Zirconium tetrachloride, reduction

Sodium tetrahydridoborate I zirconium tetrachloride Reductions with sodium tetrahydridoborate/zirconium tetrachloride under mild conditions... 

The production of sihcon tetrachloride by these methods was abandoned worldwide in the early 1980s. Industrial tetrachlorosilane derives from two processes associated with trichlorosilane, the direct reaction of hydrogen chloride on sihcon primarily produced as an intermediate for fumed sihca production, and as a by-product in the disproportionation reaction of trichlorosilane to silane utilized in microelectronics. Substantial quantities of tetrachlorosilane are produced as a by-product in the production of zirconium tetrachloride, but this source has decreased in the 1990s owing to reduction in demand for zirconium in nuclear facihties (see Nuclearreactors). The price of tetrachlorosilane varies between l/kg and 25/kg, depending on grade and container. 

Chlorination. Historically, the production of zirconium tetrachloride from zircon sand involved first a reduction to carbide nitride (see above) followed by the very exothermic reaction of the cmshed carbide nitride with chlorine gas in a water-cooled vertical shaft furnace ... 

Reduction. BrezeHus attempted the first reduction of zirconium in 1824 by the reaction of sodium with potassium fiuorozirconate. However, the first pure ductile metal was made in 1925 by the iodide thermal-dissociation method. The successfiil commercial production of pure ductile zirconium via the magnesium reduction of zirconium tetrachloride vapor in an inert gas atmosphere was the result of the intense research efforts of KroU and... 

Obtaining pure ductile zirconium by reduction of the oxide is particularly difficult because of the tendency of hot zirconium to dissolve considerable amounts of oxygen, making the metal britde at room temperature. Therefore, it is common practice to reduce oxygen-free zirconium tetrachloride. 

Other Reductions. Ductile, pure zirconium has been made by a two-stage sodium reduction of zirconium tetrachloride (68) in which the tetrachloride and sodium are continuously fed into a stirred reactor to form zirconium dichloride [13762-26-0], heating with additional sodium yields zirconium metal. Leaching with water removes the sodium chloride from the zirconium. Bomb reduction of pure zirconium tetrafluoride with calcium also produces pure metal (69). 

The tlrree impurities, iron, silicon and aluminium are present in the metal produced by the Kroll reduction of zirconium tetrachloride by magnesium to the extent of about 1100 ppm. After dre iodide refining process tire levels of these impurities are 350, 130 aird 700ppm respectively. The relative stabilities of the iodides of these metals compared to that of zirconium can be calculated from the exchange reactions... 

The Kroll process for tire reduction of tire halides of refractory metals by magnesium is exemplified by the reduction of zirconium tetrachloride to produce an impure metal which is subsequently refined with the van Arkel process to produce metal of nuclear reactor grade. After the chlorination of the impure oxide in the presence of carbon... 

The above reaction shows that the oxychloride decomposes at the sublimation temperature into the volatile tetrachloride and the nonvolatile oxide. Reduction starts as soon as the chloride vapour contacts the molten magnesium, and this exothermic reaction raises the temperature of the reaction mixture. The temperature of the reduction crucible is maintained in the range of 800 to 875 °C. The process is carefully controlled by matching the sublimation rate of zirconium tetrachloride with the reduction rate. The conclusion of the reduction is indicated by a fall in temperature and pressure. 

Zirconium metal is produced from its tetrachloride by reduction with magnesium by the Kroll process. The oxide obtained above is converted to zirconium tetrachloride by heating with carbon and chlorine. In practice, the oxide is mixed with lampblack, powdered sugar, and a little water, and pelletized. The dried pellet is then heated with chlorine in a chlorinator to produce ziro-conium tetrachloride ... 

Zirconium tetrachloride is reduced by heating with sodium, potassium or magnesium at high temperatures. Such reduction of tetrachloride has been the commerical method of producing zirconium metal ... 

The zirconium tetrachloride product must then be purified before reduction to metal. In particular, hafnium must be removed to less than 100 ppm Hf Zr because of the high neutron absorption cross-section it exhibits, and phosphorus and aluminum must be removed to even lower specifications due to their deleterious metallurgical impact on the final zirconium alloys. The tetrachloride product is first dissolved in water under carefully controlled conditions to produce an acidic ZrOCl2 solution. This solution is complexed with ammonium thiocyanate, and contacted with methyl isobutyl ketone (MIBK) solvent in a series of solvent extraction columns. Advantage is taken of the relative solubilities of Zr, Hf, and Fe thiocyanate complexes to accomplish a high degree of separation of hafnium and iron from the zirconium. 

Neutral Ti(CO)6 is an extremely unstable compound which decomposed even below -220 °C, as shown by matrix isolation spectroscopy [165]. The much more stable phosphine derivatives Ti(CO)3(dmpe)2, Ti(CO)5(dmpe), Ti(CO)5(PMe3)2, Ti(CO)4(PMe3)3 have been isolated [166-168]. In contrast, the dianionic salt [Ti(CO)6] (53) is thermally much more stable and decomposes only above 200 C. Complex 53 was obtained by reductive carbonylation of Ti(CO)3(dmpe)2 by alkali metal naphthalenides in the presence of cryptand [169]. Carbonylation of 79 also produces 53 [170]. The naph-thalenide-assisted reductive carbonylation of the zirconium tetrachloride afforded the zirconium analog [Zr(CO)6] (54) [171], which was also derived by carbonylation of the tris(diene) dianion 45 [150]. One anion [R3Sn] effectively stabilizes Ti(CO)e as an air stable monoanionic salt, [R3SnTi(CO)J [172]. 

Sulphur halides and dialkyl disulphides have been used to obtain a variety of aryithk) and alkytthio derivatives of phenols generally by electrophilic substitution. For example, phenol was treated with zirconium tetrachloride, heated to 156°C under nitrogen, kept at this temperature overnight and after reduction of this to 100°C, diethyidisulphide was added. The mixture was heated to remove ethanethiol and the product, 2-(ethylthio)phenol, isolated in 41% yield (ref. 116). 

The reduction of zirconium tetrachloride in a carrier salt with sodium as a reducing agent may be examined next. Again, as described before, complete deoxidation of the bath before reduction is the essential condition for success, if ductile metal is wanted. Zirconium tetrachloride is soluble in sodium chloride or potassium chloride (48) and a salt with about 25% zirconium tetrachloride can be melted without excessive zirconium chloride losses. Such a bath can even be obtained from powdery commercial zirconium silicide and iron dichloride, which react when heated and deliver a stream of zirconium tetrachloride, contaminated with some titanium tetrachloride and silicon tetrachloride. The gas so produced can be condensed in a fused salt bath such as potassium chloride-sodium chloride, in which only the zirconium tetrachloride dissolves (47), To obtain a low oxide metal after reduction with sodium, the conditions for fluo salt deoxidation must be observed. This process of zirconium production has no special interest, except for obtaining powder for getter purposes. A carrier salt, which might introduce oxide, is not wanted, as the reaction itself liberates sodium chloride. 

It is often desirable to employ some hydride equivalent as a nucleophile to convert epoxides to simple alcohols (i.e., reductive cleavage). Toward this end, racemic epoxides 70 can be regioselectively reduced to an enantiomerically enriched mixture of stereoisomeric alcohols 71 by treatment with zirconium tetrachloride-sodium borohydride in the presence of L-proline as a... 

The acylation of arenes with alcohols has been shown to be possible using a palladium chloride catalyst in the presence of f-butylhydroperoxide. In 2-arylpyridines, substitution is directed to the ortho-position and, after initial paUadation, the formation of intermediate (59) is likely before reductive elimination yields the acylated product. The regioselective acetoxylation of indoles, at the 3-position, has been achieved using the palladium-catalysed reaction with phenyliodonium acetate. 3-Acyl indoles may also be prepared using acetyl chlorides with zirconium tetrachloride as a Lewis acid catalyst. 

Winning of zirconium metal is commonly performed by a batch metallothermic reduction of zirconium tetrachloride using magnesium metal according to the original process devised by Kroll at the US Bureau of Mines (USBM) and summarized by the following reaction scheme ... 

Sodium metal is a strong reducing agent, and this accounts for many of its major uses. For example, it is used to obtain metals such as titanium and zirconium by reduction of their compounds. Titanium is a strong metal used in airplane and spacecraft manufacture. It is produced by reduction of titanium tetrachloride, TiCl4, obtained by chemical processing of titanium ores. The overall process can be written as follows ... 

The pyrometallurgical methods were developed based on the differences between zirconium and hafnium in oxidation and reduction characteristics [11, 12] volatility [13-16] electrochemical properties [17-19] and molten metal-molten salt equilibrium [20, 21], The extractive distillation process, using carbochlori-nation of zircon [13], is in operation by CEZUS in France. Both chlorides are sublimated and run through a vertical distillation column containing molten aluminium chloride and potassium chloride. Both hafnium and zirconium tetrachloride chlorides dissolve, but hafnium tetrachloride has a higher vapour pressure and is therefore condensed from the top of the column in a hafnium-enriched mixture. The zirconium tetrachloride is partitioned to a liquid phase and recovered from a salt, typically containing less than 50 ppm hafnium. 

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