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Ruthenium-Mediated Electrochemical Destruction of Organic Wastes by L

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Ruthenium-Mediated Electrochemical Destruction of Organic Wastes by L Ruthenium-Mediated Electrochemical Destruction of Organic Wastes By L. Davidson, Y Quinn and D. E Steele AE-4 Technology plc, Dounreay, Scotland No industrial process is 100 per cent efficient and the generation of waste, both organic and inorganic, is an unavoidable reality. The recycling of waste is becoming increasingly important as concerns about the environment and the availability of resources come more to the fore, but there remain many waste streams which are not yet suitable for recovery of their reusable content, on the grounds of cost orpracticality Historical13 the disposal of such wastes has been either via incineration or release into the environment after neutralisation or imrnobilisation, in a landfill site or into a drain or sewer, or the like. These options are becoming more restricted as regulations tighten and public perception of any but the most benign discharges worsens. This paper sets out reasons for using electrochemical oxidation with a ruthenium electro- catalyst to provide aneffective and environmentally friendly alternative to other technologies. Electrochemical oxidation can effect mineralisation of toxic organic species with minimal generation of secondary waste and eflicient recovery of the ruthenium mediator and is particularly suited for the treatment of highly chlorinated and aromatic compounds. Organic wastes, of the types which cannot furans which are highly toxic and limited, by be converted into benign biodegradable species, Regulatory bodies, to low ppb levels in the dis- are often treated by oxidation, usually inciner- charges. Toxic waste incineration has thus tended ation, although other chemical treatments are to become very 'high-tech' in recent years, with sometimes used. Many of the oxidants which only a few highly specialised facilities treating could be used are ruled out by cost or toxicity. most of the waste destined for combustion. The use of air for such oxidations, normally Public perception of incinerators, particularly by high temperature incineration, is the cheap- those treating toxic wastes, is poor or hostile, est in terms of reagents. The current best-avail- and the licensing of new facilities in most coun- able technology is capable of achieving essen- tries in the developed world is becoming very tially complete destruction of even refractory difficult and sometimes almost impossible. materials. However, the combustion products from many organic materials, in particular chlo- rinated species, contain acidic gases (for exam- Table I ple, hydrogen chloride, sulphur oxides and nitro- Comparison of Oxidation Costs* gen oxides) which must be scrubbed to very low levels before discharge. As excess air is always Oxidant Cost/rnole of [O] equivalent, f used, the volumes of gases for treatment tend to be large, leading to large scrubbers and other Electron 0.01 related equipment, and associated increased Hydrogen peroxide 0.058 costs. Incomplete combustion, possibly due to Potassium dichromate (Cr"') 0.1 8 Ceric nitrate (Ce'") 8.68 maloperation, can lead to the production of sec- ondary species, such as dioxins and dibenzo- * The Appendix contains more details of comparative costs Platinum Metals Rev., 1998, 42, (3), 90-98 90 CO+COl ottgas catholyte recycle Fig. 1 The design of the plant used for the ruthenium-mediated oxidation of highly toxic industrial waste. The cell at the centre of the process has ruthenium chloride or hydrated ruthenium oxide added to the anolyte. Platinum coated anodes are used for the flow-cells However, the use of electrochemical oxidation development by AEA Technology for some time to treat organic industrial waste gives a cheaper, as a possible process for the complete oxidation cleaner and renewable alternative: the ‘electron’. of a number of types of organic waste or the The ‘electron’is also cheaper than chemical oxi- organic waste component in a mixed waste. dants on a per/mole basis, see Table I. However, in the silver-mediated system, the In principle, electrochemical oxidation has a presence of sigdicant amounts of halogen (usu- number of advantages over oxidation using con- ally chlorine) in the organics being oxidised can ventional oxidising agents. In practice, however, result in the formation of substantial amounts direct electrochemical oxidation of organic of insoluble silver halide(s), which are, at best, species is often difficult due to mass transfer and a nuisance. kinetic restraints at the electrode surface and Here an alternative, ruthenium-mediated elec- competing reactions with the electrolyte. Many trochemical system is described, see Figure 1, of the restrictions can be overcome by the use which has many similarities to the SILVER IITM of a mediator which is easily oxidised at the system but which is not affected by the presence anode surface to a species which then reacts of halogen, and in particular by chlorine. in the bulk solution with the organic substrate. The mediator can be re-oxidised at the anode Chemical Considerations for further use and can thus be termed an elec- In order to understand the internal workings trocatalyst as it is not consumed in the overall of the ruthenium-mediated oxidation system, it reaction. is necessary to consider some aspects of the The silver-mediated electrochemical oxida- aqueous chemistry of ruthenium. Ruthenium tion of organics (SILVER IITM)has been under can form compounds with a multiplicity of Platinum Metals Rev., 1998, 42, (3) 91 oxidation states, ranging from -2 to +8. Its (iii) Partial oxidation of Ru(1V) in neutral or chemistry in aqueous solution mainly relates to acid solution, followed by disproportionation, the +3, +4, +6, +7 and +8 oxidation states, with forms ruthenium tetroxide. the +3 and +4 states being the most stable. Ruthenium is normally supplied as the trichlo- Ruthenium Tetroxide ride, "RuCl,.(H,O)," (n = 2 or 3), a very solu- Volatile RuO, @.p. - 130°C), like isostructural ble dark red-brown solid which contains a com- OsO,, is a powerful and unstable oxidising agent. plex mixture of chloro and chlorohydroxo It may be prepared from an acidic solution or complexes, many of which are polymeric and suspension of any one of a number of ruthe- contain mainly Ru(IV) (1). nium salts or hydrated RuO, by treatment with Although "ruthenium(II1) trichloride" is the a powerful oxidant, such as MnO;, Cl,, IO;, form in which ruthenium is initially added to Celt or NaOCl (bleach). Pure RuO, is not par- the ruthenium-mediated electrolytic system, ticularly stable in either the liquid or vapour Ru(IV), in the form of hydrated RuOzis of much phase and tends to decompose, eventually form- greater significance. The great insolubility of ing RuO,. It is freely soluble in organic solvents, this oxide in water ensures that its production although its reactivity limits the solvents which is favoured when ruthenium 0x0-anions in high can be used (typically CCl, or CHCl,, plus some valent states are reduced (in a similar manner polar solvents with little nucleophilic charac- to the easy formation of insoluble MnO, when ter). These solutions of RuO, are reasonably MnO; is used as an oxidant). stable if kept in the dark and with a slight excess The hydrated oxide can be dissolved oxida- of the oxidant which formed the tetroxide. It tively (for example, using oxygen, persulfate is not normally prepared in bulk quantities, but or permanganate) in alkaline solution (pH > is generated for immediate use. 12) to yield a solution of the orange ruthenate ion, Ru0,Z- (Rum)): Organic Oxidation by Ruthenium 0x0-Species RU'~O,+ 40H- + RuwO:- + 2Hz0+ 2e Ruthenate, perruthenate and, in particular, Ruthenate is only stable at high pH and in the ruthenium tetroxide have all been studied as absence of reducing agents. If the pH is low- oxidants for organic synthesis. RuO, has been ered, Ru0,Z- disproportionates to give hydrated studied fairly comprehensively and prepara- Ru(N)O, and green perruthenate, Ru(VII)O,-: tive oxidations in both the aqueous and organic phases (mainly in unreactive solvents like CHC1, 3Ru"O:- + 4H' + RuIVO2+ 2RuV"0L + 2H20 and CCl,) have been described (2, 3), with the Perruthenate solutions are unstable and exact conditions being tailored to suit the par- decompose, either with the formation of 0, and ticular synthesis. RuO,: One of the first investigations of organic oxi- dations using RuO, included the following 4Ruw0; + 4H' + 4Ru"02 + 30, + 2Hz0 description using only 10 mg of tetroxide with or, if the pH is below - 7.5, the decomposition some common solvents: can produce RuO,: "Benzene - vigorous explosion; pyridine - no 4Rum0, + 4H' + RuNOz+ 3RuW"0,+ 2H20 explosion, only flame; anhydrous ether - small explo- sion, followed by yellow jlame" (4). Important points to note from the above are: (i) The favoured reduced form of uncomplexed Of particular interest in the context of destruc- ruthenium in near-neutral aqueous solution is tive, rather than synthetic, oxidation by RuO, Ru(IV)oz. are the following properties: (ii) Uncomplexed ruthenium exists in aqueous The solubility of RuO, in both polar and non- solution as neutral or anionic species. polar organic solvents, allows oxidation to take Platinum Metals Rev., 1998,42, (3) 92 place within an immiscible organic phase rather and is the basis for a worldwide industry with than only at the aqueoudorganic interface. a capacity of millions of tonnedyear (8). RuO, cleaves many C=C bonds, usually The principal process at the anode surface yielding carbonyl compounds in the first instance. is oxidation of chloride ions (with very minor RuO, is able to oxidise saturated hydrocar- oxidation of water to form oxygen): bons under mild conditions (5). 2C1- C12 2e The complete oxidation of the highly toxic + + and relatively unreactive polychlorodibenzo-p- At the low pH normally encountered in dioxins (6) and polychlorinated biphenyls (7) chlorine cells, the product is gaseous chlorine. by RuO, has been reported. As the pH is raised, the hydrolysis of the chlo- Aromatic nuclei are attacked and are rine to form HOCl begins to predominate and completely degraded.
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