1.

INTRODUCTION
Drinking water can be contaminated by the hydrocarbons through industrial waste such as benzene, phenol, or toluene where these materials can reach underground water reservoir. Disinfection of water with chlorine may introduce halogenated hydrocarbons. Some of these materials pose potential health hazards, and are resistant to degradation and fitration through the normal mechanical ways. For example, trihalomethanes (THMS) have been found in drinking water and are believed to be carcinogens. The Environmental Protection Agency (EPA) of the USA regulates the general maximum contaminant level to be 100 pg/L. Most of these compounds are soluble and thus are difficult to remove through common water treatment techniques. Air stripping by itself has been used extensively to reduce the volatile substance amount in the drinking water [l]. In Florida, USA, The Drinking Water Research Centre introduced the high energy electron beam technique for THMS removal from water . This method proved to be successful, but it uses very high energy and hence has high cost.

High voltage DC corona was used in the past for air purification from unhealthy industrial waste gases such as SO,, NO,, and CO, . Recently pulsed corona attracted attention in industry applications research. Helfritch used wire in tube pulsed corona to decompose hydrogen sulfide contained in hydrogen. In other application, Yamamoto el. of. used nanosecond pulse corona for modifying the surface energies of aluminum, polyurethane and photoresist on silicons and for removing organic thin films on aluminum surfaces. The mechanism and applications of pulsed corona and pulsed breakdown in water also received more attention in recent years. The pulsed water breakdown depends mainly on the conductivity of the water and the duration of the pulse (or rise time). Moon et. of., studied the breakdown of three different types of gaps in water namely point to plane, point to plate with field controlling electrode and a hole to plate gap with field controlling electrode. They found that the hole-to plate gap have the lowest breakdown voltage which was due to the presence of a stable gas cavity in the hole. Short duration impulse, and the highly nonuniform field are the conditions for producing intense corona discharge in the water without leading to complete breakdown except at high voltages. The main parameters controlling the corona peak current, its duration and corona energy are the peak value of

applied voltage, pulse voltage rise time, pulse forming capacitance and the shape of the active electrode used pulsed corona for breaking up gas bubbles in water. These bubbles were deliberately introduced to enlarge the surface area between liquid and gas and hence increase the chemical reduction efficienc One of the applications of pulsed corona on water is the generation of chemical species that are lethe1 to some microorganism This paper presents results conceming the use of nanosecond pulsed corona for water treatment. The combination of air stripping and pulsed corona were used to remove the THMS from water. Voltage level, gap spacing, electrode position, water type, and flow rate of injected bubbles were the main parameters studied.

2. Experimental Setup and Procedure

In this study using specially designed thyratron switched network repetitive negative pulses were generated. The rise time of the pulse was around 30 ns, the voltage could be varied from zero to 40 kV and the pulse repetition rate from 0.1 - 200 Hz. Fig.1 shows the pulse waveform. Two rectangular water containers were used having the dimensions of

9.0 x 9.0 x 5 cm and 15 x 9 x 5 cm. Point to plane geometry was used. The point has sharp angle and the plate was rectangular having dimensions of 8 x 4.5 x 0.3 cm. Nitrogen gas was injected through a fine tube to the point creating bubbles at the high field electrode and hence increasing the interaction efficiency. Two arrangements for the high voltage point to the grounded plane geometry were employed. Fig.2 shows a schematic diagram of the experimental set up. The fmt had the point on the top and the plane in the bottom, electrode-geometry A. In this case a circular perspex plate was placed 0.5 cm above the point to prolong the residence time of the bubbles at the active electrode. The second arrangement was the plate at the top and the active point at the bottom, electrode-geomatry B so as to make the bubbles naturally flow in the same axis of the applied field. The interelectrode gap was adjusted using a 5 to 70 mm To simulate the existence of volatile substances in drinking water, a known amount of Trichlorethylene (TCE) or choloform (CHC13) was introduced in the water. Distilled, deionized, and tap water were used with their conductivities

of 1, 2.5 and 600 jdcm respectively. The contaminated water samples, subjected to specific treatment condition and duration, were analyzed for their TCE or CHCI, contents.

3. MATERIALS AND EXPERIMENTAL SETUP

Phenol of analytical grade (Merck) was used without further purication. Phenol solutions were prepared using doubledistilled water. A stock solution of 1000 mg/L was prepared bydissolving1gofphenol in 1 L of double-distilled water. The working solutions of phenol (1, 5, 10, and 20 mg/L) were prepared from the stock solution using appropriate dilution. Fig. 1 shows a schematic diagram of the treatment system. Water containing phenol is passed through a medical syringe needle as drops at a ow rate of 20 mL/min. Whenever the high voltage is applied on the needle, the water drops are sprayed, and corona streamers are formed simultaneously. Sprayed water is exposed to corona active species and collected at the ground electrode. The distance between the powered electrode (syringe needle) and the ground electrode is 4 cm. The high-voltage power supply (HVPS) generates positive high-voltage pulses up to 22 kV with a pulse duration of 9 s and a repetition frequency

of 15 kHz. A digital storage oscilloscope (type HM1508) has been used to measure the current and voltage waveforms. The voltage has been measured via voltage attenuator (1000:1), while the current was measured by measuring the voltage drop across 100- resistor. Air and oxygen gases at atmospheric pressure (static operation) have been used as working gases. Phenolic compounds can be determined photometrically using the 4-aminoantipyrine method, where the phenolic compounds react with 4-aminoantipyrine at pH of 7.9 0.1inthe presence of potassium ferricyanide to form a colored antipyrine dye. This dye is kept in aqueous solution, and the absorbance is measured at 500 nm. The color intensity is proportional to the concentration of phenol and obeys BeerLambert law. Corona streamer starts to be built up when a high-positivevoltage pulse is applied to the powered electrode (needle tip) and the plate electrode is grounded. Free electrons are naturally formed in the electrode space and then accelerated toward the tip. In the ionization region where the electric eld is strong enough, inelastic collisions between electrons and gas molecules occur, and pairs of electronpositive ion are produced. The newly free electrons are, in turn, accelerated by the electric eld and produce further ionization forming the electron avalanche. Secondary electrons, which sustain the discharge, are produced in the gas by photoionization due to photons emitted during the de-excitation processes in the plasma region. If the electric eld close to the anode tip is strong enough to provide necessary energy for ionization, the process becomes repetitive, and a space charged region starts to propagate toward the cathode plate. In other words, the positive-ion density must be large

enough to extend the ionization in front of the space charge region by eld enhancement for the whole interelectrode gap. This type of corona is called streamer. The streamer propagation is accompanied by branching of the discharge channels. Many streamers may start from the anode tip, but branching may appear as well, later on the streamer path . At the cathode (ground electrode), the electric eld is relatively low which causes the formation of positive-ion sheath near the cathode, and hence, the electric eld in the discharge region is reduced. The reduction of the electric eld in the discharge region is responsible for the collapse of the discharge and hence drops the discharge current. The duration time of the discharge (duration time of the current peak) has been found to be around 3 s. The damping oscillation behavior, shown in the current waveform, is referred to the inductive and capacitive reactances of the electric circuit. Van Veldhuizen and Rutgers have discussed the damping oscillation behavior in corona discharge in detail. Inside the streamer channels, large amount of different radicals and active species is produced. Discharges in the presence of water produce the hydroxyl radical (OH) from water molecules. In addition, corona discharge creates ozone (O3), oxygen atom (O), and hydrogen peroxide (H) . Among the produced oxidants in corona discharge, the hydroxyl radical has the highest oxidation potential (2.8 V). The oxidation potentials of atomic oxygen, ozone, and hydrogen peroxide are 2.4, 2.1, and 1.8 V, respectively . Compared with chlorine (oxidation potential of 1.3 V), the oxidants produced in corona discharge are efcient for phenol oxidation .

Various reactions sustain the formation of oxidant species in corona streamer. OH radical is produced according to the following reactions : H2O + e H + OH + e H2O2+ h OH + OH O3+ H2 O2 OH + HO2+ O2 O3+ HO2 OH +2O2 O + H2 O2 OH + HO2 O + H2 O OH + OH.

It shows the currentvoltage characteristic curve of the discharge with and without the water injection into corona discharge through the needle tip. The values of the voltage and current in the peak values of the voltage and current pulses, respectively. It can be observed that, at discharge voltage lower than 14 kV, the discharge current increases gradually while, at discharge voltage equal to or higher than 14 kV, the discharge current increases more rapidly with the discharge voltage. This two-slope behavior can be referred to the fact that the positive corona discharge can be formed in two different types, depending on the value of discharge voltage (or the strength of the electric eld). At low discharge voltage, the corona is formed locally around the tip of the powered electrode which limits the dissipated power in small volume, and hence, the slope of the currentvoltage curve appears to be small. A slight increment in the current during the presence of water can be noticed. When a drop of water at the tip of the syringe

needle is exposed to the electric eld, created by the applied oltage pulse, the shape of liquid starts to deform from the shape caused by surface tension alone. As the voltage is increased, the effect of the electric eld becomes more prominent.

3. Results and Observation

The treatment duration was the main parameter varied. To determine the influence of each specific parameter, each individual parameter was varied while the others were kept constant.

3.1 Influence of bubbles The importance of the existance of bubbles is highlighted in the introduction and was verified experimentally. show, as function of the treatment time, the per unit amount of TCE and CHCS in H20 respectively. Three situations are shown ; first when leaving the mixture in open air and with no voltage, these volatile elements will evaporate, but very slowly. In this case the reduction of TCE in 30 minutes is 28% and the reduction of

CHCI, in 15 hours is 66%. When bubbles are introduced with, zero voltage, the reduction, in TCF and CHC1, am 84% and 92% respectively. After applying the voltage in the presence of bubbles the reduction is further enhanced as will be seen later. In all test runs, the bubbles were feeded in continuous flow so as to make a common case for comparison of results for varying parameters. 3.2 Influence of Voltage and Electrode Geometry As can be seen , the introduction of impulse voltage into the gap helps in the water purification process. The presence of the voltage will cause partial discharge in the air bubbles and help in breaking these bubbles and hence enhancing the treatment process. shows the effects of electrode geometry on TCE reduction with pulse treatment. Although, the pulse effect is higher with electrodegeometry B, the total reduction in TCE with pulse treatment is higher with electrodegeometry A. In the absence of any bubbles pulse voltage has very little effect on TCE reduction, since corona does not take place in the liquid water. Also, from , it is seen that the value of voltage on the point is

more important than the average electric field (Emv). For the case, V = 30 kV, and d = 2 cm (E, = 15 kV/cm) the treatment efficiency is higher than for the case, 3.3 Influence of Pulse Repition Rate (PRR) The PRR, or the frequency of the pulse generator has a little influence on the treatment efficiency. As seen , an increase in frequency will increase the removal of the contaminants; however, the increase is moderate especially for large treatment times. Hence the frequency is not a major influencing parameter in the water treatment..

3.4 The Influence of Water Type Three types of water were tested. It was noticed that, as the water conductivity increased, the treatment efficiency increased. shows the treatment for the tap water (a = 600 ps/cm), where after 30 minutes most of the TCE has been removed from the water. One of the problems with tap water is the heating especially at higher frequencies. At f = 213 Hz the temperature of the treated water rose 55C in 20

minutes from 20C. This heating constitutes a power loss and loading to the pulse generator. In addition, the dielectric strength will decrease by the rise in temperature

4. Discussion
The experimental results have shown that it is possible to use pulsed corona in the presence of air bubbles to effectively remove the hazardous organic volatile substances in water. The generator built for this work is capable of producing pulses with rise time of - 30 ns and duration of - 100 ns. It was therefore possible to produce these pulses in both deionized, distilled water and ordinary tap water. It is however recommended that low frequency be used with tap water with high conductivity to keep the temperature rise to a minimum. The efficiency of contaminant reduction depends mainly on production of air bubble in water to be treated and field intensity of the pulse near the active (point) electrode. In the absence of any bubble the reduction in chloroform concentration was only 20%. as it was not possible to

produce corona in liquid water 181. When the bubbles were produced almost all of the chloroform was removed in about 30 minutes with pulse treatment (30 kV @ 20 Hz). In electrode geometry A, the bubbles were produced at the top electrode and with the help of an insulating spacer it was possible to increase the residence time of the bubbles near the point electrode. In addition, the presence of an insulating spacer near the active electrode enhanced the field intensity which resulted in increased corona discharge. In electrode geometry B, although bubbles were made to travel in the direction of the field, it was not possible to hold them near the point electrode for long enough to create effective corona. The chloroform reduction efficiency with electrode geometry A was therefore higher than with electrodegeometry B (Fig.5). Results have also shown that for a given electrode geometry, it is the field intensity the near point electrode which is essential in initiating corona around the point electrode rather than the average field in the gap, (Fig.6). In

summary, the water treatment method using pulsed corona depends both on pulse application and bubble production. The mechanism of THMs reduction with pulse corona is relakd to production of owne during pulse application. The amount of ozone generation depends on the rate constants of various electrochemical reactions which further depend on the pulse energy and oxygen availability. With the breaking of the bubbles, the dissolved oxygen is converted into ozone. The oxidizing agent in ozone is the nascent oxygen released when ozone reverts back to oxygen as it comes in contact with water [ll]. Further if the ozonization takes place in the presence of hydrogen peroxide, it is possible to produce readily oxidizing hydroxyl radicals. In the presence of the nascent oxygen orland hydroxyl radicals the hazardous organic compounds in water are oxidized into non-hazardous compounds. Unlike in air-stripping the THMs are not simply transferred from one medium to another with pulsed corona treatment. In order to ensure what chemicals are formed by pulsed corona treatment, further work has been planned to quantatively analyze the by-products produced during pulsed corona treatment.

5. Conclusions

In this study, it has been shown that pulsed corona in the presence of bubbles is an useful technique for removal of hazardous organic volatile substances in drinking water. The field intensity and the residence time of the bubble near the active (point) electrode are the most important parameters in effective removal of contaminants. the increase in pulse frequency did not necessarily improve the removal efficiency.

6. References
.

1. J.M. Montgomery, in "Water treatment principles and design", Wiley-Interscience, 1985. M.G. Nickelson, W.J. Copper, 2.K. Lin, C. Kurucz and T.D. Waite, "High energy beam generation of oxidents

for the treatment of benzene and toluene in the presence of radicals scaverages, Water Research, Vol. 28, No. 5, pp .1227- 1237. 3. J.S. Chang, P.A. Lawless and T. Yamamoto, "Corona Discharge Processes" IEEE Trans. On Plazma Science, Vo1.19, No.6, 1991, pp.1152-1166. 4. D.J. Hetritch, "Pulsed Corona Discharge for Hydrogen Sulfide Decomposition" IEEE Trans. On Industry Applications, Vo1.29, NOS, 1993, pp.882-886. 5. T. Yamamoto, J.R. Newsome and D.S. Ensor, "Modification of Surface Energy, Dry Etching and Organic Film Removal using Atmospheric-Pressure Pulsed Corona Plazma" IEEE Trans. On Industry Application, Vo1.31, No.3, 1995, pp.494-499. 6. J.D. Moon, J.G. Kim and D.H. Lee, "Discharges of point to plate gaps in pure water" Conference Record IEEE Industry Application Anual Meeting, 1993, pp.1611-1616. 43 1 7. M. Rea and K. Yan, "Evaluation of Pulse Voltage Generator." IEEE Trans. on Industry Applications, V01.31, h.3, 1995, pp.507-511.

8. E. Van Heesch, R.H.P. Lemmen, B. Franken, K.J. Ptasinki and F.L.S. Geurtz, "Pulsed corona for breaking up air bubbles in water" IEEE Trans. on Dielectrics and Elect. Insul. Vol.1, No.3, pp.426430, 1994. 9. M. Sato, T. Ohgiyama, and J.S. Clements, "Formation of Chemical Species and their Effects On Micoorganism Using Pulsed High Voltage Dischargein Water" Conference Record of IEEE Industry Application Annual Meeting, 1994, pp.1455-1461. C.M. Muller, W. Gujer and W. Giger, "Transfer of Volatile Substances from Water to the Atmosphere" Water Research, Vo1.15, 1981, pp.1271-1279. 10. J.S. Clements, M. Sat0 and R.H. Davis, "preliminary Investigation of Prebreakdown Phenomena and Chemical Reactions Using A Pulsed High Voltage Discharge in Water", IEEE Trans. On Industry Application, Vol.IA23, No.2, 19

PULSE CORONA TREATMENT FOR REMOVING VOLATILE MATTER FROM DRINKING WATER

SUBMITTED TO Dr. S. C. PRASAD

SUNMITTED BY KIRAN SHAH 2012EN11 M.Tech 1st yr