NOx and Soot Reduction Using Dielectric Barrier Discharge and NH 3 Selective Catalytic Reduction in Diesel Exhaust

Cha et al. 28 NOx and Soot Reduction Using Dielectric Barrier Discharge and NH 3 Selective Catalytic Reduction in Diesel Exhaust M. S. Cha, Y.-H. Song, J.-O. Lee, and S. J. Kim Environmental System Research Center, Korea Institute of Machinery & Materials, Daejeon, Korea Abstract A combined De-NOx technique of a non-thermal plasma and a selective catalytic reduction (SCR) using NH 3 has been investigated to remove NOx from a 3 hp marine diesel engine exhaust under low temperature conditions (1 2 o C). As results, De-NOx efficiencies for the combined process were increased from 2 to 8 % at 1 o C compared to a SCR sole process. Since a non-thermal plasma could convert NO into NO 2, a fast SCR reaction by which a equal amount of NO and NO 2 reduced to nitrogen could be activated in a relatively low temperature range. Furthermore from the measurement of smoke-meter, over 45 % of PM was reduced and the size distribution of PM was significantly altered after plasma process. This feature will be helpful to continuously regenerative DPF systems. Keywords non-thermal plasma, dielectric barrier discharge, NH 3 SCR, fast SCR reaction I. INTRODUCTION Recently, we are faced with the elevated regulation of NOx from combustion exhaust gases, because it caused smog, an acid rain, and a respiratory disease. Available technologies for aftertreatment of NOx, for instance, are a three-way catalyst and a selective catalytic reduction (SCR) used for gasoline engines and stationary combustion systems, respectively. However, since the three-way catalyst should be operated in stoichiometry, it can not be adopted to lean burn engines such as diesel engines. For a SCR technique especially using NH 3 as a reducing agent, though it shows a good performance for oxygen contained flue gases, there is the limitation of operating temperatures (normally its operating temperature is above 3 o C), so that de-nox efficiencies are quite poor in a low temperature range [1, 2]. In this reason, NH 3 SCR can not be used for low temperature flue gases in many stationary combustion systems as well as mobile engines which have a stop-and-go features. In these regards, catalytic processes combined with a nonthermal plasma can be considered as one of the promising candidate for treating NOx from lean burn engines with a low temperature exhaust, and recently many of researchers had interests on this field [2-7]. Another main hazardous product in diesel engines is particulate matter (PM), which is generally formed from soot particles. Since diesel engines are operated with a diffusion flame, soot particles are inevitable. In the present study, we investigated the effects of a non-thermal plasma combined with conventional NH 3 SCR process on NOx treatment in a marine diesel engine exhaust with an emphasis on the increasing de-nox efficiencies in a low temperature range, i.e., 1-2 o C. The principles and illustrative test results of the combined De-NOx process of SCR and oxidation techniques were well introduced in recent researches [2-4, 8-1]. A dielectric barrier discharge (DBD) was considered as the source of a non-thermal plasma ( or an Corresponding author: M. S. Cha e-mail address: mscha@kimm.re.kr oxidation source). We designed and constructed a planar type DBD, which showed a good performance even in humid and highly sooting conditions. Fundamental investigations, such as NO to NO 2 conversion characteristics with DBD, the effects of additives were also made with a simulated gas. In addition, the size variation and reduction of PM with the DBD reactor will be discussed. II. EXPERIMENT To investigate the basic characteristics of nonthermal plasma and SCR processes, we first considered a lab-scale experiment with a diesel exhaust-like simulated gas. Figure 1 shows the schematic of lab-scale experimental setup. The apparatus consisted of a gas supply system, a mixing and preheating unit, a constant temperature furnace, a DBD reactor and a power supply, a SCR reactor, and measurement systems. To simulate a diesel exhaust, mass flow controllers were used for compressed air, N 2, CO 2, NO, and C 3 H 6. Here, propylene was used for representing unburned hydrocarbons [11, 12] and the effect of water vapor was not considered for simplicity. The gas compositions are listed in Table 1, Air N 2 CO 2 Mixing & Pre-heating Unit 125 Temp. Controller NO Automated Power Measurement System C 3 H 6 Constant Temp. Furnace Plasma Reactor NH 3 SCR Reactor AC Power Supply Fig. 1. Schematic of lab-scale experimental setup. Exhaust Water bath FTIR Originally presented at ISNTPT-5, June 26 Revised; November 9, 26, Accepted; January 23, 27

29 International Journal of Plasma Environmental Science & Technology Vol.1, No.1, MARCH 27 TABLE I COMPOSITIONS OF DIESEL EXHAUST-LIKE SIMULATED GAS. % of Max. Load of Engine O 2 [%] Exhaust Composition CO 2 [%] NOx [ppm] C 3 H 6 [ppm] 25% 17.6 4.35 55 116 5% 15.4 5.77 63 114 [NOx] = [NO] + [NO 2 ] which correspond to 25 and 5 % of maximum load condition in a marine diesel engine used in the present study. The flow-rate of ammonia, as a reducing agent in SCR process, was also controlled with, and it was fixed as the same amount of NOx. Total flow-rate of simulated gas was fixed at 2 slpm for lab-scale test. To identify the effects of operating temperature on each process, the DBD and SCR reactors were located in the constant temperature oven. The simulated gas was mixed and heated up to a target temperature within the mixing and preheating unit, then it was introduced to the DBD reactor. The composition of a mixture was measured by Fourier transform infrared spectroscopy (FTIR, vector33, Bruker) at three different points the inlet and outlet of the DBD reactor, and the outlet of the SCR reactor. These three points represent an initial condition, the effects of plasma, and the role of a catalyst, respectively. As shown in Fig. 2, the dielectric barrier discharge (DBD) reactor (1(W) 7(D) 1(H) mm), which was constructed by stacking up a planar electrode together with spacers for gas flow, was used as a non-thermal plasma source. The planar electrode consisted of two α- Al 2 O 3 ceramic plates bonded each other. At one of the attached surface, a silver paste was coated. AC power supplies with 6Hz and 1kHz frequencies were used separately for the lab-scale test and a pilot-scale test, respectively to supply adequate electrical power in each experiment. The delivered electrical power was measured by automated power measurement system using a charge-voltage diagram (Lissajous diagram) [13] with an additional capacitor of 2 μf. For the SCR process, commercialized NH 3 SCR catalyst (SK Corp.) was used. To investigate the practical applicability of the plasma/scr combined process to real diesel exhaust, 3 hp rating marine diesel engine (Yanmar) was used (see Fig. 3). 1 Nm 3 /h was bypassed from a main exhaust stream, while the total flow-rate is about 1, Nm 3 /h at full load condition. Note that at this flow-rate Q = 1 Nm 3 /h, space velocities are S.V. = 4,5/h and 45,/h for the catalyst and the plasma reactor, respectively. NOx removal efficiencies were also measured with the FTIR spectrometer. Fig. 3. Pilot-scale plasma/scr combined system with marine diesel engine. III. RESULTS AND DISCUSSION A. Effects of Non-thermal Plasma on NOx In general, important chemical reactions relating to NO and NO 2 are as follows. NO + N N 2 + O (1) NO + O + M NO 2 + M (2) NO + O 3 NO 2 + O 2 (3) NO + OH + M HNO 2 +M (4) NO + HO 2 NO 2 + OH (5) NO 2 + N N 2 O + O (6) NO 2 + OH + M HNO 3 + M (7) NO 2 + O NO + O 2 (8) Fig. 2. Planar type DBD reactor. As can be seen in (1)-(8), radicals or molecules such as O, O 3, OH, N, and HO 2 are needed in the reactions. Since a non-thermal plasma was known to make lots of chemically active species, we used the DBD as the source of radicals.

Cha et al. 3 NO to NO 2 Conversion Rate [%] 6 5 4 3 2 1 1 o C, 5% load condition w/o HC W/ HC (C 3 H 6 ) 5 1 15 2 SED [kj/m 3 ] Fig. 4. NO to NO 2 conversion rate with SED for 5 % load condition. NO to NO 2 Conversion Rate [%] 1 8 6 4 2 Temperature [ o C] 1 15 2 25 3 5 1 15 2 SED [kj/m 3 ] 25% load Fig. 5. NO to NO 2 conversion rate with various operating temperatures for 25 % load condition. In N 2 /O 2 mixtures, much of a input energy could be used for O 2 dissociation rather than N 2 dissociation [11]. Furthermore since (1) is a relatively slow reaction, the reactions relating to N radical can not be considered for simplicity. In the present lab-scale experiment, we did not consider the effects of H 2 O. In this regard, (2), (3), and (8) can be important reactions. These O and O 3 involved reactions are composed with the oxidation of NO to NO 2 and the backward conversion of NO 2 to NO. In this point of view, one can conceive that at certain thermodynamic state including a concentration and temperature the reactions can be equilibrated, i.e., NO to NO 2 conversion can be saturated with the input power of plasma. Figure 4 shows NO to NO 2 conversion efficiencies along with a SED (specific energy density) defined as a input energy per the unit volume of a gas to be treated, i.e., SED = input power for plasma generation/gas flowrate. Here, the rectangle and circle symbols indicate simulated mixtures with and without HC (C 3 H 6 ), respectively, and a conversion efficiency was defined by the volume fraction of NO 2 for the total amount of NOx. As shown in the figure, for the case without HC, NO 2 conversion rate is relatively insensitive to SED demonstrating saturated feature at about 13 %. However, owing to the addition of HC, the production of NO 2 is significantly increased, for instance 45 % of NO is oxidized to NO 2 at SED = 2 kj/m 3. It is to be noted that the change of total amount of NOx (NO + NO 2 ) was negligible for both conditions, meaning that NOx can not be reduced to nitrogen by the sole process of a nonthermal plasma. The increase of NO to NO 2 conversion efficiency with the addition of propylene can be explained as follows. Propylene can be partially oxidized with the aid of O radical, and through this partial oxidation can produce lots of reactive species with a chain reaction [14]. Chemical reactions relating these species are NO + CH 3 O 2 NO 2 + CH 3 O (9) NO + O 2 C 2 H 4 OH NO 2 + OC 2 H 4 OH. (1) Above reactions are known as faster than (2) and (3). Furthermore in defect of O radical, the backward reaction of NO 2 to NO in (8) can be decreased. In this reason, high conversion efficiency can be obtained with the addition of HC. In Fig. 5, we plotted NO to NO 2 conversion efficiencies for various operating temperatures with the simulated gas of 25 % load condition. As can be seen, at 15 and 2 o C NO 2 conversion exhibits its optimum, while the conversion became deteriorated as the temperature increases. It partly because the temperature sensitive characteristic of (8) compared to (2), (3), (9), and (1), i.e., NO 2 to NO backward conversion reaction prevail over the NO oxidation at high temperatures. B. Characteristics of Plasma/SCR Combined Process NO NO 2 NH 3 O 2 NO + O, O 3, HO 2 NO, NO 2 + NH 2 Oxidation/Reduction Plasma Reactor NO NO 2 N 2 NH 3 N 2 O 2 NO, NO 2 + NH 3 Reduction NH 3 SCR Reactor Fig. 6. Concept of a plasma/scr hybrid system. H 2 O As discussed in the previous section, NOx can not be reduced to nitrogen with a non-thermal plasma process in the presence of oxygen. Some portion of NO was oxidized to NO 2 demonstrating negligible change of the total amount of NOx. In this regard, NH 3 SCR process was adopted after the plasma process to achieve the full reduction of NOx. In Fig. 6, the concept of plasma/scr combined process was depicted. As shown in the figure, plasma and SCR reactors are connected in series. In

31 International Journal of Plasma Environmental Science & Technology Vol.1, No.1, MARCH 27 NOx Reduction [%] 1 8 6 4 2 hybrid predicted SCR plasma plasma only (84 kj/m J/L) 3 ) SCR only plasma/scr 1 125 15 175 2 Temperature [ o C] Fig. 7. NOx reduction efficiencies for various processes for 25 % load condition of the diesel engine. NH 3 concentration is matched with that of NOx in Table I. Combustion flue gases, over 9 % of NOx consisted of NO. A plasma reactor converts a certain amount of NO to NO 2. Some portion of NO can be reduced by NH 2 radical within the plasma reactor. Then NO+NO 2 reduced to N 2 in NH 3 SCR reactor, since NO 2 or NO+NO 2 mixture could be more easily reduced at low temperature. Chemical reactions concerning NOx reduction in NH 3 SCR process are 4NO + 4NH 3 + O 2 4N 2 + 6H 2 O (11) NO + NO 2 + 2NH 3 2N 2 + 3H 2 O (12) Here, (11) represents the standard SCR reaction and (12) is correspond to so-called fast SCR reaction. The reaction rate of (12) is significantly faster than that of (11), especially when a gas temperature is lower than 2 o C [3, 8-1]. In addition, when NH 3 was injected before a plasma reactor, NH 2 radical produced from NH 3 by a plasma process also affects to NOx [3]. NH 2 + NO N 2 + H 2 O (13) NH 2 + NO 2 N 2 O + H 2 O (14) From (14), undesirable N 2 O formation occurred through a plasma process, however, in the present experiment, N 2 O leakage can not be detected after SCR reactor. Since over 9 % of NOx can be reduced to N 2 above 25 o C using a NH 3 SCR process, to identify synergetic effects with plasma process operating temperatures were varied from 1 to 2. We considered 25 % load condition in Table 1 and the amount of NH 3 was matched with that of NOx. In Fig. 7, we plotted NOx reduction rates for the non-thermal plasma, the NH 3 SCR, and the plasma/scr combined processes. As shown in the figure, for the plasma sole process with SED = 84 kj/m 3, about 3 % of NOx is removed irrespective of temperature through (13) and (14). On the contrary, for the SCR sole process, it shows significant dependence on temperatures. At 1 o C, NOx reduction rate is about 2 %, while it reaches about 85 % at 2 o C. However, the NOx reduction rate is dramatically changed for plasma/scr combined process in relatively low temperature. About 8 % of NOx can be reduced through the plasma/scr combined process in the temperature range of 1-15 o C. As depicted in Fig. 7 for 1 o C, the arithmetic sum of NOx reduction rate for plasma/scr combined process is about 36 %, i.e., 2% (plasma) + 8% (remained portion of NOx relative to the initial amount after the plasma reactor) 2% (SCR performance) = 36%. While it reaches at 8% for combined process demonstrating synergetic effect of combining two processes. This can be explained based on the fast SCR reaction, (12). A generated NO 2 within the plasma reactor can activate reaction in (12) in the SCR reactor. To clarify the synergetic results, we investigated de-nox efficiencies for the SCR sole process with flowmeter controled NO/NO 2 mixtures. As results, a NOx reduction rate for a mixture of NO+NO 2 showed its optimum at around [NO 2 ]/[NOx] =.4 to.6, which is the supportive result of fast SCR reaction. However, de-nox performance of combined process was deteriorated compared to SCR process over 17 o C as shown in Fig. 7. Through a parametric test with additives, we concluded that this result was originated from the HC addition. It was found that aldehyde, which is generated in the plasma reactor from HC, can serve as a reducing agent in catalytic process, while it reduced NO 2 to not N 2 but NO in the SCR reactor. C. NOx Removal in Diesel Engine Exhaust To investigate the applicability of the combined process in a diesel engine exhaust, we construct the 1 Nm 3 /h rating pilot-scale plasma/scr combined system as shown in Fig. 3. The engine was set to 25 % load condition throughout the whole experiments, and we put a heat exchanger into the exhaust line to control the exhaust temperature. The plasma reactor operated excellently with highly humid and sooting condition, and it worked properly even after 1, hr operatinging time. Since the NO to NO 2 conversion in plasma reactor was mainly related to the amount of C 3 H 6 addition as well as input power as shown in Fig. 4, we investigated NOx reduction rates of combined system for various input powers and C 3 H 6 addition first. It is to be noted that the additional C 3 H 6 was supplied through a mass flow controller. Figure 8 shows the NOx reduction efficiencies along with the normalized C 3 H 6 concentration for various input power conditions at 1 o C. As results, since de-nox efficiency is saturated at about 8%, we chose the combination of SED = 4 kj/m 3, which corresponds to 1.1 kw input power with flow-rate of 1 Nm 3 /h, and [C 3 H 6 ] = 1.5[NOx] = 8 ppm as an operating condition. Note that to determine an operating condition in commercial applications the comparison of fuel cost between making electricity with engine and supplying HC should be made.

Cha et al. 32 NOx Reduction Efficiency [%] 1 8 6 4 2 SED SED [kj/m [J/L] 3 ] (Q[Nm3/hr], P [kw]) 27 (2, 1.5) 4 (1, 1.1) 54 (1, 1.5) 81 (5, 1.1).5 1 1.5 2 2.5 3 3.5 [C 3 H 6 ]/[NOx] Fig. 8. NOx reduction efficiencies for various operating conditions. NOx Reduction [%] 1 8 6 4 2 4 4 kj/m J/L 3 (1 Nm 3 /hr, 1.1 kw) SCR plasma/scr [NO 2 ]/[NOx] 1 125 15 175 2 Temperature [ o C] Fig. 9. NOx reduction efficiencies for SCR and combined system together with the percentage of [NO 2 ]/[NOx] along with temperature. Figure 9 shows the NOx reduction rate for the plasma/scr combined system together with the SCR sole process along with operating temperatures for SED = 4 kj/m 3, flow-rate = 1 Nm 3 /h, [C 3 H 6 ] = 8 ppm, and [NH 3 ] = 55 ppm. Generally, the combined process exhibits superior performance to the SCR sole process. For instance, at 1 o C 2% NOx reduction occurs with the SCR sole process, while 8% of NOx can be reduced with the plasma/scr combined system. Furthermore, contrary to the results in Fig. 7, even at 2 o C 9% of NOx is reduced with combined system, while 55% reduction is obtained using the SCR sole process. It is to be noted that the portion of converted NO 2 in total NOx is in the range of 6 7% as shown in Fig. 9. Since it has been known that aldehydes can be used as reducing agents in some De-NOx processes [15], a back conversion (or incomplete reduction) of NO 2 to NO may occur in the SCR reactor by reacting with an aldehyde. In this regard, to achieve the fast SCR reaction (NO:NO 2 = 5:5) we need to convert NO to NO 2 in the plasma reactor more than 5%. However, further investigation should be needed to support aforementioned back conversion. To apply the combined system to the full-scale 3 hp rating diesel engine exhaust, we estimate the power consumption of the plasma reactor to be 5-6 kw approximately. This power can cover about 5 Nm 3 /h, which can be enough for a warming up period considering that the exhaust flow-rate is about 1, Nm 3 /h at full load. Since the estimated power corresponds to 2 % of the engine power, and moreover the plasma reactor should be turned off after exhaust temperature increases, probably the operating cost of the plasma reactor does not matter in practical applications. In addition, the degradation of catalyst from unwanted byproduct such as ammonium nitrate can be fixed by occasional high temperature (>25 o C) operations. D. Effects of Non-thermal Plasma on PM Through the present pilot-scale test, it was also found that the present planar type DBD can be effective to change the emission characteristics of PM. The size distribution and blackness of PM were measured at the outlet of the plasma reactor using a particle size analyzer and a smokemeter, respectively. Figure 1 shows the size variation of PM. As shown in the figure, the initial distribution pattern (solid line) is significantly altered by the plasma process (dotted line). With the aid of the plasma process the average size of PM is quite reduced to the order of 1 μm demonstrating the double peak of its distribution. While the average size is in the order of 1 μm for the untreated PM. Since the reduction of average size means the increase of total surface area of PM, this result can be helpful to a continuously regenerative DPF system, which used NO 2 as an oxidizing agent for PM. Furthermore, 45% reduction in the blackness can be observed with the plasma process. From the above results, we can conceive that through the plasma reactor mass reduction can be possible as well as its average size reduction. However, at present, the detailed mechanism of PM reduction is not clear, and further investigation will be a future study. Normalized Differential Volume 1.8.6.4.2 plasma on plasma off.1 1 1 1 Aerodynamic Diameter [μm] Fig. 1. Effect of plasma on the size distribution of PM in diesel exhaust. IV. CONCLUSION The non-thermal plasma process combined with

33 International Journal of Plasma Environmental Science & Technology Vol.1, No.1, MARCH 27 conventional NH 3 SCR process was successfully applied to the marine diesel engine exhaust. To treat 55 ppm of NOx from the diesel engine, we chose the flow-rate of 1 Nm 3 /hr, electric power of 1.1 kw (SED=4 kj/m 3 ), and 8 ppm C 3 H 6 addition among the various optimal operating conditions. Here, we need to supply as much amount of NH 3 as NOx, i.e., [NH 3 ] = 55 ppm for the SCR. As results, de-nox efficiencies for combined process were increased from 2 to 8 % and from 55 to 9% at 1 and 2 o C, respectively compared to the SCR sole process. We estimated that the power consumption is about 2 % of engine power. In addition to the NOx reduction, we found that PM in the diesel exhaust, mainly consists of soot, was affected by the plasma process. From the measurement of smoke-meter, over 45 % of PM were reduced after the plasma process. Furthermore, the size of PM is significantly decreased. It suggested that the non-thermal plasma process can be a viable method for PM reduction or assisted one for other DPF systems. Fundamentals and Supporting Technologies, Edited by B.M. Penetrante and S.E. Schultheis, Springer-Verlag: Berlin, Germany, p.65, 1993. [12] B.M. Penetrante, R.M. Brusasco, B.T. Merritt, W.J. Pitz, G.E. Vogtlin, M.C. Kung, H.H. Kung, C.Z. Wan, K.E. Voss, Plasma- Assisted Catalytic Reduction of NOx, SAE paper 98258, p.57, 1998. [13] R. Feng, G.S.P. Castle, S. Jayaram, Automated system for power measurement in the silent discharge, IEEE Trans. Ind. App., vol. 34, p. 563, 1998. [14] E.A. Filimonova, Y.H. Kim, S.H. Hong, Y.H. Song, Multiparametric Investigation on NOx Removal from Simulated Diesel Exhaust with Hydrocarbons by Pulsed Corona Discharge, J. Phys. D: Appl. Phys., vol. 35, p. 2795, 22. [15] T.M. Orlando, A. Alexandrov, A. Lebsack, J. Herring, J.W. Hoard, The Reactions of NO 2 and CH 3 CHO with Na-Y Zeolite and the Relevance to Plasma-Activated Lean NOx Catalysis, Catalysis Today, vol. 89, p. 151, 24. ACKNOWLEDGMENT This work was supported by National Research Lab. program of the Korean Ministry of Science and Technology, and Clean Energy program of the Korea Energy Management Corporation/R&D center. REFERENCES [1] A.G. Panov, R. Tonkyn, S. Yoon, A. Kolwaite, S. Barlow, M.L. Balmer, Effect of Simulated Diesel Exhaust Gas Composition and Temperature on NOx Reduction Behavior of Alumina and Zeolite Catalysts in Combination with Non-Thermal Plasma, SAE paper 2-1-2964, p. 73, 2. [2] T. Hammer, T. Kappes, M. Baldauf, Plasma Catalytic Hybrid Processes: Gas Discharge Initiation and Plasma Activation of Catalytic Processes, Catalysis Today, vol. 89, p. 5, 24. [3] S. Bröer, T. Hammer, Selective Catalytic Reduction of Nitrogen Oxides by Combining a Non-thermal Plasma and a V 2 O 5 - WO 3 /TiO 2 Catalyst, Applied Catalysis B: Environmental, vol. 28, p. 11, 2. [4] J. Hoard, M.L. Balmer, Analysis of Plasma-Catalysis for Diesel NOx Remediation, SAE paper 982429, p. 13, 1998. [5] T. Hammer, Pulsed Electrical Excitation of Dielectric Barrier discharge Reactor using Semiconductor Power Supplies, SAE paper 2-1-2894, p. 19, 2. [6] J. Hoard, P. Liang, M.L. Balmer, R. Tonkyn, Comparison of Plasma-Catalyst and Lean NOx Catalyst for Diesel NOx Reduction, SAE paper 2-1-2895, p. 27, 2. [7] M. Dors, J. Mizeraczyk, NOx Removal from a Flue Gas in a Corona Discharge-Catalyst Hybrid System, Catalysis Today, vol. 89, pp. 127, 24. [8] M. Koebel, G. Madia, M. Elsener, Selective Catalytic Reduction of NO and NO 2 at Low Temperatures, Catalysis Today, vol. 73, p. 239, 22. [9] M. Koebel, M. Elsener, G. Madia, Reaction Pathways in the Selective Catalytic Reduction Process with NO and NO 2 at Low Temperatures, Ind. Eng. Chem. Res., vol. 4, p. 52, 21. [1] I. Nova, C. Ciardelli, E. Tronconi, D. Chatterjee, B. Bandl-Konrad, NH 3 -NO/NO 2 Chemistry over V-based Catalysts and its Role in the Mechanism of the Fast SCR Reaction, Catalysis Today, vol. 114, p. 3, 26. [11] B.M. Penetrante, Plasma Chemistry and Power Consumption in Non-Thermal De-NOx. in proceedings of Non-Thermal Plasma Techniques for Pollution Control, Part A: Overview,