Carbon-Based Nanomaterials for Desulfurization: Classification, Preparation, and Evaluation

Carbon-Based Nanomaterials for Desulfurization: Classification, Preparation, and Evaluation

Tawfik A. Saleh (Department of Chemistry, King Fahd University of Petroleum and Minerals, Saudi Arabia), Taye Damola Shuaib (King Fahd University of Petroleum and Minerals, Saudi Arabia), Gaddafi Ibrahim Danmaliki (King Fahd University of Petroleum and Minerals, Saudi Arabia) and Mohammed A. Al-Daous (Saudi Aramco, Saudi Arabia)
DOI: 10.4018/978-1-4666-9545-0.ch005
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The special interest in ultra-low sulfur diesel (ULSD) is informed by the need to comply with the strict government policy on low sulfur content of transportation fuels. Better knowledge of different factors that concern deep desulfurization of fuels is important to achieve ultra-low sulfur fuels and cheaper way of producing ULSD. Both the capital and operating cost of the adsorptive desulfurization process is cheaper compare to the conventional hydroprocessing. The need to produce more volume of fuel such as diesel with very low sulfur content from low grade feed stocks like heavy oil and light cycle oil (LCO) in order to meet up with the global demand for sulfur-free fuels is pertinent. Several on-going researches are pointing to the use of adsorbents for removal of sulfur compounds from the hydrocarbon refining stream. In this chapter, varieties of carbon nanomaterials suitable for adsorptive desulfurization are discussed. The approach is feasible for commercial applications with any adsorbent of an adequate lifetime of activity as well as high capacity.
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1. Introduction

Desulfurization is a vital unit operation in petroleum refining since the combustion products of sulfur compounds are the main reason for acid rain and environmental pollution. In addition, sulfur is also a catalyst poison during industrial processes. Compounds with sulfur are removed catalytically at high temperature and pressure. Desulfurization is gaining a lot of attention and efforts have been channeled towards investigating several methods that are effective and economically viable. The attention is warranted by stricter environmental regulations on the amount of sulfur that should be present in transportation fuels (Song, 2003; Yang et al., 2004). Sulfur limit (mass percent) of 0.015, 0.035, and 0.2 for gasoline, diesel fuel and light fuel oil, respectively has been set. A new and more stringent limit of 0.003-0.005 mass percent (30-50 ppm) is imminent for transportation fuels in Europe and United States of America (Song, 2003; State Announcer, 2001; Babich and Monlijn, 2003). It’s worthy to note also that; desulfurization processes have found applications in converting used tires and shale oil to fuel oils. Using calcium oxide in binding up sulfur oxide in emissions has been achieved for stationary applications in the desulfurization of non-transportation fuels, but the use of the harmful compounds still a challenge (Svobodal et al., 1994). Therefore, the need to innovate effective technologies for desulfurization processes is paramount.

Several methods of desulfurization processes have been investigated for many years. The need to achieve a lower level of sulfur in fuel oils has also called for different innovative ways of achieving deep desulfurization where the synergy of methods yielding better results (Agarwal and Sharma, 2010; Sundaraman et al., 2009). Hydrodesulfurization (HDS) is a popular process, but there is wide variation in reactivity of sulfur-containing heterocyclic compounds. Alkyl-substituted derivatives of dibenzothiophene like 4-methyldibenzothiophene and 4, 6-dimethyldibenzothiophene from fuel oils have been reported to be relatively unreactive towards hydroprocessing (Gate and Tropsoe, 1997). In order to achieve deep-desulfurization and take care of attending challenges of hydrodesulfurization that include high hydrogen consumption, energy (heat) cost, catalyst volume etc. Many other methods are combined with HDS for better results (Rana et al., 2007). In recent years, efforts are being directed to other methods, including; adsorptive desulfurization, oxidative desulfurization where different catalysts are used (Kumar et al., 2012) extractive desulfurization involving ionic liquids, photochemical activation, bio-desulfurization, ultrasonic-desulfurization, microwave desulfurization and electrochemical approach (Bhatia and Sharma, 2006; Lam et al., 2012).

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