Immobilized catalyst separation method

The second important piece in the process development is the separation scheme. Several methods were suggested, such as decanting, water extraction or fractional distillation, use of hydrocyclones, hydrophobic membrane filters, etc. In the early work at EBC, many of its patents refer to facilitating catalyst separation via immobilization, although no mention is given on how activity was impacted by that immobilization. Furthermore, there were no details on how immobilization was achieved and which were the preferred means and techniques. 

Different immobilization methods were applied for Jacobsen s catalyst. The entrapment of the organometallic complex in the supercages of the dealuminated zeolite was achieved without noticeable loss of activity and selectivity. The immobilized catalysts were reusable and did not leach. For the oxidation of (-)-a-pinene the system used only O2 at RT instead of sodium hypochloride at 0 °C. There was a disadvantage in the use of pivalic aldehyde for oxygen transformation via the corresponding peracid. This results in the formation of pivalic acid, which has to be separated from the reaction mixture. 

In the context of catalyst separation and recycling, it must be noted that a system where a catalyst must not be removed from the reaction vessel is very attractive. An example comes from continuous flow methods, when the immobilized catalyst permanently resides in the reactor where it transforms the entering starting materials into the exiting products. The retention of the catalyst inside the reaction vessel can be achieved by different techniques ranging from ultrafiltration through a Mw-selective membrane to immobilization on a silica gel column. 

It is therefore not surprising that it was only when suitable methods for catalyst separation from the substrates and reaction products of homogeneous catalysis were developed that the importance of this type of process grew. The successful developments (thermal separation or chemical reaction (e. g., [26]), immobilization by means of supports and thus heterogenization (e. g., [44]), phase transfer catalysis [45], biphasic processes (e. g., [46, 47]) or separation with membrane modules [48, 49]) are described in the relevant sections of this book (cf. [50]). 

Asymmetric epoxidation (AE) of unfunctionalized alkenes catalyzed by chiral (salen)Mn(III) complex 38 (Scheme 2.13), developed by Jacobsen et al., is one of the most reliable methods [50]. As shown in Table 2.2, several different strategies have been formulated to immobilize Jacobsen s catalysts on inorganic supports [37-42]. Facilitation of catalyst separation, catalyst reuse, an increase in catalyst stability (e.g. minimization of the possibility of formahon of inachve g-oxo-manganese(lV) species [51a,b]) and sometimes improvement in enanhoselectivity are the main objectives of such research. Heterogenized Mn(salen) systems have recently been reviewed by Salvador et al. [51c] and Garcia et al. [5 Id]. Some selected cases are therefore described herein on the basis of the immobilizahon methods. 

The following three separation methods of product from the Ir-catalyst were evaluated distillation, extraction and filtration. For the last two options the preparation of new modified extractable or immobilized xyliphos ligands was necessary. However, lower activity and selectivity of these xyliphos derivatives and the additional development work that would have been required led to the decision to stay with the already well optimized soluble xyliphos system. After the hydrogenation step, a continuous aqueous extraction is performed to neutralize and eliminate the acid from the crude product. After flash distillation to remove residual water the catalyst is separated from (S)-NAA in a subsequent distillation on a thin film evaporator (see Fig. 13). From the organic distillation residue, Ir could in principle be recovered whereas the chiral ligand decomposes. Owing to the very low catalyst concentrations, Ir recovery is not economical. 

Recovery of the palladium catalysts remains a serious problem for the large-scale application of cross-coupling reactions. Many methods to immobilize the catalyti-cally active species have been designed in order to simplify catalyst separation and recyclability, the most popular strategies being filtration, centrifugation and bipha-sic extraction. 

There are numerous types of multiphasic chemical processes. The most common are biphasic although triphasic, tetraphasic and even higher number of phases can also be used to conduct chemical synthesis. All the multiphasic methods aim to overcome the major problem of homogeneous catalysis, which is catalyst recovery and product separation. The simplest systems are biphasic ones that involve immobilizing a catalyst in one solvent, which is immiscible with a second solvent in which the substrates/products are dissolved. If a gas is required as a substrate then the system could be regarded as triphasic (i.e. liquid-liquid-gas), although for the purposes of this book (and as is most commonly defined elsewhere) such as system will be referred to as biphasic. In other words, only the number of different liquid solvent phases will be used to define the phasicity of a system. 

In the search to develop new materials for immobilization of homogeneous transition metal catalyst to facilitate catalyst-product separation and catalyst recychng, the study of dendrimers and hyperbranched polymers for application in catalysis has become a subject of intense research in the last five years [68], because they have excellent solubility and a high number of easily accessible active sites. Moreover, the pseudo-spherical structure with nanometer dimensions opens the possibility of separation and recycling by nanofiltration methods. Although dendrimers allow for controlled incorporation of transition metal catalysts in the core [69] as well as at the surface [70], a serious drawback of this approach is the tedious preparation of functionalized dendrimers by multi-step synthesis. 

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