Ruthenium leaching

RCM of diallyltosylamide and other dienes toluene as co-solvent high recyclability at 25 °C ruthenium leaching ca. one order of magnitude lower than previously [44] reported tetra-substituted dienes could not be cyclised. 

While monometallic ruthenium/carbon deactivated progressively during 300 h on stream when the reaction was performed in 2-sec-butyl-phenol solvent at 180 °C and 3.5 MPa in a flow fixed-bed reactor, bimetallic ruthenium-tin/carbon catalysts exhibited a stable activity. The optimised ruthenium/tin atomic ratio of unity led to ruthenium and RuaSng alloy species. Neither tin nor ruthenium leaching occurred. In addition, the hydrogenation of the C=0 bond of levulinic acid was 100% selective. 

Amphiphilic resin supported ruthenium(II) complexes similar to those displayed in structure 1 were employed as recyclable catalysts for dimethylformamide production from supercritical C02 itself [96]. Tertiary phosphines were attached to crosslinked polystyrene-poly(ethyleneglycol) graft copolymers (PS-PEG resin) with amino groups to form an immobilized chelating phosphine. In this case recycling was not particularly effective as catalytic activity declined with each subsequent cycle, probably due to oxidation of the phosphines and metal leaching. 

When recovered from the mineral osmiridium, the mineral is fused with zinc to convert it into a zinc alloy. The alloy is then treated with hydrochloric acid to dissolve the zinc away leaving a finely divided material. This finely divided sohd then is fused with sodium peroxide and caustic soda to convert osmium and ruthenium into their water-soluble sodium salts, sodium osmate and sodium iridate, respectively. While osmium is fully converted to osmate salt, most ruthemium and a small part of iridium are converted to ruthenate and iridate, respectively. The fused mass is leached with water to separate metals from sohd residues. 

The treatment of this insoluble residue may vary. In one typical process, residue is subjected to fusion with sodium peroxide. Ruthenium and osmium are converted to water-soluble sodium ruthenate and osmate, which are leached with water. The aqueous solution is treated with chlorine gas and heated. The ruthenate and the osmate are converted to their tetroxides. Ruthenium tetroxide is distilled out and collected in hydrochloric acid. The tetroxide is converted into ruthenium chloride. Traces of osmium are removed from ruthenium chloride solution by boiling with nitric acid. 

Ruthenium and its compounds are analyzed by flame AA method using nitrous oxide-acetylene flame. ICP-AES, ICP/MS, and neutron activation analysis are also applicable. The metal or its insoluble compounds may be solubilized by fusion with alkah and leached with water. 

The use of water-soluble catalysts in this reaction has hardly been investigated. Ruthenium/edta (78) and cobalt/tppts (79) catalysts have been described. The use of palladium/tppms catalyst was also reported (80). When edta and tppms are used as ligands, leaching of the metal by the product stream takes place. In the case of the cobalt/tppts catalyst, a high CO partial pressure and a catalyst concentration of >8 mol% are necessary. The reason for this effect is not clear. 

Following the development of sponge-metal nickel catalysts by alkali leaching of Ni-Al alloys by Raney, other alloy systems were considered. These include iron [4], cobalt [5], copper [6], platinum [7], ruthenium [8], and palladium [9]. Small amounts of a third metal such as chromium [10], molybdenum [11], or zinc [12] have been added to the binary alloy to promote catalyst activity. The two most common skeletal metal catalysts currently in use are nickel and copper in unpromoted or promoted forms. Skeletal copper is less active and more selective than skeletal nickel in hydrogenation reactions. It also finds use in the selective hydrolysis of nitriles [13]. This chapter is therefore mainly concerned with the preparation, properties and applications of promoted and unpromoted skeletal nickel and skeletal copper catalysts which are produced by the selective leaching of aluminum from binary or ternary alloys. 

One of the areas gamering attention in catalysis research has been the development of green or enviromnentally benign catalytic systems. For olefin metathesis, the trend has been to develop catalytic systems that can be efficiently recycled. Success in this area has multiple implications for OM processes. First, a recyclable catalyst will give overall more turnovers per catalyst molecule, and thereby be more economical. Second, a catalyst that can be efficiently recycled (low loss of activity over repeated uses) leaches less Ruthenium into the product and thus less expensive processing costs. To this end inunobihzation of the olefin metathesis catalysts on a variety of sohd supports and utilization of nonorganic solvent systems have been explored. 

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