Fixed-Bed Reactors - Particle Beds

Important processing parameters are the maximum pressure and the rate of the pressure rise, both of which influence not only the hardness of the pellet produced, but also the integrity of the compacted particles inside. It is intended that agglomerates undergo deformation, breakdown. 

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Fluidized-bed catalytic reactors. In fluidized-bed reactors, solid material in the form of fine particles is held in suspension by the upward flow of the reacting fluid. The effect of the rapid motion of the particles is good heat transfer and temperature uniformity. This prevents the formation of the hot spots that can occur with fixed-bed reactors. 

R Liquid film flowing over solid particles with air present, trickle bed reactors, fixed bed... 

In many important cases of reactions involving gas, hquid, and solid phases, the solid phase is a porous catalyst. It may be in a fixed bed or it may be suspended in the fluid mixture. In general, the reaction occurs either in the liquid phase or at the liquid/solid interface. In fixed-bed reactors the particles have diameters of about 3 mm (0.12 in) and occupy about 50 percent of the vessel volume. Diameters of suspended particles are hmited to O.I to 0.2 mm (0.004 to 0.008 in) minimum by requirements of filterability and occupy I to 10 percent of the volume in stirred vessels. 

Figure 2.2.4 (Berty 1983) shows a tubular reactor that has a thermosiphon temperature control system. The reaction is conducted in the vertical stainless steel tube that can have various diameters, 1/2 in. being the preferred size. If used for fixed bed catalytic studies, it can be charged with a single string of catalytic particles just a bit smaller than the tube, e.g., 5/16 particles in a l/2 O.D. tube. With a smaller catalyst, a tube with an inside diameter of up to three to four particle diameters can be used. With such catalyst charges and a reasonably high Reynolds number— above 500, based on particle diameter—this reactor...

As mentioned in Section 2.2 (Fixed-Bed Reactors) and in the Micro activity test example, even fluid-bed catalysts are tested in fixed-bed reactors when working on a small scale. The reason is that the experimental conditions in laboratory fluidized-bed reactors can not even approach that in production units. Even catalyst particle size must be much smaller to get proper fluidization. The reactors of ARCO (Wachtel, et al, 1972) and that of Kraemer and deLasa (1988) are such attempts. 

Figure 4-8 shows a continuous reactor used for bubbling gaseous reactants through a liquid catalyst. This reactor allows for close temperature control. The fixed-bed (packed-bed) reactor is a tubular reactor that is packed with solid catalyst particles. The catalyst of the reactor may be placed in one or more fixed beds (i.e., layers across the reactor) or may be distributed in a series of parallel long tubes. The latter type of fixed-bed reactor is widely used in industry (e.g., ammonia synthesis) and offers several advantages over other forms of fixed beds. 

A salient feature of the fluidized bed reactor is that it operates at nearly constant temperature and is, therefore, easy to control. Also, there is no opportunity for hot spots (a condition where a small increase in the wall temperature causes the temperature in a certain region of the reactor to increase rapidly, resulting in uncontrollable reactions) to develop as in the case of the fixed bed reactor. However, the fluidized bed is not as flexible as the fixed bed in adding or removing heat. The loss of catalyst due to carryover with the gas stream from the reactor and regenerator may cause problems. In this case, particle attrition reduces their size to such an extent where they are no longer fluidized, but instead flow with the gas stream. If this occurs, cyclone separators placed in the effluent lines from the reactor and the regenerator can recover the fine particles. These cyclones remove the majority of the entrained equilibrium size catalyst particles and smaller fines. The catalyst fines are attrition products caused by... 

In the first class, the particles form a fixed bed, and the fluid phases may be in either cocurrent or countercurrent flow. Two different flow patterns are of interest, trickle flow and bubble flow. In trickle-flow reactors, the liquid flows as a film over the particle surface, and the gas forms a continuous phase. In bubble-flow reactors, the liquid holdup is higher, and the gas forms a discontinuous, bubbling phase. 

Logtenberg, S. A., Nijemeisland, M., and Dixon, A. G., Computational fluid dynamics simulations of fluid flow and heat transfer at the wall-particle contact points in a fixed-bed reactor, Chem. Eng. Sci. 54, 2433-2439 (1999). 

Few fixed-bed reactors operate in a region where the intrinsic kinetics are applicable. The particles are usually large to minimize pressure drop, and this means that diffusion within the pores. Steps 3 and 7, can limit the reaction rate. Also, the superficial fluid velocity may be low enough that the external film resistances of Steps 2 and 8 become important. A method is needed to estimate actual reaction rates given the intrinsic kinetics and operating conditions within the reactor. The usual approach is to define the effectiveness factor as... 

Traditionally, an average Sherwood number has been determined for different catalytic fixed-bed reactors assuming constant concentration or constant flux on the catalyst surface. In reality, the boundary condition on the surface has neither a constant concentration nor a constant flux. In addition, the Sh-number will vary locally around the catalyst particles and in time since mass transfer depends on both flow and concentration boundary layers. When external mass transfer becomes important at a high reaction rate, the concentration on the particle surface varies and affects both the reaction rate and selectivity, and consequently, the traditional models fail to predict this outcome. 

In contrast to the Pt catalysts discussed above, Ni based catalysts (i.e., also when supported on ZrO usually form coke at such a rapid rate that most fixed bed reactors are completely blocked after a few minutes time on stream (see Fig. 8) [16], The coke formed with the Ni catalysts is filamentous. The Ni particle remaining at the tip of the filament hardly deactivates as the coke formed on its surface seems to be transported through the metal particle into the carbon fibre, but the drastic increase in volume causes reactor plugging and prevents use of the still active catalyst (see Fig. 8). The TEM photographs indicate that the carbon filaments have similar diameters to those of the Ni particles. 

The two different concepts are depicted schematically in Figure 1.15. The fixed bed is assumed to have a cross-section Sp and a height Hp and is fiUed with non-deformable spherical particles with diameter dp, where the density of the packing (particles per m ) is denoted by n-p. The micro-channel reactor has a cross-section and a height and comprises channels of diameter d with a specific density (number of channels per m ) n-j. ... 

For a fixed bed of spherical particles, the Kozeney coefficient lies between 4.5 and 5. Hence the pressure drop in the fixed bed is up to 2.5 times larger than that in the micro-channel reactor, for otherwise comparable conditions. This suggests... 

GP 9[ [R 16]The extent of internal transport limits was analysed for the wide fixed-bed reactor, using experimental data on carbon monoxide conversion and matter and process parameter data for the reactants [78]. The analysis was based on the Weisz modulus and the Anderson criterion for judging possible differences between observed and actual reaction rates. As a result, it was found that the small particles eliminate internal transport limitations. 

In addition to the general improvement of transfer in micro reactors, there is evidence that the voltage of electroosmotic flow (for EOF see [14]) in combination with the large internal surface area in glass chips can induce hydroxide ion formation [6]. Concerning catalyst loss, there is no obvious direct correlation rather, micro reactors can act as mini fixed beds fixing heterogeneous catalyst particles. 

GL 16] [R 12] [P 15] By a plasma etch process (see description in ]R 12]), a highly porous surface stmcture can be realized which can be catalyst coated [12]. The resulting surface area of 100 m is not far from the porosity provided by the catalyst particles employed otherwise as a fixed bed. In one study, a reactor with such a waU-porous catalyst was compared with another reactor having the catalyst particles as a fixed bed. The number of channels for both reactors was not equal, which has to be considered in the following comparison. 

Solid catalysts can be subdivided further according to the reactor chosen. Dependent on the type of reactor the optimal dimensions and shapes of the catalyst particles differ. Catalysts applied in fixed beds are relatively large particles (typically several mm in diameter) in order to avoid excessive pressure drops. Extrudates, tablets, and rings are the common shapes. Figure 3.9 shows some commonly encountered particle shapes. 

In any catalyst selection procedure the first step will be the search for an active phase, be it a. solid or complexes in a. solution. For heterogeneous catalysis the. second step is also deeisive for the success of process development the choice of the optimal particle morphology. The choice of catalyst morphology (size, shape, porous texture, activity distribution, etc.) depends on intrinsic reaction kinetics as well as on diffusion rates of reactants and products. The catalyst cannot be cho.sen independently of the reactor type, because different reactor types place different demands on the catalyst. For instance, fixed-bed reactors require relatively large particles to minimize the pressure drop, while in fluidized-bed reactors relatively small particles must be used. However, an optimal choice is possible within the limits set by the reactor type. 

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