MX2014004494A - Catalyst composition for use in selective catalytic reduction of nitrogen oxides. - Google Patents
Catalyst composition for use in selective catalytic reduction of nitrogen oxides.Info
- Publication number
- MX2014004494A MX2014004494A MX2014004494A MX2014004494A MX2014004494A MX 2014004494 A MX2014004494 A MX 2014004494A MX 2014004494 A MX2014004494 A MX 2014004494A MX 2014004494 A MX2014004494 A MX 2014004494A MX 2014004494 A MX2014004494 A MX 2014004494A
- Authority
- MX
- Mexico
- Prior art keywords
- zeolite
- components
- catalyst composition
- catalyst
- beta
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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
COMPOSITION OF CATALYST AND METHOD FOR USE IN THE
SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES
Field of the Invention
The present invention relates to a catalyst composition for use in the selective reduction of nitrogen oxides in gaseous effluents by reaction with ammonia or a precursor thereof.
Background of the Invention
The catalysts for NH3-SCR, ie the selective reduction of nitrogen oxides (NOx) by the use of ammonia as a reducing agent are well known in the field. These catalysts include a zeolitic material, optionally promoted with copper or iron.
The problem to be solved by this invention is to provide a catalyst composition and a method for the reduction of nitrogen oxides with a DeNOx activity at reaction temperatures between 150 and 550 ° C.
The gaseous effluents of combustion engines of poor fuels also contain NOx, hydrocarbons, CO and soot particles which can be reduced or removed by catalytic oxidation. Accordingly, the catalyst composition and the method of this invention should also include an activity of
oxidation of soot and hydrocarbons simultaneously with the activity of DeNOx.
Recent studies revealed several examples of a pronounced synergistic effect in compound catalysts that are prepared by mechanically mixing zeolite powder or acid zeotype and metal compounds with redox activity.
It has been found that the catalyst composition comprising one or more zeolite or zeotype acid components physically mixed with one or more metal compounds with redox activity has shown improved activity in the selective reduction of nitrogen oxides and the oxidation of hydrocarbons. , CO and soot contained in the gaseous effluent.
The term "metal compounds with redox activity" as used herein refers to metal compounds which can be oxidized and reversibly reduced in terms of changes in the oxidation number, or oxidation state, of the atom or compound of metal.
Summary of the Invention
In accordance with the above findings, the present invention provides a catalyst composition for the selective reduction of oxides of
nitrogen and soot oxidation comprising one or more zeolite or zeotype acid components selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or combinations thereof physically mixed with one or more metal compounds having activity of redox selected from the group consisting of Cu / Al203, Mn / Al203, Ce02Zr02, Ce-Mn / Al203 and combinations thereof.
Detailed description of the invention
The catalyst compositions prepared by the mechanical mixing of the zeolite or zeotype materials mentioned above and the mixture of metal components with redox activity according to the invention exhibit a pronounced synergistic effect. The DeNOx activity of these compound catalysts significantly exceeds the activity of their individual components.
The zeolite component or acid zeotype can be used in protonic form or can be promoted with Fe.
Preferably, the weight ratio between the zeolite components and the redox components is between 1: 1 and 1:50.
In one embodiment of the invention, the redox components are dispersed in a support selected from the group consisting of Al203, Ti02, Si02, Ce02, Zr02 or mixtures of
the same .
It is generally preferred that the average Si / Al molar ratio of the zeolite components according to the invention be from 5 to 100.
The catalyst composition described above according to the invention can be used as a coating material or as a coating on structured bodies of metal, ceramic, metal oxide, SiC or silica materials or fibers.
In this manner, the invention further provides a monolithic structured body that is coated with a catalyst composition according to any of the disclosed embodiments of the invention.
The monolithic structured body is preferably made of metallic fiber, ceramic, metal oxide, SiC or silica materials.
The monolithic structured body can be in the form of a particulate filter, for example a structured honeycomb filter or a flow filter through the walls.
In a further embodiment, the catalyst composition is coated on the body in two to several catalyst layers separated in series or as two or several layers of catalyst in parallel and wherein the layers
They have different compositions or thicknesses of the layers.
The specific advantages resulting from the invention are
1) The addition of Ce02-Zr02, Cu / Al203, Mn / Al203 or Ce-Mn / Al203 to zeolite or acid zeotype in protonic or iron-promoted form markedly increases the activity of DeNOx in Treact < 250 ° C without increasing the amount of zeolite component. In this case, the entire volume of the catalyst is increased by the volume of the added redox component.
2) Alternatively, the amount of expensive zeolite component / zeotype in the composite catalyst can be significantly reduced by this replacement with an equivalent volume of redox component. In this case, the full volume of the catalyst remains constant, but the amount of the zeolite component can be decreased by 2-5 times, without the notable sacrifice of DeNOx performance. When the component of Ce-Mn / Al203 is used for the preparation of the catalyst, a remarkable improvement of the conversion of NOx to Treact < 250 ° C is observed despite a decreased amount of the zeolite component.
3) In addition to the favorable DeNOx activity, the compositions of [Ce02-Zr02 + zeolites / zeotypes] or [Ce-Mn / Al203 + zeolites / zeotypes] demonstrate an activity of
significant oxidation of soot, which makes them promising candidates for the development of integrated Soap DeNOx-Catalyst systems.
4) In addition to the favorable DeNOx activity, the compositions of [Ce02-Zr02 + zeolites / zeotypes] or [Ce-Mn / Al203 + zeolites / zeotypes] demonstrate a significantly lower synthesis of ammonia at a high temperature due to oxidation selective ammonia in excess.
The invention further provides a method for the selective reduction of nitrogen oxides and the oxidation of soot contained in a gaseous effluent comprising the step of contacting the gaseous effluent in the presence of ammonia with a catalyst composition comprising one or more zeolite or acid zeotype components selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or combinations thereof physically mixed with one or more metal compounds with redox activity selected from the group consisting of Cu / Al203, Mn / Al203, Ce02-Zr02, Ce-Mn / Al203 and combinations thereof.
The zeolite component or acid zeotype can be used in protonic form or can be promoted with Fe.
In one embodiment of the inventive method, one or more of the metal compounds with redox activity are dispersed in a support selected from the group consisting of
of Al203, Ti02, Si02, Zr02 or combinations thereof.
In still one embodiment of the inventive method, the catalyst composition is contacted with the gaseous effluent at a temperature below 250 ° C.
In a further embodiment of the inventive method, the excess ammonia is selectively oxidized to nitrogen by contact with the catalyst composition.
Examples
Example 1
Synergistic effect in NH3-DeN0x on catalyst compositions of Ce02-Zr02 + H-Beta zeolite
The catalyst composed of [Ce02-Zr02 + H-Beta zeolite] was prepared through the powder mixture of 74% by weight of Ce02-26% by weight of Zr02 with H-Beta powder in a weight ratio of 10. This weight ratio results in a volume ratio of the components Ce02-Zr02 / H-Beta = 3/1 due to the difference in the densities of these materials. The powders were completely ground in an agate mortar for 10-15 minutes, followed by the formation of granules. The granules were crushed and sieved by collecting the 0.2-0.4 mm fraction for the catalytic test. The compound of 74% by weight of Ce02-26% by weight of Zr02, H-Beta zeolite and similarly granulated Fe-Beta was used as reference samples.
The catalysts were tested in the NH3-DeNOx in the temperature range of 150-550 ° C. The test was carried out under the following conditions: decrease of the reaction temperature with a speed of 2 ° C / minute, composition of the feed gas: 500 ppm of NO, 540 ppm of NH3f 10% by volume of 02% 6% by volume of H20, balanced with N2 to obtain a total flow of 300 mL / minute.
Catalyst load and GHSV produced:
0. 197 g with 74% by weight of Ce02-Zr02 + 0.02 g of H-Beta zeolite, catalyst volume 0.134 ml, GHSV = 135,000 h "1.
Under these conditions, the catalyst composed of Ce02-Zr02 + H-Beta zeolite showed a DeNOx activity, which substantially exceeded the activities of 74% by weight of individual Ce02-Zr02 (0.131 g of Ce02-Zr02, catalyst volume 0.067 ml, GHSV = 270,000 h "1) and H-Beta zeolite (0.04 g, 0.067 ml catalyst volume, GHSV = 270,000 h" 1), indicating a pronounced synergistic effect between the components of the composite catalyst as shown in Figure 1.
The NOx conversion on the composite catalyst is similar to the NOx conversion on the commercial Fe-Beta zeolite (Fe-Beta) at 230-550 ° C and exceeds the conversion of NOx on Fe-Beta zeolite to 150-
200 ° C.
Example 2
Improved DeNOx performance of the catalyst composed of [Ce02-Zr02 + Fe-Beta] to Treact < 250 ° C
Two samples of the catalyst composed of [Ce02-Zr02 + Fe-Beta zeolite] were prepared by grinding powders of 74% by weight of Ce02-26% by weight of Zr02 and Fe-Beta zeolite.
A first sample was prepared by mixing powders of 74% by weight of Ce02-26% by weight of Zr02 and Fe-Beta zeolite in a weight ratio of 3.3. This weight ratio results in a component volume ratio of 74% by weight of Ce02-26% by weight of Zr02 / Fe-Beta in the composite catalyst = 1/1. A second sample was prepared by mixing powders of 74% by weight of Ce02-26% by weight of Zr02 and Fe-Beta in a weight ratio of 10. For the second sample, the volume ratio of the composite catalyst was 74% by weight. weight of Ce02-26% by weight of Zr02 / Fe-Beta zeolite is equal to 3/1.
After grinding in an agate mortar for 10-15 minutes, the combinations produced were granulated. The granules were crushed and sieved by collecting the 0.2-0.4 mm fraction for the catalytic test. Fe-Beta zeolite granulated similarly
used as a reference.
The activities of the prepared samples were tested using the following catalyst charge which maintained a constant amount of Fe-Beta zeolite component in the reactor:
The first sample with a component ratio in volume 1/1: [0.065 g of 74% Ce02-Zr02 + 0.02 g of Fe-Beta zeolite].
The second sample with a component ratio in volume 3/1: [0.197 g of 74% Ce02-Zr02 + 0.02 g of Fe-Beta zeolite].
Reference sample: 0.02 g of Fe-Beta zeolite.
The catalysts were tested in NH3-DeNOx within the temperature range of 150-550 ° C. The test was carried out under the following conditions: decrease of the reaction temperature with a speed of 2 ° C / minute, composition of the feed gas: 500 ppm of NO, 540 ppm of NH3, 10% by volume of 02, 6% in volume of H0, balanced with N2 to obtain a total flow of 300 mL / minute.
Catalyst load and GHSV produced:
[0.197 g of 74% Ce02-Zr02 + 0.02 g of Fe-Beta zeolite], catalyst volume = 0.134 ml, GHSV = 135,000 IT1;
[0.065 g of 74% Ce02-Zr02 + 0.02 g of zeolite
Fe-Beta], catalyst volume = 0.067 ml, GHSV = 270,000 h "1;
0. 02 g of Fe-Beta zeolite, catalyst volume = 0.034 ml, GHSV = 540,000 h "1.
Under these test conditions, the catalysts composed of [Ce02-Zr02 + Fe-Beta zeolite] showed enhanced DeNOx activity within a low temperature range (150-300 ° C), which significantly exceeded the activity of the zeolite of Fe-Beta individual, 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 the Ce02-Zr02 component was increased.
Example 3
Catalyst with a reduced amount of zeolite component
Three samples of the catalyst composed of [Ce02-Zr02 + Fe-Beta zeolite] were prepared through powder grinding of 74% by weight of Ce02-26% by weight of Zr02 with Fe-Beta zeolite powder:
A first sample was prepared by mixing powders of 74% by weight of Ce02-26% by weight of Zr02 and Fe-Beta in a weight ratio of 3.3. In this case, the volume ratio of 74% by weight of Ce02-26% by weight of Zr02 / zeolite
of Fe-Beta is equal to 1/1.
A second sample was prepared by mixing powders of 74% by weight of Ce02-26% by weight of Zr02 and Fe-Beta zeolite in a weight ratio of 15.5. For the second sample, the volume ratio of the components of 74% by weight of Ce02-26% by weight of Zr02 and Fe-Beta zeolite is equal to 5/1.
A third sample was prepared by mixing powders of 74% by weight of Ce02-26% by weight of Zr02 and Fe-Beta zeolite in a weight ratio of 30. For the second sample, the volume ratio of the components of % by weight of Ce02-26% by weight of Zr02 and Fe-Beta zeolite is equal to 10/1.
After grinding in an agate mortar for 10-15 minutes, the mixtures produced were granulated. The granules were crushed and sieved by collecting the 0.2-0.4 mm fraction for the catalytic test. Fe-Beta zeolite granulated in a similar manner was used as reference.
The activities of the prepared samples were tested using the following catalyst charge which maintained a constant volume of the catalyst in the reactor. In all the experiments described below, the total volume in the loaded catalyst was 0.067 mL, which results in
One GHSW ~ 270,000 h "1:
First sample (component ratio in volume 1/1): [0.065 g of 74% by weight of Ce02-Zr02 + 0.02 g of Fe-Beta zeolite].
Second sample (component ratio in volume 5/1): [0.109 g of 74% by weight of Ce02-Zr02 + 0.007 g of Fe-Beta zeolite].
Third sample (component ratio in volume 10/1): [0.119 g of 74% by weight of Ce02-Zr02 + 0.0035 g of Fe-Beta zeolite].
Reference sample: 0.02 g of Fe-beta zeolite.
Composition of the feed gas: 540 ppm of NH3, 500 ppm of NO, 10% of 02.6% of H20 balanced with N2.
Under these conditions, the catalysts composed of [Ce02-Zr02 + Fe-Beta zeolite] showed DeNOx performances, which were essentially identical to the performance of the Fe-Beta zeolite reference sample, despite a significantly reduced amount of zeolite catalyst (Fe-Beta zeolite) charged to the reactor as part of the compound of [Ce02-Zr02 + Fe-Beta zeolite].
The data in Figure 3 show that the amount of zeolite can be reduced by at least 10 times without sacrificing the DeNOx performance of [Ce02-Zr02 + zeolite
Fe-Beta] by replacing it with a corresponding volume of Ce02-Zr02.
Example 4
Improved performance of DeNOx from the catalyst composed of [Ce-Mn / Al203 + Fe-Beta zeolite] to Treact <
250 ° C
The catalysts composed of [Ce-Mn / Al203 + Fe-Beta] were prepared by thoroughly mixing powder of 15% by weight of Ce-15% by weight of Mn / Al203 with Fe-Beta powder in a weight ratio of 0.8 :1; 1.7: 1 and 3.4: 1 keeping the same total catalyst volume constant. These weight ratios result in a volume ratio of the components Ce-Mn / Al203 / Fe-Beta = 2/1; 1/1 and 1/2 due to the difference in densities of those materials. The powders were completely ground in an agate mortar for 10-15 minutes, followed by granulation. The granules were crushed and sieved by collecting the 0.2-0.4 mm fraction for the catalytic test. The similarly granulated Fe-Beta was used as a reference.
The catalysts were tested in the NH3-DeNOx in the temperature range of 150-550 ° C. The test was carried out under the following conditions: decrease in the reaction temperature with a speed
2 ° C / minute, composition of the feed gas: 500 ppm of NO, 540 ppm of NH3, 10% by volume of 02, 6% by volume of H2O, balanced with N2 to obtain a total flow of 300 mL / minute .
Catalyst loading: 0.04 g of Fe-Beta and
[0.045 g of Ce-Mn / Al203 + 0.013 g of Fe-Beta] (ratio 2/1), [0.034 g of Ce-Mn / Al203 + 0.02 g of Fe-Beta] (ratio 1/1), [0.022 g of Ce-Mn / Al203 + 0.027 g of Fe-Beta] (ratio 1/2).
Under these conditions, all the catalysts composed of [Ce-Mn / Al203 + Fe-Beta] showed DeNOx activity, which radically exceeded the activities of the individual components Ce-Mn / Al203 and Fe-Beta at temperatures below 350 ° C , indicating a pronounced synergistic effect between the composite catalyst components (Figure 4). In addition, the synthesis of ammonia in composite catalysts was significantly lower than for a reference Fe-Beta catalyst, which indicates that these compound systems can be used as integrated DeNOx-ASCs.
Example 5
Improved performance of DeNOx of catalysts composed of [10% by weight Cu / Al203 + H zeolite]
Three catalyst samples composed of [10 wt.% Cu / Al203 + H zeolite] were prepared by completely grinding powder of 10 wt.% Cu / Al203 and H-Beta, H-ZSM-5 or H- Ferrierite
A first sample was prepared by mixing powders of 10% by weight of Cu / Al203 and H-Beta (Si / Al = 20) in a weight ratio of 1/1.
A second sample was prepared by mixing powders of 10% by weight of Cu / Al203 and H-ZSM-5 (Si / Al = 20) in a weight ratio of 1/1.
A third sample was prepared by mixing powders of 10% by weight of Cu / Al203 and H-ferrierite (Si / Al = 32) in a weight ratio of 1/1.
After grinding in an agate mortar for 10-15 minutes, the mixtures produced were granulated. The granules were crushed and sieved by collecting the 0.2-0.4 mm fraction for the catalytic test. The correspondingly similar granulated zeolites (H-Beta, H-ZSM-5 and H-ferrierite) were used as a reference.
The activities of the prepared samples were tested using the following catalyst charge which kept the amount of the zeolite component constant in the reactor:
The first sample with a relation of
components in weight 1/1: [0.040 g of 10% by weight of Cu / Al203 + 0.040 g of H-Beta].
The second sample with a ratio of components in weight 1/1: [0.040 g of 10% by weight of Cu / Al203 + 0.040 g of H-ZSM-5].
The third sample with a ratio of components in weight 1/1: [0.040 g of 10% by weight of Cu / Al203 + 0.040 g of H-ferrierite].
Reference samples: 0.040 g of H-Beta; 0.040 g of H-ZSM-5 or H-ferrierite, or 0.040 g of 10% by weight of Cu / Al203.
The catalysts were tested in NH3-DeNOx within the temperature range of 150-550 ° C. The test was carried out under the following conditions: decrease of the reaction temperature with a speed of 2 ° C / minute, composition of the feed gas: 500 ppm of NO, 540 ppm of NH3, 10% by volume of 02, 6% in volume of H20, balanced with N2 to obtain a total flow of 300 mL / minute.
Catalyst load and GHSV produced:
[0.040 g of 10% by weight Cu / Al203 + 0.040 g of H-Beta], catalyst volume = 0.134 ml, GHSV = 135,000 h "1;
[0.040 g of 10% by weight Cu / Al203 + 0.040 g of H-ZSM-5], catalyst volume = 0.134 ml, GHSV = 135,000 h "1;
[0.040 g of 10% by weight of Cu / Al203 + 0.040 g of H-
ferrierite], catalyst volume = 0.134 ml, GHSV = 135, 000 tf1;
Reference catalysts
0. 040 g of H-Beta, catalyst volume = 0.067 ml,
GHSV = 270, 000 h "1
0. 040 g of H-ZSM-5, catalyst volume = 0.067 ml, GHSV = 270, 000 h "1;
0. 040 g of H-ferrierite, catalyst volume = 0.067 ml,
GHSV = 270,000 h "1;
0. 040 g Cu / Al203, catalyst volume = 0.067 ml,
GHSV = 270, 000 h "1.
Under these test conditions, the catalysts composed of [10% by weight of Cu / Al203 + H zeolite] showed an improved DeNOx within the complete temperature range (150-550 ° C), which significantly exceeded the activity of the individual components, as shown when comparing Figure 5 and the
Figure 6
Example 6
Catalyst with enhanced soot oxidation activity
[Ce02-Zr02 + Fe-Beta] with a volume ratio of components 3/1 was prepared as described in Example 2. To test the soot oxidation activity of [Ce02-Zr02 + Fe-Beta] , a part of
the granulated sample was ground and the catalyst powder was mixed with soot ("Printex U", Degussa) at a weight ratio of catalyst / soot = 1/10. The soot and the catalyst were mixed by stirring in a glass bottle for 5 minutes, thereby establishing a loose contact between the soot and the catalyst. The reference sample was prepared in a similar manner using Fe-Beta powder.
Oxidation of the soot was carried out on a ramp of temperature = 10 ° C / minute in a flow of dry air. The soot oxidation profiles on [Ce02-Zr02 + Fe-Beta] and Fe-Beta are shown in Figure 7. The [Ce02-Zr02 + Fe-Beta] has a significantly higher activity in soot oxidation than the Individual Fe-Beta, as evidenced by a change in maximum soot oxidation of ~ 600 ° C for (Fe-Beta + soot) to ~ 420 ° C for ([Ce02-Zr02 + Fe-Beta] + soot).
Claims (16)
1. A catalyst composition for the selective reduction of nitrogen oxides and soot oxidation, characterized in that it comprises one or more components of zeolite or zeotype acids selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or combinations of the same physically mixed with one or more metal compounds with redox activity selected from the group consisting of Cu / Al203, Mn / Al203, Ce02Zr02, Ce-Mn / Al203 and combinations thereof.
2. The catalyst composition according to claim 1, characterized in that the weight ratio between the zeolite components and the redox components is between 1: 1 and 1:50.
3. The catalyst composition according to claim 1 or 2, characterized in that one more of the metal compounds with redox activity is dispersed in a support selected from the group consisting of Al203, Ti02, Si02, Zr02 or combinations thereof.
4. The catalyst composition according to any of claims 1 to 3, characterized in that one or more of the zeolite or acid zeotype components are in protonic form or promoted with Fe.
5. The catalyst composition according to any of claims 1 to 4, characterized because the average molar ratio of Si / Al of one or more of the zeolite or acid zeotype components is from 5 to 100.
6. The catalyst composition according to any of the preceding claims, characterized in that one or more of the zeolite or acid zeotype components are selected from the group consisting of beta-zeolite, ZSM-5 and ferrierite.
7. A monolithic structured body, characterized in that it is coated with a catalyst composition according to any of the preceding claims.
8. The monolithic structured body according to claim 7, characterized in that the structured, monolithic body is in the form of a particle filter.
9. The monolithic structured body according to claims 7 or 8, characterized in that the catalyst composition is coated on the body in two or several layers of catalyst separated in series or as two or several layers of catalyst in parallel and where the layers have different compositions or thicknesses of the layers.
10. A method for the selective reduction of nitrogen oxides and the oxidation of soot contained in a gaseous effluent, characterized in that it comprises the step which consists in contacting the gaseous effluent in the presence of ammonia with a catalyst composition comprising one or more zeolite or zeotype acid components selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or combinations thereof. themselves physically mixed with one or more metal compounds with redox activity selected from the group consisting of Cu / Al203, Mn / Al203, Ce02-Zr02, Ce-Mn / Al203 and combinations thereof.
11. The method according to claim 10, characterized in that one more of the metal components with redox activity that are dispersed on the surface of one or more of the zeolite components contain Ce, Mn, Zr, Cr or combinations thereof .
12. The method according to claim 10 or 11, characterized in that the catalyst composition is brought into contact with the gaseous effluent at a temperature below 250 ° C.
13. The method according to any of claims 10 to 12, characterized in that the excess ammonia is selectively oxidized to nitrogen by contact with the catalyst composition.
14. The method according to any of claims 10 to 13, characterized in that one or more of the zeolite or acid zeotype components are in protonic form or promoted with Fe.
15. The method according to any of claims 10 to 14, characterized in that the average molar ratio of Si / Al of one or more of the zeolite or acid zeotype components is from 5 to 100.
16. The method according to any of claims 10 to 15, characterized in that one or more of the zeolite or acid zeotype components are selected from the group consisting of beta-zeolite, ZSM-5 and ferrierite.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2011/005344 WO2013060341A1 (en) | 2011-10-24 | 2011-10-24 | Catalyst composition for use in selective catalytic reduction of nitrogen oxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MX2014004494A true MX2014004494A (en) | 2014-07-11 |
Family
ID=46085901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX2014004494A MX2014004494A (en) | 2011-10-24 | 2011-10-24 | Catalyst composition for use in selective catalytic reduction of nitrogen oxides. |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JP6112734B2 (en) |
| KR (1) | KR101789114B1 (en) |
| CN (1) | CN103889569B (en) |
| AU (1) | AU2012327482A1 (en) |
| BR (1) | BR112014008669B1 (en) |
| CA (1) | CA2853154C (en) |
| CL (1) | CL2014000993A1 (en) |
| IN (1) | IN2014CN02950A (en) |
| MX (1) | MX2014004494A (en) |
| RU (1) | RU2608616C2 (en) |
| WO (2) | WO2013060341A1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014324B (en) * | 2014-05-14 | 2016-08-17 | 华东理工大学 | Cerium oxide base support type catalyst for denitrating flue gas and preparation method thereof |
| CN105435789A (en) * | 2014-09-09 | 2016-03-30 | 中国石油化工股份有限公司 | Preparation method for Cu-base methanol-synthesizing catalyst large-specific-surface-area carrier |
| CN104525216B (en) * | 2014-12-11 | 2017-01-04 | 清华大学 | Denitrating catalyst under the conditions of wide temperature window high-sulfur and preparation method thereof |
| CN104437540A (en) * | 2014-12-31 | 2015-03-25 | 安徽省元琛环保科技有限公司 | Phosphorus-resistant low-temperature SCR denitration catalyst and preparation method thereof |
| BR112018003261B1 (en) * | 2015-08-21 | 2021-08-03 | Basf Corporation | CATALYST, EXHAUST GAS TREATMENT SYSTEM, AND, EXHAUST GAS TREATMENT METHOD |
| EP3356019A1 (en) * | 2015-09-29 | 2018-08-08 | Johnson Matthey Public Limited Company | Catalytic filter having a soot catalyst and an scr catalyst |
| CN108348871B (en) | 2015-10-30 | 2021-11-05 | 蓝移材料有限公司 | Highly branched, non-crosslinked aerogels, method for the production thereof and use thereof |
| US9963571B2 (en) | 2016-06-08 | 2018-05-08 | Blueshift Materials, Inc. | Polymer aerogel with improved mechanical and thermal properties |
| EP3281698A1 (en) | 2016-08-11 | 2018-02-14 | Umicore AG & Co. KG | Scr active material |
| EP3496854A1 (en) | 2016-08-11 | 2019-06-19 | Umicore AG & Co. KG | Scr-active material having enhanced thermal stability |
| TW201838708A (en) * | 2017-03-02 | 2018-11-01 | 丹麥商托普索公司 | Process for the removal of sulphur oxides and nitrogen oxides contained in off-gas from an industrial plant |
| EP3720903B1 (en) | 2017-12-05 | 2024-02-07 | Blueshift Materials, Inc. | Thermally treated polyamic amide aerogel |
| DE102018100834A1 (en) | 2018-01-16 | 2019-07-18 | Umicore Ag & Co. Kg | Process for producing an SCR catalyst |
| DE102018100833A1 (en) | 2018-01-16 | 2019-07-18 | Umicore Ag & Co. Kg | Process for producing an SCR catalyst |
| BR112020016802A2 (en) * | 2018-02-19 | 2020-12-15 | Basf Corporation | SYSTEM FOR TREATING AN EXHAUST GAS CHAIN FROM AN ENGINE AND METHOD FOR TREATING AN EXHAUST GAS CHAIN |
| CN109126817B (en) * | 2018-11-07 | 2021-07-16 | 东北大学 | Iron, tungsten and zinc modified cerium oxide/manganese oxide SCR denitration catalyst and preparation method thereof |
| EP3791955A1 (en) | 2019-09-10 | 2021-03-17 | Umicore Ag & Co. Kg | Scr-catalytic material containing copper-zeolite and copper/alumina, exhaust gas treatment process with said material and method for producing said material |
| CN110586176B (en) * | 2019-09-27 | 2020-11-17 | 中国环境科学研究院 | Electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and preparation method thereof |
| CN110917829A (en) * | 2019-12-13 | 2020-03-27 | 西安润川环保科技有限公司 | Desulfurization and denitrification flue gas advanced treatment method |
| CN111111429A (en) * | 2019-12-16 | 2020-05-08 | 山东金城柯瑞化学有限公司 | Method for treating acetylfuran oxidized tail gas by using single-active-center heterogeneous catalyst technology |
| CN111389454B (en) * | 2020-04-29 | 2022-09-20 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing p-tolualdehyde from synthesis gas and toluene |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0557196A (en) * | 1991-08-29 | 1993-03-09 | Toyota Motor Corp | Production of catalyst for purifying exhaust gas |
| WO2001047634A1 (en) * | 1999-12-28 | 2001-07-05 | Corning Incorporated | Zeolite/alumina catalyst support compositions and method of making the same |
| US6770251B2 (en) * | 2000-06-28 | 2004-08-03 | Ict. Co., Ltd. | Exhaust gas purifying catalyst |
| JP3917541B2 (en) * | 2003-03-20 | 2007-05-23 | 日産ディーゼル工業株式会社 | Diesel engine exhaust purification system |
| JP2006136776A (en) * | 2004-11-10 | 2006-06-01 | Toyota Central Res & Dev Lab Inc | Nox selection reduction catalyst |
| FR2898887B1 (en) * | 2006-03-21 | 2008-05-02 | Rhodia Recherches & Tech | COMPOSITION BASED ON ZIRCONIUM OXIDE AND CERIUM OXIDE WITH HIGH REDUCIBILITY AND STABLE SPECIFIC SURFACE PROCESS FOR THE PREPARATION AND USE IN THE TREATMENT OF EXHAUST GASES |
| JP2008100152A (en) * | 2006-10-18 | 2008-05-01 | Cataler Corp | Catalyst for cleaning exhaust gas |
| US7527776B2 (en) * | 2007-01-09 | 2009-05-05 | Catalytic Solutions, Inc. | Ammonia SCR catalyst and method of using the catalyst |
| US8802582B2 (en) * | 2007-01-09 | 2014-08-12 | Catalytic Solutions, Inc. | High temperature ammonia SCR catalyst and method of using the catalyst |
| US7767175B2 (en) * | 2007-01-09 | 2010-08-03 | Catalytic Solutions, Inc. | Ammonia SCR catalyst and method of using the catalyst |
| JP5777339B2 (en) * | 2007-04-26 | 2015-09-09 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ | Transition metal / zeolite SCR catalyst |
| US20090263297A1 (en) * | 2007-09-19 | 2009-10-22 | General Electric Company | Catalyst and method of manufacture |
| WO2009141894A1 (en) * | 2008-05-20 | 2009-11-26 | イビデン株式会社 | Honeycomb structure |
| CN101722059B (en) * | 2008-10-31 | 2011-12-21 | 中国石油化工股份有限公司 | Regeneration method of absorbent composite capable of removing sulphur and/or nitrogen oxides in fume |
| EP2335810B1 (en) * | 2009-12-11 | 2012-08-01 | Umicore AG & Co. KG | Selective catalytic reduction of nitrogen oxides in the exhaust gas of diesel engines |
-
2011
- 2011-10-24 WO PCT/EP2011/005344 patent/WO2013060341A1/en active Application Filing
- 2011-10-24 MX MX2014004494A patent/MX2014004494A/en not_active Application Discontinuation
-
2012
- 2012-05-02 CN CN201280052240.5A patent/CN103889569B/en active Active
- 2012-05-02 BR BR112014008669-9A patent/BR112014008669B1/en not_active IP Right Cessation
- 2012-05-02 JP JP2014537523A patent/JP6112734B2/en not_active Expired - Fee Related
- 2012-05-02 RU RU2014120917A patent/RU2608616C2/en not_active IP Right Cessation
- 2012-05-02 AU AU2012327482A patent/AU2012327482A1/en not_active Abandoned
- 2012-05-02 IN IN2950CHN2014 patent/IN2014CN02950A/en unknown
- 2012-05-02 KR KR1020147013999A patent/KR101789114B1/en active IP Right Grant
- 2012-05-02 CA CA2853154A patent/CA2853154C/en not_active Expired - Fee Related
- 2012-05-02 WO PCT/EP2012/058003 patent/WO2013060487A1/en active Application Filing
-
2014
- 2014-04-17 CL CL2014000993A patent/CL2014000993A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IN2014CN02950A (en) | 2015-07-03 |
| RU2608616C2 (en) | 2017-01-23 |
| KR20140095512A (en) | 2014-08-01 |
| CA2853154C (en) | 2018-04-03 |
| BR112014008669A2 (en) | 2017-04-18 |
| CL2014000993A1 (en) | 2014-08-22 |
| AU2012327482A1 (en) | 2014-05-15 |
| WO2013060341A1 (en) | 2013-05-02 |
| CN103889569A (en) | 2014-06-25 |
| WO2013060487A1 (en) | 2013-05-02 |
| JP2015501210A (en) | 2015-01-15 |
| CN103889569B (en) | 2017-02-15 |
| CA2853154A1 (en) | 2013-05-02 |
| KR101789114B1 (en) | 2017-10-23 |
| RU2014120917A (en) | 2015-12-10 |
| JP6112734B2 (en) | 2017-04-12 |
| BR112014008669B1 (en) | 2019-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MX2014004494A (en) | Catalyst composition for use in selective catalytic reduction of nitrogen oxides. | |
| EP2908946B1 (en) | 8-ring small pore molecular sieve as high temperature scr catalyst | |
| CA2888512C (en) | Mixed metal 8-ring small pore molecular sieve catalyst compositions, catalytic articles, systems and methods | |
| US8575054B2 (en) | Catalyst for purifying organic nitrogen compound-containing exhaust gas and method for purifying the exhaust gas | |
| US20150290632A1 (en) | IRON AND COPPER-CONTAINING CHABAZITE ZEOLITE CATALYST FOR USE IN NOx REDUCTION | |
| US9289756B2 (en) | Copper containing ZSM-34, OFF and/or ERI zeolitic material for selective reduction of NOx | |
| EP2593212B2 (en) | Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox | |
| KR20120083941A (en) | Catalysts for treating transient nox emissions | |
| US9168517B2 (en) | Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides | |
| EP2593223A1 (en) | Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox | |
| US6759358B2 (en) | Method for washcoating a catalytic material onto a monolithic structure | |
| US20150258537A1 (en) | Exhaust gas purifying catalyst | |
| US11229901B2 (en) | SCR catalyst device containing vanadium oxide and molecular sieve containing iron | |
| EP2593222B1 (en) | Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox | |
| US20150231620A1 (en) | IRON-ZEOLITE CHABAZITE CATALYST FOR USE IN NOx REDUCTION AND METHOD OF MAKING | |
| US20120014866A1 (en) | Copper Containing ZSM-34, OFF And/Or ERI Zeolitic Material For Selective Reduction Of NOx | |
| KR20170063596A (en) | Thermally stable nh3-scr catalyst compositions | |
| WO2018065353A1 (en) | Catalyst article and method for the abatement of ammonia and nitrogen oxides | |
| WO2012167253A2 (en) | Multi-component and layered formulations for enhanced selective catalytic reduction activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FA | Abandonment or withdrawal |