Journal Archive

Platinum Metals Rev., 1974, 18, (4), 155

NEW PATENTS: October 1974


Palladium Acetylacetonate of Low Chlorine Content

bayer a. g. U.S. Patent 3,787,462

A high purity Pd acetylacetonate is obtained by precipitating a Pd compound from an aqueous alkali PdCl2 solution with an alkali metal hydroxide, converting the precipitate to the Pd acetylacetonate with acetylacetone and washing and drying the acetonate.

Compounds of Ruthenium

johnson matthey & co. ltd. U.S. Patent 3,793,355

A composition of matter has the general formula MM′M″XA6LL′L″ where M, M′ and M″ are the same or different transition metals selected from the second or third series of the periodic table; X is O, S, N, P or B; A is an anionic element or group and L, L′ or L″ are neutral or anionic ligands. A preferred compound is Ru3O(OCOMe)6(PPh3)3 and generally the Ru carboxylates are used as homogeneous catalysts.


Electrodeposition of Ruthenium

international nickel co. inc. U.S. Patent 3,793,162

An electroplating bath and process for electroplating Ru is prepared by dissolving Ru2N(OH)5 nH2O in H2SO4 or H2NSO3H and adjusting the pH to 4 or less.

Electroless Plating

toray industries inc. U.S. Patent 3,801,368

In an electroless plating method Pd or Au is deposited on a substrate in vacuum and then the substrate is electrolessly plated using the previously deposited Pd or Au as the catalyst.


pH Meter Electrodes

general electric co. British Patents 1,353,209, 1,353,210

A reference electrode, including a Ag wire coated with AgCl is positioned within an insulating tube the opposite end of which is surrounded with Pd coated with Pd oxide.


Dehydrogenation Catalyst

universal oil products co. British Patent 1,351,393

A dehydrogenation catalyst is produced by impregnating Al2O3 with a solution containing a Ge compound, a Pt group metal compound, a halide and an alkali metal compound. The product is steamed to reduce the halogen content to less than 0.1%. The impregnated and steamed support is dry heated at 204−649°C, reduced and sulphided. Pt and Pd are preferred.

Aminocyclohexyl Compound Production

badische anilin- & soda-fabrik a. g. British Patent 1,351,487

Bis(aminocyclohexyl)alkanes or ethers are produced by hydrogenation or the corresponding aminophenyl compounds over a suspended catalyst which may be Ru.

Hydroreforming Catalysts

cie. francaise de raffinage British Patent 1,351,562

A new hydroreforming catalyst consists of a refractory inorganic oxide support, e.g. Al2O3, having a surface area of more than 15 m2/g and a pore volume of more than 0.1 cm3/g carrying 0.02−2% Pt (preferably 0.1−0.7%), 0.02−2% Ir (preferably 0.1−0.7%) and 0.02−2% Sn.

Hydrogenation Catalysts

du pont of canada ltd. British Patent 1,352,737

Butyrolactam and valerolactam respectively are obtained by hydrogenation of succinimide and glutarimide in the presence of a catalyst, e.g. Pt, Pd or Re, optionally supported.

Preparation of Rhodium-containing Catalyst

shell internationale research mij. n.v. British Patent 1,354,778

Rh containing catalyst, suitable for the ringopening and saturation of cyclic hydrocarbons, is produced by mixing SiO2 and a Rh-cationcontaining solution so that ion-exchange takes place, removing the liquid and drying the ionexchanged SiO2.

Platinum-Lead Catalysts

asahi kasei k.k.k. British Patent 1,356,464

Pt-Pb catalysts supported on a carrier such as Al2O3 are regenerated by applying HCl and/or HNO3 solutions and calcining the catalysts. The catalysts may contain further metals, among them Ag, Au and Pt group metals.

Catalytic Reforming

british petroleum co. ltd. British Patent 1,356,634

Hydrocarbon reforming is catalysed by a supported mixture of a Pt group metal and As. The support, such as Al2O3, must be free from alkali and alkaline earth metals. The Pt (or other Ptgroup metal) content is 0.01−5% and the As content is 5−35 at.% of the Pt + As content.

Catalytic Reforming

universal oil products co. British Patent 1,359,728

A relatively lean octane hydrocarbon fraction is reformed using a supported Pt-Re catalyst in two stages with water excluded in the first, but not the second stage.

Methanation of Carbon Monoxide and Carbon Dioxide

institute of gas technology U.S. Patent 3,787,468

The preferential, selective and sequential methanation for reaction of gases containing CO or CO2 in the presence of H2, using catalysts of Rh and Ru metals or alloys with Pt is improved with W oxide. Typically Ru and WOx in a 85:15 ratio or Pt, Rh and WOx in a 42.5:42.5:15 ratio are used. x is unknown.

Selective Hydrogenation of Hydrocarbons

p. bernusset U.S. Patent 3,787,515

Unsaturated impurities in the purification of ethylenic gases are removed by selective hydrogenation with a Pd catalyst having an addition of V as a promoter.

Preparation of Catalysts

esso research & engineering co. U.S. Patent 3,789,020

A catalyst is formed from a mixture of one or more Group VIII metals with an optional Group IB metal, e.g. Pt and Cu, deposited on particles of a support such as Al2O3, mixed with further uncoated particles of support.

Reforming Catalyst

phillips petroleum co. U.S. Patent 3,789,024

An improved catalyst has refractory-supported Pt promoted with both Ir and Ga and exhibits increased activity and selectivity characteristics for the dehydrocyclisation and reforming of hydrocarbons. In one example, Al2O3 promoted with Pt, Ir and Ga is used in the conversion of n -heptane to benzene and toluene with substantial conversion at high selectivity.

Tetrametallic Hydrocarbon Conversion Catalyst

universal oil products co. U.S. Patent 3,790,473

A catalytic composite contains Pt or Pd, Ir, Re and Sn on a porous carrier material. It is used mainly in the conversion of hydrocarbons, particularly in the reforming of a gasoline fraction. A specific example of this catalytic composite is a combination of Pt, Ir, Re, Sn and a halogen with Al2O3 carrier material in amounts to supply approximately 0.01−2% Pt, 0.01−2% Ir, 0.01−2% Re, 0.01−5% Sn and 0.1−3.5% halogen.

Preparation of Organic Dinitriles

kurashiki rayon co. ltd. U.S. Patent 3,790,617

A process for preparing organic dinitriles by the dimerisation of acrylonitrile consists of reacting acrylonitrile with H2 in a gaseous phase at 100−450°C under a total pressure of 1−20 atm by using as catalyst Ru metal or a Ru compound reducible to Ru metal under reaction conditions. The catalytic activity of the catalyst can be increased by addition of an alkali metal hydroxide or a mixture of a halide of Ni, Cr, Mo or W with an organic P compound.

Combination Reforming Process

esso research & engineering co. U.S. Patent 3,791,961

A conventional naphthene dehydrogenation catalyst, such as a Pt-halogen/Al2O3 catalyst, is used in the initial zone or reactor in a catalytic reforming process; the tail zone or reactor contains a supported Group VIII polymetallic catalyst with platinum as one of the metallic components. In a preferred embodiment, the tail zone contains a Pt-Ir catalyst on a porous support such as Al2O3.

Preparation of Acrylic and Methacrylic Acids

national distillers & chemicals corp. U.S. Patent 3,792,086

Acrylic or methacrylic acids are selectively produced in a single step process involving the vapour phase oxidation of propylene or isobutylene, respectively, at temperatures of up to 300°C and in the presence of a catalyst composition containing H3PO4 and Pd metal.

Reforming Catalyst

ste. francaise des produits pour catalyse U.S. Patent 3,793,232

A catalyst for the conversion of hydrocarbons, particularly for reforming reactions, has Al2O3 base supporting on the following metals: 0.005−1% Pt, 0.005−1% Ir and 0.05−3% Tl or In. Optionally the catalyst may further contain from 0.1−10% of a halogen and up to 10% of Zn.

Olefin Hydroisomerisation Process

universal oil products co. U.S. Patent 3,796,766

Olefins are hydroisomerised utilising a catalytic composite containing a Pt group component and a Group IVA metallic component combined with a carrier material of Al2O3 and a finely divided crystalline aluminosilicate such as mordenite. The active metals may be Pt and Ge.

Reforming with Platinum and Tantalum or Niobium Catalyst

british petroleum co. ltd. U.S. Patent 3,799,867

A catalyst of 0.01−5% Pt on a refractory support also contains 0.01−5% of Ta or Nb. The support is preferably Al2O3 which may contain halogen. The Ta or Nb may be added at any convenient stage in the catalyst preparation, including adding it as a chloride or fluoride during the preparation of the support.

Multimetal Powder Alloy Catalyst

stamicarbon n.v. Dutch Appl. 73.16236

An alloy is formed from a complex of two metals or their compounds by reduction in situ of particles on a support. Thus Ge and Pd salts can be deposited on Al2O3 and reduced to form a Ge-Pd alloy.


Hydroformylation and Hydrogenation Catalysts

johnson matthey & co. ltd. British Patent 1,357,735

Gaseous olefins are reacted with H2 and CO (or H2 alone) in the absence of solvent but in the presence of a liquid As or Sb-containing stabilising donor ligand using as catalyst a hydrido carbonyl complex of Rh including an As- or Sb-containing ligand. An example of the catalyst is RhH(CO)2[AsPh3].

Formylindane Production

badische anilin- & soda-fabrik a.g. British Patent 1,358,081

1- and 2-formylindanes are produced by the hydroformylation of indene in the presence of a Rh carbonyl complex such as Rh(CO)(PPh3)2Cl.

Process for Producing Acyloxydodecatrienes

mitsubishi chemical industries ltd. U.S. Patent 3,789,066

Acyloxydodacatrienes are produced by reacting an octatriene, a butadiene and a carboxylic acid in the presence of a catalytic amount of a divalent Pd compound selected from organic acid salts of Pd (II), chelate complexes of Pd (II) and Pd nitrate.

Olefin Isomerisation and/or Hydrogenation

phillips petroleum co. U.S. Patent 3,793,257

Ru hydride complexes containing tertiary phosphine, arsine, or stibine ligands are employed as catalysts for isomerisation and/or hydrogenation of olefins. Terminally unsaturated olefins are selectively isomerised to internally unsaturated olefins by complexes that contain N or NH3, e.g. (tribenzyl arsine)3RuH2(NH3).

Rhodium Catalysts

johnson matthey & co. ltd. U.S. Patent 3,794,671

Nonhalogen or pseudo-halogen coordination complexes of Rh(I) containing a stabilising donor ligand are made by adding a compound which acts as a stabilising donor ligand to a solution of Rh (II) carboxylate protonated by an acid. The complexes with arsines, phosphines, etc, are useful catalysts. One example is Rh(OCOMe) (PPh3)3.

Bidentate Rhodium Cordinates

institut francais du petrole U.S. Patent 3,798,241

Bidentate coordinates of the formula R2X-R′-YR2, in which X and Y are P, As, Sb or N, R is a hydrocarbon group containing an asymmetric C atom and the R groups are hydrocarbon radicals, may be associated with Rh complexes to yield hydrogenation catalysts useful in asymmetric synthesis, e.g. in the synthesis of optically active aminoacids or amines. For example Rh2Cl2(cyclooctene)4 may be used with a diphosphinotartrate Ph2PCH2-CH(OMe)-CR2 PPh2.

Producing Acyloxydodecatrienes

mitsubishi chemicals industries ltd. U.S. Patent 3,798,260

Acyloxydodecatriene is produced by reacting an octatriene, butadiene and a carboxylic acid in the presence of a catalytic amount of Pd or Pd compound and an amine.


Layered Electrode

metallgesellschaft a.g. U.S. Patent 3,788,968

An electrode, especially useful as an anode in the electrolysis of alkali metal chlorides, includes a graphite body, a first surface covering of a hard ceramic such as Ti carbide or Ti nitride and at least one metal and/or metal oxide of the Ptgroup and a second oxide coating which is electrically porous and resistant to the electrolysis conditions. Ru/Ru oxide are used in one example.

Matrix Electrode

diamond shamrock corp. U.S. Patent 3,798,063

Finely divided RuO2 serves as an efficient and long-lived electrocatalyst when dispersed in a polymer matrix chemically and mechanically intert to an electrolyte. When applied to a substrate, generally an electrically conductive substrate, an electrode, particularly suited for use as an anode at which O2 is evolved, is obtained. A coating of polyvinylidene fluoride containing RuO2 having a particle size of less than 0.1 micron on a Ti substrate is one example.


Semiconductor Contacts

r.c.a. corp. British Patent 1,353,975

A semiconductor surface is sputter etched in the presence of a backing plate so that the two surfaces provide the components of an alloy layer. For example a silicon semiconductor and a Pt backing plate become coated with Pt silicide.

Ceramic Capacitors Metallisation

e.i. du pont de nemours & co. U.S. Patent 3,798,516

Metallising compositions with alloys of three or more metals are used in making ceramic capacitor electrodes. The alloys have a critical surface area. The metals of the alloy are Pd, Pt and Au. The metallising compositions are especially suitable for producing capacitors on ceramic dielectric substrates which contain Bi2(SnO3)3.



united states steel corp. British Patent 1,352,743

A conventional Pt thermocouple forms part of an electrolytic apparatus for the determination of oxygen in e.g. molten steel.

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