A PROCESS FOR THE ELECTROCHEMICAL DEGRADATION OF PERSISTENT ORGANIC COMPOUNDS, WITH HARMFUL OR POTENTIALLY HARMFUL PROPERTIES

Abstract: A process is described for the electrochemical degrada­ tion of at least one persistent harmful or potentially harmful organic compound. The process comprises anodically oxidising or cathodi­ cally reducing the organic compound or compounds (i.e. mix­ ture of compounds) in an aqueous liquid system in which the compound is at least partially soluble. One or more unstable cationic radicals are formed which react with a reactive com­ ponent in the liquid system which may be at least partly its solvent component to form a product or products having a lower oxidation potential in the case of anodic oxidation or a lower reduction potential in the case of cathodic reduction than that of the parent compound or compounds subjected to the electrochemical degradation.

Description: Title A PROCESS FOR THE ELECTROCHEMICAL DEGRADATION OF PERSISTENT ORGANIC COMPOUNDS, WITH HARMFUL OR POTENTIALLY HARMFUL PROPERTIES The present invention relates to a process for the electrochemical degradation of persistent organic substances, with deleterious properties. It is now a matter of common concern that various classes of organic chemical substances, which have been developed for certain valuable applications, have been found to be injurious, or potentially injurious, to mankind and other forms of life. Examples include insecticides, pesticides, herbicides and fungicides, used, for example, in agriculture and horticulture, and also compounds and formulations in toiletry preparations for human use. Some organic chemical compounds of the above kind have been found to persist in the environment. Thus, these compounds are not, or else are only partially, degraded into simpler substances by natural processes such as photolysis and microbiological actions which processes, in other instances, bring about the degradation of relatively complex molecules into simple, non-toxic residues. Many of the most persistent injurious, or potentially injurious, organic substances, which are of concern, are halogenated organic compounds. Of such substances, manufactured on a large scale and widely used, those which are halogenated with chlorine are the most common, with fluorinated compounds being the next most common. This order of use no doubt reflects the relative abundance of the halogens and the cost of their recovery on an industrial scale. In the manufacture of halogenated organic compounds, it is generally the case that the chemical syntheses thereof proceed by way of a sequence of chemical reactions in each of which the yield of the desired product or intermediate product may be significantly lower than the theoretical yield because of a variety of factors, e.g. the limiting effects of equilibrium conditions in a reversible process, or the formation of alternative co-products of the reaction system. Such factors are, of course, wellknown features of organic syntheses. Hence, at some stage in the manufacturing process, it is usually necessary to isolate the desired main product from a mixture of reaction products, by known methods such as distillation, solvent extraction and fractional crystallisation. This isolation of the desired product gives rise to the accumulation of quantities of unwanted residual substances, which then have to be disposed of. The most widely used method for the disposal of unwanted organic residues is the burning thereof in an incinerator. Organic substances are generally molecules based on straight or branched carbon chains, or on ring structures, which may be linked together in various ways. It has, therefore hitherto been considered that combustion in the presence of atmospheric oxygen Brings about the destruction of these molecules. Thus, it has been postulated that the carbon present in the molecule is oxidised to carbon dioxide, the hydrogen is oxidised to water vapour, and the other atoms, if present, enter into various combinations to form simple inorganic substances of a relatively innocuous nature, particularly after adequate dilution by dispersion in the atmosphere following discharge from a chimney, with or withoutpre-treatment in scrubbers, filters or other gas-cleaning devices. In the case of many industrial residues, these assumptions may well be valid, e.g., when the residues are known to be free from halogenated compounds. However, evidence has now accumulated that complete destruction of all organic compounds may not be achieved in the kinds of incinerators cor.monly used for this purpose. The lack of total destruction may be attributable to various factors such as an insufficient# 'residence time, the none uniformity of gas-flow distribution, the non uniformity of oxygen distribution or availability, an insufficiently high temperature, the thermal stability of the compounds present and the equilibria which occur with pyrolysis products such as free radicals. In addition, commercially, operated waste incineration units are not normally reserved for specific known materials, but usually deal with virtually undefined waste product mixtures, with the result that it is unlikely that operating conditions can be optimised. Furthermore, limitations on temperature an#d on the other operating conditions are dictated by the design of the incinerator itself. A further disadvantage of incineration is the possibility that, under the influence of the temperature sequence prevailing in the passage through the preheat, combustion and cooling stages, some substances may undergo transformations into new and stable compounds, which are not totally destructible at the maximum temperatures and residence times provided by the furnace of the incinerator. For example, it has been reported (Chem. and Eng.News, Now.20, 1978, page 7) that traces of chlorinated dioxins, including the highly toxic compound: 2,3,7,8-tetrachlorodibenzo-2-dioxin (TCDD), have been found in particular emissions from various combustion processes including incinerators, and this has been attributed to the action of heat at elevated temperatures on simpler substances such as chlorinated phenol derivatives, which are present in the materials being incinerated. Thus, there is a real possibility that incineration, which is used to destroy organic waste products, may actually add to the existing environmental contamination by persistent toxic compounds. When considering alternative conventional means for the destruction of persistent organic compounds, the practical possibilities are very limited. Letus consider, for example, the aforementioned highly toxic substance TCDD. It has been reported (Crosby, D.G.; Wong, A.S.; Plummer, J.R.; Woolson, E.A. Science (1971), Vol. 173, Page 748) that the decomposition thereof may be effected by photolysis in a suitable solvent. However, it is difficult to make practical use of this particular process in waste disposal on an industrial scale since TCDD occurs only as a trace impurity in other residues such as chlorinated phenols and derivatives thereof. Hence, the total size of the apparatus, the quantities and variety of solvents used and the means for their recovery for re-use, and the employment of considerable quantities of ultra-violet energy, all make for a costly and highly sophisticated installation, which is not without its own hazards. Another method for the destruction of TCDD and other persistent chlorinated substances has been reported by Dr. P.C. Ayres in a paper entitled: "The oxidative control of pollutants" given at the meeting of the Royal Institute of Chemistry/Chemical Society (Industrial Division) on the 26th-28th September, 1979, under the heading "Inorganic and Organic pollutants in the troposphere and natural waters". In this method, the extremely powerful oxidising agent: ruthenium tetroxide is used. It was reported that, in carbon tetrachloride solution, this agent led to an increase in the rate of oxidation with temperature to give a half-life for the TCDD of below 15 minutes at 77 OC. Other acceptable solvents, having a low nucleophilic reactivity, such as chloroform and nitromethane, were also mentioned. It was also reported that the ruthenium tetroxide oxidising agent could be regenerated in a twophase system by the use of a simple oxidant such as sodium hypochlorite. However, ruthenium tetroxide is itself toxic, and is expensive because of its limited availability. The use of ruthenium tetroxide is also complicated by the fact that the oxide has an appreciable vapour pressure. This fact and the choice of solvents needed lead to a process requiring a complicated and expensive installation with its own attendant operating risks. It has been reported that it is possible to bring about the electrochemical decomposition of complex organic molecules by the use of organic electrolytes. For example, Cauquis and Maurey-Mey (Bulletin de la Socio Chimigue de France (1972 No. 9, pages 3588-3593) found that the substance diphenylene dioxide (#ibenzo-p-dioxin) undergoes a reversible oxidation with the formation of a cation radical when dissolved in dry acetonitrile containing a small amount of lithium perchlorate, and when subjected to a voltaic field of 1.2 volts EMF (referred to a silver/silver ion electrode), using platinum electrodes. However, if water is added to the electrolyte, the process becomes imcompletely reversible, and a fraction of the cation radical undergoes further transformation to a more readily oxidisable form, so that it is progressively decomposed. Schroth, Borsdorf, Herzschuh and Seidler(Z. Chem., 10 Jg (1970), Heft 4, pages 147-148, 3rd February, 1970)have reported on the formation of dication radicals as intermediate states, when solutions of various dioxins and dithionins are subjected to voltammetric oxidation in water-free acetonitrile containing 0.1 M tetraethylammonium perchlorate, with the voltage rising to 2 volts (against a saturated calomel electrode), using rotating platinum electrodes. Furthermore, the role of the dication radicals in the formation of new complexes, e.g. with antimony pentachloride, and as intermediates in the substitution of additional groups, e.g. acetoxy and methoxy groups in the parent compound, was demonstrated. However, the above are mechanisms for the building up of even more complex substances rather than for degradation into simpler products. We have now found that an electrochemical process can be used for the safe destruction of certain injurious, or potentially injurious organic substances, which are generally regarded as stable and resistant to normal natural and other chemical methods of decomposition, by subjecting said substances to anodic oxidation or cathodic reduction in an aqueous medium, to form an unstable cationic radical, and converting said radical in said medium to a compound with a lower oxidation potential or reduction potential than that of said organic substance, in the case of anodic oxidation or cathodic reduction, respectively. The present invention provides a process for the rendering harmless, or less harmful, at least one persistent, harmful, or potentially harmful, organic compound, which comprises subjecting said compound, or compounds to electrochemical degradation, characterised in that said compound, or compounds, is, or are, anodically oxidised or cathodically reduced, in an aqueous liquid system in which said compound is at least partially soluble, to form at least one unstable cationic radical, and in that said liquid system comprises a solvent component, and a reactive component, which may be constituted by said solvent component, with which said cationic radical, or radicals, react to form a product or products having a lower oxidation potential in the case of anodic oxidation, or a lower-reduction potential in the case of cathodic reduction, than that of said compound or compounds. The aqueous liquid medium may optionally include a supporting electrolyte where needed. Furthermore, a mixture of substances all or only one or more of which may be persistent, harmful or potentially harmful substances, may be electrochemically degraded by the process of the invention, simultaneously, or where appropriate in any desired sequence. It is only necessary that the anodic oxidation potential or cathodic reduction potential should be within the range employed to bring about the degradation of any specific substance. In general if the intermediate product of either anodic oxidation or cathodic reduction is a comparatively stable radical, the liquid system advantageously includes means for preventing migration of the intermediate product back to the opposite electrode, to facilitate exhaustive oxidation or reduction, respectively. A suitable means for preventing such migration is the use of a divided cell. It should also be noted that, in some cases, the solvent component and the compound with which the cationic radical reacts may be the same compound. It may be seen from the above that it is necessary for the organic compounds which are to be degraded to be only at least partially soluble in the aqueous liquid system used. Thus, the process of the present invention will bring about the degradation of organic waste products, including halogenated and particularly chlorinated waste products, which are only sparingly soluble in the electrolyte solutions employed. This enables slurries to be successfully processed, the only practical criterion being that there should be a partial solubility, to which end the use of co-solvents has been found advantageous in some cases. Under the conditions in which the electrochemical degradation of the present invention is carried out, the generation of more undesirable products by thermal effects is avoided, and the total containment of the substances being processed can, if desired, be maintained. In addition, the present invention does not necessarily require the use of special organic electrolytes such as the aforementioned acetonitrile, and readily available simple solvents can he effectively used. Furthermore, the present invention has the advantage that the electrode materials which may be used are relatively cheap and suitable for the fabrication in any desired shape and size of practical and inexpensive apparatus. The process of the present invention may be used with particular advantage for the degradation of TCDD, 2,7-dichlorodibenzo-p-dioxin (DCDD), and polychlorinated biphenyls (PCB), and is preferably carried out under constant current conditions. The electrochemical degradation of the present invention may be performed using electrodes made of various materials, but those made of carbon, e.g. graphite, platinum and steel including stainless steel are preferred. The vessel in which the aqueous liquid system is contained may be composed of an electrically conductive material having suitable corrosion resistance, or else of an electrically non-conductive material. If the latter type is used, two electrodes, that is a cathode and an anode, are contained therein and are immersed in the aqueous liquid system to form the cell. If the former type is used, however, it is possible to use the vessel itself as one of the electrodes, and consequently only one other working electrode need he present in the aqueous liquid system. For ease of measuring the cell voltage, it is preferred to include a reference electrode such as a calomel or silver/silver cation electrode as a reference. This reference electrode should, of course, also be immersed in the aqueous liquid system. The aqueous liquid systems used in the present invention have a solvent component, optionally a supporting electrolyte, and at least one compound which reacts with the cation radicals formed in the process of the present invention to form compounds having a lower oxidation potential or reduction potential than that of the parent compound, although, as mentioned above the solvent component may itself be the reactive component. So far as anodic processes are concerned, it is reasonable to postulate that all organic compounds in which the highest occupied molecular orbital has weak electron binding will form cation radicals which are unstable. Larger and more complex molecules such as heterocyclic compounds, being "electron-rich", will be more readily able to behave in this way (by compensating for distortion of the remaining electron orbitals). In the case of compounds such as Paraquat (a compound containing the l,l'-dimethyl-4 74' -bipyridinium cation), these are ionic with a stable dicationic structure. Cathodic reduction of the stable dication produces a monocationic radical which is unstable. In both cases, it would appear that the essential feature is the size of the molecular group which, per-se, reduces the electron binding strength in the highest (outermost) occupied molecular orbital. According to a feature of the invention therefore, the organic compound or compounds has, or have, an electron configuration which is such that the formation of an unstable cationic radical or radicals, occurs or occur at a potential which is not greater than the discharge potential of the solvent component, or solvent/reactive component, of the aqueous liquid system. It is necessary that the compound to be degraded be at least partially soluble in the solvent component, which may be a single compound or a mixture of compounds. In the case of TCDD and DCDD, ethanol, ethanol/water, methylated spirits, acetonitrile and acetonitrile/water are suitable, but other alcohols than ethanol or methanol, for example, may also be used as solvents. The requirements of any solvent used as, or as part of, the solvent component of the present invention are that the solvent should: (a) either alone, or when mixed with a suitable co-solvent, provide adeauate, but not necessarily totally, solubility of the substance to be electrochemically degraded; and (b) either alone, or with suitable additions of a supporting electrolyte, permit the achievement of adequate current densities, while retaining the electrode potential in the range necessary for effective oxidation or reduction of the substance being degraded. In addition, the oxidation or reduction potential of the solvent component should normally be higher than that of the substance being degraded. In some instances, it is desirable to use a co-solvent to increase the overall solubility of the compound to be decomposed, thereby to increase the rate of degradation. Examples of suitable co-solvents are methylene chloride and toluene, methylene chloride being particularly advantageously employed in the decomposition of TCDD, because of its degree of oxidative stability. A supporting electrolyte is generally necessary in order to enable the current density to reach a level at which a useful rate of electrochemical degradation is attained. Preferred supporting electrolytes for use in the present invention are perchlorates such as sodium perchlorate and acids such as sulphuric acid. Particularly preferred supporting electrolytes are 0.1 Molar sodium perchlorate and 1.0 Molar sulphuric acid, Thus, it may be seen that the function of the supporting electrolyte, when used, is to increase the conductivity of the solvent system so that a higher current density can be maintained at the preferred electrode potentials Perchlorates have found applications for this purpose especially for voltammetric research using organic electrolytes, e.g. anhydrous acetonitrile. In simpler aqueous electrolyte systems, such as those normally used in the process of the present invention, the wider choice remains subject to practical considerations such as not being preferentially oxidised or reduced at preferred cell operating conditions, permitting good current density and correspondingly rapid rates of electrochemical activity. In addition, it is preferred that any supporting electrolyte used should not introduce unnecessary complications in materials used for construction, or in the ease of operability. The reactive component, which reacts with the cationic radical, or radicals of the present invention, to form a product having an oxidation or reduction potential lower than that of the parent compound, may be any compound having this property, but, in the case of lowering of oxidation potential, it is preferably water and/or ethanol. The use of these compounds removes, of course, the need in most cases to have an additional solvent component as aforementioned. It has been found that the following liquid systems are particularly suitable for use in the present invention, especially in the degradation of TCDD and DCDD: (a) sulphuric acid/industrial methylated spiri#water; and (b) ethanol/methylene chloride/sulphuric acid/ water. For the process of the present invention, the electrode potential at the anode and/or cathode should be high enough to ensure the degradation of the compound to be degraded, but should not be so high as to discharge components of the aqueous liquid system. For example, if ethanol is used as the compound with which the cations in anodic oxidation react to form a product of lower oxidation potential than that of the parent compound, it is necessary to ensure that the anode/reference potential be not lower than +2.0 and not higher than +2.4 V, at which level potential discharge of ethanol becomes the sole reaction, Suitable anode/ reference or cathodeireference potentials for other liquid systems may be determined by routine experimentation. For constant current work, it has been found that, with platinum electrodes, a current density of about 50 m A/cm2 is suitable,-while with graphite electrodes a current density of about 15 m A/cmê is suitable. A suitable electrical supply source is a DC power supply connected to the cell through. a rheostat and ammeter. As previously mentioned, the process of the invention may be performed by means of cathodic reduction. In such a process, persistent organic substances which normally exist in a stable cationic form, for example, the herbicides known commercially as "Paraquat" and "Diquat" 1, l-ethy-lene-2 ,2 '-bipyridiniuin salt, may be degraded Cathodic reduction produces cationic radicals which can undergo further reduction causing the complete disappearance of the original compounds. Since, in such cases, the cationic radicals formed are normally comparatively stable, it is preferred, as aforementioned, to prevent them from migrating to the anode where reoxidation will occur. A suitable way in which this migration may be prevented is, for example, by the use of a divided cell. As mentioned earlier, in the process of the present invention, the unstable cationic radicals is formed from the persistent organic compound which is to be degraded, and the cationic radical reacts with the reactive component, to form a product having a lower oxidation or reduction potential than the parent compound, dependinq upon whether anodic oxidation or cathodic reduction is carried out. In the anodic oxidation of, for example, DCDD and TCDD, unstable, dicationic radicals are formed and these then react with the reactive component to form products of lower oxidation potential. In the cathodic reduction of Paraquat and Diquat, these compounds in solution give stable dications which are reduced to moderately stable monocations When prevented from reaching the anode, as is highly desirable in practice in the case of cathodic reduction, the monocations are further reduced at the cathode. Therefore, it is not known by the applicants at this time precisely at what stage of the cathodic reduction process that reaction occurs between the cations produced and the, or each, compound present to give a product with a lower reduction potential than the parent compounds. If the cathodic potential used in the process of the present invention is of some magnitude with reference to the standard electrode,, for example when the voltage across the cell is about 2 volts or more, there exists the possibility of cathodic reduction and anodic oxidation reactions occuring simultaneously. This may be useful, for example, when processing wastes of incompletely defined composition. The electrochemical degradation process of the present invention may be used to degrade persistent organic compounds even when such compounds are present in a large excess of other residues. In addition, the process of the present invention may be readily applied in conjunction with known means for decontamination of materials with which persistent organic compounds have been in contact. For example, the solvent or solvent mixture of the aqueous liquid system may be used in a batch or continuous solvent extraction operation and then passed to the electrochemical cell used in the present invention for electrolysis. Reference is now made to the accompanying diagrammatic drawings, in which: Figure 1 represents one embodiment of electrochemical apparatus for use in carrying out the process of the invention; Figure 2 represents another embodiment of electrochemical apparatus for carrying out the process of the invention; and Figure 3 is a graph showing voltamograms for DCDD in dry and wet acetonitrile. The cell of Fig. 1 comprises an extraction vessel 1 with a solvent spray/distribution system, being extracted material being shown at 2; an electrochemical cell 7 having a conducting container acting as a cathode; an anode 8; a D.C. supply and voltage regulation system µ; a pump 3 for recirculation of solvent to the extraction vessel 1, or for transfer of extract to the electrochemical cell 7; an inlet 4 for fresh solvent feed; and valves 5, 6 for arranging recirculation and/or transfer to the electrochemical cell 7. In another application of the process of the invention, the solvents may be used without the supporting electrolyte for flushing non-absorbent surfaces such as the interiors of chemical reactors and pipe-lines, and then passed to the cell,-via an intermediate vessel where the supporting electrolyte is added, to enable the electrochemical treatment to be carried out. Figure 2 shows this einb#diment, The apparatus of Fig. 2 comprises a pipeline or reactor 11 to be rinsed with solvent; a valve 12 for controlling the supply of fresh solvent; a receiving vessel 13 for collecting contaminated solvent from the pipeline or reactor 11; a valve 14 for controlling the addition of supporting electrolyte solution; a mixer 15; an electrochemical cell 17 having a conducting container acting as cathode; an anode 18; a D.C. supply and voltage regulation system 19; and a pump 16 to transfer the contents of the vessel 13 to the electrochemical cell 17. It will be understood that the apparatus just described may be modified, if desired, so that the solvent is passed directly to the cell vessel and the supporting electrolyte is added there. In another application of the process of the invention the cell itself may be so constructed with respect to dimensions and location of anodes or cathodes, that contaminated articles may be placed in the cell bath and left there while the contamination is taken into solution and decomposed. The present invention will now be further described in detail in the following illustrative Examples. IN all the Examples, the electrochemical degradation was carried out at ambient temperature. Monitoring was by analysis of the reaction mixture using gas chromatography (G.C.) with Field ionization Detection (F.I.D.) in the cases of DCDD and the PCBs, and with Electron Capture Detection (E.C.D.) in the case of TCDD. It should be noted, however, that some of the components of the liquid system are appreciably volatile even at normal temperatures, and it is desirable, in some instance;, to provide for containment of the vapours produced e.g. by collection and condensation of the vapours in any manner suitable, as will be well known to those skilled in the art of pollution control. In the Examples, Examples 1 to 4 and 6 all relate to the use of platinum electrodes, a current density of approximately 50 m A/cmê being used under constant current conditions. Example 5 sets out a comparison of the use of platinum and graphite electrodes, with a current density of 2 substantially 15 m A/cm under constant current conditions being used for the latter, and of 2 substantially 50 m A/cm under the same conditions for the former. In all the Examples except in the first four cases in the acetonitrile/water system reported in Example 1, the current density used was high enough to ensure that the anode reference potential was not lower than +2.0 V and not higher than the oxidation potential of the solvent which, for ethanol, is +2.4 V. Example 1 As a basis for comparison, the electrochemical degradation of DCDD was carried out using acetonitrile and acetonitrile/water solutions having various solvent/ water ratios. In each case, 50 milligrams of DCDD were slurried into 10 millilitres of solvent or solvent/water solution. In the case of the anhydrous acetonitrile, the solubility of DCDD is 317 micrograms/ml, so that, in the test slurry, only about 6 percent of the total DCDD was in solution and the remainder was undissolved. The proportion of the DCDD in solution in the aqueous acetonitrile systems was even lower. IN all cases, the supporting electrolyte used was sodium perchlorate in 0.1 molar concentration. The cell voltage was measured with reference to a silver/silver cation electrode The results are set out in Table 1 (below). It is observed that, even at 25 and 50 percent by volume of water, the degradation proceeds although it is necessary to increase the cell voltage from 1.5 to 2.0 volts. TABLE 1 EFFECT OF ACETONITRILE: WATER RATIO ON THE DETOXIFICATION OF DCDD [ 50 mg DCDD slurried in 10 ml solvent] EMI19.1 <tb> <SEP> % <SEP> E(V) <SEP> Supporting <tb> (v/v) <SEP> vs. <SEP> + <SEP> Notes <SEP> on <SEP> Reaction <tb> H20 <SEP> Ag/Ag <SEP> Electrolyte <tb> <SEP> 0 <SEP> 1.5 <SEP> 0.1M <SEP> <SEP> NaC104 <SEP> <SEP> All <SEP> DCDD <SEP> lost, <SEP> blue <SEP> cation <tb> <SEP> radical <SEP> formation <SEP> observed <tb> <SEP> 5 <SEP> 1.5 <SEP> O.lM <SEP> <SEP> NaC104 <SEP> All <SEP> DCDD <SEP> lost, <SEP> blue <SEP> cation <tb> <SEP> radical <SEP> formation <SEP> still <tb> <SEP> observed, <SEP> although <SEP> it <SEP> is <tb> <SEP> rapidly <SEP> quenched <SEP> near <tb> <SEP> electrode <tb> 10 <SEP> 1.5 <SEP> O.LM <SEP> <SEP> NaClo4 <SEP> All <SEP> DCDD <SEP> lost, <SEP> still <SEP> traces <tb> <SEP> of <SEP> blue <SEP> cation <SEP> radical <tb> <SEP> formation <SEP> observed <tb> 15 <SEP> 1.5 <SEP> 0.1M <SEP> <SEP> NaClO4 <SEP> All <SEP> DCDD <SEP> lost, <SEP> no <SEP> cation <tb> <SEP> radical <SEP> observed <tb> 25 <SEP> 2.0 <SEP> O.lM <SEP> <SEP> NaClO4 <SEP> All <SEP> DCDD <SEP> lost, <SEP> reaction <SEP> only <tb> <SEP> proceeds <SEP> at <SEP> higher <SEP> potential <tb> 50 <SEP> 2.0 <SEP> O.lM <SEP> <SEP> NaClO4 <SEP> Only <SEP> part <SEP> of <SEP> DCDD <SEP> lost, <SEP> in <tb> <SEP> corresponding <SEP> time <SEP> scale <SEP> to <tb> <SEP> above. <SEP> Can <SEP> all <SEP> be <SEP> removed <tb> <SEP> after <SEP> -prolonged <SEP> <SEP> electrolysis <tb> E(V)= electrode potential in volts (Vr. Further experiments demonstrated that larger amounts of DCDD, e.g. 0.5 g/100 ml. solvent, initially presented as a suspension in aqueous acetonitrile, can be successfully degraded the course of veral hours. However, under these conditions, some fouling of the electrodes by reaction products- was observed which, together with the relatively high cost of acetonitrile, suggested that alternative solvents may be more advantageous. Example 2 Experiments showed that ethanol, with 0.1 Molar sodium perchlorate as a supporting electrolyte, behaved similarly to the above acetonitrile (Ex. 1) but with a limiting water ratio of 25 percent by volume for effective decomposition of DCDD. However, by using an 1.0 Molar solution of sulphuric acid instead of sodium perchlorate, and industrial methylated spirit (IMS) instead of pure ethanol, a very cheap electrolyte system was obtained. Suspensions of DCDD containing as much as 0.5 g in 100 mls of electrolyte solution were successfully processed, the degradation products remained soluble and no electrode fouling was observed. IMS alcohol dinatured for power purposes, normally rectified ethanol, dinatured by the addition of crude wood spirit (methanol), usually 10% (v/v), mineral naphtha or pyridine (0.4% v/v) and a purple colouring matter (unspecified) see Hackh's Chemical Dictionary, 4th Edition (1969)., Julius Grant (editor), McGraw-Hill Book Company, McGraw-Hill Inc., U.S.A. Table 2 (below sets out the results of the experiments carried out in alcoholic and aqueous alcoholic media. TABLE 2 THE EFFECT OF ALTERNATIVE SOLVENT SYSTEMS ON THE DETOXIFICATION OF DCDD [50 mg DCDD slurried in 10 ml solvent] EMI21.1 <tb> <SEP> E(V) <SEP> Supporting <SEP> Notes <SEP> on <tb> Solvent <SEP> System <SEP> vs. <tb> <SEP> Ag/Ag+ <SEP> Eltrolyte <SEP> Reaction <tb> EtOH <SEP> 1.5 <SEP> 0.1M <SEP> <SEP> NaClO4 <SEP> <SEP> All <SEP> DCDD <SEP> lost <tb> EtOH <SEP> 2.0 <SEP> 0.1M <SEP> <SEP> NaClO4 <SEP> <SEP> All <SEP> DCDD <SEP> lost, <tb> <SEP> reaction <SEP> consi <tb> <SEP> derably <SEP> faster <tb> EtOH <SEP> + <SEP> 5% <SEP> v/v <tb> H20 <SEP> 2.00 <SEP> 0.1M <SEP> <SEP> NaClO4 <SEP> <SEP> All <SEP> DCDD <SEP> lost <tb> EtOH <SEP> + <SEP> 10% <SEP> v/v <tb> H2O <SEP> 2.00 <SEP> <SEP> O.LM <SEP> <SEP> NaC104 <SEP> All <SEP> DCDD <SEP> lost <tb> EtOH <SEP> + <SEP> 25% <SEP> v/v <SEP> Only <SEP> part <SEP> of <SEP> DCDD <tb> H20 <SEP> 2.00 <SEP> 0.1M <SEP> <SEP> NaC104 <SEP> <SEP> lost <tb> EtOH <SEP> + <SEP> 10% <SEP> v/v <SEP> 2.0 <tb> H20 <SEP> (vs. <SEP> <tb> <SEP> S.C.E.) <SEP> l.OM <SEP> H2SO2 <SEP> <SEP> All <SEP> DCDD <SEP> lost <tb> IMS <SEP> + <SEP> 10% <SEP> v/v <SEP> 2.0 <tb> H20 <SEP> (vs. <tb> <SEP> S.C.E.) <SEP> 1.OM <SEP> H2S04 <SEP> All <SEP> DCDD <SEP> lost <tb> S.C.E*= Saturated Calomel Electrode. IMS = Industrial methylated spirit. E(V) = Electrode potential in volts (V). Example 3 The cyclic voltammetry at a platinum electrode of an 1 millimolar solution of DCDD in anhydrous acetonitrile indicated that, at a polarising voltage (Ep) of 1.5 V, an one-electron oxidation occurs, with the formation of a cationic radical which is reversiblv red ucible to the parent compound. If the Ep value is increased to 2.0 V, further oxidation occurs with the formation of a dication radical and this change is irreversible. Addition of water to the acetonitrile suppresses the first oxidation peak, which disappears entirely at about 20 percent by volume of water, being replaced by a water oxidation peak at about Ep = 1 V, and the oxidation to the DCDD dication radical at about Ep = 2V (see Figure 3 of the accompanying drawings, which shows the voltamograms. for DCDD in dry acetonitrile and in "wet" (CH3CN + 20% (v/v) H20) acetonitrile at a scan rate of 3 v per min. In the graph, SCE = saturated calomel electrodes; V = volts; and pA = microamps. In our experiments, although degradation of DCDD was obtained at Ep = 1.5 V, both in acetonitrile and in alcohol systems, the rate of decomposition was found to be accelerated considerably by increasing Ep to 2.OV. It was further found that, by using constant current control, even higher currents could be maintained in the cell, and the decomposition process could be completed in minutes rather than hours. Example 4 As aforementioned, the compound TCDD is closely related to DCDD but is considerably more toxic and is generally less soluble than the latter. For this reason, its destruction under the conditions described above for DCDD is very much slower. This difficulty can be overcome by the use of a co-solvent which increases the overall solubility of TCDD to a level at which a reasonable rate of degradation is obtained. Of the material tried, the most effective co-solvents were toluene and methylene chloride. Toluene was successfully used as co-solvent for the destruction of TCDD in suspension. For experimental work requiring accurate TCDD analysis, methylene chloride was preferred for its greater oxidative stability under the chosen reaction conditions. The solvent mixture used was ethanol: methylene chloride [3:1 (v/v)) with 5% 1M sulphuric acid in water. Both DCDD and TCDD were effectively destroyed under constant current conditions using platinum electrodes. The solubilities of DCDD and TCDD in various solvents and solvent mixtures are given in Table 3, as follows: TABLE 3 SOLUBILITY OF TCDD AND DCDD IN VARIOUS SOLVENTS EMI23.1 <tb> <SEP> DCDD <SEP> TCDD <tb> <SEP> Solvent <SEP> ( g/ml) <SEP> ( g/ml) <tb> CH3CN <SEP> 317 <SEP> 0.33 <tb> IMS <SEP> 188 <SEP> 0.2 <tb> IMS/toluene <SEP> (4:l) <SEP> 515 <SEP> 11.3 <tb> IMS/toluene <SEP> (:1 <SEP> <SEP> 1880 <SEP> 26.5 <tb> <SEP> EtOH/CH2Cl2 <SEP> (3:1) <SEP> - <SEP> 1.1 <tb> H20(5tv/vf <SEP> <tb> IMS = Industrial methylated spirit Example 5 Further experiments were carried out in which graphite was used for the anode, and the cell contained was metallic with an appropriate corrosion resistance. It was demonstated that graphite was equally effective as an electrode material for this application,with obvious economic and practical advantages. Table 4 (below) gives the results of comparative experiments for the electrochemical decomposition of TCDD. TABLE 4 COMPARISON OF PLATINUM AND GRAPHITE AS ANODE MATERIAL IN THE ELECTROLYSIS OF TCDD [Saturated solution in EtOH/CH2Cl2 (3:1) (58 (v/v) H20 + 1M H2S04) ] EMI24.1 <tb> * <SEP> <tb> F/mole <SEP> TCDD <SEP> [ TCDD ] <SEP> ng/ml <SEP> <tb> <SEP> Pt <SEP> C <tb> <SEP> O <SEP> <SEP> 1 <SEP> 1150 <SEP> 1150 <tb> <SEP> 0.5 <SEP> 1000 <SEP> 900 <tb> <SEP> 3 <SEP> 700 <SEP> 775 <tb> <SEP> 6 <SEP> 250 <SEP> 650 <tb> <SEP> 20 <SEP> 3.7 <SEP> 180 <tb> <SEP> 100 <SEP> (1 <SEP> 2.4 <tb> *F = Faradays Example 6 This Example demonstrates the electrochemical degradation of TCDD in the presence of a 15000-fold molar excess of 2,4,5-trichlorophenol, that i# 66 ppm TCDD with respect to 2,4,5-trichlorophenol. It was found that TCDD was readily decomposed using an EtOH/CH2C12/H2504/H20 liquid system. The results are set out in Table 5, as follows: TABLE 5 ELECTROLYSIS OF TCDD IN THE PRESENCE OF R LARGE EXCESS OF 2,4,5-TRICHLOROPHENOL Molar ratio TCDD:TCP = 1:15,000 [Electrolysis in EtOH/CH2Cl2 3:1 (5% v/v H20, 1M H2S04) - Pt anode] EMI25.1 <tb> TCDD <SEP> * <tb> (ng/ml). <SEP> <SEP> F/mole <SEP> TCP <tb> 1100 <tb> <SEP> 625 <SEP> 1 <tb> <SEP> 160 <SEP> 4 <tb> <SEP> 30 <SEP> 6 <tb> <SEP> < 1 <SEP> 12 <tb> *F = Faradays Example 7 This Experiment demonstrates the applicability of the process of the present invention to the degradation of polychlorinated biphenyls (PCB). Samples of Aroclor 1221 (ex N.E.N. Chemicals, U.K.), a low boiling point mixture of three isomers of PCB and Aroclor 1254 (ex N.E.N. Chemicals, U.K.) a higher boiling point mixture of at least 13 isomers of PCB were used. "Aroclor" is a trade mark for polychlorinated biphenyl mixtures used as lubricants and resins, which were manufactured and placed on the market in the U.K. by Monsanto Chemicals Ltd., a U.K. Company. Both samples were effectively destroyed in ethanol containing 1M H SO, and 5% v/v H20 by electrochemical treatment under constant current conditions. The progress of electrochemical degradation was monitored by removing samples at appropriate times and analysing the PCB content by Gas Chromatographic (G.C.) analysis using Field Ionisation Detection (F.I.D.). In the case of samples, no significant change in isomer distribution occurred during the destruction of the sample. No attempt has been made to isolate products from the electrolysis.

Claims: CLAIMS 1. A process for rendering harmless, or less harmful, at least one persistent, harmful, or potentially harmful, organic compound, which comprises subjecting said compound, or compounds, to electrochemical degradation, characterised in that said compound or compounds, is, or are, anodically oxidised or cathodically reduced, in an aqueous liquid system in which said compound is at least partially soluble, to form at least one unstable cationic radical, and in that said liquid system comprises a solvent component and a reactive component, which may be constituted by said solvent component, with which said cationic radical, or radicals, react to form a product or products having a lower oxidation potential in the case of anodic oxidation, or a lower-reduction potential in the case of cathodic reduction, than that of said compound or compounds. 2. A process according to Claim 1, in which said liquid system additionally comprises a supporting electrolyte. 3. A process according to Claim 1 or 2, in which said organic compound or compounds has, or have, an electron configuration which is such that the formation of an unstable cationic radical, or radicals, occurs (or occur) at a potential which is not greater than the discharge potential of the solvent component or solvent/reactive component, of the aqueous liquid system. 4. A process as claimed in any one of Claims 1 to 3, in which a mixture of two or more of said compounds is electrochemically degraded, the anodic oxidation potential, or cathodic reduction potential, of said mixture being within the range of potentials at which each said component is degraded 5. A process according to any one of Claims 1 to 4, in which any one or more compounds selected from dioxins, polychlorinated biphenyls and mixtures of any two or more thereof, in any proportions, are subjected toelectrochemical degradation. 6. A process according to any one of Claims 1 to 5, in which the liquid system includes means for preventing migration of the first products back to the opposite electrode to facilitate exhaustive oxidation or reduction, respectively. 7. A process according to Claim 6, in which means for preventing migration of said first products is a divided cell. 8. A process according to any one of Claims 1 to 7, which is used to degrade 2,3,7,8-tetrachloro dibenzo-2-dioxin (TCDD). 9. A process according to any of Claims 1 to 7, which is used to degrade 2,7-dichlorodibenzo-E-dioxin (DCDD). 10. A process according to any one of Claims 1 to 7, which is used to degrade a mixture of polychlorinated biphenyls (PCB).

Inventors: HARRISON, JOHN MICHAEL ORGANIC CHEMISTRY SECTION, WILKINSON, RODNEY GORDON ORGANIC CHEMISTRY SECTION
Applicants: CRECONSULT LIMITED
Application year: 1980
Main classification: C25B3
IPC codes: C02F1