Titanium electrolysis

Electrolysis. Electro winning of hafnium, zirconium, and titanium has been proposed as an alternative to the KroU process. Electrolysis of an all chloride hafnium salt system is inefficient because of the stabiHty of lower chlorides in these melts. The presence of fluoride salts in the melt increases the StabiHty of in solution and results in much better current efficiencies. Hafnium is produced by this procedure in Erance (17). 

The lshi2uka cell (39—41), another multipolar cell that has been ia use by Showa Titanium (Toyama, Japan), is a cylindrical cell divided ia half by a refractory wall. Each half is further divided iato an electrolysis chamber and a metal collection chamber. The electrolysis chamber contains terminal and center cathodes, with an anode placed between each cathode pair. Several bipolar electrodes are placed between each anode—cathode pair. The cell operates at 670°C and a current of 50 kA, which is equivalent to a 300 kA monopolar cell. 

The electrolysis is conducted at 90—95°C and an anode current density of about 50 120 A/m when using lead alloy anodes and lead cathodes. Using graphite electrodes, the current density is from 70 100 A/m using titanium anodes and graphite cathodes, the current density is 50 80 A/m (82). 

P. S. S. Hayfteld and W. R. Jacob, "Platinum—Iridium-Coated Titanium Anodes ia Brine Electrolysis," paper presented 2i. A.dvances in Chlor-A.lkali Technology, London, 1979. 

Aluminum. All primary aluminum as of 1995 is produced by molten salt electrolysis, which requires a feed of high purity alumina to the reduction cell. The Bayer process is a chemical purification of the bauxite ore by selective leaching of aluminum according to equation 35. Other oxide constituents of the ore, namely siUca, iron oxide, and titanium oxide remain in the residue, known as red mud. No solution purification is required and pure aluminum hydroxide is obtained by precipitation after reversing reaction 35 through a change in temperature or hydroxide concentration the precipitate is calcined to yield pure alumina. 

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. 

Selective solution of the aluminum from the ahoy using a volatile metal, such as mercury, lead, bismuth, cadmium, magnesium, or zinc, has been investigated. After extracting the aluminum from the original ahoy into the volatile metal, the volatile metal is distilled, leaving pure aluminum. Neither electrolysis nor volatile metal extraction can extract aluminum from iron aluniinide [12004-62-3J, EeAl, titanium aluniinide [12004-78-3] TiAl, or Al C. ... 

Titanium diboride, typically 96—98% pure, may also be made by the electrolysis of mineral mtile dissolved in mixed electrolytes,... 

A more recent patent describes the production of titanyl nitrate by electrolysis of titanium tetrachloride or titanyl chloride (37). Other titanium nitrogen compounds that have been described include titanous amide [15190-25-9] Ti(NH2)3, titanic amide [15792-80-0] Ti(NH)2, and various products in which amines have reacted with titanium tetrachloride (38). 

Titanium Silicides. The titanium—silicon system includes Ti Si, Ti Si, TiSi, and TiSi (154). Physical properties are summarized in Table 18. Direct synthesis by heating the elements in vacuo or in a protective atmosphere is possible. In the latter case, it is convenient to use titanium hydride instead of titanium metal. Other preparative methods include high temperature electrolysis of molten salt baths containing titanium dioxide and alkalifluorosiUcate (155) reaction of TiCl, SiCl, and H2 at ca 1150°C, using appropriate reactant quantities for both TiSi and TiSi2 (156) and, for Ti Si, reaction between titanium dioxide and calcium siUcide at ca 1200°C, followed by dissolution of excess lime and calcium siUcate in acetic acid. 

Anode Applications. Graphite has been used as the primary material for electrolysis of brine (aqueous) and fused-salt electrolytes, both as anode and cathode. Technological advances, however, have resulted in a dimensionally stable anode (DSA) consisting of precious metal oxides deposited on a titanium substrate that has replaced graphite as the primary anode (38—41) (see Alkali and chlorine products). 

Ma.nga.neseDioxide. Graphite plates used as anodes in this process are coated with MnO during electrolysis. The anodes are removed from the solution periodically and the MnO is removed by mechanical methods. Graphite can also be used as the cathode material. Titanium is used as anode materials where high quaHty MnO is desired. 

These facts would suggest that die electrolysis of molten alkali metal salts could lead to the inuoduction of mobile elecU ons which can diffuse rapidly through a melt, and any chemical reduction process resulting from a high chemical potential of the alkali metal could occur in the body of the melt, rather than being conhned to the cathode volume. This probably explains the failure of attempts to produce tire refractoty elements, such as titanium, by elecU olysis of a molten sodium chloride-titanium chloride melt, in which a metal dust is formed in the bulk of the elecU olyte. 

A number of attempts to produce tire refractory metals, such as titanium and zirconium, by molten chloride electrolysis have not met widr success with two exceptions. The electrolysis of caesium salts such as Cs2ZrCl6 and CsTaCle, and of the fluorides Na2ZrF6 and NaTaFg have produced satisfactoty products on the laboratory scale (Flengas and Pint, 1969) but other systems have produced merely metallic dusts aird dendritic deposits. These observations suggest tlrat, as in tire case of metal deposition from aqueous electrolytes, e.g. Ag from Ag(CN)/ instead of from AgNOj, tire formation of stable metal complexes in tire liquid electrolyte is the key to success. 

Titanium is the only one of the more common structural metals which is not attacked by wet chlorine gas and it is thus widely used as a heat exchange material for cooling the gas after the electrolysis stage. Preheating of sodium chloride brine is carried out in titanium plate heat exchangers, while titanium butterfly valves, demisters, and precipitators handle the chlorine gas produced in the cell. The most important use of titanium in chlorine production is as anodes in place of graphite in the electrolytic process. This is covered in more detail later. 

Recently it has been shown that the oxides of the platinum metals can have a higher corrosion resistance than the metals themselves , and have sufficient conductivity to be used as coatings for anodes, e.g. with titanium cores. Anodes with a coating of ruthenium dioxide are being developed for use in mercury cells for the electrolysis of brine to produce chlorine , since they are resistant to attack if in contact with the sodium-mercury amalgam. 

Platinum Platinum-coated titanium is the most important anode material for impressed-current cathodic protection in seawater. In electrolysis cells, platinum is attacked if the current waveform varies, if oxygen and chlorine are evolved simultaneously, or if some organic substances are present Nevertheless, platinised titanium is employed in tinplate production in Japan s. Although ruthenium dioxide is the most usual coating for dimensionally stable anodes, platinum/iridium, also deposited by thermal decomposition of a metallo-organic paint, is used in sodium chlorate manufacture. Platinum/ruthenium, applied by an immersion process, is recommended for the cathodes of membrane electrolysis cells. ... 

The largest uses of platinum group metals in electronics are ruthenium for resistors and palladium for multilayer capacitors, both applied by thick film techniques . Most anodes for brine electrolysis are coated with mixed ruthenium and titanium oxide by thermal decomposition . Chemical vapour deposition of ruthenium was patented for use on cutting tools . 

A mercury cathode finds widespread application for separations by constant current electrolysis. The most important use is the separation of the alkali and alkaline-earth metals, Al, Be, Mg, Ta, V, Zr, W, U, and the lanthanides from such elements as Fe, Cr, Ni, Co, Zn, Mo, Cd, Cu, Sn, Bi, Ag, Ge, Pd, Pt, Au, Rh, Ir, and Tl, which can, under suitable conditions, be deposited on a mercury cathode. The method is therefore of particular value for the determination of Al, etc., in steels and alloys it is also applied in the separation of iron from such elements as titanium, vanadium, and uranium. In an uncontrolled constant-current electrolysis in an acid medium the cathode potential is limited by the potential at which hydrogen ion is reduced the overpotential of hydrogen on mercury is high (about 0.8 volt), and consequently more metals are deposited from an acid solution at a mercury cathode than with a platinum cathode.10... 

J. Thonstad, Some Recent Trends in Molten Salt Electrolysis of Titanium, Magnesium and Aluminum, High Temperature Materials and Processes, Vol. 9, Nos. 2-4, p. 135,1990. 

Martin Heinrich Klaproth (1743-1817). William Gregor (1761-1817), a minister who also dabbled in experiments, discovered a type of sand in 1791 from which a mysterious white powder could be produced. Klaproth recognized the yet-unknown element, and Henri Moissan (1852-1907) prepared pure titanium by electrolysis. 

Rare, shiny, and lightest metal of the platinum group. Hardens platinum and palladium. The presence of 0.1 % of ruthenium in titanium improves its resistance to corrosion 100-fold. The spectacular catalytic properties of ruthenium are used on industrial scales (hydrogenations, sometimes enan-tioselective, and metathesis). Titanium electrodes coated with ruthenium oxide are applied in chlorine-alkaline electrolysis. Suitable for corrosion-resistant contacts and surgical instruments. 

Unlike in the other two electrolysis processes, the brine is not recirculated and the temperature in the system can be chosen according to optimum conditions and therefore comparatively little titanium is used in a diaphragm cellroom. However, there are some clear candidates. An example is the cell blanket where Permascand has a newly patented design comprising bellows welded to the anode collar. The chlorine header and also the cell top are other components that could be manufactured from... 

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