Platinum Metals Rev., 1965, 9, (1), 31
NEW PATENTS: January 1965
METALS AND ALLOYS
Palladium or Palladium Alloy Diffusion Tube for the Separation of Hydrogen from Gaseous Mixtures
johnson, matthey – co ltd. British Patent 966,122
A diffusion tube used for the separation of H2 from gaseous mixtures made of pure Pd or 75 wt.% Pd-25 wt.% Ag alloy, is made more robust and its life is prolonged by the incorporation of stainless steel or Ni coil springs or metal or ceramic rods as stiffening members, which prevent flattening of the tube walls yet permit free passage of gas.
Rhodium-containing Magnetic Alloys
e. i. du pont de nemours – co. U.S. Patent 3,144,324
Ferromagnetic materials exhibiting very good saturation magnetisation values and high Curie temperatures comprise in at.% 0.8-1.2 Fe, 0.8-1.2 Rh and 0.01-0.20 of at least one metal of Group IIA atomic no. 4-12 or Group IIIA, IVA, VA or VIA atomic no. 13-83, e.g. Al, Mg, Ge, Si, Sb, S, Ga, etc. See also 3,144,325.
Gold-Platinum Spinneret Alloy
deutsche gold- und silber- scheideanstalt German Patent 1,175,886
The material used for spinnerets, especially for viscose, is unhardened and homogeneous and consists of 68-88% Au and 12-32% Pt. See also 1=177=350.
Easily Worked Ruthenium
international nickel co. (mond) ltd. German Patent 1,177,349
Ru which is easily formed is obtained by melting Ru in the presence of one or more of the metals Zn, Cd, Bi, Ti, Ge, Ba, Hf, Ce, Er, Gd, Hm, La, Pr, Sm, Yb and Y. Zn is preferred.
Gold Alloy Coatings on Wire
Platinum Group Metal Coated Electrode for Electrochemical Processes
deutsche gold- und silber- scheideanstalt British Patent 965,958
An electrode particularly suitable for alkali-metal chloride electrolysis consists of a large flat area formed by many separate elements, each of which consists of a Cu core surrounded by a layer of Ti coated with a Pt group metal.
Electrolytic Production of Hydrogen
johnson, matthey – co. ltd. British Patent 973,810
Extremely pure H2 is produced efficiently by electrolysis using 1% H2S04 solution as electrolyte and a membrane, diaphragm or tube cathode made of an alloy containing 5-30 wt.% Ag and the balance Pd.
Method of Separating Hydrogen Isotopes
johnson, matthey – co. ltd. British Patent 973,820
H isotopes for the manufacture of deuterium as “heavy water” are separated by electrolysis or by electrolytic migration using a membrane, diaphragm or tube diffusion element made of an alloy containing 5-30 wt.% Ag and the balance Pd.
Palladium and its Alloys in the Manufacture of Platinised Noble Metal Electrodes
institut francais du petrole, des carburants et lubrifiants. French Patent 1,354,801
Platinised electrodes of improved activity are produced by immersing an Au, Pt or Pd metal electrode in an electrolyte containing halo-platinic acid and 50-200 mg/1 of a dissociated Pb salt and applying 150-350 mV at 25°C.
Platinum Electrodes for Electrolytic Cells
pittsburgh plate glass co. French Patent 1,360,905
The electrolytic cells used for the production of Cl2 and alkali metal derivatives are provided with an anode whose active surface is platinised and whose support may be Ti or Ta. If desired other Pt group metals may be used, the thickness of the active film being varied and the performance of the anode improved by a “cationic” treatment.
Combined Electrolysis Electrode
Platinum Electroplating Electrolyte
Gold-Palladium-Nickel Brazing Alloys
aerojet-general corp. U.S. Patent 3,148,053
Improved brazing alloys suitable for use in a vacuum furnace comprise 1-77 wt.% Au, 1-59 wt.% Pd and 20-61 wt.% Ni, Cr or their mixtures.
Braze-welding of Graphite to Refractory Materials
societe nationale d’etude et de construction
et moteurs d’aviation French Patent 1,355,568
Two pieces of graphite may be welded to each other or graphite may be braze-welded to a refractory metal, e.g. Hf, Ta, W, Zr, etc., by interposing between the workpieces a brazing flux consisting of one or several refractory metals and 1-50 wt.% Ru, Rh, Pt, Pd, Ir or Os.
Ruthenium Catalysts for the Hydroformy-lation of Olefines
imperial chemical industries ltd. British Patent 966,482
Olefines are hydroformylated by bringing them, together with a 3:1 to 1:3 by volume mixture of CO and H,, into contact with a catalyst containing 0.0005-0.01 wt.% Ru in the form of the metal or a compound and carrying out the reaction at 140-200°C and 200-300 atm.
Deuterium Enrichment of Hydrogen
v. e. b. vakutronik British Patent 967,000
Reference is made to the use of a Pt/C catalyst in a process for the D2 enrichment of H2 or the production of heavy water.
Olefine Hydrogenation in the Presence of Aromatic Hydrocarbons
engelhard industries inc. British Patent 967,879
Dienes in a mixture containing dienes, olefines and aromatic compounds (boiling range 100-400°F) are hydrogenated by contacting the mixture with H2 and a Pt/Al2O3 catalyst at a temperature not exceeding 210°F in conditions such that 90% of the material remains in the liquid phase.
Hydrogenation of Benzoic Acid
snia viscosa s.p.a. British Patent 967,918
Benzoic acid is hydrogenated to hexahydro-benzoic acid using a finely subdivided H2 stream and a supported Pd catalyst. See also 967,919.
Selective Hydrogenation of Hydrocarbons in the Liquid State
farbenfabriken bayer a.g. British Patent 968,337
A hydrocarbon mixture containing acetylenes, allenes and other diolefines is hydrogenated selectively by passing it in the liquid state and in an atmosphere of H2 over a Pd/Al2O3 catalyst through nets of 30-70 mm diameter vertical reaction tubes which arc externally cooled.
Palladium Catalyst in the Production of Benzonitrile
the distillers co. ltd. British Patent 968,752
Benzonitrile is produced by the vapour phase dehydrogenation of a hydogenated derivative at 400-500°C over a Pd/C catalyst containing about 1 wt.% metal.
Platinum Group Metal Reforming Process Catalyst
universal oil products co. British Patent 969,789
A hydrocarbon reforming catalyst is produced by calcining a hydrous refractory inorganic oxide followed by compounding to give 0.01-2.0 wt.% Pt group metal and 0.75-1.5 wt.% Cl2 and subsequently oxidising at 204-3 10°C for at least one hour, followed by treatment at 371-538°C to give a volatile matter content of <2.0 wt.%.
Production of Organic Bases
imperial chemical industries ltd. British Patent 969,812
Organic bases are prepared by contacting a mixture of tetrahydrofurfuryl alcohol and NH3 at elevated temperature with a catalyst of finely divided Pd preferably supported on A12O3.
Production of Porous Electrodes
brown, boveri – co. ltd. British Patent 970,576
The porous catalyst electrodes for electrochemical devices may be produced by mixing a powder of one or more of Pt, Ir, Rh and Pd with a powder of one or more of Al, Zr, Mg, W, Mo and Fe, in a 30-95 wt.% to 5-70 wt.% ratio, shaping under pressure, sintering at 350-800°C and treating with an alkaline or acidic solution to dissolve out the second metal.
Palladium and Platinum Catalysts in the Production of Acetic Acid
halcon international inc. British Patent 971,100
CH3COOH is produced by contacting a gaseous mixture of C2H4 and 03 at 150-300°C and 1- 1000 atm. with a catalyst comprising a ceramically bonded α-Al2O3 supporting 0.1-5 wt.% Pt or Pd salt or oxide and 1-20 wt.% V, Co, Mo or Mn salt or oxide.
Catalytic Treatment of Automobile Exhaust Gases
w. r. grace – co. British Patent 971,994
Pollutants in automobile exhaust gases are oxidised catalytically by mixing them with an O2- containing gas and contacting with an activated mixture of (1) 10-l00μ particle size A12O3, SiO2-Al2O3 or MgO3 or acid-treated clay containing Pt and Pd in a 0.125-2.0 Pt:Pd wt.ratio and (2) finely divided, porous A12O3, A12O3-B2O3, -TiO2 or -ZrO2 diluent providing a 5-250 dilution ratio and giving a 0.005-0.2 wt.% final content each of Pt and Pd.
Platinum Catalyst in the Production of Fuel Gas and Synthesis Gases
badische anilin- – soda-fabrik a.g. British Patent 972,263
In the production of fuel and synthesis gases by the catalytic cracking of hydrocarbons in a fluidised bed comprising a refractory oxide support carrying Pt as the active metal, the catalyst is replenished by introducing into the bed a decomposable compound of the active metal, e.g. a carbonyl.
Hydrocarbon Isomerisation Catalysts
union carbide corp. British Patent 972,832
An isomerisation catalyst comprises a partially decationised zeolitic metal aluminosilicate molecular sieve supporting 0.05-2.0 wt.% Group VIII metal, in particular Pt or Pd.
Portable I.R. Spot Heater
universal oil products co. British Patent 972,942
A portable I.R. spot heater utilising liquefied gases uses a perforate diffusion screen made of “Nichrome” “Chromel” or other Cr/Ni alloy and catalytically activated by a coating of Pt, Pd or other Pt group metal, which may be used in conjunction with smaller amounts of Th, Ru, W or Cs.
abbott laboratories. U.S. Patent 3,139,454
The hydrogenation of cycloheptanone oxime to cycloheptylamine is catalysed by 0.3-3.0% Rh when low hydrogen pressures and temperatures of 0-100°C are used.
Benzoic Acid Hydrogenation
allied chemical corp. U.S. Patent 3,141,036
Molten benzoic acid may be hydrogenated to cyclohexane carboxylic acid by treatment with H2 at 1-40 atm. in the presence of a catalyst composed of palladised charcoal.
Platinum Catalysts in the Production of Lubricating Oils
socony mobil oil co. inc. U.S. Patent 3,142,635
Catalysts consisting of 0.5-1.0 wt.% Pt supported on SiO2/Al2O3 are used in the production of high viscosity-index lubricating oils by the hydro-cracking of 750-850°F b.p. straight run fractions.
Platinum Hydrocracking Catalysts
esso research – engineering co. U.S. Patent 3,143,511
An improved paraffin hydrocracking catalyst is produced by contacting A12O3 impregnated with 0.1-5 wt.% Pt with FeCl3 vapour at 500-950°F and moist air to effect hydrolysis, this being followed by reduction to obtain a o. 1-5 wt. % Fe content on the catalyst.
Platinum or Palladium Series Hydrocracking Catalysts
socony mobil oil co. U.S. Patent 3,144,401
Hydrocarbon fractions are advantageously hydro-cracked by contacting them and hydrogen with 0.05-10 wt.% Pt or Pd series metal deposited on a refractory oxide and adding S compounds so as continuously to maintain a 0.5-5 wt.% S content during the hydrocracking process.
Noble Metal Catalysts for the Polymerisation of Olefinically Unsaturated Compounds
wacker-chemie g.m.b.h. U.S. Patent 3,145,194
Copolymers and polymers of olefinically unsaturated compounds are produced by contacting them at —80 to +50°C with 0.001-0.5 wt.% inorganic per-compound, organic peroxide or hydroperoxide, H2 at 0.1-10 atm. partial pressure and 0.00001—0.1 wt.% aqueous colloidal sol of a Pt group metal.
Platinum Hydrogenation Catalysts
e. i. du pont de nemours – co. U.S. Patent 3,145,231
Halogen-substituted aromatic amines are produced by the hydrogenation of nitro-mono-carbocyclic aromatic hydrocarbons at 30-150°C and 200-600 p.s.i.g. H2 pressure in the presence of 1 part Pt per 10000-100000 parts nitro compound and 0.01-1.5 moles cycloaliphatic base per I mole nitro compound.
Platinum Group Metal Catalysts in the Production of Carbonyl Compounds
the pure oil co. U.S. Patent 3,147,203
Carbonyl compounds are produced by oxidation of at least one oleflne at 0-200°C in the presence of an aqueous catalytic solution of a Pt group metal halide and by an electrochemical process involving regeneration of the catalyst and utilising Raney Ag, Pt, Cu, Ni, etc., electrodes.
Platinum Group Metal Hydro-refining Catalysts
esso research – engineering co. U.S. Patent 3,147,229
Pt group metal catalysts of improved activity and of longer life are produced by (1) activation of Al 2O3 by calcining to give a surface area of 230 ± 20 m2/g (2) impregnating with Pt, Pd or Rh and activating the catalyst by calcining above 1000°C and (3) halogen-treating the product under conditions giving an active metal surface of 200±20 m2/g Pt or 38O±38 m2/g Pd or Rh.
Platinum Catalyst for the Oxidation of Exhaust Gases
universal oil products co. U.S. Patent 3,148,036
An improved arrangement of an exhaust gas converter uses, as the oxidation catalyst, A12O3 spheres supporting 0.1 wt.% Pt.
Palladium Hydrogenation Catalyst in the Production of Aminophenols
universal oil products co. French Patent 1,354,430
Aminophenols are produced by the hydrogenation of corresponding nitrophenols with H2 in the presence of Pd/C catalysts at 25-100°C, 1-35 atm.
Precious Metal Catalysts in the Production of Olefinic Esters
union carbide corp. French Patent 1,355,109
Olefine esters are produced by the reaction in an inert solvent at 70-130°C of an olefine and a mono-carboxylic acid in the presence of a Pt group metal as catalyst.
Alumina-supported Palladium Hydrocracking Catalysts
gulf research – development co. French Patent 1,355,210
Low b.p. hydrocarbons are produced by the hydrocracking of hydrocarbon distillates in the presence of a catalyst consisting of an active A12O3 support, obtained by precipitation of Al(OH)3 at pH 7-8.5> carrying up to 16 wt.% Mo or W oxide and/or sulphide and about I wt.% Pd sulphide or oxide. The use of Pt in the place of Pd compounds is possible.
Hydrocracking Process and Catalyst for Hydrocarbon Oils
shell internationale research mij. n.v. French Patent 1,356,567
Improved supported Pt or Pd catalysts are obtained by co-precipitating the support oxides as a hydrogel in the presence of compounds of the catalyst metals and then processing the product to a catalyst in the usual way.
Cycloalkanone Oxime Production
sicedison s.p.a. French Patent 1,357,233
2-Halocycloalkanone oximes are dehalogenated in organic solution with a strong acid by using H2 with a palladised charcoal catalyst.
Platinum and Palladium in the Production of Acetic Acid
scientific design co. inc. French Patent 1,358,382
CH8COOH is produced by the catalytic gaseous phase oxidation of C2H4 with O2 at 200-250°C in the presence of a catalyst comprising A12O3 supporting 0.1-5 wt. % Pd or Pt and 5-20 wt. % V, Co, Mo or Mn, preferably in the form of their halides and oxides respectively.
Platinum Dehydrogenation Catalyst
scientific design co. inc. French Patent 1,358,386
A catalyst consisting of active C, which has been treated with 0.1-19% HCl and has been washed and impregnated with up to 5% Pt is used in the production of phenol by the dehydogenation of the heavy fraction arising from the oxidation of cyclohexane.
Precious Metal Hydrodealkylation Catalysts
union carbide corp. French Patent 1,358,439
Alkyl-substituted aromatic hydrocarbons are hydrodealkylated by contacting them at 400-650°C in a H2 atmosphere with a molecular sieve constituted by zeolitic aluminosilicate and carrying a small proportion of, inter alia, Pt or Pd.
Platinum Group Halogenation Catalysts
imperial chemical industries ltd. French Patent 1,359,016
Halogenated hydrocarbons are produced by contacting an define, HX and a source of O2 at 200-600°C with a catalyst comprised by an inert support and a Pt group metal, preferably Pt or Pd.
Rhodium Catalyst for Reduction of Organ-onitro Compounds
abbott laboratories French Patent 1,359,438
The hydrogenation of nitro-aromatic compounds at 20-150°C and 1 atm. to 10.5 kg/cm2 H2 in the presence of 0.01-2.0 wt.% Rh catalyst results in the formation of the corresponding aromatic amines.
PaDadium-containing Catalyst for the Oxidation of Exhaust Fumes
w. r. grace – co. French Patent 1,359,988
A catalyst suitable for incorporation into filters for the exhaust systems of internal combustion engines comprises a high specific area refractory oxide support carrying 2-20 wt.% CuO, 0.0025-0.1 wt.% Pd and 1-10 wt.% Cr203.
Platinum Oxide Catalyst in the Production of Ornithine
shell internationale research mij. n.v. French Patent 1,360,750
In the production of ornithine from acrolein and cyanuric hydride the hydrogenation step is carried out in the presence of a PtO catalyst.
Platinum Alloy or Mixture Catalysts in the Production of Hydroxylamine
inventa a. g. French Patent 1,360,983
Hydroxylamine is produced by reduction of nitrogen oxide in acid solution at pH 0.5-2.5, at 65-80°C and in the presence of 0.4-1.0 mole hydroxylamine salt and Pt, Ag, NO3-impregnated Pt or a Pt alloy with Ag, Hg, Au, Ir or Pd as catalyst supported on a suitable material.
Rhodium Catalyst in the Production of Alpha-acyloxy-propionaldehydes
ajinomoto co. inc. French Patent 1,361,797
The reaction in a liquid phase at elevated temperatures and pressures between a vinyl ester of fatty acids and H2 and CO in the presence of a Rh catalyst yields a-acyloxy- propionaldehydes.
Precious Metal Hydrogenation Catalysts
shionogi – co. ltd. French Patent 1,361,980
Unsaturated morphinanes may be hydrogenated with H2 in the presence of a Pt or Pd catalyst.
Production of Hydrogen Cyanide
imperial chemical industries ltd. German Patent 1,173,444
The NH3/CH4 reaction of this process is catalysed by a Pt metal or alloy catalyst which has been activated by pretreatment with reaction mixture to which S has been added.
Lubricating Oil Production
universal oil products co. German Patent 1,174,007
A crude oil fraction with at least 95% of its components, including condensed ring naphthalenes, boiling above 285°C is hydrogenated in the presence of a Pt metal catalyst, supported on a non-acidic carrier, to provide a lubricant feedstock.
allied chemical corp. German Patent 1,176,118
Symmetrical tetrafluorodichloroisopropanol is produced from the corresponding ketone by hydrogenation over a Pt catalyst in the liquid phase.
Production of Organic Carbonyl Compounds
consortium fur elektrochemische industrie German Patent 1,176,141
The C = C double bond of olefines is converted to CHO or CO by reaction with aqueous Pt metal salts, e.g. PdCl2.
Hydrocarbon Conversion Process
standard oil co. German Patent 1,176,306
The hydroforming of hydrocarbons is carried out in the presence of a Pt/Al2O3 catalyst which is regenerated in cycles to restore its HF-soluble content to ≮ 40 wt. % of the Pt.
Uranium Nitrate Solution Production
comitato nazionale per l’energia nucleare German Patent 1,176,631
Uranyl nitrate solutions are reduced to uranium nitrate solutions by means of gaseous hydrogen in the presence of a Pt catalyst. See also 1,176,632.
Continuous Vinyl Ester Production
consortium fur elektrochemische industrie German Patent 1,176,645
Olefines are reacted with a carboxylic acid and a supported Pt catalyst. The catalyst is reoxidised after the vinyl ester has been removed.
Catalyst for Organic Compound Hydrogenation
engelhard industries inc. German Patent 1,176,656
A catalyst especially active for aldehyde and ketone reduction consists of Ru promoted by another Pt metal on a support containing 0.1-10% total catalyst metal of which at least 20 wt.% is Ru.
Production of Alkyl Aromatic Compounds
bataafsche petroleum mij. n.v. German Patent 1,178,065
Diaryl alkanes are converted to alkyl aromatic compounds by heating at 30c-600°C in the presence of a refractory metal oxide catalyst and also a Pt or Pd dehydrogenation catalyst.
Aldehyde and Ketone Production
farbwerke hoechst a. g. Dutch Application 249,648
Alkenes with 3 or more C atoms are reacted with O2 in the presence of H2O, a redox system and a noble metal catalyst, preferably at least 0.25 mol/1 of a Pd compound such as PdCl2.
Selective Hydrogenation of Ethynes
imperial chemical industries ltd. Dutch Application 253,280
In a first phase a gas mixture with excess H2 is used over a catalyst consisting of Pd on large pore size A12O3 while in a second phase hydrogenation is catalysed by Pd on active A12O3.
universal oil products co. Dutch Application 254,008
Long life Friedel-Crafts catalyst consists of a known metal halide deposited on an inorganic oxide support impregnated with a lower valency Pt metal, e.g. Pd reduced with H2.
Production of 2-Ethyl-pyridine
Improved Fuel Cell Systems
the electric storage battery co. British Patent 970,420
In an improved fuel cell system, both the electrodes are porous conductive bodies and Ag is used as catalyst for the O2 electrode and Pd or Pt group metals act as catalysts for the H2 electrode.
Improved Fuel Cells
shell research ltd. British Patent 971,454
Electricity is generated in fuel cells which have a circular O2 electrode consisting of microporous PVC on which a μ Ag layer and 5 mg/On2 Pd black have been deposited and a central fuel electrode of exactly the same type to which a fuel comprising a mixture of 1-4 C monohydric alcohol and formaldehyde, formaldehyde polymer or HCOOH is supplied.
Precious Metal Hydrogen Diffusion Electrodes
leesona corp. U.S. Patent 3,148,089
Fuel cells utilise fuel electrodes in the form of H2 diffusion tubes constructed of Pd or Pd/Ag alloys containing 5-40 wt.% Ag.
Fuel Cell Electrode
leesona corp. French Patent 1,354,465
Electrodes for fuel cells are constructed of 0.025-1.27 mm thick foil of hydrophobic or hydrophilic polymer with 40-90% porosity which act as supports for catalytically active porous and conducting metal films, e.g. Pt, Pd, Rh, Ru.
Precious Metals in the Production of Fuel Cell Electrodes
leesona corp. French Patent 1,354,685
An electrode suitable for a fuel cell and non-porous to H2 diffusion is made of a 5-40%, Ag and 95-60% Pd alloy and one of its faces is coated with Pd black. This electrode is used advantageously as an anode in conjunction with a Ni cathode activated by Co or Ni and the Pd black face is turned towards the combustible gas used in the fuel cell.
Palladium and its Alloys in the Manufacture of Hydrogen Electrodes
electricite de france French Patent 1,359,656
The electrode membrane of H2 combustion electric cells, operated at 200-800°C, and having fused salts or oxides as electrolyte, is formed by Pd or its alloys and may be made more rigid by a special framework.