Abstract
H2/CO production via H2O/CO2 splitting powered by concentrated solar energy is a promising pathway for energy conversion/storage. Oxygen permeable membrane reactor serves as an alternative reactor concept for realizing this chemical path with the advantages of continuous production, easy integration, and high product selectivity. In this paper, a mathematical model of steady-state mass and heat transfer coupled with reaction kinetics in the oxygen permeation membrane reactor was established. CO2 splitting in the ceria membrane reactor was simulated and the effects of various factors, including inert/CO2 flow configurations, reaction conditions, and geometric parameters of the membrane, on the CO2 conversion process, were studied. The increase of operating temperature could effectively improve the CO2 conversion ratio, and the effect of decreasing the oxygen pressure of the inert gas is very limited. The oxygen accumulation in the inert gas could lead to considerably high inert demand. Furthermore, conversion-limiting factors were studied under different conditions and there are two critical rate constants of reactions signifying a transition from a chemical kinetics limited conversion to oxygen diffusion limited conversion. This work helps guide reactor design and operate toward achieving the maximum CO2 conversion ratio.
Issue Section:
Research Papers
References
1.
Lewis
, N. S.
, and Nocera
, D. G.
, 2006
, “Powering the Planet: Chemical Challenges in Solar Energy Utilization
,” Proceedings National Academy Sci.
, 103
(43
), pp. 15729
–15735
. 10.1073/pnas.06033951032.
Steinfeld
, A.
, 2005
, “Solar Thermochemical Production of Hydrogen: A Review
,” Sol. Energy
, 78
(5
), pp. 603
–615
. 10.1016/j.solener.2003.12.0123.
Meier
, A.
, and Steinfeld
, A.
, 2010
, Advances in Science and Technology
, Vol. 74
, Trans Tech Publications
, pp. 303
–312
.4.
Graves
, C.
, Ebbesen
, S. D.
, Mogensen
, M.
, and Lackner
, K. S.
, 2011
, “Sustainable Hydrocarbon Fuels by Recycling CO2 and H2O With Renewable or Nuclear Energy
,” Renewable Sustainable Energy Rev.
, 15
(1
), pp. 1
–23
. 10.1016/j.rser.2010.07.0145.
Xiao
, L.
, Wu
, S. Y.
, and Li
, Y. R.
, 2012
, “Advances in Solar Hydrogen Production via two-Step Water-Splitting Thermochemical Cycles Based on Metal Redox Reactions
,” Renewable Energy
, 41
, pp. 1
–12
. 10.1016/j.renene.2011.11.0236.
Agrafiotis
, C.
, Roeb
, M.
, and Sattler
, C.
, 2014
, “A Review on Solar Thermal Syngas Production via Redox Pair-Based Water/Carbon Dioxide Splitting Thermochemical Cycles
,” Renewable Sustainable Energy Rev.
, 42
, pp. 254
–285
. 10.1016/j.rser.2014.09.0397.
Perkins
, C.
, and Weimer
, A. W.
, 2009
, “Solar-Thermal Production of Renewable Hydrogen
,” AIChE J.
, 55
(2
), pp. 286
–293
. 10.1002/aic.118108.
Lu
, Y.
, Zhu
, L.
, Agrafiotis
, C.
, Vieten
, J.
, Roeb
, M.
, and Sattler
, C.
, 2019
, “Solar Fuels Production: Two-Step Thermochemical Cycles with Cerium-Based Oxides
,” Prog. Energy Combust. Sci.
, 75
, p. 100785
. 10.1016/j.pecs.2019.1007859.
Abanades
, S.
, Charvin
, P.
, Flamant
, G.
, and Neveu
, P.
, 2006
, “Screening of Water-Splitting Thermochemical Cycles Potentially Attractive for Hydrogen Production by Concentrated Solar Energy
,” Energy
, 31
(14
), pp. 2805
–2822
. 10.1016/j.energy.2005.11.00210.
Loutzenhiser
, P. G.
, Meier
, A.
, and Steinfeld
, A.
, 2010
, “Review of the Two-Step H2O/CO2-Splitting Solar Thermochemical Cycle Based on Zn/ZnO Redox Reactions
,” Materials
, 3
(11
), pp. 4922
–4938
. 10.3390/ma311492211.
Abanades
, S.
, and Chambon
, M.
, 2010
, “CO2 Dissociation and Upgrading From Two-Step Solar Thermochemical Processes Based on ZnO/Zn and SnO2/SnO Redox Pairs
,” Energy Fuel
, 24
(12
), pp. 6667
–6674
. 10.1021/ef101092u12.
Abanades
, S.
, Charvin
, P.
, Lemont
, F.
, and flamant
, G.
, 2008
, “Novel Two-Step SnO2/SnO Water-Splitting Cycle for Solar Thermochemical Production of Hydrogen
,” Int. J. Hydrogen Energy
, 33
(21
), pp. 6021
–6030
. 10.1016/j.ijhydene.2008.05.04213.
Tamaura
, Y.
, Ueda
, Y.
, Matsunami
, J.
, Hasegawa
, N.
, Nezuka
, M.
, Sano
, T.
, and Tsuji
, M.
, 1999
, “Solar Hydrogen Production by Using Ferrites
,” Sol. Energy
, 65
(1
), pp. 55
–57
. 10.1016/S0038-092X(98)00087-514.
Abanades
, S.
, and Villafan-Vidales
, H. I.
, 2011
, “CO2 and H2O Conversion to Solar Fuels via Two-Step Solar Thermochemical Looping Using Iron Oxide Redox Pair
,” Chem. Eng. J.
, 175
, pp. 368
–375
. 10.1016/j.cej.2011.09.12415.
Scheffe
, J. R.
, Jianhua
, L.
, Alan
, W.
, and Weimer
, 2010
, “A Spinel Ferrite/Hercynite Water-Splitting Redox Cycle
,” Int. J. Hydrogen Energy
, 35
(8
), pp. 3333
–3340
. 10.1016/j.ijhydene.2010.01.14016.
Arifin
, D.
, Aston
, V. J.
, Liang
, X.
, McDaniel
, A. H.
, and Weimer
, A. W.
, 2012
, “CoFe2O4 on a Porous Al2O3 Nanostructure for Solar Thermochemical CO2 Splitting
,” Energy Environ. Sci.
, 5
(11
), pp. 9438
–9443
. 10.1039/c2ee22090c17.
Abanades
, S.
, and Flamant
, G.
, 2006
, “Thermochemical Hydrogen Production From a Two-Step Solar-Driven Water-Splitting Cycle Based on Cerium Oxides
,” Sol. Energy
, 80
(12
), pp. 1611
–1623
. 10.1016/j.solener.2005.12.00518.
Chueh
, W. C.
, and Haile
, S. M.
, 2010
, “A Thermochemical Study of Ceria: Exploiting an old Material for New Modes of Energy Conversion and CO2 Mitigation
,” Philos Trans—R. Soc. A. Math. Phys. Eng. Sci.
, 368
(1923
), pp. 3269
–3294
. 10.1098/rsta.2010.011419.
Scheffe
, J. R.
, Weibel
, D.
, and Steinfeld
, A.
, 2013
, “Lanthanum–Strontium–Manganese Perovskites as Redox Materials for Solar Thermochemical Splitting of H2O and CO2
,” Energy Fuels
, 27
(8
), pp. 4250
–4257
. 10.1021/ef301923h20.
Demont
, A.
, Abanades
, S.
, and Beche
, E.
, 2014
, “Investigation of Perovskite Structures as Oxygen-Exchange Redox Materials for Hydrogen Production From Thermochemical Two-Step Water-Splitting Cycles
,” J. Phys. Chem. C
, 118
(24
), pp. 12682
–12692
. 10.1021/jp503484921.
Mogensen
, M.
, Sammes
, N. M.
, and Tompsett
, G. A.
, 2000
, “Physical, Chemical and Electrochemical Properties of Pure and Doped Ceria
,” Solid State Ionics
, 129
(1-4
), pp. 63
–94
. 10.1016/S0167-2738(99)00318-522.
Ackermann
, S.
, Scheffe
, J. R.
, and Steinfeld
, A.
, 2015
, “Diffusion of Oxygen in Ceria at Elevated Temperatures and Its Application to H2O/CO2 Splitting Thermochemical Redox Cycles
,” J. Phys. Chem. C
, 118
(10
), pp. 5216
–5225
. 10.1021/jp500755t23.
Yokokawa
, H.
, Horita
, T.
, Sakai
, N.
, Yamaji
, K.
, Brito
, M.
, Xiong
, Y.
, and Kishimoto
, H.
, 2006
, “Ceria: Relation Among Thermodynamic, Electronic Hole and Proton Properties
,” Solid State Ionics
, 177
(19-25
), pp. 1705
–1714
. 10.1016/j.ssi.2006.03.00624.
Lapp
, J.
, Davidson
, J. H.
, and Lipinski
, W.
, 2012
, “Efficiency of Two-Step Solar Thermochemical Non-Stoichiometric Redox Cycles With Heat Recovery
,” Energy
, 37
(1
), pp. 591
–600
. 10.1016/j.energy.2011.10.04525.
Bader
, R.
, Venstrom
, L. J.
, Davidson
, J. H.
, and Lipiński
, W.
, 2013
, “Thermodynamic Analysis of Isothermal Redox Cycling of Ceria for Solar Fuel Production
,” Energy Fuels
, 27
(9
), pp. 5533
–5544
. 10.1021/ef400132d26.
Hao
, Y.
, Yang
, C. K.
, and Haile
, S. M.
, 2013
, “High-Temperature Isothermal Chemical Cycling for Solar-Driven Fuel Production
,” Phys. Chem. Chem. Phys.
, 15
(40
), p. 17084
. 10.1039/c3cp53270d27.
Venstrom
, L. J.
, Smith
, R. M. D.
, Hao
, Y.
, Haile
, S. M.
, and Davidson
, J. H.
, 2014
, “Efficient Splitting of CO2 in an Isothermal Redox Cycle Based on Ceria
,” Energy Fuels
, 28
(4
), pp. 2732
–2742
. 10.1021/ef402492e28.
Muhich
, C. L.
, Evanko
, B. W.
, Weston
, K. C.
, Lichty
, P.
, Liang
, X.
, Martinek
, J.
, and Weimer
, A. W.
, 2013
, “Efficient Generation of H2 by Splitting Water With an Isothermal Redox Cycle
,” Science
, 341
(6145
), pp. 540
–542
. 10.1126/science.123945429.
Wang
, H.
, Hao
, Y.
, and Kong
, H.
, 2015
, “Thermodynamic Study on Solar Thermochemical Fuel Production With Oxygen Permeation Membrane Reactors
,” Int. J. Energy Res.
, 39
(13
), pp. 1790
–1799
. 10.1002/er.333530.
Uemiya
, S.
, Sato
, N.
, Ando
, H.
, Matsuda
, T.
, and Kikuchi
, E.
, 1990
, “Steam Reforming of Methane in a Hydrogen-Permeable Membrane Reactor
,” Appl. Catalysis
, 67
(1
), pp. 223
–230
. 10.1016/S0166-9834(00)84445-031.
Hacarlioglu
, P.
, Gu
, Y.
, and Oyama
, S. T.
, 2006
, “Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor
,” J. Nat. Gas Chem.
, 15
(2
), pp. 73
–81
. 10.1016/S1003-9953(06)60011-X32.
Marcoberardino
, G. D.
, Sosio
, F.
, Manzolini
, G.
, and Campanari
, S.
, 2015
, “Fixed bed Membrane Reactor for Hydrogen Production From Steam Methane Reforming: Experimental and Modeling Approach
,” Int. J. Hydrogen Energy
, 40
(24
), pp. 7559
–7567
. 10.1016/j.ijhydene.2014.11.04533.
Liguori
, S.
, Iulianelli
, A.
, Dalena
, F.
, Piemonte
, V.
, Huang
, Y.
, and Basile
, A.
, 2014
, “Methanol Steam Reforming in an Al2O3 Supported Thin Pd-Layer Membrane Reactor Over Cu/ZnO/Al2O3 Catalyst
,” Int. J. Hydrogen Energy
, 39
(32
), pp. 18702
–18710
. 10.1016/j.ijhydene.2013.11.11334.
Cecilia
, M. P.
, Hugo
, S.
, Pacheco Tanaka
, D. A.
, Liguori
, S.
, Iulianelli
, A.
, Basile
, A.
, and Mendes
, A.
, 2015
, “Cuo/Zno Catalysts for Methanol Steam Reforming: the Role of the Support Polarity Ratio and Surface Area
,” Appl. Catal., B
, 174–175
, pp. 67
–76
. 10.1016/j.apcatb.2015.02.03935.
Da Silva
, A. M.
, Mattos
, L. V.
, Múnera
, J.
, Lombardo
, E.
, Noronha
, F. B.
, and Cornaglia
, L.
, 2015
, “Study of the Performance of Rh/La2O3-SiO2 and Rh/CeO2 Catalysts for SR of Ethanol in a Conventional Fixed-Bed Reactor and a Membrane Reactor
,” Int. J. Hydrogen Energy
, 40
(11
), pp. 4154
–4166
. 10.1016/j.ijhydene.2015.01.10636.
Hedayati
, A.
, Corre
, O. L.
, Lacarrière
, B.
, and Llorca
, J.
, 2016
, “Experimental and Exergy Evaluation of Ethanol Catalytic Steam Reforming in a Membrane Reactor
,” Catal. Today
, 268
, pp. 68
–78
. 10.1016/j.cattod.2016.01.05837.
Tou
, M.
, Michalsky
, R.
, and Steinfeld
, A.
, 2017
, “Solar-Driven Thermochemical Splitting of CO2 and In situ Separation of CO and O2 Across a Ceria Redox Membrane Reactor
,” Joule
, 1
(1
), pp. 146
–154
. 10.1016/j.joule.2017.07.01538.
Tou
, M.
, Jin
, J.
, Hao
, Y.
, Steinfeld
, A.
, and Michalsky
, R.
, 2019
, “Solar-Driven Co-Thermolysis of CO2 and H2O Promoted by In situ Oxygen Removal Across a Nonstoichiometric Ceria Membrane
,” Reaction Chem. Eng.
, 8
(8
), pp. 1431
–1438
. 10.1039/C8RE00218E39.
Furler
, P.
, and Steinfeld
, A.
, 2015
, “Heat Transfer and Fluid Flow Analysis of a 4kW Solar Thermochemical Reactor for Ceria Redox Cycling
,” Chem. Eng. Sci.
, 137
, pp. 373
–383
. 10.1016/j.ces.2015.05.05640.
Lapp
, J.
, and Lipinski
, W.
, 2014
, “Transient Three-Dimensional Heat Transfer Model of a Solar Thermochemical Reactor for H2O and CO2 Splitting via Nonstoichiometric Ceria Redox Cycling
,” ASME J. Sol. Energy Eng.
, 136
(3
), p. 031006
. 10.1115/1.402646541.
Chandran
, R. B.
, Bader
, R.
, and Lipiński
, W.
, 2015
, “Transient Heat and Mass Transfer Analysis in a Porous Ceria Structure of a Novel Solar Redox Reactor
,” Int. J. Therm. Sci.
, 92
, pp. 138
–149
. 10.1016/j.ijthermalsci.2015.01.01642.
Keene
, D. J.
, Davidson
, J. H.
, and Lipiński
, W.
, 2013
, “A Model of Transient Heat and Mass Transfer in a Heterogeneous Medium of Ceria Undergoing Nonstoichiometric Reduction
,” J. Heat Trans.
, 135
(5
), p. 052701
. 10.1115/ES2012-9138043.
Fuller
, E. N.
, Schettler
, P. D.
, and Giddings
, J. C.
, 1966
, “A new Methon for Prediction of Binary Gas-Phase Diffusion Cofficient
,” Ind. Eng. Chem.
, 58
(5
), pp. 18
–27
. 10.1021/ie50677a00744.
Zhu
, L.
, Lu
, Y.
, and Shen
, S.
, 2016
, “Solar Fuel Production at High Temperatures Using Ceria as a Dense Membrane
,” Energy
, 104
, pp. 53
–63
. 10.1016/j.energy.2016.03.10845.
Blumenthal
, R. N.
, and Sharma
, R. K.
, 1975
, “Electronic Conductivity in Nonstoichiometric Cerium Dioxide
,” J. Solid State Chem.
, 13
(4
), pp. 360
–364
. 10.1016/0022-4596(75)90152-846.
Keene
, D. J.
, Lipiński
, W.
, and Davidson
, J. H.
, 2014
, “The Effects of Morphology on the Thermal Reduction of Nonstoichiometric Ceria[J]
,” Chem. Eng. Sci.
, 111
, pp. 231
–243
. 10.1016/j.ces.2014.01.01047.
Zhu
, L.
, and Lu
, Y.
, 2018
, “Reactivity and Efficiency of Ceria-Based Oxides for Solar CO2 Splitting via Isothermal and Near-Isothermal Cycles
,” Energy Fuels
, 32
(1
), pp. 736
–746
. 10.1021/acs.energyfuels.7b0328448.
Bulfin
, B.
, Hoffmann
, L.
, Oliveira
, L. D.
, Knoblauch
, N.
, Call
, F.
, Roeb
, M.
, Sattler
, C.
, and Schmücker
, M.
, 2016
, “Statistical Thermodynamics of Non-stoichiometric Ceria and Ceria Zirconia Solid Solutions
,” Phys. Chem. Chem. Phys.
, 18
(33
), p. 23147
. 10.1039/C6CP03158G49.
Gozálvez-Zafrilla
, J. M.
, Santafé-Moros
, A.
, Escolástico
, S.
, and Serra
, J. M.
, 2011
, “Fluid Dynamic Modeling of Oxygen Permeation Through Mixed Ionic–Electronic Conducting Membranes
,” J. Membr. Sci.
, 378
(1-2
), pp. 290
–300
. 10.1016/j.memsci.2011.05.01650.
Panlener
, R. J.
, Blumenthal
, R. N.
, and Garnier
, J. E.
, 1975
, “A Thermodynamic Study of Nonstoichiometric Cerium Dioxide
,” J. Phys. Chem. Solids
, 36
(11
), pp. 1213
–1222
. 10.1016/0022-3697(75)90192-451.
Bulfin
, B.
, Lowe
, A. J.
, Keogh
, K. A.
, Murphy
, B. E.
, Lübben
, O.
, Krasnikov
, S. A.
, and Shvets
, I. V.
, 2013
, “Analytical Model of CeO2 Oxidation and Reduction
,” J. Phys. Chem. C
, 117
(46
), pp. 24129
–24137
. 10.1021/jp406578z52.
Ishida
, T.
, Gokon
, N.
, Hatamachi
, T.
, and Kodama
, T.
, 2014
, “Kinetics of Thermal Reduction Step of Thermochemical Two-Step Water Splitting Using CeO2 Particles: MASTER-Plot Method for Analyzing Non-Isothermal Experiments
,” Energy Procedia
, 49
, pp. 1970
–1979
. 10.1016/j.egypro.2014.03.20953.
Bulfin
, B.
, Call
, F.
, Vieten
, J.
, Roeb
, M.
, Sattler
, C.
, and Shvets
, I. V.
, 2016
, “Oxidation and Reduction Reaction Kinetics of Mixed Cerium Zirconium Oxides
,” J. Phys. Chem. C
, 120
(4
), pp. 2027
–2035
. 10.1021/acs.jpcc.5b0872954.
Li
, S.
, Wheeler
, V. M.
, Kumar
, A.
, and Lipinski
, W.
, 2020
, “Numerical Modelling of Ceria Undergoing Reduction in a Particle-Gas Counter-Flow: Effects of Chemical Kinetics Under Isothermal Conditions
,” Chem. Eng. Sci.
, 218
, p. 115553
. 10.1016/j.ces.2020.11555355.
Le Gal
, A.
, Abanades
, S.
, and Flamant
, G.
, 2011
, “CO2 and H2O Splitting for Thermochemical Production of Solar Fuels Using Nonstoichiometric Ceria and Ceria/Zirconia Solid Solutions[J]
,” Energy Fuels
, 25
(10
), pp. 4836
–4845
. 10.1021/ef200972r56.
Bulfin
, B.
, 2019
, “Thermodynamic Limits of Countercurrent Reactor Systems, With Examples in Membrane Reactors and the Ceria Redox Cycle
,” Phys. Chem. Chem. Phys.
, 21
(4
), pp. 2186
–2195
. 10.1039/C8CP07077F57.
Li
, S.
, Wheeler
, V. M.
, Kreider
, P. B.
, and Lipinski
, W.
, 2019
, “Thermodynamic Analyses of Fuel Production Via Solar-Driven Ceria-Based Nonstoichiometric Redox Cycling: A Case Study of the Isothermal Membrane Reactor System
,” ASME J. Sol. Energy Eng.
, 141
(2
), p. 021012
. 10.1115/1.4042228Copyright © 2020 by ASME
You do not currently have access to this content.
