Membrane reactors reaction temperature

Fig. 5. Methane conversion and oxygen flux during partial oxidation of methane in a ceramic membrane reactor. Reaction conditions pressure, 1 atm temperature, 1173 K, feed gas molar ratio, CH Ar = 80/20 feed flow rate, 20 mL min-1 (NTP) catalyst mass, 1.5 g membrane surface area, 8.4 cm2 (57).

The CVI-experiments with silane as precursor did not show any increase in permselectivity of the membranes. The reaction temperature was in all cases 275°C and several oxygen pressures were tried. In each experiment, however, white powder was obtained on the membrane surface, indicating the decomposition of silane at the surface of the membrane. Reaction conditions could not be chosen in such a way that a highly separative layer was obtained. This was probably related to with the fact that the reactor temperature or the concentration of silane in the precursor gas was too low. Safety regulations, however, prohibited an increase of the silane concentration in the precursor flow. 

Brunetti, A, Caravella, A, Drioli, E, Barbieri, G. Process intensification by membrane reactors High-temperature water gas shift reaction as single stage for syngas upgrading. Chem. Eng. Technol. 2012 35(7) 1238-1248. 

Membrane Reactor. Another area of current activity uses membranes in ethane dehydrogenation to shift the ethane to ethylene equiUbrium. The use of membranes is not new, and has been used in many separation processes. However, these membranes, which are mostly biomembranes, are not suitable for dehydrogenation reactions that require high temperatures. Technology has improved to produce ceramic and other inorganic (90) membranes that can be used at high temperatures (600°C and above). In addition, the suitable catalysts can be coated without blocking the pores of the membrane. Therefore, catalyst-coated membranes can be used for reaction and separation. 

As an example the use of ceramic membranes for ethane dehydrogenation has been discussed (91). The constmction of a commercial reactor, however, is difficult, and a sweep gas is requited to shift the product composition away from equiUbrium values. The achievable conversion also depends on the permeabihty of the membrane. Figure 7 shows the equiUbrium conversion and the conversion that can be obtained from a membrane reactor by selectively removing 80% of the hydrogen produced. Another way to use membranes is only for separation and not for reaction. In this method, a conventional, multiple, fixed-bed catalytic reactor is used for the dehydrogenation. After each bed, the hydrogen is partially separated using membranes to shift the equihbrium. Since separation is independent of reaction, reaction temperature can be optimized for superior performance. Both concepts have been proven in bench-scale units, but are yet to be demonstrated in commercial reactors. 

The auto-thermal reaction of ethanol occurred in the shell side of a palladium membrane reactor in which a Zn-Cu/AlaOs industrial catalyst (MDC-3) was packed with silica powder. Ethanol-water mixture (nH2o/nEioH=l or 3) and oxygen (noa/nEioH=0.2,0.776 or 1.035) are fed concurrently to the shell side. The reaction temperatures were set at 593-723 K and the pijrasures were 3 10 atm. 

Fig.2. Ethanol autotherml reaction in the Pd/Ag membrane reactor at various temperature and...

One of the most studied applications of Catalytic Membrane Reactors (CMRs) is the dehydrogenation of alkanes. For this reaction, in conventional reactors and under classical conditions, the conversion is controlled by thermodynamics and high temperatures are required leading to a rapid catalyst deactivation and expensive operative costs In a CMR, the selective removal of hydrogen from the reaction zone through a permselective membrane will favour the conversion and then allow higher olefin yields when compared to conventional (nonmembrane) reactors [1-3]... 

Because Pd-alloy membranes operate at high temperatures in the range of WGS reaction and on the lower end of methane reforming reaction, they can be used in a membrane reactor configuration for the simultaneous separation of hydrogen. As discussed earlier,... 

Monoglyceride (MG) is one of the most important emulsifiers in food and pharmaceutical industries [280], MG is industrially produced by trans-esterification of fats and oils at high temperature with alkaline catalyst. The synthesis of MG by hydrolysis or glycerolysis of triglyceride (TG) with immobilized lipase attracted attention recently, because it has mild reaction conditions and avoids formation of side products. Silica and celite are often used as immobilization carriers [281], But the immobilized lipase particles are difficult to reuse due to adsorption of glycerol on this carriers [282], PVA/chitosan composite membrane reactor can be used for enzymatic processing of fats and oils. The immobilized activity of lipase was 2.64 IU/cm2 with a recovery of 24%. The membrane reactor was used in a two-phase system reaction to synthesize monoglyceride (MG) by hydrolysis of palm oil, which was reused for at least nine batches with yield of 32-50%. 

For the application of membrane reactors it can be concluded that these are accepted as proven technology for many biotechnological apphcations. The membranes used in this area can operate under relatively mild conditions (low temperature and aqueous systems). However, there is a tremendous potential for membrane reactors in the chemical industry, which often requires apphcation in nonaqueous systems. Long term stability of the membrane materials in these systems will require an ongoing development from the side of materials scientists. As reaction selectivity is of major importance in the production of fine chemicals and pharmaceutical products, it seems plausible to expect that membrane reactors will find their way in the production of chemicals through applications in these areas. 

Several important refinery and chemical feedstock reactions appear to be good candidates for membrane reactor systems some such reactions are listed in Table 13.4. Because of the high temperatures involved, developing the appropriate... 

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