Niobium, transfer

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. 

Another solvent extraction scheme uses the mixed anhydrous chlorides from a chlorination process as the feed (28). The chlorides, which are mostly of niobium, tantalum, and iron, are dissolved in an organic phase and are extracted with 12 Ai hydrochloric acid. The best separation occurs from a mixture of MIBK and diisobutyl ketone (DIBK). The tantalum transfers to the hydrochloric acid leaving the niobium and iron, the DIBK enhancing the separation factor in the organic phase. Niobium and iron are stripped with hot 14—20 wt % H2SO4 which is boiled to precipitate niobic acid, leaving the iron in solution. 

Sodium, potassium and sodium-potassium alloys Liquid sodium, potassium or alloys of these elements have little effect on niobium at temperatures up to 1 000°but oxygen contamination of sodium causes an increase in corrosionSodium does not alloy with niobium . In mass transfer tests, niobium exposed to sodium at 600°C exhibited a corrosion rate of approximately 1 mgcm d . However, in hot trapped sodium at 550°C no change of any kind was observed after 1 070 h . 

Loop Tests Loop test installations vary widely in size and complexity, but they may be divided into two major categories (c) thermal-convection loops and (b) forced-convection loops. In both types, the liquid medium flows through a continuous loop or harp mounted vertically, one leg being heated whilst the other is cooled to maintain a constant temperature across the system. In the former type, flow is induced by thermal convection, and the flow rate is dependent on the relative heights of the heated and cooled sections, on the temperature gradient and on the physical properties of the liquid. The principle of the thermal convective loop is illustrated in Fig. 19.26. This method was used by De Van and Sessions to study mass transfer of niobium-based alloys in flowing lithium, and by De Van and Jansen to determine the transport rates of nitrogen and carbon between vanadium alloys and stainless steels in liquid sodium. 

The extractability of such a complex is quite good. Thus, if the feed solution is low in its acidity only tantalum is extracted, while niobium remains in the raffinate. The niobiumbearing raffinate is then separately contacted with TBP after adjusting its acidity to higher values so that niobium is than transferred from aqueous to the organic phase. 

The charge transfer model suggested to rationalize the correlati on between i oni zati on potenti al and reacti vi ti es of i ron, vanadium, and niobium with dihydrogen fails for other systems. However a model that takes into account the frontier orbital interactions, although highly simplistic, does account for a variety of observations. This model suggests extensions that include... 

The reformer tubes typically operate at maximum temperatures of 1,600°F to 1,700°F and are designed for a minimum stress-to-rupture life of 100,000 operating hours. A 35/25 Ni/Cr alloy is used that is modified with niobium and microalloyed with trace elements such as titanium and zirconium. Smaller tube diameters provide better heat transfer and cooler walls. This reduces tube and fuel costs and increases tube life. But more tubes increases the pressure drop. The optimum inside tube diameter is 4 to 5 in. The wall thickness may be as low as 0.25 inch with a length of 40 to 45 ft. The lane spacing between tube rows must be enough to avoid flame impingement from the burners. Typical spacing is 6 to 8 feet. 

The coordinated ethylene is readily expelled at 25 °C by the attack of a conjugated diene and the hydride is transferred to the sterically less crowded diene terminus. Thus the niobium hydrido-olefin complexes serve as convenient reagents for the preparation of 1,2- or 1,3-dialkyl-substituted allylniobium compounds starting from butadiene, (E,E) and (/i,Z)-2,4-hcxadicnc, (E)- and (Z)-l,3-pentadiene (equation 1), 3-methyl-l,3-pentadiene and isoprene (equation 2). All the allyl niobium compounds synthesized were isolated as air-sensitive pale-yellow crystals by crystallization from hexane. 

Figure 8-42 illustrates the anodic and cathodic polarization curves observed for an outer-sphere electron transfer reaction with a typical thick film on a metallic niobium electrode. The thick film is anodically formed n-type Nb206 with a band gap of 5.3 eV and the redox particles are hydrated ferric/ferrous cyano-complexes. The Tafel constant obtained from the observed polarization curve is a- 0 for the anodic reaction and a" = 1 for the cathodic reaction these values agree with the Tafel constants for redox electron transfers via the conduction band of n-lype semiconductor electrodes already described in Sec. 8.3.2 and shown in Fig. 8-27. 

Fig. 8-42. Anodic and cathodic polarization curves observed for electron transfer of hydrated redox particles at an electrode of metallic niobium covered with a thick niobium oxide NbsOs film (12 nm thick) in acidic solution reaction is an electron transfer of hydrated redox particles, 0.25MFe(CN)6 /0.25M Fe(CN)g, in 0.1 M acetic add buffer solution of pH 4.6 at 25 C. =...

Dinuclear carbonyl anions [M2(CO)8X3] were obtained through a two-electron transfer to protons by treatment of [M(CO)6]- with HX (X = Cl, OAc, OMe) (equation 82).526 The anion has Civ symmetry. The niobium atoms are heptacoordinated with four terminal carbonyl groups each and three bridging chlorides located at the vertices of an approximately equatorial... 

Figure 6.27. The potential curves for sudden (2) and adiabatic (3) hydrogen transfer between the tetrahedral interstitial positions in niobium crystal. Curve 1 is the potential in the unrelaxed lattice. (From Chakraborty et al. [1988].)...

In the 1980 s HP 25/35 Modified alloys were developed that used metals such as molybdenum (Mo), niobium (Nb) or tungsten (W). These metals increased resistance to creep rupture and offered good ductility and weldability. With stronger alloys, wall thickness of tubes could be reduced. Thinner tube walls offered benefits such as using lighter tubes and tube supports, improved heat transfer, resistance to thermal cycling and capacity increases of up to 30%88. 

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