Rotary kiln process, calcining

In the process to produce alumina (Fig. 1), bauxite is crushed and wet ground to 100-mesh, dissolved under pressure and heated in digesters with concentrated spent caustic soda solution from a previous cycle and sufficient lime and soda ash. Sodium aluminate is formed, and the dissolved silica is precipitated as sodium aluminum silicate. The undissolved residue (red mud) is separated from the alumina solution by filtration and washing and sent to recovery. Thickeners and Kelly or drum filters are used. The filtered solution of sodium aluminate is hydrolyzed to precipitate aluminum hydroxide by cooling. The precipitate is filtered from the liquor, washed, and heated to 980°C in a rotary kiln to calcine the aluminum hydroxide. 

To obtain a calcine powder, two techniques have been developed to the demonstration stage, the spray process and the rotary kiln process. Both have specific problems, such as the replacement frequency of the spray nozzle and the general reliability of a large rotating tube. Nevertheless, both have received intensive development and have proved to be feasible. 

The development of the rotary kiln, now predominantly used for the production of Portland cement, started around the late 1870s but the technology was not patented until 1885 (Ransome [B.69]). A rotary kiln (Fig. 6.7-35) is a long refractory-lined steel cylinder that is inclined at about 3-6° to the horizontal. At the lower end is a burner (coal, oil, or gas fired) and the material to be calcined enters on the other end. While passing down the kiln, chemical and physical reactions take place in the oxidizing atmosphere. Hot clinker emerges at the burner end and must be suitably cooled before being milled to yield cement. The rotary kiln process may be carried out with wet (slurry), semi-dry, or dry feed. 

Calcination. Calcination involves a low (<1000° C) temperature soHd-state chemical reaction of the raw materials to form the desired final composition and stmcture such as perovskite for BaTiO and PZT. It can be carried out by placing the mixed powders in cmcibles in a batch or continuous kiln. A rotary kiln also can be used for this purpose to process continuously. A sufficiendy uniform temperature has to be provided for the mixed oxides, because the thermal conductivity of powdered materials is always low. 

Rotary kilns and, to a lesser extent, Fluo-SoHds kilns are used to calcine a wet precipitated calcium carbonate filter cake in the kraft or sulfate paper-pulp process (15). Lime is regenerated for use as a causticization reagent in recovering caustic soda for pulp digestion. Losses in lime recovery are replaced by purchased lime (see Paper Pulp). 

Sulphate process. The ilmenite is reacted with sulphuric acid giving titanium sulphate and ferric oxide. After separation of ferric oxide, addition of alkali allows precipitation of hydrous titanium dioxide. The washed precipitate is calcined in a rotary kiln to render titanium dioxide. The nucleation and calcination conditions determine the crystalline structure of titanium dioxide (e.g. rutile or anatase). 

At the alumina plant, the bauxite ore is further crushed to the correct particle size for efficient extraction of the alumina through digestion by hot sodium hydroxide liquor. After removal of "red mud" (the insoluble part of the bauxite) and fine solids from the process liquor, aluminum trihydrate crystals are precipitated and calcined in rotary kilns or fluidized bed calciners to produce alumina (AljOj). Some alumina processes include a liquor purification step. 

Three different types of furnaces are generally in use for calcination. The shaft furnace is considered to be the most suited for calcining coarse limestone. Furnaces of the rotary kiln type are used for handling materials of mixed particle sizes and lumps which disintegrate during the process. Calcination can be carried out in a fluidized bed-reactor for materials of small and uniform particle size. These furnaces are usually fired with gas, oil or coke in some cases electric heating is resorted to. 

Removal of volatile matter to about 0.5 wt% can be accomplished by calcining in a rotary kiln, rotary hearth, or vertical shaft calciner All of these processes heat green coke to temperatures in excess of 1000°C where shrinkage and subsequent densification take place. The volatile components are comprised primarily of methane, ethane, hydrogen, and hydrogen sulfide gases which can be employed as fuel for process heat. 

Seailles-Dyckerhoff A process for extracting aluminum from clays and other aluminous minerals rich in silica. The ore is calcined with limestone in a rotary kiln. The product is leached with aqueous sodium carbonate, yielding sodium aluminate solution, from which alumina is precipitated by carbon dioxide. Invented by J. C. Seailles and W. R. G. Dyckerhoff in 1938 piloted in Tennessee in 1942, South Carolina in 1945, and Germany during World War II. See also Pedersen. 

At the completion of the reaction, the aniline is separated from the iron oxides by steam distillation and the umeacted iron removed. The pigment is washed, filtered and dried, or calcined in rotary kilns to hematite (Plate 20.1, see p. XXXIX). Considerable control over pigment properties can be achieved in this process by varying the nature and concentration of the additives and the reaction rate the latter depends on pH, the rate of addition of iron and nitrobenzene and the type and particle size of the iron particles. Two advantages of this method are that a saleable byproduct, aniline, is produced and that there are no environmentally, harmful waste products. 

Solid-State Reactions of Iron Compounds. Black iron oxides obtained from the Laux process (see below) or other processes may be calcined in rotary kilns with an oxidizing atmosphere under countercurrent flow to produce a wide range of different red colors, depending on the starting material. The pigments are ground to the desired particle size in pendular mills, pin mills, or jet mills, depending on their hardness and intended use. 

Defluorinated Phosphate Rock. There is substantial production of defluorinated phosphate rock for fertilizer use in Japan (about 100,000 mt/year). Ground, high-grade rock is mixed with small proportions of sodium carbonate or sulfate and wet-process acid. The mixture is calcined at a temperature of 1350°C in an oil-fired rotary kiln 45.0 m in length and 2.7 m in diameter. The product contains 38-42 percent P205 of which more than 90 percent is soluble in neutral ammonium nitrate solution and is an effective fertilizer on acid soils. During the production of defluorinated phosphate rock, substantially all fluorine is driven off. Sodium bifluoride (NaHF2) is recovered as a byproduct. A similar product is made in the United States, but it is mainly used for animal feed supplement. 

Sodium aluminum sulfate. This product is now being successfully calcined in rotary kilns. In this process, the salt cake is broken up just before it enters the kiln. Calcination is for the purpose of driving off the combined water (45 percent) and sulfuric acid (3 percent). Temperatures employed are approximately 800 K. 

Batch Furnaces This type of furnace is employed mainly for the heat treatment of metals and for the drying and calcination of ceramic articles. In the chemical process industry, batch furnaces may be used for the same purposes as batch-tray and truck dryers when the drying or process temperature exceeds 600 K (620°F). They are employed also for small-batch calcinations, thermal decompositions, and other chemical reactions which, on a larger scale, are performed in rotary kilns, hearth furnaces, and shaft furnaces. 

The double rotary kiln pyrolysis is designed for mechanical coupling of a pyrolysis unit and a combustion unit. The coaxial system of two rotary kilns opens up the possibility to evaporate organics from the feed material in the inner kiln while the carbonaceous residues are transported through the external kiln to a combustion zone. The process heat of combustion is used to heat the inner kiln while the ashes leave the system [4]. Both kilns can be equipped with lifters or spiral lifters. A comparable system has been purchased by Kurimoto industries, Japan for drying and calcining processes. 

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