Platinum Metals Rev., 1970, 14, (1), 36
NEW PATENTS: January 1970
METALS AND ALLOYS
Composite Metal Articles
international nickel ltd British Patent 1,168,130
Articles for high temperature use in non-oxidising atmospheres consist of a core of Ir, Ru, W and Mo, a barrier layer and a coating of at least 95% Ir, Ru, W or Mo. The barrier layer between the core and coating consists of Au, Pd, Pd-Ag alloy or Pd-Cu alloy of specified composition.
Platinum-Iron Permanent Magnet Alloys
citizen tokei k.k. U.S. Patent 3,444,012
Pt-Fe alloys of the super-lattice type are treated to improve their magnetic characteristics by cold-working and thermal-ageing.
Dispersion Hardening of Platinum Metals and Alloys
deutsche gold- & silber-scheideanstalt Dutch Patent 69.00716
Materials comprising Pt group metal(s), Au or alloys thereof, together with an element having high O2-affinity (preferably Zr) are dispersion hardened by internal oxidation by heating at 800−1200°C in an O2-containing atmosphere for more than 5 h and preferably more than 20 h.
Production of Metallic Oxides
johnson matthey & co. ltd Swiss Patent 478,063
Electrolytic production of oxides of Pt and/or Pd or oxides of Pt and/or Pd mixed with oxides of other metals not harmful to the catalytic properties of the Pt and/or Pd oxides by electrolysis of appropriate Pt, Pd, Pt alloy or Pd alloy anode in a molten bath of alkali metal halide and nitrate. This corresponds to British Patent 1,106,814.
Manufacture of Palladium Halides
farbwerke hoechst a.g. British Patent 1,159,225
Metallic Pd is treated with O2 (or air) in the presence of a carboxylic acid solution of a halide of a metal of Group Ia, IIa or IIIb or an ammonium halide at 10−150°C. The Pd used is Pd black. It becomes converted to Pd(II) halides.
imperial chemical industries ltd British Patent 1,160,765
Ru3(CO)12 is prepared by reaction of RuCl3, Na naphthenate or Na acetyl-acetonate and a CO-H2 mixture.
Production of Carbonyl Compounds
hercules inc. British Patent 1,164,561
Carbonyl compounds are produced by reacting an organic Group VIII noble metal compound with CO to form a CO derivative of the organic group. The Group VIII reactant is formed in situ, e.g., from p-carboxy-phenyl mercuric chloride and PdCl2. The reaction of this with CO gives terephthalic acid.
lonza ltd British Patent 1,167,691
This new carbonyl compound Ru6(CO)18 is produced by heating trimeric Ru(CO)4 at 150−250°C in a closed vessel. O2 is absent, and pCO is 0.2−2 atm.
Trimeric Ruthenium Tetracarbonyl
lonza ltd U.S. Patent 3,446,591
A basic Ru carboxylate or Ru acetylacetonate is reacted with CO and H2 at 150–200 atm in an organic solvent at 140−250°C to yield orange-red trimeric [Ru(CO)4]3.
rhone-poulenc s.a. U.S. Patent 3,449,387
Ru halides are reacted with organic nitriles to give complexes of the form RuXmLn, where X is halogen and L is a nitrile. These substances may be used as catalysts for dimerisation of acetonitrile.
New Rhodium Phosphine, Arsine and Stibine Complexes
ppg industries inc. British Patent 1,159,410
The overvoltage of a Pt metal coated Ti-base electrode is reduced by depositing metallic Bi on the Pt metal surfaces and heating to at least 200°C in a non-oxidising atmosphere.
leesona corp. British Patent 1,167,541
Electricity is generated from NH3 in a cell where the catalyst consists of more than 50 at.% Pt with most of the remainder being a second Pt group metal, e.g., 93.8% Pt, 5.3% Ru, 0.9% Pb.
leesona corp. U.S. Patent 3,444,003
An electrode is made by depositing a layer of catalytic metal (Pt and Rh) from an aqueous solution of Pb and the catalytic metal on to a Pt foil or other base. This layer is followed by a second layer electrodeposited from a solution free from Pb so that the outer coating contains no Pb.
Alkali Chloride Electrolytic Mercury Cells
t. ishimatsu U.S. Patent 3,445,374
Each electrolytic Hg cell has a metallic cover, of which the inner face is coated successively with a layer of Ti and a layer of a Pt group metal (Pt, Rh, Pd and alloys) which serves as the anode in the cells.
allis-chalmers manufacturing co. U.S. Patent 3,446,725
In an electrolysis cell for the preparation of H2 and O2, a noble metal screen substrate (Pt, Pd, Rh, Ir, etc.) is interposed between an electrode of sintered Ni and the electrolyte matrix interfaces.
Brine Electrolysis Electrode
badische anilin- & soda-fabrik a.g. U.S. Patent 3,458,423
The anode has at least two porous layers of Ti, Ta or base alloys of these metals, the layers being arranged one above the other in the direction of the cathode, and the layer behind the layer facing the cathode is activated with a Pt group metal.
ELECTRODEPOSITION AND SURFACE COATINGS
international business machines corp. British Patent 1,159,980
A metallising composition comprises a finely divided metal alloy (Ag-Pt or Ag-Pd or Ag-Pt-Pd) and particles of a vitrifiable flux (Pb Bi trioxide and Pb borosilicate glass) dispersed in a liquid vehicle.
Chemical Palladium Plating
burroughs corp. British Patent 1,164,776
A stable chemical plating bath which is based on the use of divalent Pd ions chelated with both EDTA and ethylenediamine and a reducing agent.
Anodes for Salt Electrolysis
oronzio de nora impianti elettrochimici British Patent 1,167,992
A valve metal substrate such as Ti is plated with a Pt metal from an organic solution of a Pt metal complex of a compound having a −NH3, −NH4, −NH2 or =NH group, e.g. (NH4)2PtCl6.
union carbide corp. U.S. Patent 3,446,607
A graphite substrate resistant to oxidation up to 2000°C is provided with an adherent pore-free Ir coating, by applying finely divided Ir powder in a slurry, heating the substrate and Ir powder to produce a coating of sintered Ir, then vapour plating the sintered coating with Ir, and finally electrodepositing more Ir on top of this.
LABORATORY APPARATUS AND TECHNIQUE
edwards high vacuum international ltd British Patent 1,159,494
The filamentary electron-emitting cathode of an ionisation gauge consists of a Pt-Rh alloy wire coated with a rare earth oxide of low work function.
Chlorination of Toluene
tenneco chemicals inc. British Patent 1,158,987
A chlorinated C6H5CH3 mixture with an increased para-isomer content is produced by reacting C6H5CH3 with Cl2 in the presence of PtO2 but in the absence of light or Fe.
Selective Hydrogenation of C4 Fractions
farbenfabriken bayer a.g. British Patent 1,159,256
C4-acetylenes or C4-acetylene/butadienes in a butadiene containing C4-fraction are selectively hydrogenated in the trickle-phase at high pressure in the presence of a fixed Pd/carrier catalyst. At least 20% of the catalyst support consists of Li Al spinel.
Catalytic Reduction of Aromatic Ketones and Aldehydes
johnson matthey & co. ltd British Patent 1,159,967
Aromatic ketones or aldehydes are converted to the corresponding alcohol by hydrogenation on a Pd catalyst (5% Pd/C) in the presence of an amine (aniline, p-toluidine benzylamine, pyridine or quinoline).
Hydrocarbon Conversion Catalyst
standard oil co. British Patent 1,161,750
Liquid C3H8 and C4H10 and aromatics are produced from naphtha using a catalyst comprising 0.1−2 wt% noble metal such as Pt, 2−95 wt% mordenite, 0.05−5 wt% halogen such as Cl2, and 5−98 wt% Al2O3.
Saturated Aliphatic Mono-carboxylic Acids
knapsack a.g. British Patent 1,161,972
The oxidation of saturated aliphatic aldehydes to acids is catalysed by supported Pd metal, Pd oxide or Pd salt together with at least one other source of metal which includes Pt, Rh, Ru, Au and Ag.
Production of Phenol by Catalytic Dehydrogenation
institut francais du petrole des carburants et lubrifiants British Patent 1,162,397
The dehydrogenation of cyclohexanol and/or cyclohexane is catalysed by a substrate of SiO2 supporting 0.1−2 wt% Pt, 0.05−1 wt% Ir and 0.5−3 wt% alkali or alkaline earth metal. The specific surface of the catalyst must be 100−300 m2g−1 and the pore volume 0.7−1.1 ml g−1.
Process for Converting Hydrocarbons
shell internationale research
mij n.v. British Patent 1,162,969
Hydrocarbons are converted by contacting them at high temperature and pressure, in the presence of H2, with a Pd/zeolite catalyst. The zeolite is specially treated to have an alkali metals content of < 1% and a molecular SiO2/Al2O3 ratio 3–7.
Vinyl Acetate Production
kurashiki rayon k.k. British Patent 1,164,194
C2H4, O2 and aqueous CH3COOH are reacted over a metallic Pd catalyst, e.g., 0.1−5% Pd on a support, to give vinyl acetate, and CH3COOH in a form suitable for recycling.
esso research & engineering co. U.S. Patent 3,442,973
Normal 4−8 C paraffins are isomerised on a catalyst comprising Au and Pd on an Al2O3 support. It preferably contains Pd in an amount representing 5−83 wt% of the Au present.
universal oil products co. U.S. Patent 3,448,165
Mono-olefines are produced from 10−18°C n -paraffin without skeletal rearrangement, by contacting at 400−600°C with an As-attenuated Pt catalyst on lithiated Al2O3 (0.05−5 wt% Pt). See also U.S. Patent 3,448,166.
chevron research co. U.S. Patent 3,449,237
A reforming process using a Pt-Re catalyst on a process support is started up by contacting the naphtha with the catalyst in the presence of an inert gas (N2) at 650°F. Thereafter the catalyst temperature is increased to 900°F when a pressure of H2 is built up.
Hydrogenation of Pyrolysis Gasoline
universal oil products co. U.S. Patent 3,451,922
The olefines and dienes of pyrolysis gasoline are removed selectively to stabilise the product by (a ) hydrogenation of the heavier fraction over Pd and desulphurisation over Ni and (b ) bulking the fractions and hydrogenating over Pd.
Hydrocracking of Feedstocks
chevron research co. U.S. Patent 3,453,204
An improved catalyst is produced by co-gelling or co-precipitating the hydrogenating and cracking components which consist of 50−90 wt% SiO2, Al2O3 and 0.01−0.05 wt% of Pt, PtS, Pd or PdS.
Haloacetyl Halide Production
national distillers & chemical corp. U.S. Patent 3,454,632
A process is provided for preparing haloacetyl halides from polyhalomethanes by reaction with CO in the presence of a Pt or Pd triad catalyst, and optionally, a promoter for the catalyst.
Hydrogenation of Hydroxy-containing Diene
Oxidation of Organic Compounds
celanese corporation British Patent 1,159,250
Organic compounds are partially oxidised in a system including a solution of Ru catalysts and an oxidising agent for maintaining the Ru in solution. The oxidation potential of the system must be maintained within the range represented by the values for Ru(V) and Ru(VII).
celanese corporation British Patent 1,159,528
C2H4 is converted to vinyl acetate in a redox system comprising an CH3COOH solution of a salt of a Group VIII metal (a Pd(II) salt) a source of CH3COO− ions and Cl− ions, Cu(II) ions and O2.
imperial chemical industries ltd British Patent 1,159,950
The H atoms of hydrocarbons are replaced by Cl by contacting a hydrocarbon (acyclic paraffin, olefin, C6H6 and its homologues) with a mixture of molten LiCl and PdCl2, (additionally KCe).
Oligomerisation Process Using a Ruthenium Catalyst
geigy (u.k.) ltd British Patent 1,165,286
Oligomers of butadiene and/or isoprene with methyl methacrylate are produced using a Ru catalyst (e.g., RuCl3) in a 1−6 C alcohol.
Preparation of Stable Polysulphones
shell oil co. U.S. Patent 3,444,145
C2H4 is oxidised to vinyl acetate in the presence of a Pt metal salt, e.g., PdCl2 and a nitrogenous oxide compound, e.g., HNO3 or a nitrate.
general electric co. U.S. Patent 3,448,072
A polyester and an isocyanate are contacted to provide for the introduction of aliphatic unsaturation into the polyester. This reaction takes place in the presence of a Pt catalyst (H2PtCl6, Pt-C2H4 complex, etc.) with a Si hydride-bearing hydrolysable radical to produce curable compositions of a polyester with terminal silylurethane groups.
Ethyl Vinyl Sulphone
shell oil co. U.S. Patent 3,448,159
C2H4 and SO2 react in aqueous solution in the presence of a Pdhalide catalyst (PdCl2) and a co-catalyst (halide ion, especially KCl) to yield ethyl vinyl sulphone.
Preparation of Vinyl Acetate, Acetaldehyde and Acetic Acid
union oil co. of california U.S. Patent 3,450,748
C2H4 is oxidised (O2) in contact with a liquid phase containing a noble metal catalyst (PdCl2) and a soluble halide. The products are separated and recovered.
Homogeneous Hydrogenation Catalyst
shell oil co. U.S. Patent 3,454,644
Keto, nitrile, unsaturated and formyl compounds are hydrogenated in the presence of the Ru or Os complex of formula LnMZ2, where n is either 3 or 4, M is Ru or Os, Z independently is Cl, Br or H, and L independently is CO or tertiary phosphine with at least three L’s being tertiary phosphine.
Iridium Phosphine Complexes
imperial chemical industries ltd U.S. Patent 3,458,547
New catalysts for reactions involving unsaturated bonds have the formula IrH3(PR3)2, where R is the same or different alkyl, aryl, arylky, alkenyl, cycloalkenyl, alkoxy, aryloxy or heterocyclic group. They are produced by the hydride reduction of IrY2 (PR3)2, where Y is an anion.
Recovery of Hydrogen
united aircraft corporation British Patent 1,159,150
H2 is recovered from H2-containing feedstocks in a fuel cell in which the anode contains a dehydrogenation catalyst. A cathode membrane (of Pd-Ag alloy) is spaced from the anode. The cathode is selectively permeable to H2.
leesona corporation British Patent 1,159,343
An electrochemical cell electrode comprises a porous metal (Ni) substrate with one surface in intimate contact with a catalyst layer. The latter consists of Pt black and a hydrophobic polymer (PTFE) uniformly distributed throughout the catalyst layer. See also British Patents 1,159,344–1,159,346.
Fuel Cell Electrode
tokyo shibaura electric co. ltd British Patent 1,165,679
The fuel cell has a H2 electrode, composed of Pd or a Pd alloy of a Group IB metal or metals, which is coated on one side with Pt black and on the other side with a layer of Pd alloyed with Pt and/or Rh in the form of a “black”.
Fuel Cell Electrodes
leesona corporation British Patent 1,167,542
Catalyst compositions for NH3 fuel cells comprise 75−98 at.% Pt and 2−25 at.% Rh or Ru.
esso research & engineering co. U.S. Patent 3,443,998
The anode is an electrically conducting substrate coated with a physical mixture of Pt and Au. This is immersed in an anolyte containing Na molybdate dissolved in H2SO4.
Alloys for Parts in Contact with Molten Glass
international nickel ltd British Patent 1,160,748
Articles and parts which come into contact with molten glass are made of an alloy containing 0.5−4% Ti, the remainder Pt.
Coating Glass with Platinum
ELECTRICAL AND ELECTRONIC ENGINEERING
philips electronic & associated industries ltd British Patent 1,159,634
An ion-source comprises a porous W body forming a closure for a supply of alkali metal compounds. The body has a thin Os-Ir coating.
Coated Cathode for Electrical Equipment
philips electronic & associated industries ltd British Patent 1,164,413
A cathode, e.g., for electric discharge tubes, is made with a porous W body filled with Ba compounds and coated with a thin porous layer of an Os-Ir or Os-Ru alloy. The Ir alloy can contain 30−70 at.% Os and the Ru alloy 20−80 at.% Os.
western electric co. British Patent 1,166,659
A metallic pattern is formed on a substrate by depositing a layer of Ti and then a layer of Pt, masking the surface and etching away the exposed Pt. The mask is then removed and Au applied to the remaining Pt pattern.
Thin Film Conductors
plessey co. ltd British Patent 1,166,992
The precursors of a ceramic glaze, plus Ru and/or Rh compounds, are added to a solvent to produce a solution or emulsion which is applied to a substrate. The film left after eliminating the solvent is fired to give a conducting film. A typical coating composition contains Pb stearate, Si resinate and Ru resinate in diacetonal alcohol.
Noble Metal Metallising Compositions
e. i. du pont de nemours & co. U.S. Patent 3,450,545
The metallising compositions comprise 60−95% of a noble metal powder (Ag, Pd, Pt or Au), an inorganic binder powder and at least one oxide precursor (Rh, Ir, Ru, Cu, SiC or BN).