Heat transfer effects external transport

The mass transfer effects cause, in general, a decrease of the measured reaction rate. The heat transfer effects may lead in the case of endothermic reactions also to a decrease of the equilibrium value and the resulting negative effect may be more pronounced. With exothermic reactions, an insufficient heat removal causes an increase of the reaction rate. In such a case, if both the heat and mass transfer effects are operating, they can either compensate each other or one of them prevails. In the case of internal transfer, mass transport effects are usually more important than heat transport, but in the case of external transfer the opposite prevails. Heat transport effects frequently play a more important role, especially in catalytic reactions of gases. The influence of heat and mass transfer effects should be evaluated before the determination of kinetics. These effects should preferably be completely eliminated. 

The activity calculated from (7) comprises both film and pore diffusion resistance, but also the positive effect of increased temperature of the catalyst particle due to the exothermic reaction. From the observed reaction rates and mass- and heat transfer coefficients, it is found that the effect of external transport restrictions on the reaction rate is less than 5% in both laboratory and industrial plants. Thus, Table 2 shows that smaller catalyst particles are more active due to less diffusion restriction in the porous particle. For the dilute S02 gas, this effect can be analyzed by an approximate model assuming 1st order reversible and isothermal reaction. In this case, the surface effectiveness factor is calculated from... 

Heat transfer is usually effected by coils or jackets, but can also be achieved by the use of external loop heat exchangers and, in certain cases, heat is transported out of the reactor by the vapourisation of volatile material from the reactor. The treatment here mainly concerns jackets and coils. Other instances of heat transfer are illustrated in the simulation examples of Chapter 5. 

Essentially all of the surface, of porous catalyst pellets is internal (see page 295). Reaction and mass and heat transfer occur simultaneously at any position within the pellet. The resulting intrapellet concentration and temperature gradients cause the rate to vary with position. At steady state the average rate for a whole pellet will be equal to the global rate at the location of the pellet in the reactor. The concentration and temperature of the bulk fluid at this location rhay not be equal to those properties at the outer surface of the pellet. The effect of such external resistances can be accounted for by the procedures outlined in Chap. 10. The objective in the present chapter is to account for internal resistances, that is, to evaluate average rates in terms of the temperature and concentration at the outer surface. Because reaction and transport occur simultaneously, differential... 

To conclude, an overall summary of calculations based on the above results indicates that the usual order of events as transport limitations occur is to begin with no limitations—chemical reaction controls throughout the pellet. Next, internal pore diffusion begins to have an effect, followed by external heat transfer... 

The rates at which chemical transformations take place are in some circumstances strongly influenced by mass and heat transfer processes (see Sections 12.3 to 12.5). In the design of heterogeneous catalytic reactors, it is essential to utilize a rate expression that takes into account the influence of physical transport processes on the rate at which reactants are converted to products. Smith (94) has popularized the use of the term global reaction rate to characterize the overall rate of transformation of reactants to products in the presence of heat and mass transfer limitations. We shall find this term convenient for use throughout the remainder of the chapter. Global rate expressions then include both external heat and mass transfer effects on the reaction rate and the efficiency with which the internal... 

The processes are transport of the gaseous reactant A in the vicinity of the liquid, transfer of this reactant through the gas-liquid interface into the liquid, transport of the dissolved gaseous reactant and of the liquid reactant B in the vicinity of the solid, transfer of both reactants at the external surface of the catalyst, through the liquid-solid interface, diffusion and reaction into the pores of the catalyst. The product undergoes similar mass transfer steps from the catalytic active sites to the liquid phase. In the case of a reaction with a heat effect, heat transfer steps associated to the proceeding mass transfer steps have to be considered. 

Heat and mass transfer coefficients can be used to interrogate the importance of external transport phenomena and how to choose reactor size. The latter controls (i) pressure drop, (ii) residence time and thus reactant conversion or flow rate and thus power generated, (iri) the effective reaction rate and thus the process efficiency, (iv) the temperature and (v) whether a system is kinetically controlled and thus ideal for extraction of catalytic kinetics. Another application of Nu and Sh is that a 2D or 3D problem can be reduced to a computationally tractable problem by approximating the transverse transport phenomena using overall transport correlations. Such pseudo-2 D models (also called heterogeneous ID models for catalytic systems) have been used to explore the stability and performance of microbumers with a significantly lower computational effort than CFD models (e.g. [23-25]). 

The general problem of diffusion-reaction for the overall effectiveness factor D is rather complicated. However, the physical and chemical rate processes prevailing under practical conditions promote isothermal particles and negligible external mass transfer limitations. In other words, the key transport limitations are external heat transfer and internal mass transfer. External temperature gradients can be significant even when external mass transfer resistances are negligibly small. 

Part II Building on Fundamentals is devoted to skill building, particularly in the area of catalysis and catalytic reactions. It covers chemical thermodynamics, emphasizing the thermodynamics of adsorption and complex reactions the fundamentals of chemical kinetics, with special emphasis on microkinetic analysis and heat and mass transfer effects in catalysis, including transport between phases, transfer across interfaces, and effects of external heat and mass transfer. It also contains a chapter that provides readers with tooisfor making accurate kinetic measurements and analyzing the data obtained. 

Mass and heat transport may influence the effective rate of heterogeneously catalyzed and gas-solid reactions. External profiles of concentration and temperature may be established in the boundary layer between the surface of the particles and the fluid, and internal gradients may develop in the particles (although for industrial practice the influence of internal heat transfer can be usually neglected). Deviations from the ideal zero-gradient situation are usually considered by effectiveness factors. 

Though the term "slurry refers to a suspension of fine solid particles in a liquid, the term slurry reactor is often used for a three-phase system, where both gas bubbles and solid particles are suspended in a liquid phase. For a solid/liquid/gas process, slurry reactors have two obvious advantages the possibilities for very large solid/liquid surface areas and for good heat transfer to the reactor wall. Therefore the volumetric capacity of slurry reactors can be relatively large. However, effective separation of the fine catalyst from the liquid phase may offer considerable technical problems. One possibility is an external separation, e.g. with centrifuges or hydrocyclones, and a transport of a concentrated catalyst slurry back into the reactor. More often internal filters are used, usually consisting of porous tubes (sintered stainless steel, or ceramics), that are cleaned every few minutes by a periodic reversal of the flow. 

In addition to these kinetic steps, there are also physical processes of heat and mass transfer to be considered. The external transport problem is one of heat and species exchange through the boundary layer between the surrounding bulk fluid and the catalyst surface (Figure 5). Concentration and temperature gradients are necessarily present in this case and would have to be accounted for in the modeling equations. Also, there is often an internal transport problem of heat conduction through the catalytic material -- and in the case of porous catalyst particles, an internal diffusion problem as well. Internal transport problems are beyond the scope of this paper. It must be noted, however, that any model intended to describe real-life systems will have to account for these effects. 

As pointed out earlier, the major external resistance is that of mass transfer, and therefore, the effect of external heat transfer can be neglected. Furthermore, internal (intraparticle) transport effects can be neglected in slurry reactors except under some unusual reaction conditions since the size of the catalyst particles is of the order of 100 microns. In trickle-beds, however, both the internal heat and mass transport effects can be important. 

As discussed earlier, catalyst particles instead of pellets are used when the rate of deactivation is high. The typical size of the catalyst particles used in fluidized-beds ranges from 20 to 300 fxm, and therefore, diffiisional effects can be neglected. In the absence of diffusional effects, the particles are isothermal and the external mass transfer resistance is negligible (Chapter 4). The only transport resistance is external heat transfer. For these particles then, the global rate is simply ... 

Heat and mass transfer processes always proceed with finite rates. Thus, even when operating under steady state conditions, more or less pronounced concentration and temperature profiles may exist across the phase boundary and within the porous catalyst pellet as well (Fig. 2). As a consequence, the observable reaction rate may differ substantially from the intrinsic rate of the chemical transformation under bulk fluid phase conditions. Moreover, the transport of heat or mass inside the porous catalyst pellet and across the external boundary layer is governed by mechanisms other than the chemical reaction, a fact that suggests a change in the dependence of the effective rate on the operating conditions (i.e concentration and temperature). 

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