WO2012110780A1 - Catalyseurs utilisés dans des procédés d'oxydation de l'ammoniac - Google Patents

Catalyseurs utilisés dans des procédés d'oxydation de l'ammoniac Download PDF

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WO2012110780A1
WO2012110780A1 PCT/GB2012/050249 GB2012050249W WO2012110780A1 WO 2012110780 A1 WO2012110780 A1 WO 2012110780A1 GB 2012050249 W GB2012050249 W GB 2012050249W WO 2012110780 A1 WO2012110780 A1 WO 2012110780A1
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catalyst
mixed metal
oxide
cobalt oxide
metal cobalt
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PCT/GB2012/050249
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English (en)
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Duncan Roy Coupland
Alison Mary Wagland
Mark Robert Feaviour
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Johnson Matthey Public Limited Company
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B01J37/0223—Coating of particles by rotation
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/005—Spinels
    • 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
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0217—Pretreatment of the substrate before coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/24—Nitric oxide (NO)
    • C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
    • C01B21/265—Preparation by catalytic or non-catalytic oxidation of ammonia characterised by the catalyst
    • 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
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20746—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
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    • 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
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    • B01D2255/402—Perovskites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/405—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/402—Dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8634—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • This invention relates to a method for preparing supported catalysts suitable for use in an ammonia oxidation process and in particular mixed metal cobalt oxide ammonia oxidation catalysts and nitrous oxide abatement catalysts.
  • Ammonia oxidation is carried out industrially with air to generate nitric oxide, which is used to make nitric acid (the Ostwald Process) or with air and methane to generate hydrogen cyanide (the Andrussow Process).
  • the reactant gases are mixed and passed at elevated temperature and pressure through a reaction vessel in which is placed a pack of platinum/rhodium gauzes that catalyse the oxidation reactions.
  • the gauzes are typically circular and are supported on a frame or basket that holds them perpendicular to the flow of gases through the reactor.
  • the catalyst pack may also comprise one or more palladium-rich gauzes, known as "catchment gauzes" that act to capture volatilised platinum.
  • WO 99/64352 describes a process wherein a mixture of ammonia and air at an elevated temperature is fed to a catalyst comprising one or more gauzes of at least one precious metal in elemental filamentary form, and the resultant gas mixture passed through a layer of a particulate oxidic cobalt-containing catalyst placed below the gauzes.
  • nitrous oxide N 2 0
  • nitrous oxide abatement catalysts have also been included in the ammonia oxidation vessels as layers underneath the precious metal ammonia oxidation catalyst.
  • Preferred ammonia oxidation catalysts are based on mixed metal cobalt oxides. Such catalysts are described in WO 98/28073.
  • the catalyst preparation methods disclosed include combining and calcining metal oxides at high temperature; co-precipitation, drying and calcining of mixed cobalt oxides; impregnation of an oxidic support with soluble cobalt compounds followed by drying and calcining; or by applying a wash coat comprising a mixed metal cobalt oxide catalyst to a gauze, mesh or pad of steel or ceramic wires, or to a monolithic honeycomb or foam, followed by calcining.
  • the latter preparation method can be complex and expensive, and pelleted catalysts prepared from co-precipitated compositions are currently used.
  • the invention provides a method for preparing a catalyst composition suitable for use in an ammonia oxidation process, comprising the steps of:
  • the method provides the mixed cobalt oxide in an outer layer on the shaped support.
  • the invention further provides catalysts obtainable by the above method and the use of such catalysts for performing an ammonia oxidation process or for the destruction of nitrous oxide generated by an ammonia oxidation process.
  • Suitable mixed metal cobalt oxides in which the cobalt is locked-in to a structure and therefore has improved stability in the ammonia oxidation process are cobalt oxide spinels and cobalt oxide perovskites.
  • A may be selected from La, Nd, Sm and Pr
  • B may be selected from Co optionally with Ni, Cr, Mn, Cu, Fe and Y.
  • Partial substitution of the A-site e.g. up to 20mol%) may be performed with divalent or tetravalent cations e.g. Sr 2+ or Ce 4+ .
  • partial substitution of one B-site element e.g. up to 50mol%) with another may be performed.
  • Suitable perovskite materials include LaCo0 3 , La-
  • the mixed metal cobalt oxide is effective both as a nitrous oxide decomposition catalyst and for the oxidation of ammonia.
  • a particularly preferred mixed metal cobalt oxide is a particulate composition containing oxides of cobalt and other metals, particularly rare earths, for example as described in EP-B-0946290.
  • the preferred catalyst comprises oxides of (a) at least one element Vv selected from cerium and praseodymium and at least one element Vn selected from non-variable valency rare earths and yttrium, and (b) cobalt, said cobalt and elements Vv and Vn being in such proportions that the (element Vv plus element Vn) to cobalt atomic ratio is in the range 0.8 to 1.2, at least some of said oxides being present as a mixed oxide phase with less than 30% of the cobalt (by atoms) being present as free cobalt oxides.
  • the cobalt is present as free cobalt oxides, and in particular it is preferred that less than 15% (by atoms) of the cobalt is present as the cobalt monoxide, CoO.
  • the proportion of the various phases may be determined by X-ray diffraction (XRD) or by thermogravimetric analysis (TGA) making use, in the latter case, of the weight loss associated with the characteristic thermal decomposition of Co 3 0 4 which occurs at approximately 930°C in air.
  • XRD X-ray diffraction
  • TGA thermogravimetric analysis
  • less than 10%, particularly less than 5%, by weight of the composition is free cobalto-cobaltic oxide and less than 2% by weight is free cobalt monoxide.
  • a perovskite phase e.g. VnCo0 3 or VvCo0 3
  • other phases such as Vv 2 0 3 , Vn 2 0 3 , (Vv x Vn-
  • a particularly preferred mixed metal cobalt oxide is a La-
  • Such materials may be prepared according to examples of EP-B-0946290 herein incorporated by reference.
  • the particulate mixed metal cobalt oxide particles preferably have a d50 average particle size in the range 1-80 ⁇ , preferably 1-50 ⁇ , more preferably 1 to 30 ⁇ , especially 1 to 10 ⁇ .
  • the particulate mixed metal cobalt oxide is dispersed in a liquid medium, which is desirably aqueous.
  • the solids content of the slurry may suitably be in the range 10 - 60% wt.
  • the slurry may suitably be formed using milling techniques used in the preparation of catalyst wash-coats. Binder materials such as zirconia, titania, alumina or hydrated alumina sols may be included and other conventional wash-coat preparation techniques may be applied, such as milling and mixing of the dispersion to achieve the desired particle size prior to coating the support.
  • polyethylene graft co-polymers such as KollicoatTM are included in the slurry. These materials, which have been used in
  • the shaped support is in the form of shaped units such as extrudates, pellets or granules, which are typically prepared from powdered support material and which may also comprise lubricants or binders. Extrudates and pellets are preferred shaped supports. The extrudates, pellets or granules may be commercially available or a re readily prepared from suitable powders using methods known to those skilled in the art.
  • Shaped units may have a variety of shapes and particle sizes, depending upon the mould or die used in their manufacture.
  • the units may be in the form of spheres, cylinders, rings, or multi-holed units, which may be multi-lobed or fluted, e.g. of cloverleaf cross-section.
  • the extrudates or pellets may be spheres or cylindrical, i.e. circular in cross-section, but are preferably lobed or fluted to increase their geometric surface area without increasing the pressure drop through a layer formed from the units. This has the advantage that the pressure drop through a bed of the catalyst is minimised.
  • the shaped units desirably have a smallest unit dimension preferably in the range 1 mm to 50 mm.
  • the smallest dimension may be width, e.g. diameter or length, e.g. height.
  • the shaped units may have a length from 1 mm to 50 mm, preferably 1.2mm to 25 mm.
  • the cross sectional width or diameter of the shaped units may be from 1 mm to about 25 mm, preferably from 1.2 mm to 10 mm, particularly from 1.2 mm to 5 mm.
  • the aspect ratio, i.e. the largest dimension divided by the smallest dimension e.g. length/cross-section, is preferably less than 10. The use of shaped units with these dimensions is advantageous for catalyst recovery and recycle.
  • the shaped oxidic support may be a refractory oxide comprising one or more of alumina, silica, alumino-silicate, titania, zirconia, magnesia, ceria or lanthana, including layered structures in which the shaped support comprises two or more support oxides in a layered arrangement.
  • the oxidic support comprises a high-temperature-stable oxide such as a metal aluminate cement or alpha-alumina.
  • the porosity or other properties of the shaped units such as the BET surface area, attrition resistance or crush strength may be altered by a physical or chemical treatment.
  • the shaped units may be calcined to temperatures >900°C or treated with organic or inorganic compounds.
  • the attrition resistance of the coated catalysts is significantly enhanced when the shaped support is first coated with a thin layer of a particulate zirconia using the same pan coating method prior to applying the slurry of mixed metal cobalt oxide.
  • the zirconia layer is preferably present in the dried catalyst at an amount in the range 0.5 - 15% by weight, preferably 2 - 8% by weight.
  • the particulate mixed metal cobalt oxide is present within a layer on the surface of the support.
  • the layer may be applied to particulate shaped units by spraying a slurry containing the particulate mixed metal cobalt oxide onto heated, tumbling shaped support units in a pan coater, which may be of the type used in the pharmaceutical or foodstuff industry for preparing coated tableted products.
  • a pan coater which may be of the type used in the pharmaceutical or foodstuff industry for preparing coated tableted products.
  • Multiple sprays may be applied with drying in-between spraying.
  • the slurry is preferably applied to supports at temperatures in the range 30-60°C, preferably 30-50°C. In this way the support is not over- wetted and the possibility of spray-drying the slurry is avoided.
  • the resulting coated material is then dried.
  • the drying step may be performed at 20-150°C, preferably 20-120°C, more preferably 95-1 10°C, in air or under an inert gas such as nitrogen, or in a vacuum oven for a period as required up to 24 hours.
  • the thickness of the layer containing the mixed metal cobalt oxide in the dried material is preferably in the range 5 to 250 ⁇ (micrometres), but more preferably is in the range 5-150 micrometres, most preferably 10-100 micrometres. Thinner layers make more efficient use of the applied cobalt.
  • the thickness of the cobalt-containing layer may be determined by methods known to those skilled in the art. For example optical microscopy in the present case is useful for measuring the thickness of the coloured cobalt compounds in the surface of the white oxidic supports. Alternatively electron microprobe analysis may be used for determining the thickness of cobalt-containing layers.
  • Loadings of the mixed metal cobalt oxide are preferably in the range 1-15% by weight, more preferably 2 to 10% by weight on the dried catalyst.
  • the dried catalyst precursors are calcined, i.e. heated at temperatures above 250°C, for example 250-1000°C for 0.5 to 5 hours to produce a catalyst that will be stable at the operating conditions in the ammonia oxidation process.
  • calcination is not essential to provide active catalysts.
  • the dried or calcined particulate catalyst may be provided to the ammonia oxidation vessel. This may be as one or more fixed beds placed in the conventional catalyst support through which the reacting gases pass axially. Alternatively the particulate mixed metal cobalt oxide catalyst may be supported beneath the conventional Pt-based precious metal and/or Pd-based catchment gauzes.
  • the thickness of such particulate beds is typically ⁇ 500mm, preferably ⁇ 300mm, more preferably ⁇ 100mm.
  • the particulate catalyst may be provided to the ammonia oxidation vessel in a radial-flow catalyst support structure, such as that described in our application
  • the catalyst assembly may comprise 1 or 2 precious metal ammonia oxidation catalyst gauzes followed by one or more gauzes of palladium catchment, followed by a radial flow bed of shaped units of an oxidic cobalt-containing nitrous oxide decomposition catalyst.
  • the catalyst assembly may comprise 10 or fewer gauzes of a platinum or platinum-alloy ammonia oxidation catalyst, one or more gauzes of palladium catchment, a radial-flow bed of shaped units of a mixed metal rare-earth cobalt perovskite catalyst.
  • the catalyst assembly comprises 10 or fewer platinum or platinum alloy ammonia oxidation catalyst gauzes followed by one or more gauzes of palladium catchment comprising ⁇ 5% wt Rh, followed by a radial flow bed of shaped units of mixed metal rare-earth cobalt perovskite catalyst, prepared according to the present invention.
  • the oxidation process may be operated at temperatures of 750-1000°C, particularly 850-950°C, pressures of 1 (low pressure) to 15 (high pressure) bar abs., with ammonia in air concentrations of 7-13%, often about 10%, by volume.
  • Andrussow Process i.e. the oxidation of ammonia with air in the presence of methane for the manufacture of hydrogen cyanide, the operating conditions are similar.
  • the process using the catalysts made by the method described herein may provide high conversion of the ammonia with aggregate N 2 0 levels below 1600 ppm, preferably below 600 ppm, more preferably below 500 ppm and most preferably below 200 ppm, e.g. 50- 200ppm, when a particulate nitrous oxide abatement catalyst is provided.
  • Pellet coating was carried out using a Profile Automation Pilot XT bench top side vented pan coater or a Capco Conical Lab Mixer. The coating was applied with a spray gun fed by a peristaltic pump (Watson Marlow 101 U/R) that supplies the washcoat to the pan coater through silcone tubing (8 mm od, 5 mm id).
  • a peristaltic pump Wood Marlow 101 U/R
  • Attrition testing was carried out in a 135 mm diameter rotating steel pan fitted with four 20 mm steel baffles. Samples (100 g) were tumbled at 26 rpm for 15 minutes and the weight loss recorded. This gave an indication adhesion based on total weight loss but samples were also assessed by ICP analysis pre- and post attrition to assess actual coating loss as a percentage.
  • Kollicoat IR (2.36 g) was dissolved in demineralised water (200 ml) and added to the slurry (324 g) prepared in (a). The coating was applied using the pan coating equipment. During the coating the pellets were maintained at between 40 and 50 °C. The product was dried in an oven at 105 °C and calcined at 500 °C for 2 hours. Catalyst 1 was found by ICP elemental analysis to have a La 0 . 8 Ceo .2 Co0 3 loading of 3.9 %
  • Catalysts 2 and 3 were subjected to attrition testing as set out above. The results were as follows;
  • the zirconia base-coat has significantly improved the attrition resistance of the catalyst.
  • Example 4 Catalyst Selectivity.
  • Ammonia oxidation testing was carried out in laboratory apparatus using a 5% NH 3 stream at heating rate of 20 °C min " and a dwell at 800 °C for 30 minutes. Catalysts 1 and 2 were compared to a commercially available ammonia oxidation catalyst under the same conditions.

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  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Cette invention concerne un procédé de préparation d'une composition catalytique appropriée pour être utilisée dans un procédé d'oxydation de l'ammoniac, le procédé comprenant les étapes consistant à : (i) pulvériser une solution épaisse contenant des particules d'oxyde de cobalt métallique mixte à la surface d'un support façonné dans un tambour de revêtement en vue de former un matériau support enduit, et (ii) sécher et éventuellement calciner le matériau support enduit de manière à former le catalyseur doté d'une couche superficielle d'oxyde de cobalt métallique mixte. Ce catalyseur du type coquille d'œuf est utilisé pour générer de l'oxyde nitrique par oxydation de l'ammoniac avec l'air, ou pour générer du cyanure d'hydrogène par oxydation de l'ammoniac avec l'air en présence de méthane.
PCT/GB2012/050249 2011-02-14 2012-02-06 Catalyseurs utilisés dans des procédés d'oxydation de l'ammoniac WO2012110780A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106268184A (zh) * 2016-09-19 2017-01-04 清华大学 一种钴氨吸收剂同时烟气脱硫脱硝的钴络合物回收方法
CN107537514A (zh) * 2017-07-21 2018-01-05 上海纳米技术及应用国家工程研究中心有限公司 锰铁钴整体式scr低温催化剂制备方法、产品和其应用
CN109382111A (zh) * 2018-11-28 2019-02-26 泉州师范学院 一种用于苯催化氧化的四氧化三钴催化剂的制备方法
BE1028735B1 (nl) * 2021-03-07 2022-05-18 Eurochem Antwerpen Een ammoniakoxidatieoven en een methode voor de productie van ammoniumnitraat met verminderde broeikasgasemissies

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1542634A (en) * 1975-09-16 1979-03-21 Ici Ltd Cobalt oxide catalyst
US4521618A (en) * 1981-06-26 1985-06-04 Degussa Aktiengesellschaft Process for preparing acrylic or methacrylic acid
WO1998028073A1 (fr) 1996-12-20 1998-07-02 Imperial Chemical Industries Plc Catalyseur d'oxydation d'ammoniac
WO1999064352A1 (fr) 1998-06-09 1999-12-16 Imperial Chemical Industries Plc Procede catalytique d'oxydation de l'ammoniac et systeme de catalyse
WO2000029108A1 (fr) * 1998-11-12 2000-05-25 Abb Lummus Global Inc. Catalyseur a film mince resistant a l'abrasion et son procede de preparation
US6177381B1 (en) * 1998-11-03 2001-01-23 Uop Llc Layered catalyst composition and processes for preparing and using the composition
WO2002090256A2 (fr) * 2001-05-04 2002-11-14 Johnson Matthey Plc Oxydation ammoniacale
US7176159B1 (en) * 2001-08-15 2007-02-13 Iowa State University Research Foundation, Inc. Catalyst and sorbent material for the production of hydrogen
US20070098613A1 (en) * 2003-06-23 2007-05-03 Basf Aktiengesellschaft Method for removing n20 during the production of nitric acid
US20080248199A1 (en) * 2005-12-20 2008-10-09 Gajda Gregory J Selective Hydrogenation Process Using Layered Catalyst Composition and Preparation of Said Catalyst
WO2010046675A1 (fr) 2008-10-20 2010-04-29 Johnson Matthey Plc Unité de confinement d’un catalyseur
US20100137650A1 (en) * 2008-11-25 2010-06-03 Sud-Chemie Ag Shell catalyst, process for its preparation and use

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1542634A (en) * 1975-09-16 1979-03-21 Ici Ltd Cobalt oxide catalyst
US4521618A (en) * 1981-06-26 1985-06-04 Degussa Aktiengesellschaft Process for preparing acrylic or methacrylic acid
EP0946290B1 (fr) 1996-12-20 2001-10-10 Imperial Chemical Industries Plc Oxydation d'ammoniac
WO1998028073A1 (fr) 1996-12-20 1998-07-02 Imperial Chemical Industries Plc Catalyseur d'oxydation d'ammoniac
WO1999064352A1 (fr) 1998-06-09 1999-12-16 Imperial Chemical Industries Plc Procede catalytique d'oxydation de l'ammoniac et systeme de catalyse
US6177381B1 (en) * 1998-11-03 2001-01-23 Uop Llc Layered catalyst composition and processes for preparing and using the composition
WO2000029108A1 (fr) * 1998-11-12 2000-05-25 Abb Lummus Global Inc. Catalyseur a film mince resistant a l'abrasion et son procede de preparation
WO2002090256A2 (fr) * 2001-05-04 2002-11-14 Johnson Matthey Plc Oxydation ammoniacale
US7176159B1 (en) * 2001-08-15 2007-02-13 Iowa State University Research Foundation, Inc. Catalyst and sorbent material for the production of hydrogen
US20070098613A1 (en) * 2003-06-23 2007-05-03 Basf Aktiengesellschaft Method for removing n20 during the production of nitric acid
US20080248199A1 (en) * 2005-12-20 2008-10-09 Gajda Gregory J Selective Hydrogenation Process Using Layered Catalyst Composition and Preparation of Said Catalyst
WO2010046675A1 (fr) 2008-10-20 2010-04-29 Johnson Matthey Plc Unité de confinement d’un catalyseur
US20100137650A1 (en) * 2008-11-25 2010-06-03 Sud-Chemie Ag Shell catalyst, process for its preparation and use

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106268184A (zh) * 2016-09-19 2017-01-04 清华大学 一种钴氨吸收剂同时烟气脱硫脱硝的钴络合物回收方法
CN106268184B (zh) * 2016-09-19 2019-02-22 清华大学 一种钴氨吸收剂同时烟气脱硫脱硝的钴络合物回收方法
CN107537514A (zh) * 2017-07-21 2018-01-05 上海纳米技术及应用国家工程研究中心有限公司 锰铁钴整体式scr低温催化剂制备方法、产品和其应用
CN109382111A (zh) * 2018-11-28 2019-02-26 泉州师范学院 一种用于苯催化氧化的四氧化三钴催化剂的制备方法
CN109382111B (zh) * 2018-11-28 2021-09-28 泉州师范学院 一种用于苯催化氧化的四氧化三钴催化剂的制备方法
BE1028735B1 (nl) * 2021-03-07 2022-05-18 Eurochem Antwerpen Een ammoniakoxidatieoven en een methode voor de productie van ammoniumnitraat met verminderde broeikasgasemissies

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