Platinum Metals Rev., 1966, 10, (4), 153
NEW PATENTS: October 1966
METALS AND ALLOYS
international nickel ltd. British Patent 1,032,005
Ductility of Ru is improved by alloying it with 0.25−25 wt.% Re by a powder metallurgy technique.
Manufacture of High Density Alloys
the general electric co. ltd. British Patent 1,032,118
A sintered high density alloy is produced by forming a homogeneous powdered mixture of W and/or Mo and 0.01−10 wt.% one or more Pt group metal, forming a self-supporting compact, heating it at 900−2000°C in a non-oxidising atmosphere so that alloying of the constituents takes place and maintaining the high temperature until the desired degree of densification has been attained.
Metallic Appliances and Components Subjected to Contact with Molten Materials at High Temperature
comptoir lyon-alemand, louyot et cie. British Patent 1,033,317
Metallic appliances which come into contact at high temperatures with glasses, oxides, etc., comprise a composite metallic material consisting of three layers joined by cladding so that there is an inner layer of pure Pt contacting the molten material, an outer layer of Pt-Rh alloy and a central layer of Pt alloy with Ir, Ru, Rh or Os.
Inter-Metallic Compounds and their Preparation
international business machines corp. British Patent 1,035,875
The intermetallic compounds A5M2, where A is Gd, Tb, Dy or Ho and M is Pd or Pt, which have good ferromagnetic and mechanical properties, are produced by supporting a finely-divided mixture of the metal powders on a cold Cu hearth in an inert atmosphere, melting a portion out of contact with the hearth, allowing it to solidify, inverting it and repeating several times.
Processing of a Vitreous Composition in a Reducing Atmosphere
bausch & lomb inc. U.S. Patent 3,233,993
A container for processing of a vitreous composition in a reducing atmosphere has its cavity lined with Ir or an alloy of 50−100% Ir, 0−50% Rh and max. 20% Pt.
Alloys of Gold with Group VIII Metals
w. c. heraeus g.m.b.h. U.S. Patent 3,238,040
A tension strip for measuring instruments is made of an alloy of 30−80 wt.% Au and the balance Pt, Pd, Ir, Rh, Fe, Co, Ni or their mixtures.
Platinum Group Metal Alloy Tensioning Strips
w. c. heraeus g.m.b.h. U.S. Patent 3,245,781
Tensioning strips which may be used in measuring instruments are made of alloys of 1−50 wt.%, preferably 5−40 wt.%, Fe, Co, Ni, W, Mo, Cu or Ag or their mixtures and balance Pt, Pd and/or Rh.
Precious Metal Laminates
owens-corning fibreglass corp. U.S. Patent 3,248,190
Corrosion resistant and high strength laminates useful for the production of glass fibre manufacture die plates comprise a centre layer of an alloy of 75−100 wt.% Rh and 0−25 wt.% Pt sandwiched between and bonded to opposed metal layers of an alloy of 60−100 wt.% Pt and 0−40 wt.% Rh.
Noble Metal Polyphthalocyanines
Noble Metal Electrodes
amalgamated curacao patents co. n.v. U.S. Patent 3,234,110
An electrode comprises a core of Ti or its alloy, a barrier layer of TiO2 and a coating of Pt, Ir, Rh or their alloys. See also 3,236,756.
ELECTRODEPOSITION AND SURFACE COATINGS
Process and Solutions for Coating Metals and Alloys
international nickel ltd. British Patent 1,030,545
An immersion bath for the chemical plating of Ni or its alloys with Pt group metal comprises an acid aqueous solution of 1−10 g/l Pt, Pd, Rh, or Ru, 64–96 g/l HCl, 0.2–5 g/l Cu and 0–5 g/l Fe(II).
Electrodeposition of Palladium
johnson matthey & co. ltd. British Patent 1,035,850
An electroplating bath operated at 15−75°C, pH 7–10 and 1–500 A/ft2 current density is in the form of an aqueous neutral or alkaline solution containing an NH4 salt of a weak organic acid and a Pd compound.
Electroless Deposition of Palladium
LABORATORY APPARATUS AND TECHNIQUE
Reagent and Apparatus for Gas Detection
Brazing Platinum and Alloys thereof
international nickel ltd. British Patent 1,033,412
Two pieces of sheet Pt or its alloy are brazed together at a brazing temperature of at least 100°C above the melting point of the brazing metal which is an alloy of Pd and Au or Cu.
Improved Brazing or Soldering Alloys
westinghouse brake and signal co. ltd. British Patent 1,036,245
An improved brazing or soldering alloy is manufactured by heating Ag, Cu and In in a vacuum so that alloying takes place, cooling the alloy, adding Pd, heating in a H2 atmosphere so that this gas is dissolved in the alloy and then raising the temperature to ensure the alloying of the Pd with the alloy.
Catalyst Supports and Catalytic Compositions for Use in the Steam Reforming of Hydrocarbons
imperial chemical industries ltd. British Patent 1,028,753
A steam reforming catalyst comprises an improved support, 5–50 wt.% NiO 0.01–20 wt.% Pt group metal. See also 1,029,235 and 1,032,751–4.
Process for the Preparation of Carbonyl Compounds
shell internationale research mij. n.v. British Patent 1,029,175
A catalyst system for the preparation of carbonyl compounds by the reaction of an olefine and O2 at below 350°C and in the presence of steam and halogen and/or hydrogen halide comprises (i) a solid carrier, (ii) Ru, Rh, Os, or Pt but preferably Pd compound, (iii) a compound of Fe, Co, Ni or Group I or VII transition metal, and (iv) a compound of alkali metal of 11–55 at. no.
Preparation of a Glycol Ester
shell internationale research mij. n.v. British Patent 1,029,319
A glycol ester is prepared by contacting an ethylenically unsaturated compound with a Group VIII noble metal compound, preferably Pd salt, in an anhydrous liquid medium at 0−150°C, 0.1–100 atm and in the presence of an oxidising acid and optionally also a Group IB, IIB, III, IV, V, VI, VII or VIII non-precious metal compound.
Hydrogenation of Polycyclic Aromatics
the british petroleum co. ltd. and goble a.g. British Patent 1,031,031
Bicyclic aromatic hydrocarbons are hydrogenated selectively by contacting the feed stock with a refractory-supported Pt group metal catalyst at 500−900°F, in the presence of H2 and at least 0.2 wt.% combined S, preferably at 100–3000 psig.
abbott laboratories British Patent 1,031,169
Cyclohexylamine is produced by reacting phenol with NH3 and H2 at 15–150 psi, 70−150°C and in the presence of 0.02–2 wt.% Rh, based on the weight of phenol present.
Catalytic Hydrocarbon Conversion
mobil oil corp. British Patent 1,031,222
A hydrocarbon conversion catalyst comprises a mechanical mixture of particles of less than 100μ diameter of (i) a predominantly Al2O3 carrier supporting 0.5–5 wt.% group metal and (ii) a porous inert carrier supporting 0.1–40 wt.% rare earth metal oxide.
signal oil and gas co. British Patent 1,032,838
An improved process for the selective hydrogenation of mono-cyclic aromatics in a hydrocarbon stream utilises a Pt catalyst.
Hydrocatalytic Cracking of Hydrocarbons
the british petroleum co. ltd. British Patent 1,032,924
A hydrocracking catalyst comprises a refractory metal oxide supporting 5–75 wt.% Fe group metal or 0.01–5 wt.% Pt group metal, preferably Pt or Pd.
Preparation of Acetals from Acetylene
imperial chemical industries ltd. British Patent 1,033,837
Acetals are produced by reacting acetylene with a primary or secondary alcohol in the presence of a Pt, Rh, Os or Ru halogen compound.
Manufacture of Hexachlorobenzene and Pentachlorobenzene
uddeholms a.b. British Patent 1,034,069
Hexa- and pentachlorobenzenes are manufactured by passing a gaseous mixture of benzene, HCl and O2 at elevated temperature through a catalyst comprising activated Al2O3 supporting CuCl2 and Ag, Pt and/or Pd chlorides.
Hydrofining and Hydrocracking Process
esso research & engineering co. British Patent 1,034,457
A N-containing hydrocarbon feed is hydrocracked by first contacting it with a Group VI metal and Group VIII metal supported on a Group IIA, IIIA or IVB metal oxide and then with a crystalline alumino-silicate zeolite comprising 0.01–3.0 wt.% of a Pt group metal.
peter spence & sons ltd. British Patent 1,034,621
A catalyst bed for carrying out oxidation processes comprises a thick layer of CuO or γ-Al2O3 and a thinner layer of Pt or Pd or optionally some other noble metal.
Manufacture of Vinyl Compounds
farbwerke hoechst a.g. British Patent 1,035,587
A vinyl compound is produced by reacting C2H4, O2 and a nucleophilic compound having at least one readily removable H atom in the presence of a supported PdO catalyst at 20–300°C and 0.2–20 atm.
Catalytic Treatment of Exhaust Gases
w. r. grace & co. British Patent 1,036,510
A catalyst for oxidising CO and hydrocarbons present in combustion engine exhaust gases is produced by mixing Al2O3 with 5–20 wt.% CuO and 5–20 wt.% MgO, pelleting the mixture, calcining for 2–3 h at 535–760°C and 0–5 at 648°C and finally spraying with Pd nitrate to provide up to 0.03 wt.% Pd.
Catalytic Stereospecific Polymerisation of Butadiene
institut francais du petrole, des carburants et lubrifiants British Patent 1,037,001
In the stereospecific, aqueous emulsion polymerisation of 1,3-butadiene at −30 to 100°C a mixture of Rh salt and 1,3-cyclohexadiene is used as catalyst.
Catalytic Dehydrogenation of Petroleum Distillate Feed Fraction
mobil oil corp. British Patent 1,037,621
In the production of jet fuels by the catalytic dehydrogenation of a petroleum distillate feed fraction comprising paraffins, naphthenes and aromatics, the preferred catalyst is refractory oxide supported Pt.
Molecular Sieve-Group VIII Noble Metal Hydrocarbon Conversion Catalyst
union carbide corp. U.S. Patent 3,236,761
A catalyst for the coversion of hydrocarbons comprises a decationised zeolitic molecular sieve having less than 90% Al atoms associated with cations, an SiO2:Al2O3 ratio greater than 3 and 0.05–2 wt.% Group VIII noble metal, preferably Pt or Pd. See also 3,236,762 and 3,236,903–4.
Molecular Sieves Impregnated with Platinum Group Metals
esso research and engineering co. U.S. Patent 3,238,117
In the process of conversion of crude oil feedstock by a combination of coking, hydrocracking and reforming steps, a molecular sieve zeolite impregnated with a Pt group metal is used as a catalyst. See also 3,238,118–3,238,120.
Use of Platinum Group Metal Catalysts in the Production of Estrogenic Compounds
commercial solvents corp. U.S. Patent 3,239,351–7
New estrogenic compounds and animal growth promoters are produced from fermentation of estrogenic compounds and production involves reduction of an olefinic bond in the presence of a supported Pt or Pd catalyst.
Ruthenium and Rhodium Hydroformylation Catalysts
shell oil co. (new york)
U.S. Patent 3,239,566
Aldehydes and alcohols are produced by contacting a mono-olefinic hydrocarbon with CO and H2 at 100–300°C and in the presence of a complex catalyst consisting of Ru and Rh carbonyl in complex combination with trialkylphosphine. See also 3,239,570–1.
Palladium Hydrogenation Catalyst
velsicol chemical corp. U.S. Patent 3,240,762
A new polymer is produced by reacting maleic anhydride at 150−500°F with C6H6-soluble cyclo-pentadiene homopolymer which has 1,4-linkages and has been hydrogenated in the presence of a Pd catalyst to an extent of 60–95%.
Palladium Chloride Cocatalyst in the Production of Acetic Acid
halcon international inc. U.S. Patent 3,240,805
Pure CH3COOH is produced by contacting a gaseous mixture of C2H4, O2 and H2O vapour at 150−300°C and 1–1,000 atm with a refractory metal oxide supported catalyst comprising 0.1–5 wt.% PdCl2 and 5–20 wt.% V2O5.
Palladium Catalyst for the Selective Hydrogenation of Acetylenes
esso research and engineering co. U.S. Patent 3,242,226
Acetylenes are hydrogenated selectively in the presence of diolefines by contacting the hydrocarbon stream at 50−500°F and 1–1,000 psig with H2 and 10–250 m2/g Al2O3 supporting 0.01–0.2 wt.% Pd.
Platinum Hydroisomerisation Catalyst
texaco inc. U.S. Patent 3,242,228
A catalyst for the hydroisomerisation of paraffinic hydrocarbons is produced by compositing Al2O3 with 0.01–1 wt.% Pt, contacting it at 300−600°F with an organic chloride activating agent to introduce 3–10 wt.% Cl2, heating it at 400−1,000°F in contact with HCl to improve catalyst activity and displacing HCl with an inert atmosphere so that the final catalyst contains 2.5–7 wt.% Cl2. See also 3,242,229.
Noble Metal Catalyst for the Selective Hydrogenation of Acetylene
veb leuna-werke “walter ulbricht”. U.S. Patent 3,243,387
A catalyst for the selective hydrogenation of C2H2 consists of an α-Al2O3 carrier supporting up to 5 wt.% each Pd and Ag and 19–80 times their combined amount of Fe present as Fe2O3.
Use of Gauzes Made of Platinum and its Alloys in the Production of Hydrogen Cyanide
monsanto co. U.S. Patent 3,244,479
HCN is produced by passing a feed mixture of NH3, CH4 and air through a gauze made of Pt or its alloy with Ir, Pd, Rh, at 500−1,300°C and when necessary reactivating the catalyst by passing first air and then H2 at temperature gradually decreasing to 150°C.
Pre-sulphided Palladium Hydrocracking Catalyst
gulf research & development co. U.S. Patent 3,244,616
An improved catalyst for the hydrocracking of a hydrocarbon feed-stock free of asphaltic materials and of low N2 content comprises a refractory metal oxide support composited with pre-sulphided Pd.
Platinum Group Metal Catalysts in the Production of Carbonyl Compounds
union oil company of california U.S. Patent 3,245,890
Carbonyl compounds and electrical energy are produced simultaneously by connecting, via an electrolytic conductor, an anodic zone containing an acidic aqueous solution of a Pt group metal halide and a cathodic zone containing aqueous electrolyte and then introducing into them respectively, an olefine and an oxidiser and withdrawing the carbonyl compound from the anodic zone.
Platinum Group Metal Reforming Catalysts
mobil oil corp. U.S. Patent 3,247,099
A catalyst for the reforming of hydrocarbons comprises 0.01–5 wt.% Pt group metal in intimate combination with an alkali metal aluminosilicate which has 6–15 Å pores and has been base-exchanged with a rare earth metal.
Palladium-on-Carbon Hydrogenation Catalyst
ciba corp. U.S. Patent 3,247,196
The production of active derivatives of cephalosporin involves a hydrogenation stage in the presence of Pd/C catalyst.
Noble Metal Catalysts in Formaldehyde Production
huttenwerk oberhausen a.g. U.S. Patent 3,247,254
Formaldehyde is produced by passing a mixture of a lower saturated hydrocarbon and free O or a gas, containing it, through a finely divided pumice catalyst at 400−700°C and then at the same temperature through a metal netting made of Pt, Ir, Rh, Ag, Cu or their alloys.
Hydrocracking and Isomerisation Catalysts
standard oil co. U.S. Patent 3,248,316
In a two-stage hydrocracking and isomerisation process for the conversion of olefinic hydrocarbons, the first stage catalyst comprises an acidic cracking component and 0.1–2 wt.% Pt group metal and in the second stage a modified catalyst containing 0.1–1 wt.% Pt group metal.
Activated Platinum Group Metal Oxidation Catalysts
universal oil products co. U.S. Patent 3,248,344
An oxidation catalyst comprising Pt, Pd and/or their alloys as the active component, is activated by first burning hydrocarbon vapours at above 600°F and in excess air so that an oxidised coating is formed on the catalyst surface and then heating at above 1,000°F in a mixed gas stream containing a major proportion of H2 so that a finely reduced and activated catalyst is obtained.
Platinum Group Metal Isomerisation Catalysts
the british petroleum co. ltd. U.S. Patent 3,248,448–9
A catalyst system for the isomerisation of olefinic hydrocarbons comprises a halogenated Al2O3 support and 0.01–5 wt.% Pt group metal.
Platinum Group Metal Hydrocarbon Conversion Catalysts
the british petroleum co. ltd. U.S. Patent 3,250,698
A S-containing hydrocarbon feedstock containing mainly petroleum naphtha is autofined by contacting it at 700−800°F and 100–600 psig with a refractory metal oxide supporting 0.01–5 wt.% Pt group metal.
Platinum Group Metal Isomerisation Catalysts
phillips petroleum co. U.S. Patent 3,250,819
In a two-stage process for the production of cycloparaffins the isomerisation catalyst used comprises a refractory metal oxide supporting 0.01–5 wt.% Pt group metal and 0.2–5 wt.% combined halogen.
Platinum Group Metal Hydrogenation Catalysts
institut francais du petrole, des carburants et lubrifiants French Patent 1,426,900
Isoprene is produced by reacting an aqueous acidic solution of HCHO with isobutene and the product formed by hydrogenating crude 4,4-dimethyl-1,3-dioxane in the presence of Pt or Pd and hydrocracking the resultant mixture.
Vinyl Acetate Production
farbwerke hoechst a.g. German Patent 1,216,290
The reaction of C2H4, CH3COOH and O2 is catalysed by a supported Group VIII metal especially elementary Pd, with a Mn co-catalyst.
Chemical Reaction Catalyst
johnson, matthey & co. ltd. Dutch Application 65.10941
An improved catalyst for isomerisation, hydrogenation, polymerisation, oxidation and other reactions consists of an active metal salt (e.g. Ru, Rh or other Pt metal salt) dissolved in a thermally stable, low volatility salt.
leesona corp. British Patent 1,028,325
A fuel cell has at least one electrode made of an alloy of Pt with 15–60 wt.% Ir, or 15–60 wt.% Ru or 3–60 wt.% Ni.
Oxidation of Fuels
robert bosch g.m.b.h. British Patent 1,032,535
Organic fuels are subjected to electrochemical oxidation by introducing them into a cell which has a porous fuel electrode provided with a coating of radioactive material and an oxygen electrode consisting of a Au lattice fitted with Raney Pt-Ir catalyst.
Improved Fuel Cell System
leesona corp. British Patent 1,033,361
A fuel cell system comprises a unit for storage of gaseous or liquid fuels, a fuel cell unit comprising a non-porous Pd-Ag alloy H2 diffusion anode, a bi-porous Co-activated NiO cathode, and means for supplying fuel and oxidant, a reactor unit for converting fuels into impure H2 and by-products and means for feeding the impure H2 stream from the reactor unit to the fuel cell unit. See also 1,033,362–5.
Metallised Sheet Electrodes
american cyanamid co. British Patent 1,036,513
A fuel cell electrode comprises 20–60% fibrous support, 1–23% H2O-repellent compound and 25–65% metallic catalyst, preferably Pt, Pd or Ru.
Gold and Platinum Group Metal Fuel Cell Catalyst
esso research and engineering co. U.S. Patent 3,239,382
A fuel cell cathode has a supporting structure carrying as catalyst a major proportion of a Pt group metal, preferably Pt or Pd, and a minor amount of Au.
Platinum Impregnated Carbon Fuel Cell Electrode
phillips petroleum co. U.S. Patent 3,244,564
A fuel cell of improved construction, utilising an improved gelled electrolyte, has a circular C disc electrode impregnated with Pt.
Noble Metal Fuel Cell Electrode
allis-chalmers manufacturing co. U.S. Patent 3,250,646
A fuel cell electrode comprises a porous Ni plaque whose opposite spaced surfaces have a number of active centres of primary and secondary origin and monomolecular randomly distributed and distinct deposits of 10–20% Pt and the balance Pd, Ir, Rh, Os and/or Ru.
ELECTRICAL AND ELECTRONIC ENGINEERING
Magnetic Data Storage Devices
sperry rand corp. British Patent 1,034,749
A film of a ferromagnetic alloy is formed on a non-metallic substrate by treating the latter with adhesive material; applying a catalytic solution of a water-soluble compound of Pt, Pd, Ir or Au; treating this with an accelerating solution so as to reduce this compound to the elemental metal and then forming by electroless plating a film of a ferromagnetic Co-Fe-P alloy.
sprague electric co. U.S. Patent 3,243,315
A ceramic capacitor is produced by applying a slurry of ceramic material having a dielectric constant greater than 200 in a vehicle which may be evaporated without leaving a residue, on a Pt group metal inner electrode, vitrifying the ceramic material and then forming a second electrode by applying the same or different Pt group metal.
Dispenser Type Thermionic Cathode
general electric co. U.S. Patent 3,243,638
A thermionic emitter comprises a porous matrix of compressed W, Ta, or Mo silicides, borides or carbides activated by Ba and containing a reducing agent and a tightly adherent porous Pt coating over which the Ba can diffuse.
Crystals for the Manufacture of Capacitors
waddell dynamics inc. U.S. Patent 3,247,019
A capacitor is produced by applying on a conductive base a Ti-containing crystallisable material, allowing it to crystallise and repeating this process until an effective crystal layer is formed and then applying an outer electrode consisting of a Pt lamina sandwiched between two Au laminae.
Platinum Group Metal Electrical Resistors
international business machines corp. U.S. Patent 3,248,345
An electrical resistor composition which may be applied to and fired on a non-conducting ceramic base comprises (i) 30–65 wt.% finely divided borosilicate glass frit and (ii) 35–70 wt.% conductive material comprising 15–70 wt.% finely divided Pd or Rh oxide doped with up to 10 wt.% Sb, Cr, Li or Na and 0–35 wt.% finely divided Ag, Au or Pt acting as conductive element.