Chromite compounds

FIGURE 4.3 Conductivity of chromite compounds in reducing atmospheres at 700°C [41,... 

However, compounds known to be double oxides in the solid state are named as such for example, Cr2Cu04 (actually Cr203 CuO) is chromium(III) copper(II) oxide (and not copper chromite). 

Fig. 1. Simplified flow chart for the production of metallic chromium and chromium compounds from 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). 

Around 1800, the attack of chromite [53293-42-8] ore by lime and alkaU carbonate oxidation was developed as an economic process for the production of chromate compounds, which were primarily used for the manufacture of pigments (qv). Other commercially developed uses were the development of mordant dyeing using chromates in 1820, chrome tanning in 1828 (2), and chromium plating in 1926 (3) (see Dyes and dye intermediates Electroplating Leather). In 1824, the first chromyl compounds were synthesized followed by the discovery of chromous compounds 20 years later. Organochromium compounds were produced in 1919, and chromium carbonyl was made in 1927 (1,2). 

Compounds that have the empirical formulas MCr02 and DCr204 where M is a monovalent and D a divalent cation, are known as chromites. These are actually mixed oxides and probably are better written as M20-Cr203 and D0-Cr203, respectively. The oxides of D are largely spinels, ie, the oxygen atoms define a close-packed cubic array having the octahedral holes occupied by the Cr(III) cation and the tetrahedral holes occupied by D (54). Chromite ore is an important member of this class of oxides. 

Manufacture The primary iadustrial compounds of chromium made directly from chromite ore are sodium chromate, sodium dichromate, and chromic acid. Secondary chromium compounds produced ia quantity include potassium dichromate, potassium chromate, and ammonium dichromate. 

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). 

Ruthenium is excellent for hydrogenation of aliphatic carbonyl compounds (92), and it, as well as nickel, is used industrially for conversion of glucose to sorbitol (14,15,29,75,100). Nickel usually requires vigorous conditions unless large amounts of catalyst are used (11,20,27,37,60), or the catalyst is very active, such as W-6 Raney nickel (6). Copper chromite is always used at elevated temperatures and pressures and may be useful if aromatic-ring saturation is to be avoided. Rhodium has given excellent results under mild conditions when other catalysts have failed (4,5,66). It is useful in reduction of aliphatic carbonyls in molecules susceptible to hydrogenolysis. 

Chromium compounds as catalysts, 188 Chromium oxide in catalytic converter, 62 Chromium oxide catalysts, 175-184 formation of active component, 176,177 of Cr-C bonds, 177, 178 propagation centers formation of, 175-178 number of, 197, 198 change in, 183, 184 reduction of active component, 177 Clear Air Act of 1970, 59, 62 Cobalt oxide in catalytic converter, 62 Cocatalysts, 138-141, 152-154 Competitive reactions, 37-43 Copper chromite, oxidation of CO over, 86-88... 

Chromium, Cr, is a bright, lustrous, corrosion-resistant metal. Its name, which comes from the Greek word for color, was inspired by its colorful compounds. The metal is obtained from the mineral chromite, FeCr204, by reduction with carbon in an electric arc furnace ... 

The only important ore of chromium is chromite, FeCr2 O4. Reduction of chromite with coke gives ferrochrome, an iron-chromium compound FeCr2 04(.5 ) + 4 C(.5 ) FeCr2(.5 ) + 4 CO(g) Ferrochrome is... 

Chromium compounds of high purity can be produced from chromite ore without reduction to the free metal. The first step is the roasting of chromite ore in the presence of sodium carbonate ... 

In a review of the course and mechanism of the catalytic decomposition of ammonium perchlorate, the considerable effects of metal oxides in reducing the explosion temperature of the salt are described [1], Solymosi s previous work had shown reductions from 440° to about 270° by dichromium trioxide, to 260° by 10 mol% of cadmium oxide and to 200°C by 0.2% of zinc oxide. The effect of various concentrations of copper chromite , copper oxide, iron oxide and potassium permanganate on the catalysed combustion of the propellant salt was studied [2], Similar studies on the effects of compounds of 11 metals and potassium dichromate in particular, have been reported [3], Presence of calcium carbonate or calcium oxide has a stabilising effect on the salt, either alone or in admixture with polystyrene [4],... 

Ding X, Liu Y, Gao L, and Guo L. Effects of cation substitution on thermal expansion and electrical properties of lanthanum chromites. J. Alloys Compounds 2006 425 318-3 22. 

Copper Chromate Black, pigment for plastics, 7 369t Copper chromite, molecular formula, properties, and uses, 6 563t Copper chromite black spinel, formula and DCMA number, 7 348t Copper citrate, molecular formula, 6V638t Copper compounds, 7 767-783 analytical methods, 7 773-776 economic aspects, 7 773 health and safety factors, 7 776 properties and manufacture, 7 768-773 uses, 7 776-780... 

Iron cobalt chromite black spinel, formula and DCMA number, 7 348t Iron(II) complexes, 14 530-531 Iron complex geometries, 14 531 Iron compounds, 14 530-561... 

The first source of chromium was found in the mineral crocoite. Today it is obtained from the mineral chromite (FeCr O ), which is found in Cuba, Zimbabwe, South Africa, Turkey, Russia, and the Philippines. Chromite is an ordinary blackish substance that was ignored for many years. There are different grades and forms of chromium ores and compounds, based on the classification of use of the element. Most oxides of chromium are found mixed with other metals, such as iron, magnesium, or aluminum. 

The hydrogenation of carbonyl groups in compounds containing ethylenic bonds to obtain the corresponding unsaturated alcohols is a very important reaction in the fine chemicals field. Extensive work has been carried out to develop heterogeneous catalysts for these reachons, copper chromite being one of the first systems studied [69, 70]. Transihon metals are widely used catalysts for these reachons. 

Catalysts suitable specifically for reduction of carbon-oxygen bonds are based on oxides of copper, zinc and chromium Adkins catalysts). The so-called copper chromite (which is not necessarily a stoichiometric compound) is prepared by thermal decomposition of ammonium chromate and copper nitrate [50]. Its activity and stability is improved if barium nitrate is added before the thermal decomposition [57]. Similarly prepared zinc chromite is suitable for reductions of unsaturated acids and esters to unsaturated alcohols [52]. These catalysts are used specifically for reduction of carbonyl- and carboxyl-containing compounds to alcohols. Aldehydes and ketones are reduced at 150-200° and 100-150 atm, whereas esters and acids require temperatures up to 300° and pressures up to 350 atm. Because such conditions require special equipment and because all reductions achievable with copper chromite catalysts can be accomplished by hydrides and complex hydrides the use of Adkins catalyst in the laboratory is very limited. 

Raney nickel at 250° and 100-200atm afforded 88% yield of ethyl 3-cyclo-hexylpropanoate [1068], and hydrogenation of the same compound over copper chromite at 250° and 220atm gave 83% yield of 3-phenylpropanol [7057] (p. 158). 

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]. 

Gombustion catalysts are needed to obtain complete combustion of AN composite propellants. Ghromium compounds such as chromium trioxide (Gt203), ammonium dichromate ((NH4)2Ct207), and copper chromite (CuCr204) are known to... 

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