Platinum Metals Rev., 1972, 16, (1), 35
NEW PATENTS: January 1972
METALS AND ALLOYS
Permanent Magnetic Alloy
citizen watch co. ltd. U.S. Patent 3,591,373
A permanent magnetic alloy contains 15−40 at.% Pt, 5−35 at.% Au and 40 at.% Fe.
Dispersion Strengthened Metals
johnson matthey & co. ltd. German Offen. 2,102,980 Dutch Appl. 71.00,842
Au, Ag and Pt metals and their alloys are hardened by internal oxidation of an additive such as Zr. After addition of Zr the alloy is powdered, cold worked and exposed to a gas which converts the Zr to a stable refractory oxide, ZrO2. The product is compacted and sintered.
ELECTRODEPOSITION AND SURFACE COATINGS
Electrodeposition of Rhodium
deutsche gold-und silber-scheideanstalt British Patent 1,244,720
Thick craze-free Rh coatings are deposited from a bath containing a Rh sulphite-sulphate complex.
Palladium-Nickel Alloy Plating Bath
kabushiki kaisha suiva seikosha and nisshin k. k. k. U.S. Patent 3,580,820
A Pd-Ni alloy plating bath contains an ammoniacal solution of a Pd salt and a Ni salt. A sulphonate or a sulphamide brightener is added.
Bright Palladium Plating
LABORATORY APPARATUS AND TECHNIQUE
Palladium Tube in Gas Analysis
california institute of technology U.S. Patent 3,589,171
Sequential analytical determination of a vapour sample is performed by suspending the sample in a H2 carrier gas, or a mixed carrier gas of H2 and He, and passing the suspension through a gas chromatograph. More than 90% of the H2 is removed from the effluent by passing it through a heated Pd tube before analysis.
High Temperature Brazing Alloys
western gold & platinum co. U.S. Patent 3,577,233
Brazing alloys contain 25−70% Au, 5−30% Pd, 15−40% Ni, 4−12% Cr and 0.01−2% Y. These alloys have substantial ductility and high oxidation and corrosion resistance at 870−980°C and above for 100 hours or more. They are useful for joining stainless steel and super-alloys in aircraft, spacecraft, engines and components.
Hydrocarbon Steam Reforming
imperial chemical industries ltd. British Patent 1,240,453
A catalyst, for steam reforming hydrocarbons with decreased C lay-down, contains Ni and/or Co, a Pt metal and a refractory oxide support. The support contains more than 5% alkaline earth metal oxide (calculated as CaO) but less than 0.5% alkali metal compounds (calculated as K2O). Ru is the preferred Pt metal.
ube industries ltd. British Patent 1,241,255
C3H6 is converted to acrylonitrile by reaction with O2 and NH3 in the presence of a catalyst which contains 80−98 wt.% of a solid solution of Sb oxide and SnO2, and 2−20 wt.% of one or more oxides of In, Ir or Ru.
ruhrchemie a.g. British Patent 1,241,646
Isobutyraldehyde is decomposed to C3H6, CO and H2 in the presence of Rh and/or Pt.
british petroleum co. ltd. British Patent 1,242,889
S is removed from hydrocarbon fractions by the action of H2 in the presence of a crystalline mordenite of reduced alkali content and a catalytically active metal, preferably Pt or Pd.
texaco development corp. British Patent 1,242,962
The properties of lubricating oils are improved by treatment with H2 in the presence of 0.1 to 5% Pt or Pd on a H-form mordenite base.
mobil oil corp. British Patent 1,243,366
A hydrocracking catalyst consists of an active inorganic oxide supporting a catalytically active metal such as Pt or Pd.
texaco development corp. British Patent 1,247,656
The first stage in the production of a lubricating oil is the mild hydrogenation of a suitable stock in the presence of a Group VIII metal, e.g. Pd or Pt or an oxide or sulphide thereof.
Hydrocarbon Reforming Catalyst
imperial chemical industries ltd. British Patent 1,249,466
A hydrocarbon reforming catalyst contains a Pt group metal (preferably Ir or Ru) and an alkaline earth oxide such as CaO.
knapsack a.g. British Patent 1,250,265
Unsaturated esters of carboxylic acids are obtained by the oxidation of olefins in the presence of a Pd catalyst.
Hydrogen Cyanide Production
w. r. grace & co. U.S. Patent 3,577,218
A mixture of NH3 and CH4 is reacted over a Pt/mullite catalyst to give high yields of HCN. The catalyst is prepared by depositing Pt on either natural or synthetic mullite. It has improved stability and avoids carbonitridation.
Isomerisation of Alkyl Aromatics
chevron research co. U.S. Patent 3,577,475
Alkyl aromatic hydrocarbons are isomerised in the presence of H2 with a catalyst consisting of a porous solid carrier containing 0.01−3 wt.% Pt group component and 0.01−5 wt.% Re.
Cyclic Regenerative Platinum-Rhenium Reforming Process
chevron research co. U.S. Patent 3,578,582
In a cyclic regenerative reforming process where a S-free naphtha fraction is contacted with a Pt group metal-Re catalyst under reforming conditions, the process is started by sulphiding the catalyst in situ with 0.05–2 moles of S per mole of the Pt group metal-Re present.
Reforming Process with Promoted Low Platinum Content Catalyst
chevron research co. U.S. Patent 3,578,583
A naphtha is reformed in the presence of H2 with a catalyst consisting of 0.01−03% Pt, 0.01−03% Re and 0.001−0.1% Ir on a porous carrier.
Hydrocarbon Conversion Platinum-Germanium Catalyst
universal oil products co. U.S. Patent 3,578,584
A hydrocarbon conversion catalyst consists of 0.01−2.0% of Pt group metal, 0.01−5.0% Ge and 0.5−3.5% halogen on a porous carrier.
Hydrocracking of Naphtha
mobil oil corp. U.S. Patent 3,579,434
0.05−5.0% Pd deposited on a chelated hydrogen-form of zeolite Y is used as a catalyst for hydro-cracking naphtha to LPG.
universal oil products co. U.S. Patent 3,584,060
Hydrocarbons are dehydrogenated by contacting them in dehydrogenation conditions with a catalytic composite of a Pt group component, a Re component, a Sn component and a carrier.
sinclair research inc. U.S. Patent 3,586,730
4–5C hydrocarbons are dehydrogenated in the vapour phase in the presence of a catalyst consisting of a small amount of a Pt group metal, 5−50% Cr2O3, 0.1−2% alkali metal and 30% activated Al2O3.
s. a. francaise du ferodo U.S. Patent 3,589,853
A catalytic wall is permeated by a gas flowing from an internal to an external face where it reacts with another gas. The wall consists of an asbestos-based fabric support which has less catalyst on the internal than on the external face. It can be used in a catalytic heater apparatus. Pt is a suitable catalyst.
Heterogeneous Catalyst Process
esso research & engineering co. U.S. Patent 3,591,656
Heterogeneous conversion catalysts are prepared by forming complexes between a reduced transition metal, e.g. a Pt metal and a support in an inert atmosphere. The complex is stabilised by heating. The catalysts may be used for the conversion of organic feed compounds in the presence of H2.
universal oil products co. U.S. Patent 3,592,867
C3H8 is dehydrogenated to C3H6 in the presence of a non-acidic Pt metal catalyst, e.g. Pt or Pd/Al2O3. Hydrocracking C3H6 to form C2H4 is carried out over a Group VIII metal catalyst such as Ni or Rh.
g. n. maslyanskii et al. U.S. Patent 3,595,932
Alkyl benzenes are dealkylated with steam at 380−600°C in the presence of a catalyst. The catalyst is a binary system consisting of 0.05−5 wt.% Pt, Pd, Rh, Ir and/or Ru on Al2O3, an aluminosilicate, or a combination of Al2O3, with oxides of Ni or Co.
Oxidation of Methane and Low Hydrocarbons
johnson matthey & co. ltd. French Appl. 2,061,384
Methane and other hydrocarbons produced in car exhausts are oxidised to CO2 and H2O over a catalyst consisting of 35% Rh-Pt on a porous ceramic honeycomb structure such as mullite.
farbenfabriken bayer a.g. German Offen. 1,667,045
A catalyst for the reduction of NO to NH2OH is obtained by hydrolysing a soluble Pt compound in the presence of strong acid. PtO2 is deposited on a support and is reduced to Pt metal.
johnson matthey & co. ltd. German Offen. 1,667,107
Pt in active adherent form, or mixtures of Pt with up to 50% of other Pt group metals, are deposited on supports using a dispersion in a C2-C5 aliphatic alcohol.
johnson matthey & co. ltd. German Offen. 1,668,282
Glucose is oxidised to gluconic acid or glucosaccharic acid in high yield using a supported Pt metal.
institut khimicheskikh nauk a.n. kazakhski s.s.r. German Offen. 2,001,291
Pd catalysts are produced by impregnating Al2O3 with an aqueous alcoholic solution of Na2PdCl4. Another Group I or VIII salt may also be present, e.g. H2PtCl6, to give a mixed catalyst.
johnson matthey & co. ltd. German Offen. 2,061,226
A selective, poison-resistant catalyst is made by dispersing a Pt compound in an aliphatic alcohol which is polymerised and carbonised to form a Pt-containing C molecular sieve.
Catalytic Hydrogenation of m -Nitroacetophenone
johnson matthey & co. ltd. German Offen. 2,116,761
Aromatic nitro compounds containing carbonyl groups are reduced to amines by contacting the nitro compounds with H2 in the presence of Pd/celite. The carbonyl group is unaffected.
Ammonia Oxidation Catalyst
m. a. minivich et al. Dutch Appl. 69.18,466
NH3 is oxidised to NO in the presence of an alloy of Pt as catalyst. The alloy contains 75−82% Pt, 15−22% Pd, 2−3.5% Rh, 0.05−0.15% Au, Fe and Ir and optionally 0.15−2% Ru.
Catalysts for Combustion of Propane and Town Gas
Butadiene Polymerisation Catalyst
w. r. grace & co. British Patent 1,243,075
PdCl2 is reacted in an inert solvent and in the presence of Na2CO3 with an olefin to form a Pd allyl complex which is a useful butadiene polymerisation catalyst.
british petroleum co. ltd. British Patents 1,243,189 and 1,243,190
Mixed-ligand complexes of Os, Ir or preferably Rh are useful catalysts for the conversion of olefins to aldehydes or alcohols. The ligands are preferably a tertiary phosphine, CO and a β -diketone.
New Friedel-Crafts Catalysts
rhone-poulenc s.a. British Patent 1,244,311
Proposed new Friedel-Crafts catalysts are the halides of Ru, Rh, Os or Ir.
organsko hemijska industrija ‘naum naumovski borce’ British Patent 1,244,988
Vinyl polymers are produced in the presence of a catalyst which is a metal salt of EDTA, diethylenetriaminepentaacetic acid or cyclohexanediamine tetraacetic acid. The metal may be Pd.
Ruthenium Hydride Complexes
imperial chemical industries ltd. British Patent 1,246,123
Complexes which are very efficient hydrogenation catalysts in homogeneous media are obtained by reacting in solution a simple Ru salt, H2 and a ligand forming reagent, e.g. a tertiary phosphine.
b.p. chemicals ltd. British Patent 1,248,988
Olefins are converted to aldehydes by reaction with CO and H2 in the presence of a carbonyltertiary phosphine complex of Os or Ru.
imperial chemical industries ltd. British Patent 1,249,033
A polymeric catalyst consists of a metallated polymer which is a polystyrylphosphine having transition metal atoms coordinated to the P atoms. The metal may be Pt or Pd.
Production of Carboxylic Acids
monsanto co. U.S. Patents 3,579,551 and 3,579,552
The preparation of carboxylic acids by the reaction of ethylenically unsaturated compounds with CO and water is catalysed by Rh and Ir compounds together with an I promoter.
Copolymerisation of Carbon Monoxide with Alkylene Oxide
union carbide canada ltd. U.S. Patent 3,590,075
Copolymers of CO and alkylene oxides are prepared by polymerising the monomers at elevated temperatures and pressure in the presence of a salt of a Group VIII metal and an amine or alkanolamine. The salts are halides or carbonates.
Rhodium Ammino Complex Catalysts
johnson matthey & co. ltd. German Offen. 1,668,248
Water-soluble unsaturated organic compounds, especially carboxylic acids are catalytically hydrogenated in the presence of a Rh complex containing the cation HRh(NH3)52+ or HRh (NH3)4H2O2+. This corresponds to British Patent 1,197,723.
johnson matthey & co. ltd. German Offen. 2,053,218
Hydrogenation, hydroformylation or carbonylation may be carried out using a solution of RhH(CO)(MR3)2 or 3 where M is P, As or Sb or solutions of similar Pt group metal complexes also containing halogen. The solution is allowed to pass through a particle-bed; the reactant gas stream flows concurrently or countercurrently through the bed.
Rhodium Complexes in Catalytic Reactions
johnson matthey & co. ltd. German Offen. 2,064,471 Dutch Appl. 70.18,912
Hydrogenation or hydroformylation of ole-finically unsaturated compounds in the absence of an inert solvent may take place in the presence of a hydrido carbonyl complex of Rh(I) and a P-containing stabilising donor ligand.
Photosensitive Palladium Compounds
eastman kodak co. British Patent 1,240,705
Radiation-sensitive Pd compounds have the formula [Pd(L)x]yM2, where L is a ligand, M is H ion, acid ion, or onium ion, x is 0–4, y is 1–4, z is 0–2. Potassium palladium oxalate is mentioned in one example. The use of the developer is described in British Patent 1,240,706, and the compound in British Patent 1,240,707.
precision studios ltd. British Patent 1,240,832
Decalcomania for ceramic decoration consist of a paper support printed with oxides of Sn, Pb, Sb and Fe in an ethyl cellulose medium. This in turn is coated, while still tacky, with a Au, Ag and/or Pt powder. The surplus dust is removed and the product is lacquered.
Electrolytic Hygrometer Detector Element
central electricity generating board British Patent 1,245,025
A hygrometer detector element is made by (a) filling a grooved plate with platinising paste, (b) firing, (c) rhodium plating and (d) coating with a hygroscopic electrolytic material, e.g. H3PO4.
eastman kodak co. British Patent 1,245,947
An additive for a photographic Ag halide emulsion consists of a mixture of gelatine, a water-soluble latex polymer and a salt of a polyvalent metal such as Rh, Ir or Pt.
Activated Electrode for Brine Electrolysis
imperial chemical industries ltd. U.S. Patent 3,578,572
A Pt metal-coated Ti electrode for use in the electrolysis of brine is obtained by electroplating the Pt group metal on to Ti from an electrolyte containing a polybasic, hydroxy organic acid. The electrode is thereby activated. See also U.S. Patent 3,592,750.
Protective Coating for Plasma Apparatus
la soudure electrique autogene U.S. Patent 3,578,943
Plasma nozzles used in operations with reactive gases are protected by coating one face of the nozzle, preferably the front face, with Au, Pt, Pd, Rh, Ir, Os, Ru or their alloys.
johnson matthey & co. ltd. French Patent 2,032,780
A diffusion cell for the separation of H2 from gaseous mixtures uses Ag-Pd alloy as H2-permeable membranes.
grunzweig & hartmann a.g. German Offen. 2,003,168
Spinnerettes are made from Pt alloyed with another metal, e.g. Ni, which is removed by thermal treatment before and/or during use. See also German Offen. 2,003,161
Heat Reflecting Glass
asahi glass co. ltd. British Patent 1,241,889
A heat-reflecting glass is produced by dispersing microscopically divided metallic Pd into a film of metal oxide which has a higher refractive index than that of the glass. The metal oxide containing Pd is then deposited on the surface of the glass.
Glass Fibre Production
pilkington brothers ltd. British Patent 1,242,921
A die plate for drawing glass fibre consists of a main body of Pt-Ir-Rh alloy faced with Pt-Ir-Rh containing small amounts of Pd, Au and Cu.
courtaulds ltd. British Patent 1,244,721
Molten glass is poured on to filaments of C or graphite which have been metal coated by conventional means. The metal is Rh, Pd or Ru.
Glass Fibre Production
w. h. w. schuller British Patent 1,250,642
Glass filaments are drawn from nozzles in the base of an elongated drawing trough which is made of a noble metal, e.g. Pt.
Heat Resistant Metals
johnson matthey & co. ltd. German Offen. 1,621,264
An article for use at high temperature, e.g. a stirrer in contact with molten glass, consists of a core of a refractory metal (Nb, Ta, Cr or Mo flame-sprayed with Zr and ZrO2), a barrier layer of a refractory carbide, silicide, boride, sulphide, nitride or oxide and a cladding of a Pt group metal or alloy. The pressure in the interfacial space between core and sheath may be reduced.
Alloy for Handling Molten Glass
deutsche gold-und silber-scheideanstalt German Offen. 1,950,468
Articles used in handling molten glass are made from an alloy of Pd containing 10−30% Rh and/or Ir and/or 30−50% Pt.
Platinum Clad Niobium, Tantalum etc
johnson matthey & co. ltd. German Offen. 2,113,437
A refractory core of metals or alloys of Nb, Ta, Cr, Zr, V, Hf or Re are sheathed in a Pt group metal or alloy. A barrier layer of MgO and an inert gas, e.g. Ar are between the core and the sheath. Applications are stirrers, crucibles etc. in contact with molten glass.
ELECTRICAL AND ELECTRONIC ENGINEERING
Ohmic Contacts for Semiconductors
international business machines corp. British Patent 1,244,903
Ohmic contacts for semiconductors are formed by vapour deposition of Mo on to an area of a Pt or PdSi.
e. i. du pont de nemours & co. British Patent 1,246,784
Green ceramic boards are screen stencilled with a paste of nonoxidisable gas-free precious metal particles and a temporary binder and fired. The metal may be Pt, Pd, Au, Ag or their alloys.
Noble Metal Patterns
r.c.a. corp. British Patent 1,247,973
A metallic pattern may be produced on a surface such as glass with a mixture of an organic photoresist and a substantially transparent metal resinate. Resinates of Au, Pt or Pd may be used.
battelle development corp. British Patent 1,250,201
A semiconductor device is obtained by deposition of a semiconductor material on to an insulating surface which has been marked with a suitable metal. Suitable metals are Rh, Os, Ir or Re.
ferranti ltd. British Patent 1,250,248
Semiconductor devices are provided with beam leads consisting of layers of Ti, Pt and Au.
e. i. du pont de nemours & co. U.S. Patent 3,583,931
Electrically conductive oxides of formula Bi2M2O7, e.g. Bi2Ru2O7 and Bi2Ir2O7, and modifications of these oxides, e.g. PbBiRu2 and BiNdIr2O7, are prepared by firing together the appropriate precursors, e.g. the respective oxides. The compounds are useful in electrical resistors.