Desulfurization of Diesel by Selective Adsorption of Sulfur Compounds over Zeolite and Activated Carbon

제올라이트와 활성탄에서의 황화합물 선택 흡착에 의한 경유 탈황

  • Park, Jung Geun (Separation Process Research Center, Korea Institute of Energy Research) ;
  • Ko, Chang Hyun (Separation Process Research Center, Korea Institute of Energy Research) ;
  • Bhandari, Vinay M. (Separation Process Research Center, Korea Institute of Energy Research) ;
  • Lee, Yongtaek (Department of Chemical Engineering, Chungnam National University) ;
  • Kim, Jong-Nam (Separation Process Research Center, Korea Institute of Energy Research)
  • 박정근 (한국에너지기술연구원 분리공정연구센터) ;
  • 고창현 (한국에너지기술연구원 분리공정연구센터) ;
  • ;
  • 이용택 (충남대학교 화학공학과) ;
  • 김종남 (한국에너지기술연구원 분리공정연구센터)
  • Received : 2005.07.20
  • Accepted : 2005.09.01
  • Published : 2005.10.31

Abstract

We have investigated Y zeolite and activated carbon for an adsorptive desulfurization of diesel. In batch experiments, cation ($Cu^{2+}$, $Ni^{2+}$) exchanged Y zeolites showed high equilibrium adsorption capacity for sulfur compounds in model diesel, which contained BT, DBT and 4,6-DMDBT of each 50 ppmw in n-octane. But the cation exchanged Y zeolites lost its capacity in commercial diesel (186 ppmw). On the other hand, activated carbon showed reasonable adsorption capacity for sulfur compounds in both model and commercial diesel. The adsorption capacity of sulfur on Ni-Y zeolite was decreased with the increase of benzene concentration in model diesel but the sorption capacity on activated carbon was insensitive to aromatic concentration. In breakthrough test, activated carbon of 1 g could treat 15 ml of commercial diesel with 186 ppmw sulfur. Toluene showed good solvent for regenerating activated carbon among several solvents.

흡착식 경유 탈황을 위하여 Y 제올라이트와 활성탄에서의 황화합물 흡착특성을 분석하였다. n-옥탄에 BT, DBT, 4,6-DMDBT가 각각 50 ppmw씩 포함된 모사경유와 상용경유를 이용한 회분식 흡착에서 금속이온($Cu^{2+}$, $Ni^{2+}$)이 교환된 제올라이트 흡착제들이 모사경유에서는 우수한 황화합물 흡착성을 보였으나 상용경유에서는 활성탄이 더 우수한 흡착능력을 나타냈다. 모사경유에 벤젠을 첨가하였을 때, 벤젠의 함량이 증가할수록 Ni-Y 제올라이트에서의 황흡착량은 급감하였는데, 활성탄에서는 황흡착량에 큰 영향을 받지 않았다. 활성탄에서의 파과실험에서 황화합물의 평형흡착이 일어나도록 상용경유를 최적 조건의 유속으로 주입하였을 때에 활성탄 1g은 황농도 186 ppmw인 상용경유를 15 ml까지 처리할 수 있었다. 다양한 용매를 이용한 활성탄 재생실험에서 톨루엔이 가장 우수한 재생능력을 나타냈다.

Keywords

References

  1. Clean Air Conservation Act, Table 30, Preparation Standard for Transportation Fuel and Its Additives, Ministry of Environment, Korea(2004)
  2. Gates, B. C., Katzer, J. R. and Schuit, G. C. A., A Chemistry of Catalytic Processes, McGraw-Hill, New York(1979)
  3. Song, C. and Ma, X., 'New Design Approaches to Ultra-Clean Diesel Fuels by Deep Desulfurization and Deep Dearomatization,' Appl catal B: Environmental., 41(1), 207-238(2003) https://doi.org/10.1016/S0926-3373(02)00212-6
  4. http://www.szorb.com/sulfur_removal.htm
  5. Hernandez-Maldonado, A. J. and Yang, R. T., 'New Sorbents for Desulfurization of Diesel Fuels Via $\pi$-Complexation,' AIChE., 50(4), 791-801(2004) https://doi.org/10.1002/aic.10074
  6. King, C. J., Separation Processes Based on Reversible Chemical Complexation, In Handbook of Separation Process Technology, Rousseau, R.W., ed., Wiley, New York(1987)
  7. Ma, X., Velu, S., Kim, J. H. and Song, C., 'Deep Desulfurization of Gasoline by Selective Adsorption over Solid Adsorbents and Impact of Analytical Methods on ppm-level Sulfur Quantification for Fuel Applications,' Appl Catal B: Environmental., 56(1-2), 137-147(2005) https://doi.org/10.1016/j.apcatb.2004.08.010
  8. Baes, C. F. and Mesmer, R. E., The Hydrolysis of Cations, Wiley, New York(1976)
  9. Hernandez-Maldonado, A. J. and Yang, R. T., 'Desulfurization of Liquid Fuels by Adsorption Via $\pi$-Complexation with Cu(I)-Y and Ag-Y Zeolites,' Ind. Eng. Chem. Res., 42(1), 123-129(2003) https://doi.org/10.1021/ie020728j
  10. Yang, R. T., Hernandez-Maldonado, A. J. and Yang, F. H., 'Desulfurization of Transportation Fuels with Zeolites Under Ambient Conditions,' Science, 301(5629), 79-81(2003) https://doi.org/10.1126/science.30.759.79
  11. Park, Y. T., Principles and Application of Activated Carbon(1992)
  12. Martin, R. J. and Ng, W. J., 'Chemical Regeneration of Exhausted Activated Carbon-II,' Water Res., 19(12), 1527-1535(1985) https://doi.org/10.1016/0043-1354(85)90398-7
  13. Moreno-Castilla, C., Rivera-Utrilla, J., Joly, J. P., Lopez-Ramon, M. V., Ferro-Garcia, M. A. and Carrasco-Marin, F., 'Thermal Regeneration of an Activated Carbon Exhausted with Different Substituted Phenol,' Carbon., 33(10), 1417-1423(1995) https://doi.org/10.1016/0008-6223(95)00090-Z
  14. Salvador, F. and Sanchez Jimenez, C., 'A New Method For Regenerating Activated Carbon by Thermal Desorption with Liquid Water Under Subcritical Conditions,' Carbon., 34(4), 511-516(1996) https://doi.org/10.1016/0008-6223(95)00211-1
  15. Nakano, Y., Hua, L. Q., Nishijima, W., Shoto, E. and Okada, M., 'Biodegradation of Trichloroethylene(TCE) Adsorbed on Granular Activated Carbon(GAC),' Water Res., 34(17), 4139-4142(2000) https://doi.org/10.1016/S0043-1354(00)00199-8
  16. http://www.samchullyac.co.kr