Research Progress in Ethane Dehydrogenation to Cogenerate Power and Value-Added Chemicals in Solid Oxide Fuel Cells

doi:10.13208/j.electrochem.191145

Abstract

Abstract:

Increasing supplies of methane/shale gas have promoted global development of higher value chemicals such as ethylene production by ethane, which dramatically changes the markets of petrochemical industry. Clean and efficient transformation of ethane into higher value chemicals has far-reaching significance. Ethylene production through ethane steam cracking is a relatively matured technology for industrial production. However, the process consumes large amounts of energy and the presence of carbon deposition becomes a serious problem which is difficult to be solved. The cogenerated energy-chemicals solid oxide fuel cells have been widely studied because fuel gas can be converted into high-value chemicals via spontaneous reaction while releasing electrical energy. This paper summarizes the latest research progress in the electrochemical dehydrogenation of ethylene and electrical energy by using cogeneration solid oxide fuel cells, focusing on the mechanism and advantages of solid oxide fuel cells in ethane dehydrogenation, and the selections of electrolytes and electrode materials. It is demonstrated that the fuel cell technology has apparent advantages of realizing ethane symbiosis in ethylene production and electric energy generation with low energy consumption, and has great application potentials in the industrial production with high efficiency and energy saving.

Key words: ethane, ethylene, electric energy, cogeneration, solid oxide fuel cell

CLC Number:

TM911
O646

FAN Yun, WANG Qi, LI Jun, LUO Jing-li, FU Xian-zhu. Research Progress in Ethane Dehydrogenation to Cogenerate Power and Value-Added Chemicals in Solid Oxide Fuel Cells[J]. Journal of Electrochemistry, 2020, 26(2): 243-252.

Figures/Tables 6

Fig. 1

Fig. 2

Tab. 1

Fig. 3

Fig. 4

Fig. 5

References 45

[1]	Lü Y( 吕尧), Huang B( 黄波), Gu X Z( 顾习之 ), et al. Fabrication and characterization of the Ni-ScSZ composite anodes with a Cu-LSCM-CeO₂ catalyst layer in the thin film SOFC[J]. Journal of Electrochemistry( 电化学), 2014,20(5):470-475.
[2]	Vayenas C G, Farr R D . Cogeneration of electric energy and nitric oxide[J]. Science, 1980,208(4444):593-594.
[3]	Shao Z P, Zhang C M, Wang W , et al. Electric power and synjournal gas co-generation from methane with zero waste gas emission[J]. Angewandte Chemie International Edition, 2012,50(8):1792-1797. doi: 10.1002/anie.v50.8 URL
[4]	Torabi A, Barton J, Willman C , et al. Developing low-intermediate temperature fuel cells for direct conversion of methane to methanol fuel[J]. ECS Transactions, 2016,72(7):193-199.
[5]	Hugill J A, Tillemans F W A, Dijkstra J W , et al. Feasibility study on the co-generation of ethylene and electricity through oxidative coupling of methane[J]. Applied Thermal Engineering, 2015,25(8):1259-1271. doi: 10.1016/j.applthermaleng.2004.09.007 URL
[6]	Morejudo S H, Zanon R, Escolastico S , et al. Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor[J]. Science, 2016,353(6299):563-566. doi: 10.1126/science.aag0274 URL
[7]	Fu X Z, Luo J L, Sanger A R , et al. An integral proton conducting SOFC for simultaneous production of ethylene and power from ethane[J]. Chemical Communications, 2010,46(12):2052-2054. doi: 10.1039/b926928b URL
[8]	Feng Y, Luo J L, Chuang K T . Conversion of propane to propylene in a proton-conducting solid oxide fuel cell[J]. Fuel, 2007,86(1/2):123-128. doi: 10.1016/j.fuel.2006.06.012 URL
[9]	Zhang J P( 张金萍 ). The preparation and study of co-generation of electricity and ethylene solid oxide fuel cells[D]. Harbin Institute of Technology( 哈尔滨工业大学), 2017.
[10]	Gao Y F, Neal L, Ding D , et al. Recent advances in intensified ethylene production - A Review[J]. ACS Catalysis, 2019,9(9):8592-8621. doi: 10.1021/acscatal.9b02922 URL
[11]	Liu S B, Chuang K T, Luo J L . Double-layered perovskite anode with in situ exsolution of a Co-Fe alloy to cogenerate ethylene and electricity in a proton-conducting ethane fuel cell[J]. ACS Catalysis, 2016,6(2):760-768.
[12]	Jiang S P( 蒋三平 ). Advances and challenges of intermediate temperature solid oxide fuel cells: A concise review[J]. Journal of Electrochemistry( 电化学), 2012,18(6):479-495.
[13]	Fu X Z, Lin J Y, Xu S , et al. CO₂ emission free co-generation of energy and ethylene in hydrocarbon SOFC reactors with a dehydrogenation anode[J]. Physical Chemistry Chemical Physics, 2011,13(43):19615-19623.
[14]	Zhu B, Albinsson I, Andersson C , et al. Electrolysis studies based on ceria-based composites[J]. Electrochemistry Communications, 2006,8(3):495-498. doi: 10.1016/j.elecom.2006.01.011 URL
[15]	Singhal S . High-temperature solid oxide fuel cells: fundamentals, design and applications[J]. Materials Today, 2002,5(12):55.
[16]	Shi Z, Luo J L, Wang S , et al. Protonic membrane for fuel cell for co-generation of power and ethylene[J]. Journal of Power Sources, 2008,176(1):122-127.
[17]	Fu X Z, Luo J L, Sanger A R , et al. Y-doped BaCeO₃-_δ nanopowders as proton-conducting electrolyte materials for ethane fuel cells to co-generate ethylene and electricity[J]. Journal of Power Sources, 2010,195(9):2659-2663.
[18]	Wang S, Luo J L, Sanger A R , et al. Performance of ethane/oxygen fuel cells using yttrium-doped barium cerate as electrolyte at intermediate temperatures[J]. Journal of Physical Chemistry C, 2007,111(13):5069-5074.
[19]	Shao L, Si F, Fu X Z , et al. Stable SrCo_0.7Fe_0.2Zr_0.1O₃-_δ cathode material for proton conducting solid oxide fuel cell reactors[J]. International Journal of Hydrogen Energy, 2018,43(15):7511-7514.
[20]	Lin J Y, Shao L, Si F Z , et al. Multiple-doped barium cerate proton-conducting electrolytes for chemical-energy cogeneration in solid oxide fuel cells[J]. International Journal of Hydrogen Energy, 2018,43(42):17904-17910.
[21]	Fu X Z, Luo J L, Sanger A R , et al. Fabrication of bi-layered proton conducting membrane for hydrocarbon solid oxide fuel cell reactors[J]. Electrochimica Acta, 2010,55(3):1145-1149. doi: 10.1016/j.electacta.2009.10.010 URL
[22]	Han M F( 韩敏芳), Peng S P( 彭苏萍 ). Solid oxide fuel cell material and preparation[M]. Beijing: Science Press( 科学出版社), 2004.
[23]	Sun C, Stimming U . Recent anode advances in solid oxide fuel cells[J]. Journal of Power Sources, 2007,171(2):247-260. doi: 10.1016/j.jpowsour.2007.06.086 URL
[24]	Gao F, Zhao H L, Li X , et al. Preparation and electrical properties of yttrium-doped strontium titanate with B-site deficiency[J]. Journal of Power Sources, 2008,185(1):26-31.
[25]	Huang X L( 黄贤良), Zhao H L( 赵海雷), Wu W J( 吴卫江 ), et al. Research progress on anode materials of solid oxide fuel cells[J]. Journal of the Chinese Ceramic Society( 硅酸盐学报), 2005,33(11):1407-1413.
[26]	Murray E P, Tsai T, Barnett S A . A direct-methane fuel cell with a ceria-based anode[J]. Nature, 2016,400(6745):649-651.
[27]	Tsipis E V, Kharton V V, Frade J R . Mixed conducting components of solid oxide fuel cell anodes[J]. Journal of the European Ceramic Society, 2005,25(12):2623-2626.
[28]	Fu X Z, Luo X X, Luo J L , et al. Ethane dehydrogenation over nano-Cr₂O₃ anode catalyst in proton ceramic fuel cell reactors to co-produce ethylene and electricity[J]. Journal of Power Sources, 2011,196(3):1036-1041.
[29]	Mackenzie J D, Bescher E P . Chemical routes in the synjournal of nanomaterials using the sol-gel process[J]. Accounts of Chemical Research, 2007,40(9):810-818. doi: 10.1021/ar7000149 URL
[30]	Chuang K T, Luo J L, Zhou G H , et al. FeCr₂O₄ nanoparticles as anode catalyst for ethane proton conducting fuel cell reactors to coproduce ethylene and electricity[J]. Advances in Physical Chemistry, 2011,2011(22):680-694.
[31]	Lin J Y, Shao L, Si F Z , et al. Co₂CrO₄ nanopowders as an anode catalyst for simultaneous conversion of ethane to ethylene and power in proton-conducting fuel cell reactors[J]. The Journal of Physical Chemistry C, 2018,122(8):4165-4171.
[32]	Li J H, Fu X Z, Luo J L , et al. Evaluation of molybdenum carbide as anode catalyst for proton-conducting hydrogen and ethane solid oxide fuel cells[J]. Electrochemistry Communications, 2012,15(1):81-84.
[33]	Cui S H, Li J H, Luo J L , et al. Co-generation of energy and ethylene in hydrocarbon fueled SOFCs with Cr₃C₂ and WC anode catalysts[J]. Ceramics International, 2014,40(8):11781-11786. doi: 10.1016/j.ceramint.2014.04.007 URL
[34]	Liu S B, Liu Q X, Fu X Z , et al. Cogeneration of ethylene and energy in protonic fuel cell with an efficient and stable anode anchored with in-situ exsolved functional metal nanoparticles[J]. Applied Catalysis B: Environmental, 2017,220:283-289.
[35]	Yang C H, Li J, Lin Y , et al. In situ fabrication of Co Fe alloy nanoparticles structured (Pr_0.4Sr_0.6)₃(Fe_0.85Nb_0.15)₂O₇ ceramic anode for direct hydrocarbon solid oxide fuel cells[J]. Nano Energy, 2015,11:704-710.
[36]	Liu S, Behnamian Y, Chuang K T , et al. A-site deficient La_0.2Sr_0.7TiO₃-_δ anode material for proton conducting ethane fuel cell to cogenerate ethylene and electricity[J]. Journal of Power Sources, 2015,298:23-29.
[37]	Dogu D, Meyer K E, Fuller A , et al. Effect of lanthanum and chlorine doping on strontium titanates for the electrocatalytically-assisted oxidative dehydrogenation of ethane[J]. Applied Catalysis B: Environmental, 2018,227:90-101.
[38]	Mai A, Becker M, Assenmacher W , et al. Time-dependent performance of mixed-conducting SOFC cathodes[J]. Solid State Ionics, 2006,177(19/25):1965-1968.
[39]	Simner S P, Anderson M D, Coleman J E , et al. Performance of a novel La(Sr)Fe(Co)O₃-Ag SOFC cathode[J]. Journal of Power Sources, 2006,161(1):115-122.
[40]	Kim J D, Kim G D, Moon J W , et al. Characterization of LSM-YSZ composite electrode by ac impedance spectroscopy[J]. Solid State Ionics, 2001,143(3/4):379-389.
[41]	Mitterdorfer A, Gauckler L J . Reaction kinetics of the Pt, O₂(g)\|c-ZrO₂ system: precursor-mediated adsorption[J]. Solid State Ionics, 1999,120(1):211-225.
[42]	Ostergard M J L, Mogensen M . AC Impedance study of the oxygen reduction mechanism on La₁-_xSr_xMnO₃ in solid oxide fuel cells[J]. Electrochimica Acta, 1993,38(14):2015-2020.
[43]	Horita T, Yamaji K, Sakai N , et al. Imaging of oxygen transport at SOFC cathode/electrolyte interfaces by a novel technique[J]. Journal of Power Sources, 2002,106(1/2):224-230. doi: 10.1016/S0378-7753(01)01017-5 URL
[44]	Shao L, Si F, Fu X Z , et al. Stable SrCo_0.7Fe_0.2Zr_0.1O₃-_δ, cathode material for proton conducting solid oxide fuel cell reactors[J]. International Journal of Hydrogen Energy, 2018,43:7511-7514.
[45]	Zhou Y B, An B M, Guo Y M , et al. Development of high performance cathodes for IT-SOFCs through beneficial interfacial reactions[J]. Electrochemistry Communications, 2009,11(11):2216-2219.

Ethane oxidative dehydrogenation: C₂H₆(g) + O₂(g) = C₂H₄(g) + H₂O(g)
T/°C	ΔG/kJ	ΔH/kJ	Equilibrium constant K
650	-177.05	-103.497	1.04×10¹⁰
700	-181.03	-103.706	5.22×10⁹
750	-184.99	-103.938	2.79×10⁹