Product separation, membrane reactors

It has been mentioned earlier that using porous membranes for product separation during the course of an equilibrium reaction, maximum attainable conversions are limited because of reactant permeation. This is the case where the membrane forms the wall of the reactor in which a catalyst is packed. It has also been mentioned that in this mode equilibrium conversions for some slow reactions could be increased by factors ranging between 1.3 and 2.3. Another important operation mode arises when the membrane is inherently catalytic or when the catalytically active species are placed within the membrane pores (catalytically active membrane as shown in Figure 7.2b and 7.2c). In this case, reaction and separation take place simultaneously and are combined in parallel rather than in series as was the case in the previous mode. 

Processes for production of ethanol and acetone-butanol-ethanol mixture from fermentation products in membrane contactor devices were presented in Refs. [88,89]. Recovery of butanol from fermentation was reported in Ref. [90]. Use of composite membrane in a membrane reactor to separate and recover valuable biotechnology products was discussed in Refs. [91,92]. A case study on using membrane contactor modules to extract small molecular weight compounds of interest to pharmaceutical industry was shown in Ref. [93]. Extraction of protein and separation of racemic protein mixtures were discussed in Refs. [94,95]. Extractions of ethanol and lactic acid by membrane solvent extraction are reported in Refs. [96,97]. A membrane-based solvent extraction and stripping process was discussed in Ref. [98] for recovery of Phenylalanine. Extraction of aroma compounds from aqueous feed solutions into sunflower oil was investigated in Ref. [99]. 

It is now possible to prepare defect-free zeolite membranes for use in separations.221 (More details on separations can be found in Chap. 7.) A mordenite membrane on a porous alumina support had a separation factor for benzene over p xylene of more than 160.222 A ZSM-5 membrane on porous alumina separated /7-butane over isobutane by a factor of 31 at 185°C.223 The next step is to use them in membrane reactors to separate products as they form. 

The same group [2.354] has also recently reported on the performance of a membrane reactor with separate feed of reactants for the catalytic combustion of methane. In this membrane reactor methane and air streams are fed at opposite sides of a Pt/y-A Os-activated porous membrane, which also acts as catalyst for their reaction. In their study Neomagus et al. [2.354] assessed the effect of a number of operating parameters (temperature, methane feed concentration, pressure difference applied over the membrane, type and amount of catalyst, time of operation) on the attainable conversion and possible slip of unconverted methane to the air-feed side. The maximum specific heat power load, which could be attained with the most active membrane, in the absence of methane slip, was approximately 15 kW m with virtually no NO emissions. These authors report that this performance will likely be exceeded with a properly designed membrane, tailored for the purpose of energy production. 

The combination of reaction and separation at high temperature in a membrane reactor offers interesting new possibilities. In a membrane reactor, the separate product and feed compartments allow more ways to optimize both selectivity and conversion [17]. 

Product Recovery. Comparison of the electrochemical cell to a chemical reactor shows the electrochemical cell to have two general features that impact product recovery. CeU product is usuaUy Uquid, can be aqueous, and is likely to contain electrolyte. In addition, there is a second product from the counter electrode, even if this is only a gas. Electrolyte conservation and purity are usual requirements. Because product separation from the starting material may be difficult, use of reaction to completion is desirable ceUs would be mn batch or plug flow. The water balance over the whole flow sheet needs to be considered, especiaUy for divided ceUs where membranes transport a number of moles of water per Earaday. At the inception of a proposed electroorganic process, the product recovery and refining should be included in the evaluation to determine tme viabUity. Thus early ceU work needs to be carried out with the preferred electrolyte/solvent and conversion. The economic aspects of product recovery strategies have been discussed (89). Some process flow sheets are also available (61). 

Membrane reactors, where the enzyme is adsorbed or kept in solution on one side of an ultrafHtration membrane, provides a form of immobilized enzyme and the possibiHty of product 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. 

In this case study, an enzymatic hydrolysis reaction, the racemic ibuprofen ester, i.e. (R)-and (S)-ibuprofen esters in equimolar mixture, undergoes a kinetic resolution in a biphasic enzymatic membrane reactor (EMR). In kinetic resolution, the two enantiomers react at different rates lipase originated from Candida rugosa shows a greater stereopreference towards the (S)-enantiomer. The membrane module consisted of multiple bundles of polymeric hydrophilic hollow fibre. The membrane separated the two immiscible phases, i.e. organic in the shell side and aqueous in the lumen. Racemic substrate in the organic phase reacted with immobilised enzyme on the membrane where the hydrolysis reaction took place, and the product (S)-ibuprofen acid was extracted into the aqueous phase. 

Furthermore, the application of the SOD membrane in a FT reaction has been investigated. The advantages of water removal in a FT reaction are threefold (i) reduction of H20-promoted catalyst deactivation, (ii) increased reactor productivity, and (iii) displaced water gas shift (WGS) equilibrium to enhance the conversion of CO2 to hydrocarbons [53]. Khajavi etal. report a mixture of H2O/H2 separation factors 10000 and water fluxes of 2.3 kg m h under... 

Figure 4 Membrane reactor for 4-hydroxybenzoate production using phenolphosphate carboxylase. A membrane (A) separates the reaction space containing the enzyme (B) from water phase where the product is collected (C).

Membrane reactors are known on the macro scale for combining reaction and separation, with additional profits for the whole process as compared with the same separate functions. Microstructured reactors with permeable membranes are used in the same way, e.g. to increase conversion above the equilibrium limit of sole reaction [8, 10, 11, 83]. One way to achieve this is by preparing thin membranes over the pores of a mesh, e.g. by thin-fihn deposition techniques, separating reactant and product streams [11]. 

Pex, P.P.A.C. and Y.C. van Delft, Silica membranes for hydrogen fuel production by membrane water gas shift reaction and development of a mathematical model for a membrane reactor, in Carbon Dioxide Capture for Storage in Deep Geologic Formations—Results from the C02 Capture Project Capture and Separation of Carbon Dioxide from Combustion Sources, eds., D. Thomas, and B. Sally, Vol. 1, Chapter 17, 2005. 

The separation of homogeneous catalysts by means of membrane filtration has been pioneered by Wandrey and Kragl. Based on the enzyme-membrane-reactor (EMR),[3,4] that Wandrey developed and Degussa nowadays applies for the production of amino acids, they started to use polymer-bound ligands for homogeneous catalysis in a chemical membrane reactor (CMR).[5] For large enzymes, concentration polarization is less of an issue, as the dimension of an enzyme is well above the pore-size of a nanofiltration membrane. 

Figure 11.4 Schematic diagram of membrane reactor. The reaction is designed so that reagent X may pass through the membrane and is therefore available for reaction. The substrate and product cannot pass through and the phases remain separate...

The situation is somewhat different with porous membranes, where the permselectivities for all components do not equal zero but exhibit certain values determined in most cases by the Knudsen law of molecular masses. In general, when porous membranes are used as separators in a membrane reactor next to the catalyst or the reaction zone (Figure 7.2a), it has been shown experimentally (Yamada et al. 1988) and theoretically (Mohan and Govind 1986, 1988a, b, Itoh et al. 1984, 1985) that there is a maximum equilibrium shift that can be achieved. On the basis of simple mass balances one can calculate that this maximum depends on, besides the reaction mechanism, the membrane permselectivities (the difference in molecular weights of the components to be separated) and it corresponds to an optimum permeation to reaction-rate ratio for the faster permeating component (which is a reaction product). 

Novel unit operations currently being developed are membrane reactors where both reaction and separation occur simultaneously. Through selective product removal a shift of the conversion beyond thermodynamic equilibrium is possible. The membrane itself can serve in different capacities including (i) a permselective diffusion barrier, (ii) a non-reactive reactant distributor and (iii) as both a catalyst and permselective membrane [44]. 

The same hyperbranched polyglycerol modified with hydrophobic palmitoyl groups was used for a noncovalent encapsulation of hydrophilic platinum Pincer [77]. In a double Michael addition of ethyl cyanoacetate with methyl vinyl ketone, these polymer supports indicated high conversion (81 to 59%) at room temperature in dichloromethane as a solvent. The activity was stiU lower compared with the noncomplexed Pt catalyst. Product catalyst separation was performed by dialysis allowing the recovery of 97% of catalytic material. This is therefore an illustrative example for the possible apphcation of such a polymer/catalyst system in continuous membrane reactors. 

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