한국가스학회지 (Journal of the Korean Institute of Gas)

  • 제13권4호
  • /
  • Pages.8-14
  • /
  • 2009
  • /
  • 1226-8402(pISSN)
  • /
  • 2713-6922(eISSN)
한국가스학회 (The Korean Institute of GAS)
권호 표지

합성가스로부터 디메틸에테르 직접 합성

Direct Synthesis of Dimethyl Ether from Synthesis Gas

  • 함현식 (명지대학교 공과대학 화학공학과) ;
  • 김송형 (명지대학교 공과대학 화학공학과) ;
  • 강영구 (명지대학교 공과대학 화학공학과) ;
  • 신기석 (명지대학교 공과대학 화학공학과) ;
  • 안성환 (명지대학교 공과대학 화학공학과)
  • Hahm, Hyun-Sik (Department of Chemical Engineering, Myongji University) ;
  • Kim, Song-Hyoung (Department of Chemical Engineering, Myongji University) ;
  • Kang, Young-Gu (Department of Chemical Engineering, Myongji University) ;
  • Shin, Ki-Seok (Department of Chemical Engineering, Myongji University) ;
  • Ahn, Sung-Hwan (Department of Chemical Engineering, Myongji University)
  • 발행 : 2009.08.31
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

하이브리드 촉매를 이용하여 합성가스로부터 디메틸에테르(DME)를 1단계 공정으로 합성하였다. 하이브리드 촉매는 메탄올 합성반응을 위하여 Cu-ZnO-$Al_2O_3$, 메탄올 탈수반응을 위하여 aluminum phosphate 혹은 $H_3PO_4$-modified $\gamma$-alumina로 구성되었다. 제조한 촉매들은 XRD, BET, SEM, FT-IR, $NH_3$-TPD를 이용하여 특성분석을 하였다. XRD 분석을 통해 aluminum phosphate가 잘 합성되었음을 알 수 있었다. BET 분석을 통해 aluminum phosphate의 비표면적이 P/Al의 비에 따라서 달라짐을 확인할 수 있었다. 반응실험 결과 메탄올 탈수 촉매로 사용된 aluminum phosphate의 P/Al의 비가 1.2인 하이브리드 촉매에서 55%의 CO 전환율과 70%의 DME 선택도를 보여 주었다. $\gamma$-alumina를 인산으로 처리한 경우 촉매활성 감소를 막을 수 있었다. 하지만 85%의 진한인산으로 처리한 경우에는 촉매 활성 및 DME 선택도가 낮아짐을 확인할 수 있었다.

Dimethyl ether(DME) was synthesized from synthesis gas by a one-step process in which a hybrid catalyst was used. The hybrid catalyst consisted of Cu-ZnO-$Al_2O_3$ for the methanol synthesis reaction and aluminum phosphate or $H_3PO_4$-modified $\gamma$-alumina for the methanol dehydration reaction. The prepared catalysts were characterized by XRD, BET, SEM, FT-IR and $NH_3$-TPD. From the XRD analysis, it was verified that the aluminum phosphate was successfully synthesized. The specific surface areas of the synthesized aluminum phosphates were varied with the ratio of P/Al. The hybrid catalyst in which P/Al ratio of the aluminum phosphate was 1.2 showed the highest CO conversion of 55% and DME selectivity of 70%. There was no remarkable decrease in catalytic activity with the phosphoric acid treatment of $\gamma$-alumina. However, when treated with concentrated phosphoric acid(85%), the catalytic activity and DME selectivity decreased.

키워드

참고문헌

  1. Lewis, R.J. Hawley's condensed chemical dictionary, 12th ed., Van Nostrand Reinhold, New York, 810 (1993)
  2. Semelsberger, T., R. Borup and H. Greene, "Dimethyl ether (DME) as an alternative fuel", J. Power Sources, 156, 497-511 (2006) https://doi.org/10.1016/j.jpowsour.2005.05.082
  3. Wang, S., D. Mao, X. Guo, G. Wu and G. Lu, "Dimethyl ether synthesis via CO2 hydrogenation over CuO–TiO2– ZrO2/HZSM-5 bifunctional catalysts", Catalysis Communications 10(10), 1367-1370 (2009) https://doi.org/10.1016/j.catcom.2009.02.001
  4. Reubroycharoen, P., S. Teppood, T. Vitidsant, C. Chaiya, S. Butnark and N. Tsubaki, "A novel, low temperature synthesis method of dimethyl ether over Cu-Zn catalyst based on self- catalysis effect of methanol", Topics in Catalysis, 52(8), 1079-1084 (2009) https://doi.org/10.1007/s11244-009-9252-y
  5. Bae, J. W., Kang, S. H. Kang, Y. J. Lee, Jun, K. W. Jun, "Synthesis of DME from syngas on the bifunctional $Cu-ZnO-Al_{2}O_{3}$/Zr-modified ferrierite: Effect of Zr content", Applied Catalysis, B: Environmental, 90(3-4), 426-435 (2009) https://doi.org/10.1016/j.apcatb.2009.04.002
  6. Shikada, T., F. Fujimoto, M. Miyaucki and H. Tomiha, "Vapor phase carbonylation of dimethyl ether and methyl acetate with nickel-active carbon catalysts", Appl. Catal., 7, 361-367 (1983) https://doi.org/10.1016/0166-9834(83)80035-9
  7. Kim, J.H., M.J. Park, S.J. Kim, O.S. Joo and K.D. Jung, "DME synthesis from synthesis gas on the admixed catalysts of $Cu/ZnO/Al_{2}O_{3}$ and ZSM-5", Appl. Catal., A 264, 37-42 (2004) https://doi.org/10.1016/j.apcata.2003.12.058
  8. Ge, Q., Y. Huang, F. Qiu and S. Li, "Bifunctional catalysts for conversion of synthesis gas to dimethyl ether", Appl. Catal., A167, 23-29 (1998)
  9. Sun, K., W. Lu, F. Qiu, S. Liu and X. Xu, "Direct synthesis of DME over bifunctional catalyst: surface properties and catalytic performance", Appl. Catal., A252, 243-250 (2003)
  10. Xu, M., J.H. Lunsford, D.W. Goodman and A. Bhattacharyya, "Synthesis of dimethyl ether (DME) from methanol over solid-acid catalysts", Appl. Catal., A149, 269-275 (1997)
  11. European Pattent Application, EP1 174 408 A1 (23. 01. 2003)
  12. Erena, J. Ph. D. Thesis, University of the Basque Country, Bilbao, Spain (1996)
  13. Huang, Y., R. Richer and C. W. Kirby, J. Phys. Chem., B 107, 1326-1334 (2003) https://doi.org/10.1021/jp021878a
  14. Kanai, Y., T. Wanatabe, T. Fujitani, M. Saito, J. Nakamura and T. Vchijima, Energy Convers. Mgmt, 36, 6-10 (1995)