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Ce-Fe-Zr-O/MgO整体型氧载体用于化学链部分氧化甲烷制合成气

于鹤,  李法社,  祝星,  魏永刚,  郑敏,  王华,  李孔斋

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文章导航 > 燃料化学学报（中英文）  > 2015 >  43(04): 499-506
于鹤, 李法社, 祝星, 魏永刚, 郑敏, 王华, 李孔斋. Ce-Fe-Zr-O/MgO整体型氧载体用于化学链部分氧化甲烷制合成气[J]. 燃料化学学报（中英文）, 2015, 43(04): 499-506.
引用本文: 于鹤, 李法社, 祝星, 魏永刚, 郑敏, 王华, 李孔斋. Ce-Fe-Zr-O/MgO整体型氧载体用于化学链部分氧化甲烷制合成气[J]. 燃料化学学报（中英文）, 2015, 43(04): 499-506.
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YU He, LI Fa-she, ZHU Xing, WEI Yong-gang, ZHENG Min, WANG Hua, LI Kong-zhai. Monolithic Ce-Fe-Zr-O/MgO oxygen carrier for the chemical-looping partial oxidation of methane to syngas[J]. Journal of Fuel Chemistry and Technology, 2015, 43(04): 499-506.
Citation: YU He, LI Fa-she, ZHU Xing, WEI Yong-gang, ZHENG Min, WANG Hua, LI Kong-zhai. Monolithic Ce-Fe-Zr-O/MgO oxygen carrier for the chemical-looping partial oxidation of methane to syngas[J]. Journal of Fuel Chemistry and Technology, 2015, 43(04): 499-506.
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Ce-Fe-Zr-O/MgO整体型氧载体用于化学链部分氧化甲烷制合成气

  • 1.

    昆明理工大学 省部共建复杂有色金属资源清洁利用国家重点实验室, 云南 昆明 650093;

  • 2.

    昆明理工大学 化学工程学院, 云南 昆明 650500;

  • 3.

    昆明理工大学 冶能与能源工程学院, 云南 昆明 650093

基金项目: 国家自然科学基金(51374004,51174105,51204083);云南省中青年学术技术带头人后备人才(2014HB006)。
详细信息
    通讯作者:

    李法社, 李孔斋, E-mail:asan97@qq.com, kongzhai.li@aliyun.com, Tel:0871-65153405。

  • 中图分类号: O643.3

Monolithic Ce-Fe-Zr-O/MgO oxygen carrier for the chemical-looping partial oxidation of methane to syngas

  • 1.

    State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming 650093, China;

  • 2.

    Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China;

  • 3.

    Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China

    摘要
  • 摘要: 以MgO为载体,采用球磨法制备了Ce-Fe-Zr-O/MgO粉末状氧载体,进而采用挤压成型法制备了整体型氧载体。研究了两种氧载体化学链部分氧化甲烷制合成气的性能,并通过XRD、H2-TPR对氧载体进行表征。结果表明,粉末状氧载体中的储氧组分以Ce-Fe-Zr-O固溶体形式存在,而整体型氧载体的制备过程会导致Zr、Fe游离氧化物的形成。粉末状氧载体和整体型氧载体上均存在表面晶格氧和体相晶格氧,其中,体相晶格氧具有高选择性氧化甲烷的性能,可以将甲烷转化成CO和H2。粉末状氧载体与甲烷反应活性较高,但其存在高含量的表面氧,易导致甲烷的完全氧化。整体型氧载体上体相晶格氧占据优势,可将甲烷选择性氧化为CO和H2。氧化还原循环实验表明,粉末状氧载体在还原反应发生短时间内容易引起甲烷裂解导致产物气中的H2/CO物质的量比显著大于2.0,同时产生大量积炭,制约了其循环性能。而整体型氧载体经10次循环实验后,全程反应过程中合成气H2/CO物质的量比一直维持在2.0附近,显示了较高的循环稳定性能。
    Abstract: With MgO as support, powdery Ce-Fe-Zr-O/MgO oxygen carrier was prepared by a ball milling method and monolithic Ce-Fe-Zr-O/MgO oxygen carrier was further obtained by extrusion molding method. The performances of both powdery and monolithic oxygen carriers in partial oxidation of methane to syngas via a chemical looping process were investigated. The results showed that the component of the powdery carrier for oxygen storage is Ce-Fe-Zr-O solid solution, whereas the free oxides of Ce, Zr and Fe may be segregated from the solid solution in monolithic oxygen carrier upon preparation. Two kinds of oxygen species, i.e. surface lattice oxygen and bulk lattice oxygen, can be found on both powdery and monolithic oxygen carriers; bulk lattice oxygen can selectively convert methane to CO and H2, whereas the surface oxygen is very active for methane complete oxidation. Powdery oxygen carrier owns high content of surface lattice oxygen, which results in high concentration of H2O and CO2 in the product. Over the monolithic oxygen carrier, methane can be selectively oxidized to CO and H2 due to the high content of bulk lattice oxygen. Moreover, methane decomposition occurs easily over the powdery oxygen carrier in the redox tests, resulting in a high H2/CO mol ratio (much higher than 2.0) in the product. On the contrary, the monolithic oxygen carrier exhibits a high redox stability and can continuously produce syngas with a H2/CO mol ratio of 2.0 during the successive redox tests.
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  • 收稿日期:  2014-10-28
  • 刊出日期:  2015-04-30

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