3. DESCRIPCIÓN DE LOS SERVICIOS WEB LEXNET
3.2. Exclusivos para conexión con certificado de usuario
There is much yet to be understood for this multiphase system. One fundamental question is the activation of metal oxide in the presence of molten salt. It is also observed that the interface between the molten salt and the solid phase is critical to the effectiveness of the chemical conversion obtained. Identification of intermediated species with chemical probes and structural probes and a full quantitative thermodynamic picture of the involved interfacial chemical interactions would uncover much basic science on the structural evolvement. Gas-solid reactions between metal oxides and gaseous species are classic reactions. However, it is a perpetual challenge to study the reaction mechanism and to obtain the knowledge of how the atomic structure transforms during reaction. With the molten salt involvement, the metal oxide phase is transferred into the molten salt phase prior to reaction with gas molecules. The evolution of the reactant species with the molten salt phase can also provide insights to classic gas-solid reactions.
In my perspective, answering the questions mentioned above would require the combination of applying advanced tools for operando elemental and structural probing and developing new algorithms for predicting the thermodynamics of the solvation of species in the
120
molten salt phase. The focus of interest in the material system involves chemical interactions among metal oxide, molten salt and gas at operation conditions (elevated temperatures and specific gaseous environment). MgO and molten NaNO3 reaction with CO2 can continued be
used as the exemplary material system for most of the study. Ex-situ and in-situ HRTEM characterization can be used to probe the structural and chemical evolution in the multiphase system, especially at the interfaces. Study of both the rate and amount of dissolution of metal oxide or gas in molten salt, and intermediate species can challenge the current detection limit of existing technologies. Special experimental design and operation needs to be developed for non- destructive characterization techniques considering the effect of high energy electron or ion beams on molten salts.
In operando and ex situ 23Na and 25Mg magic angle spinning (MAS) NMR is needed to follow the chemical and structural change at atomic scale of the metal oxide and molten phases. Enriched 13C NMR will provide significant information on gas speciation, adsorption, dissolution into and interaction with NaNO3 and solvated MgO and formation of carbonate. In
situ Raman and IR can also be very helpful for conducting this experiment, especially with their non-destructive nature.
Highly important will be computation and simulation work for both understanding the thermodynamics of dissolution, solvation of metal oxide and chemical interactions with gas at interfaces. Based on experimental results above, intermediate species will be provided for computation work. The obtained new reaction energy pathway can provide a thorough picture of the new reaction mechanism. New algorithms will be needed for conducting this work, which involves complex solid-liquid-gas multiphase systems.
121 References
1. Metz, B., et al., IPCC Special Report on Carbon Dioxide Capture and Storage, IPCC, Editor. 2005.
2. Field, C.B., et al., Managing the risks of extreme events and disasters to advance climate
change adaptation, in Special Report of the Intergovernmental Panel on Climate Change.
2012: New York.
3. D'Alessandro, D.M., B. Smit, and J.R. Long, Carbon Dioxide Capture: Prospects for
New Materials. Angewandte Chemie International Edition, 2010. 49(35): p. 6058-6082.
4. Damle, A.S. and T.P. Dorchak, Reovery of carbon dioxide in advanced fossil energy
conversion processes using a membrane reactor. Journal of Energy and Environment
Research, 2001. 1(1): p. 77-89.
5. IEA, Technology Roadmap: Carbon Capture and Storage. 2013: Paris.
6. Herzog, H., CO2 Capture and Storage in The Economics and Politics of Climate Change.
2009, Oxford University Press. p. 263-283.
7. Pre-combustion sorbents, in Advanced Carbon Dioxide Capture R&D Program: Technology Update, May 2011, National Energy Technology Laboratory.
8. Choi, S., J.H. Drese, and C.W. Jones, Adsorbent Materials for Carbon Dioxide Capture
from Large Anthropogenic Point Sources. ChemSusChem, 2009. 2(9): p. 796-854.
9. Abanades, J.C., E.S. Rubin, and E.J. Anthony, Sorbent cost and performance in CO2
capture systems. Ind. Eng. Chem. Res., 2004. 43: p. 3462-3466.
10. Wang, Q., et al., CO2 capture by solid adsorbents and their applications: current status
and new trends. Energy & Environmental Science, 2011. 4(1): p. 42.
11. Bottoms, R.R., Process for separating acidic gases. 1930, The Girdler Corporation: United States.
12. Rochelle, G.T., Amine Scrubbing for CO2 Capture. Science, 2009. 325(5948): p. 1652- 1654.
13. Caplow, M., Kinetics of carbamate formation and breakdown. J. Am. Chem. Soc., 1968. 90(24): p. 6795-6803.
14. Donaldson, T.L. and Y.N. Nguyen, Carbon Dioxide Reaction Kinetics and Transport in
122
15. Vaidya, P.D. and E.Y. Kenig, CO2-Alkanolamine Reaction Kinetics: A Review of Recent
Studies. Chemical Engineering & Technology, 2007. 30(11): p. 1467-1474.
16. Davison, J., Performance and costs of power plants with capture and storage of CO2. Energy, 2007. 32(7): p. 1163-1176.
17. Belmabkhout, Y., G. De Weireld, and A. Sayari, Amine-Bearing Mesoporous Silica for
CO2and H2S Removal from Natural Gas and Biogas. Langmuir, 2009. 25(23): p. 13275-
13278.
18. Bertsch, L. and H.W. Habgood, An infrared spectroscopic study of the adsorption of
water and carbon dioxide by linde molecular sieve X. J. Phys. Chem., 1963. 67(8): p.
1621-1628.
19. Ward, J.W. and H.W. Habgood, The infrared spectra of carbon dioxide adsorbed on
zeolite X. The Journal of Physical Chemistry, 1966. 70(4).
20. Siriwardane, R.V., et al., Adsorption of CO2 on molecular sieves and activated carbon.
Energy & Fuels, 2001. 15: p. 279-284.
21. Inui, T., Y. Okugawa, and M. Yasuda, Relationship between properties of various
zeolites and their CO2-adsorption behaviors in pressure swing adsorption operation. Ind.
Eng. Chem. Res., 1988. 27(7): p. 1988.
22. Ko, D., R. Siriwardane, and L.T. Biegler, Optimization of a pressure-swing adsorption
process using zeolite 13X for CO2 sequestration. Ind. Eng. Chem. Res., 2003. 42: p. 339-
348.
23. Kikkinides, E.S. and R.T. Yang, Concentration and recovery of CO2 from flue gas by
pressure swing adsorption. Ind. Eng. Chem. Res., 1993. 32: p. 2714-2720.
24. Tranchemontagne, D.J., et al., Reticular Chemistry of Metal–Organic Polyhedra. Angewandte Chemie International Edition, 2008. 47(28): p. 5136-5147.
25. Yaghi, O.M., et al., Reticular synthesis and the design of new materials. Nature, 2003. 423: p. 705-714.
26. Rosi, N.L., et al., Rod packing and metal-organic frameworks constructured from rod-
shaped secondary building units. J. Am. Chem. Soc., 2005. 127: p. 1504-1518.
27. Natarajan, S. and S. Mandal, Open-Framework Structures of Transition-Metal
123
28. Millward, A.R. and O.M. Yaghi, Metal-organic frameworks with exceptionally high
capacity for storage of carbon dioxide at room temperature. J. Am. Chem. Soc., 2005.
127: p. 17998-17999.
29. Bates, E.D., et al., CO2 Capture by a Task-Specific Ionic Liquid. J. Am. Chem. Soc.,
2002. 124(6).
30. Lee, K.B., et al., Reversible chemisorbents for carbon dioxide and their potential
applications. Ind. Eng. Chem. Res., 2008. 47.
31. Hufton, J.R., S. Mayorga, and S. Sircar, Sorption-enhanced reaction process for
hydrogen production. AIChE Journal, 1999. 45(2).
32. Mayorga, S.G., et al., Carbon dioxide adsorbents containing magnesium oxide suitable
for use at high temperatures. 2001, Air Products and Chemical, Inc.: United States. p. 15.
33. Siriwardane, R.V. and R.W. Stevens, Novel regenerable magnesium hydroxide sorbents
for CO2 capture at warm gas temperatures. Ind. Eng. Chem. Res., 2009. 48(4): p. 2135-
2141.
34. Gregg, S.J. and J.D. Ramsay, Adsorption of carbon dioxide by magnesia studied by use of
infrared and isotherm measurements. Journal of the Chemical Society A: Inorganic,
Physical, Theoretical, 1970: p. 2784.
35. Singh, R., et al., High temperature materials for CO2 capture. Energy Procedia, 2009.
1(1): p. 623-630.
36. Xiao, G., et al., Advanced adsorbents based on MgO and K2CO3 for capture of CO2 at
elevated temperatures. International Journal of Greenhouse Gas Control, 2011. 5(4): p.
634-639.
37. Xu, Z., X. Sun, and M.A. Khaleel, A generalized kinetic model for heterogeneous gas-
solid reactions. The Journal of Chemical Physics, 2012. 137(7): p. 074702.
38. Bhatia, S.K. and D. D.Perlmutter, Effect of the product layer on the kinetics of the CO2-
lime reaction. AIChE Journal, 1983. 29(1): p. 79-86.
39. Feng, B., et al., Overcoming the Problem of Loss-in-Capacity of Calcium Oxide in
CO2Capture. Energy & Fuels, 2006. 20(6): p. 2417-2420.
40. Li, L., et al., Magesia-stabilized calcium oxide absorbent with improved durability for
124
41. Li, L., et al., MgAl2O4 Spinel-stabilized calcium oxide absorbents with improved
durability for high-temperature CO2 capture. Energy & Fuels, 2010. 24(6): p. 3698-3703.
42. Ohashi, T. and K. Nakagawa, Effect of potassium carbonate additive on CO2 absorption
in lithium zirconate powder. Materials Research Society, 1999. 547: p. 249-254.
43. Ida, J.-I. and Y.S. Lin, Mechanism of high-temperature CO2 sorption on lithium
zirconate. Envrion. Sci. Technol., 2003. 37: p. 1999-2004.
44. Barker, R., The reversibility of the reaction CaCO3↔ CaO+CO2. J. appl. Chem.
Biotechnol, 1973. 23: p. 733-742.
45. Silaban, A., M. Narcida, and D.P. Harrison, CHARACTERISTICS OF THE REVERSIBLE
REACTION BETWEEN CO2(g) AND CALCINED DOLOMITE. Chemical Engineering
Communications, 1996. 146(1): p. 149-162.
46. Aihara, M., et al., Development of porous solid reactant for thermal-energy storage and
temperature upgrade using carbonation/decarbonation reaction. Applied Energy, 2001.
69: p. 225-238.
47. Mayorga, S.G., S.J. Weigel, and T.R. Gaffney, Carbon dioxide adsorbents containing
magnesium oxide suitable for use at high temperatures 2001, Air Products and
Chemicals: United States
48. Nissen, D.A. and D.E. Meeker, Nitrate/nitrite chemistry in sodium nitrate-potassium
nitrate melts. American Chemical Society, 1983. 22(5): p. 716-721.
49. Freeman, E.S., The kinetics of the thermal decomposition of sodium nitrate and of the
reaction between sodium nitrite and oxygen. J. Phys. Chem., 1956. 60(11): p. 1487-1493.
50. Bauer, T., D. Laing, and R. Tamme, Recent progress in alkali nitrate-nitrite
developments for solar thermal power applications. Molten Salts Chemistry and
Technology Proceedings, 2011.
51. Hassanzadeh, A. and J. Abbasian, Regenerable MgO-based sorbents for high-
temperature CO2 removal from syngas: 1. Sorbent development, evaluation, and reaction
modeling. Fuel, 2010. 89(6): p. 1287-1297.
52. Duan, Y. and D.C. Sorescu, CO2 capture properties of alkaline earth metal oxides and
hydroxides: A combined density functional theory and lattice phonon dynamics study.
125
53. Duan, Y., et al., CO2 capture properties of M–C–O–H (M=Li, Na, K) systems: A
combined density functional theory and lattice phonon dynamics study. Journal of Solid
State Chemistry, 2011. 184(2): p. 304-311.
54. FactSage, Na2CO3-NaNO3. 2012, Fact-Web programs.
55. Janz, G.J., J. Kelly, and J.L. Perano, Melting and pre-melting phenomena in alkali metal
nitrates. Journal of Chemical and Engineering Data 1964. 9(1): p. 133-136.
56. Davies, P.J. and B. Bubela, The transformation of nesquehonite into hydromagnesite. Chemical Geology, 1973. 12(4): p. 289-300.
57. Hänchen, M., et al., Precipitation in the Mg-carbonate system—effects of temperature
and CO2 pressure. Chemical Engineering Science, 2008. 63(4): p. 1012-1028.
58. Lanas, J. and J.I. Alvarez, Dolomitic lime: thermal decomposition of nesquehonite. Thermochimica Acta, 2004. 421(1-2): p. 123-132.
59. Yoon, K.H., Y.S. Cho, and D.H. Kang, Review: Molten salt synthesis of lead-based
relaxors. Journal of Materials Science, 1998. 33: p. 2977-2984.
60. Zhang, S., et al., Molten Salt Synthesis of Magnesium Aluminate (MgAl2O4) Spinel
Powder. Journal of the American Ceramic Society, 2006. 89(5): p. 1724-1726.
61. Broda, M. and C.R. Müller, Synthesis of highly efficient, Ca-based, Al2O3-stabilized,
carbon gel-templated CO2 sorbents. Advanced Materials 2012. 24(22): p. 3059-3064.
62. Lee, K.B., et al., Chemisorption of carbon dioxide on potassium-carbonate-promoted
hydrotalcite. Journal of Colloid and Interface Science, 2007. 308(1): p. 30-39.
63. Sada, E., et al., Solubility of carbon dioxide in molten alkali halides and nitrates and their
binary mixtures. J. Chem. Eng. Data, 1981. 26: p. 279-281.
64. Martin, R.L. and J.B. West, Solubility of magnesium oxide in molten salts. J. Inorg. Nucl. Chem., 1962. 24: p. 105-111.
65. Kresse, G. and J. Hafner, Ab initio molecular dynamics for liquid metals. Physical Review B, 1993. 47(1): p. 558-561.
66. Perdew, J.P. and Y. Wang, Accurate and simple analytic representation of the electron-
gas correlation energy. Physical Review B, 1992. 45(23): p. 13244-13249.
67. Monkhorst, H.J. and J.D. Pack, Special points for Brillouin-zone integrations. Physical Review B, 1976. 13(12): p. 5188-5192.
126
69. Carper, W.R., P.G. Wahlbeck, and T.R. Griffiths, DFT Models of Molecular Species in
Carbonate Molten Salts. The Journal of Physical Chemistry B, 2012. 116(18): p. 5559-
5567.
70. Canc s, E., B. Mennucci, and J. Tomasi, A new integral equation formalism for the
polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics. The Journal of Chemical Physics, 1997. 107(8): p. 3032.
71. Dielectric Constants of Common Materials. Available from: http://www.flowmeterdirectory.com/terminologies/385-dielectric-constants-of-common- materials.html.
72. HSC CHEMISTRY 6.12. 2006, Qutotec Research Oy.
73. Starks, C.M., Phase transfer catalysis. I. Heterogeneous Reactions Involving Anion
Transfer by Quaternary Ammonium and Phosphonium Salts. J. Am. Chem. Soc. , 1971.
93(1): p. 195.
74. Leo´n, M., et al., Adsorption of CO2 on Hydrotalcite-Derived Mixed Oxdes-Sorption
Mechanisms and Consequences for Adsorption Irreversibility. Ind. Eng. Chem. Res.,
2010. 49(8): p. 3663-3671.
75. Cherginets, V.L., et al., Potentiometric investigation of oxide solubilities in molten KCl-
NaCl eutectic. Journal of Electroanalytical Chemistry, 2002. 531: p. 171-178.
76. Adamson, A.W. and A.P. Gast, Physical Chemistry of Surfaces, 6th Edition. 1997: John Wiley & Sons.
77. Molten Salts Date Center, C.L., Rensselaer Polytechic Institute, Physcial Properties Data
Compilations Relevant to Energy Storage, in IV. Molten Salts: Data on Additional Single and Multi-Component Salt Systems. 1981, U.S. Department of Commerce, National
Bureau of Standards.
78. Stern, K.H., High Temperature Properties and Decomposition of Inorganic Salts. Part 4.