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Enhancing Unconventional Reservoir Ultimate Recoveries with In-situ Nano-Catalysts
Project Number
TCF-18-15390
Last Reviewed Dated
Goal

The goal of this project is to improve both the ultimate recovery (EUR) and drainage area of unconventional reservoirs by catalytically reducing the viscosity of liquid and solid hydrocarbons. The method will utilize in-situ liquid phase reactions of hydrocarbons in the subsurface reservoirs. This approach relies on modifying the shale-bound kerogen by catalytically breaking C-C bonds to render it mobile using metal nanoparticle catalysts.

Performer

Argonne National Laboratory (ANL) – Lemont, IL 60439

Background

This project continues off a process that demonstrated that up to 50% of the carbon content in kerogen from Green River oil shale can be converted to gaseous and liquid hydrocarbons at temperatures below pyrolysis temperatures. The mobile products were analyzed by GC-MS and NMR analytical methods while the oxidation states of the metallic species and size of the resultant metal nanoparticles were determined by x-ray absorption near edge structure (XANES) and anomalous small angle x-ray scattering (ASAXS), respectively. The salient feature was the unique concept that if the metal nanoparticles are synthesized in-situ within and around the kerogen substrate that the initially formed nanoparticles can react with the kerogen while they are still quote small and therefore highly active. This in-situ approach for catalyst synthesis contrasts with conventional methods where catalysts are separately synthesized and isolated in a stable form before they are transported to the location where they are ultimately used. The new in-situ catalyst synthesis approach opens the door to higher activity catalytic C-C bond breaking down at down hole reaction temperatures.

Impact

This project continues off a process that demonstrated that up to 50% of the carbon content in kerogen from Green River oil shale can be converted to gaseous and liquid hydrocarbons at temperatures below pyrolysis temperatures. The mobile products were analyzed by GC-MS and NMR analytical methods while the oxidation states of the metallic species and size of the resultant metal nanoparticles were determined by x-ray absorption near edge structure (XANES) and anomalous small angle x-ray scattering (ASAXS), respectively. The salient feature was the unique concept that if the metal nanoparticles are synthesized in-situ within and around the kerogen substrate that the initially formed nanoparticles can react with the kerogen while they are still quote small and therefore highly active. This in-situ approach for catalyst synthesis contrasts with conventional methods where catalysts are separately synthesized and isolated in a stable form before they are transported to the location where they are ultimately used. The new in-situ catalyst synthesis approach opens the door to higher activity catalytic C-C bond breaking down at down hole reaction temperatures.

Accomplishments (most recent listed first)

Purified kerogen from Green River (GR) oil shale can be catalytically converted to liquid/gaseous hydrocarbons in 50% yield at temperatures below pyrolysis temperatures.

  • Successfully created the nickel catalysis in-situ.
  • Cracked/mobilized 5% of the kerogen in place (by weight) to produce a light oil ~C10-C15 in 11 days. (Because of project timeline constraints, work was done in an ideal environment – H2 blanket at 1750 psi and 350⁰C).
  • Presence of clays did not interfere with the reactions and may serve as a benefit (as an exchange site) as long as they are in proximity to the kerogen.
  • Unexpectedly observed that pyrite was converted to FeS. This conversion of the pyrite also created H2S, which although typically unwanted in this setting, can be useful as a downhole source of hydrogen.
Project Start
Project End
DOE Contribution

$150,000.00

Performer Contribution

$286,500.00

Contact Information

NETL – David Cercone (David.Cercone@netl.doe.gov or 412-386-6571)

ANL – Randall Winans (rewinans@anl.gov or 630-252-7479)