Niobium separation from tantalum

Preferential reduction of niobium pentachloride to the trichloride by the excess of hydrogen still present is used in the next stage, to separate from tantalum pentachloride, which remains volatile, i.e. 

Separation of tantalum from niobium requires several complicated steps. Several methods are used to commercially produce the element, including electrolysis of molten potassium fluorotantalate, reduction of potassium fluorotantalate with sodium, or reacting tantalum carbide with tantalum oxide. Twenty five isotopes of tantalum are known to exist. Natural tantalum contains two isotopes. 

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. 

Opa.nte. There are two methods used at various plants in Russia for loparite concentrate processing (12). The chlorination technique is carried out using gaseous chlorine at 800°C in the presence of carbon. The volatile chlorides are then separated from the calcium—sodium—rare-earth fused chloride, and the resultant cake dissolved in water. Alternatively, sulfuric acid digestion may be carried out using 85% sulfuric acid at 150—200°C in the presence of ammonium sulfate. The ensuing product is leached with water, while the double sulfates of the rare earths remain in the residue. The titanium, tantalum, and niobium sulfates transfer into the solution. The residue is converted to rare-earth carbonate, and then dissolved into nitric acid. 

Other Metals. AH the sodium metal produced comes from electrolysis of sodium chloride melts in Downs ceUs. The ceU consists of a cylindrical steel cathode separated from the graphite anode by a perforated steel diaphragm. Lithium is also produced by electrolysis of the chloride in a process similar to that used for sodium. The other alkaH and alkaHne-earth metals can be electrowon from molten chlorides, but thermochemical reduction is preferred commercially. The rare earths can also be electrowon but only the mixture known as mischmetal is prepared in tonnage quantity by electrochemical means. In addition, beryIHum and boron are produced by electrolysis on a commercial scale in the order of a few hundred t/yr. Processes have been developed for electrowinning titanium, tantalum, and niobium from molten salts. These metals, however, are obtained as a powdery deposit which is not easily separated from the electrolyte so that further purification is required. 

The most common oxidation state of niobium is +5, although many anhydrous compounds have been made with lower oxidation states, notably +4 and +3, and Nb can be reduced in aqueous solution to Nb by zinc. The aqueous chemistry primarily involves halo- and organic acid anionic complexes. Virtually no cationic chemistry exists because of the irreversible hydrolysis of the cation in dilute solutions. Metal—metal bonding is common. Extensive polymeric anions form. Niobium resembles tantalum and titanium in its chemistry, and separation from these elements is difficult. In the soHd state, niobium has the same atomic radius as tantalum and essentially the same ionic radius as well, ie, Nb Ta = 68 pm. This is the same size as Ti ... 

Minor amounts of tantalum, tin, lead, bismuth, and other elements also occur ia the ferroniobium. After cooling for 12—30 h, the metal is separated from the slag and cmshed and si2ed for shipment. The recovery of niobium ia the alurninothermic reaction is 87—93%. Larger reactions generally give better recoveries. 

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. 

The separation of niobium from tantalum tluough the gaseous chlorides is carried out at higher temperature, about 900 K, and it is therefore to be expected, as is the case, that the thermodynamic data will provide a useful guide. These metals form a number of chlorides, mainly the ui- tetra- and pentachlorides. These latter are much more volatile than the tetrahalides, and the exchange reaction at 900 K... 

The tantalum dissolution process takes longer compared to the preparation of the corresponding niobium solution, therefore the solution is heated and a small amount of nitric acid is added. A grey precipitate indicates saturation of the solution. The prepared solution is separated from the precipitate by filtration and used as the initial solution. 

A residual phase, usually consisting of insoluble fluorides and oxyfluorides of alkali earth and rare earth metals, is separated from the solution by filtration. The mechanism of the chemical decomposition of raw materials of the tantalum- and niobium-containing oxide type seems to be complicated, and unfortunately, the process has yet to be adequately investigated. 

Another point is related to the high acidity level of the final solution, which leads to certain limitations in the subsequent technological steps. Specifically, the high acidity of the initial solution eliminates any possibility for selective extraction, i.e. sequential separation of tantalum and then of niobium. Due to the high concentration of acids, only collective extraction (of tantalum and niobium together) can be performed, at least at the first step. In addition, extraction from a highly acidic solution might cause additional contamination of the final products with antimony and other related impurities. In order to reduce the level of contaminants in the initial solution, some special additives are applied prior to the liquid-liquid extraction. For instance, some mineral acids and base metals are added to the solution at certain temperatures to cause the precipitation of antimony [455 - 457]. 

The cake is leached with water in order to dissolve tantalum and niobium (and other related compounds) in the form of fluoride salts of ammonium. Ammonium fluoroferrate and fluoromanganate are unstable in aqueous solutions of low acidity. It is assumed that iron and manganese will form precipitates of insoluble fluorides or oxyfluorides that can be separated from the solution by filtration. 

The main advantages of the method can be formulated as follows. First, hydrofluoric acid is not needed for the decomposition stage the amount of fluorine required for the raw material decomposition can be calculated and adjusted as closely as possible to the stoichiometry of the interaction. Since the leaching of the fluorinated material is performed with water, a significant fraction of the impurities are precipitated in the form of insoluble compounds that can be separated from the solution, hence the filtrated solution is essentially purified. There is no doubt that solutions prepared in this way can be of consistent concentrations of tantalum and niobium, independent of the initial raw material composition. 

Two main schemes exist for the separation and purification of tantalum and niobium using liquid-liquid extraction. The first is based on the collective extraction of tantalum and niobium from an initial solution into an organic phase so as to separate them from impurities that remain in the aqueous media, the raffinate. The separation of tantalum and niobium is subsequently performed by fractional stripping into two different aqueous solutions. In this case, stripping of niobium is performed using relatively weak acids prior to the stripping of tantalum. Fig. 125 presents a flow chart of the process. 

Substitution of fluoride ions by other suitable ions in the complex acid so as to separate the fluorine ions from tantalum and niobium (liquid-liquid interaction) ... 

Precipitation of niobium and tantalum compounds in forms that are suitable for separation from the aqueous media (liquid-solid interaction) ... 

The interaction described in Equation (148), in which C02 separates from the solution and ammonia hydroxide is formed, reduces the acidity of the solution causing precipitation of tantalum or niobium hydroxide. The hydroxide powder precipitated using ammonium carbonate is usually coarser and has better filtering properties. Changing the ammonium carbonate concentration and temperature of the solution allows some control over the particle size and filtering properties of the precipitated hydroxides. 

Minerals such as euxenite, fergusonite, samarskite, polycrase and loparite are highly refractory and complex in nature. These minerals may be opened up by treatment with hydrofluoric acid. While metals such as niobium, tantalum and titanium form soluble fluorides, rare earth elements form an insoluble residue of their fluorides. Such insoluble fluorides are filtered out of solution and digested with hot concentrated sulfuric acid. The rare earth sulfates formed are dissolved in cold water and thus separated from the insoluble mineral impurities. Rare earth elements in the aqueous solution are then separated by displacement ion exchange techniques outlined above. 

There are several processes for extracting and refining niobium from its ores. (Payton, P.H. 1981. Niobium and Niobium Compounds. In Kirk-Othmer Encyclopedia of Chemical Technology, 3 . ed., Vol, 15, pp. 820-827. New York Wiley Interscience). The process of choice depends on nature of the ore and end use intended for the metal. Some common steps in these recovery processes involve ore preconcentration, breaking or opening the ore, obtaining pure niobium compounds, reduction of niobium compounds to niobium metal, purification or refining metal and fabrication. If niobium is extracted from a niobium-tantalum ore, the most important step is separation of niobium from tantalum, both of which are chemically very similar. 

Separation of niobium from tantalum and impurity metals is the most important step in its extraction from the ore. It may be achieved by several methods that include solvent extraction, ion exchange, fractional crystallization, fractional sublimation, and other techniques. Solvent extraction is apphed mostly in several large-scale commercial processes. Although the classical fractional crystalhzation method forms effective separation, it is a tedious... 

Tantalum was discovered by the Swedish chemist Anders Ekeberg in 1802, although for a long time after his discovery many chemists believed tantalum and niobium were the same element. In 1866, Marignac developed a fractional crystallization method for separation of tantalum from niobium. Ekeberg named the element in honor of Tantalus, who was Niobe s father in Greek mythology. 

Separation of tantalum from niobium in hydrofluoric acid is carried out by solvent extraction due to solubility difference, using a suitable organic solvent such as methyl isobutyl ketone. At low acidity tantalum partitions from water into immiscible organic solvent leaving behind niobium in the aqueous HF extract. Tantalum is thus separated from this aqueous HF solution. The acidity of the aqueous HF solution is now increased and the solution again extracted with fresh methyl isobuty ketone to recover niobium, which partitions into the organic solvent, leaving any impurity that may remain dissolved in the HF solution. 

Tantalum can be separated from niobium by recrystallization of the double potassium fluorides. In the commercial process the ore is fused with caustic soda. The insoluble sodium niobate, sodium tantalate, and... 

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