2.

Applications of Radial-Flow Reactors

The physical dimensions and operating conditions of several commercial radial-flow reactors are presented in Table 2. Illustrated in Figures 2,3, 4 and 5are radial-flow reactor designs for ammonia synthesis, ethylbenzene dehydrogenation, and catalytic reforming. Synthesis of ammonia from hydrogen and nitrogen ( Ammonia) is an exothermic reaction, and is usually carried out at 400500 C and 1421 MPa. The ammonia concentration in the reactor effluent is 1222 %, which results in a large amount of the synthesis gases being recycled. Because the radial-flow reactor has a much smaller pressure drop, choosing a radialflow reactor over an axial-flow reactor can reduce the size of the recycle gas compressor and allowuse of smaller catalyst particles to improve the catalyst efficiency. Major ammonia technology licensors, Kellogg Brown & Root (KBR), Topse, Uhde, and Ammonia Casale, have developed their own proprietary radial-flow reactor designs [14 21]. Figure 2 shows KBRs Advanced Ammonia Process converter design. It has four catalyst beds in one shell, and three interstage coolers to remove the heat of reaction from the effluents of beds 13. In all four beds, the gas flows from outside to inside. In the upper three beds, the gas flows downward in the outer annulus and upward in the inner annulus (i.e.,shaped catalyst bed). After it comes out of the inner annulus, the gas turns downward to pass through the shell side of the interstage cooler. In the bottom bed, the gas flows downward in both the outer annulus and the center pipe (i.e., Z-shaped catalyst bed). Another radial-flow reactor design for ammonia synthesis, the Topse S-200 type converter, is illustrated in Figure 3. It has two catalyst beds and two internal heat exchangers: one at the bottom of the reactor and the other in the center core of the lower catalyst bed. The cold reactor feed first flows down the annulus between the reactor shell and the shell containing the catalyst bed. There is a large pressure difference but a small temperature difference across the reactor shell, and a small pressure difference but a large temperature difference across the catalyst bed shell. The feed is heated in the bottom heat exchanger by the effluent from the upper bed (the second catalyst bed). It then mixes with a cold bypass and with a second feed stream, which is heated in the interbed heat exchanger by the first bed effluent. The mixed feed flows from the annulus toward the center of the first catalyst bed. After passing

through the shell side of the interbed exchanger, the first-bed effluent flows outward across the second catalyst bed, and then exits through an annulus and the bottom heat exchanger. The first catalyst bed has inward flow, while the second catalyst bed has outward flow. Both catalyst beds are -shaped. By : Ullmans

8.2.1 Ammonia Synthesis [11, 16] The synthesis of ammonia from nitrogen and hydrogen is one of the most important processes in the chemical industry; over 100_106 t/a of ammonia is produced worldwide. The HaberBosch process, introduced in 1913, was the first high-pressure industrial process. Ammonia synthesis is carried out at ca. 300 bar and 500_C on iron catalysts with small amounts of the promoters Al2O3, K2O, and CaO. Extensive investigations of the mechanism of ammonia synthesis have shown that the rate-determining step is the dissociation of coordinatively bound nitrogen molecules on the catalyst surface. Hydrogen is much more readily dissociated on the catalyst surface. The adsorbed species then undergo a series of insertion steps, in which ammonia is formed stepwise and is finally desorbed (Scheme 8-1). At moderately high pressures the reaction rate is independent of the hydrogen pressure and first order with respect to nitrogen. The stationary occupation by N* atoms is low, and this indicates that the dissociative adsorption of N2 is rate-determining. At higher hydrogen pressures, there is a fractional reaction order in H2 corresponding to displacement of the rate-determining step towards N* + H*_NH* The elucidation of the reaction mechanism has occupied catalysis researchers up to the present day [11]. Over 20 000 catalysts have been tested, but none has been
Dissociative chemisorption of starting materials 2) Reaction of adsorbed atoms 3) Desorption of product Scheme 8-1 Simplified mechanism of ammonia synthesis

found that operates at room temperature. Catalytic activity is exhibited by metals that chemisorb N2 dissociatively with relatively strong binding, especially the metals of Groups 68 with d gaps, on which large amounts of H2 are also rapidly chemisorbed. The activity increases with increasing heat of adsorption of N2 in the order: Cr < Mn < Fe, Mo < Ru and W < Re < Os Other metals are more active in cleaving the N_N bond (e. g., Li) but the resulting metal nitrides are too stable to take part in a catalytic cycle. For economic reasons, industrial catalysts consist of smelted iron oxides (60 70 % Fe) mixed with oxides of Al, Ca, Mg, and K, ground to 620 mm. During the activation of the catalyst by reduction, iron crystallites are formed with an interconnected pore system and an inner surface area of 1020 m2/g. The surface is partially covered by promoter oxides. The industrial production of ammonia from natural gas involves eight different catalytic steps (Scheme 8-2). The overall reaction equation is given in Equation (8-1). 3CH4 + 2N2 + 3O2_4NH3 + 3CO2 (8-1) The thermodynamic energy requirement is 2_107 kJ/t NH3, which represents the theoretical minimum for all conceivable processes. Modern processes for the production of ammonia from natural gas have energy consumptions of around 3_107 kJ/t NH3, i. e., only 1.5 times the theoretical minimum energy consumption. Today much of the energy requirement can be covered by means of heat recovery. Modern ammonia plants produce up to 2000 t/d.

8.2.2 Hydrogenation [2, 6] With increasing crude oil prices, there is a growing trend towards renewable raw materials. Fats (triglycerides) are being used in increasing quantities as raw materials in the chemical industry. The glycerides are oxidized, hydrogenated, and ami8.2 Examples of Industrial Processes 267 N2,G N2* 2 N* H2,G 2 H* N* + H* NH* NH2* NH3 * H* H* NH3 * NH3,G 1) Dissociative chemisorption of starting materials 2) Reaction of adsorbed atoms 3) Desorption of product Scheme 8-1 Simplified mechanism of ammonia synthesis

nated to remove undesired functional groups, to shorten the chain length, or to introduce other functional groups. Many of these steps are carried out catalytically, and for economic reasons should take place at low temperatures and pressures in order to attain high selectivities [5, 13]. An important process in the foods industry is the hardening of vegetable oils, for example, the production of margarine by hydrogenation of double bonds. In this process an oil is converted to a solid that should have high stability towards oxidation, which leads to rancidity. The main aim in an industrial process is to remove linolenic acid (three CC double bonds) as completely as possible while minimizing conversion of the desired oleic acid (one CC double bond) to the saturated stearic acid.