Reduction kinetics of SrFeO_3−δ/CaO∙MnO nanocomposite as effective oxygen carrier for chemical looping partial oxidation of methane

Abstract

Chemical looping reforming of methane is a novel and effective approach to convert methane to syngas, in which oxygen transfer is achieved by a redox material. Although lots of efforts have been made to develop high-performance redox materials, a few studies have focused on the redox kinetics. In this work, the kinetics of SrFeO_3−δ–CaO∙MnO nanocomposite reduction by methane was investigated both on a thermo-gravimetric analyzer and in a packed-bed microreactor. During the methane reduction, combustion occurs before the partial oxidation and there exists a transition between them. The weight loss due to combustion increases, but the transition region becomes less inconspicuous as the reduction temperature increased. The weight loss associated with the partial oxidation is much larger than that with combustion. The rate of weight loss related to the partial oxidation is well fitted by the Avrami–Erofeyev equation with n = 3 (A3 model) with an activation energy of 59.8 kJ∙mol^‒1. The rate law for the partial oxidation includes a solid conversion term whose expression is given by the A3 model and a methane pressure-dependent term represented by a power law. The partial oxidation is half order with respect to methane pressure. The proposed rate law could well predict the reduction kinetics; thus, it may be used to design and/or analyze a chemical looping reforming reactor.

Graphical abstract

Keywords

chemical looping reforming / SrFeO_3−δ/CaO·MnO nanocomposite / reduction kinetics / Avrami–Erofeyev model / pressure-dependent term

References

[1] Caballero A, Pérez P J. Methane as raw material in synthetic chemistry: the final frontier. Chemical Society Reviews, 2013, 42(23): 8809–8820

[2] Sun L, Wang Y, Guan N, Li L. Methane activation and utilization: current status and future challenges. Energy Technology, 2020, 8(8): 1900826

[3] Song H, Meng X, Wang Z J, Liu H, Ye J. Solar-energy-mediated methane conversion. Joule, 2019, 3(7): 1606–1636

[4] Olivos-Suarez A I, Szécsényi À, Hensen E J M, Ruiz-Martinez J, Pidko E A, Gascon J. Strategies for the direct catalytic valorization of methane using heterogeneous catalysis: challenges and opportunities. Chemical Reviews, 2016, 6(5): 2965–2981

[5] Schwach P, Pan X, Bao X. Direct conversion of methane to value-added chemicals over heterogeneous catalysts: challenges and prospects. Chemical Reviews, 2017, 117(13): 8497–8520

[6] Li X, Pei C, Gong J. Shale gas revolution: catalytic conversion of C₁–C₃ light alkanes to value-added chemicals. Chem, 2021, 7(7): 1755–1801

[7] Mistré M, Crénes M, Hafner M. Shale gas production costs: historical developments and outlook. Energy Strategy Reviews, 2018, 20: 20–25

[8] Tang P, Zhu Q, Wu Z, Ma D. Methane activation: the past and future. Energy & Environmental Science, 2014, 7(8): 2580–2591

[9] Guo X, Fang G, Li G, Ma H, Fan H, Yu L, Ma C, Wu X, Deng D, Wei M, Tan D, Si R, Zhang S, Li J, Sun L, Tang Z, Pan X, Bao X. Direct, nonoxidative conversion of methane to ethylene, aromatics, and hydrogen. Science, 2014, 344(6183): 616–619

[10] Liu Y, Deng D, Bao X. Catalysis for selected C1 chemistry. Chem, 2020, 6(10): 2497–2514

[11] Sushkevich V L, Palagin D, Ranocchiari M, van Bokhoven J A. Selective anaerobic oxidation of methane enables direct synthesis of methanol. Science, 2017, 356(6337): 523–527

[12] Haribal V P, Wang X J, Dudek R, Paulus C, Turk B, Gupta R, Li F. Modified ceria for “low-temperature” CO₂ utilization: a chemical looping route to exploit industrial waste heat. Advanced Energy Materials, 2019, 9(41): 1901963

[13] Lin T, Yu F, An Y, Qin T, Li L, Gong K, Zhong L, Sun Y. Cobalt carbide nanocatalysts for efficient syngas conversion to value-added chemicals with high selectivity. Accounts of Chemical Research, 2021, 54(8): 1961–1971

[14] Liu H, Li Y, He D. Recent progress of catalyst design for carbon dioxide reforming of methane to syngas. Energy Technology (Weinheim), 2020, 8(8): 1900493

[15] Yu W, Wang X, Liu Y, Wei J, Zhang J. Effect of composition on the redox performance of strontium ferrite nanocomposite. Energy & Fuels, 2020, 34(7): 8644–8652

[16] Damma D, Smirniotis P G. Recent advances in the direct conversion of syngas to oxygenates. Catalysis Science & Technology, 2021, 11(16): 5412–5431

[17] Zhu Z, Guo W, Zhang Y, Pan C, Xu J, Zhu Y, Lou Y. Research progress on methane conversion coupling photocatalysis and thermocatalysis. Carbon Energy, 2021, 3(4): 519–540

[18] Niu J, Guo F, Ran J, Qi W, Yang Z. Methane dry (CO₂) reforming to syngas (H₂/CO) in catalytic process: from experimental study and DFT calculations. International Journal of Hydrogen Energy, 2020, 45(55): 30267–30287

[19] Zhang R, Cao Y, Li H, Zhao Z, Zhao K, Jiang L. The role of CuO modified La_0.7Sr_0.3 FeO₃ perovskite on intermediate-temperature partial oxidation of methane via chemical looping scheme. International Journal of Hydrogen Energy, 2020, 45(7): 4073–4083

[20] Zhu X, Imtiaz Q, Donat F, Müller C R, Li F. Chemical looping beyond combustion—a perspective. Energy & Environmental Science, 2020, 13(3): 772–804

[21] Zeng L, Cheng Z, Fan J A, Fan L S, Gong J. Metal oxide redox chemistry for chemical looping processes. Nature Reviews. Chemistry, 2018, 2(11): 349–364

[22] Zheng Y, Li K, Wang H, Tian D, Wang Y, Zhu X, Wei Y, Zheng M, Luo Y. Designed oxygen carriers from macroporous LaFeO₃ supported CeO₂ for chemical-looping reforming of methane. Applied Catalysis B: Environmental, 2017, 202: 51–63

[23] Zhu H, Zhang P, Dai S. Recent advances of lanthanum-based perovskite oxides for catalysis. ACS Catalysis, 2015, 5(11): 6370–6385

[24] Wang X, Krzystowczyk E, Dou J, Li F. Net electronic charge as an effective electronic descriptor for oxygen release and transport properties of SrFeO₃-based oxygen sorbents. Chemistry of Materials, 2021, 33(7): 2446–2456

[25] Sedykh V D, Rybchenko O G, Suvorov E V, Ivanov A I, Kulakov V I. Oxygen vacancies and valence states of iron in SrFeO_3–δ compounds. Physics of the Solid State, 2020, 62(10): 1916–1923

[26] Ji K, Dai H, Dai J, Deng J, Wang F, Zhang H, Zhang L. PMMA-templating preparation and catalytic activities of three-dimensional macroporous strontium ferrites with high surface areas for toluene combustion. Catalysis Today, 2013, 201: 40–48

[27] Yang J, Li L, Yang X, Song S, Li J, Jing F, Chu W. Enhanced catalytic performances of in situ-assembled LaMnO₃/δ-MnO₂ hetero-structures for toluene combustion. Catalysis Today, 2019, 327: 19–27

[28] Chen J, Buchanan T, Walker E A, Toops T J, Li Z, Kunal P, Kyriakidou E A. Mechanistic understanding of methane combustion over Ni/CeO₂: a combined experimental and theoretical approach. ACS Catalysis, 2021, 11(15): 9345–9354

[29] Zhang J S, Haribal V, Li F X. Perovskite nanocomposites as effective CO₂-splitting agents in a cyclic redox scheme. Science Advances, 2017, 3(8): e1701184

[30] Wang X H, Du X C, Yu W B, Zhang J S, Wei J J. Coproduction of hydrogen and methanol from methane by chemical looping reforming. Industrial & Engineering Chemistry Research, 2019, 58(24): 10296–10306

[31] Khawam A, Flanagan D R. Solid-state kinetic models: basics and mathematical fundamentals. Journal of Physical Chemistry B, 2006, 110(35): 17315–17328

[32] Li G, Lv X, Ding C, Zhou X, Zhong D, Qiu G. Non-isothermal carbothermic reduction kinetics of calcium ferrite and hematite as oxygen carriers for chemical looping gasification applications. Applied Energy, 2020, 262: 114604

[33] Tian Y, Dudek R B, Westmoreland P R, Li F. Effect of sodium tungstate promoter on the reduction kinetics of CaMn_0.9Fe_0.1O₃ for chemical looping-oxidative dehydrogenation of ethane. Chemical Engineering Journal, 2020, 398: 125583

[34] Zhao K, Zheng A, Li H, He F, Huang Z, Wei G, Shen Y, Zhao Z. Exploration of the mechanism of chemical looping steam methane reforming using double perovskite-type oxides La_1.6Sr_0.4FeCoO₆. Applied Catalysis B: Environmental, 2017, 219: 672–682

[35] Zhao K, Li L, Zheng A, Huang Z, He F, Shen Y, Wei G, Li H, Zhao Z. Synergistic improvements in stability and performance of the double perovskite-type oxides La_2−xSr_xFeCoO₆ for chemical looping steam methane reforming. Applied Energy, 2017, 197: 393–404

[36] Tang M, Xu L, Fan M. Progress in oxygen carrier development of methane-based chemical-looping reforming: a review. Applied Energy, 2015, 151: 143–156

[37] Gao Y, Neal L M, Li F. Li-promoted La_xSr_2–xFeO_4−δ core-shell redox catalysts for oxidative dehydrogenation of ethane under a cyclic redox scheme. ACS Catalysis, 2016, 6(11): 7293–7302

[38] Cheng F, Dupont V, Twigg M V. Direct reduction of nickel catalyst with model bio-compounds. Applied Catalysis B: Environmental, 2017, 200: 121–132

[39] Fedunik-Hofman L, Bayon A, Donne S W. Kinetics of solid–gas reactions and their application to carbonate looping systems. Energies, 2019, 12(15): 2981

[40] Fogler H S. Elements of Chemical Reaction Engineering. 5th ed. New York: Pearson Education Inc., 2016,

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