Reactant distribution, membrane

The multi-faceted functionality of a GDL includes reactant distribution, liquid water transport, electron transport, heat conduction and mechanical support to the membrane-electrode-assembly. 

FIGURE 10.21 (See color insert following page 588.) Traditional applications of inorganic membrane reactors for (a) conversion enhancement by product removal, (b) permeation of products and reaction coupling, and (c) selectivity enhancement by reactant distribution. 

It has been considered traditional applications of zeolite-membrane reactors those based on reactor concepts already demonstrated using mesoporous or dense membranes. These include conversion enhancement by equilibrium displacement or by the removal of inhibitors, and selectivity enhancement by reactant distribution. For such cases, the zeolite membrane is usually catalytically inert and is coupled with a conventional fixed bed of catalyst placed on one of the membrane sides. 

The concept of reactant distribution was intensely investigated with mesoporous membranes (see Refs. [162,163]), mainly for applications in selective oxidations in instances where low-partial pressures of oxygen would favor the selective oxidation vs. total oxidation. Under these conditions, distributing oxygen was beneficial and the possibility of increasing selectivity by oxygen distribution has been demonstrated for many reactions and for both inert and catalytically active membranes. 

In this chapter a specific type of membrane reactor, the so-called distributor was analyzed theoretically. In contrast to conventional tubular fixed-bed reactors (FBR), where all reactants are introduced together at the reactor inlet (cofeed mode), packed-bed membrane reactors (PBMR) allow dosing of one or several reactants via membranes over the reactor wall along the axial coordinate (distributed-feed mode). 

Catalytic membrane reactors belong to the class of structured reactors. The catalytic membrane performs several functions (e.g., separation, reactant distribution, catalytic and/or interface roles) in order to enhance the process productivity (in terms of conversion, selectivity or yield of desired products) and/or the process safety. Due to their unique property... 

This chapter reviews the possibilities that the application of a membrane in a catalytic reactor can improve the selectivity of a catalytic oxidation process to achieve a more compact system or to otherwise increase competitiveness. Classification differentiates between those reactors using dense membranes and those using porous membranes. Dense membranes provide high selectivity towards oxygen or hydrogen and the selective separation of one of these compounds under the reaction conditions is the key element in membrane reactors using such membranes. Porous membranes may have many different operation strategies and the contribution to the reaction can be based on a variety of approaches reactant distribution, controlled contact of reactants or improved flow. Difficulties for the application of membrane reactors in industrial operation are also discussed. 

Diakov, V. and Varma, A. (2002). Reactant Distribution by Inert Membrane Enhances Packed-Bed Reactor Stability, Chem. Eng. Sci, 57, pp. 1099-1105. 

A PEFC consists of two electrodes in contact with an electrolyte membrane (Fig. 14.7). The membrane is designed as an electronic insulator material separating the reactants (H2 and 02/air) and allowing only the transport of protons towards the electrodes. The electrodes are constituted of a porous gas diffusion layer (GDL) and a catalyst (usually platinum supported on high surface area carbon) containing active layer. This assembly is sandwiched between two electrically conducting bipolar plates within which gas distribution channels are integrated [96]. 

It is evident, that in any membrane reactor operation mode there are important parameters which determine the performance of the process (Shah, Remmen and Chiang 1970). These are (1) the total and partial pressures on both sides of the membrane, (2) the total and partial pressure differences across the membrane, (3) the diffusion mechanism through the support and the membrane layer (membrane structure), (4) the thickness of the membrane, (5) the reactant configuration (i.e. whether the reactants are supplied from the same or from opposite sides of the membrane, in counter or co-current flow) and (6) the catalyst distribution. 

Distributions of water and reactants are of high interest for PEFCs as the membrane conductivity is strongly dependent on water content. The information of water distribution is instrumental for designing innovative water management schemes in a PEFC. A few authors have studied overall water balance by collection of the fuel cell effluent and condensation of the gas-phase water vapor. However, determination of the in situ distribution of water vapor is desirable at various locations within the anode and cathode gas channel flow paths. Mench et al. pioneered the use of a gas chromatograph for water distribution measurements. The technique can be used to directly map water distribution in the anode and cathode of an operating fuel cell with a time resolution of approximately 2 min and a spatial resolution limited only by the proximity of sample extraction ports located in gas channels. 

II. THE EFFECT OF THE REACTANT CONCENTRATION DISTRIBUTIONS ON THE ENZYME MEMBRANE BEHAVIORS... 

Galvanostatic discharge of a fuel cell (MRED method) provided information related to liquid water in a fuel cell in a minimally invasive manner.157 Stumper et al.158 showed that through a combination of this MRED method with a current mapping (segmented fuel cell similar to the one discussed in Stumper et al.135), it was possible to obtain the local membrane water content distribution across the cell area. The test cell was operated with a current collection plate segmented on the cathode along the reactant flow direction. In addition to the pure ohmic resistance, this experimental setup allowed the determination of the free gas volume of the unit cell (between the inlet and outlet valves). Furthermore, the total amount of liquid water presented in the anode or cathode compartment was obtained. 

Figure 13 shows the potential and concentration distributions for different values of dimensionless potential under conditions when internal pore diffusion (s = 0.1) and local mass transport (y = 10) are a factor. As expected the concentration and relative overpotential decrease further away from the free electrolyte (or membrane) due to the combined effect of diffusion mass transport and the poor penetration of current into the electrode due to ionic conductivity limitations. The major difference in the data is with respect to the variation in reactant concentrations. In the case when an internal mass transport resistance occurs (y = 10) the fall in concentration, at a fixed value of electrode overpotential, is not as great as the case when no internal mass transport resistance occurs. This is due to the resistance causing a reduction in the consumption of reactant locally, and thereby increasing available reactant concentration the effect of which is more significant at higher electrode overpotentials. 

Figure 3-10. Schematic representation of the progress of a chemical reaction in the forward direction. The barrier height to be overcome is the activation energy A (analogous to /min for crossing membranes). Only reactant molecules possessing sufficient energy to get over the barrier, whose fraction can be described by a Boltzmann energy distribution (Fig. 3-9), are converted into products.

The core to the concept of an inorganic membrane reactor is to steer a membrane-selective species of a reaction mixture in or out of the membrane, which also serves as part of the reactor boundaries, to improve either the reaction conversion or product distribution. This is accomplished primarily by equilibrium displacement due to the permselective removal of a product or by avoiding or reducing undesirable side reactions (between certain chemical species including intermediate products) via controlled addition of some key reactant to the reaction zone through the membrane. 

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