Platinum Metals Rev., 1968, 12, (1), 36
NEW PATENTS: January 1968
METALS AND ALLOYS
general electric co. (new york)
U.S. Patent 3,324,157
Highly stablised organopolysiloxanes are produced by the usual cohydrolysis method where one hydrolysable monomer is a metallocenyl silane, where “metallocenyl” is a residue of a cyclopentadienyl derivative of a transition metal. The Pt group metals are specifically mentioned.
Production of Platinum and Palladium Oxides
Anodes and Electrolytic Cells having Such Anodes
imperial metal industries (kynoch) ltd. British Patent 1,076,973
A coated anode is formed from a plurality of Ti members placed side-by-side with each member coated with a Pt metal. The members are connected together by at least one transverse rib. At least half the area of the Pt metal coating is perpendicular to the common plane of the coated members.
Electrodes for Electrolytic Cells
ELECTRODEPOSITION AND SURFACE COATINGS
Non-magnetostrictive Magnetic Electrolytic Deposit
international business machines corp. British Patent 1,081,316
A Ni-Fe alloy with a small amount of Pd is electrodeposited from an aqueous bath, containing Ni and Fe in a 50−80:1 ratio, to which 700 mg/l of Na pallidichloride has been added.
Electrically Conductive Compositions
e. i. du pont de nemours & co. British Patent 1,086,074
Fired-on conductive metal coatings are produced from a mixture of (a ) finely divided metallic Pd, PdO or Pd/Ag alloy, (b ) finely divided Ag, (c ) finely divided ceramic consisting of Bi2O3 with a Cd or Pb borate frit. The component (a ) must provide 22−35% Pd and component (b ) 48−69% Ag, based on the total composition.
Platinum Coating Method and Material
johnson, matthey & co. ltd. Italian Patent 764,009
Dispersions of PtO2 and mixtures of PtO2 with oxides of Rh, Ru, Ir, and Pd, in which Pt is at least 50 wt.% metal content, are present to 1–500 g/l in a medium of C2−C5 aliphatic alcohols with less than 37% HCHO. Pt metal deposits are formed by coating substrates with this dispersion.
Applying Designs to Metallic Bases
johnson, matthey & co. ltd. Italian Patent 767,740
A metal or alloy differing in colour from the metal base is applied in an organic base and fired to produce slight adherence, the metal or alloy then being embossed with a design. Au, Ag and Pt metals, e.g. in flake form, are suitable decorative materials. This corresponds to French Patent 1,455,917.
Electrodeposition of Palladium
Production of Hydrogen Cyanide
monsanto co. British Patent 1,077,238
A mixture of NH3, natural gas, H2 and air or O2 in the vapour phase is passed over a Pt metal or alloy catalyst at high temperature to produce HCN. A gauze made from an alloy of about 90% Pt and 10% Rh is a suitable catalyst material.
Carbonylation of Allylic Halides
national distillers & chemical corp. British Patent 1,077,773
An acyl halide is produced by reacting CO and an allyl halide in the presence of a Pt metal catalyst. The preferred catalyst is Pd metal, a Pd salt or a Pd complex of an organic compound.
Catalysts for the Isomerisation of Lower Saturated Hydrocarbons
snam s.p.a. British Patent 1,081,120
A catalyst consisting of Pt/Al2O3 is activated by heating with C2Cl6 vapour (at 180−500°C) before it is used to isomerise 1−6C alkane mixtures. A typical Al2O3 catalyst contains 0.8% Cl2 and 0.6% Pt.
Carboxylic Acid Vinyl Esters
farbwerke hoechst a.g. British Patent 1,082,564
C2H4, O2 and carboxylic acids are reacted in a gaseous state over a supported Group VIII noble metal catalyst to give a vinyl carboxylate. Pd/Al2O3-SiO2 is a suitable catalyst.
Process for Activating Catalysts
esso research & engineering co. British Patent 1,084,354
Finely divided Au, Ag and Pt metal catalysts (and alloys of those metals) are activated by wetting the catalyst with a basic solution having a pH of 8–14. Wetting, e.g. of a fuel cell catalyst, may be carried out with an alkali metal hydroxide, phosphate, metasilicate or carbonate or with 1N NH3.
Preparation of Unsaturated Nitriles
asahi kasei k.k.k. British Patent 1,084,599
Unsaturated nitriles are produced by the addition of HCN to a 2–4 C olefine in the presence of O2 and Pd, Rh, Ru, Pt, Au or Cu catalyst.
Hydrogenation of Unsaturated Aldehydes
universal oil products co. British Patent 1,086,447
The olefinic double bond of an unsaturated aldehyde is reduced selectively in the presence of a Pd catalyst and a two-phase liquid system.
geigy (u.k.) ltd. British Patent 1,086,639
Cyclododecatriene is hydrogenated until 2 mols of H2 are absorbed in the absence of solvent and in the presence of a hydrogenating catalyst, preferably a supported Pt group metal.
Preparation of Vinyl Chloride
farbwerke hoechst a.g. British Patent 1,086,785
Vinyl chloride and optionally ethyl chloride are produced from C2H4, O2 and HCl in the presence of an elementary Group VIII noble metal, especially Pd, Pt, Rh, Ru and Ir.
Activating a Composited Catalyst
gulf research & development co. British Patent 1,087,586
Catalysts consisting of Pt metals on Al2O3 are activated by heating at 510−677° in the presence of SnOaXbYc, where X is Cl, Y is another halogen, n is 1 or 2, a is 0−3 or 5, b is 2, 4, or 7, c is 0 or 1 and b+c is 2–8.
Hydrogenation of Unsaturated Hydrocarbons
shell internationale research mij. n.v. British Patent 1,087,684
The catalysts used consist of one of the six Pt metals deposited on an Al2O3 which has a bulk density of less than 0.78 g/ml. Smaller amounts of other refractory oxides may also be present.
Production of Hydrogen Cyanide
monsanto co. British Patent 1,088,903
HCN is produced by the reaction of NH3, natural gas and air in the presence of a metallic Pt or Pt alloy gauze which has been activated by the passage of a reactant mixture with a NH3:gas:air ratio of 0.7−1.0:1:0.170−0.200. A preferred gauze contains 10−20% Rh.
Catalytic Conversion of Hydrocarbons
british petroleum co. ltd. British Patent 1,088,933
The catalyst for the petroleum conversion process is a crystalline synthetic mordenite having a pore opening of at least 5Å which has been decationised by direct treatment with mineral acid to give a metal cation content of not more than 2 wt.% and on to which a Group VI or VIII metal or oxide hydrogenating component has been deposited. For hydrogenation the preferred catalyst is Pt or Pd.
Hydrogenation of Aminovinyl Ketones
eastman kodak co. U.S. Patent 3,325,491
Aminoalcohols can be produced by hydrogenating the keto and vinyl groups of aminovinyl ketones over Ru or Rh catalysts. The amino group is not touched.
Hydrocarbon Conversion Catalyst
union oil co. of california U.S. Patent 3,326,797
The catalyst consists of Pt, Pd or another transition metal hydrogenation catalyst deposited on a crystalline, zeolitic, alumino-silicate base, the base having been prepared by digesting a crystalline zeolite, with a SiO2/Al2O3 ratio of about 6−12:1, in aqueous caustic.
Catalyst for Hydrocarbon Reforming
the british petroleum co. U.S. Patent 3,328,286
Petroleum feedstocks are upgraded by hydro-reforming over a catalyst comprising Pt/Al2O3 having a reversible C6H6 chemisorption of up to 5 μ mol/g.
Hydrocarbon Conversion Catalysts
esso research & engineering co. U.S. Patent 3,329,604
An alumino-silicate zeolite is treated to replace alkali metal ions by Mn cations and then the product is used as a carrier for a Pt group metal catalyst. The catalysts can be used in cracking, hydrocracking, etc.
Platinum Group Metal Catalyst Selectivity
mobil oil co. U.S. Patent 3,330,761
In reforming naphtha at 100–1000 p.s.i.g., the selectivity of the Pt group metal catalyst is improved by contacting it, before major use, with a feedstock containing 100–2000 p.p.m. S to reduce subsequent undesirable exothermic reactions.
Steam Reforming Process
imperial chemical industries ltd. U.S. Patent 3,334,055
A Co or Ni oxide reforming catalyst is activated with 0.001−0.5 wt.% of a Pt group metal or reducible compound, preferably Pt, Pd or Rh.
Hydrogen Peroxide Production
imperial chemical industries ltd. U.S. Patent 3,336,112
H2 and O2 are reacted together in the presence of a Group VIII metal, e.g. Pd/SiO2, and H2O containing a stabiliser and a condensed phosphate activator.
Hydrogenation with Platinum Metal Sulphide Catalyst
uniroyal inc. U.S. Patent 3,336,386
Nitro- or N-nitrosoamine groups are reduced to amine groups using a Pt metal sulphide, e.g. a supported PdS. The catalysts can also be used for other reduction processes and some of the products are rubber stabilisers.
Dehydrogenating Hydroxy- and Oxo-cyclo-aliphatic Compounds
progil U.S. Patent 3,336,399
α-Naphthol and the like are produced by dehydrogenation over a finely divided metal catalyst, selected from Pt, Ir, Pd, Rh and other transition metal catalysts.
Hydrogenation of Cinnamaldehyde
johnson, matthey & co. ltd. Italian Patent 775,456
Selective hydrogenation of unsaturated aldehydes, in particular of cinnamaldehyde to cinnamyl alcohol, is catalysed by supported Pt metals in alcoholic solutions with alkali promoters, e.g 5% Pt/charcoal, Ru-Pt/charcoal, Pt/Al2O3. This corresponds to Belgian Patent 685,368.
Hydrogenation of Crotonaldehyde by Trickle Column Catalysis
Preparing High Molecular Weight Paraffinic Hydrocarbons from Carbon Monoxide and Hydrogen
h. pichler British Patent 1,076,848
CO and H2 are reacted at 80−135°C and 100−3,000 atm, to give hydrocarbons with a molecular weight of above 50,000, using a highly active Ru catalyst. This is formed in situ by reacting a highly active RuO2 with a hydrocarbon solvent to give a hydrocarbon complex.
Carboxylic Acid Preparation
shell internationale research mij. n.v. British Patent 1,080,867
The reaction of an optionally substituted olefine with CO, to produce a carboxylic acid or its derivatives, is catalysed by a halide or π-complex of Pd, Rh or Ru, e.g. PdCl2 or an C2H4-Pd complex.
imperial chemical industries ltd. British Patent 1,081,304
Copolymers of an olefine and CO are produced by heating them in the presence of a catalyst comprising an alkyl phosphine complex of a Pd salt, especially (Bu3P)2PdCl2.
Preparation of Carboxylic Acid Esters
esso research & engineering co. British Patent 1,083,597
A substituted allyl ester is produced by reacting a tertiary olefine with a source of carboxylate ions in the presence of a Pd salt and a high boiling anhydrous polar solvent at 50−150°C.
Production of α, β-Ethylenically-unsaturated Carboxylic Acids and/or β-Acyloxy Carboxylic Acids
union oil co. of california British Patent 1,083,880
These acids are produced by the oxidative carbonylation of olefines in an anhydrous reaction medium containing an aliphatic carboxylic acid solvent and 0.001−5 wt.% of a Pt metal, preferably of the Pt or Pd subgroups, as a finely divided metal, salt or chelate.
Production of Vinyl Acetate and Acetaldehyde
e. i. du pont de nemours & co. British Patent 1,083,959
The oxidative carbonylation of C2H4 takes place in an acid solution of a Pd salt, an ionisable metal chloride, cupric acetate and 0−20 wt.% of H2O.
Production of Acetaldehyde
e. i. du pont de nemours & co. British Patent 1,086,347
CH3CHO and optionally vinyl acetate are produced from C2H4, O2 and CH3COOH in the presence of 0.001−0.1 mols/l palladous salt and at least 0.5 mols/l of a Zn/Cu redox mixture.
Manufacture of Ethers
british celanese ltd. British Patent 1,086,351
C2H4 is reacted with a palladous salt and a metal salt able to oxidise Pd metal in an alcohol to form the vinyl ether of the alcohol and then the metal salt is reoxidised and regenerated with O2.
Production of Vinyl Acetate
e. i. du pont de nemours & co. British Patent 1,087,508
C2H4 is reacted with an CH3COOH solution of a palladous salt and a cupric salt at 100 psig or higher and also in the presence of 0.05−2.6 mol/l KCl.
Palladium Catalysts for Ketone Polymerisation
shell oil co. U.S. Patent 3,321,442
The catalysts are PdCl2 and (Ar3X)PdCl2, where Ar is Ph and X is P, As or Sb.
Hydrido-iridium and -osmium Complexes in Hydrogenation
standard oil co. (indiana)
U.S. Patent 3,324,018
Non-aromatic C-C unsaturation is hydrogenated selectively using a number of specified hydrido-iridium and -osmium complexes of triphenyl arsines, stibines and phosphines, e.g. IrHCl2(PPh3)3.
dow corning corp. U.S. Patent 3,328,448
The conversion of a SiH group to a SiOH group by reaction with H2O is catalysed by either H2PtCl6, Zeise’s salt, Pd, Rh or Ru.
the sperry gyroscope co. ltd. British Patent 1,084,238
A fuel cell is provided with a hydrogen-permeable membrane of Pd substantially free from pinholes. Preferably the Pd is alloyed with a minor proportion of one or more metals, such as up to 27% Ag, to improve its strength.
Plural Coated Fuel Cells
studebaker corp. U.S. Patent 3,322,576
The electrode consists of a porous metal support in the form of a Ta or Ti sheet member, a first coating of graphite in a fluorocarbon polymer and a second coating of Pt black in an amount of 0.1−20 mg/cm2.
Metallised Paper Fuel Cell Electrode
Alloy Resistant to Wetting by Glass
ELECTRICAL AND ELECTRONIC ENGINEERING
Electrical Contact Elements and Contact Assemblies
johnson, matthey & co. ltd. British Patent 1,088,541
A series of contact elements are produced on a backing strip of a different metal which is provided with a plurality of locating members corresponding to the numbers of contact elements. The object of the locating members is to locate the strip in a press tool accurately to that contact members can be pressed out precisely without leaving waste material between them. The contact metals are preferably formed of noble metals, such as Ag, Pt, Pd or Au.
Electrical Resistance Wire
johnson, matthey & co. ltd. U.S. Patent 3,320,039
The wire consists of an outer tube of Pt group metal or alloy filled with a refractory oxide selected from Al2O3, ZrO2 and MgO. A suitable tube is made from Pt with 10–40% Rh.
Cermet Resistance Element
beckman instruments inc. U.S. Patent 3,326,645
A thin resistance layer is produced on a nonconducting base layer from a cermet composition. This contains 50−95 wt.% glass and 5−50 wt.% of a Ru-Rh alloy, such as a 1:1 alloy (by weight). The composition of the alloy is matched to the glass so that the glass has a lower melting point than the alloy and at least 10 wt.% Ru is present. See also U.S. Patent 3,326,720.
Electrical Resistance Element
cts corp. U.S. Patent 3,329,526
The resistance element consists of a resistant insulating base coated with a glass film not thicker than 0.0002 inch and containing particles of Ru having hexagonal close-packed crystalline structure and acicular growth.
Sparking Plug Electrodes
johnson, matthey & co. ltd. U.S. Patent 3,331,685
Ru and Ru-Ir alloy powders are compressed and sintered to form an electrode resistant to contamination by Pb. Ranges of preferred particle sizes, sintering temperatures, and compacting conditions are claimed.