Chloride process, titanium dioxide pigment

Paints. Paints account for perhaps 3% of sulfur consumption (see Paint). The main sulfur use is for the production of titanium dioxide pigment by the sulfate process. Sulfuric acid reacts with ilmenite or titanium slag and the sulfur remains as a ferrous sulfate waste product. Difficulties with this process have led to the development of the chloride process (see Pigments, inorganic Titanium compounds). 

A high purity titanium dioxide of poorly defined crystal form (ca 80% anatase, 20% mtile) is made commercially by flame hydrolysis of titanium tetrachloride. This product is used extensively for academic photocatalytic studies (70). The gas-phase oxidation of titanium tetrachloride, the basis of the chloride process for the production of titanium dioxide pigments, can be used for the production of high purity titanium dioxide, but, as with flame hydrolysis, the product is of poorly defined crystalline form unless special dopants are added to the principal reactants (71). 

Two pigment production routes ate in commercial use. In the sulfate process, the ore is dissolved in sulfuric acid, the solution is hydrolyzed to precipitate a microcrystalline titanium dioxide, which in turn is grown by a process of calcination at temperatures of ca 900—1000°C. In the chloride process, titanium tetrachloride, formed by chlorinating the ore, is purified by distillation and is then oxidized at ca 1400—1600°C to form crystals of the required size. In both cases, the taw products are finished by coating with a layer of hydrous oxides, typically a mixture of siUca, alumina, etc. 

Two processes are used in the manufacture of titanium dioxide pigments the sulfate process and the chloride process. The chemistry of the sulfate process, the longer established of the two methods, is illustrated schematically in Scheme 9.1. In this process, crude ilmenite ore, which contains titanium dioxide together with substantial quantities of oxides of iron, is digested with concentrated sulfuric acid, giving a solution containing the sulfates of Ti(iv), Fe(m) and Fe(n). Treatment of this... 

Chloride One of the two process used today for making titanium dioxide pigment. Mineral rutile, or another mineral rich in titanium, is chlorinated with coke to produce titanium tetrachloride ... 

ICON [Integrated chlorination and oxidation] An improved version of the Chloride Process for making titanium dioxide pigment. It operates at above atmospheric pressure and is claimed to be cheaper to build. Chlorine from the oxidation section, under pressure, is introduced directly to the chlorinator. Developed by Tioxide Group, and first operated at its plant at Greatham, UK, in 1990. 

Two major processes are used for producing raw titanium dioxide pigment (1) the sulfate process, a batch process accounting for over half of current production, introduced by European makers in die early 1930s and (2) the chloride process, a continuous process, introduced in the late 1950s and accounting for most of the new plant construction since the mid-1960s. The sulfate process can handle both rutile and anatase, but the chloride process is limited to rutile. 

Monk-Irwin An unsuccessful predecessor of the Sulfate process for making titanium dioxide pigment from ilmenite. Invented by C.R. Whittemore at McGill University, Montreal, in the early 1920s and subsequently developed by J. Irwin and R.H. Monk in Canada and B. Laporte Limited in Luton, UK. Ilmenite from the deposit at Ivry, Quebec was reduced by heating with coke, leached with ferric chloride solution, and then roasted with a mixture of sulfuric acid and sodium sulfate. The resulting cake, containing titanyl sulfate, was dissolved in water and hydrolyzed, and the titania hydrate calcined. Some of the product was extended with barium sulfate. The project was abandoned in 1928. 

There are two major processes for the manufacture of titanium dioxide pigments, namely (1) sulfate route and (2) chloride route. In the sulfate process, the ore limonite, Fe0Ti02, is dissolved in sulfuric acid and the resultant solution is hydrolyzed by boiling to produce a hydrated oxide, while the iron remains in solution. The precipitated titanium hydrate is washed and leached free of soluble impurities. Controlled calcinations at about 1000°C produce pigmentary titanium dioxide of the correct crystal size distribution this material is then subjected to a finishing coating treatment and milling. The process flow sheet is shown in Fig. 7.1 [4],... 

Fi)j ire 79. Flow diagram of the chloride process for production of titanium dioxide pigment... 

These silicas are produced by a gas phase, as opposed to a solution process. There are a number of possible gas phase routes, but the predominant one is by hydration of silicon tetra-chloride. This is carried out in a flame of hydrogen and oxygen at a temperature of 1000 °C or above, and is similar to the chloride route for the manufacture of titanium dioxide pigments. Details of the process can be found in the work by Watson [39] (see also Figure 2.10). 

These ores are the principal raw materials used in the manufacture of titanium dioxide pigment The first step to purify the ore is basically a refinement, using either sulfuric acid (sulfate process Gesenhues et al., 2003) or chlorine (chloride process) as an extraction agent... 

Titanium dioxide is manufactured by two processes, the sulfate process and the chloride process. In the sulfate process, ilmenite ore (FeTiOg) is dissolved in concentrated sulfuric acid and insoluble impurities are removed by clarification, flocculation, sedimentation and filtration. The resulting solution is further purified by crystallization to remove ferrous sulfate from titanyl sulfate solution. The titanyl sulfate solution is then hydrolyzed to give hydrated titanium dioxide, which is calcined at about 900 to 1100 °C to give the titanium dioxide pigment. Both anatase and rutile-type titanium dioxide pigments are produced using this method. 

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