Platinum Metals Rev., 1972, 16, (3), 112
NEW PATENTS: July 1972
METALS AND ALLOYS
johnson matthey & co. ltd. British Patent 1,263,454
A resistance alloy contains 26−60 wt.% Ag, 0.01−2.0 wt.% B or C; or Ir, Re or Mo; or Al2O3, ZrO2 or MoS2, the balance being Pd.
siemens a.g. British Patent 1,264,298
Superconductive alloys have the general composition: (Ce1−xAx)Ru2 where A is Tb, Dy or Ho, and 0.10 x 0.24 for Tb, 0.12 x 0.27 for Dy and 0.10 x 0.28 for Ho.
Process of Preparing Noble Metal Powders
e. i. du pont de nemours & co. U.S. Patents 3,620,713 and 3,620,714
Acid chloride solutions of noble metals are prepared, the metal is precipitated as a metal ammonia complex and then is reduced to yield a relatively coarse noble metal precipitate powder. Metallisation compositions containing the noble metal powders are printed and fired to form various electrical circuit components. Au, Ag and Pt metal powders may be produced in this way. U.S. Patent 3,620,714 deals with metal alloy powders.
Improved Platinum Alloy
deutsche gold- & silber-scheideanstalt U.S. Patent 3,622,310
The high temperature strength properties of noble metals, particularly Pt, are improved by adding an element having an affinity for O2, preferably Zr, and heating either (1) at 800−1,200°C or (2) stepwise heating at 300−800°C followed by heating at 800−1,400°C.
Producing Palladium-Carbon Bond Compounds
ELECTRODEPOSITION AND SURFACE COATINGS
minnesota mining & manufacturing co. British Patent 1,263,715
A composition for use in an electroless-plating light-image-recording system includes one or more diazonium salts which will undergo photolysis when exposed to light and one or more Pd compounds which are reduced by the action of the photolysis products to Pd metal. The metal acts as a catalyst in the reduction of developer.
Electrodeposition of Ruthenium
sel-rex corp. U.S. Patent 3,630,856
Thick electrodeposits of Ru can be obtained by adding Ga, In or Tl in a stable and soluble form. The deposits obtained have low stress and no surface cracks at thicknesses up to about 10 mm.
Platinum Metal Alloy Coatings
klingspor & co. industrie-export k.g. German Offen. 2,014,406
Pd alloy coatings are deposited from a bath containing, per litre, 0.05–10 g PdCl2, 1–60 g Ni2(SO4)3, 0.1−10 g Co2(SO4)3, 0.80% Pt metal (based on the Pd content), 0.5−60 g NaH2PO2 and 0.01−20 mg Na2S2O3.
Solderable Coating on Stainless Steel
LABORATORY APPARATUS AND TECHNIQUE
Chromatography Flow Controller
asahi kasei kogyo k.k. British Patent 1,262,219
Phenyl acetates are obtained by reaction of C6H6 or an alkyl benzene with O2 and acetic acid in the presence of Pd.
instituta khimicheskoi fiziki a.n. s.s.s.r. British Patent 1,262,885
The catalyst is formed by the reduction of a complex compound of Os, Ir, Pt, Ru, Rh or Pd with an aromatic hydrocarbon, alkyl-substituted quinone, aromatic carboxylic acid, aromatic amino acid or peptide.
institut français de pétrole des carburants et lubrifiants British Patent 1,264,254
Olefins are hydrogenated in the presence of organic compounds of transition metals such as Ru, Rh, Pd, Ag, Os, Ir or Pt.
b.p. chemicals ltd. British Patent 1,264,394
A mixture of ethylene and propylene may be converted to alkyl acetate by reaction with O2 in the presence of metallic Pd and an acetate salt.
monsanto co. British Patent 1,264,609
The catalyst consists of a noble metal, preferably Pd or Pt, supported on Al2O3.
knapsack a.g. British Patents 1,266,623 and 1,266,624
Vinyl acetate is produced by reaction of C2H4, acetic acid and O2 in the presence of supported Pd.
société générale des produits réfractaires British Patent 1,268,420
A catalyst (e.g. Pt) for the oxidation of internal-combustion-engine exhaust gases is supported on a felt composed of monocrystalline fibres consisting of Al2O3 or ZrO2 with 0−15 wt.% of SiO2 and 0−0.1 wt.% each of Fe2O3, TiO2, MnO2, K2O and Na2O.
esso research and engineering co. British Patent 1,270,055
The octane rating of C5 hydrocarbons is upgraded by hydrogenation in the presence of a catalyst which may be, e.g. Pd or Pt.
institut gornogo dela British Patent 1,270,782
A device for purifying internal-combustion-engine exhaust gases includes a chamber containing granules of treated Mn ore coated with a layer of Pd or Pt.
courtaulds ltd. British Patent 1,271,041
Caprolactam is recovered from the wash liquors of polycaproamide extrudates by hydrogenation of the liquor in the presence of Pd, Pt or Ru.
chevron research co. U.S. Patent 3,617,485
A hydrocracking catalyst consists of 0.005−2% Pt, Pd and/or Ir, 0.005−2% Re and 0−5% flouride on an amorphous aluminosilicate support.
chevron research co. U.S. Patents 3,617,489, 3,617,490 and 3,617,491
A hydrocracking catalyst consists of a layered claytype crystalline aluminosilicate containing 0.01−2% Pt, Pd, Rh, Ru and/or Ir and 0.01−5% Au, Cr and/or W or Tn and/or U.
universal oil products co. U.S. Patent 3,617,510
A hydroprocessing catalyst has a crystalline aluminosilicate support carrying Pt (or other Pt group metal), Ge and Re components.
universal oil products co. U.S. Patent 3,617,519
Gasoline reforming is catalysed by a supported Pt-Re halogen catalyst with controlled S content.
Naphtha Reforming Catalyst
chevron research co. U.S. Patent 3,617,521
A naphtha feedstock is reformed in the presence of a mixture of a layered, crystalline, clay-type aluminosilicate and a Pt group metal on a solid support. Preferably Pt itself is the catalyst.
Lean Charge Stock Reforming
universal oil products co. U.S. Patent 3,617,522
A lean charge stock is reformed over a Pt-Re catalyst in the presence of added halogen.
Purifying ICE Exhaust Gases
union oil co. of california U.S. Patent 3,619,127
Dilute combustible gases are oxidised by contacting them at elevated temperatures with a catalyst consisting of a Group VIII noble metal and a Group VIB metal, supported on a carrier such as Al2O3, e.g. Pt and Cr on Al2O3.
Transition Metal Paints
mobil oil corp. U.S. Patent 3,622,367
Substrates may be metallised with transition metals using paints containing a metal π-complex dissolved in alcohol. Pt is the preferred metal, e.g. in the form of a diene complex of PtCl2.
chemical construction corp. U.S. Patent 3,627,497
Improved Pt recovery during the oxidation of NH3 is achieved by using a cylindrical Pt gauze catalyst with a ceramic fibre cylinder filter.
chevron research co. U.S. Patent 3,630,885
Low freeze point jet fuel is obtained by hydrocracking and isomerisation over a catalyst containing Al2O3, halogen and Pt, Pd or Ir.
Hydrocarbon Isomerisation Process
universal oil products co. U.S. Patent 3,630,961
A catalytic composite for hydrocarbon isomerisation consists of a refractory inorganic oxide combined with a Friedel-Crafts metal halide having uniformly dispersed on it a Pt group component and a lead component. It contains, on an elemental and Friedel-Crafts metal halidefree basis, about 0.01−2 wt.% Pt group component and Pb in an atomic ratio of Pb to Pt group component of 0.05:1–0.9:1; e.g. Pt-Pb-AlCl3 on Al2O3.
chevron research co. U.S. Patent 3,631,315
Composites of a Group VIII noble metal, Sn and an inorganic, solid, refractory oxide carrier have excellent dehydrogenation activities and little or no isomerisation and cracking activities.
chevron research co. U.S. Patents 3,623,500, 3,632,501 and 3,632,502
A hydrocracking catalyst contains 0.01−2% Pt, Pd, Rh, Ru, Ir and/or their compounds and 0.01−5% Fe and/or its compounds on a layered claytype crystalline aluminosilicate cracking component.
Hydrocarbon Reforming Catalyst
universal oil products co. U.S. Patent 3,632,503
A catalyst for hydrocarbon reforming contains 0.01−2% Pt group metal, especially Pt, 0.01−5% Sn and 0.01−5% Ge on Al2O3 or another oxide.
Dehydrogenating Normal Paraffins
monsanto co. U.S. Patent 3,632,661
Dehydrogenation catalysts contain Fe or its oxides or alloys and one or more Pt group metals deposited upon low acidity Al2O3.
monsanto co. U.S. Patent 3,632,662
In catalytic dehydrogenation of paraffins, catalyst activity is maintained relatively constant within a desired range by using a H2S-poisoned catalyst of Pt or Pd and a Group IB metal. The poison is gradually removed from the catalyst during the dehydrogenation reaction; e.g. Cu and Pt.
Propylene Oxidation in the Presence of Rhodium Metal
gulf research & development co. U.S. Patent 3,632,833
C3H6 is oxidised to acrolein, acetone, etc., by contact with O2 in the presence of Rh metal.
Hydrocarbon Isomerisation Process
universal oil products co. U.S. Patent 3,632,835
Isomerisable hydrocarbons, including paraffins, cyclo-paraffins, olefins and alkyl aromatics, are isomerised by contacting the hydrocarbon with a catalytic composite containing a Pt group component and a Re component combined with a carrier material containing Al2O3 and a finely divided crystalline aluminosilicate.
Nickel-Noble Metal Catalysts
klingspor & co. German Offen. 2,026,008
Catalysts for the oxidation of CO and aliphatic compounds consist of alloy particles precipitated from solution by phosphite or borohydride reducing agents. The alloy contains 20−40% Ni, 10−22% Co and 10−35% Pd.
Waste Gas Purification
ethyl corp. British Patent 1,263,366
Olefins are converted to carboxylic acids by reaction with CO and water in the presence of a mixture of a Pt salt with a Sn or Ge salt.
national research development corp. British Patent 1,265,564
Catalysts for polymerisation of olefins, hydrogenation, dehydrogenation, hydroformylation and hydrosilylation reactions are mixed-ligand complexes of transition metals, e.g. trimethylsilylmethyltris(triphenylphosphine)rhodium or bis(triethylphosphine)bis(trimethylsilylmethyl)platinum.
Palladium Chelates Having a Palladium-Carbon Bond
union oil co. of california U.S. Patent 3,622,607
A Pd chelate contains Pd and a halide, alkanote or hydroxyl group in a 4- or 5-membered ring with an aromatic biphyllic ligand. The chelate is an active catalyst in hydrocarboxylation reactions.
union oil co. U.S. Patent 3,625,995
Acrylates are produced by the reaction of an olefin, O2 and CO in the presence of an alcohol, Pt group metal and a heterocyclic compound. PdCl2 and pyridine oxide are used in one example.
Olefinic Acids and Esters
union oil co. U.S. Patent 3,625,996
Olefinic acids or esters are produced from acids and olefins in the presence of a phosphine, arsine or stibine complex of a Pt group metal, e.g. PdCl2 with PPh3.
Vinyl Ester Production
knapsack a.g. U.S. Patent 3,627,821
A new catalyst for the production of vinyl esters from the reaction of an olefin, oxygen and a carboxylic acid consists of Pd, U and alkali metal acetates.
Hydrocarbon Isomerisation Catalyst
universal oil products co. U.S. Patent 3,632,525
A catalytic composite for isomerisation consists of a Pt group metal component, a Sn component and a Friedel Crafts metal halide component combined with a refractory inorganic oxide.
atlantic richfield co. U.S. Patent 3,634,501
Na acrylate and methacrylate are produced by the oxidation of allyl Pd complexes of C3H6 and C4H8 respectively.
johnson matthey & co. ltd. French Patent 2,069,322
The hydroformylation or carbonylation of organic compounds in the gas phase is catalysed by a Rh carbonyl hydride complex of a tertiary phosphine, arsine or stibine, e.g. RhH(CO) (PPh3)3, which is deposited upon a solid support.
Rhodium Hydroformylation Catalyst
johnson matthey & co. ltd. French Appl. 2,072,146
The hydroformylation or hydrogenation of gaseous olefins is improved by the use of a complex of Rh hydride carbonyl with a P-containing stabilising ligand, e.g. RhH(CO)(PPh3)3.
johnson matthey & co. ltd. German Offen. 2,136,470
Dutch Appl. 71.10,076
Belgian Patent 770,310
New compounds are complexes of monovalent Rh with a stabilising donor ligand. They are used to catalyse hydrogenation, oxidation, decarbonylation and other reactions. The preferred compounds have the general formula RhAn(CO)xLy where An is an anion other than halogen or pseudohalogen, L is a stabilising donor ligand such as a tertiary phosphine, x is 0 or 1 and y is 2 or 3. A typical complex is Rh(PPh3)3 NO3.
FUEL CELLS AND BATTERIES
Fuel Cell Electrode
c.t.a.-cie. industrielle de textiles industriels et synthétiques British Patent 1,264,346
Spinnerets of large dimensions may be produced from sheets 0.026 mm thick made from 93 wt.% Pt, 4 wt.% Au and 3 wt.% Rh, or 29.5 wt.% Pt, 70 wt.% Au and 0.5 wt.% Rh.
johnson matthey & co. ltd. British Patent 1,270,926
Articles such as sheets, rods, wires, spinnerets which are made of precious metal, e.g. an alloy containing 49 wt.% Pt, 50 wt.% Au and 1 wt.% Rh, are fabricated from metal made by flame-spraying the metal in droplet form on to a cooled stationary target whereby the droplets solidify into a coherent deposit. The deposit is removed from the target and worked.
Manufacture of Glass Fibres
p.p.g. industries inc. British Patent 1,266,212
Electrically heated Pt or Pd bushings are supported on a bushing frame made of ferritic nodular cast iron.
nippon seljoc co. ltd. British Patents 1,266,521 and 1,266,524
Concentric Pt melting pots are used in the production of glass-fibre bundles of non-homogeneous composition for light conducting applications.
Platinum Alloy Spinneret
owens-corning fiberglas corp. U.S. Patent 3,622,289
A glass feeder is made from an alloy containing 14−79% Pt, 20−85% Rh and 0.01−10% Mo. The Mo is present in an amount sufficient to increase the ductility of the alloy.
Glass Melting Pot
johns-manville corp. U.S. Patent 3,623,857
Glass is melted in a Ni-Cr-Fe alloy pot and then drawn through holes in the bottom lined with Pt.
Platinum Clad Niobium, Tantalum etc.
johnson matthey & co. ltd. French Appl. 2,084,651
An article for use at high temperatures, e.g. in the glass industry, consists of a refractory core made from Nb, Ta, Cr, Zr, V, Hf, Re or alloys thereof, a barrier layer of MgO and a sheath of Pt metals or alloys thereof.
Glass Fibre Production
ELECTRICAL AND ELECTRONIC ENGINEERING
general electric co. British Patent 1,267,828
A semiconductor device has ohmic contact regions consisting of an active metal such as Pd and a contact metal such as Au, Ag or Pt.
cogar corp. U.S. Patent 3,627,647
Stable semiconductor devices are formed by coating their SiO2 surfaces with a noble metal-Si-O layer. The noble metal is preferably Pt but Au, Ag, Rh, Pd and Ir may be used.
Etched Platinum Thin Films
motorola inc. U.S. Patent 3,629,022
Pt masks are produced by first applying an Al film to the Pt thin film. The Al film is then etched away to leave the reverse image of that required in the Pt film. The Al pattern is then diffused into the Pt to give a more readily etched Pt-Al alloy. The alloy is then etched away.
Platinum Oxide Electrical Resistor
e. i. du pont de nemours & co. U.S. Patent 3,629,156
Electrical resistors are made by applying to a ceramic base and firing a rhombohedral PtCo oxide of formula PtxCoyO2, where x and y are about 0.85 and 0.15.
Brine Electrolysis Electrode
electronor corp. U.S. Patent 3,630,768
A coating of a Pt group metal on a valve metal base (e.g. Ti) is formed by coating the base with a complex of the Pt metal with an amine, NH3, etc., and then heating the coating.
chemnor a.g. U.S. Patent 3,632,498
An electrode has an electrically conductive base selected from Al, Ta, Ti, Zr, Bi, W, Nb and their alloys. Part of the surface of the base has a coating of a mixed crystal material consisting essentially of an oxide of a film-forming metal and an oxide of a Pt group metal. Typically an aqueous alcoholic solution of Ti(OBu)4 and RuCl3 is painted on a Ti base and fired.
Ruthenium Oxide Resistors
johnson matthey & co. ltd. U.S. Patent 3,637,530
An electrical resistor contains RuO2 and NbO5 in a glass matrix. The atomic ratio of metal to O2 is 1:2 and of Nb or Ru is between 1:2,000 and 1:1.
Gas Diffusion Electrode
robert bosch g.m.b.h. German Offen. 1,771,179
A porous catalyst layer is formed on a gas diffusion electrode by applying catalyst particles (e.g. PtO2/Au) in a liquid organic paint medium.