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SCIENCE CHINA Chemistry, Volume 60, Issue 7: 964-969(2017) https://doi.org/10.1007/s11426-016-9002-x

Nano CuO/ZSM-5 zeolite as a green and efficient catalyst for dehydration of 1,4-butanediol to tetrahydrofuran

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  • ReceivedNov 25, 2016
  • AcceptedJan 12, 2017
  • PublishedApr 26, 2017

Abstract

Nano CuO/ZSM-5 zeolite was prepared and used as a catalyst for dehydration of 1,4-butanediol (BDO) to tetrahydrofuran (THF) in liquid-phase. It was found that the 4.6 wt% CuO/ZSM-5 displayed good catalytic performance, and nearly 100% of BDO conversion and more than 99% of THF selectivity could be achieved by a rotary evaporator reactor at 170 °C under the atmospheric pressure. With such mild reaction conditions, 2400 g BDO could be converted to THF over 1 g catalyst under semi-continuous operation. Characterizations with X-ray diffraction (XRD), temperature-programmed reduction (TPR), NH3-temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM) and Brunauer-Emmett-Teller (BET) over fresh and used 4.6 wt% CuO/ZSM-5 were conducted. Based on the results of the characterization and catalytic performance of 4.6 wt% CuO/ZSM-5, it can be conjectured that the formed 1–3 nm CuO nanoparticles, suitable acidity of the catalyst due to the synergic interaction of CuO and ZSM-5 support promoted the dehydration of BDO to THF.


Funded by

National Natural Science Foundation of China(21173240)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21173240).


Interest statement

The authors declare that they have no conflict of interest.


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  • Scheme 1

    Synthesis of THF from BDO.

  • Figure 1

    Conversion rate of BDO in different periods.

  • Figure 2

    TGA curve of the 4.6 wt% CuO/ZSM-5.

  • Figure 3

    TEM image of 4.6 wt% CuO/ZSM-5.

  • Figure 4

    XRD patterns of 4.6 wt% CuO/ZSM-5.

  • Figure 5

    H2-TPR patterns of 4.6 wt% CuO/ZSM-5.

  • Figure 6

    NH3-TPD patterns of 4.6 wt% CuO/ZSM-5.

  • Table 1   Catalytic performance of different Cu loadings

    Catalyst

    Conversion of BDO (%)

    Selectivity of THF (%)

    2.5 wt% CuO/ZSM-5

    38

    >99

    4.6 wt% CuO/ZSM-5 b)

    89

    >99

    10 wt% CuO/ZSM-5

    57

    >99

    20 wt% CuO/ZSM-5

    43

    >99

    Reaction conditions: 50 g BDO, 2.5 g catalyst, 170 °C, 3 h; b) the actual content of Cu was analyzed by ICP.

  • Table 2   The influence of temperature on the reaction

    Reaction temperature

    Conversion of BDO (%)

    Selectivity of THF (%)

    140

    13

    >99

    150

    21

    >99

    160

    55

    >99

    170

    100

    >99

    180 b)

    100

    96

    Reaction conditions: 50 g BDO, 2.5 g catalyst, 4 h; b) the 100% conversion of BDO was achieved within 2 h.

  • Table 3   The reusability of the 4.6 wt% CuO/ZSM-5

    Reused times

    Conversion of BDO (%)

    Selectivity of THF (%)

    1

    100

    >99

    2

    67

    >99

    3

    64

    >99

    4

    63

    >99

    5

    65

    >99

    5* b)

    100

    >99

    Reaction conditions: 50 g BDO, 2.5 g catalyst, 170 °C, 4 h; b) the catalyst was calcination for 3 h at 500 °C after using 5 times.

  • Table 4   BET and XPS of different CuO/ZSM-5 samples

    Sample

    BE (eV)

    Specific surface area (m2/g)

    Pore volume (mL/g)

    Average pore radius (nm)

    H-ZSM-5

    326

    0.270

    1.66

    2.5 wt% CuO/ZSM-5

    314

    0.236

    1.61

    4.6 wt% CuO/ZSM-5

    Cu 2p3/2 934.8/Cu 2p1/2 955.2

    311

    0.229

    1.59

    10 wt% CuO/ZSM-5

    296

    0.227

    1.47

    20 wt% CuO/ZSM-5

    258

    0.208

    1.45

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