Open Access
Almarri, Masoud S.
Graduate Program:
Energy and Geo-Environmental Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
March 30, 2009
Committee Members:
  • Chunshan Song, Dissertation Advisor
  • Sridhar Komarneni, Committee Member
  • Andre Louis Boehman, Committee Member
  • Harold Harris Schobert, Committee Member
  • Chunshan Song, Committee Chair
  • Xiaoliang Ma, Committee Member
  • Light cycle oil
  • Diesel fuel
  • Desulfurization
  • Denitrogenation
  • Adsorption
  • Activated carbon
The ultimate goal of this thesis is to develop a fundamental understanding of the role of surface oxygen functional groups on carbon-based adsorbents in the adsorption of nitrogen compounds that are known to be present in liquid fuels. N2 adsorption was used to characterize pore structures. The surface chemical properties of the adsorbents were characterized by X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) techniques with a mass spectrometer to identify and quantify the type and concentration of oxygen functional groups on the basis of CO2 and CO evolution profiles. It was found that although surface area and pore size distribution are important for the adsorption process, they are not primary factors in the adsorption of nitrogen compounds. On the other hand, both the type and concentration of surface oxygen-containing functional groups play an important role in determining adsorptive denitrogenation performance. Higher concentrations of the oxygen functional groups on the adsorbents resulted in a higher adsorption capacity for the nitrogen compounds. A fundamental insight was gained into the contributions of different oxygen functional groups by analyzing the changes in the monolayer maximum adsorption capacity, qm, and the adsorption constant, K, for nitrogen compounds on different activated carbons. Acidic functional groups such as carboxylic acids and carboxylic anhydrides appear to contribute more to the adsorption of quinoline, while the basic oxygen functional groups such as carbonyls and quinones enhance the adsorption of indole. Despite the high number of publications on the adsorptive desulfurization of liquid hydrocarbon fuels, these studies did not consider the presence of coexisting nitrogen compounds. It is well-known that, to achieve ultraclean diesel fuel, sulfur must be reduced to a very low level, where the concentrations of nitrogen and sulfur compounds are comparable. The adsorptive denitrogenation and desulfurization of model diesel fuel, which contains equimolar concentrations of nitrogen (i.e., quinoline and indole), sulfur (i.e., dibenzothiophene and 4,6-dimethyldibenzothiophene), and aromatic compounds (naphthalene, 1-methylnaphthalene, and fluorene), was examined. The results revealed that when both nitrogen and sulfur compounds coexist in the fuel, the type and density of oxygen functional groups on the surface of the activated carbon are crucial for selective adsorption of nitrogen compounds but have negligible positive effects for sulfur removal. The adsorption of quinoline and indole is largely governed by specific interactions. There is enough evidence to support the importance of dipole–dipole and acid-base-specific interactions for the adsorption of both quinoline and indole. Modified carbon is a promising material for the efficient removal of the nitrogen compounds from light cycle oil (LCO). Adsorptive denitrogenation of LCO significantly improved the hydrodesulfurization (HDS) performance, especially for the removal of the refractory sulfur compounds such as 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. An essential factor in applying activated carbon for adsorptive denitrogenation and desulfurization of liquid hydrocarbon streams is regeneration after saturation. The regeneration method of the saturated adsorbents consisted of toluene washing followed by heating to remove the remaining toluene. The results show that the spent activated carbon can be regenerated to completely recover the adsorption capacity. The high capacity and selectivity of activated carbon for nitrogen compounds, along with their ability to be regenerated, indicate that activated carbon is a promising adsorbent for the deep denitrogenation of liquid hydrocarbon streams.