Precision Calcination Mechanism of CaCO3 to High-Porosity Nanoscale CaO CO2 Sorbent Revealed by Direct In Situ Observations

Martinez, Jenny; Wardini, Jenna L.; Zheng, Xueli; Moghimi, Lauren; Rakowsky, Jason; Means, Jonathan; Guo, Huiming; Kuzmenko, Ivan; Ilavsky, Jan; Zhang, Fan; Dholabhai, Pratik P.; Dresselhaus‐Marais, Leora; Bowman, William J.

doi:10.1002/admi.202300811

Precision Calcination Mechanism of CaCO₃ to High-Porosity Nanoscale CaO CO₂ Sorbent Revealed by Direct In Situ Observations

Journal Article · Fri Apr 05 00:00:00 EDT 2024 · Advanced Materials Interfaces

DOI:https://doi.org/10.1002/admi.202300811· OSTI ID:2403663

Martinez, Jenny ^[1]; Wardini, Jenna L. ^[2]; Zheng, Xueli ^[3]; Moghimi, Lauren ^[3]; Rakowsky, Jason ^[4]; Means, Jonathan ^[2]; Guo, Huiming ^[2]; Kuzmenko, Ivan ^[5]; Ilavsky, Jan ^[5]; Zhang, Fan ^[6]; Dholabhai, Pratik P. ^[4]; Dresselhaus‐Marais, Leora ^[3]; ^[2]

Univ. of California, Irvine, CA (United States); SLAC
Univ. of California, Irvine, CA (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Rochester Inst. of Technology, Rochester, NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

Deploying energy storage and carbon capture at scale is hindered by the substantial endothermic penalty of decomposing CaCO₃ to CaO and CO₂, and the rapid loss of CO₂ absorption capacity by CaO sorbent particles due to sintering at the high requisite decomposition temperatures. The decomposition reaction mechanism underlying sorbent deactivation remains unclear at the atomic level and nanoscale due to past reliance on postmortem characterization methods with insufficient spatial and temporal resolution. Thus, elucidating the important CaCO₃ decomposition reaction pathway requires direct observation by time-resolved (sub-)nanoscale methods. Here, chemical and structural dynamics during the decomposition of CaCO₃ nanoparticles to nanoporous CaO particles comprising high-surface-area CaO nanocrystallites are examined. Comparing in situ transmission electron microscopy (TEM) and synchrotron X-ray diffraction experiments gives key insights into the dynamics of nanoparticle calcination, involving anisotropic CaCO₃ thermal distortion before conversion to thermally dilated energetically stable CaO crystallites. Time-resolved TEM uncovered a novel CaO formation mechanism involving heterogeneous nucleation at extended CaCO₃ defects followed by sweeping reaction front motion across the initial CaCO₃ particle. These observations clarify longstanding, yet incomplete, reaction mechanisms and kinetic models lacking accurate information about (sub-)nanoscale dynamics, while also demonstrating calcination of CaCO₃ without sintering through rapid heating and precise temperature control.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; AC02-06CH11357

OSTI ID:: 2403663

Journal Information:: Advanced Materials Interfaces, Journal Name: Advanced Materials Interfaces Journal Issue: 14 Vol. 11; ISSN 2196-7350

Publisher:: Wiley-VCHCopyright Statement

Country of Publication:: United States

Language:: English

References (70)

The Potential Applications of Nanoporous Materials for the Adsorption, Separation, and Catalytic Conversion of Carbon Dioxide Sneddon, Gregor; Greenaway, Alex; Yiu, Humphrey H. P. Advanced Energy Materials, Vol. 4, Issue 10 https://doi.org/10.1002/aenm.201301873	journal	March 2014
The effect of CaO sintering on cyclic CO2 capture in energy systems Sun, P.; Grace, J. R.; Lim, C. J. AIChE Journal, Vol. 53, Issue 9 https://doi.org/10.1002/aic.11251	journal	January 2007
Calcination kinetics and surface area of dispersed limestone particles Borgwardt, R. H. AIChE Journal, Vol. 31, Issue 1 https://doi.org/10.1002/aic.690310112	journal	January 1985
Polymorphism of CaCO3, precipitated in a constant-composition environment Tai, Clifford Y.; Chen, F. -B. AIChE Journal, Vol. 44, Issue 8 https://doi.org/10.1002/aic.690440810	journal	August 1998
Mechanistic Understanding of CaO‐Based Sorbents for High‐Temperature CO₂ Capture: Advanced Characterization and Prospects Krödel, Maximilian; Landuyt, Annelies; Abdala, Paula M. ChemSusChem, Vol. 13, Issue 23 https://doi.org/10.1002/cssc.202002078	journal	October 2020
The thermal expansion of calcite from room temperature up to 400°C Srinivasan, R. Proceedings of the Indian Academy of Sciences - Section A, Vol. 42, Issue 2 https://doi.org/10.1007/BF03053495	journal	August 1955
Progress and current challenges for CO2 capture materials from ambient air Wang, Junya; Fu, Rong; Wen, Shikun Advanced Composites and Hybrid Materials, Vol. 5, Issue 4 https://doi.org/10.1007/s42114-022-00567-3	journal	October 2022
The mechanism of the thermal decomposition of calcium carbonate Hills, A. W. D. Chemical Engineering Science, Vol. 23, Issue 4 https://doi.org/10.1016/0009-2509(68)87002-2	journal	June 1968
Grüneisen parameters and thermal expansion of CaO and SrO Ruppin, R. Solid State Communications, Vol. 10, Issue 11 https://doi.org/10.1016/0038-1098(72)90894-0	journal	June 1972
Decomposition of limestone in a solar reactor Imhof, A. Renewable Energy, Vol. 10, Issue 2-3 https://doi.org/10.1016/0960-1481(96)00072-9	journal	February 1997
Nanocrystalline and metastable phase formation in vacuum thermal decomposition of calcium carbonate Dash, S.; Kamruddin, M.; Ajikumar, P. K. Thermochimica Acta, Vol. 363, Issue 1-2 https://doi.org/10.1016/S0040-6031(00)00604-3	journal	November 2000
Application of the Arrhenius equation to solid state kinetics: can this be justified? Galwey, Andrew K.; Brown, Michael E. Thermochimica Acta, Vol. 386, Issue 1 https://doi.org/10.1016/S0040-6031(01)00769-9	journal	April 2002
Decomposition kinetics of calcite: a new approach to the old problem L’vov, Boris V.; Polzik, Leonid K.; Ugolkov, Valery L. Thermochimica Acta, Vol. 390, Issue 1-2 https://doi.org/10.1016/S0040-6031(02)00080-1	journal	July 2002
Nano CaO grain characteristics and growth model under calcination Zhu, Yanqing; Wu, Sufang; Wang, Xieqing Chemical Engineering Journal, Vol. 175 https://doi.org/10.1016/j.cej.2011.09.084	journal	November 2011
A model on the CaO multicyclic conversion in the Ca-looping process Valverde, Jose Manuel Chemical Engineering Journal, Vol. 228 https://doi.org/10.1016/j.cej.2013.05.023	journal	July 2013
Technical and economic feasibility evaluation of calcium looping with no CO2 recirculation Hanak, Dawid P.; Erans, Maria; Nabavi, Seyed A. Chemical Engineering Journal, Vol. 335 https://doi.org/10.1016/j.cej.2017.11.022	journal	March 2018
Progress in reducing calcination reaction temperature of Calcium-Looping CO2 capture technology: A critical review Han, Rui; Wang, Yang; Xing, Shuang Chemical Engineering Journal, Vol. 450 https://doi.org/10.1016/j.cej.2022.137952	journal	December 2022
Reactivity of CaO derived from nano-sized CaCO3 particles through multiple CO2 capture-and-release cycles Florin, Nicholas H.; Harris, Andrew T. Chemical Engineering Science, Vol. 64, Issue 2 https://doi.org/10.1016/j.ces.2008.10.021	journal	January 2009
Investigation of CaO–CO2 reaction kinetics by in-situ XRD using synchrotron radiation Biasin, A.; Segre, C. U.; Salviulo, G. Chemical Engineering Science, Vol. 127 https://doi.org/10.1016/j.ces.2014.12.058	journal	May 2015
On the negative activation energy for limestone calcination at high temperatures nearby equilibrium Valverde, Jose Manuel Chemical Engineering Science, Vol. 132 https://doi.org/10.1016/j.ces.2015.04.027	journal	August 2015
General rate equation theory for gas–solid reaction kinetics and its application to CaO carbonation Li, Zhenshan Chemical Engineering Science, Vol. 227 https://doi.org/10.1016/j.ces.2020.115902	journal	December 2020
Pilot-scale calcination of limestone in steam-rich gas for direct air capture Erans, María; Nabavi, Seyed Ali; Manović, Vasilije Energy Conversion and Management: X, Vol. 1 https://doi.org/10.1016/j.ecmx.2019.100007	journal	January 2019
CO2 capture in cement plants by “Tail-End” Calcium Looping process Lena, E. De; Spinelli, M.; Romano, M. C. Energy Procedia, Vol. 148 https://doi.org/10.1016/j.egypro.2018.08.049	journal	August 2018
Review—calcination and carbonation of limestone during thermal cycling for CO2 sequestration Stanmore, B. R.; Gilot, P. Fuel Processing Technology, Vol. 86, Issue 16 https://doi.org/10.1016/j.fuproc.2005.01.023	journal	November 2005
Solvochemical carbonation of lime using ethanol: Mechanism and enhancement for direct atmospheric CO2 capture Ounoughene, Ghania; Buskens, Ellen; Santos, Rafael M. Journal of CO2 Utilization, Vol. 26 https://doi.org/10.1016/j.jcou.2018.04.024	journal	July 2018
Influence of additives on CaCO3 precursors and multicycle CO2 capture performance of CaO sorbents Yue, Wenfei; Fan, Chuigang; Song, Wenli Journal of Environmental Chemical Engineering, Vol. 10, Issue 3 https://doi.org/10.1016/j.jece.2022.107440	journal	June 2022
A Process for Capturing CO2 from the Atmosphere Keith, David W.; Holmes, Geoffrey; St. Angelo, David Joule, Vol. 2, Issue 8 https://doi.org/10.1016/j.joule.2018.05.006	journal	August 2018
The Calcium-Looping (CaCO3/CaO) process for thermochemical energy storage in Concentrating Solar Power plants Ortiz, C.; Valverde, J. M.; Chacartegui, R. Renewable and Sustainable Energy Reviews, Vol. 113 https://doi.org/10.1016/j.rser.2019.109252	journal	October 2019
Solar Energy on Demand: A Review on High Temperature Thermochemical Heat Storage Systems and Materials Carrillo, Alfonso J.; González-Aguilar, José; Romero, Manuel Chemical Reviews, Vol. 119, Issue 7 https://doi.org/10.1021/acs.chemrev.8b00315	journal	March 2019
Review of Carbonate-Based Systems for Thermochemical Energy Storage for Concentrating Solar Power Applications: State-of-the-Art and Outlook Raganati, Federica; Ammendola, Paola Energy & Fuels, Vol. 37, Issue 3 https://doi.org/10.1021/acs.energyfuels.2c03853	journal	January 2023
Zr-Modified Ni/CaO Dual Function Materials (DFMs) for Direct Methanation in an Integrated CO₂ Capture and Utilization Process Jo, Seongbin; Woo, Jin Hyeok; Nguyen, Tu Energy & Fuels, Vol. 37, Issue 24 https://doi.org/10.1021/acs.energyfuels.3c02935	journal	December 2023
Investigations on Kinetics and Mechanisms of CaCO₃ Calcination in Calcium Looping Li, Zeya; Guo, Xiaojin; Xue, Xiaoyong Industrial & Engineering Chemistry Research, Vol. 62, Issue 12 https://doi.org/10.1021/acs.iecr.2c03314	journal	March 2023
Flame-Made Durable Doped-CaO Nanosorbents for CO₂ Capture Lu, Hong; Khan, Ataullah; Pratsinis, Sotiris E. Energy & Fuels, Vol. 23, Issue 2 https://doi.org/10.1021/ef8007882	journal	December 2008
Relevant Influence of Limestone Crystallinity on CO₂ Capture in The Ca-Looping Technology at Realistic Calcination Conditions Valverde, J. M.; Sanchez-Jimenez, P. E.; Perez-Maqueda, L. A. Environmental Science & Technology, Vol. 48, Issue 16 https://doi.org/10.1021/es5014505	journal	July 2014
Determination of the Critical Product Layer Thickness in the Reaction of CaO with CO ₂ Alvarez, Diego; Abanades, J. Carlos Industrial & Engineering Chemistry Research, Vol. 44, Issue 15 https://doi.org/10.1021/ie050305s	journal	June 2005
CO ₂ Capture Capacity of CaO in Long Series of Carbonation/Calcination Cycles Grasa, Gemma S.; Abanades, J. Carlos Industrial & Engineering Chemistry Research, Vol. 45, Issue 26 https://doi.org/10.1021/ie0606946	journal	December 2006
Properties of a Nano CaO/Al₂O₃ CO₂ Sorbent Wu, Su F.; Li, Qing H.; Kim, Jong N. Industrial & Engineering Chemistry Research, Vol. 47, Issue 1 https://doi.org/10.1021/ie0704748	journal	November 2007
Limestone Calcination Nearby Equilibrium: Kinetics, CaO Crystal Structure, Sintering and Reactivity Valverde, J. M.; Sanchez-Jimenez, P. E.; Perez-Maqueda, L. A. The Journal of Physical Chemistry C, Vol. 119, Issue 4 https://doi.org/10.1021/jp508745u	journal	January 2015
Calcium oxides of high reactivity Beruto, Dario; Searcy, Alan W. Nature, Vol. 263, Issue 5574 https://doi.org/10.1038/263221a0	journal	September 1976
Ultrastructure of calcite decomposition in vacuo Towe, Kenneth M. Nature, Vol. 274, Issue 5668 https://doi.org/10.1038/274239a0	journal	July 1978
Impact production of C02 by the Cretaceous/Tertiary extinction bolide and the resultant heating of the Earth O'Keefe, John D.; Ahrens, Thomas J. Nature, Vol. 338, Issue 6212 https://doi.org/10.1038/338247a0	journal	March 1989
Experimental simulations of the photodecomposition of carbonates and sulphates on Mars Mukhin, L. M.; Koscheevi, A. P.; Dikov, Yu. P. Nature, Vol. 379, Issue 6561 https://doi.org/10.1038/379141a0	journal	January 1996
Ambient weathering of magnesium oxide for CO2 removal from air McQueen, Noah; Kelemen, Peter; Dipple, Greg Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16510-3	journal	July 2020
The technological and economic prospects for CO2 utilization and removal Hepburn, Cameron; Adlen, Ella; Beddington, John Nature, Vol. 575, Issue 7781 https://doi.org/10.1038/s41586-019-1681-6	journal	November 2019
Ca-based synthetic materials with enhanced CO ₂ capture efficiency Valverde, Jose Manuel J. Mater. Chem. A, Vol. 1, Issue 3 https://doi.org/10.1039/C2TA00096B	journal	January 2013
Crystallographic transformation of limestone during calcination under CO₂ Valverde, Jose Manuel; Medina, Santiago Physical Chemistry Chemical Physics, Vol. 17, Issue 34 https://doi.org/10.1039/C5CP02715B	journal	January 2015
Fundamental studies of carbon capture using CaO-based materials Sun, Hongman; Wang, Jianqiao; Liu, Xiaotong Journal of Materials Chemistry A, Vol. 7, Issue 16 https://doi.org/10.1039/C8TA10472G	journal	January 2019
Modulation of double-network hydrogels via seeding calcium carbonate microparticles for the engineering of ultrasensitive wearable sensors Zhang, Xiaohui; Geng, Huimin; Zhang, Xunhui Journal of Materials Chemistry A, Vol. 11, Issue 6 https://doi.org/10.1039/D2TA07834A	journal	January 2023
Climate change mitigation potential of carbon capture and utilization in the chemical industry Kätelhön, Arne; Meys, Raoul; Deutz, Sarah Proceedings of the National Academy of Sciences, Vol. 116, Issue 23 https://doi.org/10.1073/pnas.1821029116	journal	May 2019
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Development of combined microstructure and structure characterization facility for in situ and operando studies at the Advanced Photon Source Ilavsky, Jan; Zhang, Fan; Andrews, Ross N. Journal of Applied Crystallography, Vol. 51, Issue 3 https://doi.org/10.1107/S160057671800643X	journal	June 2018
XSEDE: Accelerating Scientific Discovery Towns, John; Cockerill, Timothy; Dahan, Maytal Computing in Science & Engineering, Vol. 16, Issue 5 https://doi.org/10.1109/MCSE.2014.80	journal	September 2014
Calcium Carbonate Decomposition in Carbon Dioxide Atmosphere Hyatt, Edmond P.; Cutler, Ivan B.; Wadsworth, Milton E. Journal of the American Ceramic Society, Vol. 41, Issue 2 https://doi.org/10.1111/j.1151-2916.1958.tb13521.x	journal	February 1958
Surface Areas and Morphologies of CaO Produced by Decomposition of Large CaCO3 Crystals in Vacuum Powell, Elizabeth K.; Searcy, Alan W. Journal of the American Ceramic Society, Vol. 65, Issue 3 https://doi.org/10.1111/j.1151-2916.1982.tb10395.x	journal	March 1982
Rearrangement of Porous CaO Aggregates During Calcite Decomposition in Vacuum Beruto, Dario; Barco, Luigi; Searcy, Alan W. Journal of the American Ceramic Society, Vol. 66, Issue 12 https://doi.org/10.1111/j.1151-2916.1983.tb11008.x	journal	December 1983
Formation of Nanocrystalline Calcia by the Decomposition of Calcite Singh, Alok; Dash, Sitaram; Kamruddin, Mohammed Journal of the American Ceramic Society, Vol. 85, Issue 4 https://doi.org/10.1111/j.1151-2916.2002.tb00194.x	journal	April 2002
Calcium-looping reforming of methane realizes in situ CO ₂ utilization with improved energy efficiency Tian, Sicong; Yan, Feng; Zhang, Zuotai Science Advances, Vol. 5, Issue 4 https://doi.org/10.1126/sciadv.aav5077	journal	April 2019
A new kinetic model of calcite thermal decomposition Matvienko, A. A.; Chizhik, S. A.; Sidel’nikov, A. A. Doklady Physical Chemistry, Vol. 451, Issue 2 https://doi.org/10.1134/S001250161308006X	journal	August 2013
Applicability of Carbonation/Decarbonation Reactions to High-Tempereture Thermal Energy Storage and Temperature Upgrading. Kyaw, Kyaw; Matsuda, Hitoki; Hasatani, Masanobu JOURNAL OF CHEMICAL ENGINEERING OF JAPAN, Vol. 29, Issue 1 https://doi.org/10.1252/jcej.29.119	journal	January 1996
Thermal decomposition of calcite: Mechanisms of formation and textural evolution of CaO nanocrystals Rodriguez-Navarro, C.; Ruiz-Agudo, E.; Luque, A. American Mineralogist, Vol. 94, Issue 4 https://doi.org/10.2138/am.2009.3021	journal	April 2009
The role of carbonates in the evolution of early Martian oceans Morse, J. W. American Journal of Science, Vol. 299, Issue 7-9 https://doi.org/10.2475/ajs.299.7-9.738	journal	November 1999
Probing Multiscale Disorder in Pyrochlore and Related Complex Oxides in the Transmission Electron Microscope: A Review Wardini, Jenna L.; Vahidi, Hasti; Guo, Huiming Frontiers in Chemistry, Vol. 9 https://doi.org/10.3389/fchem.2021.743025	journal	November 2021
A Review of Grain Boundary and Heterointerface Characterization in Polycrystalline Oxides by (Scanning) Transmission Electron Microscopy Vahidi, Hasti; Syed, Komal; Guo, Huiming Crystals, Vol. 11, Issue 8 https://doi.org/10.3390/cryst11080878	journal	July 2021
Kinetics of Solid-Gas Reactions and Their Application to Carbonate Looping Systems Fedunik-Hofman, Larissa; Bayon, Alicia; Donne, Scott W. Energies, Vol. 12, Issue 15 https://doi.org/10.3390/en12152981	journal	August 2019

Similar Records

Combined calcination, sintering and sulfation model for CaCO{sub 3}-SO{sub 2} reaction

Journal Article · Sun Jan 31 23:00:00 EST 1999 · AIChE Journal · OSTI ID:329248

A mathematical model for the flash calcination of dispersed CaCO/sub 3/ and Ca(OH)/sub 2/ particles

Journal Article · Tue Jan 31 23:00:00 EST 1989 · Ind. Eng. Chem. Res.; (United States) · OSTI ID:6049684

Thermodynamics and kinetics of the reaction: CaCO/sub 3/ = CaO + CO/sub 2/

Technical Report · Mon Sep 01 00:00:00 EDT 1980 · OSTI ID:5012027

Related Subjects

36 MATERIALS SCIENCE
CaCO3
calcination
in situ synchrotron x-ray diffraction
in situ transmission electron microscopy
nanoparticle
nanoporosity
sintering

Precision Calcination Mechanism of CaCO3 to High-Porosity Nanoscale CaO CO2 Sorbent Revealed by Direct In Situ Observations

Citation Formats

References (70)

Similar Records

Related Subjects

Precision Calcination Mechanism of CaCO₃ to High-Porosity Nanoscale CaO CO₂ Sorbent Revealed by Direct In Situ Observations