Fuel 89 (2010) 13071314

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Separation of CO2 from ue gas using electrochemical cells

Henry W. Pennline a, Evan J. Granite a,*, David R. Luebke a, John R. Kitchin b, James Landon b, Lisa M. Weiland c
a

US Department of Energy, National Energy Technology Laboratory, P.O. Box 10940, Pittsburgh, PA 15236, United States Carnegie Mellon University, Department of Chemical Engineering, Pittsburgh, PA 15213, United States c University of Pittsburgh, Department of Mechanical Engineering and Materials Science, Pittsburgh, PA 15261, United States
b

a r t i c l e

i n f o

a b s t r a c t
Past research with high temperature molten carbonate electrochemical cells has shown that carbon dioxide can be separated from ue gas streams produced by pulverized coal combustion for power generation. However, the presence of trace contaminants, i.e., sulfur dioxide and nitric oxides, will impact the electrolyte within the cell. If a lower temperature cell could be devised that would utilize the benets of commercially-available, upstream desulfurization and denitrication in the power plant, then this CO2 separation technique can approach more viability in the carbon sequestration area. Recent work has led to the assembly and successful operation of a low temperature electrochemical cell. In the proof-of-concept testing with this cell, an anion exchange membrane was sandwiched between gas-diffusion electrodes consisting of nickel-based anode electrocatalysts on carbon paper. When a potential was applied across the cell and a mixture of oxygen and carbon dioxide was owed over the wetted electrolyte on the cathode side, a stream of CO2 to O2 was produced on the anode side, suggesting that carbonate/bicarbonate ions are the CO2 carrier in the membrane. Since a mixture of CO2 and O2 is produced, the possibility exists to use this stream in oxy-ring of additional fuel. From this research, a novel concept for efciently producing a carbon dioxide rich efuent from combustion of a fossil fuel was proposed. Carbon dioxide and oxygen are captured from the ue gas of a fossilfuel combustor by one or more electrochemical cells or cell stacks. The separated stream is then transferred to an oxy-red combustor which uses the gas stream for ancillary combustion, ultimately resulting in an efuent rich in carbon dioxide. A portion of the resulting ow produced by the oxy-red combustor may be continuously recycled back into the oxy-red combustor for temperature control and an optimal carbon dioxide rich efuent. Published by Elsevier Ltd.

Article history: Received 23 June 2009 Received in revised form 18 November 2009 Accepted 24 November 2009 Available online 9 December 2009 Keywords: Carbon dioxide sequestration Carbon capture and separation Electrochemical separation

1. Introduction Carbon sequestration is a strategy to reduce the emissions of the greenhouse gas, carbon dioxide, from large point sources, such as fossil-red power plants. It holds the potential to provide deep reductions in greenhouse gas emissions. Because nearly one-third of the anthropogenic CO2 emissions are produced by these power generation facilities, conventional fossil fuel-burning power plants, in particular coal-red power plants, and advanced power generation plants, such as integrated gasication combined cycle (IGCC), present opportunities where carbon dioxide can be removed and then permanently stored. Although pulverized coal-red-base steam cycles have been the predominant electric power generation technology for many years, it is projected that advanced power generation technologies, i.e. gasication-based IGCC, will make in-roads in the power generation sector in the future.

* Corresponding author. Tel.: +1 412 386 4607; fax: +1 412 386 6004. E-mail address: evan.granite@netl.doe.gov (E.J. Granite). 0016-2361/$ - see front matter Published by Elsevier Ltd. doi:10.1016/j.fuel.2009.11.036

Carbon sequestration is a two-step process where the capture of carbon dioxide from a gas stream is followed by the permanent storage of it. The capture step for carbon dioxide represents a considerable cost in the overall process [1]. New technologies for the separation and capture of carbon dioxide are being developed that can have signicant impact on carbon sequestration. The US Department of Energys National Energy Technology Laboratory is conducting in-house research investigating novel techniques to separate and capture CO2 from current or advanced power generation systems and to meet certain programmatic goals [13]. The new techniques can have wide applications, but the research has focused on capture of carbon dioxide from ue gas (post-combustion streams from conventional fossil fuel-red combustors) and from fuel gas (pre-combustion streams from IGCC plants). In addition to efforts being conducted by the US Department of Energy, other domestic and international organizations are actively pursuing research in the carbon dioxide capture area [46]. For coal-red power plants, the conventional scrubbing system that is the comparative baseline for all other capture technologies is monoethanolamine (MEA) scrubbing. This wet scrubbing process

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removes the CO2 in an absorber and then regenerates the spent scrubbing liquor in a vessel by heating the solution with plant steam. Although there have been large-scale commercial demonstrations of this technology, the process has several disadvantages, such as a high heat of reaction, poor loading capacity, corrosiveness of the solution, susceptibility to poisoning, and the need to be in an aqueous solution. This latter disadvantage results in a large energy need to regenerate the spent solution, related to the sensible heating of the water that is a minimum of 70-wt.% of the solution. A systems analysis comparison between a power plant without and with the wet amine scrubbing process reveals an overall plant thermal efciency loss of near 30% [79]. Improvement to reduce this efciency loss is a target for future post-combustion capture/ separation technologies. With respect to carbon dioxide capture within recent proposed process schemes, liquids (for example MEA) or solids (sorbents) must be moved into the ue gas reaction zone to remove the CO2 and then out of the zone to regenerate the particular absorbing material. Cycling/transport of the absorbents contribute to parasitic losses and thermal inefciencies. In contrast to these capture processes, an electrochemical cell that can effectively separate CO2 from ue gas is a one-step stationary technique and has potential benets that can overcome the disadvantages of the mentioned processes. In a conceptual scheme, coal is combusted in a conventional type of furnace producing a mixture of nitrogen, unreacted oxygen, carbon dioxide, water vapor, and minor products. The total stream would enter an electrochemical cell. The cell of non-moving parts consists of an electrolyte, sandwiched between a cathode and anode across which a potential is applied. The electrolyte can consist of an ion-conducting material that enhances the migration of CO2 across it. During reaction, both carbon dioxide and oxygen, and potentially water, are transported across the membrane as carbonate/bicarbonate ions. If carbonate is the majority ion transported, the maximum molar ratio of CO2/O2 leaving the electrochemical process is 2:1; if bicarbonate is the majority ion transported, the CO2/O2 ratio leaving the separation process is 4:1. The puried ue gas stream (less the CO2 and O2) exits the power plant through the stack. The electrochemical cell separation does not produce a stream of pure CO2 but a mixture of CO2 and O2 that can feed an ancillary oxygen-red combustor. In typical oxygen-red combustion, the fuel (e.g. coal) is red with pure oxygen, rather than air, and thus the dilution effect of nitrogen in combustion air is eliminated. However, some CO2 and possibly moisture products must be recycled back to the furnace to control the ame temperature. Pure oxygen, an expensive commodity, is needed for the combustion. However, in the case of the electrochemical cell, the stream emitted from the separation will be used to feed an ancillary oxy-fuel combustor to generate additional power. This communication will discuss the technical features of this novel concept and experimental information pertaining to a key process step, the electrochemical separation. A brief discussion of the individual processes, oxy-ring and electrochemical separation, which are at the basis of the novel concept, is warranted. 1.1. Oxy-fuel combustion The objective of pulverized coal oxygen-red combustion is to combust coal in an enriched oxygen environment by using pure oxygen diluted with recycled ue gas. In this manner, the ue gas is composed primarily of CO2 and H2O, avoiding the nitrogen in air, so that a concentrated stream of CO2 is produced by condensing the water in the exhaust stream. CO2, H2O, and excess O2 are the key constituents of the ue gas, along with trace quantities of SO2, NOx, and particulates. Oxygen concentrations are low

and water vapor is readily separable by condensation at moderate temperatures. An advantage of oxycombustion is that it provides a high potential for a step-change reduction in CO2 separation and capture costs because virtually all of the exhaust efuents can be captured and sequestered (co-sequestration) [8]. There are several benets of oxycombustion technology with CO2 capture and sequestration [8,10]:  Ability to concentrate the greenhouse gas CO2 and prepare it for storage by reducing the diluent nitrogen. The volume of gas is reduced and thus smaller combustion and gas handling equipment is required.  As compared to air-red combustion, NOx formation is reduced when using ue gas recycle. This is mainly due to less thermal NOx levels resulting from the lack of nitrogen in the concentrated oxygen used for combustion. Some nitrogen is still available from the coal and potential air in-leakage.  The technology can readily be applied to new coal-red power plants and uses conventional equipment already proven in the power generation industry. The key process principles have been proven in the past including air separation and ue gas recycle.  Lower dry gas energy loss leading to higher plant efciency. A few issues exist in using this process. One is that air in-leakage into the boiler would be a disadvantage since it dilutes the resulting ue gas, negating the rationale for the pure oxygen combustion. However, improvements in boiler materials, for example sealants, will resolve this issue. A second is combustion of fuels in pure oxygen would occur at temperatures too high for existing boiler or turbine materials. This issue is resolved by diluting the oxygen using ue gas recycle, which results in an increase in the parasitic power load. Additionally, a major part of the cost for the oxycombustion technology is due to the air separation plant. Initial estimates [11] indicated that cryogenic oxygen separation uses about 23% of the net electric power output of a conventional fossil-fueled power plant. More recent systems analysis [8] reveals a loss in plant thermal efciency of 31% caused by the oxycombustion system with a major contribution by the air separation system. As mentioned above, O2 combustion cannot be simply substituted for air combustion in existing fossil-fueled power plants because of differences in the combustion characteristics. A thermal diluent is required to replace the N2 in air [10,11] (see Fig. 1). Oxygen produced from air separation would be mixed with recycled ue gas to approximate the combustion characteristics of air. In air, the N2/O2 ratio is approximately 3.65. A CO2/O2 ratio of 2.42 gives similar ame temperatures as well as similar ratios of radiant heat transfer to convective heat transfer. Others suggest that the volumetric ratio of CO2/O2 should be closer to a ratio of 4 [12].

1.2. Electrochemical cells Electrochemical pumps offer a unique way to separate CO2 from a gas stream. A generic system would consist of an electrolyte membrane sandwiched between two electrodes. The CO2 gas to be separated would ow over the cathode side, be selectively transported through the membrane, and then be concentrated on the anode side. To drive the transport, a potential is placed across the conductive medium to produce the gas separations reaction. Several factors that limit the transport of CO2 across the membrane are the conductivity of the electrolyte, thermodynamic stability of the electrolyte, and the electrode kinetics. Resistances most likely occur at the three phase boundary or interface at the gas, electrode, and electrolyte [13].

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1309

DRY (or WET RECYCLE

AIR

AIR SEPARATION PLANT

O2

COMBUSTION CHAMBER

WATER SEPARATION PRODUCT CO2 95% O2 3% Bal 2%

N2 H2O

SEPARATION OF N2 FROM AIR

REPLACE N2 WITH RECYCLED CO2 (and H2O), (keeping flame temperature normal)

SEPARATION OF H2O FROM PRODUCT

Fig. 1. Schematic of an oxycombustion system [11].

Electrode kinetics can play a key role in the separation of carbon dioxide and oxygen. The electrode must be porous to allow gas to diffuse in and out, yet continuous, to avoid short circuits. Electrodes can be formed by thermal decomposition of organometallic precursor compounds on the electrolyte surface, with metal pastes or inks, or by the use of metal catalyst on carbon paper, as described below in Section 2. The overall resistance of the electrochemical pump for transport of carbon dioxide and oxygen is the sum of the resistances due to the electrodes (adsorption and desorption of reactants and products), electrolyte (movement of bicarbonate/carbonate ions), and the electrode and electrolyte contact (charge transfer to or from the electrode). Overall resistance can be minimized by: (1) use of thin electrolyte and electrodes, (2) having intimate contact between electrode and electrolyte, and (3) selecting an electrolyte with high conductivity. Much of the past work in electrochemical separation of CO2 from ue gas has been conducted in molten carbonate cells [14,15]. The membrane consists of an alkali carbonate electrolyte contained within a ceramic membrane and operated at temperatures above 400 C. During operation of the concentrator, CO2 and O2 combine at the cathode to form a carbonate ion. The ion migrates through the membrane under an electric potential to the anode where it decomposes into CO2 and O2. Since the species diffusing across the membrane are ions, this technique is highly selective to the separation and concentration of only CO2 and O2. Advantages of this type of separation are that a continuous, in situ, production of CO2 occurs; high purity of gases is produced; the gases of interest are separated relatively easily from ue gas; and there are no moving parts, unlike sorbent or solvent-based processes. Unfortunately, there are major disadvantages in the application of molten carbonate electrochemical cells for separation of CO2 from power plant ue gas. Molten carbonate is a corrosive paste. The high temperatures of cell operation, along with the extremely corrosive nature of the molten carbonate, make fabrication and handling difcult. Also, the high temperatures necessary for cell operation are extremely difcult for integration into a post-combustion application. The small applied voltages allowable in order to avoid decomposition of the molten carbonate result in low current, where the current represents ux of carbonate anions across the membrane. This necessitates the use of huge stacks to obtain a signicant

ux of carbonate. Sulfur dioxide that is present in ue gas and at high temperature can poison the electrolyte, and electrode degradation can occur at these conditions [16]. In work done by the Winnick group [14,15], a molten carbonate electrolyte performed well and was operated at temperatures of 650 C. However, these temperatures are unrealistic in a ue gas stream because of the presence of potential poisons that cannot be removed upstream via conventional means at such high temperature, e.g. SO2, which can impact the operation of the cell. A solid electrolyte membrane for the separation of CO2 from ue gas could solve the problems of the molten carbonate system. Doping of the electrolyte could increase the ionic conductivity signicantly [16,17]. Unfortunately the temperature of the system is still relatively high, and a majority of the disadvantages would still apply to this integrated system. Although molten carbonate or solid electrolyte cells have been proposed for the separation of CO2 from power plant exhaust, these may not be a practical solution to CO2 separation. An alternative to these is the use of a polymer electrolyte membrane that can transport carbonate/bicarbonate ions. Past work with polymerbased membranes has been conducted [1820]. In these reports, a porous membrane soaked in aqueous bicarbonate electrolyte was used with nickel meshes as the electrodes. The voltages applied to the electrodes in those reports were typically in excess of 2.5 V, which is too high for economical application in a ue gas capture application. Water splitting to form hydrogen and oxygen can occur at voltages above 1.23 V, suggesting that the previous reports may have overlooked an important loss of efciency. It is hypothesized that the use of a polymer-based anion exchange membrane and gas-diffusion electrodes similar to those used in fuel cells could be a more efcient separation device. 1.3. Concept Fig. 2 is a schematic of the process for producing a carbon dioxide rich efuent that is ready for storage. A fossil fuel, coal, is combusted in a conventional type combustor. Products of combustion in the subsequent ue gas are nitrogen, unreacted oxygen, carbon dioxide, water vapor, and possible minor compounds, such as sulfur dioxide and nitric oxides. After using conventional scrubbing techniques to mitigate SO2, NOx, and mercury, the total stream would enter an electrochemical cell. The cell of non-moving parts

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Air

Combustor
Coal

N2 O2 CO2 H2O

Electrochemical Cell
O2 CO2

N2 H2O Residual O2 & CO2

Recycle

3 Coal

Combustor
CO2 H2O CO2

Fig. 2. Carbon dioxide separation process.

consists of an electrolyte, sandwiched between a cathode and anode, across which a potential is applied. Operating at post-FGD temperatures, the electrolyte consists of an ion-conducting material that enhances the migration of CO2 across it. In the process, O2 is reduced to OH at the cathode, locally increasing the pH, which can react with CO2 from the ue gas stream. The ratio of carbonate and bicarbonate ions will depend on the local pH and the rates of oxygen reduction. The anions migrate across the electrolyte under the inuence of the externally applied voltage eld. At the anode, OH is oxidized back to O2, locally decreasing the pH. Finally the remaining bicarbonate/carbonate ions are neutralized in the locally reduced pH, forming carbon dioxide gas at the opposite electrode. At the interface between the gas, metal electrode, and solid electrolyte, the overall reactions could be written as:

CO2 1=2O2 2e
CO2 3 2CO2 1=2O2 H2 O 2e
2HCO 3
The electrode must efciently adsorb CO2 and O2 so as to not limit the rate of carbon dioxide transport across the electrolyte, and it must be porous to allow gas to diffuse in and out. The reactions above show that both carbon dioxide and oxygen could be transported across the membrane as bicarbonate/carbonate ions. The molar ratio of CO2/O2 leaving the electrochemical process depends on the rates of oxygen reduction and evolution; if carbonate ions are the sole carriers the maximum ratio can be 2:1, whereas if bicarbonate ions are the sole carriers the maximum ratio can be 4:1. The oxygen concentration within the ue gas will limit the amount of CO2 that can be separated from the ue gas. The puried ue gas stream (less the CO2 and O2) exits the power plant through the stack. Note that heated air can be added before the electrochemical cell to boost the limiting O2 concentration in order to increase the percent CO2 removed. If the mechanism involves the bicarbonate migration, the presence of moisture is important. Fortunately, the moisture (H2O) content of ue gas after the FGD unit is quite high since the ue gas is saturated at that location. The stream of enriched CO2 and O2 can then be fed into an ancillary combustor where fossil fuel combustion is sustained by this stream. In that the reactants are just a fossil fuel (organic hydrocarbon) and O2 with CO2 and if the fossil fuel is burned close to stoichiometry, the resultant gas mixture will contain essentially CO2 and moisture. Theoretically, if carbonate is the transported ion, the maximum molar ratio of CO2 to O2 entering the ancillary combustor is 2:1. From the information on oxy-ring above, the possibility exists that this may not be the ideal ratio for oxy-combustion, and in order to meet the optimum ratio for internal temperature reasons, some of the CO2 and/or H2O product gases

may need to be recycled as shown in Figs. 1 and 2. Finally, the stream exiting the ancillary combustor contains moisture which needs to be condensed from the stream, leaving a pure stream of CO2. After pressurization, the CO2 can be stored (sequestered) or utilized depending on the needs at that time. Low temperature operation of the electrochemical cell presents a major advantage to obtain a clean ue gas stream for carbon dioxide separation. Particulates present in ue gas can block the electrochemical membrane by physically covering the electrode surfaces. Acid gases could poison the electrolyte by forming sulfates and nitrates. Trace contaminants such as mercury may adsorb on the electrodes, destroying their catalytic properties. Conceptually, the polymer electrochemical cell would be located downstream of the SCR for NOx control, the wet scrubber for acid gas and mercury removal, and the baghouse or electrostatic precipitator for particulate capture. Therefore, a relatively contaminant-free ue gas would contact the separator by using a low temperature polymeric electrochemical cell. The ue gas levels of sulfur dioxide, nitrogen oxide, particulates, and mercury will be dramatically eliminated as contrasted to high temperature operation of the molten carbonate separator at 650 C. Thus new materials for the electrolyte and electrodes are being developed that will permit the electrochemical cell to be operated efciently and at signicantly lower temperatures where conventional cleaning techniques can be applied upstream of the cell. In an effort to lower the temperature of operation, electrodes and electrolytes are being investigated in a joint initiative at NETL and Carnegie Mellon University. 2. Experimental In response to the challenge of low temperature electrochemical separation, a polymer electrolyte membrane (PEM) has been employed for the transport of carbon dioxide and oxygen out of ue gas. The PEM material is fabricated by the addition of charged sidegroups to polymeric chains through covalent bonds. The addition of charged sidegroups produces regions of phase separation; nanoscale clusters of charged sidegroups, counterions, and solvent reside within a hydrophobic matrix. The hydrophilic clusters are connected by ion channels which promote the transport of counterions through the polymer. The covalent bonds between the polymer chain and the charged sidegroup inhibit transport, resulting in selective conduction of the counterion species through the polymer. PEMs have recently received widespread attention for their smart material properties as well as applications in polymer electrolyte membrane fuel cells. One type of material that is commercially-available is the anion exchange membrane Neosepta, which is similar to other membrane materials such as Selemion.

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A low temperature electrochemical cell had been successfully assembled and operated for use as a gas separator. In the proofof-concept testing, an anion exchange membrane of Neosepta was sandwiched between gas-diffusion electrodes consisting of nickel and platinum-based electrocatalysts on carbon paper.

3. Results and discussion 3.1. Electrode development The electrochemistry of Pb, Sn, Ni, Pd, Pt, Cu, Ag, and Au wires (0.5 mm diameter) was rst examined in carbonate and bicarbonate electrolytes to rapidly screen electrocatalysts for activity and stability. Because Cu, Ag, Pb and Sn were not stable under the electrochemical testing conditions and rapidly corroded and deactivated, they were not considered for further development. Au showed no activity and was not considered further. The results for Ni, Pd and Pt in bicarbonate electrolytes are shown in Fig. 3. In the range of 0.81.0 V vs. SCE (the range of interest where oxygen evolution activity occurs) Ni shows the highest current. The current is directly related to the activity, thus, Ni shows the highest activity. Consequently, Ni was selected to be investigated further in the device. The activity can be further increased by using high surface area Ni particles as the electrocatalysts. For this device, nickel particles were synthesized using a polyol process by reducing NiCl2 in ethylene glycol at 160 C for an hour. To create an electrode using these particles, carbon paper supplied by Toray (TGPH-060) was used as a support. A layer of carbon black XC-72R (fuelcellstore.com) was used as a backing on the carbon paper support. This carbon powder was applied using an air brush. The nickel solution synthesized through the mentioned polyol process was then painted on top of the carbon black support yielding a highly conductive electrode with a 1 mg/cm2 loading of nickel. An SEM image is shown in Fig. 4 of these particles deposited on a carbon paper support. Particle sizes ranged from approximately 1 4 lm in diameter. Lower particle sizes of nickel could be used to further maximize the surface area to mass ratio of the catalyst. The resulting electrode showed much higher activity than a pure

Fig. 4. SEM image showing synthesized Ni particles used as electrocatalysts in this work.

Ni wire while using considerably less mass, most likely due to the substantially higher surface area (see Fig. 5). The reversible peaks formed in the forward and backward directions around 0.5-V vs. saturated calomel electrode (SCE) are likely the adsorption and desorption of carbonate ions, and the rapid increase in current at potentials more positive than 0.5 V corresponds to oxygen and CO2 evolution from the electrochemical decomposition of carbonate ions. In order to quantify the rate of CO2 and O2 evolution from carbonated electrolytes, a new experimental method to measure the volumetric ow rates of these gases at different current densities was developed. The experiment uses a commercial water electrolysis cell to decompose the carbonate or bicarbonate ions. The electrodes are made of Ni. At the anode, carbonate or bicarbonate ions are neutralized to CO2 by the local decrease in pH due to O2 evolution. The gas

Fig. 3. Cyclic voltammetry of Ni, Pd and Pt wires in 0.1 M KHCO3. Ni shows the highest activity.

Fig. 5. Comparison of synthesized Ni ink and Ni wire in carbonate electrolyte.

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bubbles are collected in a graduated cylinder where the volume is measured as a function of time. The cathode is simply a counter electrode in this experiment, and hydrogen evolves there. The volume of hydrogen accumulated was used to calculate the amount of oxygen that is evolved using the stoichiometry of the water splitting reaction. The volume of CO2 that coevolved with the oxygen was estimated by subtracting the known oxygen volume. The results for CO2 evolution from potassium bicarbonate solutions at different concentrations are shown in Fig. 6. The rate of CO2 evolution increases with the concentration of bicarbonate and with the electrolysis current. Note that hydrogen gas accumulates in the other volumetric chamber. This occurs because oxygen gas was not in contact with the cathode. The CO2 evolution rates were much higher in bicarbonate solutions than in carbonate solutions at the same current. This result is understandable because carbonate ions take two protons to neutralize and decompose into CO2, whereas bicarbonate only takes one proton to neutralize it. For every molecule of oxygen evolved two protons are formed, and thus a higher CO2 evolution rate with bicarbonate ions could be anticipated. In the absence of bicarbonate or carbonate, only oxygen evolution is observed, indicating that the electrochemical membrane could also be used to concentrate oxygen. The rate of CO2 evolution is not the only important variable to consider in Fig. 6. It is equally important to consider the ratio of the CO2 evolution rate to the O2 evolution rate. The steady-state maximum this ratio can be for bicarbonate is 4 if every proton generated neutralizes a bicarbonate ion to form CO2. The highest ratio of CO2 to O2 observed was $1 at the 3 M bicarbonate concentration. This implies that many of the protons generated by the oxygen evolution reaction are not neutralizing the bicarbonate ions, even though oxygen is evolving. One possibility for this result is that the protons are going across the membrane to the cathode where they are reduced to hydrogen gas. This is an artifact of this particular experimental device which should not be a limitation in the actual device discussed in this paper. The purpose of this experiment was to verify that the bicarbonate ions could be electrochemically decomposed, and it has been conrmed that they can be.

3.2. Cell investigation Based on the results described above, gas-diffusion electrodes on carbon paper with the Ni-based electrocatalyst were constructed for use in an electrochemical separation device. A fuel cell was adapted in the laboratory to test the performance of the electrocatalysts for CO2 separation. In this work, an anion exchange membrane, Neosepta, was used and is a commercially-available alternative to Selemion. A mass spectrometer is used to measure gas composition. With pure oxygen owing across the cathode, pure oxygen is transported across the membrane and evolved at the anode at 1.2 V, conrming that oxygen separation is feasible at potentials where water electrolysis does not occur. Once steady transport was obtained, the feed gas was switched to a 50:50 CO2/ O2 mixture (see Fig. 7). Within a few minutes of switching the feed, CO2 evolution at the anode was observed. The CO2 evolution was dependent on the cell voltage and ceased when the cell voltage was set to 0 V. More signicantly, this transport occurs at cell voltages less than 1.23 V, which means that no water splitting is occurring in this process and there is no hydrogen evolution. It is hypothesized that the device functions by reducing oxygen at the cathode to OH ions that react with gas-phase CO2 to form carbonated ions:

1 O2 H2 O 2e ! 2OH 2 2OH 2CO2 ! 2HCO 3

These ions are transported across the membrane where the reverse reactions occur at the anode, reforming oxygen and carbon dioxide gas:

2HCO ! 2OH 2CO2 3 1 2OH ! O2 H2 O 2e 2

In essence, the pH at each electrode is modied by the electrochemical reactions. At the cathode the pH is basic, and carbonation of the electrolyte occurs. At the anode, the pH is more acidic (due to OH consumption) and the carbonate ions are unstable at low pH which leads to CO2 evolution. The transport of O2 is voltage

Fig. 6. Volumetric rate of CO2 evolution from potassium bicarbonate electrolytes. A commercial water electrolyzer with Ni electrodes was used.

H.W. Pennline et al. / Fuel 89 (2010) 13071314

-

1313

4e

6.00E-08

O2, CO2 depleted

HCO3 HCO3

To Mass Spec

5.00E-08

HCO3

Arbitrary M.S. Units

HCO3

4.00E-08

50 cm /min O2, CO2

HCO3

50 cm3/min Ar

C A
3.00E-08
Pure O2 feed Switch from pure O2 feed to a 50/50 mixture O2/CO2

2.00E-08
Potential 0V

1.00E-08
Oxygen Carbon Dioxide

0.00E+00 600

700

800

900

1000

1100

1200

1300

1400

1500

Time / min
Fig. 7. Proof-of-concept for CO2 separation. At approximately 1150 min the gas feed was changed from pure oxygen to 50:50 O2/CO2, and a step change in CO2 concentration is observed at the anode. At about 1350 min, the cell voltage was turned off, and the O2 and CO2 transport ceased.

dependent as shown in Fig. 8. As cell potentials are increased, there is an increase in the current density which also corresponds to an increase in the oxygen transport through the membrane device. These results complete the proof-of-concept goal for this concept. An electrochemical membrane can be used to separate and
4eDepleted O2 To Mass Spec OHOHOHOH50cm3/min O2 OH50cm3/min Ar

concentrate CO2 from an oxygen/CO2 gas mixture at low temperatures. CO2 transport is directly coupled to oxygen transport, and that oxygen separation occurs in the absence of CO2. A minimum voltage of 0.8 V is required to observe measurable transport (current density of 1 mA/cm2) in most cases.

60

1.20E-07

50

1.00E-07

Current Density / mA cm-2

40

8.00E-08

C
30

A
6.00E-08

20

Cell Current Density Mass Spectrometer Oxygen Reading

4.00E-08

10

2.00E-08

0 0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.1

1.2

0.00E+00 1.3

Cell Potential / V
Fig. 8. Demonstration of electrochemical control of O2 transport. As the current (blue squares) changes, the transport of O2 (green circles) changes. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

Arbitrary M.S. Units

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Under these conditions the energy to concentrate the CO2 is surprisingly low, assuming the gas composition of the product stream attained is close to 4:1 CO2 to O2. Actual product ratios still need to be conrmed through further analysis. For a current density of 5 mA/cm2, a CO2 ux of 0.069 ml/(cm2 min) is calculated. At a voltage of 1.2 V, that corresponds to only 116 kJ/mol CO2. At a current density of 1 mA/cm2, the operating voltage is 0.8 V, and the energy demand is reduced to 77 kJ/mol CO2. These are electrical energy demands just for the electrochemical separation, and it must be realized that the separated stream composition could be close to 4:1 CO2 to O2. Although preliminary electrochemical results show extensive transport of carbon dioxide in comparison to oxygen, further analysis is necessary to determine exact uxes and ratios of the gas evolution. The results of the electrochemical research effort will have a direct impact on the oxy-ring characteristics of the stream and future attention will be given to the rapid advancements in the oxy-ring area. Additionally, the all important energy needs for the electrochemical separation followed by oxy-ring will be quantied to assure that the concept approaches an improvement over exiting post-combustion carbon dioxide separation techniques. 4. Conclusion A novel concept for producing a carbon dioxide rich efuent from the combustion products of a fossil fuel power generation system is discussed. Carbon dioxide and oxygen are electrochemically separated from the ue gas and sent to an oxy-red combustor which uses the stream for combustion resulting in an efuent rich in carbon dioxide. The key step in the concept is the electrochemical separation at temperatures representative of those after a conventional lime/limestone scrubber where the scrubber would remove trace contaminants, for example sulfur dioxide, which could deleteriously impact the electrodes/electrolyte materials within the cell. Results have been obtained from experimentation within a low temperature, non-optimized laboratory-scale electrochemical separator. In the proof-of-concept testing with this cell, an anion exchange membrane was sandwiched between gas-diffusion electrodes consisting of nickel-based anode electrocatalysts on carbon paper. When a potential was applied across the cell and a mixture of oxygen and carbon dioxide was owed over the wetted electrolyte on the cathode side, a stream of CO2 to O2 was produced on the anode side, suggesting that bicarbonate ions are the CO2 carrier in the membrane. Since a mixture of CO2 and O2 is produced, the possibility exists to use this stream in oxy-ring of additional fuel, as described in the original concept. Further research with the low temperature electrochemical cell will occur. Disclaimer Reference in this report to any specic commercial process, product, or service is to facilitate understanding and does not nec-

essarily imply its endorsement or favoring by the United States Department of Energy. Acknowledgements The authors appreciate the efforts of George Richards, Energy System Dynamics Focus Area Leader. The endorsement of the research by the Existing Plants, Emissions and Capture Technology Manager, Jared Ciferno, is also noted. References
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