Nickel chromite

Bis(trirnethylsiloxy)spiro[2.3]hex-4-ene (70 g. 0.27 mol) in anhyd cyclohexane (250 mL) was hydrogenated over a modified nickel chromite catalyst at 25 "C and under 100 atm pressure. After the absorption of hydrogen had ceased, the catalyst was filtered off and the solution was evaporated to remove cyclohexane. The residue was distilled under vacuum to give the product as a colorless liquid yield 55 g (78%) bp 92-94°C/12 Torr. 

SYNS CHROMIUM NICKEL OXIDE NICKEL CHROMITE NICKEL CHROMIUM OXIDE... 

NICKEL CHROMATE see NDAIOO NICKEL CHROMITE see NDAIOO NICKEL CHROMUM OXIDE see NDAIOO NICKEL, COMPOUND mth pi-CYCLOPENTADIENYL (1 2) see NDA500... 

Nickel Chromite, NiO.CrjOg, is prepared in an analogous manner to the cobalt salt (see also p. 8). 

In general, nickel in its various forms requires elevated temperature and pressure conditions for the catalytic reduction of pyridines. Hydrogenations with nickel on keiselguhr (4) or nickel chromite (5), for example, employ similar rigorous conditions. Copper chromite (6) (copper chromium oxide) has also been investigated. With this catalyst temperature conditions are usually higher than with nickel catalysts. There is a report of the use of a palladium catalyst in the reduction of some 2-(/3-hydroxyalkyl) pyridines at 130° and 200 atmospheres pressure (7). 

The effect, for this reaction, is apparently peculiar to catalysts of the nickel chromite type, since the addition of thiophene to a system containing Raney nickel, or of either thiophene or biphenyl sulfide to a similar system containing either platinum or palladium, did not lead to similar results. It may be noted that this reaction is not one involving the isolation of an intermediate product and the action of the sulfur compound seems difficult to explain. In another paper, by Adkins and Billica (44), it was also shown that the hydrogenation of ethyl lactate to 1,2-propanediol with Raney nickel is accelerated by adding small quantities of triethylamine. 

Reduction. Hydrogenation of dimethyl adipate over Raney-promoted copper chromite at 200°C and 10 MPa produces 1,6-hexanediol [629-11-8], an important chemical intermediate (32). Promoted cobalt catalysts (33) and nickel catalysts (34) are examples of other patented processes for this reaction. An eadier process, which is no longer in use, for the manufacture of the 1,6-hexanediamine from adipic acid involved hydrogenation of the acid (as its ester) to the diol, followed by ammonolysis to the diamine (35). 

Method 2 cobalt, nickel, copper, and copper chromite. 

Dicyclohexylarnine may be selectively generated by reductive alkylation of cyclohexylamine by cyclohexanone (15). Stated batch reaction conditions are specifically 0.05—2.0% Pd or Pt catalyst, which is reusable, pressures of 400—700 kPa (55—100 psi), and temperatures of 75—100°C to give complete reduction in 4 h. Continuous vapor-phase amination selective to dicyclohexylarnine is claimed for cyclohexanone (16) or mixed cyclohexanone plus cyclohexanol (17) feeds. Conditions are 5—15 s contact time of <1 1 ammonia ketone, - 3 1 hydrogen ketone at 260°C over nickel on kieselguhr. With mixed feed the preferred conditions over a mixed copper chromite plus nickel catalyst are 18-s contact time at 250 °C with ammonia alkyl = 0.6 1 and hydrogen alkyl = 1 1. 

The vapor-phase conversion of aniline to DPA over a soHd catalyst has been extensively studied (18,22). In general, the catalyst used is pure aluminum oxide or titanium oxide, prepared under special conditions (18). Promoters, such as copper chromite, nickel chloride, phosphoric acid, and ammonium fluoride, have also been recommended. Reaction temperatures are usually from 400 to 500°C. Coke formed on the catalyst is removed occasionally by burning. In this way, conversions of about 35% and yields of 95% have been reported. Carba2ole is frequently a by-product. 

Uses ndReactions. Nerol (47) and geraniol (48) can be converted to citroneUol (27) by hydrogenation over a copper chromite catalyst (121). In the absence of hydrogen and under reduced pressure, citroneUal is produced (122). If a nickel catalyst is used, a mixture of nerol, geraniol, and citroneUol is obtained and such a mixture is also useful in perfumery. Hydrogenation of both double bonds gives dimethyl octanol, another useful product. 

The preparation of methyl 12-ketostearate from methyl ricinoleate has been accompHshed using copper chromite catalyst. The ketostearate can also be prepared from methyl ricinoleate in a two-step process using Raney nickel. The first step is a rapid hydrogenation to methyl 12-hydroxystearate, the hydrogen coming from the catalyst, followed by a slower dehydrogenation to product (50,51). 

This reaction is favored by moderate temperatures (100—150°C), low pressures, and acidic solvents. High activity catalysts such as 5—10 wt % palladium on activated carbon or barium sulfate, high activity Raney nickel, or copper chromite (nonpromoted or promoted with barium) can be used. Palladium catalysts are recommended for the reduction of aromatic aldehydes, such as that of benzaldehyde to toluene. 

An acidic solvent is recommended for use with palladium. Other catalysts that have been used for this reduction include copper chromite and any of the three Raney catalysts, cobalt, iron, or nickel. 

Palladium and platinum (5—10 wt % on activated carbon) can be used with a variety of solvents as can copper carbonate on siHca and 60 wt % nickel on kieselguhr. The same is tme of nonsupported catalysts copper chromite, rhenium (VII) sulfide, rhenium (VI) oxide, and any of the Raney catalysts, copper, iron, or nickel. 

The anode material in SOF(7s is a cermet (rnetal/cerarnic composite material) of 30 to 40 percent nickel in zirconia, and the cathode is lanthanum rnanganite doped with calcium oxide or strontium oxide. Both of these materials are porous and mixed ionic/electronic conductors. The bipolar separator typically is doped lanthanum chromite, but a metal can be used in cells operating below 1073 K (1472°F). The bipolar plate materials are dense and electronically conductive. 

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. 

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-... 

Schlatter et al. found that their data with copper chromite agrees better with 0.7 order for CO concentrations (53). For crystals of nickel oxide and chromium oxide, Yu Yao and Kummer have found that the kinetics depend on CO or hydrocarbon around 0.55 order and depend on oxygen around 0.45 order (79). Hertl and Farrauto found evidence that CO adsorbs on copper as a carbonyl group, and adsorbs on chromium oxide as a unidentate carbonate. They found that the kinetics depends on CO to the first order, and depends on oxygen to the zero order (80). 

Hexavalent chromium and metals such as zinc and nickel that are present as impurities in the chromites ore are predominant pollutants associated with the sodium dichromate plant. They are generally removed through alkaline precipitation, clarification, filtration, and settling processes. The wastewater is treated with sodium sulfide to reduce hexavalent chromium to trivalent chromium,... 

Palladium catalysts, mostly palladium on carbon and Pearlman s catalyst, are used for the hydrogenolysis of the benzyl—nitrogen bond. However, in some cases, platinum, nickel, and copper chromite catalysts have also been used. 

Presence of 5% of copper(II) chloride caused explosion to occur at 170°C [1]. Of the series of additives copper chromite, copper chloride, nickel oxide, iron oxide, magnesium oxide, the earlier members have the greatest effect in increasing the sensitivity of the perchlorate to heat, impact and friction. 

Das, G. K. Acharya, S. Anand, S. Das, R. P. Acid pressure leaching of nickel-containing chromite over burden in the presence of additives. Hydrometallurgy 1995, 39, 117-128. 

Catalyst, alumina, 34, 79 35, 73 ammonium acetate, 31, 25, 27 copper chromite, 31, 32 36, 12 cuprous oxide-silver oxide, 36, 36, 37 ferric nitrate, hydrated, 31, 53 piperidine, 31, 35 piperidine acetate, 31, 57 Raney nickel, 36, 21 sulfuric acid, 34, 26 Catechol, 33, 74 Cetylmalonic acid, 34, 16 Cetylmalonic ester, 34,13 Chlorination, by sulfuryl chloride, 33, 45 ... 

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