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焙烧温度对钼锡催化剂结构和二甲醚氧化性能的影响

熊盼 高秀娟 王文秀 张俊峰 宋法恩 张清德 韩怡卓 谭猗生

熊盼, 高秀娟, 王文秀, 张俊峰, 宋法恩, 张清德, 韩怡卓, 谭猗生. 焙烧温度对钼锡催化剂结构和二甲醚氧化性能的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60120-2
引用本文: 熊盼, 高秀娟, 王文秀, 张俊峰, 宋法恩, 张清德, 韩怡卓, 谭猗生. 焙烧温度对钼锡催化剂结构和二甲醚氧化性能的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60120-2
XIONG Pan, GAO Xiu-juan, WANG Wen-xiu, ZHANG Jun-feng, SONG Fa-en, ZHANG Qing-de, HAN Yi-zhuo, TAN Yi-sheng. Effect of calcination temperature on the structure and performance of molybdenum-tin catalyst for DME oxidation[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60120-2
Citation: XIONG Pan, GAO Xiu-juan, WANG Wen-xiu, ZHANG Jun-feng, SONG Fa-en, ZHANG Qing-de, HAN Yi-zhuo, TAN Yi-sheng. Effect of calcination temperature on the structure and performance of molybdenum-tin catalyst for DME oxidation[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60120-2

焙烧温度对钼锡催化剂结构和二甲醚氧化性能的影响

doi: 10.1016/S1872-5813(21)60120-2
基金项目: 国家自然科学基金(21773283,21373253),中科院创新交叉团队项目(BK2018001),中科院洁净能源创新研究院合作基金(DNL 201903),中科院青年创新促进会人才项目(2014155)和厦门大学固体表面物理化学国家重点实验室开放基金(201624)等项目资助
详细信息
    通讯作者:

    电 话:0351-4044388 电子邮箱:qdzhang@sxicc.ac.cn

  • 中图分类号: 0643

Effect of calcination temperature on the structure and performance of molybdenum-tin catalyst for DME oxidation

Funds: The project was supported by the National Natural Science Foundation of China (21773283, 21373253), CAS Interdisciplinary Innovation Team (BK2018001), the Dalian National Laboratory For Clean Energy (DNL) Cooperation Fund, CAS (DNL 201903), the Youth Innovation Promotion Association CAS (2014155) and the Open Project Program of State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University (201624)
  • 摘要: 采用水热法制备了Mo/Sn摩尔比为1∶2的Mo1Sn2催化剂,通过改变焙烧温度(400−700 ℃),调控了钼锡催化剂的结构,并研究了催化剂结构变化对二甲醚(DME)选择氧化制甲酸甲酯(MF)性能的影响。发现400 ℃焙烧的Mo1Sn2催化剂具有良好的催化氧化二甲醚生成甲酸甲酯的性能,在110 ℃、常压条件下,DME转化率为9.2%,MF选择性可达86.9%,并且无COx生成。采用XRD、Raman、XPS、TPD、H2-TPR和in-situ IR等表征手段对催化剂的结构和表面性质进行了系统研究。结果表明,低温焙烧更利于钼锡催化剂表面形成更多的MoOx结构和Mo5+物种,由此引起的催化剂的酸性、氧化还原性的增强和中强碱性位的增多可明显促进催化剂活性的增强和甲酸甲酯的生成。
  • 图  1  不同焙烧温度Mo1Sn2催化剂的XRD谱图

    Figure  1  XRD patterns of Mo1Sn2 catalysts calcined at different temperatures

    图  2  不同焙烧温度Mo1Sn2催化剂的Raman谱图

    Figure  2  Raman spectra of Mo1Sn2 catalysts calcined at different temperatures

    图  3  不同焙烧温度Mo1Sn2催化剂的FT-IR谱图

    Figure  3  FT-IR spectra of Mo1Sn2 catalysts calcined at different temperatures

    图  4  不同焙烧温度Mo1Sn2催化剂的N2吸附-脱附等温线(a)和介孔孔径分布图(b)

    Figure  4  N2 adsorption-desorption isotherms (a) and mesoporous size distribution (b) of Mo1Sn2 catalysts calcined at different temperatures

    图  5  不同焙烧温度Mo1Sn2催化剂的NH3-TPD(a)和CO2-TPD(b)谱图

    Figure  5  NH3-TPD (a) and CO2-TPD (b) profiles of Mo1Sn2 catalyst calcined at different temperatures

    图  6  不同焙烧温度Mo1Sn2催化剂的H2-TPR谱图

    Figure  6  H2-TPR profiles of Mo1Sn2 catalysts calcined at different temperatures

    图  7  不同焙烧温度Mo1Sn2催化剂的XPS-Sn 3d谱图

    Figure  7  XPS-Sn 3d spectra of Mo1Sn2 catalysts calcined at different temperatures

    图  8  不同焙烧温度Mo1Sn2催化剂的XPS-Mo 3d谱图

    Figure  8  XPS-Mo 3d spectra of Mo1Sn2 catalysts calcined at different temperatures

    图  9  不同焙烧温度Mo1Sn2催化剂上二甲醚催化剂反应原位红外谱图

    (a): Injected DME for 20 min on different catalysts at 110 ℃; (b): Swept with Ar for 20 min on different catalysts at 110 ℃

    Figure  9  In-situ IR spectra of DME oxidation over Mo1Sn2 catalysts calcined at different temperatures

    表  1  不同焙烧温度的Mo1Sn2催化剂对二甲醚选择氧化制备甲酸甲酯的影响

    Table  1  Effect of Mo1Sn2 catalysts calcined at different temperatures on the selective oxidation of DME to MF

    CatalystDME conversion
    x /%
    Cmol-selectivity s /%
    MFFACH3OHCODMM
    Mo1Sn2-4009.286.9013.100
    Mo1Sn2-5009.777.5022.500
    Mo1Sn2-60010.672.9027.100
    Mo1Sn2-7007.265.4034.600
    Reaction conditions: tR = 110 ℃, atmospheric pressure, DME/O2 = 1, GHSV = 1800 h−1
    下载: 导出CSV

    表  2  反应温度对Mo1Sn2-400催化剂上二甲醚氧化制备甲酸甲酯的影响

    Table  2  Effect of reaction temperature on the oxidation of DME to MF over Mo1Sn2-400 catalyst

    tR(℃)DME conversion
    x /%
    Cmol-selectivity s /%
    MFFACH3OHCODMM
    905.589.8010.200
    1008.483.4016.600
    1109.286.9013.100
    12011.383.4014.52.10
    13011.582.4011.26.40
    14014.582.507.010.50
    Reaction conditions:atmospheric pressure, DME/O2 = 1, GHSV = 1800 h−1
    下载: 导出CSV

    表  3  不同焙烧温度Mo1Sn2催化剂的织构性质

    Table  3  Physical properties of Mo1Sn2 catalysts calcined at different temperatures

    CatalystBET surface area/
    (m2·g−1)
    Micropore area/
    (m2·g−1)
    External surface area/
    (m2·g−1)
    Pore volume/
    (cm3·g−1)
    Average pore diameter/
    (nm)
    Mo1Sn2-400163117460.092.3
    Mo1Sn2-50016790770.102.4
    Mo1Sn2-600152151370.102.7
    Mo1Sn2-700920920.114.8
    下载: 导出CSV

    表  4  不同焙烧温度Mo1Sn2催化剂XPS-Mo 3d 谱图分析

    Table  4  XPS-Mo 3d spectra analysis of Mo1Sn2 catalysts calcined at different temperatures

    CatalystMo6+ 3d3/2Mo6+ 3d5/2Mo5+ 3d3/2Mo5+ 3d5/2Mo5+ (%)
    Mo1Sn2-400236.19233.05235.11232.0410.02
    Mo1Sn2-500236.15233.02235.10232.018.51
    Mo1Sn2-600236.10232.95235.11231.907.06
    Mo1Sn2-700236.11232.95235.10231.916.24
    下载: 导出CSV
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  • 收稿日期:  2021-04-26
  • 修回日期:  2021-05-23
  • 网络出版日期:  2021-06-25

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