Catalysts platinum-asbestos

The platinum asbestos is removed by filtration and the product which has deposited on this catalyst is dissolved in water. Alcohol is added to the combined filtered solution and washings, and the mixture is cooled with ice to precipitate the product. A second crop of crystals may be obtained by concentrating the solution under vacuum at room temperature, then cooling and adding hydrochloric acid until the pH is below 1. The crystals are thoroughly washed with ethanol. 

A support-effect such as demonstrated in the classical case of platinum asbestos is of negligible importance with ammonia catalysts except with osmium and ruthenium. 

Zelinsky and Turowa-Pollak141 describe the specific properties of an osmium catalyst. Hydrogenation on osmium catalysts usually occurs at lower temperatures than on platinum, palladium, or nickel catalysts. Osmium asbestos is a very resistant catalyst that can be used for months on end without loss in activity disadvantages are that osmium catalysts that are not supported on carriers must be frequently regenerated and that when the temperature exceeds 150° osmium tends to decompose the material under hydrogenation. 

Preparation of 30 per cent, palladium or platinum catalysts (charcoal or asbestos carrier). 

Method A. Cool a solution of the nitrate-free dichloride, prepared from or equivalent to 5 0 g. of palladium or platinum, in 50 ml. of water and 5 ml. of concentrated hydrochloric acid in a freezing mixture, and treat it with 50 ml. of formahn (40 per cent, formaldehyde) and 11 g. of the carrier (charcoal or asbestos). Stir the mixture mechanically and add a solution of 50 g. of potassium hydroxide in 50 ml. of water, keeping the temperature below 5°. When the addition is complete, raise the temperature to 60° for 15 minutes. Wash the catalyst thoroughly by decantation with water and finally with dilute acetic acid, collect on a suction filter, and wash with hot water until free from chloride or alkali. Dry at 100° and store in a desiccator. 

Broadly speaking, the differences in effectiveness of palladium and platinum catalysts are very small the choice will generally be made on the basis of availability and current price of the two metals. Charcoal is a somewhat more efficient carrier than asbestos. 

Balthis and Bailar6 obtained tris (ethylenediamine) chromium-(III) complexes by the oxidation of chromium(II) solutions, using a procedure somewhat similar to that used for the synthesis of cobalt (III) com plexes. Mori7 described the preparation of hexaamminechromium(III) salts from the oxidation of chromium (II) salts in the presence of ammonia. The results obtained in both syntheses have been erratic.8,9 Berman noted that the foregoing syntheses are rendered dependable by the use of a catalyst of activated platinum on asbestos. Schaeffer,100 in a subsequent study, independently used colloidal platinum as a catalyst but reported some difficulty in separating it from the product.106 The procedures recommended and described here are based on the use of platinized asbestos as the catalyst. 

Tenteleff Also spelled Tentelew. An early version of the Contact process for making sulfuric acid. The catalyst was platinum supported on asbestos. Invented in 1907 and operated by the Gesellschaft der Tentelewschen Chemischen Fabrik, St. Petersberg. 

Mkaline Fuel Cell The electrolyte for NASA s space shnttle orbiter fuel cell is 35 percent potassinm hydroxide. The cell operates between 353 and 363 K (176 and I94°F) at 0.4 MPa (59 psia) on hydrogen and oxygen. The electrodes contain platinnm-palladinm and platinum-gold alloy powder catalysts bonded with polytetraflnoro-ethylene (PTFE) latex and snpported on gold-plated nickel screens for cnrrent collection and gas distribution. A variety of materials, inclnding asbestos and potassinm titanate, are used to form a micro-porous separator that retains the electrolyte between the electrodes. The cell structural materials, bipolar plates, and external housing are nsnally nickel-plated to resist corrosion. The complete orbiter fuel cell power plant is shown in Fig. 24-48. 

The impregnation of porous nickel discs with CoPc was difficult because of the limited solubility of the chelate in the usual solvents. CoPc cathodes with carbon as substrate were therefore prepared for use in H2/O2 fuel cells. A mixture of 72 mg CoPc and 48 mg acetylene black, with PTFE as binder, was pressed into a nickel mesh of area 5 cm2. Electrodes of this type were tested in an H2/O2 fuel cell with 35% KOH electrolyte in an asbestos matrix at 80° C. Figure 5 compares the current/voltage characteristics of CoPc cathodes (14 mg/cm2) with those of other catalysts, including platinum (9 mg/cm2), silver (40 mg/cm2), and pure acetylene black (20 mg/cm2). An hydrogen electrode (9 mg Pt/cm2) was used as the anode in all tests. To facilitate comparison of the activity of different cathodes, the pure ohmic internal resistance of the cells (of the order of 0.02 ohm) was eliminated. 

The most active catalyst is platinum applied in finely divided form, for example platinised asbestos. Certain elements, especially arsenic and mercury, have a powerful effect in reducing the activity of the platinum, a quantity of arsenic equal to 0-2 per cent, of the weight of the platinum reducing the activity by 50 per cent.5 These poisons, as they are termed, also include less harmful substances such as antimony, lead, bismuth, etc. The presence of small quantities of rhodium, iridium or osmium in the platinum also causes diminished yields of trioxide, but the presence of palladium or ruthenium has the opposite effect.6... 

Although the forward reaction is favored by increase in pressure, this is not employed in practice since 97 to 99% conversion of sulfur dioxide to sulfur trioxide can be accomplished at the temperature specified here, provided suitable catalysts are used. The first catalyst used for this reaction consisted of finely divided platinum dispersed in asbestos, anhydrous magnesium sulfate, or silica gel. Other catalysts were later discovered. Mixtures of ferric and cupric oxides are useful, but these are less efficient than platinum. Certain mixtures containing vanadium pentoxide (V205) and other compounds of vanadium appear to be as good as or better than platinum. There has been much controversy over the relative merits of platinum and vanadium catalysts, and only time will provide the answer as to which is best. 

In heterogeneous catalysis, the solid catalyst is more effective when in a state of fine sub-division than when used in bulk. So, a lump of platinum will have much less catalytic activity than colloidal or platinised asbestos. Finely divided nickel is a better catalyst than lumps of solid nickel, because former occupies greater surface area than the latter. 

In 1962, Lesbre and Satge360 pointed out that trialkyl(alkylthio)germanes R3GeSR were formed by condensation of trialkylgermanes and thioles in the presence of asbestos platinum. Reduced nickel proved later to be the best catalyst for the reaction346. 

Carbon monoxide undergoes activated adsorption on the surface of palladium oxide. The maximum for this process, at about 350 mm. pressure, is at about 100°C. The gas taken up during activated adsorption can only be recovered as C02 for the most part (57). In a CO-air stream a slight initial reduction of PdO occurs at 23°C., but in the absence of oxygen, there is no reduction below 76°. This process of reduction decreases in rate with time and does not go to completion below 156°. Carbon dioxide, when present in the gas phase, inhibits the reduction of the palladium at 100°C. because it is adsorbed strongly by the PdO (56). Catalysts have been prepared by the deposition of palladium and platinum on asbestos, on silica gel, and on charcoal. 

Supported Platinum. Supported platinum catalysts have been prepared usually by impregnation method, using various supports such as charcoal,158 asbestos,159 silica,160 alumina,161 and silica-alumina,162 or by ion-exchange method with silica, silica-alumina, and zeolites, using cationic platinum salts.163,164... 

Pt-C (by Kaffer).158 To 10-12 g of active carbon mixed well with water is added an aqueous solution of the calculated amount of chloroplatinic acid. The mixture is warmed on a water bath for a few hours at 50°C. After cooling, a concentrated sodium carbonate solution is added until the mixture becomes alkaline. Then a hydrazine hydrate solution is added drop by drop under stirring. Whether the amount of hydrazine is sufficient to reduce the chloroplatinic acid can be readily determined by the decoloration of a permanganate solution. The platinum-carbon suspension is further warmed for 1-2 h on a water bath, filtered, and washed with hot water until the washing is free from chloride and alkali. After dried as fully as possible between filterpapers, the catalyst is dried for half a day over calcium chloride in vacuum. Kaffer used a 10% Pt-C thus prepared for the dehydrogenation of decalin and found it much more effective than Pt-asbestos by Zelinsky. Newhall used a 5% Pt-C by Kaffer for... 

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