WO2002098799A1

WO2002098799A1 - Treatment of liquids

Info

Publication number: WO2002098799A1
Application number: PCT/GB2002/002787
Authority: WO
Inventors: Yuri Vladimirovich Zadiraka; Eduard Mikhailovich Barkhudarov; Igor Antonovich Kossyi; Merab Ivanovich Taktakishvili
Original assignee: Splits Technologies Limited
Priority date: 2001-06-07
Filing date: 2002-06-07
Publication date: 2002-12-12
Also published as: GB0113910D0

Abstract

The present invention provides an apparatus (1) suitable for use in the treatment of liquid (31). The apparatus (1) comprises a high voltage electric discharge device (8) with a first electrode (24) and a second electrode (25) spaced apart from the first electrode (24) and an electrical power supply control (13) for applying a series of high voltage pulses across said first and second electrodes (24, 25) so as to produce an extended area electrical discharge in an electric discharge zone (37) extending between the first and second electrodes (24, 25). The apparatus (1) includes a gas delivery means (14, 29, 32, 33) for feeding a series of bubbles (36) of gas (2) into the liquid (31) in said electric discharge zone (37). The first and second electrodes (24, 25), and any secondary electrodes (28) therebetween, have opposed portions (103, 104), only said opposed portions of the electrodes (24, 25) and any secondary electrodes (28) present therebetween, being covered in solid dielectric insulator material (102).

Description

TREATMENT OF LIQUIDS

The present invention relates to the treatment of liquids, and more particularly to the treatment thereof so as to improve them through processing, e.g. inactivation or decomposition, of materials dissolved or suspended therein.

Electrical discharge is widely known in gases with various practical applications e.g. for lighting, cutting through metals etc. It is also known in principle that such an electrical discharge can be obtained inside a liquid. To date though this has not found any significant practical application due to inter alia the very short working life of the electrodes in the devices used.

In our earlier Patent Application WO99/47230 there is disclosed an apparatus suitable for use in the treatment of a liquid, said apparatus comprising a high voltage electric discharge device with a first electrode and a second electrode spaced apart from said first electrode, said discharge device including electrical power supply control means formed and arranged for applying a series of high voltage pulses across said first and second electrodes in use of the apparatus with said device connected to an electrical power supply so as to produce, in use of the apparatus, an extended area electrical discharge in an electric discharge zone extending between first and second electrodes, said apparatus including a gas delivery means formed and arranged for feeding a series of bubbles of gas into a body of liquid in said electric discharge zone in use of said apparatus.

Whilst the above apparatus provides excellent results in many aqueous liquids, water with relatively high conductivity such as that found in coastal treatment works where a greater or lesser amount of salt may be present (typical conductivities of 1400 to 2000 μsiemens cm^-1) , blood waste including whole blood (typical conductivities of up to around 5400 μsiemens cm^-1) and waste water which has been used to wash down blood soaked areas (typical conductivities of around 2500 μsiemens cm^-1) , and pot ale - which is waste from whisky production and the like (typical conductivities of 2500 μsiemens cm^"1) , present particular difficulties in treatment with electric discharge apparatus requiring particularly high threshold voltages and/or resulting in reduced electrode life.

It is an object of the present invention to avoid or reduce one or more of the above disadvantages.

We have now found that these problems can be significantly reduced by means of some important new improvements to the abovedescribed apparatus.

The present invention provides in one aspect an apparatus suitable for use in the treatment of a liquid, said apparatus comprising a high voltage electric discharge device with a first electrode and a second electrode spaced apart from said first electrode, said discharge device including electrical power supply control means formed and arranged for applying a series of high voltage pulses across said first and second electrodes in use of the apparatus with said device connected to an electrical power supply so as to produce, in use of the apparatus, an extended area electrical discharge in an electric discharge zone extending between first and second electrodes, said apparatus including a gas delivery means formed and arranged for feeding a series of bubbles of gas into a body of liquid in said electric discharge zone in use of said apparatus, said first and second electrodes, and any secondary electrodes therebetween, having opposed portions, and wherein only said opposed electrode portions are exposed, other portions of said first and second electrodes and any secondary electrodes present therebetween, being covered in solid dielectric insulator material.

In another .aspect the present invention provides an apparatus suitable for use in the treatment of a liquid, said apparatus comprising a high voltage electric discharge device with a first electrode and a second electrode spaced apart from said first electrode, and dielectric support members for said first and second electrodes, with exposed opposed portions of said first and second electrodes each having a dielectric - electrode interface between the respective electrode and said supporting dielectric member whereby, in use of the apparatus, a local increase in electric field strength is induced at said exposed opposed electrode portions adjacent said dielectric support member thereby facilitating electric discharge initiation, said discharge device including electrical power supply control means formed and arranged for applying a series of high voltage pulses across exposed opposed portions of said first and second electrodes in use of the apparatus with said device connected to an electrical power supply, so as to produce and maintain, in use of the apparatus, an extended area electrical discharge in an electric discharge plasma zone extending between said exposed opposed portions of said first and second electrodes, said apparatus including a gas delivery means formed and arranged for feeding a series of bubbles of gas into a body of liquid in said electric discharge zone in direct contact with said exposed opposed portions of said first and second electrodes in use of said apparatus, said first and second electrodes, and any secondary electrodes therebetween, having opposed portions, and wherein only opposed electrode portions are exposed, other portions of said first and second electrodes and any secondary electrodes present therebetween, being covered in solid dielectric insulator material. Thus with an apparatus of the present invention it is possible to generate an electrical discharge inside a liquid for treatment of the liquid, with a relatively low voltage electrical power supply and in a way which results in substantially increased working life of the discharge device, with associated economy of construction, etc. Without in any way wishing to restrict the scope of the present invention, it is believed that a significant factor in the reduced voltage threshold required to establish the electrical discharge within the liquid in use of apparatus of the present invention is the generation of electrical discharge within the bubbles of gas passing between the electrodes.

The generation of a pulsed electrical discharge inside a liquid can induce various different and more or less powerful effects in the liquid depending on the form and type of apparatus of the invention used, which can have a strong effect on various materials present in the liquid. In general, within the immediate vicinity of the plasma discharge there are generated various more or less active species such as hydrated electrons, ions, excited atoms, and free radicals, which can react with materials present in the liquid. Zones of liquid extending beyond the immediate vicinity of the plasma discharge can be affected by UV-radiation. In the case of water containing trace amounts of material such as may be encountered in water being treated for domestic consumption, such zones may extend up to 6cms or more. The extent of such zones will naturally depend on various factors such as the intensity of the plasma discharge which in turn may depend to a greater or lesser extent on such factors as the voltage of the pulses used for the electrical discharge; and on the OD (optical density or absorbance of the liquid and any material dissolved or suspended in it) . Acoustic and shock waves may also be generated by the plasma discharge. By using suitable geometric arrangements of secondary electrodes e.g. generally toroidal, it is possible to combine and concentrate such shock waves for even greater cumulative effect. It will moreover be appreciated that unlike with conventional UV-irradiation apparatus, various embodiments of the apparatus of the present invention will have significantly more powerful effect from the UV-irradiation alone due to the avoidance of any barriers to UV-transmission between the source and the liquid being treated. Even quartz glass which has above average UV- transmission characteristics, substantially attenuates UV- radiation with a wavelength of less than 200nm. In addition, in at least some forms, the present invention can provide more or less significant synergistic effects through the combination of the UV-radiation, acoustic/shock waves generated, and plasma-chemical and photo-chemical reactions. This may be particularly significant in the treatment of liquids containing micro-organisms such as bacteria, so as to kill or inactivate these in order effectively to sterilise the liquid. The apparatus of the present invention may also be used to treat particular resistant infectious agents such as protozoal oocysts and prions.

Various liquids may be treated by use of the present invention, but the apparatus of the present invention is especially useful for the treatment of water contaminated with various different kinds of materials in order to improve the quality of the water, reduce environmental pollution etc. Thus the present invention may be used by public utility companies for the treatment of water supplied for consumption and running pools, and other uses, and for the treatment of waste water. Other liquids that may be mentioned as suitable for treatment include oils, for example used or waste transformer oil containing more or less toxic additives (e.g. PCBs - polychlorinated biphenyls) required for improving its performance, which require to be neutralised to facilitate safe disposal of the oil. Thus the present invention may also be used to decompose hazardous or toxic organo-chemicals into more or less safe and/or easily bio-degradable substances. Other organochemicals which may be mentioned as suitable for neutralisation to a greater or lesser extent by means of the present invention include alkanols e.g. methanol; aldehydes e.g. formaldehyde; phenol and substituted phenols e.g. para- chlorophenol; etc. Other applications of the present invention which may be mentioned include activation of oils and generation of ultrasound for medical purposes.

It will be appreciated that various configurations and geometries of electric discharge device and of the electrodes used therein may be used in accordance with the present invention. In a first preferred form of the invention, the first and second electrodes are substantially spaced apart and there is provided a multiplicity of spaced apart secondary electrodes distributed between opposed portions of said first and second electrodes. Conveniently there is used a device form which has a generally annular electric discharge zone, which may be defined by an internal or external cylindrical surface, and having a longitudinal axis which may be substantially rectilinear, or arcuate to a greater or lesser extent e.g. circular (corresponding to a toroidal discharge surface) or helical, and extending between generally annular opposed portions of the first and second electrodes. With such non-rectilinear axis electric discharge zones it will be appreciated that there may be obtained a degree of interaction between shock or acoustic waves generated by the electric discharge, for example, to produce a more focused and intense cumulative effect.

In the above described first form of the invention, the first electrode may also have an elongate portion extending generally parallel to the electric discharge surface and insulated therefrom by a suitable solid insulator dielectric.

Thus, for example, with an external electric discharge surface, said first electrode elongate portion could be in the form of a conductor extending generally along the central longitudinal axis of the electric discharge surface.

Conveniently the electric discharge surface is provided on the outside of a tubular insulator with an internal passage extending therealong, which is conveniently used as a gas supply passage, inside which extends said conductor. In some cases though it may be preferred to have this internal gas supply passage unobstructed by any first electrode elongate portion conductor.

Without in any way wishing to restrict the scope of the present invention, it is believed that the operating principle of the above-described first form of electric discharge device of the present invention and its main advantage are based on the sequential breakdown of a series of interelectrode gaps and quick generation of an extended multi-spark surface discharge. At the initial point as the capacitance of the interelectrode gap is much less than the capacitance between the electrode and central conductor (said first electrode elongate portion) , almost all voltage is applied to the first interelectrode gap (between the first and second electrodes) . The sequence of successive breakdowns between the neighbouring electrodes results in the electric discharge being propagated from the first electrode portion to the second electrode via the secondary electrodes along the metal-dielectric surface until the gap between the first electrode portion and the second electrode portion is fully bridged by a high-voltage pulse discharge of the kind sometimes referred to as "slipping surface" discharge. Thus the threshold of electric discharge initiation is decreased significantly and is close to the threshold of discharge between the two neighbouring electrodes e.g. the first electrode portion and the first one of the secondary electrodes. The use of the first electrode elongate portion has the particular advantage of substantially reducing, typically by 10 to 100 times, the threshold voltage required to initiate the electric spark discharge in a given device relative to that required in the same device without such a first electrode elongate portion extending alongside the electric discharge surface.

By dimensioning the internal passage in the abovedescribed type of arrangement of the first form of the invention, to have a diameter somewhat greater than that of the conductor, the passage can also serve as a conduit for gas as part of the gas delivery means. In this case the conduit may be connected to the discharge surface by a plurality of passages extending through the insulator, which may be in the form of discrete space apart passages. Alternatively there could be used an insulator with a porous or honeycombed structure providing a large multiplicity of gas passages extending therethrough and which may be interconnected with each other to a greater or lesser extent.

In accordance with the present invention only opposed electrode portions are exposed, other portions of the first and second electrodes being covered in solid dielectric insulator material. Thus in the case where the first and second electrodes have cylindrical outer surfaces, these outer surfaces are covered in solid dielectric insulator material. With such preferred forms of the device of the invention it is possible to treat reasonably efficiently liquids with relatively high conductivities, such as waste water in coastal treatment works where a greater or lesser amount of salt may be present (typical conductivities of 1400 to 2000 μsiemens cm^-1) , blood waste including whole blood (typical conductivities of up to around 5400 μsiemens cm^-1) and waste water which has been used to wash down blood soaked areas (typical conductivities of around 2500 μsiemens cm^-1) , and pot ale - which is waste from whisky production and the like (typical conductivities of 2500 μsiemens cm^-1) . In more detail, with these preferred forms of device, energy losses due to current passing through the liquid are reduced. Also the voltage required to initiate the electric arc discharge may be significantly reduced. Thus it may be possible to treat liquids with relatively high conductivities, for example, up to 50,000 μsiemens cm^""1, possibly up to 80,000 μsiemens cm^"1.

Advantageously in the case of the first form of the invention in which annular first and second electrodes and secondary electrodes therebetween, mounted on a tubular insulator, are used, the tubular insulator is recessed underneath the opposed electrode portions so that in use of the apparatus the series of bubbles of gas is mixed with the liquid before entering the electric discharge zone between the opposed electrode portions. Furthermore where the device is used in a configuration wherein the tubular insulator on which the annular electrodes are mounted, extends generally vertically, then it is preferred that the gas supply passage outlets between opposed electrode portions (of said first and second and secondary electrodes) , are disposed in close proximity to the upper ones of the respective pairs of opposed electrode portions. These modifications tend to increase the content of gas in the liquid in the electric discharge zone and to increase the residence time of gas bubbles therein, and thus have the advantage of inter alia reducing the amount of gas which needs to be pumped through the gas supply passages, thereby reducing the operating costs of the apparatus. Advantageously the tubular insulator is provided with channel form recesses underneath said opposed electrode portions of said generally annular first and second electrodes, whereby in use of said apparatus the series of bubbles of gas is mixed with said liquid before entering said electric discharge zone between the opposed electrode portions.

In general the gas delivery means comprises passage means having outlet means at or adjacent said electric discharge zone, for feeding gas to the liquid in the electric discharge zone, and inlet means for coupling, in use of the apparatus, to a gas supply means which may comprise an active device such as a compressor or pump, and/or a passive device such as a reservoir of compressed gas provided with a gas flow regulator means .

In general the gas delivery and supply means may be formed and arranged to feed gas to the liquid in said electric discharge zone at a wide variety of pressures and/or flow rates depending on various factors such as the gas used, the nature of the liquid, the size, shape and configuration of the electric discharge surface, the ambient pressure at the electric discharge surface, the high voltage pulse frequency etc. In the case of the first device form with multiple secondary electrodes, there may be used a gas feeding rate of at least 30 1 hr^"1, conveniently from 30 to 100 1 hr^_1 for an electric discharge surface having an area of around 25 cm².

The gas supply means also desirably has outlet means formed and arranged to produce relatively small bubbles in the liquid, in use of the apparatus, with, for example, a bubble diameter in the range from 0.1 to 10mm, preferably from 0.5 to 5mm, advantageously from 0.7 to 3mm.

Various gases may be used including more or less inert gases such as noble gases e.g. argon or nitrogen. Most conveniently and economically though there may simply be used air or oxygen which also have the advantage that they give rise to the production of ozone which can in turn allow the production of free radicals which can have further beneficial effects in the inactivation of contaminants.

The first and second electrodes may have various shapes and configurations depending inter alia on the shape and configuration of the electric discharge surface. Where this is generally annular, then the opposed portions of the first and second electrodes at respective end portions of the electric discharge surface may also conveniently be annular but this is not essential. With an annular electric discharge surface the secondary electrodes are also conveniently generally annular. Other configurations are also possible though which may have possible advantages, for example, in relation to generation of a more homogenous electric discharge and/or increased electrode life. Thus, for example, the secondary electrodes may be in the form of multiplicity of metallic or other electrically conducting particles embedded in or attached to the surface of an electrically insulating substrate. The particles may have various shapes or sizes, for example, from 0.1 mm to 5 mm in diameter, conveniently from 0.2 mm to 0.3 mm in diameter, and may be rounded, but more conveniently are angular, for example polygonal, regular or irregular, star-shaped etc. The particles are generally spaced apart at a separation not less than their diameter, but conveniently of a similar order of magnitude. This type of arrangement has the advantage of generating a much larger number of electric spark discharge routes thereby yielding a more homogeneous electric discharge zone.

In general it is desirable that there should be used an inter- electrode gap between neighbouring electrodes of at least 1 to 2 mm in order to ensure that an electric spark discharge occurs (i.e. substantially without electrical energy passage by other means) . Larger gaps, for example up to 10 mm or more may be used without significantly increasing the threshold voltage - typically of the order of 10 kV, and are generally preferred as they provide a more extended electric spark discharge and zone. Preferably there is used an electrode gap of from 3 to 8mm. Larger gaps may also be used but these will tend to require higher threshold voltages.

The electrical power supply control means is generally formed and arranged for conditioning a suitable available electrical power supply, in generally known manner, so as to apply across said first and second electrodes, a series of high voltage DC pulses. The voltage required to initiate and maintain an electric discharge may also be affected to some extent by various factors such as the shape and configuration of the electric discharge surface, the shape and configuration of the first and second electrodes and the secondary electrodes, as well as the number of the latter, and the liquid used. In addition we have found that by further increasing the applied voltage above the minimum threshold voltage required to initiate electrical discharge, it is possible to modify the spectral distribution of the UV radiation produced. More particularly we have found that higher voltages produce more higher energy shorter wavelength UV radiation i.e. the wavelength peak is shifted to shorter wavelengths e.g. from around 260nm which is particularly useful for inactivating bacteria and other micro-organisms, down to around 180nm which is more useful for removing formaldehyde and phenols. In addition at such shorter wavelengths there may be produced in water, new compounds such as H₂0₂ and/or 0₃ which have oxidising properties and may provide further sterilisation of water and/or removal or inactivation of other undesirable contaminants. In general there is used a voltage of at least lOkV, usually from lOkV to 50kV.

The pulses may be applied at a range of different frequencies depending on, for example, the nature of the contaminant. Thus, for example, a higher pulsing rate may be desired where a shorter treatment time is required albeit at the cost of a higher power input requirement, or where the shock wave effect is considered particularly significant in the treatment. In general there is used a pulse rate which is sufficient to maintain a substantially continuous discharge. Conveniently there may be used a pulse rate of from 1 to 200Hz, e.g. from 1 to 100 Hz.

In a further aspect the present invention provides a method of producing an electric discharge in a liquid comprising the steps of: providing an apparatus of the invention coupled to an electrical power supply and a gas supply means; providing a body of said liquid between said first and second electrodes; and applying a series of high voltage pulses to the first and second electrodes of the electric discharge device of said apparatus while feeding gas into said body of liquid.

In a yet further aspect the present invention provides a method of producing an electric discharge in a liquid comprising the steps of: providing a first form of apparatus of the invention coupled to an electrical power supply and a gas supply means; substantially immersing the electric discharge surface of the electric discharge device in the liquid; and applying a series of high voltage pulses to the first and second electrodes of the electric discharge device of said apparatus while feeding gas to the electric discharge surface thereof.

In yet another aspect the present invention provides a method of treating a liquid containing at least one hazardous contaminant, so as to decontaminate effectively the liquid said method producing and maintaining an electric discharge in said liquid by means of a method according to the present invention, for a period of time sufficient substantially to modify at least one said contaminant into a more benign form.

In accordance with the present invention the contaminant modification may have various different forms depending on the nature of the contaminant. In the case of micro-organisms the required modification should generally be at least sufficient to prevent effective propagation or reproduction of the microorganism. In the case of cellular organisms such as bacteria, suitable modification may or may not involve cell disruption. Various microbial contaminants may be inactivated by means of the present invention such as E. coli , Pseudomonas aerug±nosa , Cryptosporidium, etc.

With organo-chemicals suitable modification comprises reaction of the contaminant so as to convert it into another species which is environmentally benign per se and/or which is more or less readily bio-degradable into an environmentally benign form. The method of the invention may also be used effectively to inactivate inorganic contaminants such as metal salts and especially heavy metal salts, by converting them into an insoluble form which can be more or less readily precipitated out of the liquid.

The decontamination method of the invention may be carried out in either a continuous treatment mode or a batch treatment mode. In the latter case the liquid to be decontaminated should generally be confined in a chamber around the electric discharge device (or in a closed circuit including said chamber and liquid circulation means for circulating the liquid through the chamber) so that substantially the whole of the liquid is brought inside or into close proximity with the electric discharge zone for an effective period of time sufficient for substantial inactivation of the contaminants.

The first preferred form of apparatus of the invention is generally most convenient for such treatment. The electric discharge itself will generally provide a more or less substantial degree of mixing of the liquid in the chamber but if desired additional mixing means may be provided. In the case of a continuous treatment mode the apparatus of the invention would generally comprise a liquid containment means having an inlet for liquid to be treated, a treatment zone inside which the electric discharge surface of the electric discharge device is disposed, an outlet for treated liquid, and liquid flow control means for regulating the flow of said liquid through the liquid containment means. The second preferred form of apparatus of the invention is generally most convenient for this.

The treatment time (discharge operation time for batch mode, or residence time in the electric discharge zone for continuous mode) will depend on various factors such as the nature of the liquid, and the nature and concentration of the contaminant (s) , as well as the energy of the electric discharge. Suitable times can be readily determined by suitable trial and error for any given situation (device power and configuration, contaminant nature and loading thereof, required reduction in contaminant loading, etc.).

In order to increase efficiency in treatment of at least some contaminants of the liquid it may be desirable to control other variables as well. Thus for example in the treatment of water to inactivate micro-organisms it is preferred to use gas containing significant amounts of oxygen, and desirably to use alkaline pH values in the liquid undergoing treatment, typically from 7 to 11, preferably from 8 to 10, conveniently by means of adding alkali such as sodium hydroxide, in order to increase ozone generation and dissociation thereof to produce free radicals.

If desired, the treatments of the present invention may be combined to a greater or lesser extent with other possible treatments. Thus for example, the liquid being treated may also be heated in order to provide a more intensive and/or efficient treatment of the liquid. Also the liquid may be passed through a micro-filter.

Further preferred features and advantages of the invention will appear from the following detailed description given by way of example of some preferred embodiments and their use illustrated with reference to the accompanying drawings in which: -

Fig. 1 is a schematic side elevation of a first type of water treatment system of our earlier invention as disclosed in

WO99/47230;

Fig. 2 is side elevation of a principal part of the electric discharge device of Fig.l;

Fig. 3 is a detail side elevation of part of an electric discharge device of another embodiment according to our earlier invention; Fig. 4 is partial schematic circuit diagram of the principal parts of the power control means of the apparatus of Fig.l; and

Figs 5 to 7 are detail views corresponding to part of Fig. 2 of three modified forms of the device of Fig.2 according to the present invention.

Fig. 1 shows a water treatment system of the first form of apparatus of the invention 1 comprising a liquid containment vessel 2 in the form of an elongate chamber 3 having an inlet 4 at one end 5 and an outlet 6 at the other end 7. An electric discharge device 8 comprises an elongate body 9 mounting a series of electrodes 10 connected 11 to a high voltage power supply PS 12 via a power control means PC 13.

The elongate body 9 has an internal passage 14 (see Fig. 2) and an air inlet 15 at one end 16 connected 17 to an air compressor C 18.

As shown in more detail in Fig. 2, the elongate body 9 comprises a hollow tube 19 of polytetrafluoroethylene, or other dielectric material with high voltage threshold breakdown (e.g. ceramic), with said air inlet 15 at said one end 16 and closed at its other end 20. An electric conductor 21 extends along the hollow interior 22 of the tube 19 and passes through said closed end 20 to be connected 23 to a first ring electrode portion 24 mounted on said closed end 20. A second ring electrode 25 is mounted on the open end 16 of the tube 19 and has connected 26 to it a return conductor 27. A series of more or less closely spaced apart secondary ring electrodes 28 is mounted on the tube 19 between said first and second electrodes 24,25. A series of small bores 29 extends through the wall 30 of the tube 19 from the central passage 14 and exiting between neighbouring electrodes 24,28,25. In more detail the first electrode portion, the second electrode, and the secondary electrodes were each in the form of a titanium ring having a diameter of ca. 10mm, and axial length of 10mm, and a thickness of 2mm, with an interelectrode gap of 2mm therebetween.

In use of the apparatus liquid 31 is passed through the chamber 3 by means of a pump P 32 with a flow regulator R 33 for adjusting the liquid flow rate and air 34 is pumped into the tube 19 from which it escapes via the bores 29 as small bubbles 36. Once the tube 19 has been filled with air, the power supply 12 and power control means 13 may be activated to apply high voltage electric pulses to the first and second electrodes 24,25 to establish an electric discharge in an electric discharge zone 37 extending around the outer electric discharge surface 38 of the tube 19.

Fig. 3 shows another embodiment where the wall 39 of the tube 19 is porous defining a multiplicity of small passages 40 therethrough. On the outer surface 41 of the tube is embedded a large number of small particles of metal 42 constituting secondary electrodes which has the advantage of yielding a more homogeneous electric discharge over the electric discharge surface. In other respects the embodiment of Fig.3 may be substantially similar to the first described embodiment. Fig. 4 shows the principal parts of the power control means 13 comprising a capacitor 43 in which charge is built up from the power supply means 12 prior to application to the electric discharge device 8 and discharge therethrough upon activation of a switch means 44. The circuit also includes suitable resistor means 45,46. Typically there are used particles 42 having a diameter of the order of 0.1 to 0.3mm which are spaced apart from each other - preferably by a distance not less than the particle diameter.

Figs 5 to 7 are detail views corresponding to part of Fig. 2 of three modified embodiments of the first form of the invention, in which like parts corresponding to those of Fig. 2 have been indicated by like reference numbers.

In Fig. 5 the outer cylindrical surfaces 101 of the electrodes 24,28 are covered by a solid dielectric tubular insulator 102, conveniently of PTFE. Thus only the opposed annular end face portions 103,104 of the ring form electrodes 24,28, are exposed to contact with the liquid flow 105 which is being treated by the apparatus .

The apparatus of Fig. 6 is generally similar to that of Fig. 5 with the outer cylindrical surfaces 101 of the electrodes 24,28 covered by a solid dielectric tubular insulator 102. In this case though annular grooves or channels 106 are provided in the hollow tube 19 of dielectric material on which the electrodes 24,28 are supported, below and slightly behind the opposed annular end face portions 103,104 of the ring form electrodes 24,28. The small bores 29 extending from the central gas supply passage 14 inside the hollow tube 19 exit into these channels 106 so that the gas bubbles 36 can begin to mix with the liquid flow 105 before the bubbles 36 enter into the electric discharge zone 37 between the opposed annular end face portions 103,104 of the ring form electrodes 24,28, whereby a more effective distribution of the gas bubbles 36 in the liquid 105 inside the electric discharge zone 37 can be obtained. In this case there are provided four equiangularly distributed small bores 29 (albeit that smaller or preferably larger numbers could also be used) , which feed gas bubbles 36 into the annular channels 106 and electric discharge zones 37. It will be understood that gas bubbles 36 exiting from a downwardly directed small bore 29 will be initially retained within into the annular channels 106 and electric discharge zones 37 as they rise upwardly around the side of the hollow tube 19 at the base of the annular channel 106.

In the apparatus of Fig. 7 the electrodes 24,28 are again provided with an outer covering of insulator 102 (except at the opposed end face portions 103,104 and annular channels 106 are provided in the tubular support 19. In this case though, instead of the central tubular support 19 extending horizontally, it is arranged so as to extend generally vertically with an upward flow of liquid 105 around it. As with the Fig. 6 apparatus, channels 106 are provided in the tubular support 19. In this case though, the small bores 29 extending from the central gas supply passage 14 inside the hollow tube 19 are disposed so as to exit 107 into these channels 106 at the upper ends 108 thereof so that the gas bubbles 36 are less readily entrained by the upward liquid flow 105 whereby the residence time of the gas bubbles 36 inside the electric discharge zone 37 between the opposed annular end face portions 103,104 of the ring form electrodes 24,28. This helps to reduce the gas supply required to maintain an effective concentration of the gas bubbles 36 in the liquid 105 inside the electric discharge zone 37 thereby decreasing the overall power consumption and running costs of the apparatus. It may also be noted that in this case, unlike with the previous embodiments, the first electrode 24 does not have an electrical conductor portion 21 extending along the internal passage 14 inside the tubular insulator support 19, whereby said passage 14 provides a substantially unobstructed pathway for the gas supply to the electric discharge zone 37.

Various experiments were carried out using apparatus of the two principal types illustrated in Fig. 2 as described hereinbelow and essentially the same procedures may be used with the devices of the present invention. Two high voltage pulse supply devices having the following characteristics were used. Type I - Peak voltage : U≤40kV;

High-Voltage pulse duration : T≤150ns; Pulse energy : W≥O .1 J;

Frequency of pulses repetition : f≤50-100Hz

Type II -Peak voltage : U≤20kV;

High-voltage pulse duration : T≤lOμs; Pulse energy : W≤2J;

Frequency of pulses repetition : f≤50Hz

All chemical analyses and Cryptosporidium tests referred to in the following Examples were carried out by NAMAS accredited laboratories .

Example 1 - Treatment of Contaminated Water A vessel was filled with water (1000 ml) to which lOmg of 5 parachlorophenol (CeH₄C10H) was added as an admixture and the Electric Discharge device substantially as described above was placed in the vessel. The electric discharge device used was of cylindrical geometry containing 5 ring electrodes made of titanium with a diameter of ca. 10mm, a length of ca. 10mm and

10 width of ca . 2mm. The 4 gaps between the electrodes had a clearance of ca. 2mm each. The dielectric tube supporting the electrodes was made of ceramics. Air at approximately atmospheric pressure was fed in through the holes in the interelectrode gaps at a rate of approximately 30 l/h: 10Hz,

15 the period of irradiation - t = 8 min. After the electric discharge treatment the content of parachlorophenol was found to have been decreased by 30%.

Example 2 - Treatment of Contaminated Water

20 Water (11) containing E. coli (10⁶ organisms l^"1) was placed in a container and an electric discharge device according to Figs.l and 2 of the invention was immersed therein. An electric discharge was produced in the water and maintained for 10 minutes at a pulse rate of 10 Hz at a voltage of 20 kV.

25 Results

After treatment for 10 minutes the population of E. coli was decreased to undetectable levels.

Literature References 301. Miles, A. A. & Misra, S. S. (1938). The estimation of the bacterial power of the blood. Journal of Hygiene,

Cambridge, 38, 732-749.

2 . AZUS Environmental ( 1997 ) . Microtox Manual Volumes 1-4 .

Microbics Corporation . 2232 Rutherford Road Carlsbad, CA. 35

Claims

1. An apparatus suitable for use in the treatment of a liquid, said apparatus comprising a high voltage electric discharge device with a first electrode and a second electrode spaced apart from said first electrode, said discharge device including electrical power supply control means formed and arranged for applying a series of high voltage pulses across said first and second electrodes in use of the apparatus with said device connected to an electrical power supply so as to produce, in use of the apparatus, an extended area electrical discharge in an electric discharge zone extending between first and second electrodes, said apparatus including a gas delivery means formed and arranged for feeding a series of bubbles of gas into a body of liquid in said electric discharge zone in use of said apparatus, said first and second electrodes, and any secondary electrodes therebetween, having opposed portions, and wherein only said opposed electrode portions are exposed, other portions of said first and second electrodes and any secondary electrodes present therebetween, being covered in solid dielectric insulator material.

2. An apparatus suitable for use in the treatment of a liquid, said apparatus comprising a high voltage electric discharge device with a first electrode and a second electrode spaced apart from said first electrode, and dielectric support members for said first and second electrodes, with exposed opposed portions of said first and second electrodes each having a dielectric - electrode interface between the respective electrode and said supporting dielectric member whereby, in use of the apparatus, a local increase in electric field strength is induced at said exposed opposed electrode portions adjacent said dielectric support member thereby facilitating electric discharge initiation, said discharge device including electrical power supply control means formed and arranged for applying a series of high voltage pulses across exposed opposed portions of said first and second electrodes in use of the apparatus with said device connected to an electrical power supply, so as to produce and maintain, in use of the apparatus, an extended area electrical discharge in an electric discharge plasma zone extending between said exposed opposed portions of said first and second electrodes, said apparatus including a gas delivery means formed and arranged for feeding a series of bubbles of gas into a body of liquid in said electric discharge zone in direct contact with said exposed opposed portions of said first and second electrodes in use of said apparatus, said first and second electrodes, and any secondary electrodes therebetween, having opposed portions, and wherein only opposed electrode portions are exposed, other portions of said first and second electrodes and any secondary electrodes present therebetween, being covered in solid dielectric insulator material.

3. Apparatus according to claim 1 or claim 2 wherein the first and second electrodes are substantially spaced apart and there is provided a multiplicity of spaced apart secondary electrodes distributed between opposed portions of said first and second electrodes.

. An apparatus according to any one of claim 1 to 3 wherein said first and second electrodes are formed and arranged so as to provide an annular electric discharge zone in use of said apparatus .

5. An apparatus according to claim 4 wherein said electric discharge zone has a substantially rectilinear longitudinal axis .

6. An apparatus according to claim 4 wherein said electric discharge zone has a longitudinal axis which is at least partly arcuate.

7. An apparatus according to any one of claims 4 to 6 wherein said first and second electrodes have opposed annular portions .

8. An apparatus according to claim 7 wherein the first electrode also has an elongate portion extending generally parallel to the electric discharge surface and insulated therefrom by a suitable solid insulator dielectric.

9.An apparatus according to claim 8 wherein said first electrode elongate portion is in the form of a conductor extending generally along the central longitudinal axis of the electric discharge zone.

10. An apparatus according to claim any one of claim 4 to 9 wherein said electric discharge zone is provided on the outside of a solid dielectric tubular insulator with an internal passage extending therealong and providing a gas supply conduit.

11. An apparatus according to claim 10 wherein is provided a plurality of discrete spaced apart passage means extending through said tubular insulator for connecting said internal passage to the exterior of said tubular insulator for delivering gas to the electric discharge zone.

12. An apparatus according to claim 4 or any one of claims 5 to 11 when dependent on claim 4 wherein said secondary electrodes are annular.

13. An apparatus according to claim 4 or any one of claims 5 to 11 when dependent on claim 4 wherein said secondary electrodes are in the form of a multiplicity of metallic or other electrically conducting particles embedded in or attached to the surface of an electrically insulating substrate.

14.An apparatus according to claim 12 wherein the electrodes are spaced apart from each other by from 3 to 8 mm.

15. n apparatus according to claim 1 or claim 2 wherein said first and second electrodes are substantially spaced apart with a multiplicity of spaced apart secondary electrodes distributed between opposed portions of said first and second electrodes so as to provide a slipping surface discharge across said electrodes in use of the apparatus.

16. An apparatus according to any one of claims 1 to 15 wherein said electrical power supply control means is formed and arranged for applying said high voltage pulses at a frequency of from 1 to 200 Hz.

17.An apparatus according to any one of claims 1 to 16 wherein said electrical power supply control means is formed and arranged for applying said high voltage pulses with a pulse energy of from 0.01 to 50 J per pulse.

18.An apparatus according to claim 17 wherein is used a pulse energy of from 0.1 to 25 J per pulse.

19. An apparatus according to claim 7 or any one of claims 8 to 18 when dependent thereon, wherein said first and second electrodes and any secondary electrodes present therebetween, have cylindrical outer surfaces, which cylindrical outer surfaces are covered in solid dielectric insulator material.

20. An apparatus according to claim 10 or any one of claims 11 to 19 when dependent thereon wherein is provided a plurality of discrete spaced apart passages extending through said tubular insulator for connecting said internal passage to the exterior of said tubular insulator for delivering gas to the electric discharge zone.

5 21. An apparatus according to claim 20 wherein said tubular insulator is provided with channel form recesses underneath said opposed electrode portions of said first and second electrodes and secondary electrodes, whereby in use of said apparatus said series of bubbles of gas is mixed with said 10 liquid before entering said electric discharge zone between said opposed electrode portions.

22. An apparatus according to claim 21 wherein said tubular insulator is formed and arranged so as to extend vertically, 15 said channel form recesses in said tubular insulator have upper portions, and said discrete passages are formed and arranged so as to exit into said upper portions of said channel form recesses.

2023.A method of producing and maintaining an electric discharge plasma in a liquid comprising the steps of: providing an apparatus according to claim 1 or claim 2, coupled to an electrical power supply and a gas supply means; providing a body of said liquid between said exposed opposed portions of

25 said first and second electrodes; and applying a series of high voltage pulses to the first and second electrodes of the electric discharge device of said apparatus while feeding gas into said body of liquid.

3024.A method of treating a liquid containing at least one undesirable form of a contaminant, so as to effectively decontaminate the liquid, said method comprising the steps of producing and maintaining an electric discharge in said liquid by means of a method according to claim 23, for a period of

35 time sufficient substantially to modify at least one said contaminant into a more benign form.

25.A method according to claim 24 wherein said liquid undergoing treatment has a pH of from 7 to 11 during said 5 treatment .

26. A method according to claim 24 or claim 25 wherein a gas comprising oxygen is used.

1027. A method of according to any one of claims 24 to 26 wherein said liquid contains a microbial or another infectious agent contaminant .

28. method of decontaminating water containing a heavy metal 15 or other chemical contaminant, wherein said water is treated by a method according to any one of claims 24 to 26.