DE-FE0000408

Goal
The goals of this project are to develop a process where alkali metal will reduce and scavenge sulfur and nitrogen contained in shale oil in the presence of hydrogen, and also to demonstrate electrolysis of the alkali polysulfide to alkali metal and sulfur.

Performers
Ceramatec, Inc

Collaborators
Companies providing oil samples of at least five (5) gallons include Chevron, Oil Shale Exploration Company (OSEC), and Red Leaf Resources, Inc.

Background
Work performed by Esso/Exxon in the 1970s found sodium to be effective at removing sulfur and heavy metals from bitumen and oil refinery residues and bottoms; in one case, nitrogen level was also reduced. That effort was expanded to examine the effectiveness of sodium and lithium for nitrogen removal. Previous work by Esso/Exxon also proposed using beta aluminum as a membrane for electrolytic regeneration of sodium. This work builds on that concept but instead uses NaSicon and LiSicon-based membranes to eliminate water reactions.

This project will develop a new technology to upgrade shale oil by utilizing alkali metals to remove nitrogen, sulfur, and other heavy metals, as well as a method to electrolytically regenerate the alkali metals used in the process. The three technical focus areas include:

• Upgrading the technology development process by reacting shale oil under various conditions that are designed to increase product quality and minimize resource utilization.
• Developing an electrolytic process to regenerate alkali metal from alkali metal sulfide, as well as performing research to develop the seals and ionically-conductive membranes used in the process.
• Performing a cost and benefits analysis of these processes.

Impact
Successful development of this technology may provide potential developers of shale oil resources the ability to upgrade oil after retorting, but prior to refining. Currently, only the hydro-treating process is available, which requires considerable hydrogen and may over saturate the oil. The Green River Basin shale oil resource contains over one trillion barrels. This technology may contribute toward developing this important energy resource and reduce our nation’s dependence on foreign oil supplies.

Accomplishments

• An analysis of the operational and capital costs associated with the electrolytic process to produce sodium metal from sodium hydroxide has been conducted. The estimates are based on a 25,000 barrel per day upgrading plant. Operating costs are estimated at $1.98 per kilogram sodium and capital costs range from $0.08 to $0.15 per kg sodium.
• Electrolysis of sodium sulfide at temperatures of molten sodium has begun and is showing very encouraging results.
• Reactor tests with methane have continued with encouraging results.
• Process models of both the reactor and electrolysis processes have begun which will lead to the preliminary cost model.
• A method to synthesize sodium polysulfides by electrochemically reacting sodium metal with sulfur across a NaSicon membrane was successfully implemented.
• Researchers investigated the electrochemical stability of Tetraglyme.
• The lithium conductive membrane has dramatically improved. The “10B” membrane has been fabricated hermetically for the first time. This material is over 10x more conductive than the 45B membrane material previously demonstrated to be hermetic. Sodium conductive membranes are on the order of 2–3 mS/cm conductivity at room temperature and lithium conductive membranes are about 0.2 mS/cm.
• A lithium conductive membrane (lithium metal has been stripped from lithium polysulfide) has been tested for a total of 176 hours at 60°C with no apparent deterioration.
• A sodium conductive membrane (molten sodium metal has been stripped from sodium polysulfide) has been tested for over 40 hours at 110°C with no apparent deterioration.
• The most successful reactor run with shale oil resulted in 66.6% nitrogen and 97.7% sulfur removal with sodium as the alkali metal and hydrogen gas as the hydrogen source.
• The most successful reactor run without hydrogen resulted in 54.4% nitrogen and 40.4% sulfur removal with sodium as the alkali metal and methane gas as the hydrogen source.

Current Status (November 2011)
Current efforts are focused on upgrading heavier feedstocks using sodium as the alkali metal. The process has demonstrated high levels of sulfur and metals removal from shale oil, heavy oil or bitumen. Nitrogen removal has been less successful. In most cases, both methane and hydrogen have shown to be effective in the removal of sulfur, nitrogen, and heavy metals, and in increasing API gravity.

Project Start: October 1, 2009
Project End: March 31, 2012

DOE Contribution: $3,788,736
Performer Contribution: $947,186

Contact Information:
NETL – Robert Vagnetti (robert.vagnetti@netl.doe.gov or 304-285-1334)
Ceramatec, Inc – John Gordon (johng@ceramatec.com or 801-978-2138)
If you are unable to reach the above personnel, please contact the content manager.

Additional Information

Heavy Oil Upgrading Without Hydrogen [PDF-814KB] Paper presented at the 2011 Gas and Oil Expo and Conference, June 7-9, 2011

Progress Reports
Quarterly Progress Report [PDF-1.56MB] January - March, 2012

Quarterly Progress Report [PDF-820KB] October - December, 2011

Quarterly Progress Report [PDF-2.26MB] July - September, 2011

Quarterly Progress Report [PDF-2.05MB] April - June, 2011

Quarterly Progress Report [PDF-2.28MB] January - March, 2011

Quarterly Progress Report [PDF-1.49MB] October - December, 2010

Quarterly Progress Report [PDF-1.17MB] July - September, 2010

Quarterly Progress Report [PDF-364KB] April - June, 2010

Quarterly Progress Report [PDF-223KB] January - March, 2010

Quarterly Progress Report [PDF-358KB] October - December, 2009