DOI QR코드

DOI QR Code

저온 H2-SCR용 PtNi/W-TiO2 촉매에 조촉매 CeO2가 NOx 저감에 미치는 영향

Effect of Co-catalyst CeO2 on NOx Reduction in PtNi/W-TiO2 Catalysts for Low-temperature H2-SCR

  • 김정수 (호서대학교 벤처대학원 융합공학과) ;
  • 김영희 (호서대학교 벤처대학원 융합공학과)
  • Jungsoo Kim (Department of Convergence Engineering, Graduate School of Venture Hoseo University) ;
  • Younghee Kim (Department of Convergence Engineering, Graduate School of Venture Hoseo University)
  • 투고 : 2023.12.05
  • 심사 : 2023.12.14
  • 발행 : 2023.12.31

초록

대표적인 비암모니아성 선택적 촉매환원반응기인 H2-SCR의 활용성을 높이기 위하여 Ce를 조촉매로 활용한 PtNi/CeO2-W-TiO2의 촉매 분말을 합성하고 다공성 금속 구조(porous metal structure, PMS)에 코팅하여 선택적 촉매 환원에 의한 NOx 제거 특성을 평가하였다. CeO2를 조촉매로 사용한 H2-SCR은 CeO2를 사용하지 않은 경우에 비해 더 높은 NOx 제거 효율을 나타내었으며, CeO2 담지율 10 wt%에서는 반응온도 90℃에서 가장 높은 제거효율을 보였다. 한편, 촉매구조체인 PMS의 촉매 코팅량이 증가함에 따라 NOx 제거효율은 90℃ 이하에서는 향상되었으나, 120℃ 이상에서는 감소하는 경향을 보였고 공간속도를 4,000 h-1에서 20,000 h-1로 변경한 경우, 120℃이상의 온도에서 NOx 제거 효율이 향상되는 것을 확인할 수 있었다.

In order to increase the usability of H2-SCR, the NOx removal characteristics with catalyst powder of PtNi/CeO2-W-TiO2 using Ce as a co-catalyst was synthesized and coated on a porous metal structure (PMS) were evaluated. Catalyst powder of PtNi/CeO2-W-TiO2(PtNi nanoparticles onto W-TiO2, with the incorporation of ceria (CeO2) as a co-catalysts) was synthesized and coated onto a porous metal structure (PMS) to produce a Selective Catalytic Reduction (SCR) catalyst. H2-SCR with CeO2 as a co-catalyst exhibited higher NOx removal efficiency compared to H2-SCR without CeO2. Particularly, at a 10wt% CeO2 loading ratio, the NOx removal efficiency was highest at 90℃. As the amount of catalyst coating on PMS increased, the NOx removal efficiency was improved below 90℃, but it was decreased above 120℃. When the space velocity was changed from 4,000 h-1 to 20,000 h-1, the NOx removal efficiency improved at temperatures above 120℃. It was expected that the use of the catalyst could be reduced by applying the PMS with excellent specific surface area as a support.

키워드

과제정보

본 연구는 중소기업벤처부의 그린벤처사업에서 지원받은 연구비(No. S3023447)로 수행되었습니다.

참고문헌

  1. Damma, D., Ettireddy, P. R., Reddy, B. M., and Smirniotis, P. G., "A Review of Low Temperature NH3-SCR for Removal NOx," Catalysts, 9(4), 349 (2019).
  2. Costa, C. N. and Efstathiou, A. M., "Low-temperature H2-SCR of NO a Novel Pt/MgO-CeO2 Catalyst," Appl. Catal. B: Environ., 72, 240-252 (2007). https://doi.org/10.1016/j.apcatb.2006.11.010
  3. Costa, C. N., Savva, P. G., Fierro, J. G., and Efstathiou, A. M., "Industrial H2-SCR of NO on a Novel Pt/MgO-CeO2 Catalyst," Appl. Catal. B: Environ., 75, 147-156 (2007). https://doi.org/10.1016/j.apcatb.2007.04.018
  4. Shibata, J., Hashimoto, M., Shimizu, K., Hattori, H. T., and Satsuma, A., "Factors Controlling Activity and Selectivity for SCR of NO by Hydrogen over Supported Platinum Catalysts," J. Phys. Chem. B, 108(47), 18327-18335 (2004). https://doi.org/10.1021/jp046705v
  5. Kim, S. and Hong, S., "Relationship between the Surface Characteristics of Pt Catalsyt and Catalytic Performance on the H2 SCR," J. Ind. Eng. Chem., 16, 992-996 (2010). https://doi.org/10.1016/j.jiec.2010.07.022
  6. Cao, L., Wang, Q., and Yang, J., "Ultrafine Pt Particles Directed by Polyvinylpyrrolidone on Zeolite Beta as an Efficient Low-temperature H2-SCR Catalyst," Journal of Environmental Chemical Engineering, 8, 103631 (2020).
  7. Liu, Y., Tursun, M., Yu, H., and Wang, X., "Surface Property and Activity of Pt/Nb2O5-ZrO2 for Selective Catalytic Reduction of NO by H2," Molecular Catalysis, 464, 22-28 (2019). https://doi.org/10.1016/j.mcat.2018.12.015
  8. Wang, Xi., Wang, Xu., Yu, H., and Wang, X., "The Functions of Pt Located at Different Positions of HZSM-5 in H2-SCR," Chem. Eng. J., 355, 470-477 (2019). https://doi.org/10.1016/j.cej.2018.07.207
  9. Hong, Z., Sun, X., Wang, Z., Zhao, G., Li, X., and Zhu, Z., "Pt/SSZ-13 as an Efficient Catalyst for the Selective Catalytic Reduction of NOx with H2," Catal. Sci. Technol., 9, 3994-4001 (2019). https://doi.org/10.1039/C9CY00898E
  10. Xue, Y., Sun, W., Wang, Q., Cao, L., and Yang, J., "Sparsely Loaded Pt/MIL-96(Al) MOFs Catalyst with Enhanced Activity for H2-SCR in a Gas Diffusion Reactor under 80℃," Chem. Eng. J., 335, 612-620 (2018). https://doi.org/10.1016/j.cej.2017.11.011
  11. Tu, B., Shi, N., Sun, W., Cao, L., and Yang, J., "SO2-tolerant and H2O-promoting Pt/C Catalysts for Efficient NO Removal via Fixed-bed H2-SCR," Environ Sci. Pollut. Res., 24, 676-684 (2017). https://doi.org/10.1007/s11356-016-7788-5
  12. Sun, W., Qiao, K., Liu, J., Cao, L., Gong, X., and Yang, J., "Pt-Doged NiFe2O4 Spinel as a Highly Efficient Catalyst for H2 Selective Catalytic Reduction of NO at Room Temperature," ACS Comb. Sci., 18, 195-202 (2016). https://doi.org/10.1021/acscombsci.5b00193
  13. Gao, S., Wang, X., Li, M., Wang, X., Li, J., and Feng, J., "Nanofibrous SUZ-4 Loading Pt Used for Selective Catalytic Reduction of NOx by Hydrogen," Microporous and Mesoporous Materials, 183, 185-191 (2014). https://doi.org/10.1016/j.micromeso.2013.09.023
  14. Mihet, M., Lazar, M. D., Borodi, G., and Almasan, V., "Effect of Pt Promotion on Ni/Al2O3 for the Selective Catalytic Reduction of NO with Hydrogen," AIP Conf. Proc., 1565, 126-132 (2013).
  15. Park, S., Kim, M., KIm, E., Han, H., and Seo, G., "H2-SCR of NO on Pt-MnOx Catalyst : Reaction path via NH3 Formation," Applied Catalyst A : General, 395, 120-128 (2011). https://doi.org/10.1016/j.apcata.2011.01.033
  16. 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
  17. Duan, K., Wang, Z., Hardacre, C., Liu, Z., Chansai, S., and Stere, C., "Promoting Effect of Au on Pd/TiO2 Catalyst for the Selective Catalytic Reduction of NOx by H2," Catal. Today, 332, 69-75 (2019). https://doi.org/10.1016/j.cattod.2018.06.022
  18. Xu, C., Sun, W., Cao, L., Li, T., Cai, X., and Yang, J., "Highly Efficient Pd-doped Aluminate Spinel Catalysts with Different Divalent Cations for the Selective Catalytic Reduction of NO with H2 at Low Temperature," Chem. Eng. J., 308, 980-987 (2017). https://doi.org/10.1016/j.cej.2016.09.119
  19. Peng, Z., Li, Z., Liu, Y., Yan, S., Tong, J., Wang, D., Ye, Y., and Li, S., "Supported Pd Nanoclusters with Enhanced Hydrogen Spillover for NOx Removal via H2-SCR : the Elimination of "Volcano-type" Behaviour," Chem. Commun., 53, 5958-5961 (2017). https://doi.org/10.1039/C7CC02235B
  20. Xu, C., Sun, W., Cao, L., and Yang, J., "Highly Efficient Pd-doped Ferrite Spinel Catalysts for the Selective Catalytic Reduction of NO with H2 at Low Temperature," Chem. Eng. J., 289, 231-238 (2016). https://doi.org/10.1016/j.cej.2015.12.085
  21. Duan, K., Chen, B., Zhu, T., and Liu, Z., "Mn Promoted Pd/TiO2-Al2O3 Catalyst for the Selective Catalytic Reduction of NOx by H2," Appl. Catal. B: Environ., 176-177, 618-626 (2015). https://doi.org/10.1016/j.apcatb.2015.04.048
  22. Tu, B., Sun, W., Xue, Y., Zaman, W., Cao, L., and Yang, J., "Facile Synthesis of PtxNiy Catalyst Supported on Carbon for Low Temperature H2-SCR," ACS Sustainable Chem, Eng., 5, 5200-5207 (2017). https://doi.org/10.1021/acssuschemeng.7b00540
  23. Hu, Z. and Yang, R. T., "110th Anniversary : Recent Progress and Future Challenges in Selective Catalytic Reduction of NO by H2 in the Presence of O2," Ind. Eng. Chem. Res., 58, 10140-10153 (2019). https://doi.org/10.1021/acs.iecr.9b01843
  24. Cai, X., Sun, W., Zaman, W., Cao, L., and Yang, J., "Limited Ce Doped Ni-Co as a Highly Efficient Catalyst for H2-SCR of NO with Good Resistance to SO2 and H2O at Low Temperature," RSC Adv., 6, 91930-91939 (2016). https://doi.org/10.1039/C6RA20236E
  25. Zhang, X., Wang, X., Zhao, X., Xu, Y., Liu, Y., and Yu, Q., "Promotion Effect of Tungsten on the Activity of Pt/HZSM-5 for H2-SCR," Chem. Eng. J., 260, 419-426 (2015). https://doi.org/10.1016/j.cej.2014.09.030
  26. Valiheikki, A., Petallidou, K. C., Kalamaras, C. M., Kolli, T., Maunula, M. T., Keiski, R., and Efstathiou, A. M., "Selective Catalytic Reduction of NOx by Hydrogen (H2-SCR) on WOx-promoted CezZr1-zO2 Solids," Appl. Catal. B: Environ., 156-157, 72-83 (2014). https://doi.org/10.1016/j.apcatb.2014.03.008
  27. Olympiou, G. G. and Efstathiou, A. M., "Industrial NOx Control via H2-SCR on a Novel Supported-Pt Nanocatalyst," Chem. Eng. J., 170, 424-432 (2011). https://doi.org/10.1016/j.cej.2011.01.001
  28. Wang, J., Li, B., Yang, D., Lv, H., and Zhang, C., " Preparation Optimization and Single Cell Application of PtNi/C Octahedral Catalyst with Enhanced ORR Performance," Electrochemica Acta, 288, 126-133 (2018). https://doi.org/10.1016/j.electacta.2018.09.005
  29. Kodama, K., Nagai, T., Kuwaki, A., Jinnouchi, R., and Morimoto, Y., "Challenges in Applying Highly Active Pt-based Nanostructured Catalysts for Oxygen Reduction Reactions to Fuel Cell Vehicles," Nature Nanothchnology, 16, 140-147 (2021). https://doi.org/10.1038/s41565-020-00824-w
  30. Cai, X., Sun, W., Zaman, W. Q., Cao, L., and Yang, J., "Limited Ce Doped Ni-Co as a Highly Efficient Catalyst for H2-SCR of NO with Good Resistance to SO2 and H2O at Low Temperature," RSC Adv., 6, 91930-91939 (2016). https://doi.org/10.1039/C6RA20236E