Reactors slurry

Survey of the patent Hterature reveals companies with processes for 1,4-butanediol from maleic anhydride include BASF (94), British Petroleum (95,96), Davy McKee (93,97), Hoechst (98), Huels (99), and Tonen (100,101). Processes for the production of y-butyrolactone have been described for operation in both the gas (102—104) and Hquid (105—108) phases. In the gas phase, direct hydrogenation of maleic anhydride in hydrogen at 245°C and 1.03 MPa gives an 88% yield of y-butyrolactone (104). Du Pont has developed a process for the production of tetrahydrofuran back-integrated to a butane feedstock (109). Slurry reactor catalysts containing palladium and rhenium are used to hydrogenate aqueous maleic acid to tetrahydrofuran (110,111). 

Ethjlben ne Synthesis. The synthesis of ethylbenzene for styrene production is another process in which ZSM-5 catalysts are employed. Although some ethylbenzene is obtained direcdy from petroleum, about 90% is synthetic. In earlier processes, benzene was alkylated with high purity ethylene in liquid-phase slurry reactors with promoted AlCl catalysts or the vapor-phase reaction of benzene with a dilute ethylene-containing feedstock with a BF catalyst supported on alumina. Both of these catalysts are corrosive and their handling presents problems. 

Fig. 4. Multiphase fluid and fluid—solids reactors (a) bubble column, (b) spray column, (c) slurry reactor and auxiUaries, (d) fluidization unit, (e) gas—bquid—sobd fluidized reactor, (f) rotary kiln, and (g) traveling grate or belt drier.

Heat Release and Reactor Stability. Highly exothermic reactions, such as with phthaHc anhydride manufacture or Fischer-Tropsch synthesis, compounded with the low thermal conductivity of catalyst peUets, make fixed-bed reactors vulnerable to temperature excursions and mnaways. The larger fixed-bed reactors are more difficult to control and thus may limit the reactions to jacketed bundles of tubes with diameters under - 5 cm. The concerns may even be sufficiently large to favor the more complex but back-mixed slurry reactors. 

Emulsion Polymerization. Emulsion and suspension reactions are doubly heterogeneous the polymer is insoluble in the monomer and both are insoluble in water. Suspension reactions are similar in behavior to slurry reactors. Oil-soluble initiators are used, so the monomer—polymer droplet is like a small mass reaction. Emulsion polymerizations are more complex. Because the monomer is insoluble in the polymer particle, the simple Smith-Ewart theory does not apply (34). 

Hydrogenations can be carried out in batch reactors, in continuous slurry reactors, or in fixed-bed reactors. The material of constmetion is usually 316 L stainless steel because of its better corrosion resistance to fatty acids. The hydrogenation reaction is exothermic and provisions must be made for the effective removal or control of the heat a reduction of one IV per g of C g fatty acid releases 7.1 J (1.7 cal), which raises the temperature 1.58°C. This heat of hydrogenation is used to raise the temperature of the fatty acid to the desired reaction temperature and is maintained with cooling water to control the reaction. 

Continuous slurry reactors are generally either of one of two designs. One type uses a reactor loop, generally known as a Buss loop design the other is a co-current hydrogen/fatty acid/catalyst system mainly marketed by Lurgi. Continuous slurry reactors are more popular in Europe, Asia, and South America than in the United States. 

The use of a fluidized-bed reactor is possible only when the reactants are essentiaUy in the gaseous phase. Eluidized-beds are not suitable for middle distiUate synthesis, where a heavy wax is formed. Eor gasoline synthesis processes like the MobU MTG process and the Synthol process, such reactors are especiaUy suitable when frequent or continuous regeneration of the catalyst is required. Slurry reactors and ebuUiating-bed reactors comprising a three-phase system with very fine catalyst are, in principle, suitable for middle distiUate and wax synthesis, but have not been appHed on a commercial scale. 

Dente and Ranzi (in Albright et al., eds.. Pyrolysis Theory and Industrial Practice, Academic Press, 1983, pp. 133-175) Mathematical modehng of hydrocarbon pyrolysis reactions Shah and Sharma (in Carberry and Varma, eds.. Chemical Reaction and Reaction Engineering Handbook, Dekker, 1987, pp. 713-721) Hydroxylamine phosphate manufacture in a slurry reactor Some aspects of a kinetic model of methanol synthesis are described in the first example, which is followed by a second example that describes coping with the multiphcity of reactants and reactions of some petroleum conversion processes. Then two somewhat simph-fied industrial examples are worked out in detail mild thermal cracking and production of styrene. Even these calculations are impractical without a computer. The basic data and mathematics and some of the results are presented. 

Most industrial processes with slurry reactors are usea for gases with liquids, such as chlorination, hydrogenation, and oxidation. 

Substances that have been hydrogenated in slurry reactors include nitrobenzene with Pd-C, butynediol with Pd-CaCO,3, chlorobenzene with Pt-C, toluene with Raney Ni, and acetone with Raney Ni. 

Some contrasting characteristics of the main lands of three-phase reactors are summarized in Table 23-15. In trickle bed reactors both phases usually flow down, the liquid as a film over the packing. In flooded reactors, the gas and hquid flow upward through a fixed oed. Slurry reactors keep the solids in suspension mechanically the overflow may be a clear liquid or a slurry, and the gas disengages from the... 

Slurry Reactors with Mechanical Agitation The catalyst may be retained in the vessel or it may flow out with the fluid and be separated from the fluid downstream. In comparison with trickle beds, high heat transfer is feasible, and the residence time can be made veiy great. Pressure drop is due to sparger friction and hydrostatic head. Filtering cost is a major item. 

The Fischer-Tropsch reaction is highly exothermic. Therefore, adequate heat removal is critical. High temperatures residt in high yields of methane, as well as coking and sintering of the catalyst. Three types of reac tors (tubular fixed bed, fluidized bed, and slurry) provide good temperature control, and all three types are being used for synthesis gas conversion. The first plants used tubular or plate-type fixed-bed reactors. Later, SASOL, in South Africa, used fluidized-bed reactors, and most recently, slurry reactors have come into use. 

The effect of physical processes on reactor performance is more complex than for two-phase systems because both gas-liquid and liquid-solid interphase transport effects may be coupled with the intrinsic rate. The most common types of three-phase reactors are the slurry and trickle-bed reactors. These have found wide applications in the petroleum industry. A slurry reactor is a multi-phase flow reactor in which the reactant gas is bubbled through a solution containing solid catalyst particles. The reactor may operate continuously as a steady flow system with respect to both gas and liquid phases. Alternatively, a fixed charge of liquid is initially added to the stirred vessel, and the gas is continuously added such that the reactor is batch with respect to the liquid phase. This method is used in some hydrogenation reactions such as hydrogenation of oils in a slurry of nickel catalyst particles. Figure 4-15 shows a slurry-type reactor used for polymerization of ethylene in a sluiTy of solid catalyst particles in a solvent of cyclohexane. 

El-Halwagi, M. M. (1990). Optimization of bubble column slurry reactors via natural delayed feed addition. Chem. Eng. Commun., 92, 103-119. 

The simplest theory involved in mass transfer across an interface is film theory, as shown in Figure 3.10. In this model, the gas (CO) is transferred from the gas phase into the liquid phase and it must reach the surface of the growing cells. The rate equation for this case is similar to the slurry reactor as mentioned in Levenspiel.20... 

The catalytic hydrogenation of fatty oils, the desulfurization of liquid petroleum fractions by catalytic hydrogenation, Fischer-Tropsch-type synthesis in slurry reactors, and the manufacture of calcium bisulfite acid are familiar examples of this type of process, for which the term gas-liquid-particle process will be used in the following. 

In the second class, the particles are suspended in the liquid phase. Momentum may be transferred to the particles in different ways, and it is possible to distinguish between bubble-column slurry reactors (in which particles are suspended by bubble movement), stirred-slurry reactors (in which particles are suspended by bubble movement and mechanical stirring), and gas-liquid fluidized reactors (in which particles are suspended by bubble movement and cocurrent liquid flow). 

All these gas-liquid-particle operations are of industrial interest. For example, desulfurization of liquid petroleum fractions by catalytic hydrogenation is carried out, on the industrial scale, in trickle-flow reactors, in bubble-column slurry reactors, and in gas-liquid fluidized reactors. 

Catalytic desulfurization is at present carried out industrially by at least three of the major types of gas-liquid-particle operations referred to in Section I trickle reactors, bubble-column slurry reactors, and gas-liquid fluidized reactors. 

Epoxides such as ethylene oxide and higher olefin oxides may be produced by the catalytic oxidation of olefins in gas-liquid-particle operations of the slurry type (S7). The finely divided catalyst (for example, silver oxide on silica gel carrier) is suspended in a chemically inactive liquid, such as dibutyl-phthalate. The liquid functions as a heat sink and a heat-transfer medium, as in the three-phase Fischer-Tropsch processes. It is claimed that the process, because of the superior heat-transfer properties of the slurry reactor, may be operated at high olefin concentrations in the gaseous process stream without loss with respect to yield and selectivity, and that propylene oxide and higher... 

In bubble-column slurry reactors, momentum is transferred to the liquid phase by the movement of gas bubbles. The liquid medium is stationary in most cases. Finely divided solids with particle diameters of the order of 0.01 mm are used. The operation is usually carried out in columns with high height-to-diameter ratios. The operation may be employed for batchwise conversion of a liquid reactant, or for continuous reaction between gaseous reactants. 

Slesser and Highet (S15) have proposed a theoretical model for the case of a second-order chemical reaction taking place in a slurry reactor. This model is based on concepts very similar to those employed by Sherwood and Farkas, apart from the obvious complications resulting when one treats a second-order reaction. 

Only one publication on gas-liquid mass transfer in bubble-column slurry reactors has come to the author s attention. However, a relatively large volume of information regarding mass transfer between single bubbles or bubble swarms and pure liquid containing no suspended solids is available, and this information is probably of some relevance to the analysis of systems... 

Various methods may be used for the determination of gas holdup—for example, displacement measurements and tracer experiments. Farley and Ray (F2) have described the use of gamma-radiation absorption measurement for the determination of gas holdup in a slurry reactor for the Fischer-Tropsch synthesis. 

Calderbank et al. (C6) studied the Fischer-Tropsch reaction in slurry reactors of 2- and 10-in. diameters, at pressures of 11 and 22 atm, and at a temperature of 265°C. It was assumed that the liquid-film diffusion of hydrogen from the gas-liquid interface is a rate-determining step, whereas the mass transfer of hydrogen from the bulk liquid to the catalyst was believed to be rapid because of the high ratio between catalyst exterior surface area and bubble surface area. The experimental data were not in complete agreement with a theoretical model based on these assumptions. 

Stirred-slurry reactors are of considerable industrial importance in batch-wise processing. The catalytic hydrogenation of fats and fatty acids is an example of a process that is carried out almost exclusively in mechanically stirred slurry reactors. The operation is of less significance with respect to continuous processing. 

Mass transfer across the liquid-solid interface in mechanically agitated liquids containing suspended solid particles has been the subject of much research, and the data obtained for these systems are probably to some extent applicable to systems containing, in addition, a dispersed gas phase. Liquid-solid mass transfer in such systems has apparently not been studied separately. Recently published studies include papers by Calderbank and Jones (C3), Barker and Treybal (B5), Harriott (H4), and Marangozis and Johnson (M3, M4). Satterfield and Sherwood (S2) have reviewed this subject with specific reference to applications in slurry-reactor analysis and design. 

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