Performance Evaluation of Nonthermal Plasma Reactors for NO Oxidation in Diesel Engine Exhaust Gas Treatment

T. Yamamoto, B.S. Rajanikanth*, M. Okubo, T. Kuroki and M. Nishino Dept. of Energy Systems Engineering, Osaka Prefecture University 1-1 Gakuen-cho, Sakai-city, Osaka 599-8531, JAPAN Phone and Fax: 81-722-54-9230 E-mail: yamamoto@energy.oskafu-u.ac.jp *Dept. of High Voltage Engineering, Indian Institute of Science, Bangalore 560012, India

Abstract- The discharge plasma-chemical hybrid process for NOx removal from the flue gas emissions is an extremely effective and economical approach in comparison with the conventional selective catalytic reduction system. In this paper we bring out a relative comparison of several discharge plasma reactors from the point of NO removal efficiency. The reactors were either energized by AC or by repetitive pulses. Ferroelectric pellets were used to study the effect of pellet assisted discharges on gas cleaning. Diesel engine exhaust, at different loads, is used to a pproximately simulate the flue gas composition. Investigations were carried out at room temperature with respect to the variation of reaction products against the discharge power. Main emphasis is laid on the oxidation of NO to NO 2, without reducing NOx concentration (i.e., minimum reaction byproducts), with least power consumption. The produced NO2 will be totally converted to N2 and Na2SO4 using Na 2 SO3. The AC packed bed reactor and pelletless pulsed corona reactor showed better performance, with minimum reaction products for a given power, when the NO concentration was low (~100 ppm). At high engine loads (NO > 300ppm) there was not much decrease in NOx reduction and more or less all the reactors performed equally. The paper discusses these observations in detail. I. I NTRODUCTION Flue gas emissions and automobile emissions are chief contributors to the ever-increasing environmental problems like global warming, acid rain, smog etc. The governing laws are becoming more and more severe and in order to meet the tougher emission regulations continuous development is being taken place in the pollution abatement technology all over the globe. Among the major air pollutants, the NOx

removal from flue gases and CO removal from auto emissions are of chief concern today. In this paper, we focus our attention on the NO abatement in diesel engine exhaust gas treatment. At present, several catalytic based conventional techniques, like selective catalytic reduction process (SCR), DeNOx burners etc., exist for NO abatement. Improved NO reduction techniques like fuel injection timing, exhaust gas recirculation etc., have also been investigated. These conventional techniques, however, hardly meet the future stringent emission regulations. Therefore, the establishment of a low, cost-effective, NO/NOx after treatment technology is desired. One of the promising ways to control NOx is by using electrical discharge plasma-chemical hybrid process, which is extremely effective and economical approach in comparison with the conventional selective catalytic reduction system [1-3]. Literature is abound with many innovative nonthermal plasma techniques which have proved to be successful in controlling various air borne pollutants [1-18]. Researchers have reported several designs of plasma reactors for gas treatment. Each reactor has its own advantages depending on the gas conditions and electrical parameters. In the present paper, three commonly used nonthermal plasma reactors namely, AC energized pellet bed reactor and pulse energized reactor with/without pellets, were studied for their performance evaluation. In order to approximate the flue gas emission the real exhaust of a small-scale diesel engine was used. Experiments were carried out at room temperature and at different engine load conditions. II. EXPERIMENTAL S ETUP AND PROCEDURE Figure 1 shows the schematic of experimental setup. A 2 kW diesel generator (3600 rpm, single cylinder, direct fuel injection, Yammer diesel Co., YDG200SS-6E) was used as the source to closely simulate flue gas emissions. The load on engine was adjusted by changing the resistance of an electric

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Diesel engine Glass filter Silica gel Pump

Flow meter Power supply Plasma Thermometer reactor Oscilloscope

Discharge Power (W)

Drain pot

10 9 8 7 6 5 4 3 2 1 0 0 10

60 Hz AC 210 Hz Pulse (no pellets) 210 Hz Pulse (BaTiO3 pellets)

Heater Exhaust Gas analyzer

Probe

20 30 Output Voltage (kV)

40

50

Fig. 1 Experimental setup for gas treatment

Fig. 3 Discharge power variation of the reactors temperature). The reactor was Pyrex glass tube of 20 mm diameter with a 1.5 mm corona electrode placed co-axially. The effective length of the tube is 26 cm. The tube is wrapped with a copper mesh forming the ground electrode. For energization, a 60 Hz AC supply or a 210 Hz pulse supply (supplied through a rotary spark gap switch) was used. The applied voltage was measured by an oscilloscope (Sony Tektronix TDS380P-2GS/s) through a voltage divider (Sony Tektronix P6015A).

(a)

Fig. 2 Rising portion of the pulse for two reactors: (a) no pellets and (b) with BaTiO3 pellets

heater. A part of the exhaust gas was sampled with a vacuum diaphragm pump and coarse particles, such as carbon soot, were removed by a glass-wool filter. Smaller particles were then removed using a series of drain pots containing hollow-fiber membrane filters (0.01mm pore diameter). Moisture content in the gas is minimized using a silica gel suspension. As a result, an absolute humidity of about 0.4 mg/L (relative humidity, 2.6%) was obtained at the room temperature. An AC driven pellet-bed reactor, pulse driven pellet-bed reactor and a pulse driven pelletless reactor, were investigated for NO oxidation. The pellet bed consists of 1.7~2.0 mm diameter barium titanate (BaTiO3) ferroelectric pellets (relative dielectric constant of 10,000 at room

The gas flow was controlled using a valve and a float-type flow meter. The treated gas, before being fed into the analyzer, was made to pass through a heater to remove ozone. The heater temperature was maintained at 300C. The NO in the exhaust gas was effectively oxidized to NO 2 with moderate plasma power. The concentration of gas components such as CO, NO, and NOx was measured using a gas analyzer (Horiba Co., VIA-50). The concentrations of CO2 and humidity were measured using gas detection tubes (Gastec Co.). III. RESULTS AND DISCUSSION At first, without any energization, the gas concentrations from the diesel engine were measured at different engine loads (K). NO concentration increases from 92 to 560 ppm and NOx concentration increases from 145 to 600 ppm when K varies from 0 to 100%. On the other hand, NO2 concentration was in the range of 40~60 ppm, irrespective of K. Figure 2 shows the pulsed voltage waveforms for the reactor with and without pellets. The pulse ris e time was 6.1 ns for the pelletless reactor and 13.7 ns for that with pellets. The applied voltage was about 26 kV. The pulse duration

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1200 NO, NO2, NOx, CO concentrations (ppm) 1000 800 600

20 CO2, O2 concentrations (%)

150 100 50 0 0 0.2 0.4 0.6 Discharge Power (W) 0.8 1 NO NOx NO2 CO 600 400 200 0

Q=4.0 L/min 400 T=20

200 0 0 25 50 Load (%) 75

10 8 6 4 2 0 100

Fig.4

Initial Gas concentrations of diesel engine exhaust at different loads

250

(a)
1200 1000 800 600

NO, NOx, NO2 (ppm)

150 100 50 0 0 0.2 0.4 0.6 Discharge Power (W) 0.8 1

Figure 3 shows the power consumption of the three plasma reactors. It is clear that the pulsed corona without pellets showed the lowest power consumption, followed by the pulsed corona with BaTiO 3 pellets and 60 Hz AC packed-bed plasma reactor. Figure 4 shows the concentrations of the diesel emission plotted against the engine load K. The concentration of NOx, NO, NO2 and CO were shown in the left Y-axis and the concentration of CO2 and O , in volume %, is shown on the 2 right Y-axis. When the load K changed from 0 to 100 %, NO concentration increases from 92 to 560 ppm and NOx concentration increases from 145 to 600 ppm which is almost proportional to the load factor K. On the other hand, NO2 concentration was in the range of 40~60 ppm. The concentration of CO becomes 1,080 ppm at K=0%, decreases with increase in K and becomes minimum value of 360 ppm at K=75 %. It increases again to reach 460 ppm at K=100 %. The concentration of CO2 increases from 2.0 % to 5.3 % with increasing K. The concentration of O2 decreases from 16.7 % to 10.4 % with increasing K. Figure 5 shows the gas concentration plotted against (a) the discharge power at the reactor for AC packed-bed plasma reactor when K=0%. The flow rate and the absolute humidity were set at 3.0 L/min and 0.4 mg/L, respectively, throughout the experiments. The initial NO concentration of 105 ppm was effectively oxidized to NO2 at 0.4 W. It is important to note that the plasma reactor should operate at 0.4 W, which gives least NOx reduction, indicating minimum byproducts formation such as N2O, HNO2 and HNO3. The concentration

NO NOx NO2 CO

400 200 0

(b)
250 200 150 600 100 50 0 0 1 2 3 4 Discharge Power (W) 5 6 1200 1000 800 CO (ppm)

NO, NOx, NO2 (ppm)

NO NOx NO2 CO

400 200 0

(c) Fig. 5 Gas concentrations at different discharge powers for 0% load on diesel engine : (a) AC (b) pulse with no pellets (c) pulse with pellets

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CO (ppm)

was 1.2 ms in both the cases. The voltage and current wave forms for the AC packed-bed reactor was already reported in [4].

200

CO (ppm)

14 12

NO, NOx, NO2 (ppm)

NO NO 2 NO x

CO 18 CO 2 O2 16

250 200

1200 1000 800

of CO remained the same at any discharge power. Figure 5(b) shows the gas concentration for the pulsed corona without pellets when K=0%. The initial NO concentration was about 135 ppm but almost complete NO oxidation was achieved at 1.0 W. The higher NOx concentration compared with the initial NOx concentration was attributed to the oxidation of air. The concentration of CO increased with the power. This may be attributed to the oxidation of residual carbon soot in the reactor and/or plasma reduction of CO2 . Figure 5(c) shows the gas concentration for the pulsed corona with pellets when K=0%. The initial NO concentration of 125 ppm was totally converted to NO 2 at 5.0 W. The AC packed-bed reactor and the pulsed corona pelletless reactor achieved the best NO reduction for a given power (0.4W) while treating the low NO concentration (<130 ppm). The produced NO2 was totally converted to N and 2 sodium sulfate (Na2SO4 ) using an aqueous solution of sodium sulfite (Na2 SO3) [1-3]. The Na2 SO4 solution is water soluble and a nontoxic compound. The trace amount of reaction byproducts such as HNO2 and HNO3 can be easily neutralized by NaOH scrubbing [2,3]. Figure 6(a) shows the gas concentration plotted against the power consumption for the AC packed-bed plasma reactor when K=50%. The initial NO concentration is approximately 300 ppm and was effectively oxidized to NO2 at 5.6 W, which requires significantly greater power compared with that needed at K=0% (0.4W).
Gas Concentration (ppm)

700 Gas Concentration (ppm) 600 500 400 300 200 100 0 0 1 2 3 4 5 Discharge Power (W) 6 7
N O NOx NO2 CO

(a)
700 Gas Concentration (ppm) 600 500 400 300 200 100 0 0 0.5 1 1.5 2 Discharge Power (W) 2.5 3
NO NOx NO2 CO

(b)
700 600 500 400 300 200 100 0 0 1 2 3 4 5 Discharge Power (W) 6 7
NO NOx NO2 CO

Figure 6(b) shows the gas concentration for the pulsed corona without pellets when K=50%. The initial NO concentration was reduced by about 80%, without reducing NOx, at 2.0 W. Figure 6(c) shows the gas concentration for the pulsed corona with pellets when K=50%. The initial NO concentration was fully converted to NO2 at about 4.0 W. It is clear that the AC packed-bed reactor and the pulsed corona reactor with pellets achieved the best NO reduction. However, for a given power (2.0 W), the p ulsed corona without pellets performed better. Again, the reaction byproducts such as HNO2 and HNO3 were minimum because of less NOx reduction. The AC packed-bed reactor and the pulsed corona reactor with pellets achieved the best NOx reduction for treating medium NO concentration (~300 ppm). However, for a given power for example at 2.0 W, the pulsed corona without pellets achieved better performance. Figure 7(a) shows the gas concentration plotted against the reactor power for the AC packed-bed plasma reactor

(c) Fig. 6 Gas concentrations at different discharge powers for 50% load on diesel engine : (a) AC (b) pulse with no pellets (c) pulse with pellets

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NO, NOx, NO2 (ppm)

400 300 200 NO NO2 0 1 2 3 4 5 Discharge Power (W) 0 6 7 NOx CO 100

400 300 200 100 0

Figure 7(b) shows the gas concentration for the pulsed corona without pellets when K=100%. The NO conversion was about 40% at 2.0 W. The CO concentration was changed from 1,000 ppm to 1,280 ppm. The initial CO value contradicts with the data shown in Figure 4 (440 ppm). This was due to the change in air to fuel mixture ratio of the diesel engine itself. Figure 7(c) shows the gas concentration for the pulsed corona with pellets when K=100%. The initial NO concentration was about 40% at 5.0 W. It is clear that the all reactors performed about the same for a given power. However, the CO concentration was significantly higher for the pulsed corona with pellets. The NOx reduction from the diesel engine was limited up to 300 ppm of NO concentration using the nonequilibrium plasma. In order to treat higher NO concentration, the NO2 produced must be removed to avoid the dissociation of NO2 (NO2 + O NO + O2). In this way, we can achieve a high NOx removal efficiency plasma reactor. Now, we estimate the power consumption for the plasma-chemical hybrid process. When the flow rate is 3.0 L/min and the power consumption is 2.0 W for the case of the pulsed corona without pellets, the specific energy density becomes 40 J/L (54 eV/molecule). The electrical cost becomes $400/ton of NO ($0.05/kW-hr was assumed). The operating cost for the chemical reactor becomes about $1,800/ton of NO 2 reduction when the NO concentration is 300 ppm ($0.48/kg was assumed for Na2 SO3). Therefore, the total operating cost of the plasma-chemical hybrid system becomes $2,200/ton of NO, which is less than 1/6 of the conventional selective catalytic reduction process. IV. CONCLUSIONS Three types of plasma reactors, AC pellet bed, pulse without pellets and pulse with pellets, were evaluated for NO oxidation using a real diesel engine emission. Both AC and pulsed corona without pellets showed the best performance with minimum reaction products for a given power when the NO concentration was low (~100 ppm). However, the NOx reduction was significant with increased NO concentration and three reactors were performed more the less the same when the the engine load was high (NO>300 ppm). Also, the

(a)
700 600 NO, NOx, NO2 (ppm) 500 400 300 200 100 0 0 0.5 1 1.5 2 Discharge Power (W) 2.5 3 NO NO2 NOx CO 1400 1200 1000 800 600 400 200 0 CO (ppm)

(b)
700 600 NO, NOx, NO2 (ppm) 500 400 1000 300 200 100 0 0 1 2 3 4 5 Discharge Power (W) 6 7 1500 CO (ppm) 2000

NO NO2

NOx CO

500

(c) Fig. 7 Gas concentrations at diffrent discharge powers for 100% load on diesel engine : (a) AC (b) pulse with no pellets (c) pulse with pellets

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CO (ppm)

when K=100%, which gives the highest initial NO concentration (approximately 550 ppm). The NO to NO2 conversion was about 56% at 5.6 W. Obviously, the NO oxidation is more difficult for high NO concentration. However, the reaction byproducts were minimum because of little change in NOx.

700 600 500

800 700 600 500

CO concentration increased significantly when the engine load was high. In order to achieve the higher NOx reduction, the NO2 dissociation should be minimized. The total operating cost of the plasma-chemical hybrid system becomes $2,200/ton of NO, which is less than 1/6 of the conventional selective catalytic process. ACKNOWLEDGEMENT This work was partially supported by Grant-in-Aid for Scientific Research (B) of the Japanese Society for the Promotion of Science REFERENCES [1] T. Yamamoto, P.A. Lawless, M.K Owen, D.S. Boss and C. Boss, Decomposition of Volatile Organic Compounds by a Packed-Bed Reactor and a Pulsed Corona Reactor, Nonthermal Plasma Techniques for Pollution Control, (Ed. by B.M. Penetrante), NATO ASI series, Vol. 34, pp.223-238, 1993. B.M. Penetrante, "Plasma Chemistry and Power Consumption in Non-Thermal Plasma DeNOx." Ibid, pp.65-89, 1993. T. Yamamoto, C.L. Yang, Z. Kravets, and M. Beltran, "Plasma-Assisted Chemical Process for NOx Control," IEEE Transactions on Industry Applications, Vol. 36, No. 3, pp. 923-927, 2000. C.L Yang, T. Yamamoto, M. Beltran, and Z. Kravets, Corona-Induced Chemical Scrubber for the NOx Emission, Environmental Progress, Vol. 17, No. 3, pp. 183-189, 1998. T. Yamamoto, M. Okubo, K. Hayakawa, and K. Kitaura, Towards Ideal NOx Control Technology Using Plasma-Chemical Hybrid Process, Proceedings of the 1999 IEEE Industry Applications Conference, Phoenix AZ, pp. 1495-1504, 1999. M.B. Penetrante, "Non-Thermal Plasma Reactors for Treatment of NOx and Other Hazardous Gas Emissions," Task 1.1 Report for CRADAT, #336-92-1-C, October, 1993. A. Mizuno, K. Shimizu, K. Yanagihara, K. Kinoshita, H. Tsunoda, H. Kim and S. Katsura., "Effect of Additives and Catalysts on Removal of Nitrogen Oxides Using Pulsed Discharge," Proc. of 1996 IEEE-IAS Annual Meeting, San Diego, CA, Vol. 3, pp 1808-1812, 1996. T. Oda, T. Kato, T. Takahashi, and K. Shimizu, "Nitric Oxide Decomposition in Air by Using Non-Thermal

Plasma Processing - with Additives and Catalyst," Proc. of 1996 IEEE-IAS Annual Meeting, San Diego, CA, Vol. 3, pp 1803-1807, 1996. [9] T. Oda, T. Kato, T. Takahashi, and K. Shimizu, "Nitric Oxide Decomposition in Air by Using Non-Thermal Plasma Processing," Proc. of IEJ-ESA 1996 Joint Symposium on Electrostatics, Univ. of Tokyo, Tokyo, Japan, pp. 17-28, 1996.

[10] G.E. Vogtlin, and B.E. Penetrante, "Pulsed Corona Discharge for Removal of NOx from Flue Gas," Nonthermal Plasma Techniques for Pollution Control, (Ed. by B.M. Penetrante), NATO ASI series, pp.187-198, 1993. [11] K. Fujii, M. Higashi, and N. Suzuki, "Simultaneous Removal of NOx, COx, SOx, and Soot in Diesel Engine Exhaust," Nonthermal Plasma Techniques for Pollution Control, (Ed. by B.M. Penetrante), NATO ASI series , pp.257-279, 1993. [12] H. Shaw, "Aqueous Solution Scrubbing for NOx Control in Munitions Incineration," The American Society of Mechanical Engineers, August, 1976. [13] S. Broer, T, Hammer, and T. Kishimoto, "Pulsed Excitation of Silent Discharges for Diesel Exhaust Treatment," Proc. of the Fourth International Conference on Advanced Oxidation Technologies for Water and Air Remediation, Sept. 23-26, p. 57, 1997. [14] H.H. Kim, K. Tsunoda, S. Katsura, and A. Mizuno, "A Novel Plasma Reactor for NOx Control Using Photocatalyst and Hydrogen Peroxide Injection," Proc. of the 1997 IEEE-IAS meeting, New Orleans, pp. 1937-1941, 1997. [15] S. Futamura, A. Zhang and T. Yamamoto, Mechanisms for Formation of Inorganic Byproducts in Plasma Chemical Processing of Hazardous Air Pollutants, IEEE Transactions on Industry Applications, Vol. 35, No. 4, pp. 760-766, 1999. [16] G. Dinell, L. Civitano and M. Rea, Industrial Experiments on Pulsed Corona Simultaneous Removal of NOx and SO2 from Flue Gas, IEEE Transaction on Industry Applications, Vol. 26, 3, pp. 535-541, 1990. [17] T. Yamamoto, B.S. Rajanikanth, M. Nishino M. Okubo, and T. Kuroki, Characteristics of the plasma reactor on diesel emission control, Proc. of 12th International Symposium on High Voltage, ISH-2001, Bangalore, India, 2001 (to be published).

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[18] H.H. Kim, K. Tsunoda, K. Shimizu, S. Tanaka, T. Yamamoto and A. Mizuno, Experimental Approach to Enhance Efficiency of Non-thermal Plasma Process

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