APPLICATION OF COAXIAL DIELECTRIC BARRIER DISCHARGE FOR POTABLE AND WASTE WATER TREATMENT M. M. Kuraica1,2, B. M. Obradovi1,2, D. Manojlovi3, D. R.

Ostoji 3 and J. Puri1,2

1 2

Faculty of Physics, PO Box 368, 11001 Belgrade, Serbia and Montenegro, kuki@ff.bg.ac.yu Center for Science and Techn. Development, 11001 Belgrade, Serbia and Montenegro 3 Faculty of Chemistry, PO Box 158, 11001 Belgrade, Serbia and Montenegro

Abstract. A coaxial dielectric barrier discharge (DBD) closed system has been developed, constructed and described. DBD has obtained in the gap within layer of flowing water which covers an inner electrode and the glass tube protecting the outer electrode of the coaxial DBD closed system. In such discharge system an intensive ozone production and dissolution in water is enabled. In the waste water treatment a substantial decrease of chemical oxygen and potassium permanganate demands. Key words: dielectric barrier discharge, ozone, potable water, waste water Introduction After many years of using chlorine in water disinfection, it was concluded that its usage in potable water treatment can be harmful for human health. For instance threehalometanes, produced in such way, are cancerogene compounds. Therefore The World Health Organization recommended and some of more developed countries have already started to use ozone in potable water treatment. In about 3000 cities the potable water is supplied after oxidation and disinfection by ozone. The main advantage in using ozone instead of chlorine is in very rear production of harmful compounds in the case of bromine presence. On the other hand, there are many positive effects in using ozone. Here only main of them are listed: Large ozone efficiency in oxidation of the compounds present in water owing to large redox potential in comparison with chlorine (2.071.36 V); Large efficiency in degradation of organic compounds and biodegradation of produced byproducts; Ozone spontaneous transition to oxygen and therefore, acceptable from the reason of better environmental protection; Ozone action on the large spectrum of microorganisms.

Beside here mentioned positive effects ozone application has several disadvantages mainly of technical nature: Ozone has to be produced at the place of application because of its fast spontaneous transition to oxygen, and therefore is not transportable; Relatively small conversion efficiency in the ozone production from air (4 6%) or from oxygen (6 12%); Relatively expensive power supplies with working voltages close to 10 kV within frequency range (50 50 000 Hz); Ozone gas off is not allowed. In classical ozone generator ozone is produced by treating air or oxygen gas flowing through the inter electrode space of the electric discharge. Siemens constructed and patented for this purposes a device based on DBD (Fig 1.) in 1893th year, and thereafter in The Netherlands, for instance, the ozone application started in the production of potable water. Fig 1.

Figure 1. Siemens ozonizer

A large number of published papers and great research effort were devoted to the increasing of conversion efficiency of oxygen to ozone by optimizing discharge parameters, appropriately chousing electrode configurations, spatial materials for its construction, different catalysts, changing working frequencies or even working in pulse regime [1]. However, a progress was realized and described by Okazaki et al. [2]. This group of authors was successful in realization of DBD in the air at atmospheric pressure, believing to be impossible, up to their undertaking, to operate at 50 Hz in the glow mode. Namely before that time it was believed that the glow discharge cannot be stabilized and sustainable at atmospheric pressure. It is necessary to avoid transition to high current discharge mode, which consequently results in an arc discharge, destructive for the electrodes. The achievements, described so far, were followed by systematic research of many groups of authors attempting to optimize the parameters of DBD systems working under such conditions (in the air at atmospheric pressure). It is instructive to mention only One Atmospheric Uniform Glow Discharge Plasma (OAUGDP) [3] among many of the sources of different configurations. It is the

source of coplanar configuration very often used in medicine and industry applications such as sterilization, thin layer deposition, surface activation of different materials, etc. [4,5] At present different DBD electrode configurations are used (fig 2) with following characteristics: operation at atmospheric pressure between metal electrodes of which one is protected with insulator layer, barrier, alternate voltage with maximum higher of the discharge breakdown voltage for a given electrode gap and working gas. Different glasses and ceramics are commonly used as the isolating materials. The discharge is usually organized through a large number of filamentary channels (streamers, 100 200 m in diameter). They are form by the electron avalanche moving from one of the metal electrodes (which may, but not must be covered by insulator) and are terminated at the insulator protecting the other electrode being at that particular instant of time positive. The streamers last 10 100 ns enabling a charge transfer during that time. This negative electric charge is accumulated at very small surface element of the insulator as free surface charge. Its electric field increasing quickly, causing the current decreasing up to filamentary discharge channels termination. Number of streamers can be large enough to transfer sufficiently charge during one half period of the alternative current signal. At a registered current signal the streamer formations are presented as the series of peaks as it can be seen at Fig.3a. Such kind of the discharges operating in filamentary mode when the sign of the alternative current signal is changed the cycle of the discharge and streamers formation is repeated with the largest probability to start from the place of the surface with some charge not being transfer during previous current half period. That is why DBD is characterized by memory effect. Duration of one streamer in DBD is of great importance. It has to be short

Figure 2. Different DBD configurations. Black metal electrode, gray insulator.

enough to avoid fast increase of charge at small surface element of the insulator causing breakdown resulting in starting arc discharge. Due to that, the power supplies with 100 kHz were used before the DBD stabilization procedure at low frequency (50 Hz) was not developed and described by Okazaki et al [3]. In these types of DBD large number of streamers are starting in the whole inter electrode space at the same time instant and, therefore homogeneous diffuse discharge is obtained. A series if peaks on the registered current signals, as the characteristics of filamentary discharge are gathering in one current signal maximum. This is a verification of transition from filamentary to diffuse, i.e. transition to glow discharge mode (Fig.3b).
20 1.0

a)
10 0.5

b)
U [kV]
I [mA]

U [kV]

-10

-0.5

-20 0 5 10 15 20 25 30 35

-1.0 40

t [S] Figure 3. Voltage and current signals. a) filamentary mod with water as a barrier electrode, b) glow discharge mode.

t [ ms ]

In the classical ozonizers, as it was mention, ozone is produced in DBD from the air or oxygen gas flowing through the inter electrode gap (sometimes corona discharges were also used). Under the influence of high energy electrons within the inter electrode space the dissociation of the oxygen molecules is occurring. Atomic oxygen through the + 2 + 3 + M reaction is enebling the ozone production. A paralel concurent reaction + 3 22 is occurring, also and therefore, causes the ozone degradation. That is reason of the upper limit existence for the maximum in ozone production, i.e. limit of device efficiency. After passing through inter electrode gap the air flow which consist of nitrogen, oxygen, the other usual constituents of the air, and ozone has to be introduced into water. The process of the air flow introduction and the ozone dissolution in the water is performed using special reservoirs, injecting ozone through nozzle, meshes, mixing etc. During such introduction the main part of

I [mA]

0.0

ozone is dissolved in water, but the rest of it, together with air bubbles, comes over the water surface and form their gas mixture into the container. During the device operation the mixture pressure is increasing and consequently gas off the mixture to the atmosphere has to be provided after process of necessary ozone degradation. Experiment An experimental device used here has been specially designed in order to avoid the disadvantages of the above described DBD devices such as: the problems of mixing and ozone desolation in water, degradation of not desolated ozone before its gas off to the atmosphere. Namely, a DBD device for direct water ozonization (DWO) has been developed and constructed in our laboratory. The DWO includes simultaneous ozone production and its dissolution into the flowing water layer which is playing the role one of DBD electrode (Fig.4a). DBD described here is occurring between water layer and inner surface of the glass tube isolating outer metal electrode. The glass tube is sealed towards the atmosphere in order to isolate discharge space from the environment. The DBD

)
E1 E2
water

)
1

Figure 4. a) schematic diagram of the electric discharge device b) closed system for direct water ozonization.

device operate using 10-20kV power supply operating at 50 Hz frequency with a gap between barrier electrodes is 2-3 mm. The inner electrode is 400 mm length and 20 mm in diameter. A measured power, under such condition, using a method of Lissajous figures is found to be 7-9 W for the flow rates in the range of 200-500 ml/min. On the basis of registered current signals similar the one presented in Fig. 3a, it is concluded that the discharge is operating in the filamentary mode. A schematic diagram of the water ozonizer operation is presented in Fig.4b. The water from the reservoir (1) using a natural slope is flowing between the electrodes E1 and E2 towards the reservoir (2). The flowing water layer is taking the role of one barrier electrode. The discharge is occurring within a zone between the water layer and the glass tube isolating the outer metal electrode. In the zone the ozone is produced. A part of it is staying in gas faze into inter electrode space. The main part is dissolving into the flowing water accumulated after inside the reservoir (2) where it is mixed with so far treated water and then transported up to the reservoir (1) by using a pump (3) as it is presented in Fig.4b. A constant water flow rate through the inter electrode gap is maintained during the series of experiments by keeping constant the height difference between water levels inside the reservoirs (1) and (2). A particular water rate flow can be chosen by the corresponding height difference between water levels. Water can circulate within such closed system as long as it is necessary to obtain the ozone concentration dissolved in water without ozone gas off to atmosphere. All the investigated water samples were treated under such conditions during here described experiment. In addition, the electrode system used here, enables a synergetic effect of a simultaneous water layer exposition to the DBD and UV radiation from that discharge, during continual ozone production and its dissolution into water. Therefore, the device can be regarded as an ozone reactor appropriate for obtaining expected ozone concentrations dissolved in water as high as needed with better bacteriological purity. It is well known that some kind of bacteria from the water can be eliminated only by simultaneous water treatment by UV radiation and ozone [4, 5]. When it is combined with the presence of high energy electrons and ions, the synergetic effect can be intensified several times. The investigations of the plasma reactor efficiency in obtaining potable water with appropriate bacteriological quality are on the way in our laboratory. Results The results obtained using the plasma reactor for the potable and the waste water treatment are presented here. The efficiency of DWO is measured in bidestilated water in order to avoid the influence of ozone consumption on the possible

impurities oxidation. The ozone concentrations were measured using the standard iodometric method. As an example of the measured ozone concentration increase during ozonizer operation is given in Fig. 5. The samples are taken using a valve mounted on the reservoir 2 (Fig. 4b) in order to avoid ozone gas off to the atmosphere. The system is closed and isolated from the environment during the whole working cycle. From fig. 5 one can conclude that the ozone concentration is an increasing function on time during the reactor operation. The ozone concentrations are lower for larger water flow rates. Due to the water rate flow increase the water layer thickness is increasing around inner electrode (i.e. the thickness of the water barrier layer is enlarged in this type of DBD) what results in the production of smaller number of streamers. All the results presented in Fig. 5 are normalized to one pass through the
14

Dissolved ozone concentration [mg/l]

13 12 11 10 9 8 7 6 5 4 3 2 1 0

80 ml/min 250 ml/min 580 ml/min

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5

Time [h] Figure 5. Concentration of dissolved ozone on time for different water flow.

inter electrode system for the sake of comparison. Taking into account a spontaneous degradation of ozone dissolved in water, during the DBD reactor time operation of several hours, a continual monitoring of the ozone concentration would prove the existence of larger real values of ozone concentrations. However, the measured values of the ozone concentration are one order of magnitude exceeding the values obtained in the other devices were water is used as one electrode, even with oxygen injection in the gap between water surface and the other electrode [7]. With appropriately voltage and water flow rate the

concentration of dissolved ozone up to 30 mg/l can be obtained. The nondissolved ozone in the gas phase is closed in the reservoirs. Therefore there is no necessity for additional equipment for its burning before gas off to the atmosphere. In order to investigate the origin of ozone production within the closed DBD system described here the following experiments were performed under different conditions: (i) operating in the air at atmospheric pressure; (ii) operating with Ar and He injection. After several ours of DBD system operation the sampling of treated bidestilized water circulating between two reservoirs has been done for sake of ozone concentration measurements. All measurements have shown that in bidestilized water taken from both reservoirs of DBD operating even in the inert gases atmosphere the dissolved ozone was present. The measured concentrations were significant, although smaller than in the case of DBD system operation in the air. This may suggest that some quantity of ozone is produced from water (up to 20 %). Due to the streamers presence in DBD, the water can be evaporated from the place where they are terminated on the water surface. The water vapor enters into inter-electrode gap of the discharge where the dissociation of the water molecules is occurring enabling the ozone production. If these presumptions are correct the lowering of treated water pH can be expected. The performed measurements have verified the pH lowering. The spectroscopic measurements are on the way in order to verify the possible

Figure 6. Example of waste water before and after treatment by the ozonizer.

presence of OH- ion. The DBD device presented in fig 4b was used also for waste water treatment contaminated by the oil derivates (COD of the non-treated waste water sample was 400 mg/l). That water was treated during one pass through ozonizer and stored in hermetically glass vessels. A change of the waste water color is noticeable just after finishing one treating cycle as it is presented in fig. 6. It is a proof of efficient degradation of organic compounds of present pollutions. A systematic measurement of COD and potassium permanganate demand (PPD) during six days period of time is performed. The obtained results are presented in fig. 7. It is found that just after one pass treatment by DBD the COD of waste water decreased for 30%. The color change from dark to bright is noticed. During first 48 hours COD continually decreases for 70 % of its initial value. The similar change was measured in the case of PPD as is shown in Fig 7. The observed effect of COD decrease is very important for different technology applications. It is suggesting the presents of series of chain reactions initiated by ozone dissolved in water. Due to these reactions large organic molecules are fragmentized resulting in COD decrease. The optimization of conditions for different organic molecule degradation using special catalyst is on the way in this experiment. The tasted DBD device can be used in parallel combination as many as needed units in order to increase water flow rate during one pass through DBD device. A combination of 100 DBD parallel units was tested in treating potable water.
280 260 240 220 160

COD

PPD

180

PPD (mg/l)

COD (mg/l)

200 140 180 160 140 120 20 40 60 80 100 120 140 160 100 180 120

Time (h)
Figure 7. Time dependence of chemical oxygen demand (COD) and potassium permanganate demand (PPD) of treated waste water.

References [1] U. Kogelschatz, Fundamentals and applications of dielectric barrier discharges, HAKONE VII Int. Symp. On High Pressure Low Temperature Plasma Chemistry, Greifswald, Sept. 2000. [2] S.Okazaki, M.Kogoma, M.Uehara and Y.Kimura, J.Phys.D:Appl.Phys. 26,886(1993a) [3] J.R.Roth, Industrial plasma engineering, Vol 1,2, IOP Publishing, Bristol and Filadelfia, 2000 [4] M Laroussi, D A Mendis and M Rosenberg, New Journal of Physics 5 (2003) 41.141.10 [5] S Villeger, S Cousty, A Ricard and M Sixou, J. Phys. D: Appl. Phys. 36 (2003) L60L62 [6] Methods 2-41, 2-42 and 4-104, in Standard Methods for the Examination of Water and Wastewater, Eds. Andrew D. Eaton, Leonore C. Clesceri, Arnold E. Greenberg and Mary Ann H. Franson, American Public Health Association, Washington, 1995. [7] Tajima R, Ehara Y, Kishida H, Ito T. Proceedings of the Hakone VII, Germany: Greifswald; 2001; 2: p. 4126.