Lead chromite

The first chromium compound was discovered in the Ural mountains of Russia, during the latter half of the eighteenth century. Crocoite [14654-05-8] a natural lead chromate, found immediate and popular use as a pigment because of its beautihil, permanent orange-red color. However, this mineral was very rare, and just before the end of the same century, chromite was identified as a chrome bearing mineral and became the primary source of chromium [7440 7-3] and its compounds (1) (see Chromiumand chromium alloys). 

Recommendations by the ACGIH are classified as threshold limit values (TLV) based on 8-h TWA. Chromium metal and alloys, Cr(II) compounds and Cr(III) compounds, including chromite ore, have a TLV of 0.5 mg/m Cr in air. Water-soluble Cr(VI) compounds have a TLV of 0.05 mg/m Cr. Certain water-insoluble Cr(VI) compounds, ie, the chromates of 2inc, barium, calcium, lead, strontium, sintered chromic acid, and processing chromite ores, also have a TLV of 0.05 mg/m as well as a human carcinogen designation (145). 

Catalytic hydrogenation of furfural in the presence of copper chromite leads to furfuryl alcohol, the major intermediate of the furan resins Figure 28.1). 

The relatively high cost and lack of domestic supply of noble metals has spurred considerable efforts toward the development of nonnoble metal catalysts for automobile exhaust control. A very large number of base metal oxides and mixtures of oxides have been considered, especially the transition metals, such as copper, chromium, nickel, manganese, cobalt vanadium, and iron. Particularly prominent are the copper chromites, which are mixtures of the oxides of copper and chromium, with various promoters added. These materials are active in the oxidation of CO and hydrocarbons, as well as in the reduction of NO in the presence of CO (55-59). Rare earth oxides, such as lanthanum cobaltate and lanthanum lead manganite with Perovskite structure, have been investigated for CO oxidation, but have not been tested and shown to be sufficiently active under realistic and demanding conditions (60-63). Hopcalities are out-... 

Modification of the burning rates, pressure exponents, and temp coefficients of burning rate of the fluorocarbon composites has been accomplished with copper, lead, tin, sodium, ammonium and potassium fluoborates sodium, potassium, lithium, lead, copper and calcium fluorides potassium and ammonium dichromate lead and zinc stearate cesium carbonate potassium and ammonium sulfate copper chromite oxides of magnesium, copper and manganese boron zinc dust and carbon black (Ref 75)... 

The hydrogenation of HMF in the presence of metal catalysts (Raney nickel, supported platinum metals, copper chromite) leads to quantitative amounts of 2,5-bis(hydroxymethyl)furan used in the manufacture of polyurethanes, or 2,5-bis(hydroxymethyl)tetrahydrofuran that can be used in the preparation of polyesters [30]. The oxidation of HMF is used to prepare 5-formylfuran-2-carboxylic acid, and furan-2,5-dicarboxylic acid (a potential substitute of terephthalic acid). Oxidation by air on platinum catalysts leads quantitatively to the diacid. [32], The oxidation of HMF to dialdehyde was achieved at 90 °C with air as oxidizing in the presence of V205/Ti02 catalysts with a selectivity up to 95% at 90% conversion [33]. 

Schoenberg et al. (2008) presented the first set of Cr isotope data for rocks and Cr(ll) rich ores. Mantle derived rocks and chromite ores from layered intrusions have a uniform Cr/ Cr isotope ratio very close to the certified Cr standard NIST SRM 979. The Cr isotope composition of hydrothermal lead chromates is substantially heavier (S Cr from 0.6 to 1.0%o) than the rocks from which the chromium was leached. 

Phthalimide was hydrogenated catalytically at 60-80° over palladium on barium sulfate in acetic acid containing an equimolar quantity of sulfuric or perchloric acid to phthalimidine [7729]. The same compound was produced in 76-80% yield by hydrogenation over nickel at 200° and 200-250 atm [43 and in 75% yield over copper chromite at 250° and 190 atm [7730]. Reduction with lithium aluminum hydride, on the other hand, reduced both carbonyls and gave isoindoline (yield 5%) [7730], also obtained by electroreduction on a lead cathode in sulfuric acid (yield 72%) [7730]. 

The catalysts (lead and copper salts of aromatic acid in combination with carbon black) which were effective for DB and RDX-CMDB propellants were also found effective for dinitropiperazine (DNP) containing CMDB propellants [259]. Copper chromite (CC) and ferric oxide which are generally used for ballistic modification of composite propellants are also effective for CL-20-based aluminized CMDB propellants. However, CC is a better BRM [260]. 

The reaction of indolizines with dialkyl acetylenedicarboxylates in the presence of a dehydrogenating catalyst leads to 1,2-dicarbalkoxycycl-[3,2,2]azines.22 23 Methyl phenylpropiolate may be used instead, although attempts to effect reaction between indolizine and certain other dienophiles including diphenylacetylene, diethyl azodicarboxylate, and 1,3-cyclohexadiene were unsuccessful. Hydrolysis of the diesters yielded the corresponding acids. Subsequent decarboxylation proceeded in high yield using copper chromite in quinoline [Eq. (5)]. 

Although flotation was developed as a separation process for mineral processing and applies lo the sulfides of copper, lead, zinc, iron-molybdenum, cobalt, nickel, and arsenic and to nonsullides, such as phosphates, sodium chloride, potassium chloride, iron oxides, limestone, feldspar, fluorite, chromite, tungstates, silica, coal, and rhodochrosilc, flotation also applies to nonmineral separations. Flotation is used in the water disposal field, particularly in connection with petroleum waste water cleanup. 

Fig. 18. Comparison of a copper-chromite catalyst (Cu-Cr) and a production noble metal catalyst (II B). Aging time 140 hr, open symbols for fuel containing 0.2 g Pb/gal, closed symbols for lead-sterile fuel. [From Yao and Kummer (81).] (Reprinted with permission of the American Chemical Society.)...

In certain instances of poisoning, especially in the case of base metal catalysts, the deactivation can be simply explained by the formation of new bulk solid phases between the base metal and the poison. Examples are the formation of lead vanadates (14) in vanadia catalysts, or of sulfates in copper-chromite and other base metal catalysts (81). These catalyti-cally inactive phases are identifiable by X-ray diffraction. Often, the conditions under which deactivation occurs coincide with the conditions of stability of these inert phases. Thus, a base metal catalyst, deactivated as a sulfate, can be reactivated by bringing it to conditions where the sulfate becomes thermodynamically unstable (45). In noble metal catalysts the interaction is assumed to be, in general, confined to the surface, although bulk interactions have also been postulated. 

Chromium metal is commercially produced in the United States by the reduction of chromite ore with carbon, aluminum, or silicon, and subsequent purification. Sodium chromate and dichromate are produced by roasting chromite ore with soda ash. Most other chromium compounds are produced from sodium chromate and dichromate (Hartford 1979 Westbrook 1979). For example, basic chromic sulfate (Cr(0H)S04), commonly used in tanning, is commercially produced by the reduction of sodium dichromate with organic compounds (e.g., molasses) in the presence of sulfuric acid or by the reduction of dichromate with sulfur dioxide. Lead chromate, commonly used as a pigment, is produced by the reaction of sodium chromate with lead nitrate or by reaction of lead monoxide with chromic acid solution (IARC 1990). 

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