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Synergistic improvements in stability and performance of the double perovskite-type oxides La2−xSrxFeCoO6 for chemical looping steam methane reforming

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  • Zhao, Kun
  • Li, Luwei
  • Zheng, Anqing
  • Huang, Zhen
  • He, Fang
  • Shen, Yang
  • Wei, Guoqiang
  • Li, Haibin
  • Zhao, Zengli

Abstract

Chemical looping steam methane reforming (CL-SMR) is a potential route to efficiently co-produce syngas and hydrogen. Development of oxygen carrier with high activity, good recyclability, strong resistance to carbon deposition and excellence capacity for steam splitting is highly desired for this process. The article investigated a novel and unique structure of double perovskite-type oxides La1−xSrxFeCoO6 (x=0, 0.2, 0.4, 0.6, 0.8, 1.0) as oxygen carrier. XRD, XPS and H2-TPR technologies were adopted to characterize the physical and chemical properties of them. Meanwhile, isothermal reactions and cyclic redox reactions were carried out in a fixed-bed reactor to determine the influences of Sr-substitution on the reactivity of La1−xSrxFeCoO6. XRD results confirmed the formation of double perovskite crystal structure for all the samples, while substitution of Sr induced a certain degree of Fe/Co disorder generating oxygen vacancies and/or higher oxidation states of metal cations. Synergistic interactions between surface metal ions, such as Fe4+/Fe5+ with Co3+ which were detected by XPS, strongly enhance the reducibility of oxygen carriers. Three zones including total oxidation of methane by surface oxygen, partial oxidation of methane by lattice oxygen and carbon deposition were divided. Among the six samples with different substitution of Sr, La0.6Sr0.4FeCoO6 exhibited the best oxygen transport ability, thermal stability, as well as capacity for hydrogen generation. A stable CH4 conversion at ∼90% with desired H2/CO ratio at 2.0–2.5 in the methane reduction stage, and an average hydrogen yield at ∼5.9mmol/g oxygen carrier with ∼93.8% of hydrogen concentration in the steam oxidation stage were obtained during twenty successive redox reactions, which made them very attractive for the purpose of chemical looping partial oxidation of carbon fuel in real applications.

Suggested Citation

  • Zhao, Kun & Li, Luwei & Zheng, Anqing & Huang, Zhen & He, Fang & Shen, Yang & Wei, Guoqiang & Li, Haibin & Zhao, Zengli, 2017. "Synergistic improvements in stability and performance of the double perovskite-type oxides La2−xSrxFeCoO6 for chemical looping steam methane reforming," Applied Energy, Elsevier, vol. 197(C), pages 393-404.
    • Handle: RePEc:eee:appene:v:197:y:2017:i:c:p:393-404
    DOI: 10.1016/j.apenergy.2017.04.049
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    References listed on IDEAS

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    1. Rydén, Magnus & Leion, Henrik & Mattisson, Tobias & Lyngfelt, Anders, 2014. "Combined oxides as oxygen-carrier material for chemical-looping with oxygen uncoupling," Applied Energy, Elsevier, vol. 113(C), pages 1924-1932.
    2. Galinsky, Nathan & Mishra, Amit & Zhang, Jia & Li, Fanxing, 2015. "Ca1−xAxMnO3 (A=Sr and Ba) perovskite based oxygen carriers for chemical looping with oxygen uncoupling (CLOU)," Applied Energy, Elsevier, vol. 157(C), pages 358-367.
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    4. Zhao, Kun & He, Fang & Huang, Zhen & Wei, Guoqiang & Zheng, Anqing & Li, Haibin & Zhao, Zengli, 2016. "Perovskite-type oxides LaFe1−xCoxO3 for chemical looping steam methane reforming to syngas and hydrogen co-production," Applied Energy, Elsevier, vol. 168(C), pages 193-203.
    5. Galinsky, Nathan & Sendi, Marwan & Bowers, Lindsay & Li, Fanxing, 2016. "CaMn1−xBxO3−δ (B=Al, V, Fe, Co, and Ni) perovskite based oxygen carriers for chemical looping with oxygen uncoupling (CLOU)," Applied Energy, Elsevier, vol. 174(C), pages 80-87.
    6. Gu, Zhenhua & Li, Kongzhai & Wang, Hua & Qing, Shan & Zhu, Xing & Wei, Yonggang & Cheng, Xianming & Yu, He & Cao, Yan, 2016. "Bulk monolithic Ce–Zr–Fe–O/Al2O3 oxygen carriers for a fixed bed scheme of the chemical looping combustion: Reactivity of oxygen carrier," Applied Energy, Elsevier, vol. 163(C), pages 19-31.
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    2. Kwon, Byeong Wan & Oh, Joo Hyeng & Kim, Ghun Sik & Yoon, Sung Pil & Han, Jonghee & Nam, Suk Woo & Ham, Hyung Chul, 2018. "The novel perovskite-type Ni-doped Sr0.92Y0.08TiO3 as a reforming biogas (CH4+CO2) for H2 production," Applied Energy, Elsevier, vol. 227(C), pages 213-219.
    3. Qiu, Yu & Zhang, Shuai & Cui, Dongxu & Li, Min & Zeng, Jimin & Zeng, Dewang & Xiao, Rui, 2019. "Enhanced hydrogen production performance at intermediate temperatures through the synergistic effects of binary oxygen carriers," Applied Energy, Elsevier, vol. 252(C), pages 1-1.
    4. Marek, Ewa & Hu, Wenting & Gaultois, Michael & Grey, Clare P. & Scott, Stuart A., 2018. "The use of strontium ferrite in chemical looping systems," Applied Energy, Elsevier, vol. 223(C), pages 369-382.
    5. Kang, Dohyung & Lim, Hyun Suk & Lee, Minbeom & Lee, Jae W., 2018. "Syngas production on a Ni-enhanced Fe2O3/Al2O3 oxygen carrier via chemical looping partial oxidation with dry reforming of methane," Applied Energy, Elsevier, vol. 211(C), pages 174-186.
    6. Zhang, Yidian & Guo, Shaopeng & Tian, Zhenyu & Zhao, Yawen & Hao, Yong, 2019. "Experimental investigation of steam reforming of methanol over La2CuO4/CuZnAl-oxides nanocatalysts," Applied Energy, Elsevier, vol. 254(C).
    7. Zhu, Yanyan & Jin, Nannan & Liu, Ruilin & Sun, Xueyan & Bai, Lei & Tian, Hanjing & Ma, Xiaoxun & Wang, Xiaodong, 2020. "Bimetallic BaFe2MAl9O19 (M = Mn, Ni, and Co) hexaaluminates as oxygen carriers for chemical looping dry reforming of methane," Applied Energy, Elsevier, vol. 258(C).
    8. Jiang, Qiongqiong & Zhang, Hao & Deng, Ya'nan & Kang, Qilan & Hong, Hui & Jin, Hongguang, 2018. "Properties and reactivity of LaCuxNi1−xO3 perovskites in chemical-looping combustion for mid-temperature solar-thermal energy storage," Applied Energy, Elsevier, vol. 228(C), pages 1506-1514.
    9. Gu, Rong & Ding, Jing & Wang, Yarong & Yuan, Qinquan & Wang, Weilong & Lu, Jianfeng, 2019. "Heat transfer and storage performance of steam methane reforming in tubular reactor with focused solar simulator," Applied Energy, Elsevier, vol. 233, pages 789-801.
    10. Zhang, Haotian & Sun, Zhuxing & Hu, Yun Hang, 2021. "Steam reforming of methane: Current states of catalyst design and process upgrading," Renewable and Sustainable Energy Reviews, Elsevier, vol. 149(C).

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