Catalyst solution, recycling

The product could be quantitatively separated and the recovered IL catalyst solution recycled several times without any significant change in activity or selectivity. The RTIL [emim][OTf] was employed as the sole reaction solvent for the asymmetric hydrogenation of methyl a-benzamido cinnamate. Near-quantitative conversions were observed At 60 psi hydrogen partial pressure and 50 °C for 24 h, using both the achiral DiPFc-Rh and the chiral EtDuPHOS-Rh catalysts.Enantiomeric excess of 89% was observed for hydrogenations carried out with the chiral catalyst. 

In the one-stage process (Fig. 2), ethylene, oxygen, and recycle gas are directed to a vertical reactor for contact with the catalyst solution under slight pressure. The water evaporated during the reaction absorbs the heat evolved, and make-up water is fed as necessary to maintain the desired catalyst concentration. The gases are water-scmbbed and the resulting acetaldehyde solution is fed to a distUlation column. The tad-gas from the scmbber is recycled to the reactor. Inert materials are eliminated from the recycle gas in a bleed-stream which flows to an auxdiary reactor for additional ethylene conversion. 

Catalyst recovery is a major operational problem because rhodium is a cosdy noble metal and every trace must be recovered for an economic process. Several methods have been patented (44—46). The catalyst is often reactivated by heating in the presence of an alcohol. In another technique, water is added to the homogeneous catalyst solution so that the rhodium compounds precipitate. Another way to separate rhodium involves a two-phase Hquid such as the immiscible mixture of octane or cyclohexane and aliphatic alcohols having 4—8 carbon atoms. In a typical instance, the carbonylation reactor is operated so the desired products and other low boiling materials are flash-distilled. The reacting mixture itself may be boiled, or a sidestream can be distilled, returning the heavy ends to the reactor. In either case, the heavier materials tend to accumulate. A part of these materials is separated, then concentrated to leave only the heaviest residues, and treated with the immiscible Hquid pair. The rhodium precipitates and is taken up in anhydride for recycling. 

A Hquid-phase variation of the direct hydration was developed by Tokuyama Soda (78). The disadvantages of the gas-phase processes are largely avoided by employing a weakly acidic aqueous catalyst solution of a siHcotungstate (82). Preheated propylene, water, and recycled aqueous catalyst solution are pressurized and fed into a reaction chamber where they react in the Hquid state at 270°C and 20.3 MPa (200 atm) and form aqueous isopropyl alcohol. Propylene conversions of 60—70% per pass are obtained, and selectivity to isopropyl alcohol is 98—99 mol % of converted propylene. The catalyst is recycled and requites Htde replenishment compared to other processes. Corrosion and environmental problems are also minimized because the catalyst is a weak acid and because the system is completely closed. On account of the low gas recycle ratio, regular commercial propylene of 95% purity can be used as feedstock. 

After flashing the propylene, the aqueous solution from the separator is sent to the purification section where the catalyst is separated by a2eotropic distillation 88 wt % isopropyl alcohol is obtained overhead. The bottoms containing aqueous catalyst solution are recycled to the reactor, and the light ends are stripped of low boiling impurities, eg, diisopropyl ether and acetone. A2eotropic distillation yields dry isopropyl alcohol, and the final distillation column yields a product of more than 99.99% purity. 

The tert-huty hydroperoxide is then mixed with a catalyst solution to react with propylene. Some TBHP decomposes to TBA during this process step. The catalyst is typically an organometaHic that is soluble in the reaction mixture. The metal can be tungsten, vanadium, or molybdenum. Molybdenum complexes with naphthenates or carboxylates provide the best combination of selectivity and reactivity. Catalyst concentrations of 200—500 ppm in a solution of 55% TBHP and 45% TBA are typically used when water content is less than 0.5 wt %. The homogeneous metal catalyst must be removed from solution for disposal or recycle (137,157). Although heterogeneous catalysts can be employed, elution of some of the metal, particularly molybdenum, from the support surface occurs (158). References 159 and 160 discuss possible mechanisms for the catalytic epoxidation of olefins by hydroperoxides. 

The authors describe a clear enhancement of the catalyst activity by the addition of the ionic liquid even if the reaction medium consisted mainly of CH2CI2. In the presence of the ionic liquid, 86 % conversion of 2,2-dimethylchromene was observed after 2 h. Without the ionic liquid the same conversion was obtained only after 6 h. In both cases the enantiomeric excess was as high as 96 %. Moreover, the ionic catalyst solution could be reused several times after product extraction, although the conversion dropped from 83 % to 53 % after five recycles this was explained, according to the authors, by a slow degradation process of the Mn complex. 

Finally, it was possible to demonstrate that the ionic catalyst solution can, in principle, be recycled. By repetitive use of the ionic catalyst solution, an overall activity of 61,106 mol ethylene converted per mol catalyst could be achieved after two recycle runs. 

Heavies formation is accelerated by a variety of materials.[8] Successful Gas Recycle operation depends on keeping the catalyst solution as pristine as possible to limit heavies formation since in Gas Recycle there is no independent way to remove heavies. There are a single set of conditions for product formation, product removal and byproduct (heavies) removal. A key to successful operation is identifying conditions under which the heavies can be removed essentially at their rate of formation. A downside of Gas Recycle is that it may be difficult to recover from upsets in operation, which result in the catalyst solution containing a disproportionate amount of heavies. 

Whereas in Gas Recycle the product must be removed at the same temperature and pressure at which it is formed, in Liquid Recycle the separation of product (and byproducts) from catalyst is independent of the conditions under which the products were formed. This added degree of control brings a variety of benefits. Since large gas flows are no longer required in the reactor, the liquid expansion due to gassing is reduced and more catalyst can be contained in a specific reaction vessel. Reactor temperature and reactant concentrations can be tuned for optimum catalyst performance. The conditions in the separation system can likewise be tuned for optimum performance. In particular, more severe conditions will permit better control over the concentration of heavies in the catalyst solution. 

Another advantage of Liquid Recycle is that multiple reactors may be arranged in series with the effluent from one passing on to the next. The alkene concentration is less in the downstream reactors, but reaction conditions can be adjusted to optimize each reactor s performance. In back mixed reactors in continuous operation, the effluent from the reactor is the same as the catalyst solution throughout the reactor. By placing reactors in series, the first reactor can be optimized for high rates and later reactors for high conversion. 

An alkene which will give a polar aldehyde product and syn gas are introduced into the reactor containing a non-polar ligand modified rhodium catalyst. Catalyst solution exiting the reactor enters a Flash stage where CO/H2 are purged. The catalyst solution then enters an extractor where it is contacted with a polar solvent. The product aldehyde is captured in the polar solvent in the extractor, then concentrated in the Solvent Removal Column. Polar Solvent is recycled to the Extractor. The Non-Polar catalyst solution is recycled to the reactor (see Figure 2.5). 

In hydroformylating with a polar ligand modified rhodium catalyst to give a relatively non-polar aldehyde product, after the flash column, the catalyst solution is extracted with a non-polar solvent. Polar catalyst recycles from the extractor to the reactor. The non-polar solvent is removed and recycled to the extractor (see Figure 2.6). 

Another aspect of gas recycle that would need to be considered is the degree of catalyst solution expansion that would result from very high gas recycle flows. The catalyst solution might be blown out of the reactor, or if a very tall reactor were built, it would suffer from excessive capital costs for the large containment needed for the gas-expanded catalyst. 

Liquid Recycle is practical for octene hydroformylation. 1-Octene is readily soluble in organic based catalyst solutions, and product aldehyde and its condensation products can be separated by vaporization. 

Induced Phase Separation is also a good choice for octene hydroformylation. Octene can easily dissolve in the organic based catalyst solution, and with addition of small amounts of water, nonanal and its condensation products will readily separate from the sodium salt of a monosulfonated phosphine. To choose between Liquid Recycle and Induced Phase Separation would require a detailed technical and economic study that is outside the scope of this chapter. 

A consequence of the value of the ligand is that one of the simplest ways to restore catalyst activity is simply to add fresh catalyst precursor. Unfortunately, there are practical limits as the rhodium concentration increases. First one must consider metal complex solubility, particularly in the recycle catalyst solution in a liquid recycle system. Secondly, higher rhodium concentrations favor formation of various types of rhodium clusters.[11] As rhodium increments are added to a partially deactivated cata-... 

Selective Condensation of Vaporized Organophosphorus Ligand. Certain phosphorus ligands have sufficient volatility that portions may be volatilized when aldehyde and higher boiling aldehyde condensation byproducts are separated from the catalyst solution in, for example, a liquid recycle vaporizer. The phosphorus ligand may be condensed, recovered and returned to the catalyst solution [35] according to the procedure disclosed in US 5,110,990. 

In the early 1970 s, Bayer et al. reported the first use of soluble polymers as supports for the homogeneous catalysts. [52] They used non-crosslinked linear polystyrene (Mw ca. 100 000), which was chloromethylated and converted by treatment with potassium diphenylphosphide into soluble polydiphenyl(styrylmethyl)phosphines. Soluble macromolecular metal complexes were prepared by addition of various metal precursors e.g. [Rh(PPh3)Cl] and [RhH(CO)(PPh3)3]. The first complex was used in the hydrogenation reaction of 1-pentene at 22°C and 1 atm. H2. After 24 h (50% conversion in 3 h) the reaction solution was filtered through a polyamide membrane [53] and the catalysts could be retained quantitatively in the membrane filtration cell. [54] The catalyst was recycled 5 times. Using the second complex, a hydroformylation reaction of 1-pentene was carried out. After 72 h the reaction mixture was filtered through a polyamide membrane and recycled twice. 

After a hydroformylation run, the reaction solution was subjected to ultrafiltration using an asymmetric polyethersulfone membrane (MWCO 50 kDa) supplied by Sartorius. A retention of 99.8% was found. When the catalyst solution was recycled, virtually the same catalytic activity was observed again (165 TO h 1). Repetitive recycling experiments resulted in 2-7% loss of rhodium, which was subscribed to partial oxidation of the phosphine ligand. 

The possibility of adjusting solubility properties is of particular importance for liquid-liquid biphasic catalysis. Liquid-liquid catalysis can be realised when the ionic liquid is able to dissolve the catalyst, especially if it displays partial solubility of the substrates and poor solubility of the reaction products. Under these conditions, the product phase, which also contains the unconverted reactants, is removed by simple phase decantation. The ionic liquid containing the catalyst can then be recycled. In such a scenario the ionic catalyst solution may be seen as part of the capital investment for a potential technical process (in an ideal case) or at least as a working solution (only a small amount has to be replaced after a certain time of application). A crucial aspect of this concept is the immobilisation of the transition metal catalyst in the ionic liquid. While most transition metal catalysts easily dissolve in an ionic liquid without any special ligand design, ionic ligand systems have been applied with great success to... 

The use of the sulfoxantphos ligand (compound (b) in Figure 7.8) in the biphasic hydroformylation of 1-octene with [BMIM][PF6] has been studied by Dupont and coworkers [58], The ligand allowed recycling of the catalyst solution up to four times with no loss in activity or selectivity. Flighly regioselective hydroformylation (n/iso = 13) was reported for a Rh/phosphine-ratio of 4 (100°C, 15 bar syngas pressure). 

The ionic catalyst solution was prepared by stirring [Rh(acac)(CO)2] with four equivalents of this ligand in an acctonitrile/[BMIM][PF6] mixture for 1 h followed by removal of the volatiles. The reaction conditions for the hydroformylation of 1-octene were similar to those used by Dupont et al. [58] (see earlier). The results of seven consecutive recycling experiments are shown in Table 7.3. 

The technological circuit of ZnCFO synthesis is developed in the Ukrainian State Chemical-Technological University. ZnCFO is the product of reaction of carbamide and formaldehyde polycondensation in zinc salts solution at recycling of metalcontaining wastes of chemical manufactures. The material base of ZnCFO manufacture are fulfilled catalysts, solutions from zincing and others zinccontaining wastes of various origin. 

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