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The effect of NaF amount on solid base catalysts derived from F-Ca-Mg-Al layered double hydroxides and dimethyl carbonate synthesis

LI Feng LIAO Yun-hui ZHAO Ning XIAO Fu-kui

李枫, 廖云辉, 赵宁, 肖福魁. NaF含量对以水滑石结构为前驱体的固体碱催化剂F-Ca-Mg-Al及碳酸二甲酯合成的影响[J]. 燃料化学学报. doi: 0
引用本文: 李枫, 廖云辉, 赵宁, 肖福魁. NaF含量对以水滑石结构为前驱体的固体碱催化剂F-Ca-Mg-Al及碳酸二甲酯合成的影响[J]. 燃料化学学报. doi: 0
LI Feng, LIAO Yun-hui, ZHAO Ning, XIAO Fu-kui. The effect of NaF amount on solid base catalysts derived from F-Ca-Mg-Al layered double hydroxides and dimethyl carbonate synthesis[J]. Journal of Fuel Chemistry and Technology. doi: 0
Citation: LI Feng, LIAO Yun-hui, ZHAO Ning, XIAO Fu-kui. The effect of NaF amount on solid base catalysts derived from F-Ca-Mg-Al layered double hydroxides and dimethyl carbonate synthesis[J]. Journal of Fuel Chemistry and Technology. doi: 0

NaF含量对以水滑石结构为前驱体的固体碱催化剂F-Ca-Mg-Al及碳酸二甲酯合成的影响

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The effect of NaF amount on solid base catalysts derived from F-Ca-Mg-Al layered double hydroxides and dimethyl carbonate synthesis

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  • 摘要: 以碳酸丙烯(PC)和甲醇为原料,经酯交换反应合成的多功能、环保的碳酸二甲酯(DMC)是一种绿色、节能的合成方法。CaO固体碱催化剂对该反应具有良好的催化性能,但其再生性不理想。以F-Ca-Mg-Al水滑石(LDHs)为原料,制备了一系列不同NaF用量的固体碱催化剂,并对其进行了表征和酯交换反应测试。与不加氟的FCMA-0催化剂相比,经氟改性后的催化剂的比表面积、碱量、催化活性等性能均有明显提高。催化活性由高到低依次为:FCMA-0.8 > FCMA-0.4 > FCMA-1.2 > FCMA-1.6 > FCMA-0,这与总碱位量和强碱位量一致。FCMA-0.8催化剂活性最好,与纯CaO催化剂的相当,PC转化率为66.8%,DMC选择性为97.4%,DMC收率为65.1%。在10次循环使用后,FCMA-0.8催化剂的DMC收率仅下降3.9% (CaO催化剂下降33.2%)。FCMA-0.8在PC与甲醇酯交换制DMC方面具有良好的工业应用前景。
  • Figure  1  XRD patterns of (a) FCMAP-n precursors and (b) FCMA-n catalysts

    Figure  2  TG-DTG curve of FMCAP-n

    Figure  3  SEM images of (a) FCMAP-n and (b) FCMA-n

    Figure  4  CO2-TPD profiles of FCMA-n catalysts

    Figure  5  The catalytic performance of the catalysts

    Reaction conditions: (a): catalyst weight = 2 wt% of total reactants, T = 333 K, t = 2 h; (b): FCMA-0.8 catalyst, n (methanol) / n (PC) = 12, T = 333 K; (c), (d): n (methanol) / n (PC) = 12, catalyst weight = 2 wt% of total reactants, T = 333 K, t = 2 h.

    Figure  6  The correlation between (a): the DMC yield and the amount of strong basic sites; (b): the DMC yield and the amount of total basic sites; (c): the PC conversion and the amount of strong basic sites; (d): the PC conversion and the amount of total basic sites

    Reaction conditions: n (methanol) / n (PC) = 12, catalyst weight = 2 wt% of total reactants, T = 333 K, t = 2 h.

    Figure  7  (a) XRD patterns and (b) CO2-TPD profiles of the fresh and used FCMA-0.8 catalysts

    Table  1  The structure parameters and basicity of the FCMA-n catalysts

    CatalystsSBET (m2·g−1)Vpore (cm3·g−1)CO2 uptake (mmol·g−1)Total basic amount (mmol·g−1)
    αβγδ
    FCMA-042.30.300.090.230.540.191.05
    FCMA-0.448.20.390.240.240.680.471.63
    FCMA-0.855.60.410.230.250.720.531.73
    FCMA-1.245.30.380.270.170.650.351.44
    FCMA-1.644.10.320.200.210.580.391.38
    下载: 导出CSV

    Table  2  Composition of FCMA-n catalysts

    CatalystsComposition (mol %)F/Ca atomic ratio
    CaMgAl
    FCMA-050.9 (50.5)16.9 (16.7)32.2 (32.8)0
    FCMA-0.451.5 (50.9)17.2 (17.1)31.3 (32.0)0.38 (0.38)
    FCMA-0.852.8 (51.4)17.6 (17.5)29.6 (31.1)0.75 (0.76)
    FCMA-1.251.4 (50.8)17.1 (17.0)31.5 (32.2)1.14 (1.14)
    FCMA-1.651.3 (50.7)17.0 (16.9)31.7 (32.4)1.55 (1.54)
    The values outside and inside the parentheses were obtained by XPS and ICP measurements, respectively.
    下载: 导出CSV

    Table  3  The catalytic activity and recyclability over Ca-based solid basic catalyst

    SamplesPC conversion (%)DMC selectivity (%)DMC yield (%)DMC yield decrease (%)*References
    CaO68.8 (35.5)95.665.8 (32.6)33.2 (10)[17]
    CA-3--59.910.9 (4)[18]
    CA-253.7 (41.9)92.849.84.8 (4)
    12.6 (10)
    [16][17]
    Mg-CA55.3 (52.6)96.3 (92.5)53.3 (48.6)4.7 (10)[16]
    CA-F65.9(60.1)95.362.85.6 (10)[17]
    FCMA-0.866.897.465.13.9 (10)this work
    Reaction conditions: n (methanol) / n (PC) = 12, catalyst weight = 2 wt% of total reactants, T = 333 K, t = 2 h.
    -: The data were not reported in the literature.
    *: The data in the parenthesis stand for the recycle times.
    The other data in the parenthesis stand for the corresponding values after 10 times recycles.
    下载: 导出CSV

    Table  4  The elemental compositions of the fresh and used FCMA-0.8 catalysts

    CatalystsBulk compositions (mol %)
    Ca aMg aAl aF bCa: Mg: AlF: Ca
    Fresh FCMA-0.8 catalyst36.912.622.328.22.93: 1: 1.770.76
    Used FCMA-0.8 catalyst35.112.025.027.92.92: 1: 2.080.79
    a Determined by the ICP. b Determined by the ionic chromatography.
    下载: 导出CSV
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