Potassium heptafluorotantalate

Potassium Heptafluorotantalate. Potassium heptafluoiotantalate [16924-00-8], K TaF, ciystallizes in colodess, rhombic needles. It hydroly2es in Foiling water containing no excess of hydrofluoric acid. The solubility of potassium heptafluorotantalate in hydrofluoric acid decreases from 60 g/100 mL at 100°C to 0.5 g/100 mL at room temperature. The different solubility characteristics of K TaF and K NbOF are the fundamental basis of the Matignac process (16). A phase diagram exists for the system K TaF —NaCl—NaF—KCl (68). Potassium heptafluorotantalate has an LD q value of 2500 mg/kg. The recommended TWA maximum work lace exposure for K TaF in air is 2.5 mg /m (fluoride base) (69). 

Solvent Extraction. The industrial separation of tantalum from niobium was carried out historicahy by the Marignac process of fractional crystallization of potassium heptafluorotantalate and potassium heptafluoroniobate (15,16) or the long-estabhshed Fansteel process (17), which involved the decomposition of the ore by a caustic fusion procedure. Processors have replaced these expensive processes by procedures based on solvent extraction. This technique was developed in the United States at Ames Laboratory and the U.S. Bureau of Mines (18). Figure 2 shows the flow sheet of an industrial instahation for the hydrometahurgical processing of tantalum—niobium raw materials. 

Tantalum Compounds. Potassium heptafluorotantalate [16924-00-8] K TaF, is the most important tantalum compound produced at plant scale. This compound is used in large quantities for tantalum metal production. The fluorotantalate is prepared by adding potassium salts such as KCl and KF to the hot aqueous tantalum solution produced by the solvent extraction process. The mixture is then allowed to cool under strictiy controlled conditions to get a crystalline mass having a reproducible particle size distribution. To prevent the formation of oxyfluorides, it is necessary to start with reaction mixtures having an excess of about 5% HF on a wt/wt basis. The acid is added directiy to the reaction mixture or together with the aqueous solution of the potassium compound. Potassium heptafluorotantalate is produced either in a batch process where the quantity of output is about 300—500 kg K TaFy, or by a continuously operated process (28). 

It was assumed that tantalum, when added to the melt in the form of potassium heptafluorotantalate, K2TaF7, interacts with KF or KC1 to form a compound with an increased tantalum coordination number of up to eight. The compound is present in the melt in its dissociated form, yielding potassium ions and octa-coordinated complexes of tantalum, namely TaFg3 or TaF7Cl3. ... 

Tantalum powder is produced by reduction of potassium heptafluoro-tantalate, K2TaF7, dissolved in a molten mixture of alkali halides. The reduction is performed at high temperatures using molten sodium. The process and product performance are very sensitive to the melt composition. There is no doubt that effective process control and development of powders with improved properties require an understanding of the complex fluoride chemistry of the melts. For instance, it is very important to take into account that changes both in the concentration of potassium heptafluorotantalate and in the composition of the background melt (molten alkali halides) can initiate cardinal changes in the complex structure of the melt itself. 

The optimal temperature range for the fluorination process was found to be about 230-290°C. The resulting cake was leached with water. The prepared solution was separated from the precipitate by regular filtration and the separated insoluble precipitate was identified as lithium fluoride, LiF. The solution contained up to 90 g/1 Ta205. Solution acidity was relatively low, with a typical pH = 3-4, and was suitable for the precipitation of potassium heptafluorotantalate, K2TaF7, tantalum hydroxide or further purification by liquid-liquid extraction after appropriate adjustment of the solution acidity [113]. 

Potassium heptafluorotantalate, K2TaF7, or as it is called by its commercial name K-salt, is a starting material for tantalum metal production. K-salt is produced by adding potassium fluoride, KF, or potassium chloride, KC1, to a tantalum strip solution that results from a liquid-liquid extraction process. In order to prevent hydrolysis and co-precipitation of potassium oxyfluoro-tantalate, a small excess of HF is added to the solution [24]. Another way to avoid the possible formation and co-precipitation of oxyfluoride phases is to use potassium hydrofluoride, KHF2, as a potassium-containing agent. The yield of the precipitation depends mostly on the concentration of the potassium-containing salt and is independent of the HF concentration [535]. 

The main properties of potassium heptafluorotantalate in solid, molten and dissolved states were discussed in previous chapters of the monograph and are also collected and discussed in review [536]. 

The particle size of precipitated potassium heptafluorotantalate is one of the more important parameters. In order to achieve a certain particle size, potassium salts are added to the hot tantalum strip solution as a hot solution. The mixture is cooled down at a specific rate in order to enable the precipitation and ciystallization of K-salt in the form of small, individual crystals. 

Potassium heptafluorotantalate, K2TaF7, precipitates in the form of transparent needles. The precipitated particles must not be too fine, since fine powder usually promotes co-precipitation and adsorption of some impurities from the solution. Even niobium can be adsorbed by the surface of K2TaF7 developed during precipitation, as shown by Herak et al. [535]. On the other hand, the precipitation of large K-salt crystals should not be strived for either. Laboratory and industrial experience indicates that excessively large crystals usually contain small drops of solution trapped within the crystals. This occluded solution can remain inside of the crystal until drying and will certainly lead the hydrolysis of the material. 

Precipitated K—salt crystals are carefully filtrated and washed so as to separate them from the mother solution. Drying of filtrated K-salt is also a very delicate and important process that must be performed under conditions that avoid hydrolysis of the material. Potassium heptafluorotantalate is sensitive to water, basic compounds and alcohols, especially at elevated temperatures. The main product of K-salt hydrolysis is Marignac s salt. For a long time it was believed that the composition of Marignac s salt is K/Ta Fg. However, X-ray crystal structure analysis and precise chemical analysis of the... 

Based on the above composition, the hydrolysis of potassium heptafluorotantalate can be described as follows ... 

Additional purification of the product and improvement of particle size and shape can be achieved by re-ciystallization. The process consists of sequential dissolutions of potassium heptafluorotantalate in appropriate solutions at increased temperatures, filtration of the solution to separate possible insoluble parts of the product and cooling of the filtrated solution at a certain rate. The precipitated crystals are filtrated, washed and dried to obtain the final product. Re-crystallization can be performed both after filtration of the preliminary precipitated salt or after drying if the quality of the product is not sufficient. HF solutions of low concentrations are usually used for re-ciystallization. In general, even water can be used as a solvent if the process is performed fast enough. Nevertheless, practical experience suggested the use of a 30—40% HF solution within the temperature interval of 80-25°C, and a cooling rate of about 8-10°C per hour. The above conditions enable to achieve an acceptable process yield and good performance of the product. 

Table 67 presents some properties of potassium heptafluorotantalate, K2TaF7, as compared with potassium heptafluoniobate, K2NbF7. 

Only two processes of tantalum metal production are of worldwide commercial significance. These are the electrolysis of fluoride-chloride melts containing potassium heptafluorotantalate, K TaF , and tantalum oxide, Ta20s, and the reduction with sodium of K-salt or K—salt that is dissolved in potassium fluoride-chloride melts. 

Significant improvement of tantalum powder properties was achieved by the application of molten alkali halides as solvents for potassium heptafluorotantalate, K2TaF7. Variation of the initial concentration of K2TaF7 in the melt, stirring and rate of sodium loading enable a well-controllable production of tantalum powder with a wide variety of specific charges. Heller and Martin [590] proposed the use of a reactor equipped with a stirrer in 1960. Fig. 142 shows a typical scheme of the reactor [24, 576]. All metal parts of the reactor are made of nickel or nickel alloy. 

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