Platinum Metals Rev., 1971, 15, (2), 75
NEW PATENTS: April 1971
METALS AND ALLOYS
Gold-based Spinnerette Alloy
johnson, matthey & co. ltd. U.S. Patent 3,529,959
A gold-based spinnerette alloy contains between 50% and 80% Au, between 0.04 and 0.5% Ir and the remaining part Pt, apart from the impurities. A method of making the alloy consists of induction melting the components, casting a sheet and homogenising.
johnson, matthey & co. ltd. U.S. Patent 3,508,870
Method of preparing Os carbonyls is described. A solution of OsO4 in an inert hydrocarbon solvent is heated to an elevated temperature under super-atmospheric pressure in the presence of CO. The product is primarily Os3(CO)12 with traces of Os4O4(CO)12.
ELECTRODEPOSITION AND SURFACE COATINGS
Coating or Inlaying
johnson, matthey & co. ltd. British Patent 1,207,970
A Cu or Cu alloy is coated or inlaid with a thin layer of a noble metal such as Au, Ag, Pd or Pt or alloys thereof by interposing between the two a layer of Ni, Fe, Co, Mo, or V, and heating the three layers under pressure to bond them.
Reductive Vapour Deposition of Osmium
english electric valve co. ltd. British Patent 1,209,318
High purity Os deposits are obtained on a surface by vapour deposition from an OsO4/H2 mixture. OsO4 is dissolved in water at room temperature and H2 (or a gas containing H2) bubbled through the solution. The resulting gas is mixed with another reducing gas to give a predetermined ratio of OsO4 to reducing gas. In contact with a hot body this gas deposits metallic Os.
Electroless Noble Metal Plating
mobil oil corp. U.S. Patent 3,511,683
Pt and other noble metals are deposited on metal or mainly metal colloidal particles by displacement plating in non-aqueous solution. The particles must have an outer sheath of a reactive metal which is above the noble metal in the electrochemical series. In an example Sn-coated C black particles are coated from a solution of PtCl4 in C6H6. The coated particles are used in fuel cell manufacture. Other compounds used for displacement plating are a Au octadiene complex, Ag acetylide, Ir allyl and Ag perchlorate.
Plating Low Stress Bright Rhodium
sel-rex corp. U.S. Patent 3,528,895
An aqueous acid electrolyte for the deposition of bright low stress Rh contains Rh and Cu ions in synergistic combination with sulphamic acid.
Gold and Ruthenium Plating Baths
technic inc. U.S. Patent 3,530,049
An aqueous electroplating bath for depositing Ru contains a chelate of Ru with ethylenediamine tetraacetic acid, nitrilotriacetic acid or cyclohexanediamine tetraacetic acid. The above chelates are also used as grain refining agents in acidic Au plating baths.
Electrodeposition of Palladium
johnson, matthey & co. ltd. U.S. Patent 3,530,050
Electrolysis or electrodeposition of Pd is carried out with an aqueous neutral or alkaline bath containing a Pd compound and an ammonium salt of a weak organic acid which does not form an insoluble compound with the Pd compound.
Metallising Composition Conductor
international business machines corp. U.S. Patent 3,537,892
A conductive metallising composition for deposition and firing at 725−900°C on an insulating substrate to form a conductive element consists of a metal component of 60−70% Au, 10−20% Pt and 10−30% Pd, a vitreous frit and a vehicle.
johnson, matthey & co. ltd. German Appl. 1,959,907
A new complex suitable for electroplating baths has an anion of general formula:
Pore-free Coatings with Group VIII Metals
h. guenther et al. East German Patent 71,678
Pt coatings are produced on metals such as Ti or Tl by electrolytic polishing of the surface, then coating with a thin layer of Pt followed by a diffusion annealing treatment at 650−800°C for at least 20 min. This may be followed by the deposition of an additional Pt layer.
LABORATORY APPARATUS AND TECHNIQUE
Pulse-activated Polarographic Hydrogen Detector
johnson, matthey & co. ltd. British Patent 1,208,101
In a continuous process for the preparation of gluconic acid or glucosaccharic acid, an aqueous solution of glucose containing Na or K carbonate or bicarbonate is contacted in a trickle column with an O2-containing gas and in the presence of a supported Pt group metal.
Catalytic Conversion of Gases
shell international research mij. n.v. British Patent 1,210,867
An apparatus is described in which the activity of a catalyst, e.g. Pt, for the reduction of HNO3 tail gases, is not reduced by the presence of solid particles in the gases.
rohm & haas g.m.b.h. British Patent 1,214,793
Dicyanogen is obtained by the oxidation of gaseous HCN admixed with CO or steam in the presence of a Pt group metal, e.g. a Pt gauze.
toray industries inc. British Patent 1,214,958 Cyclohexane is produced by the hydrogenation of C6H6 in the presence of Pt on a carrier.
zaklady azotowe im. p. findeva British Patent 1,216,019
Oxidation of NH3 to HNO3 is catalysed by PtO2.
centre national d’Études spatiales British Patent 1,216,240
A catalyst for the decomposition of N2H4 and its derivatives (for use in rocketry) consists of 25–45 wt.% of Ir on a porous Al2O3 carrier, the combination being free from both S and Br2.
Curing of Organosilicon Compositions
dow corning corp. British Patent 1,217,618
Si resin compositions are cured with 0.1 ppm of Pt and a tetramethyl guanidine carboxylate in an amount representing 0.01−4 moles per g.atom of Pt.
texaco development corp. British Patent 1,217,815
High octane fuels are produced by two stage hydrocracking. The first stage uses a base metal catalyst and the second stage a noble metal catalyst.
Unsaturated Ester Production
mitsui petrochemical industries ltd. British Patent 1,219,510
The reaction of an alcohol and/or aldehyde with O2 to form an ester of an unsaturated carboxylic acid is catalysed by Ru, Rh, Pt, Pd or an oxide of one of these metals on a support.
Aromatic Compound Production
asahi kasei k. k. k. British Patent 1,219,704
Aromatic compounds are produced from petroleum fractions by contacting them with H2 at 400−650°C in the presence of a supported catalyst. The catalyst consists of Al2O3 or another support impregnated with 0.1−1% Pt, 0.1−1% Pd and 5−25% Cr oxide. The catalyst is treated with H2 after impregnation with the active metals.
sinclair research inc. U.S. Patent 3,506,566
Clarified or decant oil is converted to distillate fuel by a two-stage catalytic hydrocracking-hydroisomerisation process. The second-stage catalyst is a noble metal catalyst, e.g. Pt/Al2O3 or Pt/alumino-silicate.
Catalytic Reforming Process
chevron research co. U.S. Patent 3,507,780
A reforming process using a catalyst containing 0.01−0.3% Pt, 0.01−0.3% Re, and 0.001−0.1% Ir associated with a porous solid carrier is started up by contacting the naphtha with the catalyst in the presence of an inert gas, for example, N2. The pressure in the reforming zone should be about 200 p.s.i.g. and the catalyst temperature about 650°F when the naphtha is first contacted with the catalyst at a space velocity of 1 v/v/h. The catalyst temperature is increased to 900°F over a 2–3 hour period while building up autogeneous pressure of produced H2. See also U.S. Patent 3,507,781.
Catalytic Production of LPG
universal oil products co. U.S. Patent 3,511,773
A hydrocarbon feedstock is converted to LPG and high octane reformate using a catalyst of a Pt group component and a halogen component combined with a carrier containing Al2O3 and about 1−10% of crystalline aluminosilicate. Pt is the preferred catalyst for the selective cracking of paraffins to C3 and C4 hydrocarbons and production of a high octane reformate.
Paraffin Conversion Catalyst
shell oil co. U.S. Patent 3,511,888
A new catalyst for paraffin dehydrogenation and dehydrocyclisation consists of 0.01−5% Pt and/or Pd modified with Sn or Bi on inert SiO2.
Purifying Hydrogen Separated from a Catalytic Reforming Effluent
universal oil products co. U.S. Patent 3,520,799
A process is described for the catalytic reforming of hydrocarbons in the presence of H2 to produce high quality gasoline boiling range products. Relatively impure hydrogen for recycle purposes and other uses is provided by compressing and contacting this hydrogen with a portion of the liquid reformed product. Catalysts are e.g. Pt/Al2O3. U.S. Patent 3,520,800 is similar.
Hydrocarbon Conversion Process
universal oil products co. U.S. Patent 3,523,914
A hydrocarbon conversion catalyst consists of a Pt group metal and a Re component combined with a carrier material containing Al2O3 and a finely divided crystalline aluminosilicate. In one example it contains 0.05−1.0% Pt and 0.05−1.0% Re, combined with γ-Al2O3 carrier material having 0.5−20% of the H2 form of mordenite uniformly distributed.
universal oil products co. U.S. Patent 3,529,029
Aromatic hydrocarbons are hydrogenated to cycloparaffins in the presence of a catalyst which contains 0.01−2.0 wt.% Pt or Pd, 0.01−2.0 wt.% Re and 0.01−1.5 wt.% of an alkali metal, preferably Li.
Catalytic Dehydrogenation of Cyclohexanol and/or Cyclohexanone
institut francais de pÉtrole, des carburants et lubrifiants U.S. Patent 3,534,110
Phenol is made by the catalytic dehydrogenation of cyclohexanol or cyclohexanone where the catalyst contains Pt and preferably also Ir on a SiO2 carrier of 100–300 m2/g specific surface and 0.7−1.1 cm3/g porous volume.
Dehydrogenation over Platinum-Rhenium Catalyst
chevron research co. U.S. Patent 3,535,402
Paraffins with 3–5 C atoms are dehydrogenated by contacting the paraffins with the catalyst containing 0.1−3% Pt and 0.1−5% Re associated with a non-acidic porous solid carrier. Dehydrogenation conditions include a temperature of 900−1100°F and a pressure of 3–100 psig.
Catalytic Hydrogenation of Nitrobenzene
international nickel ltd. French Patent 1,587,963
An aqueous solution of nitrobenzene is hydro-genated to aminophenol in the presence of a Pt-Ru catalyst, e.g. Pt-Ru/C.
Hydrogenation of Unsaturated Aldehydes
johnson, matthey & co. ltd. German Appl. 1,568,861
Unsaturated aldehydes are reacted with H2 in the presence of a catalyst containing Pt activated by an alcoholic alkali metal hydroxide or oxide solution.
Improved Selective Catalyst Reduction
johnson, matthey & co. ltd. German Appl. 1,568,894
A new process is intended to increase the selectivity and thus the yield of alcohol in the reduction of an aromatic aldehyde or ketone. For the process a known Pd catalyst, e.g. palladised wood charcoal, is used in the presence of an amine, especially an aromatic amine.
w. r. grace & co. German Appl. 1,933,240
HCN is produced by the gas-phase reaction of a hydro-carbon (e.g. CH4) with NH3 in the presence of a catalyst of 0.1−0.6 wt.% Pt/mullite.
chevron research co. German Appl. 1,954,368
Hydrocarbons are dewaxed by reaction with H2 in the presence of a catalyst which consists of 0.01−3 wt.% Pt and 0.01 to 5 wt.% Re on a porous solid support.
chevron research co. German Appl. 1,956,715
A hydrocracking catalyst consists of a layered crystalline alumino-silicate on which is deposited 0.01−2% of Pt, Pd, Ir or their compounds and 0.01−2% of Re or a Re compound.
chevron research co. Dutch Appl. 70.02,354
A hydrocracking catalyst consists of a hydro-genating metal deposited on an amorphous aluminosilicatc carrying 0.0−5.0 wt.% F or fluoride. The Al2O3:SiO2 ratio is 70:30 to 5:95. The catalytic metal is 0.005−2.0% of Pt, Pd, Ir and or their compounds and 0.005−2.0% of Re and/or Re compounds.
institut francais de pÉtrole, des carburants et lubrifiants Dutch Appl. 70.04,770
A new catalyst for the dehydrogenation of saturated hydrocarbons consists of Al2O3 supporting 0.05−2 wt.% Pt and 0.01−0.5 wt.% Ir, Ru and an alkali or alkaline earth metal representing 0.3–10 times the amount of noble metals.
New Platinum Catalysts
general electric co. British Patent 1,211,699
Significantly improved hydrosilation of aliphatic unsaturated materials can be obtained by using as catalyst a Pt-siloxane complex, e.g. Pt complexed with 1,3-divinyl-tetramethyldisiloxane or 1,3-divinyltetraphenyldisiloxane.
farbenfabriken bayer a.g. British Patent 1,213,779
Organic-silicon compounds are obtained by the addition of a silane or siloxane to an olefinically unsaturated organic compound in the presence of Me3Py2PtI.
Production of Hydroquinone
lonza ltd. British Patent 1,215,568
C2H2, CO and H2 are combined at increased temperature and pressure in the presence of [Ru(CO)1]3.
Catalytic Hydrogenation or Hydroformylation
johnson, matthey & co. ltd. British Patent 1,219,763
A hydrogenation or hydroformylation process is catalysed in the presence of a base by a Pt metal hydride, halide or pseudohalide complexed by an organic isocyanide or a Group VB or VIB compound. For Rh and Ir halides a Sn or Ge dihalide may also serve as the complexing agent. Particular catalysts are (PPh3)3RuCl2 and RhH(CO)(PPh3)2.
rhone-poulenc s.a. U.S. Patent 3,522,327
New complexes of PtCl2 with triaminophosphines are useful catalysts for curing organopolysiloxane resins. They have the general formula: PtCl2,2P(NR′R″)3 and are formed by simple addition.
Homogeneous Dehydrogenation of Paraffins
ethyl corp. U.S. Patent 3,524,898
6–20 C paraffins are dehydrogenated by contacting them with a carbonyl halide Group VIII metal catalyst complex, such as IrCl(CO)(PR3)2, at 300−425°C, optionally in the presence of a H acceptor.
imperial chemical industries ltd. U.S. Patent 3,524,899
Catalysts for the hydrogenation of ethylenic or acetylenic compounds are the reaction products of a Ru compound in which the metal has a valency of two or more and a simple or complex halide of an element of Group IA, IIA or IIIB. Examples are RuCl3(H2O)3, RuCl3(SEt2)3, RuCl2(PPh3)3 and RuCl2(AsEt3)3.
Hydrocarboxylation of Olefins
union oil co. U.S. Patent 3,530,155
Olefins are hydrocarboxylated by contacting the olefin under liquid phase conditions with a catalyst which consists of a Pt or Pd complex with an aromatic phosphine, H2O and CO. High reactivity and high yields of the normal acid are obtained by incorporating an anionic or nonionic surface active agent in the reaction medium.
Three-layer Fuel Cell Electrode
union carbide corp. British Patent 1,216,794
The fuel cell electrode structure consists of a fine-pored porous metal layer on the electrolyte side, a gas-permeable plastic-bonded catalyst layer and a coarse-pored porous metal layer. The plastic-bonded layer may contain a noble metal catalyst, e.g. Pt/C in p.t.f.e.
Gas Diffusion Electrodes
robert bosch g.m.b.h. British Patent 1,220,013
Gas diffusion electrodes for fuel cells are produced by coating a gas-permeable base with a varnish containing the catalyst metal. In one example Au and Pt dioxide dispersed in a cyclised rubber varnish are used to produce a catalyst layer on a p.t.f.e. plate.
Metal Boride Fuel Cell Catalyst
leesona corp. U.S. Patent 3,513,028
New catalysts for fuel cells are Group III-VIII transition metal borides. The preferred catalysts are Ni, Ru, Rh, Pd, Os, Ir and Pt borides. They may be produced by coating a porous substrate with a metal black and then treating the coating with an alkali metal borohydride.
Fuel Cell Electrode Production
Heating of Corrosive Vapours
laporte titanium ltd. British Patent 1,219,573
TiCl4 vapour is heated in a plurality of tubes having inlets and outlets made of Pt or an alloy of Pt with Rh, Ru or Ir.
Degassing Platinum Powders
e.i. du pont de nemours & co. U.S. Patent 3,511,640
A process for preparing degassed Pt powders consists of mixing finely divided Pt powder with at least an equal volume of a diluent metal oxide powder and heating the mixture until all gases have evolved. The powder mixture is cooled and the Pt powder separated from the diluent. The degassed powders are particularly suitable for application to “green” ceramic sheets used in the production of monolithic multi-layer ceramic circuit components.
Catalytic Igniter Members
rolls-royce ltd. U.S. Patent 3,527,680
The activity of a Pt or Pt alloy catalytic igniter for a gas turbine engine is improved by etching the igniter to remove the initial surface layer, plating the member with a layer of Pt which supports catalytic ignition and heat treating.
Separation of Hydrogen from Gas Mixtures
johnson, matthey & co. ltd. German Appl. 1,567,601
A H2 diffusion membrane consists of a Pd alloy containing 0.7−0.8% B and 4.5% Ag, or 4.3% Ag and 0.75% B.
johnson, matthey & co. ltd. German Appl. 2,005,494
A device for the separation of H2 from gas mixtures consists of a stack of spaced Ag-Pd diffusion members.
Platinum Coating of Refractories
Stirrer for Molten Glass
ELECTRICAL AND ELECTRONIC ENGINEERING
erie technological products inc. British Patent 1,212,820
A capacitor consisting of a central ceramic layer sandwiched between two outer layers of the same ceramic has painted-on electrodes of Pt-Pd, for example, and electrode terminals of Ag paint.
Field Effect Transistor
telefunken patentverwertungs g.m.b.h. British Patent 1,217,665
In a field effect transistor, metal electrodes are applied to its semiconductor body as a source and drain and, together with the body, for metal-semiconductor rectifying contacts. Au, Pt and Pd are suitable contacts.
Self-regulating Heating Elements
johnson, matthey & co. ltd. U.S. Patent 3,520,043
Self-regulating heating elements have first and second components connected in parallel so that the resistivity of the element increases with temperature. Preferably one component forms a sheath for a core made from the other component. Suitable materials for the sheath include Ni-Cr and Fe-Ni-Cr alloys; suitable materials for the core (apart from Fe, Fe alloys, Ni and Ni alloys) include Co, Mo, W, Pt, Pd and Ta.
hewlett-packard co. U.S. Patent 3,521,134
A metallic contact pad is formed on stripped areas of a semiconductor to reduce the thermal and electrical resistance. Pt silicide covered with Au and Mo provides a suitable material for the pad.
beckman instruments inc. U.S. Patent 3,523,777
In a method of sealing an internal half-cell (Pt/Ag/AgCl) into a constricted portion of an inner glass tube, the constricted portion is painted with Ag paint and then sealed on to the Pt wire by induction heating.
Platinum Coated Electrode
matthey bishop inc. U.S. Patent 3,532,556
A process of coating substrates with Pt involves reacting a Pt-type oxide with a reducing and dispersing medium composed of a 2-5 C aliphatic alcohol. A water-soluble inorganic salt or acid is added and most of the dispersion medium is removed from the platinised substrate while retaining the Pt wet and oxidising residual adsorbed organic matter, and removing water. The reducing and dispersing medium preferably also includes formaldehyde.
Electric Film Resistance
siemens a.g. German Appl. 1,480,606
An electric film resistance, applied to glass or ceramic, consists of 40−60% Au, 10−15% Pt, 25−30% Pd and 5−10% Rh or Rh2O3.
Printed Heater Elements
johnson, matthey & co. ltd. German Appl. 1,912,216
Resistor compositions for use as heating elements may be applied by screen or other printing techniques to various ceramic substrates. They consist of a mixture of 10−80 wt.% (especially 46−65 wt.%) of finely divided RuO2 and balance glass. Alternative compositions include finely divided Ag and compositions of matter formed by heating RuO2 with a Group V metal oxide, such as NbO5. See also German Appl. 1,640,561.
Anode for X-Ray Tubes
metallwerke plansee a.g. German Appl. 1,952,526
The anode is made from an alloy of W containing 0.05−5% preferably 0.15−1.5%, Pt.
Brine Electrolysis Electrode
imperial metal industries (kynoch) ltd. Dutch Appl. 70.06,285
An electrode is made with a surface of film-forming metal coated with Ru and/or RuO2 mixed with a chemical compound containing the film-forming metal, Cl2 and O2. The film-forming metal may be Ti, Ta, Nb or their alloys. A suitable chemical compound is Ti oxychloride.