Mass transfer accompanied with complete reversible chemical reactions in gas-liquid systems: an overview

In many processes in the chemical industry mass transfer accompanied with reversible, complex chemical reactions in gas-liquid systems are frequently encountered. In point of view of design purposes it is very important that the absorption rates of the transferred reactants can estimated sufficiently accurate. Moreover, mass transfer phenomena can also affect substantially important process variables like selectivity and yield. Therefore large amounts of research effort has been invested in describing these processes and in the development of models that can be used for the calculation of the mass transfer rates and other parameters.\ud \ud The description of the absorption of a gas followed by a single first order irreversible reaction is simple and straightforward. For all mass transfer models, e.g. film, penetration and surface renewal respectively, this process can be analytically solved. For other processes however, only for a limited number of special cases analytical solutions are possible and therefore numerical techniques must be used for the description of these phenomena. Besides numerically solved absorption models the mass transfer rates often can be calculated satisfactory accurate by simplifying the actual process by means of approximations and/or linearizations. In this paper an overview will be given of the absorption models that are available for the calculation of the mass transfer rates in gas-liquid systems with (complex) reversible reactions. Both numerically solved and approximated models respectively will be treated and conclusions on the applicability and restrictions will be presented. Also perspectives and white spots will be indicated

On the kinetics between CO2 and alkanolamines both in aqueous and non-aqueous solutions—II. Tertiary amines

The reaction between CO2 and tertiary alkanolamines (MDEA, DMMEA, TREA) has been studied in aqueous solutions at various temperatures. Also the absorption of CO2 in a solution of MDEA in ethanol has been studied. Reaction kinetics have been established by chemically enhanced mass transfer of CO2 into the various solutions. The experiments were performed in a stirred vessel with a horizontal interface which appeared to the eye to be completely smooth. The reaction of CO2 with tertiary amines can be described satisfactorily with the base-catalysis mechanism proposed by Donaldson and Nguyen (1980). Also attention has been paid to the influence of reversibility and small amounts of impurities (primary and secondary amines) on the measured mass transfer rate. For the reaction rate constant, k2, of the reaction between carbon dioxide and tertiary amines exists a Brønsted relation. There is a linear relation between the logarithm of k2 and pKa at 293 K

On the kinetics between CO2 and alkanolamines both in aqueous and non-aqueous solutions—I. Primary and secondary amines

The reaction between CO2 and primary and secondary alkanolamines (DEA and DIPA) has been studied both in aqueous and non-aqueous solutions (ethanol and n-butanol) at various temperatures. Reaction kinetics have been established by chemically enhanced mass transfer of CO2 into the various solutions. The experiments were performed in a stirred vessel operated with a horizontal interface which appeared to the eye to be completely smooth. The reaction can be described with the zwitterion-mechanism originally proposed by Caplow (1968) and reintroduced by Danckwerts (1979). Literature data on the reaction rates can be correlated fairly well with this mechanism. As all amines react with CO2 in a reversible way, and the mass transfer models used for the interpretation of the experimental data neglect this reversibility and take only the forward reaction rate into account, the influence of the reversibility is studied. With the aid of numerical mass transfer models (Versteeg et al., 1987b,c) the experimental method with its underlying assumptions have been verified and the applicability and the limits of this method were determined. Special attention has been paid to the influence of small amounts of impurities (amines) on the measured mass transfer rates. A Brønsted relationship exists between the second-order rate constant, k2, for the formation of the zwitterion and the acid dissociation constant of the alkanolamine

A Kinetic Model for Toluene Oxidation Comprising Benzylperoxy Benzoate Ester as Reactive Intermediate in the Formation of Benzaldehyde

During the oxidation of toluene under semibatch conditions, the formation of benzyl alcohol is initially equal to the rate of formation of benzaldehyde. As the overall conversion increases the benzyl alcohol concentration at first decreases much faster than benzaldehyde, but this decrease slows down causing the benzyl alcohol concentration to reduce to zero only very slowly. To account for this phenomenon a new reaction pathway has been proposed where the formation of benzaldehyde out of benzylhydroperoxide is catalysed by benzoic acid. Incorporation of this new reaction in a model improves the description of benzyl alcohol concentration prophiles while maintaining good predictions for benzaldehyde and benzoic acid

Simultaneous dehydrogenation of organic compounds and hydrogen removal by hydride forming alloys

The applicability of hydrogen-absorbing metals in dehydrogenation reactions was investigated. Based on thermodynamic considerations, operating ranges were defined within which an increase of the reactant c onversion can be achieved owing to an in situ hydrogen removal by the alloy. Low plateau pressures (e.g. < 0.01 MPa) at high temperature (e.g. > 473 K) are required for economic applications. An (economic) improvement of the alkane-to-alkene conversion does not seem feasible owing to the extreme pressure and temperature conditions. In the present study as a model system, 2-propanol was dehydrogenated in a batch process at 473 K and 0.1-1.0 MPa over a Cu/CuO catalyst in the presence of an excess amount of Mg2.4Ni. The hydride forming metal alloy appears to be able to affect the hydrogen balance of the experimental system owing to absorption or desorption. However, an unexpected catalytic effect of the metal hydride was observed towards condensation reactions. Owing to the loss in selectivity, Mg2.4Ni, is not applicable for an improvement of the dehydrogenation processes for secondary alcohols

Absorption accompanied with chemical reaction in trickle-bed reactors.

A new development in the field of internals in packed columns is the use of structured packing types. Recently, a new structured packing type coated with a thin alumina layer (KATAPAKTM) has been developed. In this report, the results of an experimental and theoretical study concerning the possible applicability of this new packing material for hydrogenation processes in a trickle-bed reactor is presented. The palladium catalyzed hydrogenation of α-methylstryrene is used as a model reaction to study hydrodynamics and mass transfer characteristics in a trickle-bed reactor under reactive conditions. Converstions at several process conditions are measured in a pilot plant in which 3 mm spheres as well KATAPAKTM is applied as packing materials. A comparison of the results of some physical absorption experiments with the results of hydrogenation experiments showed that the resistance in series model—in which the total resistance against mass transfer is calculated from the separate resistances—is not valid in systems where heterogeneous reactions at the solid surface can enhance the mass transfer-rate at the gas-liquid interphase. With the aid of a developed trickle-bed reactor model, based on liquid diffusion, simultaneous reaction at the solid surface and zero volume mixing points, the mass transfer phenomena in trickle-bed reactors in conditions where the resistance in series model fails can be explained and described. The numerically solved model calculates the hydrogen profiles in the liquid films of the reactor and over all single pass conversions at several process conditions. These conclusions are confirmed by the results of the simulation of a model reactor, i.e. the laminar film reactor with a catalytically active wall. From the results of the measurements it could be concluded that in trickle-flow conditions, the application of KATAPAKTM does not significantly improved on the overall performance of trickle-bed reactors. The increase of the physical absorption rate due to better mass transfer characteristics of structured packings compared to dumped packing types—as reported in literature—will be eliminated to a certain extent in reactive systems due to the enhancement effect of heterogeneous reactions in trickle-flow operation

Kinetics of hydrogen absorption and desorption in LaNi5-xAlx slurries

The kinetics of hydrogen absorption and desorption in LaNi4.8Al0.2,LaNi4.9Al0.1 and LaNi5, suspended in cyclohexane and LaNi5 in ethanol have been investigated. The absorption process can be described in terms of mass transfer and reaction resistances in series. The rate-limiting steps for this process are dissolution of hydrogen in the solvent and the reaction of hydrogen with the metal alloy

An experimental study of diffusion and convection of multicomponent gases through catalytic and non-catalytic membranes

Diffusion of binary and ternary gases through catalytic and non-catalytic membranes has been studied experimentally at atmospheric pressure. These experiments were conducted in a modified Wicke-Kallenbach diffusion cell consisting of two continuously stirred gas volumes separated by a membrane. The equipment was suitable to measure fluxes of components through the membrane in the absence of gas-to-membrane mass transfer limitations.\ud \ud Transport through a porous membrane has been measured and compared with the results of the dusty-gas model, which has been used to predict transport through a membrane. With independently determined input parameters this model turned out to be able to predict the transport of a multicomponent gas mixture through a membrane within a few percent (< 5%). The Fick model extended with a convective trnasport contribution was not able to produce similar results as obtained from the dusty-gas model, especially when an overall pressure gradient was present over the membrane.\ud \ud In order to demonstrate the occurrence of surface effects, dynamic transport of a binary gas was studied in a similar experimental setup as described by Novák et al. In this setup the transport of gas mixtures containing helium, argon and nitrogen was in good agreement with the model simulations. For transport of carbon dioxide and propane through a γ-Al2O3 coated membrane, adsorption phenomena were observed, but no substantial surface mobility was detected at temperatures ranging from 293 to 433 K

A study on the reaction between CO2 and alkanolamines in aqueous solutions

Literature data on the rates of reaction between CO2 and alkanolamines (MEA, DEA, DIPA, TEA and MDEA) in aqueous solution are discussed. These data induced us to carry out absorption experiments of CO2 into aqueous DEA, DIPA, TEA and MDEA solutions from which the respective rate constants\ud \ud The results for DEA and DIPA were analysed by means of a zwitterion-mechanism which was derived from the mechanism originally proposed by Danckwerts [1\ud \ud The reaction rate of CO2 with aqueous TEA and MDEA solutions shows a significant base catalysis effect which is also reported by Donaldson and Ngu