Zirconium, extraction of, from

Hafnium, determination of, in zirconium-hafnium solution, 3 69 extraction of, from cyrtolite and separation from zirconium, 3 67, 74... 

In France, Compagnie Europnene du Zirconium (CEZUS) now owned jointly by Pechiney, Eramatome, and Cogema, uses a separation (14) based on the extractive distillation of zirconium—hafnium tetrachlorides in a molten potassium chloride—aluminum trichloride solvent at atmospheric pressure at 350°C. Eor feed, the impure zirconium—hafnium tetrachlorides from the zircon chlorination are first purified by sublimation. The purified tetrachlorides are again sublimed to vapor feed the distillation column containing the solvent salt. Hafnium tetrachloride is recovered in an enriched overhead fraction which is accumulated and reprocessed to pure hafnium tetrachloride. 

MIBK is a highly effective separating agent for metals from solutions of their salts and is used in the mining industries to extract plutonium from uranium, niobium from tantalum, and zirconium from hafnium (112,113). MIBK is also used in the production of specialty surfactants for inks (qv), paints, and pesticide formulations, examples of which are 2,4,7,9-tetramethyl-5-decyn-4,7-diol and its ethoxylated adduct. Other appHcations include as a solvent for adhesives and wax/oil separation (114), in leather (qv) finishing, textile coating, and as a denaturant for ethanol formulations. 

Chlorination. In some instances, the extraction of a pure metal is more easily achieved from the chloride than from the oxide. Oxide ores and concentrates react at high temperature with chlorine gas to produce volatile chlorides of the metal. This reaction can be used for common nonferrous metals, but it is particularly useful for refractory metals like titanium (see Titanium and titanium alloys) and 2irconium (see Zirconium and zirconium compounds), and for reactive metals like aluminum. 

Others. Oxahc acid is used for the production of cobalt, as a raw material of various agrochemicals and pharmaceuticals, for the manufacture of electronic materials (76—83), for the extraction of tungsten from ore (84), for the production of metal catalysts (85,86), as a polymerization initiator (87—89), and for the manufacture of zirconium (90) and beryhium oxide (91). 

In the initial thiocyanate-complex Hquid—Hquid extraction process (42,43), the thiocyanate complexes of hafnium and zirconium were extracted with ether from a dilute sulfuric acid solution of zirconium and hafnium to obtain hafnium. This process was modified in 1949—1950 by an Oak Ridge team and is stiH used in the United States. A solution of thiocyanic acid in methyl isobutyl ketone (MIBK) is used to extract hafnium preferentially from a concentrated zirconium—hafnium oxide chloride solution which also contains thiocyanic acid. The separated metals are recovered by precipitation as basic zirconium sulfate and hydrous hafnium oxide, respectively, and calcined to the oxide (44,45). This process is used by Teledyne Wah Chang Albany Corporation and Western Zirconium Division of Westinghouse, and was used by Carbomndum Metals Company, Reactive Metals Inc., AMAX Specialty Metals, Toyo Zirconium in Japan, and Pechiney Ugine Kuhlmann in France. 

High molecular weight primary, secondary, and tertiary amines can be employed as extractants for zirconium and hafnium in hydrochloric acid (49—51). With similar aqueous-phase conditions, the selectivity is in the order tertiary > secondary > primary amines. The addition of small amounts of nitric acid increases the separation of zirconium and hafnium but decreases the zirconium yield. Good extraction of zirconium and hafnium from ca 1 Af sulfuric acid has been effected with tertiary amines (52—54), with separation factors of 10 or more. A system of this type, using trioctylarnine in kerosene as the organic solvent, is used by Nippon Mining of Japan in the production of zirconium (55). 

Extraction of Bertrandite. Bertrandite-containing tuff from the Spor Mountain deposits is wet milled to provide a thixotropic, pumpable slurry of below 840 p.m (—20 mesh) particles. This slurry is leached with sulfuric acid at temperatures near the boiling point. The resulting beryUium sulfate [13510-49-1] solution is separated from unreacted soflds by countercurrent decantation thickener operations. The solution contains 0.4—0.7 g/L Be, 4.7 g/L Al, 3—5 g/L Mg, and 1.5 g/L Fe, plus minor impurities including uranium [7440-61-1/, rare earths, zirconium [7440-67-7] titanium [7440-32-6] and zinc [7440-66-6]. Water conservation practices are essential in semiarid Utah, so the wash water introduced in the countercurrent decantation separation of beryUium solutions from soflds is utilized in the wet milling operation. 

The extraction of metals by liquid amines has been widely investigated and depends on the formation of anionic complexes of the metals in aqueous solution. Such applications are illustrated by the use of Amberlite LA.l for extraction of zirconium and hafnium from hydrochloric acid solutions, and the use of liquid amines for extraction of uranium from sulphuric acid solutions.42,43... 

In the drying of compound intermediates of refractory and reactive metals, particular attention is given to the environment and to the materials so that the compound does not pick up impurities during the process. A good example is the drying of zirconium hydroxide. After the solvent extraction separation from hafnium, which co-occurs with zirconium in the mineral zircon, the zirconium values are precipitated as zirconium hydroxide. The hydroxide is dried first at 250 °C for 12 h in air in stainless steel trays and then at 850 °C on the silicon carbide hearth of a muffle furnace. 

Solvent extraction is often applied to separate two chemically similar metals such as nickel/ cobalt, adjacent rare earths, niobium/tantalum, zirconium/hafnium, etc. For the purpose of elaboration, the example of the separation of two chemically similar elements such as zirconium and hafnium from their nitrate solution, using TBP as an extractant is considered. The solvent extraction process in this case is chemically constant (K) is given by ... 

The use of sulfoxides in the separation of zirconium and hafnium has met with some success, and diheptyl sulfoxide has been patented as an extractant for this purpose (185). Mixtures of sulfoxides have also been used in the extraction of zirconium and hafnium from acid solutions (463). 

In aqueous solution, zirconium(IV) and hafnium(IV) form complexes M(NCS)4-", where n = 1-8.104 Selective extraction of hafnium thiocyanate complexes from acidic aqueous solution by methyl isobutyl ketone is a widely used industrial method for the separation of zirconium and hafnium. Separation methods have been reviewed by Vinarov.105... 

The reasons for the selective extraction of hafnium over zirconium from thiocyanate solutions by solvating extractants are not well understood. Hence, a recent review of the chemistry of these metals described the separation process but offered no explanation for the observed selectivity.306 There is no evidence that differences in the stabilities of the thiocyanate complexes of hafnium(IV) and zirconium(IV) are responsible for the selective extraction of the former, since the formation constants of the respective complexes are essentially identical for both metals.307 However, there is some indication that the hafnium thiocyanates are more readily solvated by the extractant than are the corresponding complexes of zirconium. 

Most frequently, the number of thiocyanate moieties in the extracted complex is equal to two, although some authors consider that the extracted species changes progressively to the trithio-cyanato complex (x = 1) and tetrathiocyanato complex (x = 0) on the successive extraction of a given aqueous phase.312 IR data show that the thiocyanate groups are bound to the metal via the nitrogen atom,315 as would be expected from the distinct A-character of zirconium(IV). 

As was observed in the case of the extraction of zirconium and hafnium from nitrate media, it is probable that the different tendencies of the metals towards hydrolysis has some effect on the selectivity observed,298 313 expecially in view of the proved extraction of hydroxo complexes. The extraction of both metals decreases markedly in the presence of sulfate ions in the aqueous phase (a feature that is utilized in the stripping of the loaded hafnium with sulfuric acid), although the selectivity for hafnium over zirconium is simultaneously increased on account of the higher stability constants of the inextractable sulfato complexes of zirconium.298... 

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