GB1590451A - Catalysts containing platinum group metals - Google Patents
Catalysts containing platinum group metals Download PDFInfo
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- GB1590451A GB1590451A GB4656/77A GB465677A GB1590451A GB 1590451 A GB1590451 A GB 1590451A GB 4656/77 A GB4656/77 A GB 4656/77A GB 465677 A GB465677 A GB 465677A GB 1590451 A GB1590451 A GB 1590451A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of actinides
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D5/00—Coating with enamels or vitreous layers
- C23D5/10—Coating with enamels or vitreous layers with refractory materials
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Description
(54) IMPROVEMENTS IN AND RELATING TO CATALYSTS
CONTAINING PLATINUM GROUP METALS
(71) We, JOHNSON, MATTHEY & CO., LIMITED, a British Company, of 43
Hatton Garden, London, EC1N 8EE, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to catalysts containing platinum group metals, to new compositions of matter containing platinum group metals and to chemical reactions which may be more effectively performed with the said catalysts.
In many gaseous oxidation reactions in which a precious metal acts as a heterogeneous catalyst, quantities of the catalyst are frequently lost by factors such as oxidation and volatilization. One reaction in which such a loss is particularly important is in the catalytic oxidation of ammonia during the manufacture of nitric acid.
With few exceptions the oxidation of ammonia gas during the manufacture of nitric acid is carried out on a catalyst comprising a multiplicity or a pack of, fine wire gauzes fabricated from a platinum-base alloy. Typically, in a high pressure installation 20-40 gauzes would be employed woven at 80 meshes per linear inch from 0.003 inch diameter 10% rhodiumplatinum wire or strip.
Air mixed with ammonia gas in an approximate ratio of 9 1 (by volume) is preheated to about 250"C and then passed at a relatively high velocity through the gauzes. The ensuing catalysed exothermic reaction results in a gauze operating temperature of 850"C - 950"C, and the oxidation of the ammonia gas is efficiently catalysed to nitrogen oxides and water.
The nitrogen oxides are cooled and absorbed in further water to form nitric acid.
During this oxidation process, some of the precious metal of the wire or strip from which the gauze pack is made is lost by a combination of oxidation and volatilisation, and is carried away in the gas stream. Various methods have been adopted in the past to reduce these losses including catchment gauzes, trays, filters etc., designed to recapture the precious metal from the gas stream after it has been volatilised. These methods have not proved wholly satisfactory, and it is one object of the present invention to reduce the platinum metal losses at source by more rigidly bonding platinum metal atoms to the surface of the catalyst.
Catalysts in accordance with the present invention are not restricted to use in the oxidation of ammonia and may be used in both oxidising and reducing environments where, for example, high temperature, pressure, throughput or some other factor results in a loss of platinum group metal. Examples of other reactions in which catalysts of the invention have applications are (i) the vapour phase oxidation of gases such as SO2, CO,HCN and organic molecules such as the hydrocarbons; (ii) the petroleum reforming and hydroforming reactions using a platinum catalyst and, a hydrocarbon feedstock; (iii) the reduction of one or more oxides of nitrogen with a gaseous reducing fuel such as methane; and (iv) the methanation reaction.
We have now found that certain intermetallic compounds of Ru, Rh, Pd, Ir and Pt with one or more base metals have high thermodynamic stability and simultaneously maintain high efficiency when used as catalysts in, for example, catalytic oxidation reactions such as the conversion of ammonia to oxides of nitrogen. The intermetallic compounds may be formed with one or more base metals selected from the group consisting of Al, Sc, Y, the lanthanides, Ti, Zr, Hf, V, Nb and Ta. Of these base metals we prefer Sc, Hf, Nb and V.
Some examples of high stability compounds are AlPt3, TiPt3, ZrPt3, HfPt3, YPd3, LnPd,
LnPd3 and Ln5Pd2 (where Ln = Sm, Gd, Dy, Ho and Er) HfIr3, TaIr3, NbIr3, HfIr, TaPd,
TiRu, ZrRu, NbIr, TaRh3, VIr3 and CeRu2.
Generally speaking, most of the intermetallic compounds included within the scope of the present invention exhibit extreme hardness or brittleness and it is not practicable to draw and weave them into, for example, a gauze for use in ammonia oxidation.
It is a further object of the present invention to enable intermetallic compounds exhibiting such properties and falling within the scope of the invention to be disposed in a form in which they can be used in severe catalytic reactions, e.g. the oxidation of ammonia.
Accordingly the present invention includes a catalyst comprising a substrate having deposited thereon a first surface coating containing a refractory metal oxide and having deposited upon the said oxide one or more intermetallic compounds of the general formula AXBy where A is selected from the group consisting of Ru, Rh, Pd, Ir and Pt, and B is selected from the group consisting of Al, Sc, Y, the lanthanides, Ti, Zr, Hf, V, Nb, and Ta, and where x and y are integral and may have values of 1 or more.
The substrate may be made from either metallic or non-metallic, e.g. ceramic materials.
Many compounds of the type AXBy are miscible with one another and structures in which the surface coatings deposited upon the said refractory metal oxide contains more than one compound of the type AXBy are within the scope of this invention.
A number of different techniques may be employed to produce a coating in the form of a thin continuous or discontinuous layer or coating of the intermetallic compound upon the said refractory metal oxide coated metallic or non-metallic substrate.
By way of example, aluminium may be deposited onto the surface of a platinum impregnated oxide by a pack-aluminising process. In this process the platinum impregnated oxide coated onto a substrate is placed in a heat-resistant container in an appropriate mixture of chemicals such that aluminium is transferred via the vapour phase onto the oxide surface. At the aluminising temperature, typically 800-1000"C, interaction between the platinum and aluminium occurs to give the required intermetallic compound, AlPt3.
Alternatively, chemical vapour deposition from ZrCl4 can be used to form a layer of
Pt3Zr, or electrodeposition may be used either from aqueous or fused salt electrolysis to
give the requisite compound.
Whichever method is adopted, the prupose is to form a layer of the intermetallic
compound which is preferably, but not essentially, firmly adherent to the substrate bearing
the refractory metal oxide coating.
In another technique the metals forming the intermetallic compound are prepared as an
appropriate solution in water or an organic solvent. The compound is deposited upon the
oxide coated mtallic substrate by the addition of a reducing agent. The substrate is placed in the solution whilst the precipitation is taking place and becomes coated with a uniform, microcrystalline layer of the intermetallic compound.
In certain circumstances metallic substrates in the form of metallic monoliths are preferred as supports since generally speaking they exhibit lower pressure drops and possess 1l/2 - 3 times the surface to volume ratio that can be obtained with a ceramic honeycomb substrate. The normal ceramic substrate has a surface to volume ratio of the order of 600-700 sq.ft. per cubic foot of substrate. Examples are proprietary products Ex20
(Corning Glass) which has a surface area of 576 st.ft./ft3 and Grace 400 which is 780 sq.ft/ft3. This is the highest obtained so far and should be compared with 1100 st.ft/ft3 for 0.003" thick Kanthal (Registered Trade Mark) D sheet and 2000 st.ft./ft3 for 0.002" thick
Kanthal D sheet.
A metal substrate is conveniently made from corrugated foil of thickness between 0.0015 and 0.0045 inch (and preferably of thickness 0.002 inch) which is assembled to form a structure having approximately 400 cells per square inch when considered in cross section.
A preferred range of cell sizes is 200-800 cells per square inch. Suitable surface to volume ratios are 1200 sq. ft per cubic foot with 400 cells per square inch and 2000 sq. ft. per cubic foot with 800 cells per square inch.
Metals which may be used for fabrication of the monolith support are those capable of withstanding high temperature and rigorous oxidising conditions. Examples of such base metal alloys are nickel and chromium alloys having an aggregate Ni + Cr content greater than 20% by weight and alloys of iron including at least one of the elements chromium (3-40 wt %), aluminium (1-10 wt %), cobalt (trace - 5 wt %), nickel (trace - 72 weight %) and carbon (trace - 0.5 weight %). Additional trace elements which may be present in such alloys to improve strength and oxidation - and heat - resistance are: WIW Si 0.2 0.9
Mn 0.2 0.7
Zr 0.01 0.20
Cu 0.01 0.15
Nb 0.01 0.3
Ta 0.8 1.2
Ti 0.8 1.2
Ce 0.01 1.0
Ca 0.01 0.5
Other examples of base metal alloys capable of withstanding the rigorous conditions required are the iron-aluminium-chromium alloys which also contain yttrium. These contain 0.5 - 12 wt % Al, 0.1 - 3.0 wt % Y.O - 20 wt % Cr and balance Fe. These are described in United States Patent No. 3298826. Another range of Fe-Cu-Al-Y alloys contain 0.5 - 4 wt % Al, 0.5 - 3.0 % Y, 20.0 - 95.0 wt % Cr and balance Fe. These alloys are described in United Patent No. 3027252.
A metallic substrate which has been mechanically deformed to produce an extended surface area possesses when compared with a plain non-deformed substrate, a very much increased exposed surface area for the same volume. Typically, the increased surface area may be achieved by corrugating or folding in a former and winding up a flat foil and a corrugated foil together into a tube having a spiral cross section.
In one embodiment of the present invention, the metallic substrate which is employed as the monolith support for the catalyst is first crimped, corrugated, folded, indented and/or perforated in such a way that a very much more exposed surface area is produced. Such a surface area is normally much greater than that obtained with a ceramic honeycomb or with particulate catalyst supports for the same given volume. An example of a metallic substrate made in accordance with this invention comprises a roll of corrugated sheet of a heat resisting alloy interleaved with a non-corrugated sheet of such alloy. Alternatively, two corrugates sheets may be used with the corrugations in each sheet parallel or transverse relative to each other. A coiled substrate is then provided with a firmly adherent oxide coating which is porous and absorbent and has a high surface area and which acts as the carrier for the second catalytically active layer containing one or more of the catalytic intermetallic compounds as herein defined.
The heat resistant alloys comprising the extended metal substrate are alternatively alloys having a minimum nickel plus chromium content of 20% by weight. Typical alloys which, therefore, may be used for the extended metal substrate are high nickel and chromium stainless steels and proprietary products such as "INCONEL" (Registered Trade Mark) 600 and "INCONEL" 601.
The metallic honeycomb structure which has thereon a first coating of a refractory metal oxide, is then further impregnated or coated with one or more of the intermetallic compounds specified above. Suitable refractory metal oxides comprising the said first coating are one or more of the oxides of Al, Si, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, and the lanthanides and the actinides, for example Th. Preferred refractory metal oxide layers comprise members of the gamma or activated alumina family. This can be prepared, for example, by precipitating a hydrous alumina gel and, thereafter, drying and calcining to expel hydrated water and provide active gamma alumina. A particularly preferred active refractory metal oxide is obtained by drying and calcining at temperatures of 300C to 800C a precursor mixture. of hydrous alumina phases predominating in crystalline trihydrate, that is, containing in excess of 50 per cent by weight of the total alumina hydrate composition, preferably from 65 - 95 per cent by weight of one or more of the trihydrate forms of gibbsite, bayerite and norstrandite by X-ray diffraction. We prefer to use British
Aluminium Co. grade MH170 alumina hydrate and convert it to activated alumina by drying and firing as described above. We prefer to provide the metallic substrate with a first firmly adherent oxide layer in an essentially two stage process. In the first stage the metallic substrate is thermally oxidised to provide a thin first oxide layer which acts as a key. We prefer to carry out thermal oxidation by maintaining the formed metallic substrate at from 1000 - 1200"C in air or moist cracked ammonia vapour, for 1 hour. The higher temperature is required with very oxidation resistant alloys such as the Kanthal range and the moist hydrogen atmosphere is preferred with alloys having a high Ni content.
The adherent oxygen-containing or oxide film for application to both metallic and non-metallic substrates may be produced by any one of several known methods including chemical techniques. The film must be of sufficient thickness to provide adequate absorptive capacity for retaining the catalytically active alloy comprising one or more of the platinum group metals. The film is preferably from 0.0004 to 0.001 inches thick.
Where aluminium is present in the alloy forming the extended metal substrate the oxide film may be produced by treating the aluminium containing surface with a solution of an alkaline carbonate usually a sodium carbonate-chromate solution. The film may be produced by the anodic oxidation of the metal surface whereby the metal is made the anode in an electrolytic solution. In anodising aluminium-containing surfaces, a 15% sulphuric acid solution is commonly employed as the electrolyte but other acid electrolytes such as chromic acid, oxalic acid, phosphoric acid and, sometimes, boric acid may be used. The oxide film to which this invention relates is deliberately positioned and does not include the relatively thin natural oxide films which sometimes occur on metal surfaces which have been exposed to the atmosphere.
One method of forming an alumina layer on these alloys which do not contain sufficient aluminium to form their own alumina layer upon oxidation is the use of Calorising (Trade
Mark). This involves the vapour deposition of an aluminium coating followed by anodising or heating in an oxygen-containing gas. Alternative coatings such as chromate, phosphate, silica or silicate or zirconia may all be deposited by known methods.
The ceramic supports may be either of the particulate e.g. pellet type or they may be monolithic. Monolithic ceramic supports are preferably of the "honeycomb" type having a regular array of gas flow channels. Suitable materials which may be used to constitute the ceramic support are zircon-mullite, mullite, alpha alumina, sillimanite, magnesium silicates, kaolin clays, zircon, petalite, spodumene, cordierite and most other aluminosilicates.
Proprietary products which may be used are described in Talsma U.S. Patent No.
3,397,154 Stiles U.S. Patent No. 3,498,927 and Corning British Patent No. 882,484.
Examples are "Torvex" (Trade Mark) which is a mullite honeycomb having eight corrugations per inch and bearing an alumina washcoat; "Thermacomb" (Trade Mark), a cordierite honeycomb supplied by the American Lava Corporation and EX 20 a cordierite honeycomb supplied by Corning Glass.
Suitable supports of the pelleted or granular type include porous silica, for example that sold under the trade mark "Silocel", alpha or gamma alumina granules or pellets, naturally occurring or synthetic alumino-silicates, magnesia, diatomaceous earth, bauxite, titania, zirconia, limestone, magnesium silicate, silicon carbide, and activated and inactivated carbons, for example granular charcoal. The above materials may be in the form of regularly or irregularly shaped particles such as capillary tubes, extrudates, rods, balls, broken pieces or tiles.
The ceramic particulate support or honeycomb structure has deposited thereon a first coating of a refractory metal oxide which is further impregnated or coated with one or more of the intermetallic compounds mentioned above. Suitable refractory metal oxides comprising the said first coating are one or more of the oxides of Al, Si, Be, Mg, Ca, Sr, Ba,
Sc, Y, Ti, Zr, Hf, and the lanthanides and the actinides, for example Th. Preferred refractory metal oxide layers comprise members of the gamma or activated alumina family.
This can be prepared, for example, by precipitating a hydrous alumina gel and, thereafter, drying and calcining to expel hydrated water and provide active gamma alumina. A particularly preferred active refractory metal oxide is obtained by drying and calcining at temperatures of 400O to 8000C a precursor mixture of hydrous alumina phases predominating in crystalline trihydrate, that is, containing in excess of 50 per cent by weight of the total alumina hydrate composition, preferably from 65 to 95 per cent by weight of one or more of the trihydrate forms of gibbsite, bayerite and norstrandite by X-ray diffraction. We prefer to use British Aluminium Co grade MH 170 alumina hydrate and convert it to activated alumina by drying and firing as described above.
There are many different techniques for the preparation of a high surface area catalytically active refractory metal oxide wash coat containing one or more of the refractory metal oxides which convert beneficial properties as regards ageing and inertness to the deposited intermetallic compounds at high temperature under oxidising and reducing conditions.
A preferred adherent oxide coating deposited upon the extended metallic or the non-metallic substrate is alumina in which the surface area of the alumina falls within the range 50-500 square metres per gram of alumina.
One method for the deposition of hydrous alumina is proposed in United States Patent
No. 2,406,420. Any convenient aluminium compound such as alkali metal aluminates and aluminium salts may be used as the starting material. Either acidic or basic precipitants are used, depending upon the character of the starting material. Suitable acidic precipitants are ammonium chloride, ammonium sulphate, ammonium nitrate, hydrochloric acid, nitric acid, etc. Suitable basic precipitants are ammonium hydroxide, sodium hydroxide, hexamethylenetetramine, etc.
A further method is to precipitate the hydrous alumina from an alkali metal aluminate solution containing excess aluminium and alkali metal hydroxide directly onto the metal or ceramic substrates forming part of the present invention. If the aluminate solution is maintained at a temperature of 60 - 85"C a film or coating of alpha alumina trihydrate (Gibbsite) is deposited. Subsequent heating at 250 - 1800C converts the tri-hydrate to the monohydrate and further heating at 5400C converts the monohydrate to gamma alumina without loss of the very high surface area coating which is produced by this method.
The high surface area results from the formation of hexagonal crystal aggregates of approximate size 8 x 8 x 20 microns. Micropores of size 40A diameter are present in the hexagonal crystal aggregates but appear to play no part in the catalytic activity of the structure.
We prefer a washcoat loading which is within the range of 5 - 30% by weight of the metallic monolith substrate. A suitable loading of Al203 on Kanthal D (Registered Trade
Mark) having 400 cells per square inch is 10% by weight. The surface area of the alumina is 50 - 500 square metres per gram of alumina. The aluminate method of deposition of alumina, described above, gives a surface area of from 120 - 160 square meters per gram of alumina.
Yet a further method for the deposition of an adherent alumina washcoat on a metallic or ceramic substrate is to prepare a slurry of a preactivated Gibbsite (alumina trihydrate) and an alumina monohydrate having a solid-liquid ratio of vbetween 25 and 50% and a pH less than 7 and using this to impregnate the shaped substrate by complete immersion. The exact strength of the slurry used (which may be determined by trial and error) should be sufficient to produce an alumina washcoat of the required thickness. The substrate is then allowed to dry in warm air and finally fired for 2 hours at 4500C to form chi and gamma alumina in adherent coating up to 0.002 in. thick on the metallic substrate. Crystal aggregates of diameter 3 - 7 microns are produced having micropores of approximately the same size, i.e.
40A in diameter.
A still further method of depositing an adherent alumina washcoat on the substrate is to use a slurry of alpha alumina monohydrate. After firing at 450"C gamma alumina is formed having a surface area between 180 and 300 square metres per gram. Gamma alumina is added to alpha alumina monohydrate at the slurring stage before firing in order to form a thixotropic mixture. Crystallite or crystal aggregates of 20 - 100 A diameter are formed.
Micropores diameters remain the same at 40 A.
Suitable proprietary alumina tryhydrates (Gibbsite) are "FRF 80" supplied by British
Aluminium Chemicals Ltd., and "C 333" supplied by Conoco. Suitable alumina monohydrates (Boehmite) are "Sol-Gel alumina" supplied by the United Kingdom Atomic
Energy Authority. "Dispal M" supplied by Conoco Registered Trade Mark) and "Condea
F" supplied by the Condea Group. Gibbsite is added to "Sol-Gel Alumina" (which is microcrystalline Boehmite) at the slurrying state in order to form a thixotropic mixture.
Optionally, one or more of the oxides titania, zirconia, hafnia and thoria may be present in the alumina for the purpose of providing additional stabilisation of the intermediate oxide (washcoat) layer. Other rare earth oxides, alkaline earth oxides and alkali metal oxides may also be used.
Many of the aluminium-containing metallic substrates according to the present invention have the property of oxidising "inwards". That is to say we believe that a factor contributory to the success of the present invention is the fact that the extended metal substrate itself, which forms part of the catalytic structure of the present invention has a tendency to oxidise under very strongly oxidising conditions in such a way that the first layer of adherent oxide film does not tend to grow over or cover the outermost layer of intermetallic compound.
As mentioned previously, the coating of the intermetallic compound may be continuous or discontinuous but, if desired, the said coating may be in the form of a fine microcrystalline dispersion.
WHAT WE CLAIM IS:
1. A catalyst comprising a substrate having deposited thereon a first coating containing a refractory metal oxide and having deposited upon the said oxide one or more intermetallic compounds of the general formula AxBy, where A is selected from the group consisting of
Ru, Rh, Pd, Ir and Pt, and B is selected from the group consisting of Al, Sc, Y, the lanthanides, Ti, Zr, Hf, V, Nb, and Ta, and where x andy are integral and may have values of 1 or more.
2. A catalyst according to Claim 1 wherein the substrate is metallic.
3. A catalyst according to Claim 2 wherein the metallic substrate is made from an alloy containing nickel and chromium having an aggregate nickel and chromium content greater than 20 wt.%.
4. A catalyst according to Claim 2 wherein the metallic substrate is made from an iron alloy including at least one of the following elements:
chromium 3 - 40 wt %;
aluminium 1 - 10 wt %;
cobalt trace to 5 wt %;
nickel trace - 72 wt %, and
carbon trace - 0.5 wt %.
5. A catalyst according to Claim 4 wherein the metallic substrate includes at least one of the following elements present from a trace to the percentage stated:
silicon 0.2
manganese 0.2
zirconium 0.01
copper 0.01
niobium 0.01
tantalum 0.08
titanium 0.08
cerium 0.01 and
calcium 0.01.
6. A catalyst according to Claim 2 wherein the metallic substrate comprises 0.5 to 12 wt % aluminium, 0.1 to 3.0 wt % yttrium, 0 to 20 wt % chromium and balance iron.
7. A catalyst according to Claim 2 wherein the metallic substrate comprises 0.5 to 4 wt % aluminium, 0.5 to 3.0 wt % yttrium, 20 to 95 wt % chromium and balance iron.
8. A catalyst according to Claim 1 wherein the substrate is made from a ceramic material.
9. A catalyst according to Claim 8 wherein the substrate is monolithic and is made from a material selected from the groups consisting of zircon-mullite, mullite, alpha-alumina, sillimanite, magnesium silicates, zircon, petalite, spodumene, cordierite and other alumino-silicates.
10. A catalyst according to Claim 8 wherein the substrate is in the form of pellets or granules and is made from a material selected from the group consisting of alpha or gamma
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (12)
1. A catalyst comprising a substrate having deposited thereon a first coating containing a refractory metal oxide and having deposited upon the said oxide one or more intermetallic compounds of the general formula AxBy, where A is selected from the group consisting of
Ru, Rh, Pd, Ir and Pt, and B is selected from the group consisting of Al, Sc, Y, the lanthanides, Ti, Zr, Hf, V, Nb, and Ta, and where x andy are integral and may have values of 1 or more.
2. A catalyst according to Claim 1 wherein the substrate is metallic.
3. A catalyst according to Claim 2 wherein the metallic substrate is made from an alloy containing nickel and chromium having an aggregate nickel and chromium content greater than 20 wt.%.
4. A catalyst according to Claim 2 wherein the metallic substrate is made from an iron alloy including at least one of the following elements:
chromium 3 - 40 wt %;
aluminium 1 - 10 wt %;
cobalt trace to 5 wt %;
nickel trace - 72 wt %, and
carbon trace - 0.5 wt %.
5. A catalyst according to Claim 4 wherein the metallic substrate includes at least one of the following elements present from a trace to the percentage stated:
silicon 0.2
manganese 0.2
zirconium 0.01
copper 0.01
niobium 0.01
tantalum 0.08
titanium 0.08
cerium 0.01 and
calcium 0.01.
6. A catalyst according to Claim 2 wherein the metallic substrate comprises 0.5 to 12 wt % aluminium, 0.1 to 3.0 wt % yttrium, 0 to 20 wt % chromium and balance iron.
7. A catalyst according to Claim 2 wherein the metallic substrate comprises 0.5 to 4 wt % aluminium, 0.5 to 3.0 wt % yttrium, 20 to 95 wt % chromium and balance iron.
8. A catalyst according to Claim 1 wherein the substrate is made from a ceramic material.
9. A catalyst according to Claim 8 wherein the substrate is monolithic and is made from a material selected from the groups consisting of zircon-mullite, mullite, alpha-alumina, sillimanite, magnesium silicates, zircon, petalite, spodumene, cordierite and other alumino-silicates.
10. A catalyst according to Claim 8 wherein the substrate is in the form of pellets or granules and is made from a material selected from the group consisting of alpha or gamma
alumina granules or pellets, naturally occurring or synthetic alumino-silicates, magnesia, diatomaceous earth, bauxite, titania, zirconia, limestone, magnesium silicate, silicon carbide, and activated and inactivated carbons, for example granular charcoal.
11. A catalyst according to Claim 1 wherein the first coating comprises at least one metal oxide selected from the group of metal consisting of Al, Si, Be, Mg, Ca, Sr, Ba, Sc,
Y, Ti, Zr, Hf, and the lanthanides and the actinides, for example Th.
12. A catalyst according to Claim 1 wherein the intermetallic compound AxB is selected from the group consisting of TiPt3, ZrPt3, HfPt3, YPd3, LnPd, LnPd3 and Ln5d2 (where Ln = Sm, Gd, Dy, Ho and Er) Her3, TaIr3, NbIr3, HfIr, TaPd, TiRu, ZrHu, NbIr,
TaRh3, VIr3 and CeRu2.
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB4656/77A GB1590451A (en) | 1977-02-04 | 1977-02-04 | Catalysts containing platinum group metals |
SE7800987A SE7800987L (en) | 1977-02-04 | 1978-01-26 | CATALYST |
US05/872,747 US4189405A (en) | 1977-02-04 | 1978-01-27 | Intermetallic catalysts |
NO780321A NO780321L (en) | 1977-02-04 | 1978-01-27 | CATALYST. |
ZA00780528A ZA78528B (en) | 1977-02-04 | 1978-01-27 | Improvements in and relating to catalysis |
JP1138978A JPS53122693A (en) | 1977-02-04 | 1978-02-03 | Catalyst |
NL7801298A NL7801298A (en) | 1977-02-04 | 1978-02-03 | CATALYST. |
FR7803006A FR2379317A1 (en) | 1977-02-04 | 1978-02-03 | DEVELOPMENT FOR CATALYSTS |
ES466619A ES466619A1 (en) | 1977-02-04 | 1978-02-03 | Intermetallic catalysts |
DE19782804660 DE2804660A1 (en) | 1977-02-04 | 1978-02-03 | CATALYST |
DK49778A DK49778A (en) | 1977-02-04 | 1978-02-03 | CATALYST |
BE184894A BE863642A (en) | 1977-02-04 | 1978-02-03 | DEVELOPMENT FOR CATALYSTS |
IT20016/78A IT1093707B (en) | 1977-02-04 | 1978-02-06 | REFINEMENTS FOR THE CATALYST CONTAINING METALS OF THE PLATINUM GROUP |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB4656/77A GB1590451A (en) | 1977-02-04 | 1977-02-04 | Catalysts containing platinum group metals |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1590451A true GB1590451A (en) | 1981-06-03 |
Family
ID=9781319
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB4656/77A Expired GB1590451A (en) | 1977-02-04 | 1977-02-04 | Catalysts containing platinum group metals |
Country Status (2)
Country | Link |
---|---|
GB (1) | GB1590451A (en) |
ZA (1) | ZA78528B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2263650B (en) * | 1990-05-31 | 1995-01-11 | Monsanto Co | Monolithic catalysts for conversion of sulfur dioxide to sulfur trioxide |
-
1977
- 1977-02-04 GB GB4656/77A patent/GB1590451A/en not_active Expired
-
1978
- 1978-01-27 ZA ZA00780528A patent/ZA78528B/en unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2263650B (en) * | 1990-05-31 | 1995-01-11 | Monsanto Co | Monolithic catalysts for conversion of sulfur dioxide to sulfur trioxide |
Also Published As
Publication number | Publication date |
---|---|
ZA78528B (en) | 1979-01-31 |
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CSNS | Application of which complete specification have been accepted and published, but patent is not sealed |