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Modeling the kinetics of sulfidation over NiMo/Al2O3 catalyst for thiophene hydrodesulfurization

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Abstract

A kinetic model has been developed for the sulfidation of NiMo/Al2O3 hydrodesulfurization (HDS) catalyst, which quantitatively establishes a relationship between the HDS activity and sulfidation conditions. The model parameters were estimated by fitting a series of experimental thiophene HDS conversion data over the catalysts sulfurized under different operations. The results show that the developed model satisfactorily predicts the HDS conversion with a total average relative deviation of less than 4 %. Moreover, parametric studies were made to validate the accuracy of the model. The comparison results show that the proposed model is fairly effective in simulating the sulfidation process. It is expected that the model will be used to guide the sulfidation research of supported Mo-based catalysts and to optimize laboratory/pilot-plant sulfiding procedures.

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Abbreviations

A, B, C :

Model parameter

ARD :

Average relative deviation, %

E a :

Activation energy of HDS reaction

E 1 :

Relative activation energy of sulfidation reaction

E 2 :

Relative activation energy of grain growth

f M :

Dispersion indicator of the active metal

k :

Rate constant of HDS reaction

k o :

Pre-exponential factor of HDS reaction

k 1 :

Rate constant of sulfidation reaction

k 2 :

Rate constant of grain growth

\(k_{10}^{'}\) :

Pre-exponential factor of sulfidation reaction

\(k_{20}^{'}\) :

Pre-exponential factor of grain growth

L :

MoS2/WS2 crystal slab length

L r :

Relative slab length (L r = L/L max)

M s :

Total content of surface active metal

M e(IV):

Number of atoms in the active surface (edges)

M t(IV):

Total number of Mo atoms in the crystal

N a :

Amount of active sites

N :

Number of Mo atoms along one edge of a MoS2 slab

n 1, n 2 :

Model parameter

R s :

Sulfidation degree

R :

Gas constant

T :

Relative sulfidation temperature (T = T s/673 K)

T s :

Sulfidation temperature

T :

Relative sulfidation time (t = t s/60 min)

t s :

Sulfidation time

x :

Conversion

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Acknowledgments

This work is supported by the National Natural Science Foundation of China (21473143, 21303140, 21073147), the Ministry of Science and Technology of China (2010CB226903) and the Fundamental Research Funds for the Central Universities (2012121022).

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Authors and Affiliations

  1. National Engineering Laboratory for Green Chemical Productions of Alcohols- Ethers-Esters, State Key Laboratory for Physical Chemistry of the Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Weikun Lai, Yingrui Xu, Jinbao Zheng, Xiaodong Yi & Weiping Fang

  2. Petrochemical Research Institute of PetroChina Company Limited, Beijing, 100195, China

    Yusheng Zhao

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  1. Weikun Lai
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  2. Yingrui Xu
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  3. Yusheng Zhao
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  4. Jinbao Zheng
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  5. Xiaodong Yi
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  6. Weiping Fang
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Correspondence to Weiping Fang.

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Lai, W., Xu, Y., Zhao, Y. et al. Modeling the kinetics of sulfidation over NiMo/Al2O3 catalyst for thiophene hydrodesulfurization. Reac Kinet Mech Cat 115, 635–649 (2015). https://doi.org/10.1007/s11144-015-0859-7

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