Platinum Metals Rev., 1975, 19, (1), 37
NEW PATENTS: January 1975
METALS AND ALLOYS
Palladium Alloy for Hydrogen Membranes
Synthesis of Silyl Metal Complexes
ELECTRODEPOSITION AND SURFACE COATINGS
Ruthenium Dioxide Electrode Coating
electronor corp. British Patent 1,370,529
Finely-divided RuO2 having a particulate size of 0.1 μ or less dispersed in an organic polymer, resistant to degradation in an electrolytic process exhibits a low oxygen overvoltage for a surprisingly long period of time. Also a combination of finely-divided RuO2 and organic polymer on an electrically-conductive substrate provides an efficient electrode for many electrochemical reactions.
texaco development corp. British Patent 1,363,179
The hydrogenation of aromatic hydrocarbons in the presence of S may be achieved by adding CO to the feedstock before it passes over a fluorided Pt/Al2O3.
Deuterium from Hydrogen-containing Compounds
gulf research & development co. British Patent 1,364,714
A vapour of a deuterium-containing hydrocarbon undergoes deuterium transfer to another hydrocarbon at high temperature in the presence of a hydrogenation-dehydrogenation catalyst, especially Pt.
ste. francais des produits pour catalyse British Patent 1,364,744
Hydrocarbon reforming is catalysed by an Al2O3 support carrying 0.005−1% Pt, 0.005−1% Ir and 0.05−3% Tl and/or In.
Combination Reforming Process
esso research & engineering co. British Patent 1,364,875
The naphthene content of a paraffin/naptha feedstock is increased in contact with a Pt group metal and then the product stream is mixed with H and contacted with a support mixture of Pt with either Ir, Rh or Ru. Suitably, 0.01−2% of both metals are present on an Al2O3 support.
Trimethyl Hydroquinone Production
kuraray co. ltd. British Patent 1,365,035
2,3,6-Trimethyl-p-benzoquinone is reduced to the corresponding hydroquinone using H in the presence of a Pd catalyst and an aliphatic ketone solvent, e.g. Pd/C plus MIBK.
eszakmagyarorszagi vegyionuk British Patent 1,365,106
N -Isopropylaniline is obtained when aniline and acetone are reacted in a hydrogen atmosphere at elevated temperatures and pressures using a Pt catalyst, for example, 1% Pt/Al2O3.
Hydrocarbon Conversion Catalyst
universal oil products co. British Patent 1,366,334
A reforming catalyst is obtained by impregnating a support (Al2O3) with a complex Sn-Pt group metal anionic species and calcining in the usual way. An acidic SnCl solution mixed with a H2PtCl6 solution supplies a suitable impregnating solution.
Saturated Hydrocarbon Isomerisation
nippon oil co. ltd. British Patent 1,366,784
The isomerisation of hydrocarbons, e.g. straight chain paraffins, is catalysed by a mixture of 0.01−5% Pt or Pd and 0.01−15% halogen on a mordenite support where the halogen is introduced by contact with a fluorohalohydrocarbon, e.g. CHCl2F.
s. d. searle & co. British Patent 1,368,731
Spirolactones are produced in a process where an epoxy androstene furandione is hydrogenated over Pd/C to give the corresponding androstane derivative.
Platinum-Cobalt Catalyst Bed for Flameless Catalytic Heater
bruest industries inc. U.S. Patent 3,802,856
A catalyst bed unit employing a measured amount of cobalt in conjunction with Pt forms the fuel-reactive catalyst of the unit to render the heater capable of operation at low CO emission levels. The catalyst is applied to its support by dissolving chloroplatinic acid and cobalt nitrate in a solution of methanol and water, spraying the mixture on to the support and heating the unit to reduce the H2PtCl6 and Co nitrite to Pt and Co metals.
Catalyst of Zinc Lanthanide Exchanged Zeolite
mobil oil corp. U.S. Patent 3,804,780
Pt and Pd catalysts may be supported on a crystalline zeolite having 6−13% lanthanide cations and less than 2.5% Zn cations.
johnson matthey & co. ltd. U.S. Patent 3,806,582
A process is described for the purification of gases containing NOx formed in the manufacture of HNO2. A gas containing the oxides and including O and a gaseous reducing fuel, is passed at a temperature above the ignition temperature of the gas and the fuel through a catalyst comprising an inert ceramic material impregnated or coated with a mixture or alloy of Pt and Rh metals in which Rh ranges from 20−50% by weight but is preferably present to the extent of 35% by weight of the catalytic metal content of the catalyst.
Preparing Amino-substituted Phosphonates
the gates rubber co. U.S. Patent 3,813,456
The preparation of amino-substituted phosphonates from their corresponding cyanosubstituted phophonate precursors, consists of hydrogenating the cyanosubstituted phosphonates in the presence of NH3 and Rh catalyst.
Ruthenium NOx Removal Catalyst
ford motor co. U.S. Patent 3,819,536
A fixing compound, selected from an alkaline earth material or a rare earth material which decomposes to an oxide of the material, is deposited on a catalytic support. A hydrated, halogenated Ru compound which reduces to Ru is also deposited on the catalytic support. The materials on the support are heated in a reducing atmosphere to form the Ru metal. After the reducing step the materials are fixed by heating them to a ruthenate-forming temperature.
Platinum Reforming Catalyst
ste. francais de produits pour catalyse French Appl. 2,196,192
The catalyst, for use in hydrocarbon reforming, has an Al2O3 support, 0.005−1.0% Pt, 0.005−1.0% Ir and 0.005−5.0% Nb.
Acetic Acid Production
Carbon Monoxide Copolymerisation Catalyst
shell internationale research mij. b.v. British Patent 1,362,908
High molecular weight polymers are produced from CO and other monomers, e.g. C2H2, in the presence of an aryl phosphine-palladium halide complex, e.g. (PPh3)2PdCl2 or Pd(PR3)4.
Cationic Platinum Catalysts
bp chemicals international ltd. British Patent 1,362,997
New catalysts for alcohol carbonylation and other reactions are complexes of univalent or trivalent Rh or Ir with acetonitrile, benzonitrile, butyl isocyanate, benzene, toluene, phosphite or phosphine; the anion must be a phosphate, sulphate, perchlorate, borate, iodate or bromate. A typical catalyst is Rh(P(OPh)3)4BPh4.
dow corning corp. British Patent 1,363,157
Pt, Pd and Ni phosphine complexes are used to catalyse the reaction of a Si2Cl2 and a halide to form mixed substituted silanes. For example, PhSiCl3 is prepared by the reaction of Si2Cl2 and PhCl in the presence of Pd(PPhMe2)2Cl2.
Unsaturated Organosilicon Compounds
ceskoslovenska akademie ved British Patent 1,363,317
Silane addition to a diene is catalysed by an inorganic Pd compound or organic complex. For example, the addition of triethoxysilane to butadiene is catalysed by bis(allyl)Pd chloride.
Cyanobenzoic Acid Hydrogenation
asahi kasei k.k.k. British Patent 1,368,415
p-Aminomethyl benzoic acid is produced in one step by the reaction of an alkyl ester of p-cyanobenzoic acid in aqueous alkaline medium containing a catalyst, e.g. Rh, Ru, RuO2, RhO2, etc.
New Rhodium Complex
johnson matthey & co. ltd. British Patent 1,368,431
New complexes of Rh(I) for use in catalysing hydrogenation, oxidation, decarbonylation, isomerisation, hydroformylation and other reactions are obtained by adding excess of an arsine, phosphine, stibine, sulphide or amine stabilising ligand (susceptible to oxidation) to a Rh(II) carboxylate solution protonated by an acid. The complexes are of the type Rh(CO)(PPh3)3BF4, e.g. prepared from a rhodium acetate (HBF4) phosphine solution by bubbling through carbon monoxide.
Palladium Complex in Oligomer Production
mitsubishi chemical industries ltd. British Patent 1,369,128
A chain oligomer is produced from a vinyl or vinylidene aromatic compound in the presence of a Pd compound, a compound containing a fluoro complex or perchlorate anion and a trivalent organic P compound, e.g. methallyl Pd chloride, tributyl phosphine and Ag chlorate or borofluoride.
Producing Oligomers of Unsaturated Compounds
mitsubishi chemical industries ltd. U.S. Patent 3,803,254
Pd phosphine, arsine and stibine complexes, e.g. [PdL2(PPh3)][BF4]2, where L is benzonitrile, are used to oligomerise styrene and other unsaturated compounds.
rhone-poulenc s.a. U.S. Patents 3,804,868 & 3,804,869
New Ru complexes of the formula Ru(diket)2Ln in which (diket) represents a bidentate ligand derived from a β-diketone and L is a tertiary phosphine ligand, are useful as catalysts in, for example, isomerisations (such as the REPPE synthesis), hydrogenations and dimerisations (such as the hydrodimerisation of acrylonitrile to adiponitrile).
Ruthenium(II) Complexes as Selective Hydrogenation Catalysts
phillips petroleum co. U.S. Patent 3,804,914
Cyclic polyenes are selectively hydrogenated to cyclic monoenes in the presence of a Ru(II) catalyst complex having the general formula LnRuXm where L is a ligand, X is a halogen or hydrogen, n is 2, 3 or 4, m is 2 or 3 and the sum of n+m is 4, 5 or 6, e.g. (Ph3)2(CO)2RuCl2.
Platinum Catalyst for Siloxane Curing
wacker-chemie a.g. U.S. Patent 3,814,731
Polyorganosiloxanes in non-stick coatings are cured with a reaction product of H2PtCl6 and a ketone.
Production of Carboxylic Acids
monsanto co. U.S. Patents 3,816,488 & 3,816,489
An improved process for the production of carboxylic acids by the reaction of ethylenically unsaturated compounds with CO and water uses catalyst compositions consisting of Rh compounds and complexes together with an iodide promoter in critical proportions, e.g. RhCl3 promoted with HI, and Ir compounds and complexes together with an iodide promoter in critical proportions, e.g. IrCl3 and HI.
Preparing Linear Fatty Acids
ELECTRICAL AND ELECTRONIC ENGINEERING
Electrodes for Acid Electrolytes
badische anilin- & soda-fabrik a.g. British Patent 1,360,255
Two electrically conducting bodies, e.g. Pt foil and a metal electrode base, are cemented together by an ethylene-unsaturated acid copolymer filled with an electrically conducting medium, e.g. Au, Pt, silvered Ti, gilded Ti, platinised Ti, etc.
Electron Discharge Heater
g.t.e. sylvania inc. British Patent 1,366,007
A dark heater coating consists of Al, Zr or Be oxide coated with 2−2.5% W which is protected from oxidation by Pt or Ir.
Lead-based Alloys for Electrode
badische anilin- & soda-fabrik a.g. British Patent 1,369,707
Pb-based alloys used for solid or grid electrodes are further improved in their efficiency and life when they contain Pd as a component. A preferred Pb alloy contains 0.05 to 0.15% of Cu, 0.05 to 0.15% of Sn and 0.05 to 0.2% of Pd. In one example 0.1% of each of these was used.
Bilevel Thin Film Integrated Circuit
bell telephone laboratories inc. U.S. Patent 3,811,973
Bilevel thin film circuits having Au metallised through holes require protection from attack by Au conductor etchants. A new procedure for this involves plating an etch stop such as Rh or Pt on the walls of the through holes and around the entrance and exit ports. Since Rh plating is normally required in the fabrication of such circuits for solderable components, the through hole protection and Rh plating may be performed simultaneously.
Gold Alloy Metallisation for Capacitor Electrodes
nuclear battery corp. British Patents 1,370,382–1,370,386
Thermopiles for use in human bodies contain a semiconductor thermoelectric wired up using a wire made of Au, Ag, Pt or their alloys.
british iron & steel research association British Patent 1,370,465
Temperatures in steelmaking furnaces, for example, are measured by a couple formed by dissimilar metal conductors placed side-by-side in a refractory insulating matrix with a conducting path between their ends in the furnace. In one example, Pt and Pt-Rh conductors are embedded in magnesia.
High Temperature Thermocouple Alloy Systems
u.s. atomic energy commission U.S. Patent 3,817,793
A thermocouple system capable of delivering a substantially linear EMF response as a function of temperature up to 1800°C in a thermal neutron environment has a positive leg and a negative leg consisting of a Cr-base binary alloy having sufficient ductility to be drawn into wire form; the alloy contains 15−25 at.% Ru, 15−20 at.% Os and the balance Cr.