DEEP DESULFURIZATION OF DIESEL FUELS BY A NOVEL INTEGRATED APPROACH

The overall objective of this project is to explore a new desulfurization system concept, which consists of efficient separation of the refractory sulfur compounds from diesel fuel by selective adsorption, and effective hydrodesulfurization of the concentrated fraction of the refractory sulfur compounds in diesel fuels. Our approaches focused on (1) selecting and developing new adsorbents for selective adsorption of sulfur or sulfur compounds in commercial diesel fuel; (2) conducting the adsorption desulfurization of model fuels and real diesel fuels by the selective-adsorption-for-removing-sulfur (PSUSARS) process over various developed adsorbents, and examining the adsorptive desulfurization performance of various adsorbents; (3) developing and evaluating the regeneration methods for various spent adsorbent; (4) developing new catalysts for hydrodesulfurization of the refractory sulfur existing in the commercial diesel fuel; (5) on the basis of the fundamental understanding of the adsorptive performance and regeneration natures of the adsorbents, further confirming and improving the conceptual design of the novel PSU-SARS process for deep desulfurization of diesel fuel Three types of adsorbents, the metal-chloride-based adsorbents, the activated nickel-based adsorbents and the metal-sulfide-based adsorbents, have been developed for selective adsorption desulfurization of liquid hydrocarbons. All of three types of the adsorbents exhibit the significant selectivity for sulfur compounds, including alkyl dibenzothiophenes (DBTs), in diesel fuel. Adsorption desulfurization of real diesel fuels (regular diesel fuel (DF), S: 325 ppmw; low sulfur diesel fuel (LSD-I), S: 47 ppmw) over the nickel-based adsorbents (A-2 and A-5) has been conducted at different conditions by using a flowing system. The adsorption capacity of DF over A-2 corresponding to an outlet sulfur level of 30 ppmw is 2.8 mg-S/g-A. The adsorption capacity of LSD-I over A-5 corresponding to the break-through point at 5.0 ppmw sulfur level is 0.35 mg-S/g-A. The spent A-5 can be regenerated by using H2 gas at a flowing rate of 40-50 ml/min, 500 C, and ambient pressure. Adsorption desulfurization of model diesel fuels over metal-sulfide-based adsorbents (A-6-1 and A-6-2) has been conducted at different temperatures to examine the capacity and selectivity of the adsorbents. A regeneration method for the spent metal-sulfide-based adsorbents has been developed. The spent A-6-1 can be easily regenerated by washing the spent adsorbent with a polar solvent followed by heating the adsorbent bed to remove the remainder solvent. Almost all adsorption capacity of the fresh A-6-1 can be recovered after the regeneration. On the other hand, a MCM-41-supported HDS catalyst was developed for deep desulfurization of the refractory sulfur compounds. The results show that the developed MCM-41-supported catalyst demonstrates consistently higher activity for the HDS of the refractory dibenzothiophenic sulfur compounds than the commercial catalyst. On the basis of the fundamental understanding of the adsorptive performance and regeneration natures of the adsorbents, the conceptual design of the novel PSU-SARS process for deep desulfurization of diesel fuel is confirmed and improved further

Correlation between Asphaltene Stability in n-Heptane and Crude Oil Composition Revealed with Chemical Imaging

Five crude oil samples with different physical properties have been studied with respect to asphaltene stability. The attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopic imaging approach of n-heptane-induced precipitation has been used to monitor crude oil behaviour under dilution with a flocculation agent. For each sample, the dynamics of asphaltene precipitation has been observed by applying this chemical imaging method. Based on these data, the stability of crude oil samples has been compared and the correlation between asphaltene stability and crude oil properties has been proposed

In situ XPS investigations of Cu<SUB>1-x</SUB>Ni<SUB>x</SUB>ZnAl-mixed metal oxide catalysts used in the oxidative steam reforming of bio-ethanol

A series of CuNiZnAl-multicomponent mixed metal oxide catalysts with various Cu/Ni ratios were prepared by the thermal decomposition of Cu1-xNixZnAl-hydrotalcite-like precursors and tested for oxidative steam reforming of bio-ethanol. Dehydrogenation of EtOH to CH3CHO is favored by Cu-rich catalyst. Introduction of Ni leads to C&#8212;C bond rupture and producing CO, CO2 and CH4. H2 yield (selectivity) varied between 2.6-3.0 mol/mol of ethanol converted (50-55%) for all catalysts at 300&#176;C. The above catalysts were subjected to in situ XPS studies to understand the nature of active species involved in the catalytic reaction. Core level and valence band XPS as well as Auger electron spectroscopy revealed the existence of Cu2+, Ni2+ and Zn2+ ions on calcined materials. Upon in situ reduction at reactions temperatures, the Cu2+ was fully reduced to Cu0, while Ni2+ and Zn2+ were partially reduced to Ni0 and Zn0, respectively. On reduction, the nature of ZnO on Cu-rich catalyst changes from crystalline to amorphous, relatively inert and highly stabilized electronically. Relative concentration of the Ni0 and Zn0 increases upon reduction with decreasing Cu-content. Valence band results demonstrated that the overlap between 3d bands of Cu and Ni was marginal on calcined materials, and no overlap due to metallic clusters formation after reduction. Nonetheless, the density of states at Fermi level increases dramatically for Ni-rich catalysts and likely this influences the product selectivity

Investigation of mechanical characteristics of coir fibre/hexagonal boron nitride reinforced polymer composite

Coir fibre, derived from the husk of coconuts, is a natural resource and they are biodegradable and renewable. By incorporating them, any product can become more lightweight and durable, meeting the global desire for eco-friendly and efficient designs. This study has the potential to significantly alter the design of components such as switches and enclosures and it has an international research impact on engineering applications. Coir fibres and Hexagonal-Boron Nitride (h-BN) possess superior mechanical, thermal and physical qualities when reinforced with polymers. Hence novel study is carried out to examinecoir fibre/h-BN reinforcement in epoxy polymer composites. Response Surface Methodology via Box-Behnken Design (BBD) is utilized to investigate the mechanical properties such as Tensile Strength, Impact Strength and Young’s Modulus of coir fibre/h-BN reinforced epoxy polymer composite. The effect of input parameters onresponse is evaluated through regression equation and analysis of variance by using statistical Minitab software. The response optimization represents the maximum Young’s modulus (1597 MPa) by combining coir fibre (5 wt%), Coir fibre powder size (75 μ m) and h-BN (1 wt%). The response optimization portrays the maximum Ultimate Tensile strength(36.83 MPa) by combining coir fibre (1 wt%), coir fibre powder size (220 μ m) and h-BN (3.78 wt%). The response optimization reveals the maximum Impact strength (98.35 J m ^−2 ) by combining coir fibre (5 wt%), coir fibre powder size (225 μ m) and h-BN(1 wt%). This work emphasises the use of composite materials that are environmental friendly in a variety of industries such as automotive, electrical, etc

Effect of surface chemistry and roughness on the high temperature deposition of a model asphaltene

Fouling of processing units because of asphaltene deposition is a common phenomenon that interrupts the operation of oil refineries. In this study, the deposition behavior of a model archipelago asphaltene in the temperature range of 150 to 350 °C was investigated. For a fixed surface chemistry, the differences in deposit chemistry with fouling temperature is a function of the thermochemical properties of the model asphaltene. Under static high-pressure and high-temperature fouling conditions, both surface roughness and chemistry play an important role in asphaltene deposition. Rough surfaces are shown to develop larger deposits because of less restrictive physical barriers to inhibit deposit growth. Passivating the surface with an alumina chemistry significantly reduces the impact of surface roughness, as well as the total amount of deposition. This beneficial effect of using a protective alumina chemistry is attributed to its high thermal stability and low diffusivity that inhibit the uncontrolled formation of thiolate and sulfide deposits that are found on unpassivated steels. Instead, alumina modifies the surface reaction to a self-limiting chemisorption and oxidation process that produces thin sulfate deposits at the surface. With further consideration to the reactive species present in solution, the findings of this study may be extended to determine suitable surface conditions that mitigate asphaltene fouling

Evaluation of Ultra Clean Fuels from Natural Gas

ConocoPhillips, in conjunction with Nexant Inc., Penn State University, and Cummins Engine Co., joined with the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL) in a cooperative agreement to perform a comprehensive study of new ultra clean fuels (UCFs) produced from remote sources of natural gas. The project study consists of three primary tasks: an environmental Life Cycle Assessment (LCA), a Market Study, and a series of Engine Tests to evaluate the potential markets for Ultra Clean Fuels. The overall objective of DOE's Ultra Clean Transportation Fuels Initiative is to develop and deploy technologies that will produce ultra-clean burning transportation fuels for the 21st century from both petroleum and non-petroleum resources. These fuels will: (1) Enable vehicles to comply with future emission requirements; (2) Be compatible with the existing liquid fuels infrastructure; (3) Enable vehicle efficiencies to be significantly increased, with concomitantly reduced CO{sub 2} emissions; (4) Be obtainable from a fossil resource, alone or in combination with other hydrocarbon materials such as refinery wastes, municipal wastes, biomass, and coal; and (5) Be competitive with current petroleum fuels. The objectives of the ConocoPhillips Ultra Clean Fuels Project are to perform a comprehensive life cycle analysis and to conduct a market study on ultra clean fuels of commercial interest produced from natural gas, and, in addition, perform engine tests for Fisher-Tropsch diesel and methanol in neat, blended or special formulations to obtain data on emissions. This resulting data will be used to optimize fuel compositions and engine operation in order to minimize the release of atmospheric pollutants resulting from the fuel combustion. Development and testing of both direct and indirect methanol fuel cells was to be conducted and the optimum properties of a suitable fuel-grade methanol was to be defined. The results of the study are also applicable to coal-derived FT liquid fuels. After different gas clean up processes steps, the coal-derived syngas will produce FT liquid fuels that have similar properties to natural gas derived FT liquids