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Y分子筛表面高分散铜活性物种构建及甲醇氧化羰基化性能

张志浩 许贞军 任坤 王佳君 李忠 付廷俊

张志浩, 许贞军, 任坤, 王佳君, 李忠, 付廷俊. Y分子筛表面高分散铜活性物种构建及甲醇氧化羰基化性能[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022043
引用本文: 张志浩, 许贞军, 任坤, 王佳君, 李忠, 付廷俊. Y分子筛表面高分散铜活性物种构建及甲醇氧化羰基化性能[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022043
ZHANG Zhi-hao, XU Zhen-jun, REN Kun, WANG Jia-jun, LI Zhong, FU Ting-jun. Construction of highly dispersed active copper species on Y molecular sieve and performance of methanol oxidation carbonylation[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022043
Citation: ZHANG Zhi-hao, XU Zhen-jun, REN Kun, WANG Jia-jun, LI Zhong, FU Ting-jun. Construction of highly dispersed active copper species on Y molecular sieve and performance of methanol oxidation carbonylation[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022043

Y分子筛表面高分散铜活性物种构建及甲醇氧化羰基化性能

doi: 10.19906/j.cnki.JFCT.2022043
基金项目: 国家自然科学基金项目(U1510203);山西省重点研发计划项目(201803D421011)
详细信息
    通讯作者:

    Email: lizhong@tyut.edu.cn

    futingjun@tyut.edu.cn

  • 中图分类号: TQ072

Construction of highly dispersed active copper species on Y molecular sieve and performance of methanol oxidation carbonylation

Funds: The project was supported by Natural Science Foundation of China (U1510203) and Key Research and Development Project of Shanxi Province (201803D421011).
  • 摘要: CuY催化剂中铜物种状态的控制是提高甲醇氧化羰基化反应性能的关键。本研究采用溶液离子交换法制备了不同载量的CuY催化剂,结合XRD、TEM、H2-TPR、XPS、NH3-TPD和CH3OH-TPD等分析CuY微观结构,探讨了铜氨溶液浓度及活化温度对CuY表面铜物种状态及性能的影响规律。发现增大交换溶液浓度虽会降低催化剂孔隙率,但能将铜载量由2.21%显著提升至9.95%,并仍保持着铜物种的高分散,铜粒径不足4 nm。溶液交换会破坏表面酸结构而减少表面弱酸位,抑制副反应进而提高DMC选择性。低载量催化剂铜物种以离子态铜为主,增加铜含量提升离子态铜含量的同时,也显著增加了CuOX,能使催化性能迅速提高,甲醇转化率和DMC收率分别达到9.07%和396.27 mg/(g·h)。控制催化剂活化温度研究铜物种活化过程发现,适宜温度的活化会促进表面铜物种向分子筛内部孔道的扩散和交换,并减弱甲醇的吸附强度,利于性能的提升。高载量催化剂相比低载量催化剂能在低温下活化获得更多的Cu+和CuOX而表现出高催化活性。本工作研究结果为高性能CuY催化剂的设计和制备提供了理论基础。
  • 图  1  催化剂的(a)N2物理吸附脱附等温线及(b)织构性质

    Figure  1  (a) N2 physical adsorption and desorption isotherms and (b) texture properties of catalysts

    图  2  (a)铜氨溶液浓度与铜载量间的关系及一次离心结束时离心液照片和(b)催化剂的XRD谱图

    Figure  2  (a) The relationship between copper ammonia solution concentration and copper load and the photo of centrifugal fluid at the end of the first centrifugation and (b) XRD patterns of catalysts

    图  3  催化剂的TEM图及铜粒径分布图

    Figure  3  TEM images of catalysts and copper particle size distribution histogram

    图  4  催化剂的(a)H2-TPR谱图和(b)铜物种的耗氢量

    Figure  4  (a) H2-TPR patterns of catalysts and (b) hydrogen consumption of copper species

    图  5  催化剂的(a)NH3-TPD谱图和(b)弱酸密度

    Figure  5  (a) NH3-TPD patterns and (b) the density of weak acid sites of the catalysts

    图  6  催化剂的(a)甲醇转化率(b)DMC选择性、(c)DMC时空收率和(d)铜含量与收率的关系

    Figure  6  (a) Methanol conversion, (b) selectivity of DMC, (c) space time yield of DMC of catalyst and (d) relationship between copper load and yield

    图  7  催化剂的(a)甲醇转化率、(b)DMC时空收率、(c)XRD谱图和(d)N2物理吸附脱附等温线

    Figure  7  (a) Methanol conversion, (b) space time yield of DMC, (c) XRD patterns and (d) N2 physical adsorption and desorption isotherms of catalysts

    图  8  催化剂的H2-TPR谱图

    Figure  8  H2-TPR patterns of catalysts

    图  9  催化剂的(a)Cu 2p XPS谱图、(b)表面铜含量和(c)TEM图

    Figure  9  (a) Cu 2p XPS patterns, (b) copper content on the surface and (c) TEM images of catalysts

    图  10  催化剂的CH3OH-TPD谱图

    Figure  10  CH3OH-TPD patterns of catalysts

    表  1  不同浓度交换溶液制备的CuY催化剂的活性

    Table  1  Activity of CuY catalysts prepared with different exchange solutions

    SampleCu content/
    (%)
    xCH3OH/
    (%)
    sDMC/
    (%)
    STYDMC/
    (mg·g−1·h−1)
    Y-0.02 2.11 1.03 48.56 33.69
    Y-0.04 4.44 2.52 60.93 103.66
    Y-0.06 7.48 6.61 64.16 286.21
    Y-0.08 7.86 7.66 64.94 335.76
    Y-0.10 8.59 9.07 64.66 396.27
    Y-0.12 9.95 9.02 64.84 394.47
    下载: 导出CSV

    表  2  不同催化剂的活性及织构性质

    Table  2  The reactivities and texture properties of different catalysts

    SamplexCH3OH/
    (%)
    sDMC/
    (%)
    STYDMC/
    (mg·g−1·h−1)
    SBET/
    (m2·g−1)
    Daverage/
    (nm)
    Vtotal/
    (cm3·g−1)
    Y7441.940.37
    Y0.04-2000.7741.4221.916472.190.35
    Y0.04-4001.1130.2922.636502.200.35
    Y0.04-6002.1864.4594.766512.120.35
    Y0.04-8000.03001.5337.660.01
    Y0.10-2001.4075.4172.355832.230.33
    Y0.10-4008.2366.33368.926062.180.33
    Y0.10-6008.8267.42401.526552.090.34
    Y0.01-8000.88000.4194.700.01
    下载: 导出CSV
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  • 收稿日期:  2022-04-14
  • 录用日期:  2022-05-16
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  • 网络出版日期:  2022-06-09

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