Pellet Transport Properties

Transport Properties. Because the feed is primarily air and because substantial amounts of N2 and 02 are present in the effluent stream, we will assume that the fluid viscosity is that of air for purposes of pressure drop calculations. For the temperature range of interest, the fluid viscosity may be taken as equal to 320 micropoise. The pressure range of interest does not extend to levels where variations of viscosity with pressure need be considered. The effective diffusivities of naphthalene and phthalic anhydride in the catalyst pellet may be evaluated using the techniques developed in Section 12.2. 

It will be supposed that the kinetics of all the reactions that are going on and the thermodynamical and molecular transport properties of all the substances present are known, and that it is desired to find out how the composition of the effluent from a reactor depends on the conditions that are imposed. The conditions that must be fixed are the composition, pressure, temperature, and flow rate of the reactant mixture, the dimensions of the reactor and of the catalyst pellets, and enough properties of the heat-transfer medium to determine a relation between the temperature of the tube wall and the heat flux through it. 

The general approach for modelling catalyst deactivation is schematically organised in Figure 2. The central part are the mass balances of reactants, intermediates, and metal deposits. In these mass balances, coefficients are present to describe reaction kinetics (reaction rate constant), mass transfer (diffusion coefficient), and catalyst porous texture (accessible porosity and effective transport properties). The mass balances together with the initial and boundary conditions define the catalyst deactivation model. The boundary conditions are determined by the axial position in the reactor. Simulations result in metal deposition profiles in catalyst pellets and catalyst life-time predictions. 

S.C. Reyes and E. Iglesia, Simulation techniques for the characterization of structural and transport properties of catalyst pellets, in Computer-Aided Design of Catalysts E.R. Becker, and C.J. Pereira, cds., Dekker, New York, 1993. 

Equation (11-77) shows that the maximum temperature rise depends on the heat of reaction, transport properties of the pellet, and the surface concentration of reactant. It permits a simple method of estimating whether intrapellet temperature differences are significant (see Example 11-9). 

The combined application of PFG NMR self-diffusion and tracer desorption experiments has thus proved to be an effective tool for studying the hydrothermal stability of A-type zeolites with respect to their transport properties [186]. It turns out that with commercial adsorbent samples there are considerable variations in hydrothermal stability between different batches of product and even between different pellets from the same batch. As an example. Fig. 24 shows the distribution curves [A(Tin,ra) versus Ti ,r.j] measured with ethane as a probe molecule at 293 K for two different samples of commercial 5A zeolites. Evidently batch 1 is more resistant to hydrothermal deterioration, because the lengthening of Tjn,ra is less dramatic than with batch 2. Since the intracrystalline diffusivity was the same for all samples, the deterioration can be attributed to the formation of a surface barrier. 

This chapter treated, the fixed-bed reactor, a tubular reactor packed with, catalyst pellets. We started with a general overview of the transport and reactio.n events that take place in. the fixed-bed reactor transport by convection in the fluid diffusion inside the catalyst pores. and adsorption, reaction and desorption on the catalyst surface. We summarized the transport properties of the catalyst particles, and described bulk and Knudsen diffusion phenomena. 

Figure 5. Pellet intruded at Sbara. Once the alloy is able to pass through pores at the pellet surface, it floods through the pellet. The large macroporous voids act as conduits for flow throughout the pellet. The pellet thus appears to have good internal diffusion transport properties.

Throughout this book various transport properties and transfer coefficients have been used. These include effective diffusivity and thermial conductivity for mass and heat transport in catalyst pellets, film transfer coefficients for mass and heat transfer across the pellet-bulk fluid interface, transport properties for the degree of dispersion of mass and heat in the reactor, and heat transfer coefficients for heat exchange between the cooling medium and the reactor. In this chapter these transport properties and transfer coefficients are treated in detail, including experimental methods for obtaining these properties. 

Fixed-beds packed with inert pellets are usually used for the determination of transport properties and transfer coefficients. The solution of a steady-state mass or heat balance equation is compared with concentration or temperature measurements for the determination. For thermal properties, for instance, radial temperature... 

While the previously described techniques were measuring the nanoscopic and microscopic properties of the catalyst pellets, respectively, fluid transport within... 

The catalyst activity depends not only on the chemical composition but also on the diffusion properties of the catalyst material and on the size and shape of the catalyst pellets because transport limitations through the gas boundary layer around the pellets and through the porous material reduce the overall reaction rate. The influence of gas film restrictions, which depends on the pellet size and gas velocity, is usually low in sulphuric acid converters. The effective diffusivity in the catalyst depends on the porosity, the pore size distribution, and the tortuosity of the pore system. It may be improved in the design of the carrier by e.g. increasing the porosity or the pore size, but usually such improvements will also lead to a reduction of mechanical strength. The effect of transport restrictions is normally expressed as an effectiveness factor q defined as the ratio between observed reaction rate for a catalyst pellet and the intrinsic reaction rate, i.e. the hypothetical reaction rate if bulk or surface conditions (temperature, pressure, concentrations) prevailed throughout the pellet [11], For particles with the same intrinsic reaction rate and the same pore system, the surface effectiveness factor only depends on an equivalent particle diameter given by... 

In the electrode with CuS alone, which has negligible conductivity, the precipitate ISE with a silicone rubber matrix has better properties than the electrode with a pressed pellet [314], The ISE with a mixture of CuS and Agi S finds broad application [325]. If the membrane is prepared by pressing, the grains of these two compounds combine to form jalpaite, Agi.55C%.4sS [180], This substance is a mixed conductor with transport numbers of Ag, 0.69 Cu(I), 0.30 and electrons, 0.01, at 25 C [175]. The sintered electrode also contains Ag1.2Cuo.8S or Ago.93Cu1.07S. Oxidation of these phases leads to considerable deterioration in the electrode function [180]. Good electrodes... 

The effective diffusivity Dn decreases rapidly as carbon number increases. The readsorption rate constant kr n depends on the intrinsic chemistry of the catalytic site and on experimental conditions but not on chain size. The rest of the equation contains only structural catalyst properties pellet size (L), porosity (e), active site density (0), and pore radius (Rp). High values of the Damkohler number lead to transport-enhanced a-olefin readsorption and chain initiation. The structural parameters in the Damkohler number account for two phenomena that control the extent of an intrapellet secondary reaction the intrapellet residence time of a-olefins and the number of readsorption sites (0) that they encounter as they diffuse through a catalyst particle. For example, high site densities can compensate for low catalyst surface areas, small pellets, and large pores by increasing the probability of readsorption even at short residence times. This is the case, for example, for unsupported Ru, Co, and Fe powders. 

While the above criteria are useful for diagnosing the effects of transport limitations on reaction rates of heterogeneous catalytic reactions, they require knowledge of many physical characteristics of the reacting system. Experimental properties like effective diffusivity in catalyst pores, heat and mass transfer coefficients at the fluid-particle interface, and the thermal conductivity of the catalyst are needed to utilize Equations (6.5.1) through (6.5.5). However, it is difficult to obtain accurate values of those critical parameters. For example, the diffusional characteristics of a catalyst may vary throughout a pellet because of the compression procedures used to form the final catalyst pellets. The accuracy of the heat transfer coefficient obtained from known correlations is also questionable because of the low flow rates and small particle sizes typically used in laboratory packed bed reactors. 

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