Platinum Metals Rev., 1971, 15, (4), 154
NEW PATENTS: October 1971
METALS AND ALLOYS
Platinum Group Metal Alloys
johnson matthey & co. ltd. British Patent 1,238,013German Offen. 1,758,549
Pt group metals, particularly Rh, Pt and Pd or their alloys, are dispersion strengthened by the addition of up to 20 at.% of at least one of the following: a lanthanide, Sc, Ti, V, Y, Zr, Hf and Ta.
johnson matthey & co. ltd. U.S. Patent 3,561,956
Resistance wires having a high electrical resistivity are made from alloys of 74−98.5 wt.% Pd, 1−15 wt.% V and 0.5−11 wt.% Mo. From 0.5 to 8 wt.% Au may also be present.
johnson matthey & co. ltd. German Offen. 1,621,254
A refractory metal or alloy article (not Mo or W) is sheathed in a Pt group metal or alloy, optionally with an intermediate barrier layer of, for example, a rare earth metal carbide. Applications are stated to be stirrers, crucibles, dies etc., in contact with molten glass. This corresponds to British Patent 1,190,266.
johnson matthey & co. ltd. German Offen. 1,758,310
An alloy of high specific resistance and low temperature coefficient of resistance has the composition 74−98.5 wt.% Pd, 1−15 wt.% V and 0.5−11 wt.% Au, Mo and/or Al.
Dispersion Hardened Materials
deutsche gold- und silber-scheideanstalt German Offen. 1,783,074
Dispersion hardened materials based on Pt metals or Au alloyed with metals and other elements such as Zr, are produced in two stages. In the first stage the material is soaked at 300−800°C. During the second stage it is subjected to oxidative treatment at 800−1400°C.
Alloy for Contact with Molten Glass
Preparation of Ruthenium Carbonyl
imperial chemical industries ltd. U.S. Patent 3,561,924
A process for the preparation of Ru3CO12 consists of reacting a liquid solution of a Ru salt, an alkali metal or alkaline earth metal compound of an organic acid or of an enolisable compound with CO and H2.
johnson matthey & co. ltd. German Offen. 2,034,908; French Patent 2,055,059
A new composition of matter is a Ru carboxylate of formula Ru2(OCOR)4, where R is an optionally substituted alkyl or aryl group. It is produced by heating together a soluble Ru salt, a soluble carboxylate and the corresponding carboxylic acid, e.g., acetic acid. The compounds may be stabilised by complexing them with pyridine or a phosphine.
ELECTRODEPOSITION AND SURFACE COATINGS
Electrodeposition of Ruthenium
international nickel co. inc. U.S. Patent 3,576,724
Ru complex compounds are produced in which the anion has the general formula [RuzN(H2O)x Yy]z+ where Y is a chloro or bromo group, x is 2, 3 or 4, x–y is 10 and z is 5–x and the cation is preferably monovalent, e.g., NH4+, Li, Na or K. A plating bath is prepared using the Ru complex compounds in aqueous acidic solution.
Electrodeposition of a Bright Platinum-Rhenium Alloy
g. haensel and a. erben East German Patent 73,435
Bright Pt-Re alloy deposits are obtained from fluoroborate baths containing 20g Pt(NH3)2 (NO2)2, 12g ammonium perrhenate, 50g HBF4 and 100g NaBF4 per litre. This gives at 80°C and 2.5 A/dm2 a bright adherent deposit 7.5 μ thick containing 5% Re and having 230 kg/mm2 Vickers hardness.
Ammonia Dissociation Catalyst
general electric co. British Patent 1,229,858
A method for dissociating NH3 using a heated catalyst comprising one of Ru, Rh, Pd, Os, Ir, Pt or their alloys is described. O2 is premixed with NH3 to the extent of 5−21 wt.% and the initial reaction is used to heat the catalyst bed to its operating temperature of 500°C. Ir and Ir alloys are preferred catalysts.
universal oil products co. British Patent 1,231,151
Olefins are obtained by dehydrogenation of 6–20 C normal paraffins in the presence of a Pt group metal supported on Al2O3 and impregnated with an alkali or alkaline earth metal compound. Preferably one of As, Sb, Bi, S, Se or Te or their compounds is also present. An example of use is a feedstock for detergent manufacturer.
Purification of Exhaust Gases
universal oil products co. British Patent 1,231,276
Exhaust gases are passed over Al2O3 which has been impregnated with an alkaline earth metal compound and a solution containing a dicarboxylic acid and a catalyst metal (e.g. Pt).
chevron research co. British Patent 1,231,970
Waxy hydrocarbon oil is dewaxed by reaction with H2 in the presence of porous Al2O3 with 0.2−1 wt.% of Pt and 0.1−2 wt.% of Re.
mobil oil corp. British Patent 1,232,472
Hydrocarbons in the naphtha boiling range are reformed over a catalyst containing 0.3−0.45 wt.% of Pt.
Manufacture of Nitric Acid
hercules inc. British Patent 1,232,903
NH3 is oxidised to HNO3 with atmospheric O2 over a Pt–Rh catalyst.
esso research and engineering co. British Patent 1,234,960
Isoparaffinic jet fuel is obtained from a quality-deficient kerosene fraction by isomerisation and hydrogenation in the presence of a catalyst which is Pt/Al2O3.
universal oil products co. British Patent 1,236,341
S-containing pyrolysis gasoline is hydrogenated over Pd/lithiated Al2O3.
british petroleum co. ltd. British Patent 1,236,533
Alkylaromatic hydrocarbons, particularly xylenes, are isomerised in the presence of a catalyst which consists of a decationised mordenite carrying a hydrogenating metal such as Pt, Pd or Ag.
Production of Nitric Oxide
instytut nawozow sztucznych British Patent 1,236,819
Nitric oxide (NO) is obtained by the oxidation of NH3 with O2 and water vapour at 750−900°C first with a Pt and then with a metal oxide catalyst. The first catalyst is a gauze of Pt or Pt-Rh alloy, the second a mixture of Cr2O3 and Fe2O3 with graphite and an activator which is an oxide of a metal, e.g. Cu or Ag.
continental oil co. British Patent 1,236,890
Ziegler alcohols are converted to normal aliphatic alcohols by hydrogenation in the presence of a catalyst which may be Rh or Ru on Al2O3 or Pt/C.
universal oil products co. British Patent 1,237,550
Linear detergent alkylate is obtained by dehydrogenation of a normal paraffin feedstock in the presence of a Pt group metal.
antar petroles de l’atlantique British Patent 1,238,042
Petroleum reforming is carried out at a controlled temperature in an elongated reactor. Pt/Al2O3 is distributed in several separate zones in the reactor.
Catalytic Reforming of Hydrocarbons
universal oil products co. U.S. Patent 3,562,147
A continuous process for the catalytic reforming of a gasoline fraction to produce a high octane reformate stream uses a Pt group metallic component, a Re component, a halogen component, and a S component, all of which are composited with an Al2O3 carrier material.
Hydroforming with a Promoted Iridium Catalyst
esso research & engineering co. U.S. Patent 3,567,625
In a hydroforming process the catalyst is Ir and a metal selected from Au, Cu or Ag supported on a high surface area support.
Method of Removing Nitrogen Oxides from Gases
w. r. grace & co. U.S. Patent 3,567,367
The catalytic reduction of N oxides in tail gas from HNO3 synthesis is improved when water is added to the tail gas prior to and after final reduction so as to give increased reduction, longer catalyst life, and increased energy available for recovery in the treated effluent. The catalysts may be Pt, Rh or Pd.
Hydrocarbon Conversion Process
texaco inc. U.S. Patent 3,567,796
A hydrocarbon conversion process is described in which a catalyst consisting essentially of (1) Al2O3, (2) a metal selected from Ru, Rh, Pd and Pt and (3) Cl2 or Br2 is used. At least a part of the Cl2 or Br2 is introduced into the catalyst by contacting a composite of Al2O3 and the metal at elevated temperature with a selected organic compound in the presence of Cl2 or Br2.
Hydrocarbon Conversion Process
universal oil products co. U.S. Patent 3,574,092
A catalytic composite consists of a Pt group metallic component and a Tc component combined with a carrier material containing Al2O3 and a finely divided crystalline aluminosilicate. An example of the catalytic composite is a combination of 0.01−1.0% Pt and 0.01−1.0% Tc with a γ-Al2O3 carrier material having 0.5−20 wt.% of the H form of mordenite uniformly distributed.
chevron research co. U.S. Patent 3,576,736
A hydrocracking catalyst has a crystalline zeolite molecular sieve cracking component, 0.01−2.0% of a hydrogenating component selected from Pt, Pd, Rh, Ru, Ir and their compounds and 0.01−5.0% of a Au or Au compound cracking component.
universal oil products co. U.S. Patent 3,576,766
Hydrocarbons are dehydrogenated by contacting them with a composite containing catalytically effective amounts of a Pt group component, a Re component, and a Sn component with a porous carrier material. A specific example is a combination of Pt, Re, Sn and an alkali or alkaline earth component with an Al2O3 carrier material.
institut francais du petrole, des carburants et lubrifiants French Patent 1,588,196
A catalyst for a hydrocarbon process consists of Pt/Al2O3 obtained by impregnating an Al2O3 gel with a halogen acid and then cooling suddenly to retain the halogen.
Hydrogenated Phthalic Acids
polycarbon chemie–g.m.b.h. German Offen. 1,593,226
A low melting mixture of hydrogenated acids is obtained by the isomerisation of tetrahydrophthalic anhydride in the presence of a supported Pd, Pt and/or Ru catalyst.
Carboxylic Acid Production
knapsack a.g. German Offen. 1,618,589
Carboxylic acids are produced by the oxidation of 2−6C aldehydes in the presence of a supported catalyst containing Pd metal, Pd oxide and/or a Pd salt and at least one other component which may be another Pt metal, Ag or Au.
johnson matthey & co. ltd. German Offen. 1,668,202
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 trickel column with an O2-containing gas in the presence of a supported Pt group metal. This corresponds to British Patent 1,208,101.
Purification of Gases
johnson matthey & co. ltd. German Offen. 2,045, 487
N oxides are removed from a gas containing O2 and at least one N oxide by mixing the gas with a gaseous reducing fuel and passing it, at a temperature above the ignition temperature, over a catalyst. The catalyst consists of an inert support coated or impregnated with a mixture of Pt and 20−50 wt.% Rh. The inert support may be in the form of a ceramic honeycomb. This corresponds to French Patent 2,061,385.
Removal of Organic Pollutants from Waste Gases
johnson matthey & co. ltd. German Offen. 2,045,488
Organic compounds (including CO and hydrocarbons) which are present in waste gases and which would otherwise cause atmospheric contamination are oxidised to CO2 and H2O by passage, together with O2 over a supported mixture or alloy containing 50−80 wt.% Pt and 50−20 wt.% Rh.
johnson matthey & co. ltd. German Offen. 2,047,748; Dutch Appl. 70.14,341
Solid catalysts for hydrogenation, hydroformylation or carbonylation are obtained by treatment of an inert solid porous support with a solution of a complex of an hydridocarbonyl bis- or tris-(trisubstituted phosphine)Rh complex. Alternatively, a solution of a halogen– or pseudohalogen–containing complex of Rh in which at least one stabilising donor ligand is present may be used.
universal oil products Dutch Appl. 70.09,855
An Al2O3-supported catalyst contains 0.05−1 wt.% Pt, 0.05−1 wt.% Re, 0.05−2 wt.% Ge and 0.5−1.5 wt.% Cl2. The catalyst is used for reforming, isomerising and hydrocracking.
johnson matthey & co. ltd. Dutch Appl. 70.16,532
Organic compounds are hydroformylated in the vapour phase with carbon monoxide and hydrogen in the presence of a Rh hydride carbonyl bis- or tris(trisubstituted phosphine, arsine or stibine) deposited upon a solid support as catalyst. The solid support may be a ceramic honeycomb or a porous organic polymer.
imperial chemical industries ltd. British Patent 1,232,015
Unsaturated organic compounds are selectively hydrogenated in the presence of a soluble compound of Rh, Pd, Os, Ir or Pt and an organic polar hydroxylic solvent.
Catalyst for Production of Aromatic Isocyanates
olin corp. British Patent 1,232,863
A nitro-compound can be converted directly to the corresponding isocyanate by reaction with CO in the presence of Pd or Rh halide or oxide with at least one oxide of V, Mo, W, Nb, Cr or Ta. See also British Patent 1,232,865.
asahi kasei k.k.k. British Patent 1,237,510
Dimethylstyrene is obtained by reaction of xylene with C2H4 and O2 in the presence of a lower aliphatic carboxylate of Pd activated with an oxide or lower aliphatic carboxylate of a metal such as Cu or Ag.
Aliphatic Acid and Ester Production
union oil co. U.S. Patent 3,573,332
The telomerisation of C2H4 in the presence of dihalo- and trihaloacetic acids and their esters is catalysed by Pd(CN)2 to produce halogenated long chain fatty acids. In a typical reaction C2H4 is contacted with chloracetic acid in the presence of Pd(CN)2.
Hydrogenation of Unsaturated Carboxylic Acids
johnson matthey & co. ltd. U.S. Patent 3,574,734
A process for the hydrogenation of water-soluble, unsaturated lower aliphatic hydrocarbon carboxylic acids comprises mixing an aqueous solution of the unsaturated acid with a catalyst in the form of an ionic water-soluble ammino compound of Rh, the cation of which has the formula [HRh(NH3)]52+ or [HRh(NH3)4H2O]2+.
institut francais du petrole French Appl. 2,041,776
New hydroformylation catalysts are Rh carbonyl complexes of As-, Sb- or P-containing ligands, e.g. the reaction product of Rh2Cl2(CO)4 with dipiperidinophenylphosphine.
Transition Metal Carboxylate Catalysts
johnson matthey & co. ltd. German Offen. 2,034,909
Transition metal compounds useful for catalysis are obtained by complexing a Pt group metal or other transition metal carboxylate, thiocarboxylate or dithiocarboxylate with a stabilising ligand. In one example a Rh benzoate catalyst is stabilised by a phosphine. Protonation of these compounds with strong acids produces species of the type (where M is the transition metal used) showing a high activity for the catalysis of hydrogenation and other reactions. Preferred Pt group metals are Rh and Ru. This corresponds to French Patent 2,055,060.
FUEL CELLS AND BATTERIES
Fuel Cell Electrode
Coated Titanium Electrodes
p.p.g. industries inc. British Patent 1,231,995
An anode for electrolysis of aqueous alkali metal chloride solutions is obtained by (1) coating a Ti base with a mixture of thermally decomposable compounds of Ti and a Pt group metal such as Ti and Ru resinates, and (2) heating to produce the metal.
Hydrogen Pumping Apparatus
general electric co. U.S. Patent 3,568,410
A gas pump of simplified, sturdy construction employs Pd maintained at a high temperature to permit efficient evacuation of gas from a region of low pressure to a region where partial pressure of the gas is several orders of magnitude higher.
Electrochemical Production of Olefin Oxides
ELECTRICAL AND ELECTRONIC ENGINEERING
Thorium Film Cathodes
siemens a.g. British Patent 1,234,905
A Th film cathode for an electrical discharge vessel is formed from a cathode blank of a high-melting metal (preferably W) containing ThO2. The formed blank is then coated with a layer of metallic Rh, Os, Pt, Ir or Re.
fujisu ltd. British Patent 1,238,747
In a semiconductor device the terminal block consists of a layer of Cr, Mo, V, Ti, Zr or Hf, covered with a layer of Pt, Pd or Rh.
Pattern Deposit by Laser
international standard electric corp. U.S. Patent 3,560,258
A technique for forming an interconnection pattern on a substrate consists of placing opposite the substrate a film of a vaporisable material disposed on a glass plate. A beam of intense radiant energy scans the metallic film through the glass plate to evaporate selectively portions of the film which deposit on the semiconductor substrate in accordance with the desired pattern. Pt is the preferred vaporisable material.
Ceramic Electrical Resistors
e.i. du pont de nemours & co. U.S. Patent 3,565,682
Pd oxides of formula PdMO2, where M is Co, Cr, Rh or a mixture of Cr with Rh, can be mixed with a vitreous enamel or glass frit and optionally other additives to form ceramic resistor compositions. Such compositions are applied to a ceramic dielectric substrate and fired, forming the conductive coating of a ceramic electrical resistor.