Fuel Processing Technology 86 (2005) 1423 1434 www.elsevier.

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Review of novel methods for carbon dioxide separation from flue and fuel gases
Evan J. GraniteT, Thomas OBrien
United States Department of Energy, National Energy Technology Laboratory, P.O. Box 10940, MS 58-106, Pittsburgh, PA 15236-0940, United States

Abstract This paper reviews some of the more novel methods for carbon dioxide separation from flue and fuel gas streams. These methods include electrochemical pumps, membranes, and chemical looping approaches to CO2 separation. Electrochemical pumps discussed include carbonate and proton conductors. Selective membranes for hydrogen separation are discussed as a method for carbon dioxide concentration in fuel gas streams. The selective membranes include mixed ionicelectronic (solid electrolytemetal) films as well as palladium-based materials. Chemical looping combustion is briefly discussed. The fundamental mechanisms behind these techniques will be explained, and recent advances in these methods are emphasized. Future research directions are suggested and an extensive list of references is provided. Published by Elsevier B.V.
Keywords: Carbon dioxide; Separation; Electrochemical pumps; Membrane; Chemical looping

1. Introduction The President recently announced the U.S. Global Climate Change Initiative (GCCI) to reduce greenhouse gas (GHG) intensity by 18% by 2012 [1]. The GCCI proposal would slow the growth in U.S. emissions of carbon dioxide. Alkaline sorbents and scrubbing solutions are often employed to separate carbon dioxide from various gas matrices.

T Corresponding author. Tel.: +1 412 386 4607; fax: +1 412 386 6004. E-mail address: evan.granite@netl.doe.gov (E.J. Granite). 0378-3820/$ - see front matter. Published by Elsevier B.V. doi:10.1016/j.fuproc.2005.01.001

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Cryogenic separation of carbon dioxide is also commonly used. A comprehensive review of carbon dioxide capture methods is given by White [24]. Novel methods have the potential to reduce the cost of carbon dioxide sequestration. These methods include electrochemical, membrane, enzymatic, photosynthesis, catalytic routes, and chemical looping combustion for CO2 separation or conversion [26].

2. Electrochemical pumps for separation of CO2 from flue gas 2.1. Carbonate ion pumps The molten carbonate and aqueous alkaline fuel cells have been studied for use in separating carbon dioxide from both air and flue gases [714]. Operation of the molten carbonate fuel cell in a closed circuit mode (with application of an external emf) will result in the transport of carbonate ions across the membrane [714]. The molten carbonate electrochemical separator requires oxidizing conditions for the formation of carbonate from carbon dioxide, and is less applicable for direct separation of CO2 from fuel gases. This pioneering work was first performed by Winnick [79]. Winnick proposed the use of molten carbonate fuel cell membranes for separation of carbon dioxide from air for space flight (Sky Lab) [79]. Winnick first examined molten carbonate membranes for separation of CO2 from power plant flue gas [79]. More recently the Osaka Research Institute in Japan, British Petroleum in the UK, and Ansaldo Fuel Cells in Italy have also experimented with molten carbonate electrochemical systems for CO2 capture from flue gas [1014]. There are several advantages of molten carbonate electrochemical cells for CO2 separation. A large knowledge base exists for the use and application of molten carbonate from its use in fuel cells. Molten carbonate is nearly 100% selective for the transport of carbonate anions at elevated temperatures. It exhibits high conductivity of around 1 S/cm at 600 8C, or equivalently a diffusivity of 105 cm2/s for the carbonate anion [79]. The parasitic power requirements for the separation of carbon dioxide from power plant flue gases are low and estimated to be less than 5% [9]. The cost for CO2 capture from flue gas was estimated at $20/ton in 1990 by Winnick [9]. Unfortunately there are major disadvantages in the application of molten carbonate electrochemical cells for separation of carbon dioxide from power plant flue gas. Molten carbonate is a corrosive paste. The high temperatures, along with the extremely corrosive nature of the molten carbonate, make fabrication and handling extremely difficult. The small applied voltages allowable in order to avoid decomposition of the molten carbonate result in low currents. The current represents the flux of carbonate anions across the membrane. This necessitates the use of huge stacks to obtain a significant flux of carbonate ions across the device [914]. Sulfur dioxide present in flue gas poisons the cell, resulting in sulfate formation [914]. There are also severe problems with electrolyte segregation and electrode degradation in the severe high temperature flue gas environment [914]. A solid electrolyte membrane for the separation of carbon dioxide from flue gas could solve many of the problems associated with molten carbonate [1517]. Solid electrolytes are solid ionic conductors, and are used in sensors, catalyst studies, and fuel cells [18].

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Millions are used in automobiles as the oxide airfuel ratio sensors. Most solid electrolytes are ceramics. Solid electrolytes often operate at lower temperatures than molten carbonate cells. A solid electrolyte would be easier to handle, have far reduced corrosion problems, and would possess a longer operating life than its molten carbonate counterpart. The development of a highly conductive carbonate ion solid electrolyte is an area of active research [1517]. The possibility of using alkali carbonate or alkaline earth carbonate solid electrolytes for the separation of carbon dioxide from flue gas is discussed by Granite [15 17]. Granite and Pennline propose doping alkaline earth carbonates in order to increase the ionic conductivity by orders of magnitude [1517]. There are many solids that are excellent conductors of oxygen anions or protons. The carbonate anion is significantly larger than the oxygen anion or proton, suggesting that it will be difficult to obtain mobile carbonate anions within a solid electrolyte matrix.

3. Electrochemical pumps for concentrating CO2 from fuel gas 3.1. Proton pumps Hydrogen gas can be produced by IGCC plants, steam gasification reactions, the pyrolysis of coal, the electrolysis of water, and biochemically. Each of these processes generates hydrogen with associated impurities, such as carbon monoxide, carbon dioxide, methane, nitrogen, water, and oxygen. Oxygen must be removed from hydrogen streams in order to avoid explosion hazards. Previous hydrogen purification processes involved the step-wise removal of the impurities through absorption processes such as MEA (ethanolamine) washing to remove the carbon dioxide, TEG (glycol) dehydration of the gas, as well as the catalytic (Pt) removal of trace oxygen. A far simpler and potentially more cost-effective means of hydrogen separation and carbon dioxide concentration can be accomplished in one step by an electrochemical pump [1823]. These electrochemical pumps are efficient, silent, and non-polluting. Electrochemical pumps for hydrogen separation can be based upon the readily available hW alumina, nafion, and barium cerium oxide solid electrolytes [1823]. An analysis of the electrochemical hydrogen pump, similar to the analysis of the carbon dioxide pump above, follows. The application of an external EMF (voltage) to a proton-conducting solid electrolyte through a closed circuit will cause hydrogen to be selectively transported (pumped) to/or from a metal electrode. The rate of hydrogen transport is given by the current (flux of protons) across the membrane as: flux of H2 I =2F 1

where F is Faradays constant, 96,487 C/mol. There are several factors which limit the transport of hydrogen (current) across the membrane, and these are the conductivity of the electrolyte, thermodynamic stability of the electrolyte, and the electrode kinetics. For an ohmic membrane (V =IR ), current is inversely proportional to the resistance or proportional to the conductivity. The doped barium cerium oxide, BaCe0.9Y0.1O2.95, has a

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conductivity of 101 V1 cm1 at 1000 8C [1921]. The conductivity of hW alumina is 106 V1 cm1 at 100 8C [18,22,23]. Nafion (polymer electrolyte) is typically employed at temperatures of around 100 8C. The higher conductivity of the doped barium cerium oxide allows a higher flux of protons to be pumped to a metal electrode. The maximum value for the applied external voltage is determined by the decomposition potential of the solid electrolyte. This is found from the thermodynamic stability, the free energy of formation, DG f, of the material, namely: DGf nFE 2

where E is the maximum applied voltage. More stable electrolytes can be subjected to higher applied voltages. Typically a 12 V potential can be applied to a ceramic membrane. Therefore, the rate of transport of protons across the membrane is limited by both the conductivity (resistance) and stability of the electrolyte. Electrode kinetics also plays a key role in the rate of separation of hydrogen. Consider the example of a closed hW alumina electrochemical cell having palladium electrodes: Hydrogen must be first adsorbed from the impure gas stream on to the palladium electrode. Hydrogen then dissociates to hydrogen atoms. Charge transfer occurs, with protons forming. The protons migrate across the electrolyte under the influence of the externally applied field (voltage). Finally, the protons reverse the earlier steps, and form hydrogen gas at the opposite palladium electrode. At the interface between the gas, metal electrode, and solid electrolyte (the three-phase boundary), the overall reaction can be written as: H2gas 2H 2e 3

Therefore an electrode must efficiently adsorb and dissociate hydrogen so as to not limit the rate of hydrogen transport across the electrolyte. 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 or with metal pastes. The overall resistance of the pump is the sum of the resistances due to the electrode, electrolyte, and the electrode and electrolyte contact. Overall resistance can be minimized by: (1) use of a thin electrolyte and electrodes, (2) having intimate contact between electrode and electrolyte, and (3) selecting an electrolyte with high conductivity. The power consumed by the membrane separator is given by: Power V I I 2 R 4

For the lab-scale separator, with an applied voltage of around one volt, and a resulting current in the milliamp range, the power requirements will be on the order of milliwatts. Granite and Jorne applied external voltages to hW alumina and barium cerium oxide membranes to obtain the selective transport of deuterium from D2N2 mixtures [18,22,23]. Balachandran recently applied an external voltage to an yttria-doped barium cerium oxide membrane to obtain the selective transport of protons [1921]. The mechanism of proton conduction by SrCe0.95Y0.05O3d is discussed by Balachandran [21].

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4. Membranes for separation of CO2 The development of a membrane separator for the selective removal of CO2 in the presence of CO, H2, H2O, and H2S (fuel gas) or N2, O2, H2O, SO2, NO, and HCl (flue gas) would be of tremendous economic value. A membrane separation process requires far less expenditure for maintenance and energy than does a comparable absorption (alkanolamine or alkaline salt solution) process for the purification of concentrated CO2 streams [24]. A membrane material which either allows the selective transport (diffusion) or selective exclusion of CO2 is desired. Membranes can separate carbon dioxide from a gas stream by size exclusion or by chemical affinity [2527]. Chemical affinity membranes are often impregnated with a scrubbing solution or chemical functional group (e.g., amine) selective for carbon dioxide, and will not be discussed here. The scrubbing solutions, as well as functional groups on the surface of sorbents, are discussed in the critical review papers [24]. A large body of research has been conducted on the properties of carbon dioxide selective membranes based upon inorganic materials such as zeolites, alumina, carbon, and silica. Some recent work on these membranes has been presented at an NETL-sponsored conference. Noble and Falconer examined CO2 separations from simple two component mixtures using zeolite membranes [28]. Shih suggests that the gas permeabilities of zeolites are limited by the tortuous pore structures, and the selectivity between carbon dioxide and nitrogen is low because of the similar molecular diameters [29]. Andrews proposed the separation of carbon dioxide from flue gases by carbon-multiwall nanotube membranes [30]. His experimental work used a packed bed of carbon nanotube sorbent and CO2N2 mixtures. The carbon selectively adsorbed carbon dioxide from the simple two component mixture at temperatures ranging from 30 8C to 150 8C. This result prompted the author to further examine the potential of carbon nanotube materials for membrane separation of carbon dioxide [30]. Inorganic membranes have been reviewed by Shekhawat et al. [27]. Substantial advances in the selectivity, permeability, and chemical stability of inorganic membranes are needed for successful application to flue or fuel gas mixtures. Polymer membranes have been successfully applied for the separation of carbon dioxide from natural gas streams [3142]. The harsh chemically reactive and high temperature matrix that is flue and fuel gas makes the use of polymer membranes unlikely for these applications. Hendriks recently examined the use of polymer membranes for the separation of carbon dioxide from flue gas [43]. He treated flue gas as a two component mixture (CO2 N2). This simplification essentially divides flue gas into two groups consisting of fast permeating and slow permeating compounds. Hendriks concluded that a polymer membrane would require a CO2N2 selectivity greater than 200 and a permeability of more than 5109 m3/m2 Pa s [43]. The available polymer membranes are not economically competitive with other separation methods for flue gas. A review on polymer membranes for carbon dioxide separation was recently written by Shekhawat et al. [27]. 4.1. Palladium-based membranes for concentrating CO2 from fuel gas Palladium membranes have been extensively studied and used for the separation of hydrogen from various gas streams [44,45]. The metal can absorb enormous quantities of

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hydrogen; at 1800 8F it absorbs enough to correspond to the formula PdH0.6 [44]. An excellent reference on the properties of palladium relevant in the separation of hydrogen is provided by Buxbaum and Kinney [45]. Palladium is readily fabricated into a variety of shapes and sizes, and has excellent chemical resistance to carbon monoxide, steam, and hydrocarbons [45]. Palladium membranes have been studied for potential application for fuel gas mixtures for hydrogen separation, leaving a gas residue enriched in carbon dioxide. Palladium is an active oxidation catalyst and therefore not an appropriate membrane for hydrogen separation from streams that contain oxygen. Palladium is not inert; it chemisorbs and reacts with sulfur and chlorine species present in fuel gas. There are a rich variety of compounds which can form between palladium and chlorine. Hydrogen embrittlement can occur in palladium. Undesirable phase changes also occur in palladium at elevated temperatures. Therefore alternative metal membranes are necessary for hydrogen separation from fuel gas mixtures. Govind prepared composite palladium membranes for selective hydrogen separation at high temperature [46]. He formed a thin palladium film on a silver substrate, and found the resulting membrane had promising mechanical strength and selectivity for hydrogen from argon streams at 370 8C to 407 8C. Buxbaum proposed the use of tubular membranes of palladium-coated tantalum and niobium for the separation of hydrogen from hot gas streams [45]. He demonstrated continuous separation of hydrogen from argon at 420 8C over a 31-day period using the tubular membranes. Buxbaum suggests that the economics of hydrogen separation using the palladium-coated refractory metals are promising [45]. Morreale obtained an Arrhenius type expression for the hydrogen permeability of palladium and examined the mechanism of hydrogen transport within palladium at elevated temperatures and pressures [47]. Ciocco examined the permeability of hydrogen through thin-film palladium membranes [48]. Palladium films, palladium coated tantalum, and palladium coated stainless steel membranes were examined for their hydrogen transport characteristics [48]. Thin films of palladium were utilized in order to minimize the material cost of the precious metal. The tantalum and stainless steel substrates were employed in an attempt to improve the material properties of the membrane. Damle studied the use of thin palladiumsilver alloy films deposited on a ceramic substrate for hydrogen separation from carbon dioxide [49]. Alloying palladium with silver increases the permeability for hydrogen, and reduces hydrogen embrittlement. Commercially available alumina ceramics were used as the substrate. Way and McCormick recently examined the use of palladiumcopper alloy composite membranes for high temperature hydrogen separation from fuel gas streams [50]. The palladiumcopper alloy was used in order to improve resistance to poisoning by hydrogen sulfide, enhance the hydrogen permeability, and reduce hydrogen embrittlement. Further improvements in the material properties of metal membranes are needed for their use in fuel gas mixtures. 4.2. Mixed ionicelectronic conducting membranes for concentrating CO2 from fuel gas The use of proton-conducting membranes with application of an external emf in a closed circuit was discussed in the section on electrochemical separations. A

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disadvantage of the use of proton pumps for hydrogen separation (and carbon dioxide concentration) is the need for an externally applied voltage. The rate of proton transport across a hydrogen solid electrolyte ceramic membrane is determined by diffusion and will be small in the absence of an external emf. One method proposed to avoid the need for an externally applied voltage is through the use of mixed ionicelectronic conducting membranes [5153]. Gade studied the use of a proprietary proton-conducting ceramic sandwiched between outer nickel films [51]. The initial work has focused on the fabrication of the novel membranes. This design is envisioned to be incorporated within a monolithic, multimembrane hydrogen separation module for Vision 21 plants. Eltron recently employed cerates doped with transition metals to impart electronic conductivity for hydrogen separation [52]. Roark found that a large flux of hydrogen passed through this membrane without the application of an external emf [52]. Data is provided for hydrogen separation from helium at temperatures of 650 8C to 950 8C by the proprietary Eltron membranes. Rothenberger examined dense cermet membranes for hydrogen separation from simulated syngas at temperatures of 600 8C to 900 8C [53]. Barium cerium yttrium oxide ceramic was doped with proprietary metals to obtain high permeabilities for hydrogen. Hydrogen fluxes through the membranes of varying thickness were measured. The hydrogen flux through the most promising membrane exhibited no reduction over a 190 h test at 900 8C in a simulated syngas consisting of 66% H2, 33% CO, and 1% CO2. Further research is needed to develop highly selective and permeable mixed ionicelectronic membranes which are also chemically stable in hot fuel gas streams.

5. Chemical looping Chemical looping combustion is a novel method to facilitate carbon dioxide separation from flue gases [5476]. Ishida has championed the potential of chemical looping for simplifying the separation of carbon dioxide from flue gases [5475]. The oxygen for combustion of the fuel is provided by a regenerable metal oxide catalyst. The use of lattice oxygen from a metal oxide catalyst as the oxidizing agent, in lieu of gasphase oxygen from air, results in a flue gas that is not diluted by nitrogen. This results in a flue gas that is concentrated in carbon dioxide. Because air is not used in the combustion of the fuel, NOx emissions are low. The chemical looping scheme can be presented in the general form: HC metal oxideYCO2 H2 O lower oxideand=or metal Lower oxideand=or metal O2 Ymetal oxide 5 6

Reaction (5) is the combustion of the fuel (typically natural gas) in the absence of gasphase oxygen using a reactive oxide oxidation catalyst. Step (6) is the regeneration of the catalyst for reuse in step (5). Reactions (5) and (6) take place in separate vessels. Nickel oxide has been extensively examined as a candidate oxygen carrier oxide catalyst for the chemical looping combustion of methane. Alumina and yttria-stabilized

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Table 1 X-ray diffraction study of metal oxide reduction in methane [18] Sample 20% Li-doped NiO 20% Li-doped NiO NiO CaO MoO3 Bi2O3 Cu2O YSZa Temperature (8C) 700 515 400 530 535 515 530 400 Resulting phases major Ni major Ni Ni reference [111] no reduction major MoO3 minor Mo2O5 major Bi2O3 trace Bi major Cu2O minor Cu no reduction

Reducing atmosphere: 100% CH4 for 6 h, unless noted. a Reducing atmosphere: 2% CO in He for 21 h.

zirconia (YSZ) have been suggested as supports for nickel oxide catalysts to be employed within chemical looping combustion schemes. For nickel oxide, reactions (5) and (6) can be written as: CH4 4NiOYCO2 2H2 O 4Ni 4Ni 2O2 Y4NiO 7 8

Nickel oxide is readily reduced to nickel by methane at temperatures as low as 400 8C [77]. Granite conducted an X-ray diffraction study of metal oxide reduction in methane [18]. Several oxides were exposed to a methane atmosphere for 6 h. The phase changes were determined via X-ray diffraction, and are summarized in Table 1. Nickel oxide and lithium-doped nickel oxides were readily reduced to nickel, whereas other oxides were more difficult to reduce. It is noted that chemical looping combustion would be conducted at higher temperatures than those reported in Table 1, which should facilitate reduction of the oxides. The economics of chemical looping depend upon robust and active oxide oxidation catalysts that can be regenerated for numerous cycles. Catalyst attrition and deactivation are obviously important issues for the technical success of the process. Catalyst deactivation by carbon deposition has been investigated by Jin and Ishida [73]. Preliminary cost analyses of chemical looping as a strategy for carbon dioxide capture from flue gases have been very promising [76].

6. Conclusions The novel CO2 capture technologies have advantages and disadvantages when installed in a power-generation system. Initial evaluations by Herzog et al. [78] indicate that certain technologies for CO2 control from flue gas from conventional PC-fired power plants create a substantial thermal efficiency power loss. A study by Kosugi et al. [79] investigated the

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various technologies by using a graphical evaluation and review technique. The target CO2 capture technologies were compared for different levels of development. Although some of the technologies presently have larger penalties than others, future research and development will improve the projected energy efficiencies. Electrochemical membranes have the potential to economically separate carbon dioxide from flue gas. Material science issues such as reducing corrosion (molten carbonate pumps) and increasing conductivity (solid electrolyte pumps) need to be addressed. More research on electrochemical methods for the separation of carbon dioxide from flue and fuel gases is recommended. Chemical looping combustion strategies also have great promise for facilitating the capture of carbon dioxide from flue gas. A large body of knowledge exists on potential oxide oxidation catalysts for use in chemical looping. Materials research promises the continuing development of more active and robust oxide catalysts. Additional research on chemical looping combustion as a strategy for producing a concentrated carbon dioxide flue gas is also suggested.

Acknowledgements The authors thank NETL colleagues Henry Pennline, Curt White, Brian Strazisar, Jim Hoffman, Rich Hargis, Dave Luebke, and Dan Fauth for helpful suggestions. This paper is dedicated to Philip Granite on the occasion of his 75th birthday.

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