CIESC Journal ›› 2019, Vol. 70 ›› Issue (4): 1409-1419.doi: 10.11949/j.issn.0438-1157.20181466

• Catalysis, kinetics and reactors • Previous Articles     Next Articles

Influence of calcination temperature on CuMgAl catalytic performance for hydrogenation of furfuralcohol to pentanediol

Caiyun WEI(),Jingjing TAN(),Xiaoli XIA,Yongxiang ZHAO()   

  1. Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, Shanxi, China
  • Received:2018-12-10 Revised:2019-01-07 Online:2019-04-05 Published:2019-01-07
  • Contact: Jingjing TAN,Yongxiang ZHAO E-mail:cywei216@126.com;tanjingjing@sxu.edu.cn;yxzhao@sxu.edu.cn

Abstract:

The CuMgAl hydrotalcite-type (CMA-HT) precursors was prepared by co-precipitation process, in which the molar ratio of n(Cu2+)∶n(Mg2+)∶n(Al3+) was 10∶65∶25. The CuMgAl hydrotalcite catalysts were obtained by calcining at various temperatures. The catalysts were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), N2-adsorption, H2-temperature programmed reduction (H2-TPR), H2-temperature programmed desorption (H2-TPD), CO2-temperature programmed desorption (CO2-TPD) and NH3-temperature programmed desorption (NH3-TPD). The catalytic performance of CMA catalysts for the hydrogenation of furfuryl alcohol to 1,2-pentanediol and 1,5-pentanediol were investigated in the autoclave. The results indicated that the calcination temperatures had significantly influence on the structure and catalytic activity of the catalyst. The metal sites and basic sites increased firstly and then decreased with rising the calcined temperatures. The sample calcined at 600℃ possesses the suitable metal and basic sites. It exhibited the superior activity for the hydrogenolysis of furfuryl alcohol as the synergistic effect between the surface metal sites and the basic sites. Under the condition of 140℃ and H2 pressure of 4 MPa, the conversion of sterol and the yield of pentanediol reached 74.13% and 58.36%, respectively, after 8 h of reaction.

Key words: furfuryl alcohol, 1,2-pentanediol, 1,5-pentanediol, hydrogenation, LDHs

CLC Number: 

  • O 643.36

Fig.1

Reaction scheme for FFA hydrogenation"

Fig.2

XRD patterns of CMA-HT and CMA-t catalysts"

Fig.3

XRD patterns of reduced CMA-t catalysts"

Fig.4

SEM images of CMA-HT and CMA-t catalysts"

Fig.6

TG curve and MS analysis of released gases of CMA hydrotalcite-type precursor"

Fig.7

FTIR spectrum of CMA-HT and CMA-t catalysts"

Table 1

Textural properties of catalysts"

CatalystSBET/(m2/g)Vp/(cm3/g)Dp/nmnCu/(mmol/g)
CMA-300131.030.6914.130.32
CMA-400220.341.1113.410.50
CMA-500192.301.0516.270.42
CMA-600204.191.0916.311.07
CMA-700171.211.0419.940.74

Fig.8

H2-TPR profiles of CMA-t catalysts"

Fig.9

CO2-TPD and NH3-TPD profiles of reduced CMA-t catalysts"

Fig.10

Proposed reaction paths for FFA hydrogenation over CMA-t catalyst"

Table 2

Selevitity and conversion of CMA-t catalysts in hydrogenation of FFA on 120℃"

CatalystConversion/%Selevitity/%Yield/%
2-MFn-POHTHFA1,2-PeD1,5-PeD
CMA-30019.895.909.573.8051.1129.6216.06
CMA-40035.543.307.457.1152.929.2429.19
CMA-50045.084.9111.163.9153.9526.0636.07
CMA-60052.442.069.063.4059.2726.2144.83
CMA-70034.645.3110.623.7330.4329.9127.83

Fig.11

Relationship between catalytic activities of CMA-t and metal and basic sites for hydrogenation of FFA at 140℃(reaction conditions: FFA: 0.5 g; catalyst: 0.2 g; H2: 4 MPa; isopropyl alcohol 10 g as solvent; T=140℃; t=8 h)FFA—furfuryl alcohol; PeD—1,2+1,5-pentanediol"

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