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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

邮发代号 80-969

2019 Impact Factor: 3.552

Frontiers of Chemical Science and Engineering  2019, Vol. 13 Issue (4): 744-758   https://doi.org/10.1007/s11705-019-1839-7
  本期目录
Experimental and theoretical study of microwave enhanced catalytic hydrodesulfurization of thiophene in a continuous-flow reactor
Hui Shang1(), Pengfei Ye1, Yude Yue1, Tianye Wang1, Wenhui Zhang1, Sainab Omar2, Jiawei Wang2()
1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China
2. European Bioenergy Research Institute, Aston University, Birmingham, B4 7ET, UK
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Abstract

Hydrodesulfurization (HDS) of thiophene, as a gasoline model oil, over an industrial Ni-Mo/Al2O3 catalyst was investigated in a continuous system under microwave irradiation. The HDS efficiency was much higher (5%–14%) under microwave irradiation than conventional heating. It was proved that the reaction was enhanced by both microwave thermal and non-thermal effects. Microwave selective heating caused hot spots inside the catalyst, thus improved the reaction rate. From the analysis of the non-thermal effect, the molecular collisions were significantly increased under microwave irradiation. However, instead of being reduced, the apparent activation energy increased. This may be due to the microwave treatment hindering the adsorption though upright S-bind (η1) and enhancing the parallel adsorption (η5), both adsorptions were considered to favor to the direct desulfurization route and the hydrogenation route respectively. Therefore, the HDS process was considered to proceed along the hydrogenation route under microwave irradiation.

Key wordsthiophene    microwave irradiation    hydrodesulfurization    non-thermal microwave effect
收稿日期: 2019-02-25      出版日期: 2019-12-04
Corresponding Author(s): Hui Shang,Jiawei Wang   
 引用本文:   
. [J]. Frontiers of Chemical Science and Engineering, 2019, 13(4): 744-758.
Hui Shang, Pengfei Ye, Yude Yue, Tianye Wang, Wenhui Zhang, Sainab Omar, Jiawei Wang. Experimental and theoretical study of microwave enhanced catalytic hydrodesulfurization of thiophene in a continuous-flow reactor. Front. Chem. Sci. Eng., 2019, 13(4): 744-758.
 链接本文:  
https://academic.hep.com.cn/fcse/CN/10.1007/s11705-019-1839-7
https://academic.hep.com.cn/fcse/CN/Y2019/V13/I4/744
Fig.1  
Fig.2  
Fig.3  
Fig.4  
Theory DFT
Software Materials Studio 6.1
Module Dmol3
Functional GGA/RPBE
Basis set DNP
Density mixing charge 0.03
SCF tolerance 1.0×10?6 Ha
Convergence tolerance of energy 1×10?5 Ha
Convergence tolerance of Max. force 0.002 Hatree/Å
Convergence tolerance of Max. displacement 0.005 Å
Tab.1  
Fig.5  
Fig.6  
Fig.7  
Temperature /°C k (conventional heating) /s–1 k (microwave heating) /s–1 k (adjusted for microwave )/s–1
200 0.07 0.09 0.09
220 0.11 0.14 0.12
240 0.14 0.21 0.19
260 0.20 0.32 0.27
280 0.28 0.40 0.37
Tab.2  
Fig.8  
Fig.9  
Factors Conventional heating Microwave heating
EA /(kJ?mol?1) 36.2 41.7
A/s?1 707 3633
Tab.3  
Temperature /°C CS2/ppm Thiophene /ppm 1-Butanethiol /ppm Tetrahydrothiophene /ppm Total sulfur /ppm Thiophene removal /%
Raw material 3.65 277.49 0 0 281.14
200 MW 7.66 116.78 0.68 3.58 128.7 57.92
220 MW 16.04 58.52 0.43 1.59 76.58 78.91
240 MW 11.21 28.7 0.28 0.63 40.82 89.66
260 MW 4.95 10.79 0.10 0.46 16.3 96.11
280 MW 1.54 5.42 0.22 0.90 8.08 98.05
200 5.67 140.29 0.73 1.28 147.97 49.44
220 17.49 88.91 0.48 1.19 108.07 67.96
240 14.11 63.4 0.59 1.87 79.97 77.15
260 5.27 42.04 0.29 0.61 48.21 84.85
280 4.22 18.57 0.15 0.57 23.51 93.31
Tab.4  
Material Thiophene Tetrahydrothiophene 2,3-Dihydro-thiophene 1-Butanethiol Butadiene CS2
m /debye 0.3679 1.9588 1.4573 1.6724 0.0022 0.0006
Tab.5  
Factors Conventional heating Microwave heating
EA /(kJ?mol?1) 29.1 33.0
A /s?1 166 465
Tab.6  
Fig.10  
Fig.11  
Temperature /°C HDS ratio (conventional heating) /% HDS ratio (microwave heating) /% k (conventional heating) /s–1 k (microwave heating) /s–1
240 81.06 84.73 0.18 0.21
250 84.50 87.66 0.21 0.23
260 87.77 91.64 0.23 0.28
270 90.46 94.12 0.26 0.32
280 93.58 96.11 0.30 0.36
Tab.7  
Fig.12  
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