,

, 171

e-mail: yhsong@mailgw.kimm.re.kr

I.

, .

NH3 SCR , VOCs (Volatile Organic Compounds), , PFC

CFC, , HCl, .

,

[1, 2, 3, 4, 5, 6].

1) , 2) 2 , 3)

, 4) [7, 8].

[5, 9, 10], NOx [11, 12, 13], [14, 15],

VOCs [16, 17, 18], PFC [19] .

, , . review paper

[20, 21, 22, 23], 6 .

, .

II.

( ) , . ,

, . (thermal plasma) (non-thermal

plasma) , 10,000 K , (Glow Discharge)

1000 K [20]. 1

. 1

, (Glow Discharge).

,

(electrical field intensity: E = kV/cm) (n: molecule , cm-3). E/n

(Towsend number, kVcm2) , 1 Towsend 100 Towsend [21].

E/n , E/n , E , emitter

(ground) .

, . 2 , 2

(Positive Corona) (Negative Corona) ,

[20].

1. -

2.

2 .

, .

. ,

.

. 3 100 Intensified CCD

light emission 3-(a)3-(b) .

emitting wire ground plate . wire 1.2 mm , wire plate 30 mm

. 3

.

.

(a) (b)

3. (a) DC 24 kV , (b) nano-pulse 22 kV

, 1) pulse , 2) , 3)

. pulse 4 (a) emitting wire needle . carrier gas

, 1) , 2) magnetic pulse compressor

, 3) [24]. 4 (b)

emitter ground tube pellets , coronasilent discharge (barrier discharge)

. Siemens 19,

[18]. carrier gas spark corona,

[25, 26].

4 (a) needle-plate

4 (b) barrier discharge

NO C2H4 pulse coronabarrier discharge

, 5. pulse

300 nsec , barrier discharge glass pellets 60 Hz. 5

(eV) , . carrier gas , NO 60 %

C2H4 66.7 %. Penetrante[27] pulse corona barrier discharge

, . Penetrante 1)

PFC, CH4gas , 2)

,

.

5. NO C2H4 pulsed corona barrier discharge

III.

NO C2H4NO VOCs .

30

, [27, 28, 22, 23].

, [23]. ,

1) carrier gas( ), 2)

(chemical species) .

N2 + O2 + NO N2 + NO NO .

OH radical OH radical , O radical NO (NO + O + M → NO2 + M)

[22].

(R1) NO + N → N2 + O k: 3.25 × 10-11 cm3/sec

(R2) NO + O3 → NO2 + O2 k: 4.6 × 10-14 cm3/sec

(R3) NO2 + O → NO + O2 k: 5.2 × 10-12 exp (+ 200/T) cm3/sec

6 carrier gas , NONO 1) NO

, 2) . , NO

95 % NO2 NOx (R1)

. NO , NONO 1) NO

(R2) O radical NO2 R(3), 2) NO O radical life time

(msec ) O radical (R3)(R2) . , life time O radical

O3 life timeNO , O3 NO NO2

chemiluminescense analyzerO3 [29].

6. NO NO

1) carrier gas O3 NO(R2) , 2) N radical (R1) , 3)

NO (R2) (R3) NO

. (R3) NONO2 1) NO2 N2 ,

2) , (R3)

.

NO N2 (R1) N2 carrier gasNO packed bed NO

. N2 carrier gas NONO NO ,

O radical life time msec N radicalNO . NO

NO 7NO , carrier gas

NO2 NO N2 R(1). NO 60 %

20 W , 310 eV/NO molecule specific energycarrier gas NO 60 % specific energy 40 eV/NO molecule

. carrier gas (R1). NO

NO (R1) N2, Yan, et al. [30]

carrier gas O2 3.6 % NO NO2

. chemical kinetic simulation

, 8.

7. N2 + NO NO NO2

8. N2 + NO gas NO, NO2, O3

NO C2H4 VOCs (Volatile Organic Compounds)[16, 19],

.

O + VOCs → COx + H2O + byproducts

OH + VOCs → COx + H2O + byproducts

O3 + VOCs → COx + H2O + byproducts

e + VOCs → COx + H2O + byproducts

X- + VOCs → COx + H2O + byproducts

e , X- . byproductsNxOy VOCs , O3byproducts . NO O3 NO

O3 , VOCs O3NO [31] VOCs O3

. C2H4,

byproducts .

9 carrier gas C2H4 packed bed ,

C2H4 . life time O3

O3 O, ,

O3 . , C2H4 O3toluene C3H8

, C2H4. O3 NO O3

VOCs O3 1) O3 , 2) O3

. toluene ,

[32].

9. C2H4

VOCs O3 O3N2 carrier gas C2H4 . 10

N2 carrier gases C2H4, carrier gas C2H4

C2H4. 10 55 % C2H4 40 W

, 600 eV/C2H4 molecule specific energy67 % C2H4 specific energy 40 eV/C2H4 molecule

15 . O3

. NO O3VOCs O3

O3 O3.

10. Carrier gas N2 Air C2H4

NO C2H4carrier gas ,

. O3 , OH radical NO

. , SO2 OH radicalNO NO2

[33].

IV.

a.

. ,

. MeV,

1-20 eV.

'70 (JAERI)

(Bench-Scale) , EBARA

100 MW [34, 35]. '80,

, , , .

95 %, 80 % , 1.5 % . ,

1) , 2)

. 80 %

[35].

'80 [7, 8].

(ENEL) [36], 80 0.3 MW. 80 %, 60 % ,

5.4 %. , ENEL

, 40 % .

.

'94 , , '96

0.5 MW . 11 0.5 MW2,000 Nm3/hr , 30 kW

. 95 %, 80 %, 1.5 - 2 % [9, 37].

11. - - 0.5 MW

0.5 MW ENELENEL

0.5 MW. Lawrence

Rivermore National Lab[38],

. , Masuda Lab

30 % [39] [4].

, .

, , , .

, 1) spark-gap switch, 2) thyrister, 3) thyratron, 4) magnetic pulse switch . spark-gap switch 106 shot

, Thyrister micro . , Thyratron

nano 109 shot300 Hz 1 - 2 .

nano micro thyratronmagnetic pulse compressor [40]. magnetic pulse compressors

1010 300 Hz 1 .

30 kW, 80 % Thyratron

magnetic pulse compressors , magnetic pulse compressors 0.5 MW

.

0.5 MW , , ,

. 1, , .

10 MW, '99 .

1.

b.

NOx , VOCs, PFC, , , , , CO2

. , NH3 SCR (Selective

Catalytic Reduction) NOx PFC .

5 % gasoline 1% 3 way catalyst .

CO2 lean burn , lean burn NOx

. lean burn NOx

2,000 Nm3/hr 35,000 Nm3/hr

- : 95 %, : 80 % - : 3.3 Whr/Nm3

- NH3/- /

10,000 Nm3/hr

- : 80.5 %, : 46 %

3,000 Nm3/hr

- : 28 %, : -

- NH3

5,000 Nm3/hr

- : 95 %, : 60 % - : 2.6 Whr/Nm3

- NH3/

1,000 Nm3/hr

- : 42 % - : 23 Whr/Nm3

-

, lean burn NOx 1) , 2) , 3)

[41].

Lawrence Livermore Nat'l Lab Engelhard plasma[11], 1) NO HC

(hydrocarbon) NO NO2 , 2) γ-Al2O3 NO2

. HCNH3 SCR NH3

. Plasma/catalyst Ford [12] Fraunfoufer [42] .

, NH3 SCR temperature windowspace velocity Siemens AG

[13]. NOx 95 % NO NO2 , NH3SCR NO2/NO temperature space velocity , size . Siemens AGNH3 ,

100 C.

PFC1200 C ppm order

99.9 % gas enthalpy. NOx

. SWRI Los Alamos Nat'l LabPFC ,

[19]. KC tech ( ) '98 ,

. KC tech 2 kW pulse LG ( ) , pulse

100 nsec IGBT.

VOCs [16, 17], , NOx, [14,15]

, .

, - , ,

.

VI.

. , .

/ , , by-product , .

, VOCs PFC , NOx .

1. , " NO ", , 45 , 9 , pp. 1324-1330, 1996

2. , , , , "", 11 2 , pp. 185-190, 1995

3. , , , , " Pellet VOCs (I)", , 18 , 5 , pp. 543-

550, 1996

4. , , , , , , , , , , " ",

, 12 , 4 , pp. 487-494, 1996

5. Mok, Y-S., I-S., Nam, R-W., Chang, S-W., Ham, S-H., Kim, and Y-M., Jo "Application of Positive Pulsed Corona Discharge to Removal of SO2 and NOx", Proceedings of 7th International Conference on Electrostatic Precipitation, September 20-25, Kyongju, Korea, 1998

6. Chae, J-O., Kim, B-G., Kwon, Y., Kim, J-S., "DeNOx Pilot Plant Scale Experiment with Exhaust from Stainless Steel Production Plant", Proceedings of 7th International Conference on Electrostatic Precipitation, September 20-25, Kyongju, Korea, 1998

7. L. Civitano, "Industrial application of pulsed corona processing to flue gas", NATO ASI Series, Vol. G34, Part B, Electron Beam and Elec. Discharge Processing, pp. 103-130, 1993

8. S. Masuda, "Report on novel dry DeNOx/DeSOx technology for cleaning combustion gases from utility thermal power plant boilers", NATO ASI Series, Vol. G34, Part B, Electron Beam and Elec. Discharge Processing, pp. 131-137, 1993

9. Song, Y-H., Shin, W-H., Choi, Y-S., Kim, S-J., Paik, M-S., Jang, G-H., "Industrial Application of Pulsed Corona Process for Treating Combustion Flue Gases", J. Advanced Oxidation Technologies, in press 1999

10. Song, Y-H., Shin, W-H., Choi, Y-S., Kim, S-J., Paik, M-S., Jang, G-H., "Effects of Chemical additives on Pulsd Corona Process to Treat Combustion Flue Gases", Proceedings of 7th International Conference on Electrostatic Precipitation, September 20-25, Kyongju, Korea, 1998

11. B.M. Penetrante, R.M. Brusasco, B.T. Merritt, W.J. Pitz, G.E. Vogtlin, M.C. Kung, H.H. Kung, C.Z. Wan, and K.E. Voss, "Plasma-Assisted Catalytic Reduction of NOx", SAE982508, 1998

12. J. Hoard and M.L. Balmer, "Analysis of Plasma-Catalysis for Diesel NOx Remediation", SAE 982429, 1998

13. T. Hammer and S. Broer, "Plasma Enhanced Selective Catalytic Reduction of NOx for Diesel Cars", SAE 982428, 1998

14. A. Tamaki and S. Hosokawa, "Reduction of Chemical Pollutants in the Exhaust Gas of the Municipal Waste Incinerator by PPCP", Proceedings of 6th International Conference on Electrostatic Precipitation, June 18-21, Budapest, Hungary, 1996

15. J.S. Carlow, R.F. King, and R. McAdams, "The Use of Pulsed Corona Technology to Destroy VOCs, Dioxins and Furans at a Municipal Solid Waste Incinerator", Proceedings of 6th International Conference on Electrostatic Precipitation, June 18-21, Budapest, Hungary, 1996

16. Yamamoto, T., K. Mizuno, I. Tamori, A. Ogata, M. Nifuku, M. Michalska, and G. Prieto, "Catalysis Assisted Plasma Technology for Carbon Tetrachloride Destruction", IEEE Trans. Ind. Appl. 32(1), 100-105, 1996

17. Yamamoto, T., "VOC Decomposition by Nonthermal Plasma Processing - A New Approach, J. of Electrostatics, 42, 227-238, 1998

18. L.A. Rosocha, G.K. Anderson, L.A. Bechtold, J.J. Coogan, H.G. Heck, M. Kang, W.H. McCulla, R.A. Tennant, and P.J. Wantuck, "Treatment of Hazadous Organic Wastes Using Silent Discharge Plasmas", NATO ASI Series, Vol. G34, Part B, Electron Beam and Elec. Discharge Processing, pp. 281-308, 1993

19. Coogan, Jassal, and Artar, "Silent Discharge Plasma for Point-of-Use Abatement of VOC Emissions", Technology Transfer #97023244A-ENG,

http://www.Sematech.org/public/docubase

20. T.G. Beuthe and J.S. Chang, "Gas discharge phenomena", Handbook of Electrostatic Process, Marcel Dekker, Inc., pp. 147-193

21. B. Eliasson and U. Kogelshatz, "Nonequilibrium Volume Plasma Chemical Processing, IEEE Trans. Plasma Science, Vol. 19, pp. 1065-1077, 1991

22. H. Mazing, "Chemical Kinetics of Flue Gas Cleaning By Irradiation with Electrons", Advances in Chemical Physics Volume LXXX, John Wiley & Sons, Inc., 1991

23. G.E. Vogtlin and B.M. Penetrante, "Pulsed corona discharge for removal of NOx from flue gas", NATO ASI Series, Vol. G34, Part B, Electron Beam and Elec. Discharge Processing, pp. 187-198, 1993

24. E.L. Neau, "Environmental and industrial applications of pulsed power systems", IEEE Trans. Plasma Science, Vol. 22, NO.1, pp. 2-10, 1994

25. S. Kanazawa, J.S. Chang, G.F. Round, G. Sheng, T. Ohkubo, Y. Nomoto, and T. Adachi, "Reduction of NOx from Flue Gas by Corona Discharge Activated Ammonia Radical Showers", Combus. Sci. and Tech., vol 133, pp. 93-105, 1998

26. O. M. Yardimic, L.A. Kennedy, S.A. Nester, A.V. Saveliev, and A.A. Fridman, "Plasma-Catalytic Treatment of Organic Compounds in Atmospheric Pressure Non-Equillibrium

Discharges" SAE 982427, 1998

27. Penetrante, B.M., "Comparison of Electrical Discharge Techniques for Non-Thermal Plasma Processing of NO in N2", IEEE Trans. Plasma Sci. 23, 679, 1995

28. Lowke, J.J. and R. Morrow, "Theoretical Analysis of Removal of Oxides of Sulfur and Nitrogen in Pulsed Operation of Electrostatic Precipitators", IEEE Trans Plasma Science, Vol. 23, No. 4, pp. 661-671, 1995

29. , , , " NO ", , 1999

30. K. Yan, S. Kanazawa, T. Ohkubo, and Y. Nomoto, "Oxidation and Reduction Processing During NOx Removal in N2 + O2 with Corona Induced Non Thermal Plasma", Proceedings of 7th International Conference on Electrostatic Precipitation, September 20-25, Kyongju, Korea, 1998

31. Atkinson, R. "Kinetics and Mechnisma of the Gas-Phase Reactions of the Hydroxyl Radical with Organic Compounds under Atmospheric Conditions", Chemical Reviews, 85(1), 69-201, 1985

32. , , , "" , 1999

33. H.H. Kim, C. Wu, S. Katsura, and A. Mizuno, "Non-thermal Plasma Processing for De-NOx/SOx", Proceedings of 7th International Conference on Electrostatic Precipitation,September 20-25, Kyongju, Korea, 1998

34. N. Frank and S. Hirano, "The History of Electron Beam Processing for Environmental Pollution Control and Work Performed in the United States", NATO ASI Series, Vol. G34, Part B, Electron Beam and Elec. Discharge Processing, pp. 1-26, 1993

35. A. Maezawa and M. Izutsu, "Application of e-beam Treatment to Flue Gas Cleanup in Japan", NATO ASI Series, Vol. G34, Part B, Electron Beam and Elec. Discharge Processing, pp. 47-54, 1993

36. G. Dinelli, L. Civitano, and M. Rea, "Industrial experiments on pulse corona simultaneous removal of NOx and SO2 from flue gas", IEEE Trans. Ind. Applicat., Vol. 26, NO. 3, pp. 535-541, 1990

37. Kim, S-J., "Recent R&D of Non-Thermal Plasma Technology in Korea", Proceedings of The Asia-Pacific Workshop on Advanced Oxidation Technologies, December 17-19, Tsukuba, Japan, 1998

38. Penetrante, B.M. (1993) Pollution Control Applications of Pulsed Power Technology, Proceedings of 9th IEEE International Pulsed Power Conference, June 21-23, 1993, Albuquerque, NM, USA

39. S. Masuda and H. Nakao, "Control of NOx by positive and negative pulsed corona discharges", IEEE Trans. Ind. Applicat., Vol. 26, NO. 2, pp. 374-383, 1990

40. J.S. Oh, S.S. Park, S.D. Jang, M.H. Cho, I.S. Ko, and W. Namkung, "Prototype 2-stage

magnetic compression modulator for pulse power applications", presented at the 1996 Twenty-Second International power Modulator Symposium, Boca Raton, Florida, USA, June, 24-27, 1996

41. V.I. Parvulescu, P. Grange, and B. Delmon, "Catalytic Removal of NO", Catalysis Today, 46, pp 233-316, 1998

42. G. Lepperhoff, K. Hentschel, P. Wolters, W. Neff, K. Pochner, and F.J. Trompeter, "Lean-Combustion Spark-Ignition Engine Exhaust Aftertreatment Using Non-Thermal Plasma", SAE 982512, 1998