Oil & Natural Gas Projects
Exploration and Production Technologies
Characterization and Reaction Behavior of Sterically Hindered Sulfur Compounds
in Heavy Crudes with Nano-Sized Molybdenum Disulfide
This project was funded through DOE's Natural Gas and Oil Technology Partnership
Program. The program establishes alliances that combine the resources and experience
of the nation's petroleum industry with the capabilities of the national laboratories
to expedite research, development, and demonstration of advanced technologies
for improved natural gas and oil recovery.
The goal of this project is to develop a methodology to remove sulfur in refined
fuels to ultralow levels of below 30 parts per million (ppm).
Brookhaven National Laboratory (BNL)
Argonne National Laboratory (ANL)
The results of this project are expected to lead to a new catalyst system for
ultradeep sulfur removal from heavy oils.
The methods developed in this project will allow efficient removal of sulfur
compounds from refined fuels and thereby reduce air contamination from vehicles.
During 2002, BNL developed a synthesis procedure that would allow convenient
and reproducible preparation of nanocatalytic materials. A newly emerging sonochemical
synthesis technique was utilized to synthesize nanoparticles (mean particle
diameter <30 nanometers, or nm) of several molybdenum sulfate (MoS2)-based
complexes for use as hydrodesulfurization (HDS) catalysts used in refining.
Sonolysis in hexadecane solvent produced cavitation that successfully resulted
in the production of nano-sized MoS2 in greater than 90% yields. This project
continued the work by focusing on characterization of nano-sized materials that
have been synthesized for evaluation as potential HDS catalysts.
The objective of the proposal is to use evolving sonolysis techniques and synthesize
nano-sized particles of MoS2. The focus of this study was to understand the
interaction of sterically hindered organic sulfur compounds with size-dependent
The unique aspect of this approach is to use nano-sized MoS2 particles for
two reasons: 1) Nanosizing increases surface area and therefore the number of
"active-edge sites" per unit catalyst volume, and 2) amorphous nanoparticles
may overcome steric resistance in sulfur-containing large aromatic molecule,s
making the rings susceptible to catalytic attack during HDS. This approach has
three aspects: 1) characterization of sterically hindered organic sulfur compounds
that are typically present in crudes but resistant to conventional HDS catalysts,
2) reaction behavior of these sterically hindered sulfur compounds with nano-sized
MoS2, and 3) formulation and evaluation of supported nano MoS2-based system
for ultradeep catalytic HDS of heavy oils and distillates.
The sonolysis unit was customized to produce nanoparticles. This included a
jacketed reaction flask to control reaction temperature during sonolysis. After
shake-down of the sonolysis unit, the sonolysis technique was further refined
with a goal to synthesize 10-100 grams of nano MoS2 . Previous studies showed
that a high surface area of unsupported nanometer particles of Fe, Mo, and MoS2
was produced in quantitative yields by sonolysis of Fe(CO)5, Mo(CO)6, and Mo(CO)6/S,
respectively. During the study, several hydrocarbons were evaluated as solvents
to optimize "cavitation" that is critical to produce nano Mo metal
particles by decomposition of molybdenum hexacarbonyl.
The synthesis of supported and bimetallic systems that are potential HDS catalysts
was successfully completed. With a known ratio of Co2(CO)8/Mo(CO)6, the method
produced nano Co/MoS2. Sonolysis of Mo(CO)6 in the presence of ?-Al2O3 produced
supported nano Mo, i.e., nano MoS2/?-Al2O3. The yields of all nano-sized materials
were >90% based on the starting Mo(CO)6. Each material has been produced
in several-gram quantities.
Current Status (November 2005)
The project has been completed.
Project Start: March 27, 2002
Project End: March 26, 2004
Anticipated DOE Contribution: $290,000
Performer Contribution: $90,000 (24% of total)
NETL - Kathleen Stirling (email@example.com or 918-699-2008)
Brookhaven - Leon Petrakis (firstname.lastname@example.org or 516-344-3037)