Nickel alloys carbonyl

In atomization, a stream of molten metal is stmck with air or water jets. The particles formed are collected, sieved, and aimealed. This is the most common commercial method in use for all powders. Reduction of iron oxides or other compounds in soHd or gaseous media gives sponge iron or hydrogen-reduced mill scale. Decomposition of Hquid or gaseous metal carbonyls (qv) (iron or nickel) yields a fine powder (see Nickel and nickel alloys). Electrolytic deposition from molten salts or solutions either gives powder direcdy, or an adherent mass that has to be mechanically comminuted. 

Nickel [7440-02-0] Ni, recognized as an element as early as 1754 (1), was not isolated until 1820 (2). It was mined from arsenic sulfide mineral deposits (3) and first used in an alloy called German Silver (4). Soon after, nickel was used as an anode in solutions of nickel sulfate [7786-81 A] NiSO, and nickel chloride [7718-54-9] NiCl, to electroplate jewelry. Nickel carbonyl [13463-39-3] Ni(C02)4, was discovered in 1890 (see Carbonyls). This material, distilled as a hquid, decomposes into carbon monoxide and pure nickel powder, a method used in nickel refining (5) (see Nickel and nickel alloys). 

Reduction of various aldehydes and ketones by Raney nickel alloy in aqueous sodium hydroxide below 20° was recommended by Cook 316 this gave good yields of the corresponding alcohols from salicylaldehyde, vanillin, acetophenone, and other carbonyl compounds. 

In the INCO process the matte is crushed and a nickel alloy is magnetically separated. This fraction also contains the cobalt. The alloy is melted and granulated, and the nickel is volatilized as Ni(CO),inthe carbonyl process. The residue is dissolved and cobalt obtained as cathode plates in an electrolytic process. 

Following the intense work on the carbonylation reaction during the 1920s by BASF and British Celanese [1], Reppe and his research group discovered that cobalt diiodide operating at 680 bar and 250 °C catalyzes this reaction [2, 3]. But it was necessary to solve harsh corrosion problems, until 1950, when highly resistant molybdenum/nickel alloys (whose trademark is Hastelloy ) were discovered and commercialized [1]. The process developed by BASF in 1960 was not selective as the yield in acetic acid was 90% based on methanol and 70% based on CO [4] due to the large amounts of CO2 coproduced by the water-gas shift (WGS) reaction (Eq. 20.2). 

The matte can be treated in different ways, depending on the copper content and on the desired product. In some cases, the copper content of the Bessemer matte is low enough to allow the material to be cast directly into sulfide anodes for electrolytic refining. Usually it is necessary first to separate the nickel and copper sulfides. The copper—nickel matte is cooled slowly for ca 4 d to faciUtate grain growth of mineral crystals of copper sulfide, nickel—sulfide, and a nickel—copper alloy. This matte is pulverized, the nickel and copper sulfides isolated by flotation, and the alloy extracted magnetically and refined electrolyticaHy. The nickel sulfide is cast into anodes for electrolysis or, more commonly, is roasted to nickel oxide and further reduced to metal for refining by electrolysis or by the carbonyl method. Alternatively, the nickel sulfide may be roasted to provide a nickel oxide sinter that is suitable for direct use by the steel industry. 

Nickel is a silver-white, lustrous, hard, malleable, ductile, ferromagnetic metal that is relatively resistant to corrosion and is a fair conductor of heat and electricity. Nickel is a ubiquitous trace metal that occurs in soil, water, air, and in the biosphere. The average content in the earth s crust is about 0.008%. Nickel ore deposits are accumulations of nickel sulfide minerals (mostly pentlandite) and laterites. Nickel exists in five major forms elemental nickel and its alloys inorganic, water-soluble compounds (e.g., nickel chloride, nickel sulfate, and nickel nitrate) inorganic, water-insoluble compounds (e.g., nickel carbonate, nickel sulfide, and nickel oxide) organic, water-insoluble compounds and nickel carbonyl Ni(CO). ... 

Reduction of unsaturated ketones to saturated alcohols is achieved by catalytic hydrogenation using a nickel catalyst [49], a copper chromite catalyst [50, 887] or by treatment with a nickel-aluminum alloy in sodium hydroxide [555]. If the double bond is conjugated, complete reduction can also be obtained with some hydrides. 2-Cyclopentenone was reduced to cyclopentanol in 83.5% yield with lithium aluminum hydride in tetrahydrofuran [764], with lithium tris tert-butoxy)aluminium hydride (88.8% yield) [764], and with sodium borohydride in ethanol at 78° (yield 100%) [764], Most frequently, however, only the carbonyl is reduced, especially with application of the inverse technique (p. 21). 

Nickel carbonate (see Nickel and nickel compounds) Nickel carbonyl (see Nickel and nickel compounds) Nickel chloride (see Nickel and nickel compounds) Nickel-gallium alloy (see Nickel and nickel compounds) Nickel hydroxide (see Nickel and nickel compounds) Nickelocene (see Nickel and nickel compounds)... 

In addition to its importance in alloys (for example, alnico, vicalloy, and stellite), cobalt is of use as a catalyst in the Fisher-Tropsch process in which carbon monoxide is hydrogenated to a mixture of hydrocarbons. It appears likely here that one or more carbonyl derivatives of cobalt act as intermediates. Nickel is of importance in a number of alloys Monel metal, alnico, stainless steel, etc.). In a very finely divided state Raney nickel), it is of use to the organic chemist in hydrogenation reactions, for it will absorb large quantities of hydrogen gas with probable breakage of the molecules to atoms (p. 27). 

Various active nickel catalysts obtained not via reduction of nickel oxide with hydrogen have been described in the literature. Among these are the catalysts obtained by the decomposition of nickel carbonyl 10 by thermal decomposition of nickel formate or oxalate 11 by treating Ni-Si alloy or, more commonly, Ni-Al alloy with caustic alkali (or with heated water or steam) (Raney Ni) 12 by reducing nickel salts with a more electropositive metal,13 particularly by zinc dust followed by activation with an alkali or acid (Urushibara Ni) 14-16 and by reducing nickel salts with sodium boro-hydride (Ni boride catalyst)17-19 or other reducing agents.20-24... 

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