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Modeling of A Direct Carbon Fuel Cell System
Modeling of A Direct Carbon Fuel Cell System
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K. Hemmes
Delft University of Technology
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Keywords: fuel cells, direct carbon fuel cells, integrated fuel cell systems, flow-sheeting,
fuel cell system analysis, exergy analysis
1 Introduction mass, and methane via some process into their components
共among which is fixed carbon兲 and subsequently using the fixed
Direct carbon fuel cells 共DCFCs, also known in literature as
carbon in a DCFC has advantages in terms of overall conversion
direct carbon conversion cells, DCCCs兲 offer specific thermody-
efficiency when compared with the 共direct兲 conversion of these
namic advantages compared with other fuel cell types. DCFCs
fuels in alternative fuel cell systems. Gasifying coal and biomass
electrochemically convert solid carbon fuel into CO2 and/or CO. and using the product gas in MCFCs and SOFCs and the direct
Because the entropy change in the overall cell reaction is around use of methane in SOFCs are options with relatively high overall
zero 共for CO2 as reaction product兲 or even positive 共for CO as system net electric efficiencies as well 共efficiencies up to 50%,
product兲, the theoretical reversible electric efficiency 共commonly based on fuel lower heating value, LHV兲 关4兴. Still, the option to
defined as ⌬G / ⌬H of the overall cell reaction兲 of a DCFC can be split these solid and gaseous fuels into their components and using
around 100%. The development of DCFCs has been limited by the obtained fixed carbon in DCFCs can lead to relatively high
low anode reaction rates, accumulation of impurities in the elec- electric and overall efficiencies, especially in co-production appli-
trolyte and logistics of refueling the cell. These problems are be- cations. Co-producing hydrogen besides electricity from methane,
ing addressed by recent developments in the production of clean for example, is an application in which DCFC systems are very
and highly reactive carbon materials 共e.g., from natural gas兲, low- suitable. Via the cracking of the methane, hydrogen and solid
cost techniques for separation of ash from coal, the possibility of carbon, particulate matter can be obtained. The hydrogen can be
pneumatic distribution of solid particulate fuel to the cells or the directly used in industrial processes, it can be mixed into the
use of a slurry of carbon particles in a molten carbonate, and the natural gas pipeline system, or it can be used in other types of fuel
availability of technology developed for the MCFC developments cells 共preferably low temperature兲. The solid carbon can produce
共electrodes and electrolytes兲 关1兴. electricity in a DCFC with relatively high efficiency. The use of
The DCFC configuration and theoretical principles resemble DCFCs is therefore envisaged to be especially suitable in the co-
those of the MCFC and solid oxide fuel cell 共SOFC兲. The reac- production of electricity and hydrogen at high overall system ef-
tions that take place in the cell are comparable and cathode, elec- ficiency.
trolyte, and current collector materials are similar. This paper will The objective of this research is to present a DCFC system
not focus on cell design, cell configuration, and cell material de- model with simulation outcomes in order to provide a theoretical
tails. We will take the design presented in Ref. 关1兴 and assume that basis for DCFC 共system兲 performance. In this paper, a complete
it can be scaled up and operated at reasonable current density fuel cell system including a DCFC is modeled and its operation
共100– 150 mA/ cm2兲. Research and development 共R&D兲 has been characteristics and overall performance 共efficiency兲 are deter-
focused on development of the cell itself on a lab scale and bench mined. The simulation results of a carbon fuelled, CO2-producing
scale. Steinberg and co-workers 关2,3兴 have proposed a number of DCFC system model will be shown. DCFC system research is still
system configurations with a DCFC, but up till now no flow sheet in the beginning stage and the calculations are therefore of an
calculations on a DCFC system have been performed. explorative nature.
In this study, we will evaluate the DCFC system performance This paper will cover the following topics:
by flow sheet calculations using the program CYCLE-TEMPO© 共CT兲. • a concise overview of the salient thermodynamic advantages
One may wonder if the total system of converting coal, bio- of DCFCs when compared with other fuel cell types
• the design of a carbon fuelled, CO2-producing DCFC sys-
1
Corresponding author.
tem model in the CYCLE-TEMPO©, thermodynamic equilib-
Manuscript received May 26, 2009, final manuscript received November 27, rium, flow-sheeting software
2009; published online July 16, 2010. Review conducted by Ravindranathan Thampi. • simulation calculations of the system model providing sys-
Journal of Fuel Cell Science and Technology OCTOBER 2010, Vol. 7 / 051008-1
Copyright © 2010 by ASME
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tem performance information and exergy analysis data to loss. In addition to these Nernst losses or utilization losses, Ref.
validate theoretical predictions and to underline perfor- 关2兴 reported the possibility for the carbon fuel that is introduced in
mance data numbers found in earlier literature the cell to be fully consumed in a single pass. The idea is that no
carbon will exit the fuel cell and that all the carbon that enters the
fuel cell will be converted into either CO or CO2. So, in principle,
2 DCFC Performance
the DCFC can operate at 100% fuel utilization with almost zero
The DCFC cell reactions are similar to those for the MCFC. Nernst loss 关11兴, whereas full utilization of hydrogen is princi-
The fuel reacting at the anode is carbon and the oxidant supplied pally impossible in a MCFC or SOFC. So, both forms of utiliza-
to the cathode is air. Possible overall cell reactions are: tion losses in hydrogen consuming fuel cells 共losses due to chang-
C + O2 → CO2 共1兲 ing gas compositions and losses because of inherent incomplete
utilization兲 do not occur in CO2-producing DCFCs. The ratio be-
or tween the actual work delivered by the fuel cell WFC and the
1
C + 2 O2 → CO 共2兲 reversible fuel cell work WFC,rev can be expressed in terms of the
ratio of the operating cell voltage Vcell to the reversible cell volt-
If molten carbonate is chosen as the electrolyte, the anode and age Vcell,rev
cathode reactions are as follows:
3 → 3CO2 + 4e
Anode: C + 2CO2− −
WFC n · F · Vcell Vcell
= = 共5兲
WFC,rev n · F · Vcell,rev Vcell,rev
Cathode: O2 + 2CO2 + 4e− → 2CO2−
3 共1⬘兲
The electric efficiency of an actual fuel cell 共including irrevers-
or ible losses兲 FC can now be expressed as
3 → CO + CO2 + 2e
Anode: C + CO2− −
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Table 1 Overview of the modeling assumptions and DCFC
model parameters
3 兲.
Electrolyte is molten carbonate 共CO2−
WGS and methane reforming reactions are not modeled for the anode
chamber.
Journal of Fuel Cell Science and Technology OCTOBER 2010, Vol. 7 / 051008-3
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Table 2 Overview of the general DCFC system model
assumptions
The power output of the systems is specified by setting the carbon mass
flow entering the systems at 1 kg/s.
When specified for heat exchangers, the high and low terminal
temperature differences are taken as 30° C and 20° C, respectively.
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Table 4 System performance of a DCFC system model coming air to the system is due to the difference in the air and
Baehr environment composition. The exergy losses in the remain-
Out ing sub systems are acceptable 共see Table 5兲.
Dividing the air preheating heat exchangers HX 1 and HX 2
DCFC electric power production 25,705.34 kW
Total auxiliary power consumption 168.81 kW
into more parallel positioned heat exchangers could mitigate the
System net electric power production 25,536.53 kW exergy losses associated with the air preheating part of the system.
Making use of the remaining exergy contained in the CO2 and air
In process streams leaving the system could mitigate the exergy
C-fuel mass flow to DCFC 1.00 kg/s losses accompanying these streams. Preheating of the carbon fuel
LHV/HHV of C-fuel 32,761.29 kJ/kg with these streams for example could decrease the exergy losses.
System power consumption 32,761.29 kW
Table 5 Exergy losses per subsystem of carbon fuelled DCFC system model „note: in
©
CYCLE-TEMPO exergy values have been calculated relative to the Baehr environment of 15° C and
1.01325 bars…
Journal of Fuel Cell Science and Technology OCTOBER 2010, Vol. 7 / 051008-5
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producing system models have not been developed. How- References
ever, a new CT version has been developed with which CO 关1兴 Cooper, J. F., 2004, “Direct Conversion of Coal and Coal-Derived Carbon in
production can be modeled. The new CT version is ready at Fuel Cells,” ASME Paper No. KH-3.
this point and the DCFC system models discussed in this 关2兴 Cooper, J. F., Cherepy, N., Berry, G., Pasternak, A., Surles, T., and Steinberg,
paper will be implemented in this new version in the future. M., 2000, “Direct Carbon Conversion: Application to the Efficient Conversion
of Fossil Fuels to Electricity,” Proceedings of the Global Warming Conference,
Carbon, methane, coal, and biomass shall be used as pos-
The Electrochemical Society, Paper No. PV 20-2000.
sible fuels. In a separate paper, we report on the modeling of 关3兴 Steinberg, M., 2003, An Innovative Highly Efficient Combined Cycle Fossil
a methane fueled direct carbon fuel cell system. and Biomass Fuel Power Generation and Hydrogen Production Plant With
• Also, the possibility of developing a DCFC model that is Zero CO2 Emission, Brookhaven, Upton, NY.
based on the SOFC configuration and theoretical principles 关4兴 Houwing, M., 2003, “Modeling and Analysis of Energy Systems Based on
should be investigated. Biomass Gasifiers and Solid Oxide Fuel Cells,” MS thesis, Section of Energy
Technology, Faculty of Mechanical Engineering, Delft University of Technol-
ogy, Delft, The Netherlands.
Acknowledgment 关5兴 Hemmes, K., and Cassir, M., 2004, “A Theoretical Study of the Carbon/
Mr. T. van der Stelt and Mr. T. Woudstra, M.Sc., are acknowl- Carbonate/Hydroxide 共Electro-兲 Chemical System in a Direct Carbon Fuel
edged for their help in realizing the system models and for assist- Cell,” Second International Conference on Fuel Cell Science, Engineering and
Technology, ASME, Rochester, NY, Jun.
ing in the interpretation of the results of the model simulations. 关6兴 Smith, J. M., Van Ness, H. C., and Abbott, M. M., 1996, Introduction to
Chemical Engineering Thermodynamics, 5th ed., McGraw-Hill, Singapore.
Nomenclature 关7兴 Moran, M. J., and Shapiro, H. N., 1998, Fundamentals of Engineering Ther-
modynamics, 3rd ed., Wiley, UK.
⌬G ⫽ Gibbs free energy change of a reaction, J/g 关8兴 Standaert, F., Hemmes, K., and Woudstra, N., 1996, “Analytical Fuel Cell
⌬H ⫽ enthalpy change, kJ/mol Modeling,” J. Power Sources, 63, pp. 221–234.
⌬S ⫽ entropy change, J / mol K 关9兴 Standaert, F., Hemmes, K., and Woudstra, N., 1998, “Analytical Fuel Cell
F ⫽ Faraday’s constant, C/mol Modeling; Non-Isothermal Fuel Cells,” J. Power Sources, 70, pp. 181–199.
关10兴 Hemmes, K., 2004, “Fuel Cells,” Modern Aspects of Electrochemistry, Vol. 37,
HHV ⫽ higher heating value, kJ/kg R. E. White, B. E. Conway, and C. G. Vayenas, eds., Kluwer, New York. pp.
LHV ⫽ lower heating value, kJ/kg 131–251.
n ⫽ number of electrons per molecule fuel 关11兴 Au, S. F., 2002, “Innovative High Temperature Fuel Cell Systems,” Ph.D.
FC,rev ⫽ reversible electric fuel cell efficiency thesis, Faculty of Mechanical Engineering, Delft University of Technology,
FC ⫽ electric fuel cell efficiency Delft, The Netherlands.
关12兴 Peelen, W. H. A., 1997, “Stability and Reactivity of Oxygen, Nickel and Co-
DCFC ⫽ direct carbon fuel cell efficiency balt Species in Molten Carbonate,” Ph.D. thesis, Delft University of Technol-
p ⫽ pressure, bar ogy, Delft, The Netherlands.
T ⫽ temperature, K or °C 关13兴 de Groot, A., 2004, “Advanced Exergy Analysis of High Temperature Fuel
Vcell,rev ⫽ reversible cell voltage, V Cell Systems,” Ph.D. thesis, Energy Research Center of the Netherlands
共ECN兲, Petten, The Netherlands.
Vcell ⫽ operating cell voltage, V 关14兴 Hemmes, K., Houwing, M., and Woudstra, N., “Modeling of a Methane Fu-
WFC,rev ⫽ reversible fuel cell work, W elled Direct Carbon Fuel Cell System,” ASME J. Fuel Cell Sci. Technol. 共in
WFC ⫽ actual fuel cell work, W press兲.
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