Zirconium processing production

The pyrochemical process of zirconium-hafnium separation is particularly attractive not only because it makes the entire process of nuclear-grade zirconium metal production from zircon more economical than that involving a hydrometallurgical separation stage, but also... 

Fluoride is known to separate zirconium fission product and plutonium from solvent degradation products. (5) Since fluoride is used to speed dissolution of thoria in nitric acid, and is already present in thorium solvent extraction process feed solutions, it was the first choice as an agent to use to improve thorium-DPB separation. 

For the Hanford Production Reactors, the gas system protects the moderator. In NPR, the reactor atmosphere must also protect the zirconium process tubes from hydrogen embrittlement by maintaining the oxide film on the OD of the process tube. At the present operating temperatures, hydrogen embrittlement of the zirconium tubes in KET and KW Reactors will not be a problem. 

Fig. 9.7. Extraction of hafnium (zirconium by-product, oxide, carbide, iodide decomposition process).

Formation of CpCp Zr(SiH2Ph)Cl by the method of equation 4 is rapid, but complicated by decomposition of the zirconium silyl product to CpCp ZrHCl and H(SiHPh)nH. The latter decomposition reaction represents a (T-bond metathesis process that converts Zr-Si and Si-H bonds to Zr-H and Si-Si bonds. To obtain more detailed information on how an M-SiH2Ph derivative could decompose to metal hydride and... 

Electro-refining process production of pure Zirconium... 

Decomposition of Zircon. Zircon sand is inert and refractory. Therefore the first extractive step is to convert the zirconium and hafnium portions into active forms amenable to the subsequent processing scheme. For the production of hafnium, this is done in the United States by carbochlorination as shown in Figure 1. In the Ukraine, fluorosiUcate fusion is used. Caustic fusion is the usual starting procedure for the production of aqueous zirconium chemicals, which usually does not involve hafnium separation. Other methods of decomposing zircon such as plasma dissociation or lime fusions are used for production of some grades of zirconium oxide. 

Hafnium dioxide is formed by ignition of hafnium metal, carbide, tetrachloride, sulfide, boride, nitride, or hydrous oxide. Commercial hafnium oxide, the product of the separation process for zirconium and hafnium, contains 97—99% hafnium oxide. Purer forms, up to 99.99%, are available. 

Eabrication techniques must take into account the metallurgical properties of the metals to be joined and the possibiUty of undesirable diffusion at the interface during hot forming, heat treating, and welding. Compatible alloys, ie, those that do not form intermetaUic compounds upon alloying, eg, nickel and nickel alloys (qv), copper and copper alloys (qv), and stainless steel alloys clad to steel, may be treated by the traditional techniques developed for clads produced by other processes. On the other hand, incompatible combinations, eg, titanium, zirconium, or aluminum to steel, require special techniques designed to limit the production at the interface of undesirable intermetaUics which would jeopardize bond ductihty. 

Condensation of metal vapors followed by deposition on cooler surfaces yields metal powders as does decomposition of metal hydrides. Vacuum treatment of metal hydrides gives powders of fine particle size. Reaction of a metal haHde and molten magnesium, known as the KroU process, is used for titanium and zirconium. This results in a sponge-like product. 

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. 

Mixed zircon, coke, iron oxide, and lime reduced together produce zirconium ferrosiUcon [71503-20-3] 15 wt % Zr, which is an alloy agent. Fused zirconia [1314-23-4] has been made from zircon but baddeleyite is now the preferred feed for the production of fused zirconia and fused alumina—zirconia by electric-arc-fumace processing. 

Electrolysis. Electrowinning of zirconium has long been considered as an alternative to the KroU process, and at one time zirconium was produced electrolyticaHy in a prototype production cell (70). Electrolysis of an aH-chloride molten-salt system is inefficient because of the stabiUty of lower chlorides in these melts. The presence of fluoride salts in the melt increases the stabiUty of in solution, decreasing the concentration of lower valence zirconium ions, and results in much higher current efficiencies. The chloride—electrolyte systems and electrolysis approaches are reviewed in References 71 and 72. The recovery of zirconium metal by electrolysis of aqueous solutions in not thermodynamically feasible, although efforts in this direction persist. 

Zirconium phosphate [13772-29-7] also absorbs cesium and other radioactive-decay daughter products, and has been proposed as part of permanent disposal systems for nuclear fuel waste processing. 

Carbonates. Basic zirconium carbonate [37356-18-6] is produced in a two-step process in which zirconium is precipitated as a basic sulfate from an oxychloride solution. The carbonate is formed by an exchange reaction between a water slurry of basic zirconium sulfate and sodium carbonate or ammonium carbonate at 80°C (203). The particulate product is easily filtered. Freshly precipitated zirconium hydroxide, dispersed in water under carbon dioxide in a pressure vessel at ca 200—300 kPa (2—3 atm), absorbs carbon dioxide to form the basic zirconium carbonate (204). Washed free of other anions, it can be dissolved in organic acids such as lactic, acetic, citric, oxaUc, and tartaric to form zirconium oxy salts of these acids. 

The scale of production also influences efficiency. Small-scale batch processing for metals such as titanium, tungsten, and zirconium leads to higher energy use and costs. 

In the chemical process industry molybdenum has found use as washers and bolts to patch glass-lined vessels used in sulphuric acid and acid environments where nascent hydrogen is produced. Molybdenum thermocouples and valves have also been used in sulphuric acid applications, and molybdenum alloys have been used as reactor linings in plant used for the production of n-butyl chloride by reactions involving hydrochloric and sulphuric acids at temperatures in excess of 170°C. Miscellaneous applications where molybdenum has been used include the liquid phase Zircex hydrochlorination process, the Van Arkel Iodide process for zirconium production and the Metal Hydrides process for the production of super-pure thorium from thorium iodide. 

CVD developed slowly in the next fifty years and was limited mostly to extraction and pyrometallurgy for the production of high-purity refractory metals such as tantalum, titanium, and zirconium. Several classical CVD reactionswere developedatthattimeincludingthecarbonyl cycle (the Mond process), the iodide decomposition (the de Boer-Van Arkelprocess)andthemagnesium-reduction reaction (the Kroll process). 

Note that the main difference between zirconium hydride and tantalum hydride is that tantalum hydride is formally a d 8-electron Ta complex. On the one hand, a direct oxidative addition of the carbon-carbon bond of ethane or other alkanes could explain the products such a type of elementary step is rare and is usually a high energy process. On the other hand, formation of tantalum alkyl intermediates via C - H bond activation, a process already ob-... 

Examples of metals which are prepared by the metallothermic reduction of oxides include manganese, chromium, vanadium, zirconium, and niobium. In a manner similar to the production of magnesium by the Pidgeon process, some of the rare earth metals have been produced by the metallothermic reduction-distillation process. 

Metallothermic reduction of chlorides has been the basis of some very important processes for reactive metals production. Examples include the Kroll and Hunter processes for the preparation of zirconium and titanium, and calcium or lithium reduction processes for the rare earths. 

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