16. ADVANCED FOSSIL FUELS RESEARCH
For the foreseeable future, the energy needed to sustain economic growth will continue to come largely from fossil fuels. In supplying this energy need, however, the Nation must address growing global and regional environmental concerns, supply issues, and energy prices. Maintaining low-cost energy in the face of growing demand, diminishing supply, and increasing environmental pressure requires new technologies and diversified energy supplies. These technologies must allow the Nation to use all of its indigenous resources more wisely, cleanly, and efficiently. These resources include inherently clean natural gas and the Nation’s most abundant and lowest cost resource, coal. Grant applications are sought only in the following subtopics:
a. Hydrogen Fuels and Technologies—Clean forms of energy are needed to support sustainable global economic growth while mitigating greenhouse gas emissions and impacts on air quality. Hydrogen systems can provide viable, sustainable options for meeting energy requirements in all energy sectors – transportation, buildings, utilities and industry. However, hydrogen energy systems still face a number of technical and economic barriers that must be overcome for hydrogen to become a competitive energy carrier. Advances must be made in hydrogen production, storage, transport, and utilization technologies and in the integration of these components into complete energy systems.
Domestic coal can be a major source of hydrogen. Long-term research will improve technology that will lower the cost to produce hydrogen from coal, and also enable sequestration of carbon. An important component of hydrogen production from coal syngas is the water-gas shift process. Therefore, grant applications are sought for improved catalysts that will enable water-gas shift chemistry at lower temperatures or with faster kinetics or that are impurity tolerant, thereby lowering the cost of producing hydrogen from coal syngas. These catalysts not only would be potentially useful for providing hydrogen from hydrocarbons for stationary and vehicular fuel cells, but also would be a welcome improvement to other hydrogen production processes and other chemical transformations.
b. Biogeochemical Carbon Sequestration/Conversion—Carbon sequestration is a relatively new approach to the stabilization of greenhouse gas concentration (i.e., new compared to the other two pathways – improving the efficiency of energy use and reducing the carbon content of fuels). Current approaches include the conversion of carbon dioxide to benign, stable compounds for long-term storage or to value added products for reuse. Grant applications are sought to develop practical methods to: (1) grossly accelerate the natural bioconversion of carbon dioxide to methane in geologic reservoirs by employing methanogen microorganisms as catalysts, as well as other geochemical reactants, (2) apply similar processes to the capture of carbon dioxide at large point sources, and (3) efficiently employ microorganisms and/or biomimetic catalysts to convert carbon dioxide in flue gas to intermediates that can be subsequently reacted to calcium/magnesium carbonates for terminal sequestration.
c. Instrumentation for Surface Science Investigations of Electrochemically Active Solid Oxide Materials—In the electrode boundary regions of Solid Oxide Fuel Cells (SOFCs) charge transfer takes place at electrochemically active oxide surfaces, as neutral gas phase atoms become part of the ionic solid. The electrode oxides are structurally defective, both atomically and electronically, in ways that are not yet fully characterized. Current surface science investigations are limited by the environmental constraints of high temperature (> ~600 C) and oxidizing gas concentrations (~2 kPa pO2) that affect the mobility and defect density of the active surfaces. Traditional surface science tools (for example, photo-electron spectroscopy and low energy electron diffraction) employ high vacuum systems to inhibit the gas absorption of the excitation source (electrons, UV light, etc.) and allow for the spectroscopic detection of the emitted response. New tools such as scanning tunneling microscopy (STM) have been successfully employed at high temperatures, but usually in high vacuum environments to prevent oxidation of the STM components and allow effective thermal shielding of critical parts. Synchrotron-radiation-based x-ray techniques may allow for in situ X-ray Photo-emission Spectroscopy (with total electron yield detection), x-ray absorption spectroscopy, and grazing incidence x-ray diffraction, but these techniques will require specialized sample manipulation and signal detection schemes.
Therefore, grant applications are sought to develop surface science analytical instruments capable of investigating solid oxide materials under appropriate chemical and thermal boundary conditions (high T, high pO2). For the SOFC materials, parameters of interest include the concentration and mobility of surface vacancies, the electronic structure of mixed ionic/electronic conducting surface states, the valence and oxygen coordination of surface cations, and the distribution and nature of electrochemically active atomic surface defects. All of these physical parameters should be investigated as a function of the electrochemical potential (which, at one extreme, is simply modified by changing the partial pressure of gas phase oxygen). Approaches must demonstrate the relevance of the new instrument to high-temperature solid-oxide electrochemistry, and must include examples of typical experiments that would be enabled by the new instrument.
d. A More Economic Method for Making Liquid Fuels from Coal by Hydrogenation—An added source of distillate fuels is needed as world demand grows and sources of petroleum diminish. Coal could be a potential source, and could provide energy for a long time, if the cost of converting coal to liquid fuels cold be substantially reduced. Current processes, which involve the direct high-temperature hydrogenation of coal, are not competitive. Therefore, grant applications are sought to define process chemistries and/or reactor designs that can provide a slate of transportation fuel products from coal, at a cost that is competitive with currently used fuels. Possible approaches include improvements to two liquefaction processes, already under development:
(1) A new technology for the hydrogenation of hydrocarbons, which could lead to the required cost reduction, has been published. It is based on the treatment of HCOOH (formic acid) over a noble metal catalyst at 450 C. Under these process conditions, this HCOOH has the character of a supercritical solvent, which is known to be a superior solvent for coal derived organics. (Note that the feed to such a reactor would likely be the product of a first liquefaction stage, so that the coal-derived organics are mostly in solution.) The process was shown to saturate selected olefinic and ring compounds at the relatively mild conditions of 1200-3000 psi and 80-200 C; however, the required noble metal catalysts that are required have not yet been shown to be sulfur tolerant. A significant task would be identifying or developing an economic source or process to provide the formic acid feed.
(2) The DOE has developed a process that largely uses bubble column reactors. Although workable, there are significant weaknesses in the process design of the slurry-phase. For example, the reactants in the reactor are nearly fully mixed, leading to over-reaction that tends to result in undesirable conversion to tars and over-consumption of hydrogen through conversion to gaseous hydrocarbons. (By comparison, a plug flow reactor would permit more complete reaction.) At the same time, the dispersion of the hydrogen gas phase and its mixing intensity are poor, slowing its contact with the incompletely reacted coal and partially reacted liquids.
References:
Subtopic a: Hydrogen Fuels and Technologies
1. Office of Fossil Energy – Hydrogen Program Plan, U.S. Department of Energy Hydrogen Coordination Group, June 2003. (Full text available at: http://www.fossil.energy.gov/programs/fuels/hydrogen/programplans/2003/fehydrogenplan2003.pdf)
2. Basic Research Needs for the Hydrogen Economy: Report on the Basic Energy Sciences Workshop on Hydrogen Production, Storage and Use, [Rockville, MD], May 13-15, 2003, U.S. Department of Energy Office of Science, February 2004. (Full text available at: http://www.sc.doe.gov/bes/hydrogen.pdf)
3. Song, C., “Fuel Processing for Low-Temperature and High-Temperature Fuel Cells – Challenges, and Opportunities for Sustainable Development in the 21st Century,” Catalysis Today, 77(1-2):17-49, 2002. (ISSN: 0920-5861)
4. Elam, C. C., et al., “Realizing the Hydrogen Future: The International Energy Agency’s Efforts to Advance Hydrogen Energy Technologies,” International Journal of Hydrogen Energy, 28(6):601-607, 2003. (ISSN: 0360-3199)
5. Swartz, S. L, et al., “Fuel Processing Catalysts Based on Nanoscale Ceria,” Fuel Cells Bulletin, 4(30):7-10, March 2001. (ISSN: 1464-2859)(For ordering information and to view abstract, see: www.sciencedirect.com/science/journal/14642859)
6. Fu, Q., et al., “Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts,” Science Express (on-line), July 3, 2003. (Available via author’s Web site: http://ase.tufts.edu/chemical/faculty-staff/faculty/stephanopoulos.asp, under “Selected Recent Publications”)
Subtopic b: Biogeochemical Carbon Sequestration/Conversion
7. Beecy, D. J., et al., “Biogenic Methane: A Long-Term CO2 Recycle Concept,” presented at the First National Conference on Carbon Sequestration, Session 5A, May 14-17, 2001. (Full text available at: http://www.netl.doe.gov/publications/proceedings/01/carbon_seq/5a1.pdf
8. Schoell, M., “Multiple Origins of Methane in the Earth,” Chemical Geology, 71:1-10, 1988. (ISSN: 0009-2541)
9. Rice, D. D. and Claypool, G. E., “Generation, Accumulation, and Resource Potential of Biogenic Gas,” American Association of Petroleum Geologists Bulletin, 65:5-25, 1981. (ISSN: 0149-1423)
10. Scott, A. R., “Improving Coal Gas Recovery with Microbially Enhanced Coalbed Methane,” Coalbed Methane: Scientific, Environmental, and Economic Evaluations, pp. 89-111, July 1999. (ISBN: 0792356985)
11. Wolfe, R. S., “1776-1996: Alessandro Volta’s Combustible Air,” ASM News (American Society for Microbiology), 62(10):529-534, October 1996. (ISSN: 0044-7897)
12. Putting Carbon Back in the Ground, IEA Greenhouse Gas R&D Programme Report, February 2001. (ISBN: 1-898373-28-0)(Available at: http://www.co2net.com/public/about/putcback.pdf)
13. Stevens, S. and Gale, J., “Geologic CO2 Sequestration,” Oil and Gas Journal, 98(20):40-44, May 15, 2000. (ISSN: 0030-1388)
14. Bond, G. M., et al., “Enzymatic Catalysis and CO2 Sequestration,” World Resource Review, 11(4):603-619, 1999. (ISSN: 1042-8011)
Subtopic c: Instrumentation for Surface Science Investigations of Electrochemically Active Solid Oxide Materials
15. Singhal, S. C. and Kendall, K., eds., High Temperature Solid Oxide Fuel Cells: Fundamentals, Design and Applications, Elsevier, 2003. (ISBN: 1856173879)
16. Solid State Energy Conversion Alliance, http://www.seca.doe.gov/
17. Bai, W., et al., “The process, structure and performance of pen cells for the intermediate temperature SOFCS,” Solid State Ionics, 113-115(1-4):259-263, December 1, 1998. (ISSN: 0167-2738)
18. Hu, H. and Liu, M., “Interfacial studies of solid-state cells based on electrolytes of mixed ionic–electronic conductors,” Solid State Ionics, 109(3-4):259-272, 1998. (ISSN: 0167-2738)
19. Herbstritt, D., et al., “Modeling and DC-polarisation of a three dimensional electrode/electrolyte interface,” Journal of the European Ceramics Society, 21(10-11):1813-1816, 2001. (ISSN: 0955-2219)
20. Bouwmeester, H. J. and Gellings, P. J., Handbook of Solid State Electrochemistry, CRC Press, 1996. (ISBN: 0849389569)
Subtopic d: A More Economic Method for Making Liquid Fuels from Coal by Hydrogenation
21. Comolli, A. G., et al., “Low Severity Catalytic Two-Stage Liquefaction Process,” U.S. Department of Energy, September, 1988. (Report No. DOE/PC/80002-9)(NTIS Order No. DE89003441)(See Solicitation General Information and Guidelines, Section 7.1.)
22. Hyde, Jason R. et al., “Supercritical Hydrogenation and Acid-Catalyzed Reactions without Gases,” Chemical Communications, (13):1482-1486, June 24, 2004. (ISSN: 1359-7345)
23. Guin, S. A. et al., “Mechanisms of Coal Particle Dissolution,” Industrial & Engineering Chemistry Process Design & Development, 15(4):490-494, 1976. (ISSN: 0196-4305)
24. Simpson, T. B., “Improved Methods for Conversion of Our Fossil Resources to Fuels,” Energy and Fuels, 16(6):1599-1600, November 2002. (ISSN: 0887-0624)
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