Nickel elimination

Although the copper mediated Ullmann reaction is a well known method for biaryl synthesis, drastic conditions in the range of 150-280 °C are required. Zerovalent nickel complexes such as bis(l,5-cyclooctadiene)nickel or tetrakis(triphenylphosphine)nickel have been shown to be acceptable coupling reagents under mild conditions however, the complexes are unstable and not easy to prepare. The method using activated metallic nickel eliminates most of these problems and provides an attractive alternative for carrying out aryl coupling reactions(36,38). 

Data are limited on nickel concentrations in terrestrial invertebrates. Earthworms from uncontaminated soils may contain as much as 38 mg Ni/kg DW, and workers of certain termite species may normally contain as much as 5000 mg Ni/kg DW (Table 6.6). Larvae of the gypsy moth (Porthetria dispar) near a nickel smelter had 20.4 mg Ni/kg DW concentrations in pupae and adults were lower because these stages have higher nickel elimination rates than larvae (Bagatto et al. 1996). 

If these catalysts are heated to 80° C. in a stream of CO, nickel is removed from the carrier as nickel carbonyl that volatilizes out of the heated sample (7). The amount of nickel eliminated can be determined by heating the gas stream after it has passed the catalyst sample. A nickel mirror is then deposited on the wall of the reaction vessel and can be weighed. After one day about 90-95 % of the nickel proves to be removed. The remaining residues have surface areas (Fr) that still are related to the original Ni content... 

Other heavy fuel contaminants are metals (vanadium, nickel, sodium) coming from the crude oil itself or metallic salts (aluminum silicates) coming from catalysts in conversion steps. The aluminum silicates should not exceed 300 ppm (30 ppm of aluminum), for these materials exert a strong abrasive action on the engine cylinders and injection systems. They can however be eliminated partially by centrifuging and filtration. 

Fortunately, in the presence of excess copper(II)nitrate, the elimination reaction is an order of magnitude slower than the desired Diels-Alder reaction with cyclopentadiene, so that upon addition of an excess of cyclopentadiene and copper(II)nitrate, 4.51 is converted smoothly into copper complex 4.53. Removal of the copper ions by treatment with an aqueous EDTA solution afforded in 71% yield crude Diels-Alder adduct 4.54. Catalysis of the Diels-Alder reaction by nickel(II)nitrate is also... 

The resulting macrocyclic ligand was then metallated with nickel(II) acetate. Hydride abstraction by the strongly electrophilic trityl cation and proton elimination resulted in the formation of carbon-carbon double bonds (T.J. Truex, 1972). 

Hydrogen-storage alloys (18,19) are commercially available from several companies in the United States, Japan, and Europe. A commercial use has been developed in rechargeable nickel—metal hydride batteries which are superior to nickel—cadmium batteries by virtue of improved capacity and elimination of the toxic metal cadmium (see BATTERIES, SECONDARYCELLS-ALKALINe). Other uses are expected to develop in nonpolluting internal combustion engines and fuel cells (qv), heat pumps and refrigerators, and electric utility peak-load shaving. 

Many electroless coppers also have extended process Hves. Bailout, the process solution that is removed and periodically replaced by Hquid replenishment solution, must still be treated. Better waste treatment processes mean that removal of the copper from electroless copper complexes is easier. Methods have been developed to eliminate formaldehyde in wastewater, using hydrogen peroxide (qv) or other chemicals, or by electrochemical methods. Ion exchange (qv) and electro dialysis methods are available for bath life extension and waste minimi2ation of electroless nickel plating baths (see... 

Pyrometa.llurgica.1 Processes. Nickel oxide ores are processed by pyrometaHurgical or hydrometaHurgical methods. In the former, oxide ores are smelted with a sulfiding material, eg, gypsum, to produce an iron—nickel matte that can be treated similarly to the matte obtained from sulfide ores. The iron—nickel matte may be processed in a converter to eliminate iron. The nickel matte then can be cast into anodes and refined electrolyticaHy. 

Although most nickel sensitization results from nonoccupational exposures, nickel dermatitis was historically a problem in workplaces where there was a high risk of continuous contact with soluble nickel, eg, in electroplating (qv) shops. Improved personal and industrial hygiene has largely eliminated this problem. However, there are a few occupations involving wet nickel work, particularly where detergents faciUtate the penetration of skin by nickel, where hand eczema may occur (126). 

To reduce or eliminate the scattering of cadmium in the environment, the disposal of nickel —cadmium batteries is under study. Already a large share of industrial batteries are being reclaimed for the value of their materials. Voluntary battery collection and reclaiming efforts are under way in both Europe and Japan. However the collection of small batteries is not without difficulties. Consideration is being given to deposit approaches to motivate battery returns for collection and reclamation. 

Dehalogenation of monochlorotoluenes can be readily effected with hydrogen and noble metal catalysts (34). Conversion of -chlorotoluene to Ncyanotoluene is accompHshed by reaction with tetraethyl ammonium cyanide and zero-valent Group (VIII) metal complexes, such as those of nickel or palladium (35). The reaction proceeds by initial oxidative addition of the aryl haHde to the zerovalent metal complex, followed by attack of cyanide ion on the metal and reductive elimination of the aryl cyanide. Methylstyrene is prepared from -chlorotoluene by a vinylation reaction using ethylene as the reagent and a catalyst derived from zinc, a triarylphosphine, and a nickel salt (36). 

Lateritic Ores. The process used at the Nicaro plant in Cuba requires that the dried ore be roasted in a reducing atmosphere of carbon monoxide at 760°C for 90 minutes. The reduced ore is cooled and discharged into an ammoniacal leaching solution. Nickel and cobalt are held in solution until the soflds are precipitated. The solution is then thickened, filtered, and steam heated to eliminate the ammonia. Nickel and cobalt are precipitated from solution as carbonates and sulfates. This method (8) has several disadvantages (/) a relatively high reduction temperature and a long reaction time (2) formation of nickel oxides (J) a low recovery of nickel and the contamination of nickel with cobalt and (4) low cobalt recovery. Modifications to this process have been proposed but all include the undesirable high 760°C reduction temperature (9). 

The best heat resistance is obtained when nickel dibutyldithiocarbamate [13927-77-0] (NBC) is incorporated into the compound. NBC contributes to the heat resistance by causing the elimination of unused sulfonyl chloride groups which are then unavailable for additional cross-linking during heat aging. The presence of large amounts of Htharge probably also result in some ionic cross-link formation. 

The dry powder process has several additional advantages over the wet process. For example, much less waste of enamel occurs because the dry over-spray is airborne and recycled in a closed system. No-pidde ground coats have broadened the apphcation of both wet-process and dry-process systems. These enamels are appHed over cleaned-only metal. Thus the problems of disposing of pickling acid wastes containing iron sulfates and nickel wastes are eliminated (see Metal surface treatments) (7). 

---