DOI QR코드

DOI QR Code

상용 탈질 SCR 폐촉매의 현장 재생 효과 고찰

A Study on the In situ Regeneration Effects of Commercial Deactivated SCR Catalyst

  • 박해경 (한서대학교 촉매공정기술연구원) ;
  • 전민기 (한서대학교 촉매공정기술연구원) ;
  • 김문찬 (청주대학교 환경공학과)
  • Park, Hea-Kyung (Research Institute of Catalyst Technology, Hanseo University) ;
  • Jun, Min-Kee (Research Institute of Catalyst Technology, Hanseo University) ;
  • Kim, Moon-Chan (Department of Environmental Engineering, Cheongju University)
  • 투고 : 2012.10.17
  • 심사 : 2012.10.26
  • 발행 : 2012.10.30

초록

상용 중유 발전소 배가스에 장기간 노출되어 활성이 현저히 저하된 탈질 SCR 폐촉매를 대상으로 현장 시스템을 모사하여 증류수 및 산성용액에 의한 세척과정을 거쳐 모사된 현장 조건으로 촉매를 재생하였다. 산성용액의 제조조건 및 처리조건에 따른 촉매의 물성변화를 확인하였고 질소산화물($NO_x$) 전환 촉매 활성 실험을 수행하여 촉매성능 변화를 고찰하였다. 촉매의 특성분석은 BET, Porosimeter, EDX (Energy Dispersive X-ray spectrometer), ICP (Inductively Coupled Plasma) 등을 이용하여 수행하였고, $NO_x$ 전환 반응실험은 중유 발전소 배가스를 모사하여 마이크로 반응기에서 SCR 반응을 수행하였다. 촉매특성 분석결과 재생된 촉매의 경우 비표면적은 신품 촉매 대비 95% 이상 회복되었고, $NO_x$ 전환활성은 산성용액 농도 3~6 M 범위에서 신품 촉매 대비 90% 이상을 회복한 것으로 나타났다. 이러한 촉매활성의 향상은 산성용액에 의한 촉매표면의 불순물들이 제거되면서 일어난 결과로 밝혀졌다.

A study on the in situ regeneration effect of commercial deactivated SCR catalyst which had been exposed to the off gas from the heavy oil fired power plant for a long time was carried out in a simulated in situ conditions by washing with distilled water and various acid solutions in a short time. The catalytic performance test of the regenerated SCR catalysts was carried out in the micro reactor with simulated off gas of the heavy oil fired power plant and all prepared catalysts were characterized by BET, Porosimeter, EDX (Energy Dispersive X-ray spectrometer) and ICP (Inductively Coupled Plasma) to investigate correlations between catalytic activity and surface characteristics of them. The characterization results of the regenerated catalysts showed that the specific surface area was restored 95% more than that of fresh catalyst. Under this study, the activity of the regenerated catalysts with acid solution (3~6 M) without using ultrasonic wave in a simulated in situ conditions was restored 90% more than that of the fresh catalyst. It was found that improved activity of regenerated catalyst was caused by removing the deactivating materials from the surface of the deactivated SCR catalyst through acid washing.

키워드

과제정보

연구 과제 주관 기관 : 지식경제부

참고문헌

  1. Vargas, M. A. L., Casanova, M., Trovarelli, A. and Busca, G., "An IR study of thermally stable $V_{2}O_{5}-WO_{3}/TiO_{2}$ SCR catalysts modified with silica and rare-earths (Ce, Tb, Er)," Appl. Catal. B: Environ., 75, 303-304(2007). https://doi.org/10.1016/j.apcatb.2007.04.022
  2. Kobayashi, M. and Miyoshi, K., "$WO_{3}-TiO_{2}$ monolithic catalysts for high temperature SCR of NO by$NH_{3}$: Influence of preparation method on structural and physico chemical properties, activity and durability," Appl. Catal. B: Environ., 72, 253-254(2007). https://doi.org/10.1016/j.apcatb.2006.11.007
  3. Bosch, H. and Janssen, F., "Catalytic reduction of nitrogen oxides-a review on the fundamentals and technology," Catal. Today, 2, 369-532(1988). https://doi.org/10.1016/0920-5861(88)80002-6
  4. Baik, J. H., Yim, S. D., Nam, I. S., Mok, Y. S., Lee, J. H., Cho, B. K. and Oh, S. H., "Control of $NO_{x}$ emissions from diesel engine by selective catalytic reduction (SCR) with urea," Topics in Cata1., 30/31, 37-41(2004). https://doi.org/10.1023/B:TOCA.0000029725.88068.97
  5. Blanco, J., Avila, P., Suares, S., Yates, M., Martin, J. A., Marzo, L. and Knapp, C., "CuO/NiO monolithic catalysts for $NO_{x}$ removal from nitric acid plant f1ue gas," Chem. Eng. J., 97, 1-9(2004). https://doi.org/10.1016/S1385-8947(03)00085-8
  6. Lietti, L., "Reactivity of $V_{2}O_{5}-WO_{3}/TiO_{2}$ $deNO_{x}$catalysts by transient methods," Appl. Catal. B: Environ., 10, 281-297 (1996). https://doi.org/10.1016/S0926-3373(97)80001-X
  7. Burch, R. and Millington, P. J., "Selective reduction of nitrogen oxide by hydrocarbons under lean-burn conditions using supported platinum group metal catalysts," Catal. Today, 26, 185-206(1995). https://doi.org/10.1016/0920-5861(95)00136-4
  8. Inomata, M., Mori, K., Miyamoto, A., Ui, T. and Murakami, Y., "Structures of supported vanadium oxide catalysts.1. Vanadium (V) oxide/titanium dioxide (anatase), vanadium (V) oxide/titanium dioxide (rutile), and vanadium (V) oxide/ titanium dioxide (mixture of anatase with ruti1e)," J. Phys. Chem., 87(5) 754-761(1983). https://doi.org/10.1021/j100228a013
  9. Teng, H. and Huang, T. S., "Control of $NO_{x}$ emissions through combustion modifications for reheating furnaces in steel plants," Fuel, 75(2), 149-156(1996). https://doi.org/10.1016/0016-2361(95)00231-6
  10. Forzatti, P. and Lietti, L., "Selective catalytic reduction of $NO_{x}$ by $NH_3$ from stationary sources," La Chimica e l'industria., 78(6), 685-691(1996).
  11. Raziyeh, K. and C. U. Ingemar, O., "Deactivating effects of lead on the selective catalytic reduction of nitric oxide with ammonia over a $V_{2}O_{5}-WO_{3}/TiO_{2}$catalyst for waste incineration applications," lnd. Eng. Chem. Res., 37(4), 1196-1202 (1998). https://doi.org/10.1021/ie9706065
  12. Shin, B. S., Lim, S. Y. and Choung, S. J., "$WO_{3}$ and$MoO_{3}$addition effect on $V_2O_5/TiO_2$ as promoters for removal of $NO_{x}$ and $SO_{x}$ from stationary sources," Korean J. Chem. Eng., 11(4), 254-260(1994). https://doi.org/10.1007/BF02697392
  13. Broer, S. and Hammer, T., "Selective catalytic reduction of nitrogen oxide by combining a non-thermal plasma and a $V_{2}O_{5}-WO_{3}/TiO_{2}$catalysts," Appl. Catal. B: Environ., 28(2), 101-111(2000). https://doi.org/10.1016/S0926-3373(00)00166-1
  14. Raziyeh, K. and C. U. Ingemar, O., "Regeneration of commercial SCR catalysts by washing and sulphation effect of sulphate groups on the activity," Appl. Catal. B: Environ., 33(4), 277-291(2001). https://doi.org/10.1016/S0926-3373(01)00193-X
  15. Chen, J. P. and Yang, R. T., "Role of$WO_{3}$in mixed $V_{2}O_{5}-WO_{3}/TiO_{2}$catalysts for selective catalytic reduction of nitric oxide with ammonia," Appl. Catal. A Gen., 80(1), 135-148 (1992). https://doi.org/10.1016/0926-860X(92)85113-P
  16. Nicolaos, V. E., Donovan, A. P. and Panagiotis, G. S., "Comparison of $TiO_{2}$base oxide catalysts for the selective catalytic reduction of NO effect of aging the vanadium precursor solution," Appl. Catal. B: Environ., 23(2), 123-134(1999). https://doi.org/10.1016/S0926-3373(99)00070-3
  17. Lim, J. S., Kim, T. W., Park, H. K. and Yoo, M. S., "A study on the deactivation of commercial SCR catalyst ($V_{2}O_{5}-WO_{3}/TiO_{2}$) for the reduction of$NO_{x}$," Korean Soc. Environ. Eng., 26(10), 1125-1130(2004).
  18. Ham, S. W., Soh, B. W. and Nam, I. S., "Sulfur Poisoning and Tolerance of SCR Catalyst to remove NO by $NH_{3}$," J. Korea lnd. Eng. Chem., 15(4). 373-385(2004).
  19. Lisi, L., Lasorella, G., Malloggi, S. and Russo, G., "Single and combined deactivation effect of alkali metals and HCl on commercial SCR catalysts," Appl. Catal. B: Environ., 50, 251-258(2004). https://doi.org/10.1016/j.apcatb.2004.01.007
  20. Raziyeh, K. and C. U. Ingemar, O., "Regeneration of commercial $V_{2}O_{5}-WO_{3}/TiO_{2}$ SCR catalysts used in bio fuel plants," Appl. Catal. B: Environ., 30, 87-99(2001). https://doi.org/10.1016/S0926-3373(00)00227-7