Journal of the Korean Institute of Gas (한국가스학회지)

The Korean Institute of GAS (한국가스학회)
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Effects of La Addition and Preparation Methods on Catalytic Activities for Methane Partial Oxidation Catalysts

메탄 부분산화반응 촉매에 La 첨가 및 제조방법에 따른 촉매활성에 미치는 영향

  • Cheon, Han-Jin (Department of Chemical Engineering, Myongji University) ;
  • Shin, Ki-Seok (Department of Chemical Engineering, Myongji University) ;
  • Ahn, Sung-Hwan (Department of Chemical Engineering, Myongji University) ;
  • Yoon, Cheol-Hun (Department of Chemical Engineering, Myongji University) ;
  • Hahm, Hyun-Sik (Department of Chemical Engineering, Myongji University)
  • 천한진 (명지대학교 공과대학 화학공학과) ;
  • 신기석 (명지대학교 공과대학 화학공학과) ;
  • 안성환 (명지대학교 공과대학 화학공학과) ;
  • 윤철훈 (명지대학교 공과대학 화학공학과) ;
  • 함현식 (명지대학교 공과대학 화학공학과)
  • Received : 2009.12.03
  • Accepted : 2010.04.03
  • Published : 2010.04.30
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Abstract

Synthesis gas was produced by the partial oxidation of methane. For the preparation of catalysts, Ni, known to be active in this reaction and cheap, was used as the active component and $CeO_2$, having high oxygen storage capability and high redox ability, was used as the support. The catalysts were prepared by the impregnation and urea methods. The catalyst prepared by the urea method showed about 11 times higher surface area and finer particle size than that prepared by the impregnation method. The catalysts prepared by the urea method showed higher methane conversion and synthesis gas selectivity than that prepared by the impregnation method. In this reaction, carbon deposition is a problem to be solved, so La was added to the catalyst system to reduce the carbon deposition. TGA analysis results showed that there was 2% carbon deposition with La-added catalysts and 16% with La-free catalysts. It was found that the addition of La decreases the amount of carbon deposition and prevents catalyst deactivation.

메탄의 부분산화에 의하여 합성가스를 제조하였다. 저렴하며 본 반응에 활성이 좋은 것으로 알려진 Ni을 활성 물질로, 우수한 산소 저장능력과 높은 산화 환원 특성을 지닌 $CeO_2$를 담체로 하여, 함침법과 우레아법으로 촉매를 제조하였다. 반응은 고정층 반응기를 이용하여 1 atm, $650{\sim}800^{\circ}C$에서 실시하였다. 표면적 측정 장치를 이용하여 촉매 제조법에 따른 표면적 차이를 비교해 본 결과 우레아법으로 제조한 촉매가 함침법으로 제조한 촉매보다 표면적이 약 11배 이상 큼을 알 수 있었고, SEM으로 표면 구조를 조사해본 결과 우레아법으로 제조한 촉매가 훨씬 더 미세하고 균일함을 알 수 있었다. 우레아법으로 제조한 촉매가 함침법으로 제조한 촉매보다 더 높은 메탄 전환율 및 합성가스 선택도를 나타내었다. 본 반응의 문제점인 탄소 침적을 줄이기 위하여 La을 첨가하여 탄소 침적에 미치는 La의 영향을 알아보았다. TGA(열중량 분석기) 분석 결과 La이 첨가되지 않은 촉매에는 약 16%의 탄소 침적이, La을 첨가한 촉매에는 약 2%의 탄소 침적이 형성되었다. 따라서 La 첨가는 탄소 침적을 줄여서 촉매 비활성화를 막은 것으로 추정된다.

Keywords

References

  1. Wang, M., W. Weng, H. Zheng, X. Yi, C. Huang and H. Wan, "Oscillations during partial oxidation of methane to synthesis gas over $RU/Al_{2}O_{3}$catalyst", Journal of Natural Gas Chemistry, 18(3), 300-305 (2009) https://doi.org/10.1016/S1003-9953(08)60126-7
  2. Nielsen, J.R.R. and I. Alstrup, "Innovation and science in the process industry: steam reforming and hydrogenolysis", Catalysis Today, 53, 311-316 (1999) https://doi.org/10.1016/S0920-5861(99)00125-X
  3. Liu, D., X.Y. Quek, H.H.A. Wah, A. Hui, G. Zeng, Y. Li and Y. Yang, "Carbon dioxide reforming of methane over nickel-grafted SBA-15 and MCM-41 catalysts", Catalysis Today, 148(3-4), 243-250 (2009) https://doi.org/10.1016/j.cattod.2009.08.014
  4. Sazonova, N.N., V.A. Sadykov, A.S. Bobin, S.A. Pokrovskaya, E.L. Gubanova and C. Mirodatos, "Partial oxidation of methane into syngas on Pt-supported mixed oxides", Reaction Kinetics and Catalysis Letters, 98(1), 27-33 (2009) https://doi.org/10.1007/s11144-009-0063-8
  5. Wang, H.Y. and E. Ruckenstein, "Partial oxidation of methane to synthesis gas over alkaline earth metal oxide supported cobalt catalysts", J. Catal., 199, 309-317 (2001) https://doi.org/10.1006/jcat.2001.3190
  6. Wang, H.Y. and E. Ruckenstein, "Catalytic partial oxidation of methane to synthesis gas over $\gamma$ -$Al_{2}O_{3}$- supported rhodium catalysts", Catal. Lett., 59, 121-127 (1999) https://doi.org/10.1023/A:1019045210412
  7. Hegarty, M.E.S., A. M. O'Connor and J.R.H. Ross, "Syngas production from natural gas using $ZrO_{2}$-supported metals", Catalysis Today, 42, 225-232 (1998) https://doi.org/10.1016/S0920-5861(98)00096-0
  8. Takenaka, S., Y. Orita, H. Umebayashi, H. Matsune and M. Kishida, "High resistance to carbon deposition of silica-coated Ni catalysts in propane steam reforming", Appl. Catal. A: Gen., 351(2), 189-194 (2008) https://doi.org/10.1016/j.apcata.2008.09.017
  9. Drago, R.S., K. Jurczyk, N. Kob, A. Bhattacharyya and J. Masin, "Partial oxidation of methane to syngas using NiO-supported catalysts", Catal. Lett., 51, 177-181 (1998) https://doi.org/10.1023/A:1019005605676
  10. Zhu, T. and M. F. Stephanopoulos, "Catalytic partial oxidation of methane to synthesis gas over Ni-$CeO_{2}$", Appl. Catal. A:Gen., 208, 403-417 (2001) https://doi.org/10.1016/S0926-860X(00)00728-6
  11. Liu, S., G. Xiong, H. Dong and W. Yang, "Effect of carbon dioxide on the reaction performance of partial oxidation of methane over a LiLaNiO/$\gamma$-$Al_{2}O_{3}$ Catalyst", Appl. catal. A: Gen., 202, 141-146 (2000) https://doi.org/10.1016/S0926-860X(00)00460-9
  12. Pino, L., A. Vita, M. Cordaro, V. Recupero and M.S. Hegde, "A comparative study of Pt/$CeO_{2}$ catalysts for catalytic partial oxidation of methane to syngas for application in fuel cell electric vehicles", Appl. Catal. A: Gen., 243, 135-146 (2003) https://doi.org/10.1016/S0926-860X(02)00542-2
  13. Anilkumar, M., S.R. Dhage and V. Ravi, " Synthesis of bismuth titanate by the urea method", Materials Letters, 59(4), 514-516 (2005) https://doi.org/10.1016/j.matlet.2004.10.038
  14. Takehira, K., T. Shishido, P. Wang, T. Kosaka and K. Takaki, "Autothermal reforming of $CH_{4}$ over supported Ni catalysts prepared from Mg-Al hydrotalcite-like anionic clay", J. Catal., 221(1), 43-54 (2004) https://doi.org/10.1016/j.jcat.2003.07.001