Journal of the Korean Applied Science and Technology (한국응용과학기술학회지)

The Korean Society of Applied Science and Technology (한국응용과학기술학회)
권호 표지
DOI QR코드

DOI QR Code

A Study on the Propane Dehydrogenation activity of Pt-Sn catalyst using MgAl2O4 support

MgAl2O4 지지체를 이용한 Pt-Sn/MgAl2O4의 프로판 탈수소 활성 연구

  • Byun, Hyun-Joon (Department of Chemical Engineering, Hankyong National University) ;
  • Koh, Hyounglim (Department of Chemical Engineering, Hankyong National University)
  • 변현준 (국립 한경대학교 화학공학과) ;
  • 고형림 (국립 한경대학교 화학공학과)
  • Received : 2018.08.03
  • Accepted : 2018.09.18
  • Published : 2018.09.30
Download PDF
⟨ Previous Next ⟩

Abstract

In the propane dehydrogenation reaction proceeding at high temperature, the main cause of deactivation of the catalyst is coke deposition and sintering. In order to investigate the catalysts for reducing such inactivation, we have investigated the applicability of $MgAl_2O_4$ as a carrier for the catalytic dehydrogenation reaction. $MgAl_2O_4$ was prepared by Alcohthermal method at calcination temperature of 800, 900, $1000^{\circ}C$, and $Pt-Sn/MgAl_2O_4$ catalyst was prepared by supporting Pt and Sn by co-impregnation method. The reaction temperature was conducted at a high temperature of 650, $600^{\circ}C$ to confirm the thermal stability. As a result of the reaction experiment, it was confirmed that the conversion rate and yield of propane dehydrogenation reaction test were higher than that of the carrier-applied catalyst having a carrier calcination temperature of 900 and $1000^{\circ}C$, when the carrier-applied catalyst having a calcination temperature of $800^{\circ}C$ was used, It was found that the yield was higher than that of $Pt-Sn/{\theta}-Al_2O_3$ at $650^{\circ}C$. TGA, BET, XRD, CO-chemisorption, and SEM-EDS analyzes were performed for characterization. $MgAl_2O_4-800^{\circ}C$ was correlated with the relationship between good yield, Pt dispersion and low deactivation rate.

고온에서 진행되는 프로판 탈수소 반응에서 촉매의 불활성화의 주된 원인은 코크 침적, 소결현상이 있다. 이러한 불활성화를 줄이는 촉매를 연구하기 위해, 본 연구에서는 열적 안정성이 높은 $MgAl_2O_4$ 를 담체로 적용하여 프로판 탈수소 반응용 촉매로의 활용성을 확인하고자 하였다. Alcohthermal method로 $MgAl_2O_4$를 소성온도 800, 900, $1000^{\circ}C$로 달리하여 제조하였고, Pt와 Sn을 공동함침법으로 담지하여$Pt-Sn/MgAl_2O_4$촉매를 제조하였다. 열적안정성의 확인을 위해 반응온도를 고온의 650, $600^{\circ}C$에서 진행하였다. 반응실험 결과 반응온도에 상관없이 담체의 소성온도가 $800^{\circ}C$인 담체적용 촉매일 때 프로판 탈수소반응 실험의 전환율과 수율이 담체소성온도가 900, $1000^{\circ}C$인 담체적용 촉매보다 높은 것을 확인하였고, 반응온도가 고온인 $650^{\circ}C$일 때는 $Pt-Sn/{\theta}-Al_2O_3$보다도 더 높은 수율을 가지는 것을 볼 수 있었다. 특성분석으로는 TGA, BET, XRD, CO-화학흡착, SEM-EDS 분석을 실시하였다. $MgAl_2O_4-800^{\circ}C$가 좋은 수율과 Pt분산도 및 적은 불활성화 정도의 관계를 서로 연관 지어 확인하였다.

Keywords

References

  1. Soo Young Kim, Ga Hee Kim, Hyoung Lim Koh, "Effect of Hydrogen Ratio and Tin Addition on the Coke Formation of Platinum Catalyst for Propane Dehydrogenation Reaction", Clen Technology, Vol. 22, No.2, pp. 82-88, (2016). https://doi.org/10.7464/ksct.2016.22.2.082
  2. Jae Won Jung, Hyoung Lim Koh, "Effect of Pt-Sn/$Al_2O_3$ catalysts mixed with metal oxides for propane dehydrogenation", J. of Korean Oil Chemists' Soc., Vol. 33, No. 2, pp. 401-410, (2016). https://doi.org/10.12925/jkocs.2016.33.2.401
  3. M. Sheintuch, O. Liron, A. Ricca, V. Palma, "Propane dehydrogenation kinetics on supported Pt catalyst", Applied Catalysis A: General, Vol.516, pp. 17-29, (2016). https://doi.org/10.1016/j.apcata.2016.02.009
  4. Mansoureh Rashidi, Manouchehr Nikazar, Mohammad Rahmani, Zahra Mohamadghasemi, "Kinetic modeling of simultaneous dehydrogenation of propane and isobutane on Pt-Sn-K/$Al_2O_3$ catalyst", Chemical Engineering Research and Design, Vol.95, pp. 239-247, (2015). https://doi.org/10.1016/j.cherd.2014.11.002
  5. Sang-Bum Kim, Eun-Seok Park, Han-Jin Cheon, Young-Kook Kim, Myung-Soo Kim, Hong-Soo Park, Hyun-Sik Hahm, "Activity Changes of Supported Nickel Catalysts with Respect to Ni Loading", J. of Korean Oil Chemists' Soc, Vol. 20, No. 3, pp. 230-236, (2003).
  6. Bao Khanh Vu, Myoung Bok Song, In Young Ahn, Young-Woong Suh, Dong Jin Suh, Won-Il Kim, Hyoung-Lim Koh, Young Gyo Choi, Eun Woo Shin, "Pt-Sn alloy phases and coke mobility over Pt-Sn/$Al_2O_3$ and Pt-Sn/Zn$Al_2O_4$ catalysts for propane dehydrogenation", Applied Catalysis A: General, Vol.400, pp. 25-33, (2011). https://doi.org/10.1016/j.apcata.2011.03.057
  7. HE Song-bo, Bl Wen-Jun, LAI Yu-Long, RONG Xing, YANG Xu, SUN Cheng-Lin, " Effect of Sn promoter on the performance of Pt-Sn/r-$Al_2O_3$ catalysts for n-dodecane dehydrogenation", Journal of Fuel Chemistry and Technology, Vol.38, No.4 pp. 452-457, (2010). https://doi.org/10.1016/S1872-5813(10)60039-4
  8. Haibo Zhu, Dalaver H. Anjum, Qingxiao Wang, Edy Abou-Hamad, Lyndon emsley, Hailin Dong, Paco Laveille, Lidong Li, Akshaya K. Samal, Jean-Marie Basset, "Sn surface-enriched Pt-Sn bimetallic nanoparticles as a selective and stable catalyst for propane dehydrogenation", Journal of Catalysis, Vol.320, pp. 52-62, (2014). https://doi.org/10.1016/j.jcat.2014.09.013
  9. Sonia A. Bocanegra, A. Guerrero-Ruiz, Sergio R. de Miguel, Osvaldo A. Scelza, "Performance of PtSn catalsys supported on M$Al_2O_4$ (M = Mg or Zn) in n-butane dehydrogenation: characterization of the metallic phase", Applied Catalysis A: General, Vol.277, pp. 11-22, (2004). https://doi.org/10.1016/j.apcata.2004.08.016
  10. Lidan Deng, Tetsuya Shishido, Kentaro Teramura, Tsunehiro Tanaka, "Effect of redurction method on the activity of Pt-Sn/$SiO_2$ for dehydrogenation of propane", Catalysis Today, Vol.232, pp. 33-39, (2014). https://doi.org/10.1016/j.cattod.2013.10.064
  11. Sonia A. Bocanegra, Alberto A. Castro, Osvaldo A. Scelza, Sergio R. de Miguel, "Characterization and catalytic behavior in the n-butane dehydrogenation of trimetallic InPtSn/Mg$Al_2O_4$ catalysts", Applied Catalysis A: General, Vol.333, pp. 49-56, (2007). https://doi.org/10.1016/j.apcata.2007.09.002
  12. Yulong Lai, Songbo He, Xianru Li, Chenglin Sun, K. Seshan, "Dehydrogenation of n-dodecane over Pt-Sn/Mg-Al-O catalysts: Investigating the catalyst performance while monitoring the products", Applied Catalysis A: General, Vol.469, pp. 74-80, (2014). https://doi.org/10.1016/j.apcata.2013.09.042
  13. Patricia D. Zgolicz, Virginia I. Rodriguez, Irene M.J. Vilella, Sergio R. de Miguel, Osvaldo A. Scelza, "Catalytic performance in selective hydrogenation of citral of bimetallic Pt-Sn catalysts supported on Mg$Al_2O_4$ and r-$Al_2O_3$", Applied Catalysis A: General, Vol.392, pp. 208-217, (2011). https://doi.org/10.1016/j.apcata.2010.11.017
  14. Yu-Ling Shan, Ting Wang, Zhi-Jun Sui, Yi-An Zhu, Xing-Gui Zhou, "Hierarchical Mg$Al_2O_4$ supported Pt-Sn as a highly thermostable catalyst for propane dehydrogenation", Catalysis Communications, Vol.84, pp. 85-88, (2016). https://doi.org/10.1016/j.catcom.2016.06.005
  15. Bin Ren, Limei Zhang, Chengli Tang, Lichun Dong, Jing Li, "Construction of hierarchical Mg$Al_2O_4$ spinel as catalytic supports", Materials Letters, Vol.159, pp. 204-206, (2015). https://doi.org/10.1016/j.matlet.2015.07.007
  16. Sonia A. Bocanegra, Adriana D. Ballarini, Osvaldo A. Scelza, Sergio R. de Miguel, "The influence of the synthesis routes of Mg$Al_2O_4$ on its properties and behavior as support of dehydrogenation catalysts", Materials Chemistry and Physics, Vol.111, pp. 534-541, (2008). https://doi.org/10.1016/j.matchemphys.2008.05.002
  17. Wei-Zhenn Li, Lei, Nie, Yingwen Cheng, Libor Kovarik, Jun Liu, Yong Wang, "Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on Mg$Al_2O_4$ spinel in oxidizing atmosphere", Catalysis Communications, Vol. 93, pp. 57-61, (2017). https://doi.org/10.1016/j.catcom.2017.01.012
  18. G. Aguilar-Rios, P. Salas, M.A. Valenzuela, H. Armendariz, J.A. Wang, J. Salmones, "Propane dehydrogenation activity of Pt and Pt-Sn catalysts supported on magnesium aluminate: influence of steam and hydrogen", Catalysis Letters, Vol. 60, pp. 21-25, (1999). https://doi.org/10.1023/A:1019086419498
  19. Fen Wang, Wei-Zhen Li, Jing-Dong Lin, Zhi-Qiang Chen, Yong Wang, "Crucial support effect on the durability of Pt/Mg$Al_2O_4$ for partial oxidation of methane to syngas", Applied Catalysis B: Environmetal, Vol. 231, pp. 292-298, (2018). https://doi.org/10.1016/j.apcatb.2018.03.018
  20. Laurence Schreyeck, Alexandre Wlosik, Herve Fuzellier, "Influence of the synthesis route on Mg$Al_2O_4$ spinel properties", Journal of Materials Chemistry, Vol. 11, pp. 483-486, (2001). https://doi.org/10.1039/b005215i
  21. Kateryna Artyushkova, Barr Halevi, Monica Padilla, Plamen Atanassov, Elena A. Baranova, "Mechanistic Study of Electrooxidation of Ethanol on PtSn Nanoparticles in Alkaline and Acid Media", Journal of The Electrochemical Society, Vol. 162, No.6, pp. 345-351, (2015). https://doi.org/10.1149/2.0401506jes
  22. Jose Salmones, Jin-An Wang, Jose A. Galicia, Gabriel Aguilar-Rios, "$H_2$ reduction behaviors and catalytic performance of bimetallic tin-modified platinum catalysts for propane dehydrogenation", Journal of Molecular Catalysis A: Chemical, Vol. 184, pp. 203-213, (2002). https://doi.org/10.1016/S1381-1169(01)00525-8
  23. Yulong Lai, Songbo He, Sha Luo, Wenjun Bi, Xianru Li, Chenglin Sun, K. Seshan, "Hydrogen peroxide modified Mg-Al-O oxides supported Pt-Sn catalysts for paraffin dehydrogenation", Catalysis Communications, Vol. 69, pp. 39-42, (2015). https://doi.org/10.1016/j.catcom.2015.05.019