Sulfate process

Fig. 3. Flow chart for the sulfate process for production of the pigment titanium white.

Factors such as reaction temperature, excess of oxygen, water addition, addition of other minor reactants, eg, AlCl to promote the formation of mtile, mixing conditions inside the reactor, and many others influence the quaUty of Ti02 pigment. In general, titanium white pigments produced by the chloride process exhibit better lightness than those produced by the sulfate process. 

Kraft Process. The dominant chemical wood pulping process is the kraft or sulfate process. The alkaline pulping Hquor or digesting solution contains about a three-to-one ratio of sodium hydroxide, NaOH, and sodium sulfide, Na2S. The name kraft, which means strength in German,... 

Chemithon secured patents on a somewhat similar oleum-type continuous sulfonation and sulfation process (259,260). So-called dominant bath sulfonation processes function well because they appear to operate ia or near the homogeneous area of the phase diagram (1) and heat removal is readily controllable with relatively small iacremental reaction. 

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). 

Sulfate Process. In the sulfate process (Fig. 2), ihnenite ore is treated with sulfuric acid at 150—180°C ... 

Precipitation of a hydrated titanium oxide by mixing aqueous solutions of titanium chloride with alkaU forms the precipitation seeds, which are used to initiate precipitation in the Mecklenburg (50) variant of the sulfate process for the production of pigmentary titanium dioxide. Hydrolysis of aqueous solutions of titanium chloride is also used for the preparation of high purity (>99.999%) titanium dioxide for electroceramic appHcations (see Ceramics). In addition, hydrated titanium dioxide is used as a pure starting material for the manufacture of other titanium compounds. 

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. 

The resultant slag, a complex mixture of titanates, may contain 70—85% Ti02- The slag route is particularly useful when ilmenite is closely associated with haematite, from which it cannot economically be separated mechanically. Because the iron content of the slag is low, its use reduces the quantity of iron sulfate in the Hquid effluent of sulfate process plants. Slag used as a feedstock for TiCl production must be low in magnesium and calcium. A variety of other ilmenite beneficiation or synthetic mtile processes have been pursued, primarily to provide alternative chloride process feedstocks. Low grade ilmenite... 

The Sulfate Process. A flow diagram for the sulfate process is shown in Figure 1. The strongly exothermic digestion of the dried, milled feedstock in 85—95°/ sulfuric acid converts metal oxides into soluble sulfates, primarily titanium and iron. 

There are two main processes for the synthesis of ethyl alcohol from ethylene. The eadiest to be developed (in 1930 by Union Carbide Corp.) was the indirect hydration process, variously called the strong sulfuric acid—ethylene process, the ethyl sulfate process, the esterification—hydrolysis process, or the sulfation—hydrolysis process. This process is stiU in use in Russia. The other synthesis process, designed to eliminate the use of sulfuric acid and which, since the early 1970s, has completely supplanted the old sulfuric acid process in the United States, is the direct hydration process. This process, the catalytic vapor-phase hydration of ethylene, is now practiced by only three U.S. companies Union Carbide Corp. (UCC), Quantum Chemical Corp., and Eastman Chemical Co. (a Division of Eastman Kodak Co.). UCC imports cmde industrial ethanol, CIE, from SADAF (the joint venture of SABIC and Pecten [Shell]) in Saudi Arabia, and refines it to industrial grade. 

It is most economical when high-grade ores are used, becoming less economical with poorer feed materials containing iron, because of the production of chloride wastes from which the chlorine cannot be recovered. By contrast the sulfate process cannot make use of rutile which does not dissolve in sulfuric acid, but is able to operate on lower grade ores. However, the capital cost of plant for the sulfate process is higher, and disposal of waste has proved environmentally more difficult, so that most new plant is designed for the chloride process. 

The sulfate process is based on the attack of activated beryl by sulfuric acid to form water-soluble Be and A1 sulfates and insoluble silica. A flow diagram summarizing this process is given in Scheme 1. Activated beryl must be used since the natural ore is resistant to acid attack except by HF, which is prohibitively expensive. High-grade beryl ore (> 10% BeO) is normally activated by a heat-treatment process... 

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