Platinum Metals Rev., 1969, 13, (1), 39
NEW PATENTS: January 1969
METALS AND ALLOYS
international business machines corp. British Patent 1,125,690
Magnetic thin films for computer storage elements may be made from an alloy of 69.9−80 at.% Ni, 18−20.2 at.% Fe and 1–12 at.% Pd.
Finely Divided Noble Metal Alloys
e. i. du pont de nemours & co. U.S. Patent 3,390,981
Alloys of two noble metals selected from Ag, Au, Pt and Pd are produced by mixing solutions of salts of these metals and then reducing the mixture (e.g. of Pd and Ag nitrates) to give an alloy in finely divided form. H3PO2 is a suitable reducing agent.
A Niobium-Tungsten Alloy
birmingham small arms co. ltd U.S. Patent 3,395,012
An alloy consists of at least 30% Nb, 10−25% W, up to 40% Ta, and 0.1−10% of at least one element selected from Ru, Os and Ir.
Laminated Metal Plates and Strip
johnson, matthey & co. ltd German Patent 1,271,494
The bonding of Pt or Pt alloy to Ti, Ta, Nb, V or Zr mechanically, especially to produce electrodes, is improved by using pressures of 80−800 kp/cm2 at 800−950°C.
Fountain Pen Ruthenium Alloy
Trimeric Ruthenium Carbonyl
Porous Electrodes for Electrochemical Cells
gulf general atomic inc. British Patent 1,124,362
Metal porous electrodes are produced by shaping a mixture of metal particles, e.g. Ni, with C particles using heat and pressure and then removing the C by electrolysis. The porous Ni matrix is impregnated using a thermally unstable organic salt of a Pt metal.
Anodes for Electrolytic Cells
tsurumi soda co. ltd British Patent 1,128,136
Anodes for the electrolysis of halide compounds (e.g. NaCl) are produced from an alloy of 3−80% Pd and 97−20% Rh or of 5−80% Pd and 95−20% Pt which is subjected to oxidative treatment at 180−1350°C in an oxidising atmosphere, or electrolytic oxidation in a fused salt bath.
ELECTRODEPOSITION AND SURFACE COATINGS
e. i. du pont de nemours & co. U.S. Patent 3,385,799
Electroconducting areas are produced on nonconducting surfaces, especially ceramics, using a mixture of 30−90% noble metal alloy powder, dispersed in 10−70% of an inert liquid organic vehicle; the powder has 90% of the particles not greater than 5 microns in size and is made from two noble metals selected from Ag, Au, Pt and Pd.
Platinum Metal Chemical Plating
Refractory Metal-to-Ceramic Seal
a. e. milch et al. U.S. Patent 3,386,160
Ceramic surfaces are provided with a layer of spongy Mo and/or W and a wetting alloy, selected from Ta-Rh, Rh-Mo and Ru-Mo alloys, is melted on the spongy layer so that brazing to Ta and Nb alloys can take place.
Noble-metal-coated Ceramic for Seals
Process for Isomerising Terminal Olefines
ethyl corp. British Patent 1,122,056
Internal olefines are produced from terminal olefines when contacted with one or more Group VIII metals, optionally together with an alcohol or aldehyde promoter. The preferred catalysts contain Ru with one or two other Group VIII metals.
Production of Hydroxylamine Sulphate
inventa a.g. British Patent 1,122,103
HNO3 is reduced with H2 in aqueous H2SO4 in the presence of a Pt catalyst, e.g. Pt/C, to give hydroxylamine sulphate.
Improvements Relating to the Treatment of Oils
unilever ltd. British Patent 1,122,398
The linoleic acid of edible vegetable oils is hydrogenated selectively to linolenic acid at 150−250°C in the presence of a mixture of Cu and a more active metal, especially Pd or Pt.
Improvements in or Relating to the Production of Esters
distillers co. ltd British Patent 1,122,444
Better yields of vinyl acetate are obtained in the oxidation of C2H4 over a Pt group catalyst in the presence of 5−15 wt% H2O, acetate ions, CH3COOH and halide ions.
Production of a Mixture of Stereoisomers of 4,4′-Methyldenedi-(cyclohexylamine)
e. i. du pont de nemours & co. British Patent 1,122,609
Essentially complete hydrogenation of p, p′-methylene-dianiline to give this mixture of isomers is achieved at high pressure and temperature in the presence of NH3, inert organic solvent and a special Ru catalyst. The catalyst consists of (a ) Ru supported on CaCO3 and/or a rare earth oxide or (b ) Ru supported on Al2O3, BaSO4 or kieselguhr and moderated with 0.1−15% of a basic alkali metal compound.
Production of Carboxylic Acids or Esters
badische anilin- & soda-fabrik a.g. British Patent 1,123,367
An unsaturated compound is reacted with CO and H2O, an alcohol or a phenol at elevated temperature in the presence of Pd metal or a Pd chalcogenide with an acid and an organic phosphine and/or nitrile. Pd/SiO2 and PdO are examples of the catalyst.
Catalytic Hydrogenation of Unsaturated Aldehydes
johnson, matthey & co. ltd British Patent 1,123,837
The catalyst for the selective hydrogenation of an unsaturated aldehyde to an unsaturated alcohol comprises Pt promoted with an alkaline hydroxide in an alcoholic solvent, e.g. Pd/C promoted with alcoholic KOH.
Dehydrogenative Coupling of Organic Compounds
british petroleum co. ltd British Patent 1,123,874
Diphenyl is obtained from C6H6 by dehydrogenative coupling over Pt or Pd metal supported on a non-acidic inorganic support, e.g. SiO2, quartz wool or Al2O3.
Improvements in and Relating to Catalysts
johnson, matthey & co. ltd British Patent 1,124,504
Catalysts of enhanced activity and comprising intimate homogeneous mixtures of the oxides of two or more Pt group metals (but excluding mixtures containing OsO4 and mixtures of Pt and Rh oxides and Pt and Ru oxides) are prepared by the Adams method.
Preparation of Cyclohexanone
inventa a.g. British Patent 1,125,199
Cyclohexanone is prepared by the hydrogenation of liquid C6H5OH as it trickles over a Pt group metal catalyst at up to 250°C in the presence of
H2. The only catalyst specified in the examples is Pd/Al2O3.
Hydrogenation of C4-Hydrocarbons containing Butadiene and n -But-1-ene
farbenfabriken bayer a.g. British Patent 1,126,848
Hydrogenation of butadiene mainly to the n -butene-2 isomer takes place in a descending stream over a fixed catalyst, especially Pd/Al2O3 or zeolite chips.
Preparing cis -Cyclodecene
universal oil products co. British Patent 1,127,702
The selective hydrogenation of trans, cis – 1,5 – cyclodecadiene to this compound at 0.100°C and 13.6–68 atm is catalysed by Pt/Al2O3.
Preparation of Urethanes
american cyanamid co. British Patent 1,127,988
A route avoiding the use of isocyanates in the production of urethanes consists of reacting an organic N compound, an organic hydroxyl compound and CO in the presence of a Lewis acid – noble metal catalyst. “Noble metal” is defined as one of the six Pt metals and the catalyst can be in the form of the metal or a salt of it. A typical catalyst consists of Pd/C and FeCl3.
Production of Vinyl Acetate
b.p. chemicals (u.k.) ltd British Patent 1,128,993
A new catalyst for C2H4 oxidation in the presence of CH3COOH is a Pt group metal deposited on TiO2, an alkali, alkaline earth, Zn, Co, Ni, or Fe silicate and/or their mixtures. A typical catalyst is PdCl2 on TiO2.
Manufacture of β-Pinene
farbwerke hoechst a.g. British Patent 1,129,622
The isomerisation of α-pinene to β-pinene is catalysed by a Pd/C catalyst in the presence of H2 at 140−200°C.
Production of Organic Esters
farbenfabriken bayer a.g. British Patent 1,129,668
Anolefine with 3 or more C atoms or an alkyl benzene is reacted with O2 and an organic acid having a higher molecular weight than CH3COOH in the presence of Pd metal catalyst at elevated temperature. In 1,129,669 the Pd metal catalyst is accompanied by the alkali or alkaline earth metal salt of an organic acid.
Preparation of Hydroformylation Products
deutsche gold-und silber-scheideanstalt British Patent 1,129,809
Tetrahydrophthalic acid anhydride or esters are hydroformylated with H2/CO in the presence of a Rh, Ir or Ru catalyst or a compound of these metals forming a carbonyl in the reaction conditions. A typical catalyst is Rh2O3.
monsanto co. British Patent 1,131,983
Saturated hydrocarbons are dehydrogenated to olefines over a catalyst. The catalyst is prepared by impregnating Al2O3 with 0.02−5 wt% of a noble metal compound and then reducing the compound to the metal. Pt is the preferred metal.
monsanto co. British Patent 1,131,984
A dehydrogenation catalyst is produced from an Al2O3 support having a macropore volume of at least 0.05 cc/g with an alkali or alkaline earth compounds and noble metal compound to deposit at least 0.01 wt% alkali or alkaline earth metal and 0.02−5 wt% noble metal (especially Pd or Pt).
mobil oil corp. U.S. Patent 3,384,572
A high aromatic feedstock is cracked over a catalyst consisting of a hydrogenation component having an activity of 5–35 on a crystalline aluminosilicate, e.g. Pt on a rare earth aluminosilicate.
esso research & engineering co. U.S. Patent 3,385,781
Selective hydrocracking, especially of a pre-cracked feed, is carried out over a Pt catalyst supported on an aluminosilicate zeolite having pore openings of a 6−15Å and containing less than 10 wt% alkali metal oxide.
chevron research co. U.S. Patent 3,385,782
Light 1−4C hydrocarbon gases are produced from heavy hydrocarbons by hydrocracking over a Group VIII metal catalyst on a crystalline aluminosilicate zeolite. A typical Group VIII metal is Pd.
Alkyl Mononitrile Production
commercial solvents corp. U.S. Patent 3,385,880
Mononitriles are produced by the vapour phase reduction of nitroalkanes over Pt catalysts, e.g. Pt/Al2O3.
Two-stage Steam Reforming
catalysts and chemicals inc. U.S. Patent 3,388,074
A steam-gas hydrocarbon reforming catalyst promoted with Pt or Pd supplies heat to the system while giving combustion and reforming in the first stage.
universal oil products co. U.S. Patent 3,388,077
A catalyst for oxidising noxious gases consists of an Al2O3 porous carrier containing a Ca, Sr or Ba oxide uniformly distributed throughout it; 1−20 wt% of Pt is present as an embedded layer below the surface of the carrier.
texaco inc. U.S. Patent 3,389,191
The hydroisomerisation of n -C4H10 with a chloride-activated Pt/Al2O3 is improved when the catalyst is spent, by treating it with H2 under “non-flowing” conditions at 450−700°F.
stamicarbon n.v. U.S. Patent 3,390,954
Hydroxylamine is produced by the hydrogenation of an alkyl nitrite in an acidic medium over a noble metal catalyst, especially Pd/C.
Preparation of Cyclic Olefins
stamicarbon n.v. U.S. Patent 3,391,206
These compounds, especially cyclohexene, are produced from aromatic compounds by hydrogenation in the presence of a lower alkanol solvent in the presence of a Ru catalyst, e.g. Ru black.
Catalytic Dehydrogenation of Paraffins
universal oil products co. U.S. Patent 3,391,218
A 3–20 C paraffin is dehydrogenated in the presence of hydrogen and an aromatic hydrocarbon over a Group VIII noble metal catalyst, especially an As-attenuated supported Pt catalyst.
Hydroisomerisation of Paraffins
universal oil products co. U.S. Patent 3,391,220
A 4–5 C paraffin is isomerised in the presence of a Pt metal-halogen supported catalyst, a halide promoter and a small amount of C6H14.
Noble Metal-Alumina Catalysts
e. i. du pont de nemours & co. U.S. Patent 3,397,154
Catalysts for ICE combustion consist of (a ) oxides and mixed oxides of Fe, Co, Ni, V, Cr, Mn, Cu, Zn, Mo, Ag, Sn, Ba, Ce, W, Pb, or Bi, (b ) Ru, Pt, Pd, Rh, Os or Ir metal and (c ) an Al2O3 support having a crystalline cellular structure with walls of 0.3–200 mils thickness.
trans -1,4-Diene Production
b. f. goodrich co. U.S. Patent 3,398,209
These dienes may be obtained by the reaction of a 4–6 C 1,3-diene and C2H4 in the presence of reduced Pd obtained from a Pd compound and an alkyl Al halide.
ste francais des produits pour catalyse French Patent 1,517,713
Products of high octane number are obtained by reforming over a Pt/Cl/Al2O3 catalyst obtained in a specified way. Al2O3 is treated with aqueous HCl representing 0.5−5% Cl2, based on the Al2O3 and dried at 540−600°C until its IR spectra shows the absence of OH absorption bands. Pt is then incorporated in the usual way.
johnson, matthey & co. ltd French Patent 1,519,568
Butyraldehyde is produced by the hydrogenation of crotonaldehyde in a trickle column over a supported Pd catalyst, e.g. Pd/Al2O3.
Suspended Platinum Hydrogenation Catalyst
deutsche gold- und silber-scheideanstalt German Patent 1,272,292
Suspended, unsupported Pt metal catalysts in a liquid organic medium are recovered from the liquid by means of a carbon filter with a maximum pore width of 15μ. The catalyst particles have a diameter of 0.01−1μ.
Production of Epoxy Organic Hydrogen Polysiloxanes
farbenfabriken bayer a.g. German Patent 1,272,550
Sill-group addition to an olefinic epoxide is catalysed by finely divided Pt or Pd, optionally in the presence of an inert solvent.
New Organic Rhodium Complexes
imperial chemical industries ltd British Patent 1,121,642
New Rh catalysts, especially for chemical reactions, are new complexes of formula Rh(X) (YRR′R″)3, where Y is P, As or Sb, X is an anionic element or group, especially Cl or NCS, and R, R′ and R″ are hydrocarbon groups.
Preparation of Oxygen-containing Organic Compounds
lummus co. British Patent 1,122,040
Acetals, ketals, cyclic ethers, aldehydes, ketones, etc., are produced by reacting unsaturated compounds with alcohols in the presence of Group VIII noble metal catalysts, especially in 0.001–0.1 M proportions. Usually PdCl2 is used with CuCl2.
halcon international inc. British Patent 1,122,702
Hydrogenolysis of an alpha-aralkyl alcohol to remove the OH group is catalysed at 50−120°C in the liquid phase by a Pt group metal catalyst, e.g. PdCl2.
Production of Unsaturated Lactones Having a Five-membered Ring
badische anilin- & soda-fabrik a.g. British Patent 1,123,018
Lactones with side chains are obtained from an olefin, CO and (a ) a Pd catalyst in an amount of 0.01−20% of the olefin and 20−150%, based on the Pd, of a hydrogen halide or (b ) 0.01−20% of a Pd halide, based on the olefin. PdI2 is a suitable catalyst.
Decomposition of Formic Acid
imperial chemical industries ltd. British Patent 1,126,022
HCOOH in admixture with another carboxylic acid is destroyed by contacting the mixture with a Pt group metal in the presence of a base. Ir, e.g. as H2PtCl6, is a suitable metal.
now corning corp. British Patent 1,127,675
A new catalyst for the SiH addition reaction is a reaction product of H2PtCl6 and at least one siloxane. These catalysts are more compatible with the reactants and less Pt is used.
aerojet-general corp. British Patent 1,128,103
N2F4 is produced by the oxidation of N, N–difluorocarbamate in the presence of an alkali metal complex salt and a higher metal halide, including Pt (IV), Ru (VIII) and Ir (VI) halides. For example, RuCl8 may be used with KMnO4.
Manufacture of Urethanes
imperial chemical industries ltd British Patent 1,129,551
The production of urethanes by reacting hydroxylic compounds, CO and N compounds, such as azoxy compounds, is catalysed by transition metal complexes, especially phosphine complexes of Ir, Rh, Pt and Pd.
Preparation of Glyoxal
imperial chemical industries ltd British Patent 1,130,760
C2H4 is oxidised to glyoxal by HNO3 in aqueous medium in the presence of a catalytic mixture of a Li salt and Pd metal or a Pd compound, e.g. PdCl2 and Li2CO3.
uniroyal inc. British Patent 1,131,160
The polymerisation of cyclic olefines is catalysed by an Ir trihalide, especially a complex of the trihalide with an olefine, e.g. Ir monochloride cyclooctene.
Platinum Catalyst for SiH-Olefin Addition Reactions
general electric co. (new york)
U.S. Patent 3,385,876
A catalyst soluble in organic solvents is produced by reacting H2PtCl6 with Ti alkoxy, e.g. Ti(OBu)4.
Catalyst for Cyclooctadiene Isomerisation
phillips petroleum co. U.S. Patent 3,387,045
An unconjugated cyclooctadiene is isomerised to a conjugated diene over a complex catalyst formed from a nitrile and a Pt or Pd chloride or bromide, e.g. bis(benzonitrile)palladium dichloride.
Oxalic Ester Production
union oil co. of california U.S. Patent 3,393,136
Oxalates are obtained when CO is reacted with a substantially anhydrous alcoholic medium containing 0.001−2 wt% of a Pt metal (e.g. PdCl2) and 0.05−5 wt% of a soluble cupric or ferric redox salt.
Allyl Complexes of Palladium
monsanto co. U.S. Patent 3,397,214
Pd catalysts and additives are obtained by reacting bis-aryl cyanide-Pd(II) dihalides with tetraalkyl-allenes to give tetraalkyl-allyl palladium dihalides.
e. i. du pont de nemours & co. U.S. Patent 3,397,252
Dienes are produced from monoethylenically unsaturated compounds having a terminal halogen atom by their reaction with a stannous salt in the presence of a Pt group metal, e.g. IrCl3, Na3IrCl6, PdCl2 or (Et4N)4Sn8Pt3Cl20.
Unsaturated Gamma-Lactone Production
badische anilin- & soda-fabrik a.g. German Patent 1,276,029
These lactones may be produced from olefines and CO at elevated temperatures and pressures in the presence of PdCl2/PdBr2/PdI2, optionally in the presence of excess halogen acid or Pd.
Production of Isopropenyl Carboxylic Esters
Method of Preparing Fuel Cell Catalysts
american cyanamid co. British Patent 1,123,957
Catalytic electrodes of enhanced activity are produced by reducing a noble metal compound, in the presence of an electroconductive filler, using a di- or tri-substituted silane containing a SiH group, dissolved in alcohol, so that the deposited noble metal has a crystallite size of 20–35Å. In an example graphite is suspended in C2H5OH and a mixture of H2PtCl6 and RhCl3 dissolved in the alcohol. Diphenyl silane is added to reduce the salts to Pt and Rh.
Electrochemical Combustion of Methanol
robert bosch g.m.b.h. British Patent 1,130,733
The fuel cell catalyst is a Raney alloy of Ru which one or more Group VIII Pt metals and/or Au, e.g. a 4:3:3 alloy of Ru, Ir and Au.
Hydrogen Diffusion Anode for a Fuel Cell
leesona corp. U.S. Patent 3,393,098
A sandwich anode of three layers is used which comprises (in contact with the electrolyte) a non-porous H2 diffusion membrane, a Group VIII metal black layer and a catalyst layer (in contact with the fuel). One combination that is proposed is Pd-Ag alloy/Pd black/Zn-Cu-Cr.
Porous Electrode Production
esso research & engineering co. U.S. Patent 3,395,049
A mixture is formed from a finely divided halogenated hydrocarbon polymer, an active catalyst (including Group VIII metals and alloys) and a decomposable particulate filler. The mixture is shaped, the shaped product is heated to decompose the filler and further catalytic metal is deposited in the pores of the product. A catalyst may be Pt-Ir or Pt-Re deposited on C.
ELECTRICAL AND ELECTRONIC ENGINEERING
Cermet Resistance Element
beckman instruments inc. U.S. Patent 3,386,165
Noble metal conductors are attached to cermet resistors by applying a mixture of glass frit and noble metal particles to both items and firing them in contact. “Noble metal” is especially Ag, Pd, Pt, Rh and their alloys.
Metallic Coatings on Printed Circuit Boards
matsushita electric industrial co. ltd U.S. Patent 3,391,455
A board base is dipped in a synthetic resin adhesive and then coated, by scattering, with a metal powder containing Cu, Fe, Co, Al, Ni, Au, Ag, Be, Pt, Pd, Rh or their alloys. The board is stoved after the powder has been pressed into the surface of the adhesive. The projecting particles of powder form a base for subsequent chemical (electroless) plating.
Production of a Tantalum Electrolytic Capacitor
Electrical Resistance Thermometers
rosemount engineering co. ltd British Patent 1,127,946
A strip of metal is formed into a roll with the adjacent layers insulated from one another, it is sliced in parallel planes normal to the axis of the roll to give spiral elements and these are attached to a ceramic disc. Pt foil may especially be treated in this way.
Noble Metal Thermometer Wires
deutsche gold- und silber-scheideanstalt German Patent 1,274,344
Noble metal, especially Pd wires are produced by making very fine powders by reduction at temperatures below 500°C, preferably below 350°C, to give a particle smaller than 0.06 mm. The powders are boiled in acidified water, dried at low temperature, compressed, sintered at 1300−1500°F for 2–8 hours and cold shaped to wire without an intermediate anneal. The wire is stress-relieving annealed at 1300−1500°C for 5–20 minutes.