Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Selective Catalytic Reduction of NO by H2 over Pt-MnOx/ZrO2-SiO2 Catalyst

Pt-MnOx/ZrO2-SiO2 촉매에서 수소에 의한 일산화질소의 선택적 촉매 환원반응

  • Kim, Juyoung (School of Applied Chemical Engineering, Chonnam National University) ;
  • Ha, Kwang (School of Applied Chemical Engineering, Chonnam National University) ;
  • Seo, Gon (School of Applied Chemical Engineering, Chonnam National University)
  • 김주영 (전남대학교 응용화학공학부) ;
  • 하광 (전남대학교 응용화학공학부) ;
  • 서곤 (전남대학교 응용화학공학부)
  • Received : 2014.02.10
  • Accepted : 2014.03.18
  • Published : 2014.08.01
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Abstract

Selective catalytic reduction of nitrogen monoxide by hydrogen ($H_2$-SCR of NO) over platinum catalysts impregnated on zirconia-incorporated silica ($ZrO_2-SiO_2$) and manganese oxide ($MnO_x$) was investigated. $Pt-MnO_x$ catalyst showed low conversions and low yields of $N_2O$ and $NO_2$ at $100{\sim}350^{\circ}C$. On the other hand, NO conversions over $Pt/ZrO_2-SiO_2$ were very high, but $N_2O$ was predominantly produced at $100-150^{\circ}C$ and the yield of $NO_2$ increased with temperature at $200-300^{\circ}C$, resulting in poor $N_2$ yields. $Pt-MnO_x/ZrO_2-SiO_2$ exhibited a small enhancement in $N_2$ yield at $100-150^{\circ}C$ due to the synergy of $MnO_x$ and $ZrO_2-SiO_2$. The surface composition and oxidation state of the catalyst components and the acidity of the catalysts were examined. IR spectra of the adsorption of NO and their subsequent reactions with hydrogen on these catalysts were also recorded. The variations of conversion and product yield according to the catalyst components in the $H_2$-SCR of NO were discussed in relation to their catalytic roles.

지르코니아를 고정한 실리카($ZrO_2-SiO_2$)와 망가니즈 산화물($MnO_x$)에 백금을 담지하여 제조한 촉매에서 수소에 의한 일산화질소의 선택적 촉매 환원($H_2$-SCR) 반응을 조사하였다. $Pt-MnO_x$ 촉매에서는 NO 전환율이 낮으며, $N_2O$와 $NO_2$ 생성이 억제되었다. 반면, $Pt/ZrO_2-SiO_2$ 촉매에서는 NO 전환율이 높지만, $100{\sim}150^{\circ}C$에서는 $N_2O$가, $200{\sim}300^{\circ}C$에서는 온도가 높아지면 $NO_2$ 수율이 높아져, $N_2$ 수율이 낮았다. $ZrO_2-SiO_2$에 $MnO_x$와 백금을 같이 담지한 $Pt-MnO_x/ZrO_2-SiO_2$촉매에서는 $100{\sim}150^{\circ}C$에서 이들 성분의 상승작용으로 $N_2$ 수율이 조금 높아졌다. 이들 촉매에서 표면 조성, 산화 상태, 산성도를 조사하고, NO가 흡착되어 수소와 반응하는 과정의 IR 스펙트럼을 그렸다. NO의 $H_2$-SCR 반응에서 전환율과 생성물 수율을 촉매 구성 성분의 촉매작용과 연계지어 고찰하였다.

Keywords

References

  1. Association des Constructures Europeens d'Automobiles, "New passenger car registrations," (2012).
  2. http://www.doosan.com/doosanengine/kr/media/engineschool/history/index.page.
  3. Liu, Z. and Woo, S. I., "Recent Advances in Catalytic $DeNO_x$ Science and Technology," Cat. Rev. Sci. Eng., 48, 43-89(2006). https://doi.org/10.1080/01614940500439891
  4. Takahashi, N., Shinjoh, H., Iijima, T., Suzuki, T., Yamazaki, K., Yokota, K., Suzuki, H., Miyoshi, N., Matsumoto, S., Tanizawa, T., Tanaka, T., Tateishi, S. and Kasahara, K., "The New Concept 3-way Catalysts for Automotive Lean-burn Engine: $NO_x$ Storage and Reduction Catalyst," Catal. Today, 27, 63-69(1996). https://doi.org/10.1016/0920-5861(95)00173-5
  5. Shelef, M., "Selective Catalytic Reduction of $NO_x$ with N-free Reductants," Chem. Rev., 95, 209-225(1995). https://doi.org/10.1021/cr00033a008
  6. Jeong, S. K., Park, T. S. and Hong, S. C., "Selective Catalytic Reduction of NO on Manganese Sulfates," Korean Chem. Eng. Res., 46(3) 473-478(2008).
  7. Kim, J.-K., Park, K.-H., Hong, S.-C., Lee, E.-D. and Kang, Y., "Effects of Calcium on the Activity of $V_2O_5/TiO_2$ Catalysts in SCR Processes," Korean Chem. Eng. Res., 50(5) 772-777(2012). https://doi.org/10.9713/kcer.2012.50.5.772
  8. Park, S. M., Kim, M. Y., Kim, E. S., Han, H. S. and Seo, G., "$H_2$-SCR of NO on Pt-$MnO_x$ Catalysts: Reaction Path via $NH_3$ Formation," Appl. Catal. A: Gen., 395, 120-128(2011). https://doi.org/10.1016/j.apcata.2011.01.033
  9. Ham, S. W., Nam, I. S. and Kim, Y. G., "Activity and Durability of Iron-exchanged Mordenite-type Zeolite Catalyst for the Reduction of NO by $NH_3$," Korean J. Chem. Eng., 17(3), 318-324(2000). https://doi.org/10.1007/BF02699047
  10. Miller, W., "Development of Urea-SCR for Heavy Duty Trucks Demonstration Update," 6th DEER Workshop(2000).
  11. Hamada, H. and Haneda, M., "A Review of Selective Catalytic Reduction of Nitrogen Oxides with Hydrogen and Carbon Mo$NO_x$ide," Appl. Catal. A: Gen., 421-422, 1-13(2012). https://doi.org/10.1016/j.apcata.2012.02.005
  12. Fu, L. and Chuang, K. T., "Control of Nitrogen Oxide ($NO_x$) Emissions by Selective Catalytic Reduction with Hydrogen over Hydrophobic Catalysts," Energy Fuels, 3, 740-743(1989). https://doi.org/10.1021/ef00018a015
  13. Liu, Z., Li, J. and Woo, S. I., "Recent Advances in the Selective Catalytic Reduction of $NO_x$ by Hydrogen in the Presence of Oxygen," Energy Environ. Sci., 5, 8799-8814(2012). https://doi.org/10.1039/c2ee22190j
  14. Costa, C. N. and Efstathiou, A. M., "Low-temperature $H_2$-SCR of NO on a Novel Pt/MgO-$CeO_2$ Catalyst," Appl. Catal. B: Environ., 72, 240-252(2007). https://doi.org/10.1016/j.apcatb.2006.11.010
  15. Costa, C. N., Savva, P. G., Fierro, J. L. G. and Efstathiou, A. M., "Industrial $H_2$-SCR of NO on a Novel Pt/MgO-$CeO_2$ Catalyst," Appl. Catal. B: Environ., 75, 147-156(2007). https://doi.org/10.1016/j.apcatb.2007.04.018
  16. Park, S. M., Jang, H.-G. Kim, E. S., Han, H. S. and Seo, G., "Incorporation of Zirconia onto Silica for Improved Pt/$SiO_2$ Catalysts for the Selective Catalytic Reduction of NO by $H_2$," Appl. Catal. A: Gen., 427-428, 155-164(2012). https://doi.org/10.1016/j.apcata.2012.03.045
  17. Si, H., Wang, H., Shen, H., Zhou, C., Li, S., Lou, S., Xu, W., Du, Z. and Li, L. S., "Controlled Synthesis of Monodisperse Manganese Oxide Nanocrystals," Cryst. Eng. Comm., 11, 1128-1132(2009). https://doi.org/10.1039/b901603c
  18. Pitchon, V. and Fritz, A., "The Relation Between Surface State and Reactivity in the $DeNO_x$ Mechanism on Platinum-based Catalysts," J. Catal., 186, 64-74(1999). https://doi.org/10.1006/jcat.1999.2543
  19. Oku, M., Hirokawa, K. and Ikeda, S., "X-ray Photoelectron Spectroscopy of Manganese-oxygen Systems," J. Electron Spectrosc. Relat. Phenom., 7, 465-473(1975). https://doi.org/10.1016/0368-2048(75)85010-9
  20. Wagner, C. D., Riggs, W. M., Davis, L. E., Moulder, J. F. and Muilenberg, G. E., Handbook of X-ray Photoelectron Spectroscopy, Perkin-Elmer Corporation, USA(1979).
  21. Tanabe, K., Misono, M., Ono, Y. and Hattori, H., "New Solid Acids and Bases: Their Catalytic Properties," Stud. Surf. Sci. Catal., 51, (1989).
  22. Costa, C. N. and Efstathiou, A. M., "Mechanistic Aspects of the $H_2$-SCR of NO on a Novel Pt/MgO-$CeO_2$ Catalyst," J. Phys. Chem. C, 111, 3010-3020(2007).
  23. Wu, P., Li, L., Yu, Q., Wu, G. and Guan, N., "Study on Pt/Al-MCM-41 for NO Selective Reduction by Hydrogen," Catal. Today, 158, 228-234(2010). https://doi.org/10.1016/j.cattod.2010.03.023
  24. Hadjiivanov, K., "Use of Overtones and Combination Modes for the Identification of Surface $NO_x$ Anionic Species by IR Spectroscopy," Catal. Today, 68, 157-161(2000).
  25. Sedlmair, C., Seshan, K., Jentys, A. and Lercher, J. A., "Elementary Steps of $NO_x$ Adsorption and Surface Reaction on a Commercial Storage-reduction Catalyst," J. Catal., 214, 308-316(2003). https://doi.org/10.1016/S0021-9517(02)00085-4
  26. Yang, S., Wang, X., Chu, W., Song, Z. and Zhao, S., "An Investigation of the Surface Intermediates of $H_2$-SCR of $NO_x$ over Pt/ H-FER," Appl. Catal. B: Environ., 107, 380-385(2011). https://doi.org/10.1016/j.apcatb.2011.08.001

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