Partial, methane using membrane

In the early 1990s, Balachandran et al. (51,64,65) of the Argonne National Laboratory, in collaboration with Amoco (now part of BP), investigated the partial oxidation of methane using membrane materials consisting of Sr-Fe-Co-O mixed oxides with the perovskite structure, which have high oxygen permeabilities. In their experiments (51,66), the membrane tubes, which were... 

Fig. 7.18 Partial oxidation of methane using a mixed ion-conducting membrane.

One example of membrane reactors is oxidation, in which oxygen from one phase diffuses from one side of an oxygen-permeable membrane to react with a fuel on the other side of the membrane. This avoids a high concentration of O2 on the fuel side, which would be flammable. A catalyst on the fuel side of the membrane oxidizes the fuel to partial oxidation products. One important process using a membrane reactor is the reaction to oxidize methane to form syngas,... 

The viability of one particular use of a membrane reactor for partial oxidation reactions has been studied through mathematical modeling. The partial oxidation of methane has been used as a model selective oxidation reaction, where the intermediate product is much more reactive than the reactant. Kinetic data for V205/Si02 catalysts for methane partial oxidation are available in the literature and have been used in the modeling. Values have been selected for the other key parameters which appear in the dimensionless form of the reactor design equations based upon the physical properties of commercially available membrane materials. This parametric study has identified which parameters are most important, and what the values of these parameters must be to realize a performance enhancement over a plug-flow reactor. 

The present study investigates a different approach. The membrane is used to allow the desired intermediate product to escape from the reaction zone before it is consumed by further reaction. This use of a membrane reactor was first suggested by Michaels [15]. The partial oxidation of methane, which is a challenging reaction of the type propos for this application of membrane reactors, has been analyzed herein. There is no thermodynamic limitation for the production of carbon dioxide and water, actually these products are favored. It is desired to remove any partial oxidation product, for example formaldehyde, before it has a chance to be further oxidized. 

Several profound theoretical and experimental studies performed on the laboratory scale have been reported which focus on the use of various configurations of membrane reactors as a reactant distributor in order to improve selectivity-conversion performances. In particular, several industrially relevant partial oxidations have been investigated, including the oxidative coupling of methane [56], the oxidative dehydrogenations of propane [57], butane [58], methanol [59, 60], the epoxidation of ethylene [61], and the oxidation of butane to maleic anhydride [62]. 

The use of Pd-based membrane reactors can increase the hydrogenation rates of several olefins by more than 10 times higher than those in conventional premixed fixed>bed reactors. Furthermore, it has been pointed out that the type and state of the oxygen used to carry out partial oxidation of methane can significantly affect the conversion and selectivity of the reaction. The use of a solid oxide membrane (e.g., a yttria-stabilized zirconia membrane) not only can achieve an industrially acceptable C2 hydrocarbon yield but also may eliminate undesirable gas-phase reactions of oxygen with methane or its intermediates because oxygen first reaches the catalyst through the solid oxide wall [Eng and Stoukides, 1991]. 

Figure 2 Flux of methane ( ), ethane, ( ), propane ( ), n-buiane ( ), and iso>butane (A) through a silicalite-1 membrane as a function of partial pressure on the feed side (T = 298 K, = 100 kPa). Feed was composed of hydrocarbon and balance helium sweep gas used was helium. There was no absolute pressure difference across the membrane. (Adapted from Ref. 14.)...

Many studies demonstrate that Pd-based membranes with ideally infinite selectivity for H2 can be used to increase the equilibrium conversion of steam reforming of methane by H2 removal [10,11]. The driving force in this process is the partial pressure difference. 

The mixed-conducting perovskite oxides have attracted particular interest for use as dense ceramic membrane to control partial oxidation of methane to C2 products or syngas. Such a process bypasses the use of costly oxygen since air can be used as oxidant on the oxygen-rich of the membrane. 

In the catalytic partial oxidation of methane to produce syngas the use of permselective dense perovskite membranes avoids (or minimizes) the need of air separation, the most costly step in the process. Although both these O2- and H2-permeoselective membranes (based on perovskites or thin supported Pd-based dense films, respectively) have still to be further developed for commercial applications the outlook appears quite interesting for intensifying various large chemical processes. 

Theoretical infinite selectivity can be achieved for hydrogen separation by Pd or Pd-alloy membranes [40]. The reaction is carried out at high temperature, about above 1000 K, because of the equihbrium of the endothermic reactions involved in the process. Many studies demonstrate that Pd-based membranes with ideally infinite selectivity for H2 can be used to increase the equihbrium conversion of methane steam to H2 removal [36, 40]. The driving force in this process is the partial pressure difference. The high cost, hmited hfetime, and low permeabihty are relevant hmits of Pd and Pd-ahoy membrane. To overcome these drawbacks, the studies have been carried out for the preparation of supported metaUic membranes in which a thin metallic layer is supported on a thicker sublayer [73]. 

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