Niobium minerals

Niobium occurs primarily in two minerals, columbite and pyrochlore. The original name columbium was taken from the first of these minerals. Niobium always occurs with tantalum in these minerals. Separating the two elements is always the most difficult step in their preparation. 

Gr. Tantalos, mythological character, father of Niobe) Discovered in 1802 by Ekeberg, but many chemists thought niobium and tantalum were identical elements until Rowe in 1844, and Marignac, in 1866, showed that niobic and tantalic acids were two different acids. The early investigators only isolated the impure metal. The first relatively pure ductile tantalum was produced by von Bolton in 1903. Tantalum occurs principally in the mineral columbite-tantalite. 

Some elements found in body tissues have no apparent physiological role, but have not been shown to be toxic. Examples are mbidium, strontium, titanium, niobium, germanium, and lanthanum. Other elements are toxic when found in greater than trace amounts, and sometimes in trace amounts. These latter elements include arsenic, mercury, lead, cadmium, silver, zirconium, beryUium, and thallium. Numerous other elements are used in medicine in nonnutrient roles. These include lithium, bismuth, antimony, bromine, platinum, and gold (Eig. 1). The interactions of mineral nutrients with... 

Occurrence. Niobium and tantalum usually occur together. Niobium never occurs as the metal, ie, ia the free state. Sometimes it occurs as a hydroxide, siUcate, or borate most often it is combiaed with oxygen and another metal, forming a niobate or tantalate ia which the niobium and tantalum isomorphously replace one another with Htde change ia physical properties except density. Ore concentrations of niobium usually occur as carbonatites and are associated with tantalum ia pegmatites and alluvial deposits. Principal niobium-beariag minerals can be divided iato two groups, the titano- and tantalo-niobates. 

Columbium (Niobium) and Tantalum in 1994 U.S. Bureau of Mines, Mineral Industry Survey, 1995. 

The menstmum niobium—carbide process (7) utilizes either columbite [1310-23-2] mineral concentrates or ferroniobium as starting materials. A low level of TaC in soHd solution with NbC commonly occurs, as Ta and Nb occur together in ores. The properties of NbC are given in Table 1. The grayish brown NbC powder is used in cemented carbides to replace TaC. TaC—NbC soHd solutions that have 3 1, 2 1, 1 1, and 1 2 ratios and the corresponding ternary and quaternary soHd solutions with TiC and WC are common. 

The elements of Group 5 are in many ways similar to their predecessors in Group 4. They react with most non-metals, giving products which are frequently interstitial and nonstoichiometric, but they require high temperatures to do so. Their general resistance to corrosion is largely due to the formation of surface films of oxides which are particularly effective in the case of tantalum. Unless heated, tantalum is appreciably attacked only by oleum, hydrofluoric acid or, more particularly, a hydrofluoric/nitric acid mixture. Fused alkalis will also attack it. In addition to these reagents, vanadium and niobium are attacked by other hot concentrated mineral acids but are resistant to fused alkali. 

Niobium and tantalum are rare elements. The content of niobium and of tantalum in the Earth s crust is lxl0"3 and 2x1 O 4 wt. %, respectively [21]. Niobium and tantalum are encountered in nature together, mostly in the form of oxides that are derived from orthoniobic (orthotantalic), metaniobic (metatantalic) and pyroniobic (pyrotantalic) acids. The main minerals are listed in Table 2, which reveals that the most important source of tantalum and niobium is tantalite-columbite, (Fe,Mn)(Nb,Ta)206. 

Deposits of niobium-tantalum ores are found in Australia, Brazil, Canada, China, Malaysia, Namibia, Nigeria, Russia, Rwanda, Spain, Thailand, Zaire, and Zimbabwe. A more detailed analysis of worldwide tantalum mineral raw material supply can be found in Linden s comprehensive overview [22,23]. 

Table 2. Composition of main tantalum-niobium-containing minerals [21,24]...

Two main methods exist for the production of tantalum and niobium from the mineral raw material. The first method is based on the chlorination of raw material, followed by separation and purification by distillation of tantalum and niobium in the form of pentachlorides, TaCl5 and NbCl5 [24, 29]. Boiling points of tantalum and niobium pentachlorides (236°C and 248°C, respectively) are relatively low and are far enough apart to enable separation by distillation. 

The processing of tantalum and niobium begins with the fluorination of the raw material, which always consists of complex oxide compounds containing tantalum and niobium. The main types of tantalum- and niobium-containing minerals are discussed in Chapter 1, and typical compositions of such minerals are presented in Table 2. 

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]. 

It is recommended that the concentration of sulfuric acid in the initial solution be kept at 2-4 mol per liter for the extraction of tantalum, whereas for the extraction of niobium, the concentration of sulfuric acid must be increased to a minimum of 6 mol per liter [458,481]. In some cases, the presence, in the initial solution, of titanium in the form of fluorotitanic acid ensures the successful and selective extraction and purification of tantalum and niobium with no addition of any other mineral acid [482]. 

The examination and analysis of minerals have provided x-ray emission spectrography with a challenge and an opportunity. This situation has arisen because of a great growth of interest in uranium and thorium minerals in the rare-earth oxides and in metals such as tantalum and niobium, or hafnium and zirconium. On the whole, x-ray emission spectrography has met the challenge successfully, and the investigations that prove this also demonstrate the versatility and the value of the method.70"72... 

For papers on the analysis and examination of tantalum and niobium minerals by x-ray emission, see the following references listed in Appendix VI 17, 65, 82, 89. 

Table 1.15 Chemical composition of the principal niobium-tantalum-bearing minerals.

Minerals belonging to the category of insoluble oxide and silicate minerals are many in number. Insoluble oxide minerals include those superficially oxidized and those of oxide type. The former category comprises mainly superficially oxidized sulfide minerals, including metals such as aluminum, tin, manganese, and iron which are won from their oxidic sources. As far as silicate minerals are concerned, there can be a ready reference to several metals such as beryllium, lithium, titanium, zirconium, and niobium which are known for their occurrence as (or are associated with) complex silicates in relatively low-grade deposits. 

Apart from structures that are built of slabs, modular structures that can be constructed of columns in a jigsawlike assembly are well known. In the complex chemistry of the cuprate superconductors and related inorganic oxides, series of structures that are described as tubular, stairlike, and so on have been characterized. Alloy structures that are built of columns of intersecting structures are also well known. Structures built of linked columns, tunnels, and intersecting slabs are also found in minerals. Only one of these more complex structure types will be described, the niobium oxide block structures, chosen as they played a significant role in the history of nonstoichiometry. 

The most important tin mineral is cassiterite (Sn02). Theoretically, the tin content of cassiterite is 78%. However, in the majority of cases, cassiterite contains impurities and the tin content may vary from 65% to 78%. The major impurities of cassiterite include tantalum, niobium, titanium and other elements, usually in the form of solid solutions. The impurities in the cassiterite often have a pronounced effect on flotation properties of cassiterite. 

The coarse-grained tin ores are usually represented by cassiterite-quartz and pegmatitic formations. These ores can be a complex formation containing varieties of gangue minerals. The pegmatitic ore type, in addition to tin, can contain significant amounts of tantalum and niobium. 

Niobium minerals, especially columbite, are also associated with other valuable minerals, such as tantalum, zircon and rare earth minerals. Pyrochlore and a mixture of pyrochlore and columbite have different origins, and therefore, beneficiation of pyrochlore and columbite are different from that of the mixed tantalum niobium ores. In actual plant practice, the treatment process is significantly different from that used for mixed niobium tantalum ores. This is due to the fact that the beneficiation process is largely determined by the nature of gangue minerals present in the ore. In most cases, the beneficiation process applicable for pyrochlore ore cannot be successfully applied for beneficiation of tantalum/ niobium ores. 

Pegmatite-containing niobium ores can be relatively complex and may contain biotite, enargite, albite, feldspar and ziron as the main gangue minerals. Some pegmatite ores (Araxa, Brazil) have a simple gangue composition, consisting mainly of quartz. 

Collectors from the PM series were specifically developed for beneficiation of niobium ores that contain nepheline/cyanite as the major gangue minerals. The collector is composed of a mixture of phosphate ester collector (SM15, Clariant) and phosphonic acid treated with octanol. From an ore that assays 0.5% Nb20s, a concentrate grade of 49% Nb205 at a recovery of 73% was achieved. 

There are approximately 130 different minerals that contain tantalum and niobium, from which about 80 are Ta/Nb only. The other minerals contain tantalum and niobium in the form of impurities. There is very little information available on beneficiation of Ta/Nb-containing ores. In actual practice, there are three basic methods for production of Ta/Nb concentrate (a) physical preconcentration, (b) combination of physical preconcentration and flotation and (c) direct flotation. In most cases, Ta/Nb ores contain significant quantities of zircon and rare earth ores (REO). 

Ta/Nb minerals often occur as impurities in ilmenite, rutile, cassiterite, wolframite and perovskite, most of which contain REE. Because tantalite and columbite have similar chemical properties, they often replace each other, and are usually found as isomorph mixtures. Tantalum and niobium can also be found as separate minerals. Tantalite and microlite are primary sources of tantalum. 

Pegmatite deposits are the most abundant. They contain a variety of minerals including tantalum, niobium, lithium and beryllium, as well as REE and zircon. 

The results showed that amines normally used for pyrochlore flotation did not work for flotation of Ta/Nb. Therefore, collector selection is very dependent on the type of niobium minerals present in the ore. 

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