Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Effects of Calcium on the Activity of V2O5/TiO2 Catalysts in SCR Processes

SCR 공정에서 Calcium 성분이 V2O5/TiO2 촉매 활성에 미치는 영향

  • Kim, Jin-Kil (Department of Chemical Engineering, Chungnam National University) ;
  • Park, Kwang-Hee (Department of Environmental Energy Systems Engineering, Graduate school of Kyonggi University) ;
  • Hong, Sung-Chang (Department of Environmental Energy Systems Engineering, Graduate school of Kyonggi University) ;
  • Lee, Eui-Dong (HANA I&E) ;
  • Kang, Yong (Department of Chemical Engineering, Chungnam National University)
  • 김진길 (충남대학교 화학공학과) ;
  • 박광희 (경기대학교 일반대학원 환경에너지시스템 공학과) ;
  • 홍성창 (경기대학교 일반대학원 환경에너지시스템 공학과) ;
  • 이의동 (하나검사기술(주)) ;
  • 강용 (충남대학교 화학공학과)
  • Received : 2012.03.08
  • Accepted : 2012.06.20
  • Published : 2012.10.01
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Abstract

Factors acting on the deactivation of $V_2O_5/TiO_2$ catalysts were investigated in the selective catalytic reduction(SCR) process for long term operation. The activity of $V_2O_5/TiO_2$ catalysts was decreased rapidly after 8 months from the starting of operation in the selective catalytic reaction processes. From ICP-AES analysis, the deactivation of the used catalysts could be caused from the calcium component included in urea solution as a reducing agent. It was found from the $NH_3$-TPD experiments that the strong basic element like Ca component drastically affected the acidity of the $V_2O_5/TiO_2$ catalyst. The results gave an explanation on the reason why the component of Ca, even though its concentration is very low, could lead to the deactivation of $V_2O_5/TiO_2$ catalyst in the selective catalytic reaction processes.

장기간 운전되는 선택적 촉매 반응공정(SCR Process)에서 $V_2O_5/TiO_2$ 촉매의 활성저하에 미치는 요소들에 대해 고찰하였다. $V_2O_5/TiO_2$ 촉매의 활성은 공정이 8개월 정도 운전되었을 때 급격히 감소하였다. ICP-AES 분석결과, 공정에서 사용된 $V_2O_5/TiO_2$ 촉매의 활성이 저하되는 것은 선택적 촉매반응공정에서 환원제로 요소용액에 첨가된 칼슘성분에 기인되는 것으로 사료되었다. $NH_3$-TPD 실험결과, 칼슘성분과 같은 강한 염기성 성분은 촉매의 산도에 매우 큰 영향을 미치는 것으로 나타났다. 이와 같은 결과로 비록 농도가 매우 적은 범위라도 칼슘성분이 선택적 촉매 반응공정에서 촉매의 활성도 저하의 원인이 되는 것으로 사료되었다.

Keywords

References

  1. Bosch, H. and Janssen, F., "Formation and Control of Nitrogen Oxides," Catal. Today., 2(4), 369-379(1988). https://doi.org/10.1016/0920-5861(88)80002-6
  2. Forzatti, P. and Lietti, L., "Recent Advances in De-NOxing Catalysis for Stationary Applications," Heterogen. Chem. Rev., 3, 33-51 (1996). https://doi.org/10.1002/(SICI)1234-985X(199603)3:1<33::AID-HCR54>3.0.CO;2-R
  3. Alemany, L. J. and Berti, F., "Characterization and Composition of Commercial $V_{2}O_{5}- WO_{3}-TiO_{2} $ SCR Catalysts," Appl. Catal. B: Environ., 10(4), 299-311(1996). https://doi.org/10.1016/S0926-3373(96)00032-X
  4. Cho, S. M., "Properly Apply Selective Catalytic Reduction for $NO_{x}$ Removal," Chem. Eng. Prog., 90(1), 39-45(1994).
  5. Madia, G., Elsener, M., Koebel, M., Raimondi, F. and Wokaun, A., "Thermal Stability of Vanadia-tungsta-titania Catalysts in the SCR Process," Appl. Catal. B: Environ., 39(2), 181-190(2002). https://doi.org/10.1016/S0926-3373(02)00099-1
  6. Saleh, R. Y., Wachs, I. E., Chan, S. S. and Chersich, C. C., "The Interaction of $V_{2}O_{5}$ with $TiO_{2}$(anatase): Catalyst Evolution with Calcination Temperature and O-xylene Oxidation," J. Catal., 98(1), 102-114(1986). https://doi.org/10.1016/0021-9517(86)90300-3
  7. Nikolov, V. and Anastasov, A., "Preteatment of a Vanadia-titania Catalyst for Partial Oxidation of o-xylene Under Industral Conditions," Ind. Eng. Chem. Res., 31(1), 80-88(1992). https://doi.org/10.1021/ie00001a012
  8. Gas, J., Chem, G., Fu, X., Yin, Y., Wu, S. and Qin, Y., "Enhancement Mechnism of $SO_{2}$ Removal with Clacium Hydroxide in the Presence of $NO_{2}$," Korean J. Chem. Eng., 29(2), 263-269 (2012). https://doi.org/10.1007/s11814-011-0157-7
  9. Seo, J. H., Chae, H. J., Kim, T. W., Jeong, K. E., Kim, C. U., Lee, S. B. and Jeong, S. Y., "Influence of Binder on Fe-based Extradate as Fisher-Tropsch Catalysts," Korean Chem. Eng. Res. (HWAHAK KONGHAK), 49(6), 726-731(2011). https://doi.org/10.9713/kcer.2011.49.6.726
  10. Tang, F., Xu, B., Shi, H., Qiu, J. and Fan, Y., "The Poisoning Effect of $Na^{+}$ and $Ca^{2+}$ Ions Doped on the $V_{2}O_{5}/TiO_{2}$Catalysts for Selective Catalytic Reduction of No by $NH_{3}$," Appl. Catal. B: Environ., 94(1-2), 71-76(2010). https://doi.org/10.1016/j.apcatb.2009.10.022
  11. Shikada, T. and Fujimoto K., "Effect of Added Alkali Salts on the Activities of Supported Vanadium Oxide Catalysts for Nitric Oxide Reduction," Chem. Lett., 12, 77-80(1983).
  12. Abu-Ramadan, E., Saha, K. and Li, X., "Modeling the Depleting Mechanism of Urea-water-solution Droplet for Automotive Selective Catalytic Reduction Systems," AIChE J., 57(11), 3210- 3225(2011). https://doi.org/10.1002/aic.12523
  13. Park, K. H., Lee, J. Y., Hong, S. H., Choi, S. H. and Hong, S. C., "A Strudy on the Deactivation of Commercial $DeNO_{X}$ Catalyst in Fired Power Plant," J. Korean Ind. Eng. Chem., 19(4), 376- 381(2008).
  14. Serwicka, E., "Surface Area and Porosity, X-ray Diffraction and Chemical Analyses," Catal. Today , 56(13), 335-346(2000). https://doi.org/10.1016/S0920-5861(99)00293-X
  15. Forzatti, P., Nova, I. and Beretta, A., "Catalytic Properties in $deNO_{X}$ and $SO_{2}-SO_{3}$ Reactions," Catal. Today, 56(4), 431-441 (2000). https://doi.org/10.1016/S0920-5861(99)00302-8
  16. Nicosia, D., Czekaj, I. and Krocher, O., "Chemical Deactivation of $V_{2}O_{5}/WO_{3}-TiO_{2}$ SCR Catalysts by Additives and Impurites from Fuels, Lubrication Oils and Urea Solution: Part II. Characterization Study of the Effect of Alkali And Alkaline Earth Metals," Appl. Catal. B: Environ., 77, 228-236(2008). https://doi.org/10.1016/j.apcatb.2007.07.032
  17. Krocher, O. and Elsener, M., "Chemical Deactivation of $V_{2}O_{5}/WO_{3}-TiO_{2}$ SCR Catalysts by Additives from Fuels, Lubrication Oils, and Urea Solution: I. Catalytic Studies," Appl. Catal. B: Environ., 77(3-4), 215-227(2008). https://doi.org/10.1016/j.apcatb.2007.04.021
  18. Nicosia, D., Elsener, M., Krocher, O. and Jansohn, P., "Basic Investigation of the Chemical Deactivation of $V_{2}O_{5}/WO_{3}-TiO_{2}$ SCR Catalysts by Potassium, Calcium, and Phosphate," Top. Catal., 42-43(1-4), 333-336(2007). https://doi.org/10.1007/s11244-007-0200-4
  19. Lietti, L., "Reactivity of $V_{2}O_{5}-WO_{3}-TiO_{2}$ de-NOX Catalysts by Transient Methods," Appl. Catal. B: Environ., 10(4), 281-297(1996). https://doi.org/10.1016/S0926-3373(97)80001-X
  20. Topsoe, N. Y., "Mechnism of the Selective Catalytic Reduction of Nitric Oxide by Ammonia Elucidated by in Situ On-Line Fourier Transform Infrared Spectroscopy," Science, 265, 1217- 1219(1994). https://doi.org/10.1126/science.265.5176.1217

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