CO2 Absorption on Na2ZrO3:  A Kinetic Analysis of the Chemisorption and Diffusion Processes

Alcerreca-Corte, Itzel; Fregoso-Israel, E.; Pfeiffer, Heriberto

doi:10.1021/jp710475g

Cited by 108 publications

(126 citation statements)

References 26 publications

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“…[16] Among a variety of materials reported in this category, this section describes in detail adsorption on a representative oxide, calcium oxide, along with a discussion of other important metal-based adsorbents including magnesium oxides and lithium zirconates. Although we focus attention here on calcium oxides and magnesium oxides, it should be noted that many other metal oxides display some CO 2 adsorption properties under selected conditions including lithium oxides, [98] sodium oxides, [99][100][101][102] potassium oxides, [103,104] rubidium oxides, [105] cesium oxides, [106] barium oxides, [107] iron oxides, [108][109][110][111][112] tantalum oxides, [113] copper oxides, [114,115] chromium oxides, [116][117][118][119][120] and aluminum oxides. [121][122][123][124][125][126] where M can be, for example, Mg, Ca, Sr, Ba.…”

Section: Metal-based Adsorbentsmentioning

confidence: 99%

Adsorbent Materials for Carbon Dioxide Capture from Large Anthropogenic Point Sources

2009

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Since the time of the industrial revolution, the atmospheric CO(2) concentration has risen by nearly 35 % to its current level of 383 ppm. The increased carbon dioxide concentration in the atmosphere has been suggested to be a leading contributor to global climate change. To slow the increase, reductions in anthropogenic CO(2) emissions are necessary. Large emission point sources, such as fossil-fuel-based power generation facilities, are the first targets for these reductions. A benchmark, mature technology for the separation of dilute CO(2) from gas streams is via absorption with aqueous amines. However, the use of solid adsorbents is now being widely considered as an alternative, potentially less-energy-intensive separation technology. This Review describes the CO(2) adsorption behavior of several different classes of solid carbon dioxide adsorbents, including zeolites, activated carbons, calcium oxides, hydrotalcites, organic-inorganic hybrids, and metal-organic frameworks. These adsorbents are evaluated in terms of their equilibrium CO(2) capacities as well as other important parameters such as adsorption-desorption kinetics, operating windows, stability, and regenerability. The scope of currently available CO(2) adsorbents and their critical properties that will ultimately affect their incorporation into large-scale separation processes is presented.

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Section: Metal-based Adsorbentsmentioning

confidence: 99%

Adsorbent Materials for Carbon Dioxide Capture from Large Anthropogenic Point Sources

2009

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“…For example, alkali zirconates, Li 2 ZrO 3 , and Na 2 ZrO 3 , only can absorb 0.287 g CO2 /g ceramic and 0.237 g CO2 /g ceramic , respectively. 4,5,20 Finally, Li 4 SiO 4 is able to absorb theoretically up to 0.733 g CO2 /g ceramic , assuming that the whole lithium participate in the reaction. Figure 2.…”

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confidence: 99%

“…Although this kind of thermal trend has not been observed for other lithium ceramics, it has been published that other alkali ceramics presents a similar behavior. 5,20 In those cases, the whole chemisorption process is divided in two steps: First, at low temperatures, a superficial reaction is produced. At this moment, an external alkali carbonate shell is formed over the surface of the ceramic particles.…”

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confidence: 99%

Lithium Cuprate (Li2CuO2): A New Possible Ceramic Material for CO2 Chemisorption

Palacios-Romero¹,

Pfeiffer²

2008

Chemistry Letters

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Li 2 CuO 2 was used for the CO 2 chemisorption process. Li 2 CuO 2 was thermally treated under a flux of CO 2 , dynamically (from 25 to 1000 C) and isothermically. The results clearly showed that Li 2 CuO 2 is able to chemisorb CO 2 in a wider range of temperatures than those presented by other lithium ceramics. Therefore, this ceramic may become a new option as CO 2 captor.In the last ten years, some lithium ceramics have been proposed as possible CO 2 captors because of the chemisorption process produced between CO 2 and lithium atoms present in the ceramic structure.1-5 Some of the ceramics proposed up to now are; lithium oxide (Li 2 O), lithium zirconates (Li 2 ZrO 3 and Li 6 Zr 2 O 6 ), lithium orthosilicate (Li 4 SiO 4 ), and lithium orthotitanate (Li 4 TiO 4 ). [6][7][8][9][10][11][12][13] In general, all these materials show a similar chemisorption mechanism. First, CO 2 reacts over the ceramic particle surface, producing a lithium carbonate (Li 2 CO 3 ) external shell and the corresponding residual oxide. Then, in order to continue the CO 2 chemisorption, lithium atoms have to diffuse from the core of the particles toward the surface to complete the reaction. 6 Additionally, it has been proposed that one of the most important steps, and perhaps the limiting one, of the whole process is the diffusion. On the other hand, lithium cuprate (Li 2 CuO 2 ) has been used for different electrical applications such as cathodes for lithium batteries and as a superconductor material, owing to the excellent lithium diffusion.14-19 The high lithium diffusion and structural characteristics have been reported for Li 2 CuO 2 ; therefore, the aim of the work reported here was to study and demonstrate whether or not Li 2 CuO 2 is able to capture CO 2 , by a mechanism similar to that reported previously for other lithium ceramics.Li 2 CuO 2 sample was obtained by a coprecipitation method using 10 wt % excess of lithium, and its diffractogram is shown in Figure 1. Li 2 CuO 2 was the main phase, and only small quantities of copper oxide (CuO) were detected. The presence of CuO indicates that excess lithium was not enough to complete the reaction. However, the volume fraction of this phase should not exceed 5% of the total system, and as CuO does not capture CO 2 , it would not interfere with the CO 2 capture analysis. The same figure shows the morphology of the Li 2 CuO 2 particles. As can be seen, the particles presented a dense polyhedral shape, with a particle size distribution of 11 AE 2 mm. Additionally, the particles presented some kind of texture; the surface of the particles seems to be corrugated. This kind of morphology and particle size are similar to those obtained for other lithium ceramics that have been tested as CO 2 captors. It could be useful for comparison reasons.Once Li 2 CuO 2 was characterized, the material was thermally treated under a CO 2 stream to analyze whether or not this material is able to act as a CO 2 captor. If Li 2 CuO 2 traps chemically CO 2 , the following reaction may occur (reaction 1):...

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“…Their results showed that nanocrystalline Na 2 ZrO 3 is a very promising CO 2 acceptor for different applications due to its excellent stability and durability 17 and to be able to work at CO 2 partial pressure as low as 0.025 bar. Based on measuring the isotherms of CO 2 sorption and kinetic analysis, Alcerreca-Corte et al 18 investigated the CO 2 absorption on Na 2 ZrO 3 and found that there are two different processes taking place: (1) CO 2 chemsorption over surface of the particles; (2) once the Na 2 CO 3 shell formed, the second process of Na diffusion from core of the particles to the surface to reactive the first chemsorption process. Obviously, the second step is the limiting step of the total absorption process as the estimated activation energies of these two steps are 33.866 kJ/mol and 48.009 kJ/mol, respectively.…”

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confidence: 99%

A first-principles density functional theory study of the electronic structural and thermodynamic properties of M2ZrO3 and M2CO3 (M = Na, K) and their capabilities for CO2 capture

Duan

2012

Journal of Renewable and Sustainable Energy

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Isotopic effect on the vibrational lifetime of the carbon-deuterium stretch excitation on graphene J. Chem. Phys. 135, 114506 (2011) Vibrational properties of graphene fluoride and graphane Appl. Phys. Lett. 98, 051914 (2011) Electronic structural and electrochemical properties of lithium zirconates and their capabilities of CO2 capture: A first-principles density-functional theory and phonon dynamics approach J. Alkali metal zirconates could be used as solid sorbents for CO 2 capture. The structural, electronic, and phonon properties of Na 2 ZrO 3 , K 2 ZrO 3 , Na 2 CO 3 , and K 2 CO 3 are investigated by combining the density functional theory with lattice phonon dynamics. The thermodynamics of CO 2 absorption/desorption reactions of these two zirconates are analyzed. The calculated results show that their optimized structures are in a good agreement with experimental measurements. The calculated band gaps are 4.339 eV (indirect), 3.641 eV (direct), 3.935 eV (indirect), and 3.697 eV (direct) for Na 2 ZrO 3 , K 2 ZrO 3 , Na 2 CO 3 , and K 2 CO 3 , respectively. The calculated phonon dispersions and phonon density of states for M 2 ZrO 3 and M 2 CO 3 (M ¼ K, Na, Li) revealed that from K to Na to Li, their frequency peaks are shifted to high frequencies due to the molecular weight decreased from K to Li. From the calculated reaction heats and relationships of free energy change versus temperatures and CO 2 pressures of the M 2 ZrO 3 (M ¼ K, Na, Li) reacting with CO 2 , we found that the performance of Na 2 ZrO 3 capturing CO 2 is similar to that of Li 2 ZrO 3 and is better than that of K 2 ZrO 3 . Therefore, Na 2 ZrO 3 and Li 2 ZrO 3 are good candidates of high temperature CO 2 sorbents and could be used for postcombustion CO 2 capture technologies.

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CO₂ Absorption on Na₂ZrO₃: A Kinetic Analysis of the Chemisorption and Diffusion Processes

Cited by 108 publications

References 26 publications

Adsorbent Materials for Carbon Dioxide Capture from Large Anthropogenic Point Sources

Adsorbent Materials for Carbon Dioxide Capture from Large Anthropogenic Point Sources

Lithium Cuprate (Li2CuO2): A New Possible Ceramic Material for CO2 Chemisorption

A first-principles density functional theory study of the electronic structural and thermodynamic properties of M2ZrO3 and M2CO3 (M = Na, K) and their capabilities for CO2 capture

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