Characteristics of Oxidative Desulfurization(ODS) of Sulfur Compounds in Diesel Fuel over Ti-grafted SBA-15 Catalyst

Ti-grafted SBA-15 촉매를 이용한 경유유분 중의 황화합물의 선택산화탈황 특성

  • 조진수 (한국화학연구원 석유대체연구센터) ;
  • 정광은 (한국화학연구원 석유대체연구센터) ;
  • 채호정 (한국화학연구원 석유대체연구센터) ;
  • 김철웅 (한국화학연구원 석유대체연구센터) ;
  • 정순용 (한국화학연구원 석유대체연구센터) ;
  • 오성근 (한양대학교 응용화공생명공학부)
  • Received : 2008.03.26
  • Accepted : 2008.04.16
  • Published : 2008.10.31

Abstract

Oxidative desulfurizaton of model sulfur compounds and Industrial diesel fuel(LCO; Light Cycle Oil) over Ti-grafted SBA-15 catalyst was studied in a batch reactor with tert-Butyl Hydroperoxide(TBHP) as oxidant. Effects of Ti loading, TBHP/Sulfur mole ratio, reaction temperature on ODS activity and kinetic parameters were investigated. Ti-grafted SBA-15 catalyst showed higher sulfur removal activity in the oxidative desulfurization reaction of refractory sulfur compounds(DBT and 4, 6-DMDBT) and LCO, suggesting that Ti-grafted SBA-15 catalyst could be a good candidate for ODS catalyst.

티타늄이 그라프팅(grafting)된 SBA-15 촉매(Ti-grafted SBA-15)상에서 TBHP(tert-butylhydroperoxide)를 산화제로 사용하여 회분식 반응기에서 모델 황화합물 및 실제 디젤 유분(LCO; Light Cylcle Oil)의 선택산화탈황(ODS; Oxidative Desulfurization) 반응을 수행하였으며, 티타늄 함량, 산화제/황의 몰비, 반응온도의 효과 및 반응속도상수와 활성화 에너지를 조사하였다. 티타늄이 5 wt% 도입된 Ti-grafted SBA-15 촉매는 난분해성 황화합물인 디벤조티오펜(DBT; Dibenzothiophene)과 4, 6-디메틸디벤조티오펜(4, 6-Dimethyldibenzothiophene)의 설폰(sulfone) 화합물로의 산화반응 시 표준반응조건(TBHP/S=2.5, $80^{\circ}C$, 1 atm)에서 반응개시 후 20분 뒤 100% 전환되는 우수한 활성을 나타내었다. 실제 디젤유분인 LCO를 원료로 성능 시험을 한 결과 활성이 우수하게 나타났으며 Ti-grafted SBA-15 촉매는 LCO에 함유 되어 있는 난분해성 황화합물의 선택적 산화탈황촉매로써 응용 가능성을 보였다.

Keywords

References

  1. Lu, Li., Cheng, S., Gao, J., Gao, G. and He, M. Y., "Deep Oxidative Desulfurization of Fuels Catalyzed by Ionic Liquid in the Presence of $H_{2}O_{2}$," Energy& Fuels, 21, 383-384(2007) https://doi.org/10.1021/ef060345o
  2. Wang, D., Qian, E. W., Amano, H., Okata, K., Ishihara, A. and Kabe, T., "Oxidative Desulfurization of Fuel Oil: Part I. Oxidation of Dibenzothiophenes Using Tert-butyl Hydroperoxide," Appl. Catal A: General, 253, 91-99(2003) https://doi.org/10.1016/S0926-860X(03)00528-3
  3. Ishihara, A., Wang, D., Dumeignil, F., Amano, H. and Kabe, T., "Oxidative Desulfurization and Denitrogenation of A Light Gas Oil Using An Oxidation/adsorption Continuous Flow Process," Appl. Catal A: General, 279, 279-287(2005) https://doi.org/10.1016/j.apcata.2004.10.037
  4. Sampanthar, J. T., Xiao, H., Dou, J. and Nah, T. Y., "A Novel Oxidative Desulfurization Process to Remove Refractory Sulfur Compounds From Diesel Fuel," Appl. Catal B: Environmental, 63, 85-93(2006) https://doi.org/10.1016/j.apcatb.2005.09.007
  5. Otsuki, S., Nonaka, T., Takashima, N., Qian, W., Ishihara, A., Imai, T. and Kabe, T., "Oxidative Desulfurization of Light Gas Oil and Vacuum Gas Oil by Oxidation and Solvent Extraction," Energy & Fuels, 14, 1232-1239(2000) https://doi.org/10.1021/ef000096i
  6. Campos-Martin, J. M., Capel-Sanchez, M. C. and Fierro, J. L. G., "Highly Efficient Deep Desulfurization of Fuels by Chemical Oxidation," Green Chem., 6, 557-562(2004) https://doi.org/10.1039/b409882j
  7. Zhu, W., Li, H., Jiang, X. and Yan, Y., "Oxidative Desulfurization of Fuels Catalyzed by Peroxotungsten and Peroxomolybdenum Complexes in Ionic Liquids," Energy & Fuels, 21, 2514-2516(2007) https://doi.org/10.1021/ef700310r
  8. Wang, Y., Li, G., Wang, X. and Jin, C., "Oxidative Desulphurization of 4,6-Dimethyldibenzothiophene with Hydrogen Peroxide over Ti-HMS," Energy & Fuels, 21, 1415-1419(2007) https://doi.org/10.1021/ef070006a
  9. Chica, A., Corma, A. and Domine, M. E., "Catalytic Oxidative Desulfurization (ODS) of Diesel Fuel on a Continuous Fixed-bed Reactor," J. Catal., 242, 299-308(2006) https://doi.org/10.1016/j.jcat.2006.06.013
  10. Chen, Y., Huang, Y. and Xiu, J., "Direct Synthesis, Characterization and Catalytic Activity of Tianium-substituted SBA-15 Mesoporous Molecular Sieves," Appl. Catal A; General, 273, 185-191(2004) https://doi.org/10.1016/j.apcata.2004.06.030
  11. Wu, P. and Tatsumi, T., "Postsynthesis, Characterization, and Catalytic Properties in Alkene Epoxidation of Hydrothermally Stable Mesoporous Ti-SBA-15," Chem. Mater., 14, 1657-1664(2002) https://doi.org/10.1021/cm010910v
  12. Zhao, D., Feng, J. and Huo, Q., "Triblock Copolymer Synthesed of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores," Science, 279, 548-552(1998) https://doi.org/10.1126/science.279.5350.548
  13. Ban, H. J., Lee, K. Y., Lee, J. K., Chung, S. T. and Ahn, W. S., "Propylene Epoxidation using Titanium-containing Zeolite Catalysts," Korean Chem. Eng. Res., 44, 121-128(2006)
  14. Kong, L., Li, G. and Wang, X., "Kinetics and Mechanism of Liquid-phase Oxidation of Thiophene over TS-1 Using $H_{2}O_{2}$ Under Mild Conditions," Catal Lett., 92, 163-167(2004) https://doi.org/10.1023/B:CATL.0000014340.08449.d0
  15. Otsuki, S., Nonaka, T. and Takashima, N., "Oxidative Desulfurization of Light Gas Oil and Vacuum Gas Oil by Oxidation and Solvent Extraction," Energy & Fuels, 14, 1232-1239(2000) https://doi.org/10.1021/ef000096i
  16. Hulea, V., Fajula, F., Bousquent, J., "Mild Oxidation with H2O2 over Ti-Containing Molecular Sieves-A very Efficient Method for Removing Aromatic Sulfur Compounds from Fuels," J. Catal., 198, 179(2001) https://doi.org/10.1006/jcat.2000.3149