Niobium solubility

Solvent extraction techniques are useful in the quantitative analysis of niobium. The fluoro complexes are amenable to extraction by a wide variety of ketones. Some of the water-insoluble complexes with organic precipitants are extractable by organic solvents and colorimetry is performed on the extract. An example is the extraction of the niobium—oxine complex with chloroform (41). The extraction of the niobium—pyrocatechol violet complex with tridodecylethylammonium bromide and the extraction of niobium—pyrocatechol—sparteine complex with chloroform are examples of extractions of water-soluble complexes. Colorimetry is performed on the extract (42,43). Colorimetry may also be performed directly on the water-soluble complex, eg, using ascorbic acid and 5-nitrosahcyhc acid (44,45). 

Niobium Pent chloride. Niobium pentachloride can be prepared in a variety of ways but most easily by direct chlorination of niobium metal. The reaction takes place at 300—350°C. Chlorination of a niobium pentoxide—carbon mixture also yields the pentachloride however, generally the latter is contaminated with niobium oxide trichloride. The pentachloride is a lemon-yeUow crystalline soHd that melts to a red-orange Hquid and hydrolyzes readily to hydrochloric acid and niobic acid. It is soluble in concentrated hydrochloric and sulfuric acids, sulfur monochloride, and many organic solvents. 

Niobium Pentabromide. Niobium pentabromide is most conveniently prepared by reaction of bromine with niobium metal at ca 500°C. It is a fairly volatile yellow-red compound that is hygroscopic and readily hydrolyzes. It is soluble in water, alcohol, and ethyl bromide. 

Niobic Acid. Niobic acid, Nb20 XH2O, includes all hydrated forms of niobium pentoxide, where the degree of hydration depends on the method of preparation, age, etc. It is a white insoluble precipitate formed by acid hydrolysis of niobates that are prepared by alkaH pyrosulfate, carbonate, or hydroxide fusion base hydrolysis of niobium fluoride solutions or aqueous hydrolysis of chlorides or bromides. When it is formed in the presence of tannin, a volurninous red complex forms. Freshly precipitated niobic acid usually is coUoidal and is peptized by water washing, thus it is difficult to free from traces of electrolyte. Its properties vary with age and reactivity is noticeably diminished on standing for even a few days. It is soluble in concentrated hydrochloric and sulfuric acids but is reprecipitated on dilution and boiling and can be complexed when it is freshly made with oxaHc or tartaric acid. It is soluble in hydrofluoric acid of any concentration. 

Sodium niobate(7 6) [12201 -59-17, 7Na20 6Nb20 3IH2O or Naj4Nbj2 037-31H2 0, forms a crystalline precipitate when a hot solution of a soluble niobium compound is added to a hot concentrated sodium hydroxide solution. It is insoluble in the presence of excess sodium hydroxide but is sparingly soluble in pure water. It also can be formed by addition of sodium hydroxide or chloride to a solution of the 4 3 potassium niobate. 

Uranium Purification. Subsequent uranium cycles provide additional separation from residual plutonium and fission products, particularly zirconium— niobium and mthenium (30). This is accompHshed by repeating the extraction/stripping cycle. Decontamination factors greater than 10 at losses of less than 0.1 wt % are routinely attainable. However, mthenium can exist in several valence states simultaneously and can form several nitrosyl—nitrate complexes, some for which are extracted readily by TBP. Under certain conditions, the nitrates of zirconium and niobium form soluble compounds or hydrous coUoids that compHcate the Hquid—Hquid extraction. SiUca-gel adsorption or one of the similar Hquid—soHd techniques may also be used to further purify the product streams. 

Zinc Molten zinc is reported to attack niobium at a significant rate at temperatures above 450°C . It is attacked by zinc at 600°C and shows increasing solubility with temperature up to 850°C. 

Precipitation of fluoride compounds from solutions of hydrofluoric acid, HF, is performed by the addition of certain soluble compounds to solutions containing niobium or tantalum. Initial solutions can be prepared by dissolving metals or oxides of tantalum or niobium in HF solution. Naturally, a higher concentration of HF leads to a higher dissolution rate, but it is recommended to use a commercial 40-48% HF acid. A 70% HF solution is also available, but it is usually heavily contaminated by H2SiF6 and other impurities, and the handling of such solutions is extremely dangerous. 

Synthesis of the compounds from such HF solutions is performed by adding soluble fluoride compounds to the tantalum or niobium solution or by recrystallization of prepared fluoride compounds from water or HF solutions of different concentrations. In the first case, the composition of the compounds obtained depends on the ratio between Ta/Nb and the added metal and on the initial concentration of the HF used, whereas in the second case, it depends only on the HF concentration. 

The compound (NIDsNbaOFig can be prepared by adding ammonium fluoride, NH4F, to a solution containing Nb (3.20 M/l) and F (27.10 M/l). The solubility isotherm (25°) of this compound is presented in Fig. 5. The minimum point on the solubility isotherm approximately corresponds to the stoichiometrical ammonium-niobium ratio of the compound (NfLOsNbsOFig. 

Based on a comprehensive investigation of solubility isotherms and of conductometric and potentiometric titration in the NbF5 - HF - H2O system, Nicolaev and Buslaev [288] concluded that H2NbOF5 is the predominant niobium-containing form present in such solutions. 

The purpose of the decomposition of raw materials is to convert tantalum and niobium compounds into a soluble form and prepare the solution for use in subsequent procedures. Fig. 116 presents the process flow chart. The most typical and frequently used raw materials are columbite-tantalite concentrates with the general formula (Fe, Mn)(Nb, Ta Cfo. 

Hydrofluoric acid, at relatively high concentrations and at elevated temperatures, dissolves columbite-tantalite concentrates at a reasonable rate. The dissolution process is based on the fluorination of tantalum, niobium and other metal oxides and their conversion into soluble complex fluoride acids yielding complex fluoride ions. 

In the case of a mixture of hydrofluoric and sulfuric acids, the process is more complex. It can be noted that sulfuric acid most probably interacts mainly with iron and manganese, whereas hydrofluoric acid serves mostly in the dissolution of tantalum and niobium and their conversion into soluble fluoride complexes. Nevertheless, due to the high acidity of the solution, here too the formation of hexafluorotantalate and hexafluoroniobate complex ions, TaF6" and NbF6, is expected. Hence, it is noted that the acid dissolution of tantalum-and niobium-containing raw material leads to the formation of hexafluoro-acids — HTaF6 and HNbF6. 

In both cases, the fluorination of the complex oxides of tantalum and niobium leads to the formation of the water-soluble compounds (NH4)2TaF7 and (NH4)3NbOF6, the insoluble lithium fluoride and die gaseous components H20, NH3 and HF. 

Another way of applying the selective extraction method directly on the initial solution is to produce a solution of low acidity. This can be achieved by using the hydrofluoride method for fluorination and decomposition of raw material. As was discussed in Paragraph 8.2.2, the raw material is fluorinated by molten ammonium hydrofluoride yielding soluble complex fluorides of ammonium and tantalum or niobium. The cake obtained following fluorination is dissolved in water, leading to a solution of low initial acidity that is related for the most part to the partial hydrolysis of complex fluoride compounds. The acidity of the solution is first adjusted to ensure selective tantalum extraction. In the second step, the acidity of the raffinate is increased to provide the necessary conditions for niobium extraction. 

Alcohols with a C8 - Cn chain length, characterized by low solubility in aqueous media, may have a particular commercial potential as perspective extractants for tantalum and niobium hydrometallurgical processing. Particular emphasis has been placed recently on the investigation of tantalum and niobium extraction using octanol (C8Hi80) in the forms of 1-octanol and 2-octanol [462,466-473]. 

Sodium reduction development directions, 336 diluted melts, 331-332 of K-Salt, 327-328 principals, 326 Solid-phase interaction mechanism, 34-37 niobium oxyfluorides, 26-31 tantalum oxyfluorides, 32-34 Solubility diagrams (NH4)5Nb3OF18, 22 K2NbF7 in HF solutions, 14 K2TaF7 in HF solutions, 14 RbsNbjOF,, 22-23 Solubility of peroxides, 307 Specific conductivity, 153, 164 Spontaneous polarization, 223 Structural characteristics for X Me=8, 61,... 

Similar relationships can be written for the dissolution of hydrogen and oxygen. These relationships are expressions of Sievert s law which can be stated thus the solubility of a diatomic gas in a liquid metal is proportional to the square root of its partial pressure in the gas in equilibrium with the metal. The Sievert s law behaviour of nitrogen in niobium is illustrated in Figure 3.8. The law predicts that the amount of a gas dissolved in a metal can be reduced merely by reducing the partial pressure of that gas, as for example, by evacuation. In practice, however, degassing is not as simple as this. Usually, Sievert s law is obeyed in pure liquid metals only when the solute gas is present in very low concentrations. At higher concentrations deviations from the law occur. 

Oxygen and carbon have substantial solid solubilities in niobium at the temperatures normally required for reduction. As the activity coefficients of both carbon and oxygen in niobium are low, their retention in the niobium metal produced by the carbothermic reduction of niobium oxide is expected. It is, however, possible (as explained later) to remove these residual impurities by extending the pyrovacuum treatment to still higher temperatures and lower pressures. 

Niobium(III) chloride-Dimethoxyethane, NbCl3 DME (1). This soluble Nb(III) reagent is obtained as a brick-red solid by reduction of NbCl> in DME with Bu,SnH. 

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. 

Niobium metal absorbs nitrogen, similar to hydrogen, forming interstitial solid solution. The absorption occurs at 300°C and the solubility of nitrogen in the metal is directly proportional to the square root of the partial pressure of nitrogen. The reaction is exothermic and the composition of such interstitial solid solution varies with the temperature. When the metal is heated with nitrogen at temperatures between 700 to 1,100°C, the product is niobium nitride, Nb2N or (NbNo.s) [12033-43-1]. When heated with ammonia at these temperatures, niobium forms this nitride. Another niobium nitride exists, NbN [24621-21-4], with a face-centered cubic crystalline structure. 

---