Three-Phase Catalytic Membrane Reactors

In Chapter 2 we discussed a number of studies with three-phase catalytic membrane reactors. In these reactors the catalyst is impregnated within the membrane, which serves as a contactor between the gas phase (B) and liquid phase reactants (A), and the catalyst that resides within the membrane pores. When gas/liquid reactions occur in conventional (packed, -trickle or fluidized-bed) multiphase catalytic reactors the solid catalyst is wetted by a liquid film as a result, the gas, before reaching the catalyst particle surface or pore, has to diffuse through the liquid layer, which acts as an additional mass transfer resistance between the gas and the solid. In the case of a catalytic membrane reactor, as shown schematically in Fig. 5.16, the active membrane pores are filled simultaneously with the liquid and gas reactants, ensuring an effective contact between the three phases (gas/ liquid, and catalyst). One of the earliest studies of this type of reactor was reported by Akyurtlu et al [5.58], who developed a semi-analytical model coupling analytical results with a numerical solution for this type of reactor. Harold and coworkers (Harold and Ng 

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Some recent models have also appeared discussing the operation of three phase catalytic membrane reactors by Torres et al. [82]. The models which represent extension of prior models by Akyurtlu et al. [79] and Cini and Harold [80] are numerically analyzed and appear to simulate well the experimental results of the nitrobenzene hydrogenation reaction in a three phase catalytic membrane reactor. 

Three-phase catalytic membrane reactor systems, in our opinion, show significant promise, for near term application to hydrogenation reactions for fine chemicals synthesis. These reactions generally require mild operating conditions which will place less stringent requirements on the available and future commercial membranes. 

O. Monticelli, A. Bezzi, A. Bottino, G. Capannelli, and A. Servida, in "Hydrogenation of Cinnamaldehyde the Use of Three Phase Catalytic Membrane Reactors", Proc. Fourth Workshop Optimisation of Catalytic Membrane Reactors Systems, Oslo, Norway, May, 1997, 109. 

Key words catalytic membrane, three-phase catalytic membrane reactor, multi-phase reactions. 

The main effort of researchers was initially oriented to exploring the possibilities and the characteristics of catalytic membrane reactors, especially in three-phase systems. Only a few papers are devoted to the application of catalytic membrane reactors to liquid-liquid systems. An excellent and comprehensive review of three-phase catalytic membrane reactors has been published by Dittmeyer et al. (2004). This exhaustive review covers several aspects of the application of catalytic membranes as three-phase reactors and critically discusses some examples in the literature. 

Gas solubility in liquid phase is usually very low and therefore it can be a limiting factor influencing the overall reaction rate. Most reactions of interest for the application of three-phase catalytic membrane reactors are hydrogenation reactions using hydrogen and oxidation reactions with air. 

Several authors have reported modelling of multi-phase membrane reactors and, in particular, of three-phase catalytic membrane reactors. Harold and Watson (1993) have considered the situation of a porous catalytic slab partially wetted by a liquid from one side and by a gas phase on the other side, and they have pointed out the complexity of the problem in presence of an exothermic reaction, capillary condensation and vaporization. 

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. 

Table 4.3 lists some typical gas-liquid hydrogenation reactions investigated in order to explore the features of three-phase catalytic membrane reactors. An example of the application of three-phase catalytic membrane reactors to the hydrogenation of sunflower seed oil can be found in Veldsmk (2001), where it was shown that for this hydrogenation running under kinet-ically controlled conditions the interfacial transport resistances and intraparticle diffusion limitations did not have any effect. Unfortunately the catalyst underwent a serious deactivation process. 

In particular, Bottino et al. (2004) explored the performance of different catalytic membranes in the hydrogenation-isomerization of methylene-cyclohexane,in a temperature range between 288 and 343 K.The performance of the three-phase catalytic membrane reactor has been compared with that of a slurry reactor, resulting in a wider operating temperature range without mass transfer limitations. 

Bottino, A., Capannelli, G, Comite, A., Di Felice, R., 2002. Polymeric and ceramic membranes in three-phase catalytic membrane reactors for the hydrogenation of methylenecyclohexane. Desalination 144,411 16. 

Espro, C., Arena, F.,Frusteri,F., Parmaliana, A.,2001. On the potential of the multifunctional three phase catalytic membrane reactor in the selective oxidation of light alkanes by Fej -HjOj Fenton system. Catalysis Today 67,247-256. 

Veldsink, J.W., 2001. Selective hydrogenation of sunflower seed oil in a three-phase catalytic membrane reactor. Journal of the American Oil Chemists Society 78, 443 46. 

The selective oxygenation of methane and light alkanes (Ci-Cj) by the Fe(II)/H202 Fenton system was performed in the three-phase catalytic membrane reactor, enabling simultaneous reaction and product separation. Frusteri et al. reported that Nafion-based catalytic membranes catalyze the selective oxidation of... 

Hydrogenation reactions have also been studied with catalytic membrane reactors using porous membranes. In this case the membrane, in addition to being used as a contactor between the liquid and gaseous reactants, could, potentially, also act as a host for the catalyst, which is placed in the porous framework of the membrane. As previously noted a triple-point interface between the three different phases (gas, liquid, and the solid catalyst) is then created in the membrane. The first application was reported by Cini and Harold... 

At the turn of 1990s catalytic membrane reactors were proposed as a novel type of structured three-phase reactors which could improve the contact and the mass transfer of the reacting species on the catalyst. From that time many papers have been published on this specific topic. The simple concept was to use a thin catalytic membrane as a well-defined reacting interface between two fluid phases, in order to minimize the diffusion resistance and enhance the effectiveness of the catalyst (Fig. 4.2). 

As can be observed, the main difference between conventional three-phase reactors and catalytic membrane reactors hes in the relative positions of the mass transfer resistances with respect to the catalytic phase. In a conventional porous catalyst the catalytic sites in the pores have only one way or path of access. The gaseous reactant will encounter the first two mass transfer resistances at the gas-liquid interface, where the solvation equilibrium of the species from one phase to the other wiU take place. The dissolved species will diffuse towards the surface of the catalytic pellet for quite a long path in the hquid phase and will meet an additional mass transfer resistance at the hquid-sohd catalyst interface. It then needs to diffuse and react in the porous structure of the catalyst as well as the other reactant already present in the liquid phase. In the case of a traditional three-phase reactor (Fig. 4.3a), the concentration of at least one of the reacting species is hmited by its solubility and diffusion in the other fluid phase with a long diffusion path and in some cases unknown interfadal area (e.g., bubbles with variable size depending on the type of the gas feeding and distribution device in slurry reactors, not uniform phase contact and distribution in trickle-bed reactors). 

Contact modalities and concentration profiles in catalytic membrane reactors for three-phase systems.The concentration of reactants is represented on the y-axis and the spatial coordinate along the membrane cross-section is represented on the x-axis. Below the scheme of each case the sequence of the mass transfer (MT) resistances and of the reaction event (R) are reported. (a)Traditional slurry reactor (b) supported thin porous catalytic layer with the liquid impregnating the porosity and the gas phase in contact with the catalytic layer (c) supported thin porous catalytic layer with the liquid impregnating the porosity and the liquid phase in contact with the catalytic layer (d) supported dense membrane which is perm-selective to the gas-phase reactant (e) dense catalytic membrane perm-selective to both reactants in the gas and liquid phases (f) forced flow of the liquid phase enriched with the gas-phase reactant through the thin catalytic membrane layer. 

Related to the experimental studies performed in our laboratory, in this review packed-bed membrane reactors were discussed. It should be mentioned that there are significant investigational activities devoted to study catalytically active membranes where the catalyst is deposited in either the membrane pores or on the inner or outer surface of the tubes [11]. Another similarly interesting and promising principle is based on using the Contactor type of membrane reactors, where the reactants are fed from different sides and react within the membrane [79]. Significant efforts have been made to exploit this principle for heterogeneously catalyzed gas-liquid reactions (three-phase membrane reactors) [80, 81]. 

Yawalkar et al. (2001) has developed a model for a three-phase reactor based on the use of a dense polymeric composite membrane containing discrete cubic zeolite particles (Fig. 4.5) for the epoxidation reaction of alkene. Catalytic particles of the same size are assumed vdth a cubic shape and uniformly dispersed across the polymer membrane cross-section. Effects of various parameters, such as peroxide and alkene concentration in liquid phase, sorption coefficient of the membrane for peroxide and alkene, membrane-catalyst distribution coefficient for peroxide and alkene and catalyst loading, have been studied. The results have been discussed in terms of a peroxide effidency defined as the ratio of flux of peroxide through the membrane utilized for alkene oxidation to the total flux of organic peroxide through the membrane. The paper aimed to show that, by using an organophilic dense membrane and the catalysts confined in the polymeric matrix, the oxidant concentration (in that reaction peroxides) can be controlled on the active site with an improvement of the peroxide efficiency and selectivity to desired products. 

In catalytic multi-phase membrane reactors the catalytic membrane usually plays the role of interface between the two fluid phases. As discussed in the previous subsections, especially in the case of porous catalytic membranes, a strict control of the position of the inter-phase interface in proximity to the catalytic layer is of paramount importance in order to minimize the diffusion resistances. Figure 4.6 reports a simplified outline of a three-phase experimental rig as can be found in several publications. A req cle loop for the liquid phase has been considered in order to achieve the desired conversion. 

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