Transfer, mass effects

Discussion of the concepts and procedures involved in designing packed gas absorption systems shall first be confined to simple gas absorption processes without compHcations isothermal absorption of a solute from a mixture containing an inert gas into a nonvolatile solvent without chemical reaction. Gas and Hquid are assumed to move through the packing in a plug-flow fashion. Deviations such as nonisotherma1 operation, multicomponent mass transfer effects, and departure from plug flow are treated in later sections. 

Reactor Configuration. The horizontal cross-sectional area of a reactor is a critical parameter with respect to oxygen mass-transfer effects in LPO since it influences the degree of interaction of the two types of zones. Reactions with high intrinsic rates, such as aldehyde oxidations, are largely mass-transfer rate-limited under common operating conditions. Such reactions can be conducted effectively in reactors with small horizontal cross sections. Slower reactions, however, may require larger horizontal cross sections for stable operation. 

Heat transfer and mass transfer occur simultaneously whenever a transfer operation involves a change in phase or a chemical reaction. Of these two situations, only the first is considered herein because in reacting systems the complications of chemical reaction mechanisms and pathways are usually primary (see HeaT-EXCHANGETECHNOLOGy). Even in processes involving phase changes, design is frequendy based on the heat-transfer process alone mass transfer is presumed to add no compHcations. But in fact mass transfer effects do influence and can even limit the process rate. 

One goal of catalyst designers is to constmct bench-scale reactors that allow determination of performance data truly indicative of performance in a full-scale commercial reactor. This has been accompHshed in a number of areas, but in general, larger pilot-scale reactors are preferred because they can be more fully instmmented and can provide better engineering data for ultimate scale-up. In reactor selection thought must be given to parameters such as space velocity, linear velocity, and the number of catalyst bodies per reactor diameter in order to properly model heat- and mass-transfer effects. 

When two-phase mass transfer is required to supply reactants by mixing for a chemical reaction, the most important factor to consider is whether the mass transfer controls the operation or whether the chemical reaction controls it. This can be done by increasing the mixer speed to a point w here mass transfer effects become very high and the operation is limited by the chemical reaction. 

The mass transfer effect is relevant when the chemical reaction is far faster than the molecular diffusion, i.e. Ha > 1. The rapid formation of precipitate particles should then occur spatially distributed. The relative rate of particle formation to chemical reaction and/or diffusion can as yet be evaluated only via lengthy calculations. 

When fluid swirling is prominent, it is difficult or impossible to reproduce the same mass transfer effect in any other size vessel, and hence cannot be reproduced by geometric similarity [21]. 

Very recently, Luckner et al. (116) obtained initial rate data for the metathesis of propene using the W0r-Si02 catalyst at flow rates where mass transfer effects were found to be negligible. Their experimental data referring to measurements at 0.1 to 0.9 MNm-2 and 672 to 727 K could be correlated by Eq. (53). 

Among the earlier studies of reaction kinetics in mechanically stirred slurry reactors may be noted the papers of Davis et al. (D3), Price and Schiewitz (P5), and Littman and Bliss (L6). The latter investigated the hydrogenation of toluene catalyzed by Raney-nickel with a view to establishing the mechanism of the reaction and reaction orders, the study being a typical example of the application of mechanically stirred reactors for investigations of chemical kinetics in the absence of mass-transfer effects. 

In this region, the mass transfer effects are small and the rate is determined almost entirely by the reaction kinetics. 

Thus t]X s 1, corresponding to the region where mass transfer effects dominate. The concentration profile is given by equation 10.198 as ... 

As a second process, the hydrogenation of a-methylstyrene is a standard process for elucidating mass transfer effects in catalyst pellets and in fixed-bed reactors... 

The oxidation of benzyl alcohol to benzaldehyde is carried out for elucidating mass transfer effects in a mini trickle-bed reactor [58]. 

Kita H, Ye S, Gao Y. 1992. Mass transfer effect in hydrogen evolution reaction on Pt singlecrystal electrodes in acid solution. J Electroanal Chem 334 351-357. 

PFE is based on the adjustment of known extraction conditions of traditional solvent extraction to higher temperatures and pressures. The main reasons for enhanced extraction performance at elevated temperature and pressure are (i) solubility and mass transfer effects and (ii) disruption of surface equilibria [487]. In PFE, a certain minimum pressure is required to maintain the extraction solvent in the liquid state at a temperature above the atmospheric boiling point. High pressure elevates the boiling point of the solvent and also enhances penetration of the solvent into the sample matrix. This accelerates the desorption of analytes from the sample surface and their dissolution into the solvent. The final result is improved extraction efficiency along with short extraction time and low solvent requirements. While pressures well above the values required to keep the extraction solvent from boiling should be used, no influence on the ASE extraction efficiency is noticeable by variations from 100 to 300 bar [122]. 

If the accommodation coefficient CA is equal or close to unity for liquid metals, as appears most likely for clean systems, then bubble growth in such liquids is little affected by mass transfer effects. It has been illustrated that the growth rate curves for CA = 1 and CA = are not very far apart. 

In electrochemistry, spherical and hemispherical electrodes have been commonly used in the laboratory investigations. The spherical geometry has the advantage that in the absence of mass transfer effect, its primary and secondary current distributions are uniform. However, the limiting current distribution on a rotating sphere is not uniform. The limiting current density is highest at the pole, and decreases with... 

Table 3 Madon-Boudart test for the absence of mass transfer effects, reaction conditions 45 psig hydrogen / 298 K / 700 RPM.

FI Do you think these mass transfer effects would become more serious at low or high mobile phase flow rates ... 

One often finds that either external or intraparticle mass transfer effects are significant in reactors of this type. Although the treatments... 

Schematic representation of shift in activation energy when intraparticle mass transfer effects become significant.

To illustrate the masking effects that arise from intraparticle and external mass transfer effects, consider a surface reaction whose intrinsic kinetics are second-order in species A. For this rate expression, equation 12.4.20 can be written as... 

Schematic representation of reactant concentration profiles in various global rate regimes. I External mass transfer limits rate. II Pore diffusion limits rate. Ill Both mass transfer effects are present. IV Mass transfer has no influence on rate.

This procedure obviously requires machine computation capability if it is to employed in reactor design calculations. Fortunately, there are many reactions for which the global rate reduces to the intrinsic rate, which avoids the necessity for calculations of this type. On the other hand, several high tonnage processes (e.g., S02 oxidation) are influenced by heat and mass transfer effects and one must be fully cognizant of their implications for design purposes. 

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