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Title: A theoretical study on reaction mechanisms and kinetics of thiophene hydrodesulfurization over MoS2 catalysts

Journal Article · · Catalysis Today
 [1];  [1];  [2];  [1];  [2];  [3]
  1. Beijing Univ. of Chemical Technology, Beijing (China)
  2. Beijing Univ. of Chemical Technology, Beijing (China); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
+ Show Author Affiliations

In the present study, thiophene hydrodesulphurization (HDS) over the Mo-edge, the S-edge, and the Mo-S connection edge of MoS2 catalyst with 50% sulfur coverage was studied using first-principles based microkinetic modeling. Two parallel HDS routes, i.e., direct desulfurization (DDS) and hydrogenation (HYD) were taken into account. It has been found that the major reaction route of thiophene HDS on the Mo- and the Mo-S edges is temperature dependent. In the low temperature range of 500–600 K, the HYD route is dominant, leading to the C4H8 formation. As the temperature increases, the DDS route becomes competitive with the HYD route. At the temperature above 650 K, the DDS route will be the dominant HDS reaction route on the Mo- and the Mo-S edges. The DDS route leading to the formation of C4H6 is the major thiophene HDS reaction route on the S-edge in the entire temperature range of 500–750 K. The microkinetic modeling results show the overall HDS activity on the S-edge is lower than it on the Mo- and the Mo-S edges. The Mo-S edge also provides a preferential reaction pathway, which facilitates 2-hydrothiophene migration from the Mo-edge to the S-edge, followed by remaining elementary steps with lower activation barriers in the DDS route.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
91534201; 21476012; 21571012; 21407007; AC05-76RL01830
OSTI ID:
1420437
Alternate ID(s):
OSTI ID: 1591660
Report Number(s):
PNNL-SA-130462; PII: S0920586118300646; TRN: US1801495
Journal Information:
Catalysis Today, Vol. 312; ISSN 0920-5861
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

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Cited By (1)

The on-and-off dynamics of thiophene on a nickel cluster enables efficient hydrodesulfurization and excellent stability at high temperatures journal January 2019

Figures / Tables (12)

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Thiophene
Hydrodesulphurization
MoS2
DFT
Microkinetic modeling