Catalyst continued recovery

Palladium catalyst stability, recovery and recycle are the key to viable commercial technology. Continuous palladium recovery and recycle at 99.9% efficiency is critical to the economics of the process. Traditional catalyst recovery methods fail since the adipic acid precursor, dimethyl hex- -enedioate, is high boiling and the palladium catalytic species are thermally unstable above 125 C. Because of this problem, a non-traditional solvent extraction approach to catalyst recovery has been worked out and implemented at the pilot plant scale. Since patents have not issued, process detail on catalyst separation, secondary palladium recovery, and product recovery cannot be included in this review. 

Figure 8 Schematic representation of different reactor types for the continuous recovery of soluble polymer-bound catalyst ...

The difficulty from a practical perspective is that most of these catalysts will never perform sufficiently well at a commercial scale to be useful. Many catalysts developed in academia are also homogeneous catalysts and recovery is often not possible, but when it is possible, the recovery process can be problematic. From a sustainability perspective the use of the platinum group metals creates a number of challenges [65,66]. Most of these metals come from only two regions of the world Russia and South Africa. Russia has recently had pohtical and economic conflicts with Europe and the United States, while South Africa has a continued history of labor unrest related to the conditions under... 

In a patent assigned to BASF [22], a process for the continuous recovery of caprolactam from nylon 6 fibers containing carpet waste has been described. Nylon 6 fiber scrap obtained from the carpet separation is fed to a depolymerizing reactor at temperature of at least the melting point of nylon 6 in the presence of catalyst and superheated steam to produce caprolactam containing distillate which is separated from other volatiles and purified. 

The rate at which the catalyst is lost or degrades has a major influence on the design. If degradation is rapid, the catalyst needs to be regenerated or replaced on a continuous basis. In addition to the cost implications, there are also environmental implications, since the lost or degraded catalyst represents waste. While it is often possible to recover useful materials from degraded catalyst and to recycle those materials in the manufacture of new catalyst, this still inevitably creates waste, since the recovery of material can never be complete. 

Since the catalyst is in the gaseous state, it is being continually removed from the mixing chambers. Its recovery, and the necessity of continual charging of the incoming gases with it, make the lead chamber plant complicated by comparison with that of the Contact process. 

Figure 2 illustrates the three-step MIBK process employed by Hibernia Scholven (83). This process is designed to permit the intermediate recovery of refined diacetone alcohol and mesityl oxide. In the first step acetone and dilute sodium hydroxide are fed continuously to a reactor at low temperature and with a reactor residence time of approximately one hour. The product is then stabilized with phosphoric acid and stripped of unreacted acetone to yield a cmde diacetone alcohol stream. More phosphoric acid is then added, and the diacetone alcohol dehydrated to mesityl oxide in a distillation column. Mesityl oxide is recovered overhead in this column and fed to a further distillation column where residual acetone is removed and recycled to yield a tails stream containing 98—99% mesityl oxide. The mesityl oxide is then hydrogenated to MIBK in a reactive distillation conducted at atmospheric pressure and 110°C. Simultaneous hydrogenation and rectification are achieved in a column fitted with a palladium catalyst bed, and yields of mesityl oxide to MIBK exceeding 96% are obtained. 

The processiag costs associated with separation and corrosion are stiU significant ia the low pressure process for the process to be economical, the efficiency of recovery and recycle of the rhodium must be very high. Consequently, researchers have continued to seek new ways to faciUtate the separation and confine the corrosion. Extensive research was done with rhodium phosphine complexes bonded to soHd supports, but the resulting catalysts were not sufficiently stable, as rhodium was leached iato the product solution (27,28). A mote successful solution to the engineering problem resulted from the apphcation of a two-phase Hquid-Hquid process (29). The catalyst is synthesized with polar -SO Na groups on the phenyl rings of the triphenylphosphine. 

Polymer-supported catalysts incorporating organometaUic complexes also behave in much the same way as their soluble analogues (28). Extensive research has been done in attempts to develop supported rhodium complex catalysts for olefin hydroformylation and methanol carbonylation, but the effort has not been commercially successful. The difficulty is that the polymer-supported catalysts are not sufftciendy stable the valuable metal is continuously leached into the product stream (28). Consequendy, the soHd catalysts fail to eliminate the problems of corrosion and catalyst recovery and recycle that are characteristic of solution catalysis. 

The process consists of a reactor section, continuous catalyst regeneration unit (CCR), and product recovery section. Stacked radial-flow reactors are used to minimize pressure drop and to facilitate catalyst recirculation to and from the CCR. The reactor feed consists solely of LPG plus the recycle of unconverted feed components no hydrogen is recycled. The liquid product contains about 92 wt% benzene, toluene, and xylenes (BTX) (Figure 6-7), with a balance of Cg aromatics and a low nonaromatic content. Therefore, the product could be used directly for the recovery of benzene by fractional distillation (without the extraction step needed in catalytic reforming). 

This comprehensive article supplies details of a new catalytic process for the degradation of municipal waste plastics in a glass reactor. The degradation of plastics was carried out at atmospheric pressure and 410 degrees C in batch and continuous feed operation. The waste plastics and simulated mixed plastics are composed of polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile butadiene styrene, and polyethylene terephthalate. In the study, the degradation rate and yield of fuel oil recovery promoted by the use of silica alumina catalysts are compared with the non-catalytic thermal degradation. 9 refs. lAPAN... 

Thermomorphic solvent mixtures have been tested for hydroformylation of 1-octene and 1-dodecene to determine the ease of product recovery and catalyst recycling. Using both batch and continuous reactors, we demonstrated the efficacy of a biphasic, thermomorphic, system that had the following advantages ... 

An aspect of the hydroformylation reaction which is of particular importance in continuous commercial operation is the separation of the catalyst from product aldehyde and/or alcohol, together with its recovery and recycle into the reactant stream. This feature is of considerable economic and process importance for cobalt reactions and of extreme economic importance for rhodium reactions. 

Size The molecular enlargement achieved by dendrylation can be variously utilized. For example, the separation of the dendrylated component from smaller molecular species by means of ultrafiltration makes use of a size difference This procedure is particularly advantageous with respect to catalytically active focal functionalities, because it simplifies the recovery of the catalyst and allows even continuous diaphragm processes.14,10 14 17-221... 

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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