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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

Front. Chem. Sci. Eng.    2021, Vol. 15 Issue (2) : 288-298    https://doi.org/10.1007/s11705-020-1932-y
RESEARH ARTICLE
Conversion of phenol to cyclohexane in the aqueous phase over Ni/zeolite bi-functional catalysts
Jimei Zhang1,2, Fuping Tian3, Junwen Chen4, Yanchun Shi2, Hongbin Cao2, Pengge Ning2, Shanshan Sun2, Yongbing Xie2()
1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
2. CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
3. College of Chemistry, Dalian University of Technology, Dalian 116024, China
4. State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
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Abstract

A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation (HDO) of phenol. The Ni dispersibility and particle sizes were shown to be directly related to the porosity and crystal sizes of the parent zeolites, which further influenced the catalytic performances. The large pores and small crystal sizes of the parent zeolites were beneficial for dispersing Ni and forming small Ni particles, and the corresponding Ni/zeolite catalyst exhibited a higher phenol conversion and selectivity towards hydrocarbons. Importantly, the Ni/HIM-5 bi-functional catalyst exhibited a high activity (98.3%) and high selectivity for hydrocarbons (98.8%) when heated at 220°C for 1 h and is thus a new potential catalyst for the HDO of phenolics to form hydrocarbons in the aqueous phase.

Keywords aqueous-phase hydrodeoxygenation      phenol      hydrocarbons      Ni/HIM-5      bi-functional catalyst     
Corresponding Author(s): Yongbing Xie   
Just Accepted Date: 09 April 2020   Online First Date: 12 June 2020    Issue Date: 10 March 2021
 Cite this article:   
Jimei Zhang,Fuping Tian,Junwen Chen, et al. Conversion of phenol to cyclohexane in the aqueous phase over Ni/zeolite bi-functional catalysts[J]. Front. Chem. Sci. Eng., 2021, 15(2): 288-298.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1932-y
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I2/288
Catalysts Reaction conditions Conversion /% Selectivity /% Ref.
Benzene Cyclo-hexane Cyclo-hexene Cyclo-hexanol Cyclo-hexanone
5 wt-% Pd/C
(0.02 g)
1 g phenol in 80 mL H2O; 80°C, 5 MPa H2, 7 h ~50 ? - ? >90 ? [19]
5 wt-% Pd/C
(0.04 g)
1 g phenol in 80 mL H2O; 200°C, 5 MPa H2, 0.5 h 100 ? - ? 98 2 [20]
1 g phenol in 80 mL NaOH-H2O; 200°C, 5 MPa H2, 0.5 h 100 ? - ? 97 3
1 g phenol in 80 mL H3PO4-H2O; 200°C, 5 MPa H2, 0.5 h 99 ? 85 ? 10 4
5 wt-% Pd/C; 1 g HZSM-5 0.94 g phenol in 80 mL H2O; 200°C, 5 MPa H2, 2 h 100 ? 100 ? ? ? [21]
MoS2 (0.075 g) 0.3 g phenol in 19.7 g n-decane; 350°C, 2.8 MPa H2, 1 h 30 20.3 34.5 29.0 ? 16.2 [16]
9.2 wt-% Ni/HZSM-5 (0.1 g) 5 g phenol in 80 mL H2O; 220°C, 5 MPa H2, 100 min 10 ? ~15 ~10 ~45 ~30 [22]
9.3 wt-% Ni/HZSM-5-Al2O3 (0.1 g) 5 g phenol in 80 mL H2O; 220°C, 5 MPa H2, 100 min ~34 ? ~55 ~2.5 ~2.5 ~40 [22]
Tab.1  Catalytic performance of phenol conversion over the diverse catalysts in the references.
Fig.1  TEM images of the Ni/HZ-5-10 (a), Ni/HIM-5-16 (b), Ni/HZ-5-90 (c) and Ni/HZP-5-90 (d) catalysts.
Fig.2  SEM images of the HZ-5-10 (a), HIM-5-16 (b), HZ-5-90 (c) and HZP-5-90 (d) zeolites.
Samples SiO2/Al2O3 Ni/wt-% SBET/(m2·g?1) Smicro
/(m2·g?1)
Sext/(m2·g?1) Vmicro/(cm3·g?1) Vtotal/(cm3·g?1)
Ni/HZ-5-10 20 11.1 371 363 8 0.15 0.17
Ni/HIM-5-16 32 11.2 285 236 50 0.09 0.28
Ni/HZ-5-90 180 10.5 413 379 34 0.15 0.17
Ni/HZP-5-90 172 10.3 367 320 47 0.13 0.26
Tab.2  Textural properties and chemical components of the Ni/HZ-5-10, Ni/HIM-5-16, Ni/HZ-5-90 and Ni/HZP-5-90 bi-functional catalysts
Fig.3  XRD patterns of the Ni/HZ-5-10, Ni/HIM-5-16, Ni/HZ-5-90 and Ni/HZP-5-90 catalysts.
Fig.4  H2-TPR curves of the calcined Ni/HZ-5-10, Ni/HIM-5-16, Ni/HZ-5-90 and Ni/HZP-5-90 catalysts.
Fig.5  H2-TPD curves of the Ni/HZ-5-10, Ni/HIM-5-16, Ni/HZ-5-90 and Ni/HZP-5-90 catalysts.
Fig.6  NH3-TPD curves of the Ni/HZ-5-10, Ni/HIM-5-16, Ni/HZ-5-90 and Ni/HZP-5-90 catalysts.
Fig.7  Phenol conversion and products selectivity over the Ni/HZ-5-10, Ni/HIM-5-16, Ni/HZ-5-90 and Ni/HZP-5-90 catalysts (reaction condition: 6 g phenol, 94 mL H2O, 0.5 g catalyst, 220°C, 4.5 MPa H2, 1 h).
Fig.8  Reaction (a) temperature and (b) time effects on the catalytic performance of the Ni/HIM-5-16 catalyst (Reaction conditions: (a) 6 g phenol, 94 mL H2O, 0.5 g catalyst, 4.5 MPa H2, 1 h; (b) 6 g phenol, 94 mL H2O, 0.5 g catalyst, 220°C, 4.5 MPa H2).
Fig.9  Stability of the Ni/HIM-5 catalyst during phenol conversion in the aqueous phase (Reaction condition: 6 g phenol, 94 mL H2O, 0.46–0.5 g catalysts, 220°C, 4.5 MPa H2, 1 h).
Fig.10  (a) FTIR analysis of the Ni/HIM-5 catalysts before and after the cycle runs, (b) TEM images of Ni/HIM-5-Re1.
Samples Ni leaching/(mg·L−1) Leaching efficiency/% Mass of catalysts/g Mass of recovery reaction solution/g
Ni/HIM-5-1st 0 0 0.50 >99.9
Ni/HIM-5-2nd 1.5 0.3 0.48 >99.9
Ni/HIM-5-3rd 2.3 0.5 0.47 >99.9
Ni/HIM-5-Re1 4.0 0.8 0.46 >99.9
Tab.3  Ni leaching in the three recycles, as determined by ICP analysis
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