Metal separation using supported liquid

Cost. The catalytically active component(s) in many supported catalysts are expensive metals. By using a catalyst in which the active component is but a very small fraction of the weight of the total catalyst, lower costs can be achieved. As an example, hydrogenation of an aromatic nucleus requires the use of rhenium, rhodium, or mthenium. This can be accomplished with as fittie as 0.5 wt % of the metal finely dispersed on alumina or activated carbon. Furthermore, it is almost always easier to recover the metal from a spent supported catalyst bed than to attempt to separate a finely divided metal from a liquid product stream. If recovery is efficient, the actual cost of the catalyst is the time value of the cost of the metal less processing expenses, assuming a nondeclining market value for the metal. Precious metals used in catalytic processes are often leased. 

Adsorbers, distillation colunuis, and packed lowers are more complicated vessels and as a result, the potential exists for more serious hazards. These vessels are subject to tlie same potential haz. uds discussed previously in relation to leaks, corrosion, and stress. However, llicse separation columns contain a wide variety of internals or separation devices. Adsorbers or strippers usually contain packing, packing supports, liquid distributors, hold-down plates, and weirs. Depending on tlie physical and chemical properties of the fluids being passed tlirough tlie tower, potential liazards may result if incompatible materials are used for llie internals. Reactivity with llie metals used may cause undesirable reactions, which may lead to elevated temperatures and pressures and, ullinialely, to vessel rupture. Distillation columns may contain internals such as sieve trays, bubble caps, and valve plates, wliicli are also in conlacl with tlie... 

The solubilities of the various gases in [BMIM][PFg] suggests that this IL should be an excellent candidate for a wide variety of industrially important gas separations. There is also the possibility of performing higher-temperature gas separations, thanks to the high thermal stability of the ILs. For supported liquid membranes this would require the use of ceramic or metallic membranes rather than polymeric ones. Both water vapor and CO2 should be removed easily from natural gas since the ratios of Henry s law constants at 25 °C are -9950 and 32, respectively. It should be possible to scrub CO2 from stack gases composed of N2 and O2. Since we know of no measurements of H2S, SO, or NO solubility in [BMIM][PFg], we do not loiow if it would be possible to remove these contaminants as well. Nonetheless, there appears to be ample opportunity for use of ILs for gas separations on the basis of the widely varying gas solubilities measured thus far. 

Ionic liquids have already been demonstrated to be effective membrane materials for gas separation when supported within a porous polymer support. However, supported ionic liquid membranes offer another versatile approach by which to perform two-phase catalysis. This technology combines some of the advantages of the ionic liquid as a catalyst solvent with the ruggedness of the ionic liquid-polymer gels. Transition metal complexes based on palladium or rhodium have been incorporated into gas-permeable polymer gels composed of [BMIM][PFg] and poly(vinyli-dene fluoride)-hexafluoropropylene copolymer and have been used to investigate the hydrogenation of propene [21]. 

The discussion so far implies that membrane materials are organic polymers, and in fact most membranes used commercially are polymer-based. However, in recent years, interest in membranes made of less conventional materials has increased. Ceramic membranes, a special class of microporous membranes, are being used in ultrafiltration and microfiltration applications for which solvent resistance and thermal stability are required. Dense, metal membranes, particularly palladium membranes, are being considered for the separation of hydrogen from gas mixtures, and supported liquid films are being developed for carrier-facilitated transport processes. 

Sorption of Cu(tfac)2 on a column depends on the amount of the compound injected, the content of the liquid phase in the bed, the nature of the support and temperature. Substantial sorption of Cu(tfac)2 by glass tubing and glass-wool plugs was observed. It was also shown that sorption of the copper chelate by the bed is partialy reversible . The retention data for Cr(dik)3, Co(dik)3 and Al(dik)3 complexes were measured at various temperatures and various flow rates. The results enable one to select conditions for the GC separation of Cr, Al and Co S-diketonates. Retention of tfac and hfac of various metals on various supports were also studied and were widely used for the determination of the metals. Both adsorption and partition coefficients were found to be functions of the average thickness of the film of the stationary phase . Specific retention volumes, adsorption isotherms, molar heats and entropy of solution were determined from the GC data . The retention of metal chelates on various stationary phases is mainly due to adsorption at the gas-liquid interface. However, the classical equation which describes the retention when mixed mechanisms occur is inappropriate to represent the behavior of such systems. This failure occurs because both adsorption and partition coefficients are functions of the average thickness of the film of the stationary phase. It was pointed out that the main problem is lack of stability under GC conditions. Dissociation of the chelates results in a smaller peak and a build-up of reactive metal ions. An improvement of the method could be achieved by addition of tfaH to the carrier gas of the GC equipped with aTCD" orFID" . ... 

Ho, W.S. and Wang, B., Inventors Commodore Separation Technologies Inc., Assinee. Combined supported liquid membrane/stripping dispersion process for removal and recovery of metals Dialkyl monothiophosphoric acids and their use as extractants, US Patent... 

Liquid-liquid methods include solvent extraction with immiscible liquid-liquid systems in which a suitable ligand is dissolved in an organic phase and contacted with a metal ion containing an aqueous phase and liquid membranes. Separations can also be achieved with pseudo-phase systems such as micelles, microemulsions, and vesicles. Such separations can be solid-liquid or liquid-liquid and include separations with normal- and reversed-phase silica, and polymeric supports where the mobile phase contains the organized molecular assembly (OMA) of micelles, microemulsions, or vesicles. Separation of metal ions using the pseudo-phase systems is stiU in its infancy and a brief account will be provided here. 

Promising results are shown by recently developed integrated SLM-ELM [84, 85] systems. These techniques are known as supported liquid membrane with strip dispersion (SLMSD), pseudo-emulsion-based hollow fiber strip dispersion (PEHFSD), emulsion pertraction technology (EPP), and strip dispersion hybrid Hquid membrane (SDHLM). AH techniques are the same the organic phase (carrier, dissolved in diluent) and back extraction aqueous phase are emulsified before injection into the module and can be separated at the module outlet. The difference is only in the type of the SLM contactors hoUow fiber or flat sheet and in the Hquid membrane (carrier) composition. These techniques have been successfuUy demonstrated for the removal and recovery of metals from wastewaters. Nevertheless, the techniques stiU need to be tested in specific apphcations to evaluate the suitabUity of the technology for commercial use. 

An important requirement for all homogeneous catalytic processes is that the dissolved catalyst must be separated from the liquid product and recycled to the reactor without significant catalyst loss the need is acute when the metal is as expensive as rhodium. One approach to aid this separation process is to immobilize (anchor) the soluble catalyst on a solid support in order to confine the catalyst to the reactor and overcome the need for a catalyst recycle step. A number of types of solid support have been employed to anchor rhodium catalysts for use in methanol carbon-ylation with liquid- or gas-phase reactants. These were reviewed by Howard et al. in 1993 [8] and include activated carbon, inorganic oxides, zeolites, and a range of polymeric materials. 

The solubility of different gases in the various ILs, as discussed above, suggests that ILs should be excellent candidates for a wide variety of industrially important gas separations. There is also the possibility of doing higher temperature gas separations due to the high thermal stability of the ILs. For supported liquid membranes this would require the use of ceramic or metallic membranes rather than polymeric... 

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