Platinum Metals Rev., 1972, 16, (4), 151
NEW PATENTS: October 1972
METALS AND ALLOYS
Dispersion Strengthening of Metals
johnson matthey & co. ltd. British Patent 1,280,815
Platinum group metals are dispersion strengthened by spraying the metal or alloy with ∼0.1 wt.% reactive metal, e.g. Zr, through an atmosphere which reacts preferentially with the reactive metal to form a dispersion strengthening material, e.g. ZrO2.
Dispersion Hardening of Pt Group Metals
johnson matthey & co. ltd. U.S. Patent 3,640,705
An oxidation resistant and high mechanical strength alloy is made by alloying a Pt group metal with an element capable of forming a stable refractory compound, and heating the alloy in a gas, e.g. air or O2, to form the refractory compound within the alloy. This corresponds to British Patent 1,139,897.
Treatment of Metals and Alloys
ELECTRODEPOSITION AND SURFACE COATINGS
gulf & western industrial products co. British Patent 1,277,145
It has been found that in the electroless plating of polypropylene articles, much better results are obtained if Pd(NO3)2 rather than PdCl2 is used as the activator.
Platinum Coatings on Cobalt Alloys
deutsche edelstahlwerke a.g. British Patent 1,282,530
Turbine blades and other metal parts exposed to high temperatures are made from Co alloys coated with Pt group metals, e.g., Pt itself, optionally plated on over Ni.
LABORATORY APPARATUS AND TECHNIQUE
maruzen oil co. British Patent 1,272,728
Selective hydrogenation of polyunsaturated hydrocarbons can be carried out in the presence of specified proportions of CO and a catalyst which is preferably supported, Cu-free Pd.
f.m.c. corp. British Patent 1,273,280
In the production of H2O2 by the anthraquinone process, the hydrogenation catalyst is Pd metal supported on Al2O3 spheres of specified dimensions.
b.p. chemicals international ltd. British Patent 1,273,874
12-Aminododecanoic acid (for use in the manufacture of nylon-12) is obtained by hydrogenation of 11-cyano-undecanoic acid in the presence of Ru metal deposited on a SiO2 support.
v.e.b. leuna-werke ‘walter ulbricht’ British Patent 1,275,830
Normal paraffins are dehydrogenated to linear monoolefins in the presence of a catalyst which contains 0.5−5 wt.% Pt and 0.3−0.6 wt.% alkali metal.
monsanto co. British Patent 1,277,242
Carboxylic acids and esters are obtained by reaction of alcohols with CO in the presence of a solid catalyst containing (a ) a support, (b ) a Rh component and (c ) another metal.
compagnie francaise de raffinage British Patent 1,278,001
The catalyst is a porous refractory inorganic oxide support carrying 0.02 to 2 wt.% of a metal catalyst which is a Pt group metal with 0.02−2 wt.% of Pb and/or Sn.
Ammonia Oxidation Catalyst
m. a. miniovich et al. British Patent 1,282,000
A catalyst for the oxidation of NH3 to NO consists of 75−82% Pt, 15−22% Pd, 2−3.5% Rh and 0.05−0.15 Au, Fe and Ir. This catalyst is more active but costs less than known catalysts.
Catalytic Hydrogenation of Hydrocarbon Oils
shell internationale research mij. n.v. British Patent 1,282,774
A catalyst for the hydrogenation of hydrocarbon oils consists of 0.25−5 wt.% Pt or Rh on an Al2O3 carrier the total alkali content of which is less than 0.01 wt.%.
accumulatorenwerk hoppecke carl zoellner & sohn k.g. British Patent 1,283,138
H2 and O2 generated by electrical accumulators are catalytically re-formed into H2O using a Pt metal catalyst, thus minimising the need for periodic topping up.
Exhaust Gas Treatment
esso research & engineering co. U.S. Patent 3,637,344
A new improved catalyst for the treatment of ICE exhaust gases is a mixture of Ru and Ir.
Exhaust Gas Treatment
oxy-catalyst inc. U.S. Patent 3,637,353
ICE exhaust gases are treated in three coaxial chambers. The central chamber contains a Pt-plated catalyst.
chevron research co. U.S. Patent 3,637,527
Hydrocracking and denitrification multicomponent catalysts are produced by co-precipitating a Pd compound (e.g. sulphide) with a Zr, Ti, Th, etc. compound and also a metal chloride.
Aromatic Hydrocarbon Hydrogenation
universal oil products co. U.S. Patent 3,637,879
Cycloparaffins are produced from aromatics by reduction in contact with a catalyst containing 0.01−2% Pt group metal, 0.02−5% Ge component, 0.01−1.5% alkali metal compound and a porous carrier. Pt and Pd are preferred.
chevron research co. U.S. Patent 3,639,273
A catalyst useful particularly for reforming is a particulate mixture of (1) a layered crystalline clay type aluminosilicate and (2) a Pt group component in association with an Al2O3 carrier or a SiO2 carrier, e.g. Pt.
gulf research & development co. U.S. Patent 3,641,139
C2H4 is oxidised to CH3COOH without O2 in the presence of Ir metal. See also U.S. Patents 3,641,510 and 3,641,511.
Hydrocarbon Isomerisation Process
universal oil products co. U.S. Patent 3,642,925
Hydrocarbons are isomerised using a catalytic composite of a Pt group component, a Sn component and a Re component on a porous carrier, e.g. Pt, Sn and Re/Al2O3.
universal oil products co. U.S. Patent 3,644,198
The hydroprocessing of hydrocarbons is catalysed by a supported mixture of Ni, Group VIII metal and Group IVA metal, e.g. Ni, Pt and Ge on a crystalline aluminosilicate.
Catalytic Reforming Process
universal oil co. U.S. Patent 3,645,888
A gasoline fraction is catalytically reformed together with H2 and H2O over a catalyst containing a Pt group component, Ge and a halogen on a porous support; e.g. Pt, Ge and Cl.
universal oil products co. U.S. Patent 3,647,719
The dehydrogenation of hydrocarbons is catalysed by a mixture of Pt group metal, Ge and an alkali or alkaline earth metal on a porous support. A typical catalyst contains Pt, Ge and Li.
universal oil products co. U.S. Patent 3,647,911
Saturated hydrocarbons are dehydrogenated over an Al2O3-supported mixture of As and Pt with 0.01−1.5% Li. The ratio of As to Pt is 0.15−0.45 : 1. Other Pt group metals can replace Pt.
Selective Hydrogenation of Acetylenic Hydrocarbons
universal oil products co. U.S. Patent 3,651,167
Selective hydrogenation of 4C acetylenes, for example ethylacetylene and/or dimethylacetylene, mixed with butadiene, is carried out in a fixed-bed system using a Group VIII noble metal component catalyst. A preferred catalyst contains 0.01−0.2% Pd.
Hydrocarbon Isomerisation Catalyst
universal oil products co. U.S. Patent 3,652,697
Hydrocarbons are isomerised using a Pt group metal-Ge-Friedel Crafts halide catalyst. A typical catalyst contains Re, Ge and Pt on Al2O3 treated with the chlorides of these metals to produce AlCl3 as the Friedel-Crafts halide.
texaco inc. U.S. Patent 3,652,709
Hydroisomerisation of 4−7 C hydrocarbons is carried out in the presence of a chloride-activated metal-Al2O3 catalyst, the metal being Ru, Rh, Pd or Pt. The selectivity of the catalyst is improved by treating it with a C oxide at 50−400°F.
Refractory Catalyst Supports
badische anilin- & soda-fabrik a.g. British Patent 1,273,042
Aldehydes and alconols are produced by reaction of olefins with CO and H2 in the presence of a tertiary phosphine adduct of a Group VIII metal carbonyl complex of preferably Rh or Pt.
shell internationale research mij. n.v. British Patent 1,275,370
Methyl esters of aliphatic carboxylic acids are obtained by reaction of mixtures of C2H4 and CH3OH in the presence of a complex of Ru with CO and a triaryl phosphine.
toray industries inc. British Patent 1,278,072
An organosilicon compound is produced by reaction of an olefinically unsaturated compound with a hydrosilane in the presence of a catalyst which is a zerovalent complex of Pd with a P-, As- or Sb-containing ligand.
Dicarboxylic Acid Production
monsanto co. British Patent 1,278,353
Dicarboxylic acids are produced by reacting a non-vicinal glycol (or one of its derivatives) with CO in a solution containing a halogen-promoted Rh or Ir compound and H2O (where both OH groups of the glycol are substituted). Rh carbonyl bromides and chlorides and their phosphine complexes are described in the examples.
Adipic Acid Production
monsanto co. British Patent 1,278,354
Adipic acid is produced by the reaction of butane-1,4-diol with CO in the presence of a halogenpromoted Rh or Ir catalyst. The preferred catalysts are phosphine or phosphine/carbonyl complexes of Rh monohalides.
Production of Octadienes
imperial chemical industries ltd. British Patent 1,278,806
1,6- and/or 1,7-octadienes are produced by contacting one or more acyclic conjugated dienes with a metallic Pt, Pd, Os, Rh or Ru or one of their compounds in the presence of a polar solvent and a reducing agent.
Catalytic Carbonylation of Nitro Compounds
olin corp. U.S. Patent 3,636,027
An organic isocyanate is produced by reacting an organic nitro compound with CO in the presence of a catalyst system containing a S-containing heteroaromatic compound and a halide of a noble metal. Thiophene and dibenzothiophene are the preferred heteroaromatic compounds, and the noble metal halide is preferably a halide of Pd, Rh, Ir and/or Pt, e.g. RhCl3-thiophene. See also U.S. Patents 3,636,028 and 3,636 029.
Unsaturated Ester Production
mobil oil corp. U.S. Patent 3,646,115
Unsaturated esters are prepared from an olefin, carboxylic acid and O2 in the presence of a Rh or Ir catalyst complexed with CO, phosphine, arsine or stibine.
Aromatic Isocyanate Production
olin mathieson chemical corp. U.S. Patent 3,637,785
Aromatic isocyanates are produced by the reaction of an aromatic nitro compound with CO in the presence of a noble metal halide and an amide or thioamide, e.g., Pd halide and dimethyl formamide. See also U.S. Patent 3,637,786.
Diene Synthesis Catalyst
e. i. du pont de nemours & co. U.S. Patent 3,640,898
Dienes are synthesised from olefins and conjugated dienes in the presence of Rh(III) salt catalysts complexed with amides, phosphoramides, phosphine oxide, etc.
Cyclic Olefin Isomerisation
sun oil co. U.S. Patent 3,647,896
Exocyclic-unsaturated olefins are produced by isomerisation in the presence of a Group VIII complex, especially an Os or Ru phosphine halide and/or carbonyl.
olin mathieson chemical corp. U.S. Patent 3,654,279
New catalysts, especially for isocyanate production, have the formula PdL(CO)X2, where X is halogen and L is a Lewis base and particularly a heteroaromatic N compound such as pyridine.
Stabilised Rhodium Carbonyl Complexes
FUEL CELLS AND BATTERIES
Fuel Cell Electrodes
Platinum in Silicone Elastomers
Glass Fibre Production
ELECTRICAL AND ELECTRONIC ENGINEERING
electronor corp. British Patent 1,273,486
A Ti anode for use in electrolysis of brine is coated with an electrocatalytic layer of a semiconductor composition. The composition contains a major portion of TiO2 and a minor portion of an oxide of a Pt group metal.
telefunken patentverwertungs g.m.b.h. British Patent 1,274,500
A solar cell includes a semiconductor body and a contact which consists of a layer of Ag, a layer of Ti and a layer of a noble metal other than Ag (e.g. Pd or Pt).
johnson matthey & co. ltd. British Patent 1,278,411
An electrical heater element is made from a high temperature resistant non-conducting substrate with a layer of the resistor composition of British Patent 1,210,493. This consists of 91−20% finely divided glass and 9−80% of the product of heating RuO2 with one or more Group V oxides, e.g. Nb2O5.
johnson matthey & co. ltd. U.S. Patent 3,637,530
A resistor composition suitable for firing on to a ceramic substrate has the form of an oxide containing Nb and Ru in which the atomic ratio of metal to O2 is 1 : 2 and in which the atomic ratio of Nb to Ru is within the range 1:2000–1:1.
Palladium Films on Silicon Semiconductors
matsushita electronics corp. U.S. Patent 3,642,528
Pd films on SiO2 layers peel off when exposed to H2. This discovery is used in making selective deposits on Si semiconductors. The area not to be coated is treated to produce a layer of SiO2. The whole body is coated with Pd and treated with H2 so that the Pd over the oxide peels off.
Palladium Phosphide Chalcogenides
e. i. du pont de nemours & co. U.S. Patent 3,655,348
At high pressures and ∼1,000°C, Pd, P and a chalcogen, S or Se, combine to form compounds of formula PdPyX2−y in which y is 0.67 when X is S and y is 0.4–0.8 when X is Se. The compounds have a pyrite-type crystal structure. They are electrical conductors with a zero temperature coefficient of resistance from liquid He temperature to room temperature. They are useful as electrical resistors.