Rhodium separation

Rhodium. Separate 0SHA standards exist for metal fumes and dusts at 0.1 mg/cu m and soluble salts at 1.0 ug/cu m. The analysis of fume and dust samples is done with an air-acetylene flame using the 343.5 nm line, S-188 fumes and dusts, and the... 

SuperLig materials have been used to recover at high purity Rh, Pt, and Pd from spent catalyst [36]. These individual elements can be recovered at purity levels of > 99.9%. The separation and recovery of rhodium is particularly difficult because of the similarity of its chemical properties to those of the remaining platinum metals. An MRT process has been developed that is effective for rhodium separations and recovery. This process is used commercially for rhodium production. An example of rhodium separation and recovery is given in Table 8. Another case of precious metal... 

The JM process is a rare example of a commercial process in which long-chain branched olefins can be processed using rhodium-catalyzed hydroformylation. It is based on a special rhodium separation process. This enables much of the rhodium to be recovered, which is the basic requirement for any economically viable hydroformylation process based on this metal. Processing under severe conditions is required. This is a basic limitation for the process, as the use of ligands, which play a considerable part in the superiority of rhodium-based processes, is possible - if at all - only with very inexpensive ligands. 

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. 

The use of silver fluoroborate as a catalyst or reagent often depends on the precipitation of a silver haUde. Thus the silver ion abstracts a CU from a rhodium chloride complex, ((CgH )2As)2(CO)RhCl, yielding the cationic rhodium fluoroborate [30935-54-7] hydrogenation catalyst (99). The complexing tendency of olefins for AgBF has led to the development of chemisorption methods for ethylene separation (100,101). Copper(I) fluoroborate [14708-11-3] also forms complexes with olefins hydrocarbon separations are effected by similar means (102). 

Meth5l-l,3-propanediol is produced as a by-product. The hydroformylation reaction employs a rhodium catalyst having a large excess of TPP (1) and an equimolar (to rhodium) amount of 1,4-diphenylphosphinobutane (DPPB) (4). Aqueous extraction/decantation is also used in this reaction as an alternative means of product/catalyst separation. 

Homogeneous rhodium-catalyzed hydroformylation (135,136) of propene to -butyraldehyde (qv) was commercialized in 1976. -Butyraldehyde is a key intermediate in the synthesis of 2-ethyIhexanol, an important plasticizer alcohol. Hydroformylation is carried out at <2 MPa (<290 psi) at 100°C. A large excess of triphenyl phosphine contributes to catalyst life and high selectivity for -butyraldehyde (>10 1) yielding few side products (137). Normally, product separation from the catalyst [Rh(P(C2H2)3)3(CO)H] [17185-29-4] is achieved by distillation. 

In the mid-1980s, Ruhrchemie (now Hoechst) converted its oxo capacity to a proprietary water soluble rhodium catalyzed process (27,28), a technology developed jointly with Rhc ne-Poulenc. Product separation in this process is by decantation. Isomer ratios of n- to isobutyraldehyde of about 20 1 are obtained. 

The hydroformylation reaction is carried out in the Hquid phase using a metal carbonyl catalyst such as HCo(CO)4 (36), HCo(CO)2[P( -C4H2)] (37), or HRh(CO)2[P(CgH3)2]2 (38,39). The phosphine-substituted rhodium compound is the catalyst of choice for new commercial plants that can operate at 353—383 K and 0.7—2 MPa (7—20 atm) (39). The differences among the catalysts are found in their intrinsic activity, their selectivity to straight-chain product, their abiHty to isomerize the olefin feedstock and hydrogenate the product aldehyde to alcohol, and the ease with which they are separated from the reaction medium (36). 

A new homogeneous process for hydroformylation of olefins using a water-soluble catalyst has been developed (40). The catalyst is based on a rhodium complex and utilizes a water-soluble phosphine such as tri(M-sulfophenyl)phosphine. The use of an aqueous phase simplifies the separation of the catalyst and products (see Oxo process). 

Separation Processes. Separation of the catalyst from the products is a significant expense the process flow diagram and the processing cost are often dominated by the separations. Many soluble catalysts are expensive, eg, rhodium complexes, and must be recovered and recycled with high efficiency. The most common separation devices are distiUation columns extraction is also appHed. 

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. 

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. 

The rhodium catalyst previously discussed is employed in the hydrogenation of / -hydroxybenzoic acid. The resulting mixture of cis and trans products is separated by virtue of the ready formation of the lactone of the cis product, which is then hydrolized to the hydroxy acid. 

Closely related to the use of rhodium catalysts for the hydrogenation of phenols is their use in the reduction of anilines. The procedure gives details for the preparation of the catalyst and its use to carry out the low-pressure reduction of /j-aminobenzoic acid. Then, as in the preceding experiment, advantage is taken of the formation of a cyclic product to carry out the separation of a mixture of cis and trans cyclohexyl isomers. 

The major advantage of the use of two-phase catalysis is the easy separation of the catalyst and product phases. FFowever, the co-miscibility of the product and catalyst phases can be problematic. An example is given by the biphasic aqueous hydro-formylation of ethene to propanal. Firstly, the propanal formed contains water, which has to be removed by distillation. This is difficult, due to formation of azeotropic mixtures. Secondly, a significant proportion of the rhodium catalyst is extracted from the reactor with the products, which prevents its efficient recovery. Nevertheless, the reaction of ethene itself in the water-based Rh-TPPTS system is fast. It is the high solubility of water in the propanal that prevents the application of the aqueous biphasic process [5]. 

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]. 

Gold coatings on separable electric contacts and slip rings make use of the high hardness possible with electrodeposition to resist wear. Rhodium is another metal which can be exceptionally hard. Thick coatings have a cracked-sealed structure similar to that of chromium. 

This index is divided by element into eight parts. Each part is subdivided into sections devoted to each oxidation state, preceded by a general section. Thus if you want to fmd out about phosphine complexes of Rhodium, there is a general entry to phosphine complexes as well as separate references to phosphine complexes trader the headings of Rhodium(0), (I), (II) and (III). 

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