Catalytic ceramic membranes

ANDERSON ETAL. Catalytic Ceramic Membranes Membrane Reactors 199... 

A simple example of catalytic ceramic membrane reactor is shown in Figure 1.4. The membrane is a barrier that allows rally certain components... 

Tan, X., Li, K., Thursfield, A. and Metcalfe, I.S. (2008) Oxyfuel combustion using a catalytic ceramic membrane reactor. Catalysis Today, 131,292-304. 

Porous metal membranes are commercially available in stainless steel and some other alloys (e.g.. Inconel, Hastelloy) and they are characterized by a macroporous structure. On the other hand, porous ceramic membranes can be found commercially in various oxides and combination of oxides (e.g., Al203,li02,Zr02, Si02) and pore size families in the mesopore and macropore ranges (e.g., from 1 nm to several microns). Most of the literature studies on three-phase catalytic membrane reactors have been carried out by developing catalytic ceramic membranes. The deposition techniques for the preparation of catalytic ceramic membranes involve methods widely used for the preparation of traditional supported catalysts (Pinna, 1998), and methods specifically developed for the preparation of structured catalysts (Cybulski and Moulijn, 2006). Other methods to introduce a catalytic species on a porous support include the chemical vapour deposition and physical vapour deposition (Daub et al, 2001). The catalyst deposition method has a strong influence on the catalytic membrane reactor performance. 

Bottino, A., Capannelli, G, Comite, A., Del Borghi, A., Di Felice, R., 2004. Catalytic ceramic membrane in a three-phase reactor for the competitive hydrogenation-isomerisation of methylenecyclohexane. Separation and Purification Technology 34,239-245. 

The control of thermal stability enables alumina and other oxides to be used as support for applications at high temperatures such as in combustion, hydrocarbon reforming and catalytic ceramics membranes. Moreover, other advantages of using lanthanum as dopant have been recognized, besides thermal stability, which has motivated its applications for other purposes, as shown in Table 1. 

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 ceramic membrane has a great potential and market. It represents a distinct class of inorganic membrane. In particular, metallic coated membranes have many industrial applications. The potential of ceramic membranes in separation, filtration and catalytic reactions has favoured research on synthesis, characterisation and property improvement of inorganic membranes because of their unique features compared with other types of membrane. Much attention has focused on inorganic membranes, which are superior to organic ones in thermal, chemical and mechanical stability and resistance to microbial degradation. 

Schematics of an oxygen membrane reactor for catalytic POx of methane. A blown up section on the left-hand side shows the details of the ceramic membrane wall explaining the mechanism of oxygen permeation across the membrane. /- is the chemical potential of oxygen and ai and

Porous ceramic membrane layers are formed on top of macroporous supports, for enhanced mechanical resistance. The flow through the support may consist of contributions due to both Knudsen-diffusion and convective nonseparative flow. Supports with large pores are preferred due to their low resistance to the flow. Supports with high resistance to the flow decrease the effective pressure drop over the membrane separation layer, thus diminishing the separation efficiency of the membrane (van Vuren et al. 1987). For this reason in a membrane reactor it is more effective to place the reaction (catalytic) zone at the top layer side of the membrane while purging at the support side of the membrane. 

Coronas, J. and Santamaria, J. (1999) Catalytic reactors based on porous ceramic membranes. Catalysis Today, 51, 377—389. 

Porous ceramic membranes for catalytic reactors - overview and new ideas. Journal of Membrane Science, 181, 3-20. 

Pore Size Limitations. Although there are many potential commercial applications for ultrafiltration using currently available ceramic membranes, the pore sizes in these membranes are seldom less than 40 A in diameter, thereby limiting their applications in gas separations and in ceramic catalytic reactors. 

Ceramic membranes can be used in catalytic systems in three modes ... 

Forccd flow mode. Invertase, an enzyme, can be chemically immobilized to the surfaces of ceramic membrane pores by the technique of covalent bonding of silane-glutaraldehyde [Nakajima et al., 1989b]. The substrate (reactant), during the sucrose conversion process, enters the membrane reactor in a crossflow mode. Under suction from the other side of the membrane, the substrate flows into the enzyme-immobilized membrane pores where the bioconversion takes place. Both the product and the unreacted substrate indiscriminately pass through the membrane pores. Thus, no permselective properties are utilized in this case. The primary purpose of the membrane is to provide a well-engineered catalytic path for the reactant, sucrose. 

One of the potentially wide-spread applications under development is catalytic filters for air pollution control. This combines separation and catalytic oxidation into one unit operation. One possibility is the oxidation of volatile organic carbon (VOC) by employing a porous honeycomb monolithic ceramic membrane filter. Inside the pores are deposited an oxidation catalyst such as precious metals. The resulting VOC removal efficiency can exceed 99% [Bishop et al., 1994]. 

Many of the metal oxide materials used for making ceramic membranes, particularly the porous type, have also been used or studied as catalysts or catalyst supports. Thus, they are naturally suitable to be the membrane as well as the catalyst. For example, alumina surface is known to contain acidic sites which can catalyze some reactions. Alumina is inherently catalytic to the Claus reaction and the dehydration reaction for amine production. Silica is used for nitration of benzene and production of carbon bisulfide from methanol and sulfur. These and other examples are highlighted in Table 9.6. 

Shown in Table 9.7 are some examples of incorporating catalysts into porous ceramic membranes. Both metal and oxide catalysts have been introduced to a variety of ceramic membranes (e.g., alumina, silica, Vycor glass and titania) to make them catalytically active. The impregnation/heat U eatment procedures do not appear to show a consistent cause-and-effeci relationship with the resulting membrane permeability. For example, no noticeable change is observed when platinum is impregnated into porous Vycor glass... 

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