WO2015197036A1 - Cobalt-containing beta zeolite, method of its preparation, and use thereof in catalyzed reduction of nitrogen oxides - Google Patents

Cobalt-containing beta zeolite, method of its preparation, and use thereof in catalyzed reduction of nitrogen oxides Download PDF

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WO2015197036A1
WO2015197036A1 PCT/CZ2015/000053 CZ2015000053W WO2015197036A1 WO 2015197036 A1 WO2015197036 A1 WO 2015197036A1 CZ 2015000053 W CZ2015000053 W CZ 2015000053W WO 2015197036 A1 WO2015197036 A1 WO 2015197036A1
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nitrogen oxides
catalyst
catalyst according
beta zeolite
zeolite
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French (fr)
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Petr SAZAMA
Alena VONDROVÁ
Jiři DĚDEČEK
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USTAV FYZIKALNI CHEMIE J HEYROVSKEHO AV CR VVI
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USTAV FYZIKALNI CHEMIE J HEYROVSKEHO AV CR VVI
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80Mixtures of different zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404Removing only nitrogen compounds
    • B01D53/9409Nitrogen oxides
    • B01D53/9413Processes characterised by a specific catalyst
    • B01D53/9418Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72Crystalline 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
    • B01J29/76Iron group metals or copper
    • B01J29/7615Zeolite Beta
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20746Cobalt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/50Zeolites
    • B01D2255/502Beta zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/40Nitrogen compounds
    • B01D2257/402Dinitrogen oxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/01Engine exhaust gases
    • B01D2258/012Diesel engines and lean burn gasoline engines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • B01J29/24Iron group metals or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline 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
    • B01J29/42Crystalline 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
    • B01J29/46Iron group metals or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65Crystalline 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
    • B01J29/66Crystalline 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
    • B01J29/68Iron group metals or copper
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/10Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Definitions

  • Cobalt-containing beta zeolite method of its preparation, and use thereof in catalyzed reduction of nitrogen oxides
  • the invention relates to the elimination of nitrogen oxides from emissions of combustion and technological processes using a zeolite-based catalyst, which can be prepared without use of organic templates.
  • the catalyst has a high content of aluminium and it contains cobalt in non-lattice positions.
  • the invention further relates to a method of preparation of the above mentioned catalyst and to a method of a selective catalytic reduction of nitrogen oxides into nitrogen gas.
  • N 2 0 nitrogen oxides
  • N 2 0 3 ⁇ N 0 4 and N 2 0 as side products of combustion of the so called poor fuel mixtures or from chemical production processes, represent a severe environmental problem.
  • the emissions are being limited by legislative regulations.
  • a selective catalytic reduction of nitrogen oxides (NO, N0 2 ) into nitrogen and water vapors using ammonia is an efficient and a widely used process for abatement emissions of NO and N0 2 .
  • N 2 0 is usually converted into nitrogen and oxygen at high temperatures by its catalytic decomposition.
  • the selective catalytic reduction using ammonia is utilized mainly for stationary sources of NO and N0 2 (chemical processes such as nitric acid production, emissions from nitration processes etc.), and during fuel combustion during energy production (power station, heating plant) or incineration.
  • Literature often describes a process of selective catalytic reduction of nitrogen oxides using hydrocarbons (CH-SCR-NO x ). It is a promising method of nitrogen oxide elimination from oxygen-containing emissions.
  • the reducing agent hydrocarbons or derivatives thereof
  • the resulting gas mixture flows over a catalytic bed on which the reduction of nitrogen oxides occurs.
  • the main drawback of this process is the insufficient activity/selectivity of the hitherto known catalysts or insufficient stability of NO x conversion at high temperatures.
  • Precious metal-based catalysts show a certain activity at low temperatures, but they are suitable only for a very limited range of temperatures.
  • Ionic form of cobalt shows a catalytic activity when placed in non-lattice positions of zeolites. The activity of such catalysts, however, is not sufficient to be used in practice. Therefore, the significance of the above mentioned catalysts in the current technologies is negligible.
  • Beta zeolite (according to IZA called BEA* and composed of three polymorphs A, B, and C) consists of 4-, 5- and 6-membered rings, forming a three- dimensional channel structure with 12-membered entrance holes of 6.6 x 6.7 A (Ch. Baerlocher, L.B. McCusker and D.H. Olson, Atlas of Zeolite Framework Types, 6th revised edition, 2007).
  • Beta zeolite was first described in US3308069.
  • One disadvantage with respect to industrial use of beta zeolites prepared by classical methods is the need to use a relatively expensive tetramethylammoniumhydroxide (TMAOH) or an analogical organic template during the hydrothermal synthesis of such zeolite.
  • TMAOH tetramethylammoniumhydroxide
  • Another disadvantage of such procedures is the limitation of maximum aluminium content in the lattice of zeolites, corresponding to the Si/Al ratio > 11. US5869013 uses this type of beta zeolite.
  • the present invention aims to solve the problem of elimination of all nitrogen oxides from emissions by their selective catalytic reduction, using preferably hydrocarbons as the reducing agents.
  • the present invention provides a unique and highly efficient catalyst, based on cobalt ions distributed in beta zeolite with high lattice content of aluminium. Such catalytic process provides a high conversion of NO, N0 2j N 2 0 5 and N 2 0 into nitrogen.
  • the present invention uses beta zeolites, which are prepared without the use of organic templates.
  • the beta zeolites used in this invention are prepared by the method of synthesis using addition of beta zeolite into aluminium silicate gel as a source of crystal nuclei, and have a high lattice content of aluminium (being molar ratio Si/Al from 3 to 8). They are used to prepare cobalt-based catalysts for selective catalytic reduction of nitrogen oxides.
  • Such catalysts according to the present invention provide high activities, significantly exceeding those of the materials known in the art.
  • the object of the present invention is a catalyst which contains beta zeolite having the content of aluminium in the lattice corresponding to Si/Al ratio in the range of from 3 to 8, and containing cobalt ions as active centers.
  • such catalyst is obtainable by addition of beta zeolite as a source of crystal nuclei into aluminium silicate gel, followed by crystallization, and ion-exchange process using Co 2+ ions.
  • the catalyst is obtainable without the use of organic templates.
  • the catalyst has main peaks in its XRD diffraction pattern obtained using CU & radiation in Bragg-Brentano geometry in the following ranges: 7.2- 8.4; 21.7-22.4; 24.8-25.2; 28.2-28.7 and 29.1-29.4 degree 2-theta.
  • the content of the cobalt ions in the catalyst lies between 1 and 20 % (w/w), more preferably between 7 and 12 % (w/w).
  • the catalyst contains up to 25 % (w/w) of a dopant selected from a group containing IIA, IIIA, IV A, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIIIB metal ions.
  • a dopant selected from a group containing IIA, IIIA, IV A, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIIIB metal ions.
  • the presence of the dopant may increase the efficiency of the beta zeolite based catalyst according to the present invention.
  • the dopant is selected from alkaline earth metal ions and or transition metal ions and/or precious metal ions, in particular from a group containing Ca 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Pd 2+ .
  • Most preferable dopant is barium in an ion-exchange form in non-lattice positions of the zeolite.
  • the catalyst according to the present invention further contains zeolites of different crystalographical structures, preferably zeolites of structural topology MOR, FER and/or MFI.
  • the present invention further provides a method of preparation of the catalyst according to the present invention.
  • beta zeolite is added into aluminium silicate gel as a source of crystal nuclei
  • in a second step the crystallization of the beta zeolite is carried out
  • in a third step ion-exchange process with Co solution occurs.
  • the method of preparation of the catalyst utilizes solution and/or solid state ion exchange. It can also rely on the impregnation using cobalt salts.
  • the Co solution is typically a solution of Co(II) salt, such as nitrate, halogenide, sulfate, carbonate, acetate, or any other soluble Co(II) salt.
  • the Co 2+ solution may be used, for example, in an amount of about 1 to about 100 ml per 1 g of beta zeolite, and in a concentration of 0.01 to 10 M. Most suitable amount is 50 ml of 0.05 M Co 2 ⁇ solution per 1 g of beta zeolite.
  • the method of preparation of the catalyst uses in the ion-exchange step Co 2+ and dopant solution, wherein the dopant is selected from the group containing IIA, IIIA, IV A, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIIIB metal ions, preferably selected from Ca 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Pd 2+ .
  • the dopant salts used can be any salts soluble in the solvent which is used for the ion-exchange, such as nitrates, halogenides, sulfates, carbonates, acetates, or any other soluble salts.
  • the solvent used for ion exchange is typically water, however other polar solvents might also be used. When the method of impregnation is used, cobalt salts and salts of metals suitable as dopants are utilized.
  • the present invention further includes a method of catalytic reduction of nitrogen oxides using the catalyst according to the present invention.
  • the temperature of the reduction reaction lies in a range of from 150 °C to 550 °C, preferably from 300 °C to 450 °C, the pressure is equal or higher than atmospheric and the reducing agent is present in a concentration of 50 to 10 000 ppm (from 0.5 mol. equiv. to 10 mol. equiv. of nitrogen oxides, which are being reduced).
  • nitrogen oxides are selected from the group containing NO, ⁇ 0 2 , N 2 0, 2O5 and mixtures thereof.
  • the reducing agent is preferably selected from the group containing diesel fuel, bio-diesel fuel, gasoline, oil, paraffin, ammonia, urea, and C
  • the present invention further includes the use of the catalyst according to the present invention for the elimination of nitrogen oxides from emissions.
  • the beta zeolite-based catalyst with a high aluminium content (molar ratio Si/Al is from 3 to 8) and cobalt ions as active centers, prepared without the use of organic template, can be placed as a catalytic bed in a reactor space in the form of extrudates. It can also be applied on the surface of a monolite of a suitable shape and channel diameter or it can be used in the form of pellets, tablets or other suitable shapes.
  • the beta zeolite based catalyst according to the present invention can thus be used in selective catalytic reduction of nitrogen oxides present in emissions from various sources, such as from combustion processes in heat and electric energy production, diesel combustion motors, and chemical technological processes (nitric acid production etc.).
  • Fig. 1 XRD diffractogram of the Co-BEA-5 catalyst, prepared according to Example 1.
  • Fig. 2 XRD diffractogram of the CoBa-BEA-4 catalyst, prepared according to Example 2.
  • Fig. 3 XRD diffractogram of the Co-BEA/MOR-4.5 catalyst, prepared according to Example 13. Examples
  • the catalyst Co-BEA-5 was prepared by an ion-exchange of beta zeolite with high content of lattice aluminium (molar ratio Si/Al was 5) prepared by addition of beta zeolite into aluminium silicate gel as a source of crystal nuclei and subsequent crystallization, i.e. without use of an organic template. The ionic exchange was repeated three times, using 0.05 M Co(N0 3 )2 (50 ml of the solution per 1 g of zeolite). The obtained catalyst contained 8.1 % (w/w) of cobalt in a form of highly dispersed Co 2+ ions in non-lattice positions of the zeolite. The catalyst showed an XRD diffractogram (see Fig. 1).
  • Co-BEA-11 was prepared.
  • Co-BEA-11 was prepared by an ion-exchange of beta zeolite (molar ratio Si/Al was 11) prepared using an organic template. The ionic exchange was repeated three times, using 0.05 M Co(N03) 2 (50 ml of the solution per 1 g of zeolite).
  • the obtained catalyst contained 4 % (w/w) of cobalt in a form of highly dispersed Co ions in non-lattice positions of the zeolite.
  • the catalyst CoBa-BEA-4 was prepared by an ion-exchange of beta zeolite with high content of lattice aluminium (molar ratio Si/Al was 4) prepared by addition of beta zeolite into aluminium silicate gel as a source of crystal nuclei and subsequent crystallization, i.e. without use of an organic template.
  • the ionic exchange was repeated three times, using a solution containing 0.05 M Co(N0 3 ) 2 and 0.05 M Ba(N0 3 ) 2 (50 ml of the solution per 1 g of zeolite).
  • the obtained catalyst contained cobalt in a form of highly dispersed Co 2+ ions (7.5 % (w/w)) in non-lattice positions of the zeolite and Ba 2+ ions (2 % (w/w)) in non- lattice positions of the zeolite.
  • the catalyst CoBa-BEA-1 1 was prepared by an ion-exchange of beta zeolite (molar ratio Si/Al was 11) prepared using an organic template. The ionic exchange was repeated three times, using a solution containing 0.05 M Co(N03) 2 and 0.05 M Ba(N0 3 )2 (50 ml of the solution per 1 g of zeolite). The obtained catalyst contained cobalt in a form of highly dispersed Co 2+ ions (3 %(w/w)) in non-lattice positions of the zeolite and Ba 2+ ions (1 % (w/w)) in non-lattice positions of the zeolite.
  • the intensities and patterns of the X-ray diffraction lines for Co/Ba-BEA-11 obtained using CU Q radiation in Bragg-Brentano geometry were characteristic of the well-developed crystalline structure of BEA* topology. All observed reflections are shifted by 0.3 degree 2-theta to the lower values compared to CoBa-BEA-4 indicating the low concentration of Al for Co/Ba-BEA-11.
  • a flow of emissions composed of 960 ppm NO, 40 ppm N0 2 , 1000 ppm C 3 H 8 , 0.7 % H 2 0, 3 % 0 2 at the temperature of from 300 °C to 450 °C was driven to a reactor with a catalytic bed containing the catalyst prepared according to Example 1.
  • the weight of the catalyst was 100 mg and the spatial velocity was 90 000 h "1 .
  • the same experiment was repeated with the catalyst prepared in Comparative example 1A.
  • the dependence of the conversion of nitrogen oxides into nitrogen on temperature is listed in Table 1.
  • a flow of emissions composed of 960 ppm NO, 40 ppm N0 2 , 1000 ppm C 3 3 ⁇ 4, 3 % H 2 0, 3 % 0 2 at the temperature of 400 °C was driven to a reactor with a catalytic bed containing the catalyst prepared according to Example 1.
  • the weight of the catalyst was 100 mg and the spatial velocity was 90 000 h "! .
  • the conversion of nitrogen oxides into nitrogen was 96%.
  • a flow of emissions composed of 960 ppm NO, 40 ppm N0 2s 3000 ppm CH 4 , 10 % H 2 0, 3 % 0 2 at the temperature of 400 °C was driven to a reactor with a catalytic bed containing the catalyst prepared according to Example 1.
  • the weight of the catalyst was 100 mg and the spatial velocity was 90 000 h "1 .
  • the conversion of nitrogen oxides into nitrogen was 95%.
  • a flow of emissions composed of 250 ppm NO, 800 ppm N0 2 , 1000 ppm N 2 0, 3000 ppm CH4, 0.7 % H 2 0, 3 % 0 2 at the temperature of from 350 °C to 400 °C was driven to a reactor with a catalytic bed containing the catalyst Co-BEA-5 prepared according to Example 1.
  • the weight of the catalyst was 100 mg and the spatial velocity was 11 250 h "1 .
  • the dependence of the conversion of nitrogen oxides into nitrogen on temperature is listed in Table 2.
  • a flow of emissions composed of 1000 ppm NO, 3000 ppm CH 4 , 0.7 % H 2 0, 3 % 0 2 at the temperature of from 400 °C to 450 °C was driven to a reactor with the catalytic bed containing a catalyst Co-BEA-5 prepared according to Example 1.
  • the weight of the catalyst was 100 mg and the spatial velocity was 11 250 h "1 .
  • the dependence of the conversion of nitrogen oxides into nitrogen on temperature is listed in Table 3.
  • a flow of emissions composed of 250 ppm NO, 800 ppm N0 2 , 1000 ppm N 2 0, 3000 ppm CHU, 0.7 % 3 ⁇ 40, 3 % 0 2 at the temperature of from 350 °C to 450 °C was driven to a reactor with a catalytic bed containing the catalyst prepared according to Example 2.
  • the weight of the catalyst was 100 mg and the spatial velocity was 15 000 h "1 .
  • the same experiment was repeated using the catalyst of Comparative example 2A.
  • the dependence of the conversion of nitrogen oxides into nitrogen on temperature is listed in Table 4.
  • a flow of emissions composed of 1000 ppm NO, 1000 ppm N 2 0, 1000 ppm C 3 H 8 , 0.7 % H 2 0, 3 % 0 2 at the temperature of from 350 °C to 450 °C was driven to a reactor with a catalytic bed containing a catalyst prepared according to Example 2.
  • the weight of the catalyst was 100 mg and the spatial velocity was 200 000 h "1 .
  • the same experiment was repeated using the catalyst of Comparative example 2 A.
  • the dependence of the conversion of nitrogen oxides into nitrogen on temperature is listed in Table 5.
  • the catalyst Co/Pd/Fe-BEA-6 was prepared by an ion-exchange of beta zeolite with high content of lattice aluminium (molar ratio Si/Al was 6) prepared by addition of beta zeolite into aluminium silicate gel as a source of crystal nuclei and subsequent crystallization, i.e. without use of an organic template.
  • the ionic exchange was performed using 0.1 M Co(N0 3 ) 2 (10 ml of the solution per 1 g of zeolite) to obtain Co-BEA-6.
  • Fe was introduced into Co-BEA-6 by its impregnation with anhydrous FeCl 3 in acetylacetone, following calcination in air at 550 °C for 2 h.
  • Pd was introduced into Co/Fe-BEA-6 by impregnation with aqueous solution of Pd(N0 3 ) 2 , following calcination in air at 450 °C for 2 h.
  • the obtained catalyst contained 4% (w/w) of cobalt, 7% (w/w) of iron and 0.5% (w/w) of palladium.
  • a flow of emissions composed of 450 ppm NO, 60 ppm N0 2 , 520 ppm N3 ⁇ 4, 10 % H 2 0, 8 % 0 2 at the temperature of from 150 °C to 300 °C was driven to a reactor with a catalytic bed containing a catalyst prepared according to Example 10.
  • the weight of the catalyst was 20 mg and the spatial velocity was 600 000 h "1 .
  • the dependence of the conversion of nitrogen oxides into nitrogen on temperature is listed in Table 6.
  • a flow of emissions composed of 450 ppm NO, 60 ppm N0 2; 200 ppm decane, 10 % H 2 0, 8 % 0 2 at the temperature of from 250 °C to 350 °C was driven to a reactor with a catalytic bed containing a catalyst prepared according to Example 1.
  • the weight of the catalyst was 100 mg and the spatial velocity was 42 000 h "1 .
  • the dependence of the conversion of nitrogen oxides into nitrogen on temperature is listed in Table 7.
  • the catalyst Co-BEA/MOR-4.5 was prepared by an ion-exchange of beta zeolite with high content of lattice aluminium (molar ratio Si/Al was 5) and zeolite structural topology MOR prepared by addition of beta and mordenite (MOR) zeolite into aluminium silicate gel as a source of crystal nuclei and subsequent crystallization, i.e. without use of an organic template.
  • the ionic exchange was repeated three times, using 0.05 M Co(N0 3 ) 2 (50 ml of the solution per 1 g of zeolite).
  • the obtained catalyst contained 9.2 % (w/w) of cobalt in a form of highly dispersed Co 2+ ions in non-lattice positions of the zeolite.
  • the catalyst showed an XRD diffractogram (see Fig. 3).
  • the XRD diffraction pattern was obtained using Cuj a radiation in Bragg-Brentano geometry in the following ranges: 7.2-8.4; 21.7- 22.4; 24.8-25.2; 28.2-28.7 and 29.1-29.4 degree 2-theta reflecting the beta zeolite, and 6.2- 6.6, 9.4-9.9, 13.1-13.9, 15.0-15.4, 19.4-19.7 and 26.0-26.4 degree 2-theta reflecting the mordenite zeolite.
  • a flow of emissions composed of 960 ppm NO, 40 ppm N0 2 , 1000 ppm 0 3 3 ⁇ 4, 0.7 % H 2 0, 3 % 0 2 at the temperature of from 300 °C to 450 °C was driven to a reactor with a catalytic bed containing the catalyst prepared according to Example 13.
  • the weight of the catalyst was 100 mg and the spatial velocity was 90 000 h "1 .
  • the dependence of the conversion of nitrogen oxides into nitrogen on temperature is listed in Table 8.

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PCT/CZ2015/000053 2014-06-27 2015-05-26 Cobalt-containing beta zeolite, method of its preparation, and use thereof in catalyzed reduction of nitrogen oxides Ceased WO2015197036A1 (en)

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