(100c) Desulfurization and Denitrogenation Of Silica-Based Adsorbents For CLEAN Fossile Fuels
AIChE Annual Meeting
2013
2013 AIChE Annual Meeting
Separations Division
Adsorption and Ion Exchange Plenary: Fundamentals and Applications
Monday, November 4, 2013 - 1:12pm to 1:33pm
DesuLfurization and denitrogenation of silica-based adsorbents for clean fossile Fuels
Chang Ha Lee
Department of Chemical and Biomolecular Engineering, Yonsei University,
50 Yonsei-ro, Seodaemun-gu, Seoul, 120-749, Korea
E-mail: leech@yonsei.ac.kr
Due to increasingly stringent environmental regulations for transportation fuels, the desulfurization and denitrogenation of fuels have become very important research topics in the production of clean automotive fuels with ultra-low sulfur levels. According to the new environmental protection agency (EPA) Tier II regulations, the maximum allowable sulfur content in US diesel fuel is less than 15ppmw. In addition, some fuel cells will require deep-desulfurized fuels with sulfur content <1 ppmw in order to avoid poisoning and deactivation of the reformer catalyst.
Heavy low-quality crude oil and natural gas are rich in highly refractory nitrogen and sulfur compounds. During catalytic hydrotreating, denitrogenation (HDN) and desulfurization (HDS) are performed simultaneously. The ability to adsorb nitrogen compounds is generally higher when compared to aromatic thiophene derivatives, which have to compete with nitrogen compounds for active sites on catalysts during HDS processes. In addition, the HDN is the most difficult hydrotreatment reaction and slower than the HDS. Therefore, nitrogen compound residue remains on active sites longer than sulfur compounds. In addition, the removal of sulfur-containing compounds from natural, municipal or shale gas has also traditionally been achieved by the catalytic HDS process operated at elevated temperatures and pressures.
As an alternative method, selective adsorption appears to be a promising approach to ultra-deep desulfurization and denitrogenation because the process can be run at ambient temperature and atmospheric pressure without consuming pressurized hydrogen or oxygen gas.
In the presentation, a class of highly sulfur- and nitrogen-compounds selective silica-based porous adsorbents (Zr-Si cogel, mesoporous YSP, magnetite-mesoporous silica composite, MCF-Li, MgO silica composite) is introduced. Adsorption and desorption equilibrium by using real residue hydrodesulfurization diesel (RHDS DSL) were studied at ambient temperature and pressure. The dynamic behaviors of adsorption and desorption for RHDS DSL and municipal gas will be also presented.
Keywords: Silica, Adsorption, desulfurization, denitrogenation, fossil fuel
References
1. A. Koriakin, Y.H. Kim, C.H. Lee, "Adsorptive Desulfurization of Natural Gas Using Lithium-Modified Mesoporous Silica," Ind. Eng. Chem. Res., 51 (2012), 14489.
2. S.H. Lim, E.J. Woo, H. Lee, C.H. Lee, "Synthesis of Magnetite-Mesoporous Silica Composites as Adsorbents for Desulfurization from Natural Gas," Applied Catalysis B: Environmental, 85 (2008) 71.
3. A. Koriakin, K.M. Ponvel, C.H. Lee, “Denitrogenation of Raw Diesel Fuel by Lithium-modified Mesoporous Silica,” Chem. Eng. J., 162 (2010) 649.
4. J.M. Kwon, J.H. Moon, Y.S. Bae, D.G. Lee, H.C. Sohn, C.H. Lee, "Adsorptive Desulfurization and Denitrogenation of Refinery Fuels by Mesoporous Silica Adsorbents" ChemSusChem, 1 (2008) 307.
5. Y.S. Bae, M.B. Kim, H.J. Lee, J.U. Ryu, C.H. Lee, "Adsorptive Denitrogenation of Light Gas Oil by Silica-Zirconia Cogel at Ambient Condition," AIChE J., 52 (2006), 510.