Membrane reactors reactions

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).

In membrane reactors, reaction and separation can be carried out simultaneously (Fig. 9.2), and it is possible to remove one of the products before it can further react and lead to undesired by-products. A reactant can be added in a con-... 

Non-permselective membranes can also be used to provide a location for a reaction zone. One reactant is fed on the tube side of the membrane, and the other reactant is fed on the shell side. The partial-pressure gradients have to be chosen such that the two reactants permeate towards each other inside the membrane, where they can react. Usually, the membrane itself contains a suitable catalyst. In this type of membrane reactor, reactions are performed at a strict stoichiometric ratio. For fast reactions, this results in a reaction plane, whereas for slower reactions a reaction zone will be formed. This is shown schematically in Fig. 5.4. Balancing reaction rate and permeability can result in a reaction zone entirely located inside the membrane. When breakthrough of reactants can be avoided, and the product diffuses out on one side only, this can simplify the further separations required. 

Membrane reactors Reaction equilibrium can be shifted by removing one or more of the species from the reaction space or reactant can be provided through the membrane... 

Validity of the CFD model for the membrane reactor Reaction conditions... 

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. 

Catalytic A catalytic-membrane reactor is a combination heterogeneous catalyst and permselective membrane that promotes a reaction, allowing one component to permeate. Many of the reactions studied involve H9. Membranes are metal (Pd, Ag), nonporous metal oxides, and porous structures of ceran iic and glass. Falconer, Noble, and Speriy [in Noble and Stern (eds.), op. cit., pp. 669-709] review status and potential developments. 

Catalytic Membrane Reactors Membrane reactors combine reaction and separation in a single vessel. By removing one of the... 

Two reactions for the production of L-phenylalanine that can be performed particularly well in an enzyme membrane reactor (EMR) are shown in reaction 5 and 6. The recently discovered enzyme phenylalanine dehydrogenase plays an important role. As can be seen, the reactions are coenzyme dependent and the production of L-phenylalanine is by reductive animation of phenylpyruvic add. Electrons can be transported from formic add to phenylpyruvic add so that two substrates have to be used formic add and an a-keto add phenylpyruvic add (reaction 5). Also electrons can be transported from an a-hydroxy add to form phenylpyruvic add which can be aminated so that only one substrate has to be used a-hydroxy acid phenyllactic acid (reaction 6). 

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. 

Substrate and product inhibitions analyses involved considerations of competitive, uncompetitive, non-competitive and mixed inhibition models. The kinetic studies of the enantiomeric hydrolysis reaction in the membrane reactor included inhibition effects by substrate (ibuprofen ester) and product (2-ethoxyethanol) while varying substrate concentration (5-50 mmol-I ). The initial reaction rate obtained from experimental data was used in the primary (Hanes-Woolf plot) and secondary plots (1/Vmax versus inhibitor concentration), which gave estimates of substrate inhibition (K[s) and product inhibition constants (A jp). The inhibitor constant (K[s or K[v) is a measure of enzyme-inhibitor affinity. It is the dissociation constant of the enzyme-inhibitor complex. 

The inhibition analyses were examined differently for free lipase in a batch and immobilised lipase in membrane reactor system. Figure 5.14 shows the kinetics plot for substrate inhibition of the free lipase in the batch system, where [5] is the concentration of (S)-ibuprofen ester in isooctane, and v0 is the initial reaction rate for (S)-ester conversion. The data for immobilised lipase are shown in Figure 5.15 that is, the kinetics plot for substrate inhibition for immobilised lipase in the EMR system. The Hanes-Woolf plots in both systems show similar trends for substrate inhibition. The graphical presentation of rate curves for immobilised lipase shows higher values compared with free enzymes. The value for the... 

A packed-bed nonpermselective membrane reactor (PBNMR) is presented by Diakov et al. [31], who increased the operational stability in the partial oxidation of methanol by feeding oxygen directly and methanol through a macroporous stainless steel membrane to the PB. Al-Juaied et al. [32] used an inert membrane to distribute either oxygen or ethylene in the selective ethylene oxidation. By accounting for the proper kinetics of the reaction, the selectivity and yield of ethylene oxide could be enhanced over the fixed-bed reactor operation. 

Table 10.2 Performance of several zeolite membrane reactors in the xylene isomerization reaction. 

Autothermal reaction of ethanol through Pd-Ag membrane reactor prepared by sequential electroless deposition... 

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...

A further application of this technology will certainly be the fabrication of membranes of these materials. Membrane reactors have shown great utility in many systems, where one component of a reaction mixture can be separated by permeation through a membrane, thus driving a reaction forwards, by continuous separation. Such continuous processes can themselves save a great deal of waste. 

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).

Enzymatic degradation of pectin can be satisfactory performed in UF-membrane reactors which have been proved to be helpful tool for laboratory scale investigations. Reaction products can be continuously recovered in a sequence of filtration stages. The obtained product distribution depends on the enzyme to substrate ratio, which affects particularly the... 

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]... 

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]. 

A special version of the membrane reactor using Pd was made for separating hydrogen and oxygen and their controlled reaction. 

Figure 3.28 Unexpected increase in NO/N2 selectivity for ammonia oxidation reaction in a micro membrane reactor [19],...

GP 11] ]R 20] Investigations with a Pd membrane reactor relied on reaction of streams separated via a membrane (to prevent complete mixing of reactants, not to enhance conversion) [11]. A hydrogen/nitrogen stream is guided parallel to an oxygen stream, both separated by the membrane and water is thereby formed. The membranes, made by thin-film processes, can sustain a pressure up to 5 bar. 

An important problem in emulsified organic-aqueous systems is that of scale-up, which is concerned with the realization of stable emulsions and the separation of phases after the reaction. The use of biphasic membrane systems that contain the enzyme and keep the two phases separated is likely to solve this problem. In the case of 5-naproxen an ee of 92% has been demonstrated without any decay in activity over a period of two weeks of continuous operation. A number of examples of biocatalytic membrane reactors have been provided by Giorno and Drioli (2000) and include the conversion of fumaric acid to L-aspartic acid, L-aspartic acid to L-alanine, and cortexolone to hydrocortisone and prednisolone. 

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