DOI QR코드

DOI QR Code

Effect of Containing Promoter on SCR Catalysts

SCR 촉매에 포함된 조촉매 영향

  • Seo, Choong-Kil (Department of Automotive & Mechanical Engineering, Howon University)
  • 서충길 (호원대학교 자동차기계공학과)
  • Received : 2018.06.04
  • Accepted : 2018.09.07
  • Published : 2018.09.30

Abstract

The policy-making and technological development of eco-friendly automobiles designed to increase their supply is ongoing, but the internal combustion engine still accounts for approximately 95% of automobiles in use. To meet the stricter emission regulations of internal combustion engines based on fossil fuels, the proportion of after-treatments for vehicles and (ocean going) vessels is increasing continuously. As diesel engines have high power and good fuel economy in addition to less CO2 emissions, their market share is increasing not only in commercial vehicles, but also in passenger cars. Because of the characteristics of the diesel combustion, however, NOx is generated in localized high-temperature combustion regions, and particulates are formed in the zones of diffusion combustion. LNT and urea-SCR catalysts have been developed for the after-treatment of exhaust gas to reduce NOx in diesel vehicles. This study examined the effect of a containing promoter on SCR catalysts to cope with the severe exhaust gas regulation. The de-NOx performance of the Mn-SCR catalyst was the best, and the de-NOx performance was improved as the ion exchange rate between Mn ion and Zeolyst was good and the activation energy was low. The de-NOx performance of the 7Cu-15Ba/78Zeoyst catalyst was 32% at $200^{\circ}C$ and 30% at $500^{\circ}C$, and showed the highest performance. The NOx storage material of BaO loaded as a promoter was well dispersed in the Cu-SCR catalyst and the additional de-NOx performance of BaO was affected by the reduction reaction of the Cu-SCR catalyst. Among the three catalysts, the 7Cu-15Ba/Zeolyst SCR catalyst was resistant to thermal degradation. The same type of CuO due to thermal degradation migrates and agglomerates because BaO reduces the agglomeration of the main catalyst CuO particles.

친환경자동차의 보급 확대를 위한 정책수립과 기술개발이 지속적으로 이루어지고 있는 실정이나 아직까지도 내연기관이 차지하는 비중은 약 95% 차지하고 있다. 화석연료를 기반으로 하는 내연기관의 엄격한 배기가스규제를 충족시키기 위해 자동차와 선박용 후처리장치의 비중이 점차로 증가하고 있다. 디젤엔진은 이산화탄소 배출량이 적고 강력한 파워와 연료의 경제성을 가지고 있으며, 상용차뿐만 아니라 승용차에서도 시장의 수요가 증가하고 있다. 디젤 연료 특성으로 인하여 질소산화물은 국부적인 고온연소 영역에서 생성되며, 입자상물질은 확산연소 영역에서 생성된다. 희박한 LNT(질소산화물 흡장촉매)와 urea-SCR(선택적인촉매환원장치)는 디젤엔진에서 질소산화물을 저감시키기 위한 후처리장치로 개발되어져왔다. 이 연구는 가혹해지고 있는 배기가스 규제 대응을 위해 선택적인촉매환원장치의 촉매에 포함됨 조촉매의 영향을 파악하는 것이다. 망간-선택적인촉매환원장치의 질소산화물 저감 성능이 가장 우수하였으며, 망간 이온과 Zeolyst의 Al과의 이온교환이 잘 되었고, 활성화 에너지가 낮아 반응 속도가 빨라짐에 따라 질소산화물 저감 성능이 향상되었다. 7Cu-15Ba/78Zeolyst SCR 촉매의 질소산화물 저감 성능은 200도에서 32%, 500도에서 30%를 나타내며 가장 높은 성능을 나타내었고, 조촉매로 첨가된 산화바륨의 질소산화물의 흡장 물질이 Cu-SCR 촉매에 잘 분산되어 있고 Cu-SCR 촉매의 환원 반응과 더불어 산화바륨의 추가적인 질소산화물 저감 성능이 영향을 끼쳤기 때문이다. 7Cu-15Ba/Zeolyst SCR 촉매는 3종 촉매 중 열적 열화에서 내구성이 강하였다. 열적 열화에 따른 동종 성분 산화구리가 이동하여 응집되는데, 산화바륨이 주촉매 산화구리 입자의 응집을 감소시켰기 때문이다.

Keywords

References

  1. C. K. Seo, "Research for Performance Improvement of De-NOx of Cu-SCR Catalysts", Journal of the Korea Academia-Industrial cooperation Society, Vol.19, No.3, pp.112-118, 2018. DOI: https://dx.doi.org/10.5762/KAIS.2018.19.3.112
  2. C. K. Seo, B. Choi, H. Kim, C. H. Lee, C. B. Lee, "Effect of $ZrO_{2}$ addition on de-NOx performance of Cu-ZSM-5 for SCR catalyst", Chemical Engineering Journal, Vol.191, No.15, pp.331-340, 2012. DOI: https://dx.doi.org/10.1016/j.cej.2012.03.027
  3. K. Kubo, H. Iida, S. Namba, A. Igarashi, "Ultra-high steaming stability of Cu-ZSM-5 zeolite as naphtha cracking catalyst to produce light olefin", Catalysis Communications, Vol.29, No.5, pp.162-165, 2012. DOI: https://dx.doi.org/10.1016/j.catcom.2012.10.004
  4. L. Pang, C. Fan, L. Shao, K. Song, J. Yi, X. Cai, J. Wang, M. Kang, T. Li, "The Ce doping Cu/ZSM-5 as a new superior catalyst to remove NO from diesel engine exhaust", Chemical Engineering Journal, Vol.253, pp.394-401, 2014. DOI: https://dx.doi.org/10.1016/j.cej.2014.05.090
  5. F. Marchitti, I. Nova, E. Tronconi, "Experimental study of the interaction between soot combustion and $NH_{3}$-SCR reactivity over a Cu-Zeolite SDPF catalyst", Catalysis Today, Vol.267, No.1, pp.110-118, 2016. DOI: https://dx.doi.org/10.1016/j.cattod.2016.01.027
  6. A. Grossale, I. Nova, E. Tronconi, "Study of a Fe-zeolite-based system as $NH_{3}$-SCR catalyst for diesel exhaust aftertreatment", Catalysis Today, Vol.136, No.1-2, pp.18-27, 2008 DOI: https://dx.doi.org/10.1016/j.cattod.2007.10.117
  7. M. Klimczak, P. Kern, T. Heinzelmann, M. Lucas, P. Claus, "High-throughput study of the effects of inorganic additives and poisons on $NH_{3}$-SCR catalysts-Part I: $V_{2}O_{5}-WO_{3}/TiO_{2} $ catalysts", Applied Catalysis B: Environmental, Vol.95, No.1-2, pp.39-47. 2010. DOI: https://dx.doi.org/10.1016/j.apcatb.2009.12.007
  8. L. Xu, "Impact of a Cu-zeolite SCR Catalyst on the Performance of a Diesel LNT+SCR System", SAE No.2009-010285
  9. C. K. Seo, H. Kim, B. Choi, M. T. Lim, C. H. Lee, C. B. Lee, "De-NOx characteristics of a combined system of LNT and SCR catalysts according to hydrothermal aging and sulfur poisoning", Catalysis Today, Vol.164, No.1, pp.507-514, 2012. DOI: https://dx.doi.org/10.1016/j.cattod.2010.10.010
  10. J. R. Sohn, S. G. Ryu, Y. I. Pae, "Structure and Thermal Properties of Chromium Oxide Supported on Zirconia", Journal of the Korean Institute of Chemical Engineers, Vol.30, No.5, pp.586-593, 1992.
  11. S. H. Zhang, M. F. Wu, T. T. Tang, Q. J. Xing, C. Q. Peng, F. Li, H. Liu, X. B. Luo, J. P. Zou, X. B. Min, J. M. Luo, "Mechanism investigation of anoxic Cr(VI) removal by nano zero-valent iron based on XPS analysis in time scale", Chemical Engineering Journal, Vol.335, pp.945-953, 2018. DOI: https://dx.doi.org/10.1016/j.cej.2017.10.182
  12. K. H. Hong, J. H. Kim, K. Chang, J. Kwon, "The role of Cr on oxide formation in Ni-Cr alloys: A theoretical study", Computational Materials Science, Vol.142, pp.85-191, 2018. DOI: https://dx.doi.org/10.1016/j.commatsci.2017.09.056
  13. G. Y. Jung, W. C. Jeon, S. Lee, S. H. Jung, S. G. Cho, "Reaction Characteristics of Ni-Al nanolayers by molecular dynamics simulation", Journal of Industrial and Engineering Chemistry, Vol.57, pp.290-296, 2018. DOI: https://dx.doi.org/10.1016/j.jiec.2017.08.035
  14. C. K. Seo, "Optimization of an LNT-SCR combined System to de-NOx the Diesel Engine Exhaust Gas", Dissertation for the degree of Ph. D., Chonnam National University, pp.20. 2012.