Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Oxidative Desulfurization of Marine Diesel Using WOx/SBA-15 Catalyst and Hydrogen Peroxide

WOx/SBA-15 촉매와 과산화수소를 이용한 선박용 경유의 산화 탈황 연구

  • Oh, Hyeonwoo (Department of Chemical Engineering, Pukyong National University) ;
  • Kim, Ji Man (Department of Chemistry, Sungkyunkwan University) ;
  • Huh, Kwang-Sun (Department of Advanced Materials and Chemical Engineering, Kyungnam College of Information & Technology) ;
  • Woo, Hee Chul (Department of Chemical Engineering, Pukyong National University)
  • 오현우 (부경대학교 화학공학과) ;
  • 김지만 (성균관대학교 화학과) ;
  • 허광선 (경남정보대학교 신소재응용화학과) ;
  • 우희철 (부경대학교 화학공학과)
  • Received : 2017.03.28
  • Accepted : 2017.05.22
  • Published : 2017.08.01
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Abstract

In this work, tungsten oxide ($WO_x$) supported on SBA-15 (mesoporous silica) were prepared and applied for oxidative desulfurization of sulfur compounds in marine diesel containing about 230 ppmw of sulfur concentration. Prepared catalysts were examined by two steps; at first step, oxidation reaction carried out with hydrogen peroxide as oxidant and then the oxidized sulfur compounds were extracted by acetonitrile as solvent. Catalysts were characterized by using X-ray diffraction, X-ray fluorescence, X-ray photoelectron spectroscopy and $N_2$ adsorption-desorption isotherms. Tungsten oxide exists as monoclinic crystal system on SBA-15 and over about 10 wt% of the $WO_x$ loading took the form of multi-layers on SBA-15. The 13 wt% $WO_x$/SBA-15 catalyst exhibite highest activity, achieving about 76.3% sulfur removal in the reaction conditions, such as catalyst amount of 0.1 g, reaction temperature at $90^{\circ}C$, reaction time for 3 h and O/S molar ratio of 10. One time oxidation reaction is enough oxidize the sulfur compounds in marine diesel completely. The repetition experiment of extraction process indicated that sulfur removal could reach 94.4% after 5 times.

선박용 경유(황 농도 약 230 ppmw)의 황화합물 제거를 위해 산화텅스텐($WO_x$)을 실리카로 이루어진 다공성 물질인 SBA-15에 담지한 산화 촉매를 제조하였으며 산화제로 과산화수소를 이용한 산화공정과 추출 용매로 아세토니트릴을 이용한 추출공정을 통해 촉매의 산화성능을 확인하였다. XRD 및 XRF, XPS 분석과 BET 이론을 통해 제조한 촉매의 물리적 특성에 대해 조사하였다. 담지된 $WO_x$는 삼산화텅스텐($WO_3$)으로 존재하였으며 실제 담지율이 약 10 wt% 부근일 때 단일층을 형성하는 것으로 판단된다. 제조한 촉매의 산화성능을 확인한 결과, 0.1 g의 13 wt% $WO_x$/SBA-15 촉매와 과산화수소(산소/황 몰 비=10)를 도입하여 $90^{\circ}C$에서 3시간 동안 반응이 이루어졌을 때 76.3%의 가장 높은 황 제거율을 나타냈다. 연속반응 비교 실험을 통해 1회의 산화반응으로 황 화합물의 산화가 충분히 일어났음을 확인하였다. 또한 5회의 추출공정을 통해 최대 94.4%의 황 제거율을 나타냈다.

Keywords

References

  1. Chandra Srivastava, V., "An Evaluation of Desulfurization Technologies for Sulfur Removal from Liquid Fuels," RSC Adv., 2(3), 759-783(2012). https://doi.org/10.1039/C1RA00309G
  2. Jiang, W., Zhu, W., Chang, Y., Chao, Y., Yin, S., Liu, H., Zhu, F. and Li, H., "Ionic Liquid Extraction and Catalytic Oxidative Desulfurization of Fuels Using Dialkylpiperidinium Tetrachloroferrates Catalysts," Chem. Eng. J., 250, 48-54(2014). https://doi.org/10.1016/j.cej.2014.03.074
  3. Jung, G. S., Park, D. H., Lee, D. H., Lee, H. C., Hong, S. B. and Woo, H. C., "Adsorptive Removal of Tert-butylmercaptan and Tetrahydrothiophene Using Microporous Molecular Sieve ETS-10," Appl. Catal., B, 100, 264-270(2010). https://doi.org/10.1016/j.apcatb.2010.08.002
  4. van Biert, L., Godjevac, M., Visser, K. and Aravind, P. V., "A Review of Fuel Cell Systems for Maritime Applications," J. of Power Sources, 327, 345-364(2016). https://doi.org/10.1016/j.jpowsour.2016.07.007
  5. Ho, H. P., Kim, W. H., Lee, S. Y., Son, H. R., Kim, N. H., Kim, J. K., Park, J. Y. and Woo, H. C., "Adsorptive Desulfurization of Diesel for Fuel Cell Applications: A Screening Test," Clean Technol., 20(1), 88-94(2014). https://doi.org/10.7464/ksct.2014.20.1.088
  6. Yang, Y.-Z., Liu, X.-G. and Xu, B.-S., "Recent Advances in Molecular Imprinting Technology for the Deep Desulfurization of Fuel Oils," New Carbon Mater., 29(1), 1-14(2014). https://doi.org/10.1016/S1872-5805(14)60121-9
  7. Ho, P. H., Lee, S.-Y., Lee, D. and Woo, H.-C., "Selective Adsorption of Tert-butylmercaptan and Tetrahydrothiophene on Modified Activated Carbons for Fuel Processing in Fuel Cell Applications," Int. J. Hydrogen. Energ., 39, 6737-6745(2014). https://doi.org/10.1016/j.ijhydene.2014.02.011
  8. Sammes, N., Fuel Cell Technology: Reaching Towards Commercialization, Springer London (2006).
  9. Ho, P. H., Lee, S. C., Kim, J., Lee, D. and Woo, H. C., "High Performance of Manganese Oxide Octahedral Molecular Sieve Adsorbents for Removing Sulfur Compounds from Fuel Gas," Korean J. Chem. Eng., 32(9), 1766-1773(2015). https://doi.org/10.1007/s11814-015-0031-0
  10. Ho, H. P., Kasinathan, P., Kim, J., Lee, D. and Woo, H. C., "Deep Desulfurization of Fuel Gas by Adsorption on Cu-impregnated Activated Carbons in Practical Conditions," Korean J. Chem. Eng., 33(6), 1908-1916(2016). https://doi.org/10.1007/s11814-016-0018-5
  11. de Souza, W. F., Guimaraes, I. R., Guerreiro, M. C. and Oliveira, L. C. A., "Catalytic Oxidation of Sulfur and Nitrogen Compounds from Diesel Fuel," Appl. Catal., A, 360(2), 205-209(2009). https://doi.org/10.1016/j.apcata.2009.03.023
  12. Cho, C. S., Jeong, K. E., Chae, H. J.. Kim, C. U., Jeong, S. Y. and Oh, S. G., "Characteristics of Oxidative Desulfurization (ODS) of Sulfur Compounds in Diesel Fuel over Ti-grafted SBA-15 Catalyst," Korean Chem. Eng. Res., 46(5), 845-851(2008).
  13. Zhang, J., Wang, A., Wang, Y., Wang, H. and Gui, J., "Heterogeneous Oxidative Desulfurization of Diesel Oil by Hydrogen Peroxide: Catalysis of An Amphipathic Hybrid Material Supported on $SiO_2$," Chem. Eng. J., 245, 65-70(2014). https://doi.org/10.1016/j.cej.2014.01.103
  14. Bakar, W. A. W. A., Ali, R., Kadir, A. A. A. and Mokhtar, W. N. A. W., "Effect of Transition Metal Oxides Catalysts on Oxidative Desulfurization of Model Diesel," Fuel Process. Technol., 101, 78-84(2012). https://doi.org/10.1016/j.fuproc.2012.04.004
  15. Sundararaman, R. and Song, C., "Oxidative Desulfurization of Crude Oil Incorporating Sulfone Decomposition by Alkaline Earth Metal Oxides," Energy Fuels, 27(11), 6372-6376(2013). https://doi.org/10.1021/ef401450t
  16. Ma, C., Dai, B., Liu, P., Zhou, N., Shi, A., Ban, L. and Chen, H., "Deep Oxidative Desulfurization of Model Fuel Using Ozone Generated by Dielectric Barrier Discharge Plasma Combined with Ionic Liquid Extraction," J. Ind. Eng. Chem., 20(5), 2769-2774(2014). https://doi.org/10.1016/j.jiec.2013.11.005
  17. Li, F.-T., Liu, Y., Sun, Z.-M., Zhao, Y., Liu, R.-H., Chen, L.-J. and Zhao, D.-S., "Photocatalytic Oxidative Desulfurization of Dibenzothiophene Under Simulated Sunlight Irradiation with Mixed-phase $Fe_2O_3$ Prepared by Solution Combustion," Catal. Sci. Technol., 2(7), 1455-1462(2012). https://doi.org/10.1039/c2cy00485b
  18. Han, X., Wang, A., Wang, X., Li, X., Wang, Y. and Hu, Y., "Catalytic Performance of P-modified $MoO_3/SiO_2$ in Oxidative Desulfurization by Cumene Hydroperoxide," Catal. Commun., 42, 6-9(2013). https://doi.org/10.1016/j.catcom.2013.07.027
  19. Sattler, A. and Parkin, G., "Cleaving Carbon-carbon Bonds by Inserting Tungsten Into Unstrained Aromatic Rings," Nature, 463(7280), 523-526(2010). https://doi.org/10.1038/nature08730
  20. Long, Z., Yang, C., Zeng, G., Peng, L., Dai, C. and He, H., "Catalytic Oxidative Desulfurization of Dibenzothiophene Using Catalyst of Tungsten Supported on Resin D152," Fuel, 130, 19-24(2014). https://doi.org/10.1016/j.fuel.2014.04.005
  21. Kasztelan, S., Payen, E. and Moffat, J. B., "The Existence and Stability of the Silica-supported 12-molybdophosphoric Acid Keggin Unit as Shown by Raman, XPS, and $^{31}P$ NMR Spectroscopic Studies," J. Catal., 125, 45-53(1990). https://doi.org/10.1016/0021-9517(90)90076-V
  22. Yang, X.-L., Dai, W.-L., Gao, R. and Fan, K., "Characterization and Catalytic Behavior of Highly Active Tungsten-doped SBA-15 Catalyst in the Synthesis of Glutaraldehyde Using An Anhydrous Approach," J. Catal., 249(2), 278-288(2007). https://doi.org/10.1016/j.jcat.2007.05.002
  23. Wang, D., Liu, N., Zhang, J., Zhao, X., Zhang, W. and Zhang, M., "Oxidative Desulfurization Using Ordered Mesoporous Silicas as Catalysts," J. Mol. Catal. A: Chem., 393, 47-55(2014). https://doi.org/10.1016/j.molcata.2014.05.026
  24. Tang, L., Luo, G., Zhu, M., Kang, L. and Dai, B., "Preparation, Characterization and Catalytic Performance of HPW-TUD-1 Catalyst on Oxidative Desulfurization," J. Ind. Eng. Chem., 19(2), 620-626(2013). https://doi.org/10.1016/j.jiec.2012.09.015
  25. Li, Z., Xu, J., Li, D. and Li, C., "Extraction Process of Sulfur Compounds from Fuels with Protic Ionic Liquids," RSC Adv., 5, 15892-15897(2015). https://doi.org/10.1039/C4RA16186F

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