Titanium separation from

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 ... 

Titanium slag and synthetic mtile are also used as raw materials in the production of titanium whites. Titanium slag results from a metaHurgical process during which iron (qv) is removed from ilmenite by reduction with coke in an electric arc furnace at 1200—1600°C. Under these conditions, iron oxide is reduced to metal, melts, and separates from the formed titanium slag. Titanium slag contains 70—75% Ti02 and only 5—8% iron. 

Impurities that form volatile chlorides leave as gases at the top of the furnace together with the TiCl. By cooling those gases, most impurities, with the exception of vanadium and siUcon chlorides can be separated from the titanium tetrachloride [7550-45-0]. Vanadium chlorides can be reduced to lower oxidation state chlorides that are soHds highly volatile SiCl can be removed from TiCl by fractional distillation. 

The volatile chlorides ate collected and the unreactedsohds and nonvolatile chlorides ate discarded. Titanium tetrachloride is separated from the other chlorides by double distillation (12). Vanadium oxychloride, VOCl, which has a boiling point close to TiCl, is separated by complexing with mineral oil, reducing with H2S to VOCI2, or complexing with copper. The TiCl is finally oxidized at 985°C to Ti02 and the chlorine gas is recycled (8,11) (see also... 

A number of high temperature processes for the production of titanium carbide from ores have been reported (28,29). The aim is to manufacture a titanium carbide that can subsequently be chlorinated to yield titanium tetrachloride. In one process, a titanium-bearing ore is mixed with an alkah-metal chloride and carbonaceous material and heated to 2000°C to yield, ultimately, a highly pure TiC (28). Production of titanium carbide from ores, eg, ilmenite [12168-52-4], EeTiO, and perovskite [12194-71 -7], CaTiO, has been described (30). A mixture of perovskite and carbon was heated in an arc furnace at ca 2100°C, ground, and then leached with water to decompose the calcium carbide to acetjdene. The TiC was then separated from the aqueous slurry by elutriation. Approximately 72% of the titanium was recovered as the purified product. In the case of ilmenite, it was necessary to reduce the ilmenite carbothermaHy in the presence of lime at ca 1260°C. Molten iron was separated and the remaining CaTiO was then processed as perovskite. 

Both anatase and mtile are broad band gap semiconductors iu which a fiUed valence band, derived from the O 2p orbitals, is separated from an empty conduction band, derived from the Ti >d orbitals, by a band gap of ca 3 eV. Consequendy the electrical conductivity depends critically on the presence of impurities and defects such as oxygen vacancies (7). For very pure thin films, prepared by vacuum evaporation of titanium metal and then oxidation, conductivities of 10 S/cm have been reported. For both siugle-crystal and ceramic samples, the electrical conductivity depends on both the state of reduction of the and on dopant levels. At 300 K, a maximum conductivity of 1 S/cm has been reported at an oxygen deficiency of... 

Extraction of Bertrandite. Bertrandite-containing tuff from the Spor Mountain deposits is wet milled to provide a thixotropic, pumpable slurry of below 840 p.m (—20 mesh) particles. This slurry is leached with sulfuric acid at temperatures near the boiling point. The resulting beryUium sulfate [13510-49-1] solution is separated from unreacted soflds by countercurrent decantation thickener operations. The solution contains 0.4—0.7 g/L Be, 4.7 g/L Al, 3—5 g/L Mg, and 1.5 g/L Fe, plus minor impurities including uranium [7440-61-1/, rare earths, zirconium [7440-67-7] titanium [7440-32-6] and zinc [7440-66-6]. Water conservation practices are essential in semiarid Utah, so the wash water introduced in the countercurrent decantation separation of beryUium solutions from soflds is utilized in the wet milling operation. 

Many of the metals used by ancient man— coppei (cuprum, Cu), silver (argentum, Ag), gold (aurum, Au), tin (stannum, Sn), and lead (plumbum, Pb)—are in relatively short supply. Ancient man found deposits of the first three occurring as the elementary metals. These three may also be separated from their ores by relatively simple chemical processes. On the othei hand, aluminum and titanium, though abundant, are much more difficult to prepare from their ores. Fluorine is more abundant in the earth than chlorine but chlorine and its compounds are much more common—they are easier to prepare and easier to handle. However, as the best sources of the elements now common to us become depleted, we will have to turn to the elements that are now little used. 

Determination of titanium with tannic acid and phenazone Discussion. This method affords a separation from iron, aluminium, chromium, manganese, nickel, cobalt, and zinc, and is applicable in the presence of phosphates and silicates. Small quantities of titanium (2-50 mg) may be readily determined. 

This section is concerned with elements other than titanium however, it is sometimes difficult to treat this element separately from the others because several authors49,190 compared in the same work the relative reactivity of different catalysts. In most cases, a mechanism has not been suggested, nor has the effidency of the catalyst been characterized. The order with respect to catalyst is almost never given. 

Figure 4.23 Vacuum distillation assembly for separation of zirconium/titanium metals from reduction products.

Titanium sponge is separated from sodium chloride and excess sodium by leaching with water. 

A separate continuous DAF operation conducted by Krofta and Wang59 under 33.3% recycle flow pressurization mode demonstrated that aluminum sulfate, sodium aluminate, and polyelectrolyte combination at pH 6.2 also effectively recovered both fibers and titanium dioxide from the same white water containing 500mg/L of titanium dioxide and 1000 mg/L of cotton fibers. 

Liposomes (SUVs) were prepared by probe sonication according to standard procedures (31) in the presence of STPP. A mixture of lecithin, cholesterol, and STPP (PC/Ch/STPP = 65/15/20, molar ratio final total lipid 25 mg/ mL) was dissolved in chloroform followed by removal of the organic solvent using a rotary evaporator. After adding 5 mM HEPES (pH 7.4) to the dry lipid film, the sample was probe sonicated with a Sonic Dismembrator (Model 100, Fischer Scientific) at a power output of approximately 10 W for 30 minutes. To remove any titanium particles, which have been shed from the tip of the probe during sonication, the sample was centrifuged for 10 minutes at 3000 X g. The formed liposomes were separated from free, i.e., nonincorporated, STPP by gel filtration chromatography on a Sephadex G-15 column. 

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. 

Titanium tetrachloride is prepared by heating titanium dioxide or the ores ihnenite or rutde with carbon to red heat in a stream of chlorine. When ihnetite is used, ferric chloride also is produced. Titanium tetrachloride is separated from ferric chloride and other impurities by fractionation. 

The concentration of the acid recycled to the digestion process depends on the quality of the titanium-containing raw material. For raw materials with a high titanium content, the 65-70% sulfuric acid separated from the metal sulfates must be further concentrated to give 80-87% acid (stage 5). 

NH1CONH2 + H2O. The processing is complicated because of the severe corrosiveness of the reactants, usually requiring reaction vessels that are lined with lead, titanium, zirconium, silver, or stainless steel. The second step of the process requires a temperature of about 200 C to effect the dehydration of the ammonium carbamate. The processing pressure ranges from 160 to 250 atmospheres. Only about one-half of the ammonium carbamate is dehydrated in the first pass. Thus, the excess carbamate, after separation from the urea, must be recycled to the urea reactor or used for other products, such as the production of ammonium sulfate. 

This selectivity advantage, combined with the advantages of regenerability and the ease of separation from products that characterize any solid catalyst, justified the increased attention paid to these materials. The discovery and application of titanium silicalite are regarded as milestones in zeolite catalysis (Holderich, 1989). 

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