Exploration and Production Technologies

Peer-Review Publication of State-of-the-Art Thermodynamic Property Measurements Completed by Bartlesville Thermodynamics Group

DE-IA26-02NT15338

Project Goal
DOE's thermodynamics laboratory in Bartlesville, OK, was closed down and moved to Oak Ridge National Laboratory (ORNL) before a portion of the data—which had been developed with DOE funding—could be published. There are extensive data available, and priority for analysis and publication will be placed on those data that are most relevant to today's petroleum and petrochemical industries. This project seeks to review and publish the most critical data.

Performer 
National Institute of Standards & Technology (NIST), Boulder, CO

Background 
In 1943 a laboratory was established in Bartlesville, OK, by Hugh M. Huffman to measure the thermophysical properties of the components of petroleum, jet fuels, and other strategic chemicals. Over the next 55 years this laboratory established an undisputed world-renowned reputation for the highest-quality measurements on the thermochemical and thermophysical properties of organic and organometallic compounds.

Impact 
Publication of the thermodynamic property data on series of compounds provides the physical-property data upon which chemical processing procedures and plants (units) are designed. Information related to required heat input, reaction stability, reactivity of chemical compounds defining the boundaries between kinetic and thermodynamic control, and reactions that occur in refineries are examples of the type of data that can be obtained from this project. Knowing how chemicals react, their heat of activation, how much heat is required to distill a representative compound, etc., helps process engineers design more-efficient, safer processes and plants. More-efficient plants equate to a lower cost of processing or cleaner products, which benefits the public.

Accomplishments 
NIST continues to analyze data and reports from previously conducted research and to publish a series of peer-reviewed publications based on the results of the research conducted at DOE's thermodynamics laboratory in Bartlesville, OK, before it closed on November 8, 1998. As part of an ongoing program to disseminate the previously acquired thermodynamic data, four publications were completed and published in FY2004, and two were published in FY2005. Two additional papers have been submitted to a refereed journal for consideration for publication.

Results of numerous state-of-the-art thermodynamic-property measurements remained unpublished at the time the laboratory was closed. From the late 1970s until closing of the laboratory, the DOE invested more than $1,000,000 per year in support of this world-class research laboratory. Unpublished results exist for a variety of organic compounds, the processing of which is key to the production of environmentally acceptable fuels from petroleum. Compound types include saturated and unsaturated aromatic hydrocarbons, as well as their sulfur- and nitrogen-containing analogs. Compiling and publishing these results will aid the development of new processing technologies by serving as benchmarks for improved computational chemistry methods, estimations, and correlations.

Part of the work being reported by NIST was done in conjunction with DIPPR (Design Institute for Physical Property Research), the oldest of the America Institute of Chemical Engineers’ (AIChE) active Industry Technology Alliances. DIPPR had 36 sponsors from industry and government bodies. Its purpose is to make possible, through joint sponsorship, thermophysical property data measurement, correlation, and dissemination. DIPPR’s project steering committees recognized the Bartlesville facility as the only remaining thermodynamics laboratory in the United States with the full-range capability to obtain the type and quality of data required by the sponsors. With the transfer of senior staff and equipment from Bartlesville to the Thermophysical Property Group within the Chemical Technology Separations Group at ORNL, the full-range capability was maintained.

Current Status (September 2009)
This project has complete all requirements. Published articles have been submitted to NETL. Recent articles accepted for publication or published:

  • Thermodynamic properties of methylquinolines (J. Chem. Thermodyn. 2007, 39, 698-711)
  • Thermodynamic properties of 1,2-Dihydronaphthalene: Glassy Crystals and Missing Entropy (J. Chem. Thermodyn. 2008. In press.
  • Thermodynamic properties of Norbornane submitted to the Journal of Chemical Thermodynamics
  • Thermodynamic properties of Aniline submitted to the Journal of Chemical Thermodynamics.

Project Start: July 23, 2002 
Project End: February 28, 2009

Anticipated DOE Contribution: $140,000 
Performer Contribution: $0

Contract Information
NETL – Jesse Garcia (jesse.garcia@netl.doe.gov or 918-699-2036) 
NIST, Robert D. Chirico (Chirico@boulder.nist.gov or 303-497-4126)

Publications
A historical summary of the Bartlesville Thermodynamics Group is included in Downstream Details, Summer 2003, published by NETL and available at the NETL website.

Steele, W.V., Chirico, R.D., Cowell, A.B., Nguyen, A., Knipmeyer, S.E., “The Thermodynamic Properties of 1,2,3,4-tetrahydrodibenzothiophene, Possible Precursors and Products of Deep Hydrodesulfurization of Gasoline and Distillate Fuels III,” J. Chem. Thermodynamics, V. 36, 2004, pp. 497-509.

Steele, W.V., Chirico, R.D., Knipmeyer, S.E., and Nguyen A., “Heat Capacities, Enthalpy Increments, and Derived Thermodynamic Functions for Dicyclohexylsulfide between the Temperatures (5 and 520)K, Possible Precursors and Products of Deep Hydrodesulfurization of Gasoline and Distillate Fuels IV,” J. Chem. Thermodynamics, V. 36, 2004, pp. 845-855.

Chirico, R.D., and Steele, W.V., “High-Energy Components of Designer Gasoline and Designer Diesel Fuel I. Heat Capacities, Enthalpy Increments, Vapor Pressures, Critical Properties, and Derived Thermodynamic Functions for Bicyclopentyl between the Temperatures T = (10 to 600)K,” J. Chem. Thermodynamics, V. 36, 2004, pp. 633-643.

Chirico, R.D., and Steele, W.V., “The Thermodynamic Properties of 2-methylquino-line and 8-methylquinoline,” J. Chem. Eng. Data V. 50, 2005, pp. 697-708.

Chirico, R.D., and Steele, W.V., “The Thermodynamic Properties of Diphenylmethane,” J. Chem. Eng. Data, V. 50, 2005, pp. 1052-1059.

Chirico, R.D., and Steele, W.V., “The Thermodynamic Properties of 1,2-dihydronaphthalene,” to be published in the Journal of Chemical & Engineering Data, March 2007

Chirico, R. D., R. D. Johnson III, W. V. Steele, “Thermodynamic properties of methylquinolines: Experimental results for 2,6-dimethylquinoline and mutual validation between experiments and computational methods for methylquinolines,” accepted for publication in Journal of Chemical Thermodynamics October 2006; available as doi:10.1016/jj.jct.2006.10.012

Boundaries between the kinetic and thermodynamic control regions 
for hydrodesulfurization of thiophenes.

Rob Chirico at the adiabatic calorimeter console, circa 1984.

 
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