Reactor for homogeneous catalysis

Goetheer ELV, Verkerk AW, van den Broeke UP, de Wolf E, Deelman B-J, van Koten G, and Keurentjes JTF. Membrane reactor for homogeneous catalysis in supercritical carbon dioxide. J. Catal. 2003 219 126-133. 

Fouling of the reactor and other equipment is another problem specific for homogeneous catalysis. 

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. 

Ultrafiltration has been used for the separation of dendritic polymeric supports in multi-step syntheses as well as for the separation of dendritic polymer-sup-ported reagents [4, 21]. However, this technique has most frequently been employed for the separation of polymer-supported catalysts (see Section 7.5) [18]. In the latter case, continuous flow UF-systems, so-called membrane reactors, were used for homogeneous catalysis, with catalysts complexed to dendritic ligands [23-27]. A critical issue for dendritic catalysts is the retention of the catalyst by the membrane (Fig. 7.2b, see also Section 7.5). 

J. Kim and R. Datta, Supported liquid-phase catalytic membrane reactor-separator for homogeneous catalysis. AIChE ]., 3711 (1991) 165. 

Riisager A, Fehrmann R, Haumann M et al (2006) Supported ionic liquid phase (SILP) catalysis an innovative concept for homogeneous catalysis in continuous fixed-bed reactors. Eur... 

Figure 2 illustrates the enormous importance of the biphase technique for homogeneous catalysis the aqueous catalyst solution is charged in the reactor with the reactants A and B, which react to form the solvent-dissolved reaction products C and D. C and D are less polar than the aqueous catalyst solution and are therefore simple to separate from the aqueous phase (which is recycled directly into the reactor) in the downstream phase separator (decanter). 

Figure 2 General reactor scheme for homogeneous catalysis using SCFs.

New types of reactor, such as the membrane reactor, wiU in future be applied to additional areas of apphcation. Already today this type of reactor is being used not only for homogeneous catalysis, but also for selective hydrogenation. Selective oxidation reactions in a membrane reactor appear promising. 

This review puts its focus on high-throughput preparation of heterogeneous catalysts, that is, solid-state materials that are apphed in fixed-bed reactors for gas-phase reactions and in trickle-bed or stirred-tank reactors for liquid or gas-hquid reactions, respectively. Other fields of catalysis are not discussed since very different catalytic systems are used. We refer to the following reviews for homogeneous catalysis (2, 3), where combinatorial catalysis deals mainly with variation of ligands and for electrochemical catalysis [4,5], where catalysts are prepared as arrays of thin films in electrochemical cells. 

Catalysis in a single fluid phase (liquid, gas or supercritical fluid) is called homogeneous catalysis because the phase in which it occurs is relatively unifonn or homogeneous. The catalyst may be molecular or ionic. Catalysis at an interface (usually a solid surface) is called heterogeneous catalysis, an implication of this tenn is that more than one phase is present in the reactor, and the reactants are usually concentrated in a fluid phase in contact with the catalyst, e.g., a gas in contact with a solid. Most catalysts used in the largest teclmological processes are solids. The tenn catalytic site (or active site) describes the groups on the surface to which reactants bond for catalysis to occur the identities of the catalytic sites are often unknown because most solid surfaces are nonunifonn in stmcture and composition and difficult to characterize well, and the active sites often constitute a small minority of the surface sites. 

Several L-amino acids are produced on a large scale by enzymatic resolution of N-acetyl-D,L-amino adds (Figure A8.4). Acylase immobilised on DEAE-Sephadex is for example employed in a continuous process while Degussa uses the free acylase retained in a membrane reactor. In the latter process the advantage of reuse of the enzyme and homogeneous catalysis are combined. 

The traditional catalyst used for esterification of acids to methyl esters is sulfuric acid. Homogeneous sulfuric acid catalysis has many downsides. When using sulfuric acid, much capital expense is required for Hastalloy and/or other specialty metals of construction. Homogeneous catalysis results in the contamination of the product by sulfur containing species. Therefore, neutralization and removal of acid is required to meet biodiesel specifications and to protect the downstream transesterification reactor. Inevitably, when using sulfuric acid, organic sulfur compounds will be produced. These products will cause the resultant biodiesel to fail specification tests. 

A wide variety of new approaches to the problem of product separation in homogeneous catalysis has been discussed in the preceding chapters. Few of the new approaches has so far been commercialised, with the exceptions of a the use of aqueous biphasic systems for propene hydroformylation (Chapter 5) and the use of a phosphonium based ionic liquid for the Lewis acid catalysed isomerisation of butadiene monoxide to dihydrofuran (see Equation 9.1). This process has been operated by Eastman for the last 8 years without any loss or replenishment of ionic liquid [1], It has the advantage that the product is sufficiently volatile to be distilled from the reactor at the reaction temperature so the process can be run continuously with built in product catalyst separation. Production of lower volatility products by such a process would be more problematic. A side reaction leads to the conversion of butadiene oxide to high molecular weight oligomers. The ionic liquid has been designed to facilitate their separation from the catalyst (see Section 9.7)... 

An excellent production figure for (R)-mandelonitrile (2400 g/1 per day) was achieved by Kragl et al. [105] using a continuously stirred tank reactor in which an ultrafiltration membrane enables continuous homogenous catalysis to occur from an enzyme (PaHnl) which is retained within the reaction vessel. In order to quench the reaction the outlet of this vessel was fed into a vessel containing a mixture of chloroform and hydrochloric acid, which allowed for accurate product analysis. 

The activated Ba(OH)2 was used as a basic catalyst for the Claisen-Schmidt (CS) condensation of a variety of ketones and aromatic aldehydes (288). The reactions were performed in ethanol as solvent at reflux temperature. Excellent yields of the condensation products were obtained (80-100%) within 1 h in a batch reactor. Reaction rates and yields were generally higher than those reported for alkali metal hydroxides as catalysts. Neither the Cannizaro reaction nor self-aldol condensation of the ketone was observed, a result that was attributed to the catalyst s being more nucleophilic than basic. Thus, better selectivity to the condensation product was observed than in homogeneous catalysis under similar conditions. It was found that the reaction takes place on the catalyst surface, and when the reactants were small ketones, the rate-determining step was found to be the surface reaction, whereas with sterically hindered ketones the adsorption process was rate determining. 

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