Beta zeolite] composite catalyst was prepared by thorough mixing 74wt%Ce02-26wt%Zr02 powder with Pi- Beta powder at a weight ratio of 10. This weight ratio re- suits in volume ratio of components Ce02-Zr02/H-Beta = 3/1 due to difference in densities of these materials. The powders were thoroughly grinded in agate mortar for 10-15 min, followed by pelletization . The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized 74wt%Ce02-26wt%Zr02, H-Beta, and Fe- Beta zeolite were used as reference samples.
The catalysts were tested in the NH3-DeN0x in the temperature range of 150-550 °C. The test was performed under fol- lowing conditions: decreasing reaction temperature with a rate of 2°C/min, feed gas composition: 500 ppm NO, 540 ppm NH3, 10 vol% 02, 6 vol% H20, balanced with N2 to obtain a total flow of 300 mL/min.
Catalyst loading and resulted GHSV:
0.197g with 74wt%Ce02-Zr02 + 0.02g H-Beta zeolite, catalyst volume 0.134 ml, GHSV = 135 000 h"1
Under these conditions Ce02-Zr02 + H-Beta zeolite composite catalyst showed DeNOx activity, which substantially
exceeded activities of individual 74wt%Ce02-Zr02 (0.131g Ce02-Zr02, catalyst volume 0.067 ml, GHSV = 270,000 h"1) and H-Beta zeolite (0.04g, catalyst volume 0.067 ml, GHSV = 270 000 h-1) , indicating pronounced synergistic effect between components of composite catalyst as shown in Figure 1.
Οχ conversion over composite catalyst is similar to NOx conversion over commercial Fe-Beta zeolite (Fe-Beta) at 230-550°C, and exceeds NOx conversion over Fe-Beta zeolite at 150-200°C. Example 2
Enhanced DeNOx performance of [Ce02-Zr02 + Fe-Beta] composite catalyst at Treact < 250°C
Two samples of [Ce02-Zr02 + Fe-Beta zeolite] composite catalyst were prepared by thorough grinding of 74wt%Ce02- 26wt%Zr02 and Fe-Beta zeolite powders.
A first sample was prepared by mixing 74wt%Ce02-26wt%Zr02 and Fe-Beta zeolite powders at a weight ratio of 3.3. This weight ratio results in a volume ratio of 74wt%Ce02- 26wt%Zr02/Fe-Beta components in composite catalyst = 1/1. A second sample was prepared by mixing 74wt%Ce02-26wt%Zr02 and Fe-Beta powders at a weight ratio of 10. For the second sample volume ratio of 74wt%Ce02-26wt%Zr02/Fe-Beta zeolite equals 3/1.
After grinding in agate mortar for 10-15 min, the resulted mixtures were pelletized. The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized Fe-Beta zeolite was used as reference. Activities of the prepared samples were tested using the following catalyst loading which kept constant amount of Fe-Beta zeolite component in the reactor: The first sample with 1/1 volume component ratio: [0.065g 74%Ce02-Zr02 + 0.02g Fe-Beta zeolite];
The second sample with 3/1 volume component ratio: [0.197g 74%Ce02-Zr02 + 0.02g Fe-Beta zeolite];
Reference sample: 0.02 g Fe-Beta zeolite;
The catalysts were tested in NH3-DeNOx within the temperature range of 150-550 °C. The test was performed under following conditions: decreasing reaction temperature with a rate of 2°C/min, feed gas composition: 500 ppm NO, 540 ppm NH3, 10 vol% 02, 6 vol% H20, balanced with N2 to obtain a total flow of 300 mL/min.
Catalyst loading and resulted GHSV:
[0.197g 74%Ce02-Zr02 + 0.02g Fe-Beta zeolite], catalyst vol. = 0.134 ml, GHSV = 135 000 h"1;
[0.065g 74%Ce02-Zr02 + 0.02g Fe-Beta zeolite], catalyst vol. = 0.067 ml, GHSV = 270 000 h"1;
0.02 Fe-Beta zeolite, catalyst vol. = 0.034 ml, GHSV = 540 000 h_1; Under these test conditions [Ce02-Zr02 + Fe-Beta zeolite] composite catalysts showed enhanced DeNOx activity within low-temperature range (150-300°C) , which significantly exceeded activity of individual Fe-Beta zeolite, as shown in Figure 2. It is important to note that the activity of [Ce02-Zr02 + Fe-Beta zeolite] is improved when the amount of Ce02-Zr02 component was increased. Exam le 3
Catalyst with reduced amount of zeolite component Three samples of [Ce02-Zr02 + Fe-Beta zeolite] composite catalyst were prepared by thorough grinding of 74wt%CeC>2- 26wt%Zr02 powder with Fe-Beta zeolite powder:
A first sample was prepared by mixing 74wt%Ce02-26wt%ZrC>2 and Fe-Beta powders at a weight ratio of 3.3. In this case volume ratio of 74wt% Ce02- 26wt% Zr02 /Fe-Beta zeolite equals 1/1.
A second sample was prepared by mixing 74wt%Ce02-26wt%Zr02 and Fe-Beta zeolite powders at a weight ratio of 15.5. For the second sample volume ratio of 74wt%Ce02-26wt%Zr02 and Fe-Beta zeolite components equals 5/1.
A third sample was prepared by was prepared by mixing 74wt%Ce02-26wt%Zr02 and Fe-Beta zeolite powders at a weight ratio of 30. For the second sample volume ratio of 74wt%Ce02-26wt%Zr02 and Fe-Beta zeolite components equals 10/1. After grinding in agate mortar for 10-15 min, the resulted mixtures were pelletized. The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized Fe-Beta zeolite was used as reference. Activities of the prepared samples were tested using the following catalyst loading which kept constant volume of the catalyst in the reactor. In all experiments described below overall volume on the catalyst loaded was 0.067 ml, which results in GHSW ~ 270 000 h"1 :
First sample (1/1 vol component ratio): [0.065g 74wt%Ce02- Zr02 + 0.02g Fe-Beta zeolite];
Second sample (5/1 vol component ratio): [0.109g 74wt%Ce02- Zr02 + 0.007g Fe-Beta zeolite];
Third sample (10/1 vol component ratio): [0.119g 74wt%Ce02- Zr02 + 0.0035g Fe-Beta zeolite];
Reference sample: 0.02 g Fe beta-zeolite.
Feed gas composition: 540 ppm NH3, 500 ppm NO, 10 % 02, 6 % H20 balance with N2
Under these conditions [Ce02-Zr02 + Fe-Beta zeolite] com- posite catalysts showed DeNOx performances, which were essentially identical to the performance of reference Fe-Beta zeolite sample, despite significantly reduced amount of zeolite catalyst (Fe-Beta zeolite) loaded into the reactor as a part of composite [Ce02-Zr02 + Fe-Beta zeolite] .
The data in Figure 3 show that amount of zeolite can be reduced at least 10 times without sacrificing DeNOx performance of [Ce02-Zr02 + Fe-Beta zeolite] by its replacement with corresponding volume of Ce02-Zr02.
Example 4
Enhanced DeNOx performance of [Ce-Mn/Al203 + Fe-Beta zeolite] composite catalyst at Treact < 250°C [Ce-Mn/Al203 + Fe-Beta] composite catalysts were prepared by thorough mixing 15wt%Ce-15wt%Mn/Al203 powder with Fe- Beta powder at a weight ratio of 0,8:1; 1,7:1 and 3,4:1 keeping the same total volume of the catalyst constant. These weight ratios result in volume ratio of components Ce-Mn/Al203/Fe-Beta = 2/1; 1/1 and 1/2 due to difference in densities of these materials. The powders were thoroughly grinded in agate mortar for 10-15 min, followed by pelleti- zation. The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly pelletized Fe-Beta was used as reference. The catalysts were tested in the NH3-DeNOx in the temperature range of 150-550 °C . The test was performed under following conditions: decreasing reaction temperature with a rate of 2°C/min, feed gas composition: 500 ppm NO, 540 ppm NH3 , 10 vol% 02, 6 vol% H20, balanced with N2 to obtain a total flow of 300 mL/min.
Catalyst load: 0.04g Fe-Beta and
[0.045g Ce-Mn/Al203 + 0.013g Fe-Beta] (2/1 ratio), [0.034g
Ce-Mn/Al203 + 0.02g Fe-Beta] (1/1 ratio), [0.022g Ce- Mn/Al203 + 0.027g Fe-Beta] (1/2 ratio)
Under these conditions all [Ce-Mn/Al203+ Fe-Beta] composite catalysts showed DeNOx activity, which radically exceeded activities of individual Ce-Mn/Al203 and Fe-Beta at tem- peratures below 350°C, indicating pronounced synergistic effect between components of composite catalyst (Figure 4) . Besides that, ammonia slip on composite catalysts was significantly lower than for a reference Fe-Beta catalyst indicating that those composite systems can be used as inte- grated DeNOx-ASC . Example 5
Enhanced DeNOx performance of [10wt%Cu/Al2O3 + H-zeolite] composite catalysts
Three samples of [10wt%Cu/Al2O3 + H-zeolite] composite catalyst were prepared by thorough grinding of 10wt%Cu/Al2O3 and H-Beta, H-ZSM-5, or H-ferrierite powder. A first sample was prepared by mixing 10wt%Cu/Al2O3 and H- Beta (Si/Al = 20) powders at a weight ratio of 1/1.
A second sample was prepared by mixing 10wt%Cu/Al2O3 and H- ZSM-5 powders (Si/Al = 20) at a weight ratio of 1/1.
A third sample was prepared by mixing 10wt%Cu/Al2O3 and H- ferrierite powders (Si/Al = 32) at a weight ratio of 1/1.
After grinding in agate mortar for 10-15 min, the resulted mixtures were pelletized. The pellets were crushed and sieved collecting 0.2 - 0.4 mm fraction for catalytic test. Similarly corresponding pelletized zeolites (H-Beta, H-ZSM- 5, and H-ferrierite) were used as reference. Activities of the prepared samples were tested using the following catalyst loading which kept constant amount of zeolite component in the reactor:
The first sample with 1/1 weight component ratio: [0.040g 10wt%Cu/Al2O3 + 0.040g H-Beta];
The second sample with 1/1 weight component ratio: [0.040g 10wt%Cu/Al2O3 + 0.040g H-ZSM-5]; The third sample with 1/1 weight component ratio: [0.040g 10wt%Cu/Al2O3 + 0.040g H-ferrierite] ;
Reference samples: 0.040 g H-Beta; 0.040g H-ZSM-5, or H- ferrierite, or 0.040 g 10wt%Cu/Al2O3
The catalysts were tested in NH3-DeNOx within the temperature range of 150-550 °C. The test was performed under following conditions: decreasing reaction temperature with a rate of 2°C/min, feed gas composition: 500 ppm NO, 540 ppm NH3, 10 vol% 02, 6 vol% H20, balanced with N2 to obtain a total flow of 300 mL/min.
Catalyst loading and resulted GHSV:
[0.040g 10wt%Cu/Al2O3 + 0.040g H-Beta], catalyst vol. = 0.134 ml, GHSV = 135 000 h"1;
[0.040g 10wt%Cu/Al2O3 + 0.040g H-ZSM-5] , catalyst vol. = 0.134 ml, GHSV = 135 000 h"1;
[0.040g 10wt%Cu/Al2O3 + 0.040g H-ferrierite] , catalyst vol. = 0.134 ml, GHSV = 135 000 h"1;
Reference catalysts
0.040g H-Beta, catalyst vol. = 0.067 ml,
GHSV = 270, 000 h"1;
0.040g H-ZSM-5, catalyst vol. = 0.067 ml,
GHSV = 270,000 h_1;
0.040g H-ferrierite, catalyst vol. = 0.067 ml,
GHSV = 270, 000 h"1;
0.040g Cu/Al203, catalyst vol. = 0.067 ml,
GHSV = 270, 000 h"1;
Under these test conditions [ 10wt%Cu/Al2O3 + H-zeolite] composite catalysts showed enhanced DeNOx within the whole temperature range (150-550°C) , which significantly exceeded activity of individual components, as shown by comparing Figure 5 and Figure 6.
Example 6
Catalyst with enhanced soot oxidation activity
[Ce02-Zr02 + Fe-Beta] with 3/1 vol. component ratio was prepared as described in Example 2. For testing soot oxidation activity of [Ce02-Zr02 + Fe-Beta] a part of pelletized sample was crushed, and the catalyst powder was mixed with soot ("Printex U" , Degussa) at a weight ratio catalyst/soot = 1/10. Soot and catalyst were mixed by shaking in a glass bottle for 5 min, thus establishing loose contact between soot and the catalyst. Reference sample was prepared in a similar manner using Fe-Beta powder.
Soot oxidation was carried out at temperature ramp = 10°C/min in a flow of dried air. Profiles of soot oxidation over [Ce02-Zr02 + Fe-Beta] and Fe-Beta are displayed in Figure 7. [Ce02-Zr02 + Fe-Beta] significantly higher activity in soot oxidation then individual Fe-Beta, as evidenced by a shift of soot oxidation maximum from ~ 600°C for (Fe- Beta + soot) to ~ 420°C for ( [Ce02-Zr02 + Fe-Beta] + soot)

Claims

CLAIMS:
1. Catalyst composition for selective reduction of nitrogen oxides and soot oxidation comprising physical mixture of one or more acidic zeolite or zeotype components and one ore more redox active metal compounds .
2. The catalyst composition of claim 1, wherein the one or more acidic zeolite or zeotype components are selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or mixtures thereof.
3. The catalyst composition of claim 1 or 2 , wherein the one or more redox active metal components are selected from the group consisting of Cu/Al203, n/Al203, Ce02-Zr02/ Ce- Mn/Al203 and mixtures thereof.
4. The catalyst composition of according to anyone of claims 1 to 3, wherein weight ratio between the zeolite components and the redox components is between 1:1 and 1:50
5. The catalyst according to anyone of claims 1 to 4 , wherein the redox components are dispersed on a support selected from the group consisting of Al203, Ti02, Si02, Zr02 or mixtures thereof.
6. The catalyst composition according to anyone of claims 1 to 5 , wherein mean molar ratio Si/Al of the zeolite or zeotype components is from 5 to 100.
7. The catalyst composition according to anyone of claims 1 to 6 , wherein the one or more redox active metal compo- nents are physically mixed with the one or more zeolite or zeotype components or dispersed on surface of the zeolite or zeotype components.
8. The catalyst composition of claim 7, wherein the one or more redox active metal components dispersed on the surface of the one or more zeolite or zeotype components contain Ce, Mn, Zr, Cr or mixtures thereof.
9. A monolithic structured body being coated with a catalyst composition according to anyone of the preceding claims .
10. The monolithic structured body of claim 9, wherein the monolithic structured body is in a form of a particle filter .
11. The monolithic structured body of claims 9 or 10, wherein the catalyst composition is coated on the body in two or several separate catalyst layers in series or as two or several catalyst layers in parallel and wherein the layers have different compositions or layer thicknesses.
12. Method for the selective reduction of nitrogen oxides and oxidation of soot contained in an off-gas comprising the step of contacting the off-gas in presence of ammonia with a catalyst composition comprising a physical mixture of one or more acidic zeolite or zeotype components and one ore more redox active metal compounds.
13. The method of claim 12, wherein the redox components are dispersed on a support selected from the group consisting of AI2O3, Ti02, Si02, Zr02 or mixtures thereof.
14. The method according to anyone of claim 12 or 13, wherein the one or more redox active metal components are physically mixed with the one or more zeolite components or dispersed on surface of the zeolite components.
15. The method according to anyone of claim 12 to 14, wherein the one ore more redox active metal components dispersed on the surface of the one or more zeolite components contain Ce, Mn, Zr, Cr or mixtures thereof.
16. The method of according to anyone of claim 12 to 15, wherein the catalyst composition is contacted with the off- gas at a temperature below 250°C.
17. The method according to anyone of claim 12 to 16, wherein excess of ammonia is selectively oxidized to nitrogen by contact with the catalyst composition.
18. The catalyst composition of claim 2, wherein the one or more acidic zeolite or zeotype components are in protonic form or promoted with Fe .
19. The method of claim 12, wherein the one or more acidic zeolite or zeotype components are selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR and mixtures thereof and the one or more redox active metal components are selected from the group consisting of Cu/Al203, Mn/Al203, Ce02-Zr02, Ce-Mn/Al203 and mixtures thereof.
20. The method according to claim 12 or 13, wherein the one or more acidic zeolite or zeotype components are in pro- tonic form or promoted with Fe.
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CA2853154C (en) 2018-04-03
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BR112014008669B1 (en) 2019-07-02
KR20140095512A (en) 2014-08-01
AU2012327482A1 (en) 2014-05-15
RU2608616C2 (en) 2017-01-23
CA2853154A1 (en) 2013-05-02
KR101789114B1 (en) 2017-10-23
CN103889569A (en) 2014-06-25
MX2014004494A (en) 2014-07-11
CN103889569B (en) 2017-02-15
RU2014120917A (en) 2015-12-10
JP2015501210A (en) 2015-01-15
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WO2013060487A1 (en) 2013-05-02
JP6112734B2 (en) 2017-04-12

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