Chromium-uranium oxides

Carbide-based cermets have particles of carbides of tungsten, chromium, and titanium. Tungsten carbide in a cobalt matrix is used in machine parts requiring very high hardness such as wire-drawing dies, valves, etc. Chromium carbide in a cobalt matrix has high corrosion and abrasion resistance it also has a coefficient of thermal expansion close to that of steel, so is well-suited for use in valves. Titanium carbide in either a nickel or a cobalt matrix is often used in high-temperature applications such as turbine parts. Cermets are also used as nuclear reactor fuel elements and control rods. Fuel elements can be uranium oxide particles in stainless steel ceramic, whereas boron carbide in stainless steel is used for control rods. 

Strangely enough, a combination similar to the ammonia catalyst, iron oxide plus alumina, yielded particularly good results (32). Together with Ch. Beck, the author found that other combinations such as iron oxide with chromium oxide, zinc oxide with chromium oxide, lead oxide with uranium oxide, copper oxide with zirconium oxide, manganese oxide with chromium oxide, and similar multicomponent systems were quite effective catalysts for the same reaction (33). 

Oxides.—Amongst the simple oxides may be classed —oxide of chromium, oxide of iron, oxide of uranium, oxide of manganese, oxide of zinc, oxide of cobalt, oxide of antimony, oxide of copper, oxide of tin. 

Certain types of catalyst uranium oxide and chromium oxide may be used as a promoter. This is reported to give a higher resistance to catalyst poisoning by sulfur components and a lower tendency to form carbon deposits. 

In a much earlier patent, the removal of organics from exhaust gases by oxidation over a supported uranium oxide catalyst was reported by Hofer and Anderson [39]. The catalyst was 4% U3O8 supported on alumina spheres. The authors used the incipient wetness technique to impregnate alumina with uranyl nitrate solution. In this case the catalyst precursors were calcined at 700°C for 3 h to decompose the uranium salt. The use of other uranium compounds as starting materials was mentioned and these included uranyl acetate, uranium ammonium carbonate and uranyl chloride. The alumina-supported catalyst had a surface area of ca 400m g and further added components, such as copper, chromium and iron, were highlighted as efficient additives to increase activity. 

The catalysts were evaluated by exposure to a simulated automobile exhaust gas stream composed of 0.2% isopentane, 2% carbon monoxide, 4% oxygen and a balance of nitrogen. The temperature required to oxidize the isopentane and carbon monoxide was used to compare catalyst performance. The chromium-promoted catalyst oxidized isopentane at the lowest temperature, and a mixed chromium/copper-promoted catalyst proved the most efficient for oxidizing carbon monoxide and isopentane. It is interesting to note that the test rig used a stationary engine with 21 pounds of catalyst. Although the catalyst was very effective it is difficult to envisage uranium oxide catalysts employed for emission control of mobile sources. 

T1 ecent investigations have shown that chromium, manganese, cobalt, nickel, copper, and zinc oxides react with uranium oxides at elevated temperatures to form double oxides with the formulas MUO4 and MU3O10. Table I lists eight compounds for which some structural and thermal stability information has been reported. 

Among the transition metals from chromium through zinc, iron remains the only element for which no double oxide formation with uranium oxide has been reported. Both the l.T and 1 3 compounds of mainganese, cobalt, and copper have been prepared, while only the 1 1 compound of chromium, and the 1 3 compound of nickel and zinc are known. 

O2CI2N2RUC12H8, Ruthenium(II), dicarbo-nyldichloro(2,2 -bipyridine)-, 25 108 02CrF2, Chromium fluoride oxide, 24 67 O2F2U, Uranium(VI), difluorodioxo-,... 

Studies of the decomposition of methanol over various catalysts show that the same catalysts are active toward the decomposition reaction cat pressures of one atmosphere as are active toward the synthesis at the higher pressures. Indeed, to Patart is attributed the statement that the results from the work of Sabatier on the catalytic decomposition of methanol led directly to the use of certain of the methanol synthesis catalysts.188 144 Smith and Hawk 145 found that zinc oxide made by igniting die carbonate, mixtures of zinc and chromium oxides in the atomic proportions of 4 zinc to 1 chromium, mixtures of zinc and uranium oxides,... 

Cermet fuel is one of the advanced concepts that has been considered in the case of thorium. It envisages kernels of uranium oxide coated with nickel and chromium dispersed in a matrix of thorium metal. A certain level of success has been achieved in coating uranium oxide micro spheres with nickel. 

Manning, Ball, and Menis (162) have carried out polarographic and coulometric reductions of molybdenum (VI) in a nitrilotriacetic acid medium and have applied their findings to the analysis of thorium-uranium oxide mixtures. The determination of molybdenum in steel using coulometric techniques has been reported by Ibrahim and Nair (163) who reduced molybdenum at —0.40 V vs. SCE in a sodium acetate buffered chloride medium. Chromium interference can be removed by pre-reduction with alcohol. The catalytic effect of lower oxidation states of molybdenum in the reduction of perchlorate has been used as an indirect electro-analytical method for the determination of perchlorate (159, 164). 

Any canning metal had to be compatible not only with the uranium oxide fuel but with carbon dioxide. A form of stainless steel (containing 20% chromium and 25% nickel together with niobium) was found to be satisfactory at temperatures up to about 850°C. It had a melting point of almost 1,500°C. The maximum can surface temperature selected was 650°C (this meant the system could produce steam at the same temperature as conventional power stations), which allowed for local hot spots. One drawback to stainless steel was that it had a relatively high cross-section area for thermal neutrons, which meant using enriched fuel, of the order of 2.5% enrichment. 

Catalysts used for preparing amines from alcohols iaclude cobalt promoted with tirconium, lanthanum, cerium, or uranium (52) the metals and oxides of nickel, cobalt, and/or copper (53,54,56,60,61) metal oxides of antimony, tin, and manganese on alumina support (55) copper, nickel, and a metal belonging to the platinum group 8—10 (57) copper formate (58) nickel promoted with chromium and/or iron on alumina support (53,59) and cobalt, copper, and either iron, 2iac, or zirconium (62). 

Other ions which are reduced in the reductor to a definite lower oxidation state are those of titanium to Ti3+, chromium to Cr2+, molybdenum to Mo3+, niobium to Nb3+, and vanadium to V2 +. Uranium is reduced to a mixture of U3 + and U4+, but by bubbling a stream of air through the solution in the filter flask for a few minutes, the dirty dark-green colour changes to the bright apple-green colour characteristic of pure uranium(I V) salts. Tungsten is reduced, but not to any definite lower oxidation state. 

With the exception of iron(II) and uranium(IV), the reduced solutions are extremely unstable and readily re-oxidise upon exposure to air. They are best stabilised in a five-fold excess of a solution of 150g of ammonium iron(III) sulphate and 150 mL of concentrated sulphuric acid per litre [approximately 0.3M with respect to iron] contained in the filter flask. The iron(II) formed is then titrated with a standard solution of a suitable oxidising agent. Titanium and chromium are completely oxidised and produce an equivalent amount of iron(II) sulphate molybdenum is re-oxidised to the Mo(V) (red) stage, which is fairly stable in air, and complete oxidation is effected by the permanganate, but the net result is the same, viz. Mo(III)- Mo(VI) vanadium is re-oxidised to the V(IV), condition, which is stable in air, and the final oxidation is completed by slow titration with potassium permanganate solution or with cerium(IV) sulphate solution. 

Biological activity can be used in two ways for the bioremediation of metal-contaminated soils to immobilize the contaminants in situ or to remove them permanently from the soil matrix, depending on the properties of the reduced elements. Chromium and uranium are typical candidates for in situ immobilization processes. The bioreduction of Cr(VI) and Ur(VI) transforms highly soluble ions such as CrO and UO + to insoluble solid compounds, such as Cr(OH)3 and U02. The selenate anions SeO are also reduced to insoluble elemental selenium Se°. Bioprecipitation of heavy metals, such as Pb, Cd, and Zn, in the form of sulfides, is another in situ immobilization option that exploits the metabolic activity of sulfate-reducing bacteria without altering the valence state of metals. The removal of contaminants from the soil matrix is the most appropriate remediation strategy when bioreduction results in species that are more soluble compared to the initial oxidized element. This is the case for As(V) and Pu(IV), which are transformed to the more soluble As(III) and Pu(III) forms. This treatment option presupposes an installation for the efficient recovery and treatment of the aqueous phase containing the solubilized contaminants. 

Mellor, 1940, Vol. 8, 436 1943, Vol. 11, 162 1942, Vol. 12, 32 Pyrophoric chromium attains incandescence in the oxide, while calcium, potassium and uranium need heating before ignition occurs, when combustion is brilliant in the 53% oxygen content. 

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