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Lumped kinetic model for the hydrodeoxygenation of full-range middle-low temperature coal tar

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Abstract

Based on the experimental data of full-range middle-low temperature coal tar (LTCT) hydrodeoxidation (HDO), the phenolic compounds (PC) in feedstock were divided into three lumps, four lumps or five lumps according to different reaction activities. Three corresponding lumping kinetic models of LTCT HDO were established. The Levenberg–Marguardt algorithm was used to calculate the kinetic parameters of each model. The fitting results of the three models are in good agreement with the experimental data, as the average relative error is less than 1.01%. Three types of lumped dynamic models are compared in detail, and the five-lumped model has an average relative error of less than 0.91%. Hence, this model can reliably predict PC removal and showed a good extrapolation performance. The effects of liquid hourly space velocity (LHSV), initial hydrogen pressure (P) and reaction temperature (T) on the HDO process of LTCT were analyzed by five-lumped model calculation, and the reaction law of HDO was obtained. The results show that the order of influence of various factors on the oxygen content of hydrogenated oil is LHSV > P ≥ T. Moreover, the hydrogenation process conditions were optimized by simulation: T = 663 K, P = 14 MPa, LHSV = 0.3 h−1 and V(H2)/V(Oil) of 1100:1, under which the expected oxygen content was 468.28 μg g−1. The results of this study can also provide a scientific understanding of HDO mechanism, greatly reduce the number of LTCT industrial tests, reduce the oil inspection frequency, and help to improve the industrial hydrogenation process.

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Abbreviations

LTCT:

Middle-low temperature coal tar

HDO:

Hydrodeoxygenation

PC:

Phenolic compounds

T :

Reaction temperature (K)

P :

Initial hydrogen pressure (MPa)

LHSV :

Liquid hourly space velocity (h−1)

V(H2)/V(Oil):

Volume ratio of hydrogen under standard conditions to the volume of feed oil

t:

Reaction time (h)

xi :

The ratio of lump-i oxygen content to total oxygen content in the feedstock (%)

ki0 :

Pre-exponential factor of Arrhenius equation of lump-i (h−1)

ki :

Apparent reaction rate constant of lump-i

w0 :

Oxygen content in feed (μg g−1)

W:

Oxygen content in product (μg g−1)

wi0 :

Oxygen content of lump-i in feed (μg g−1)

wi :

Oxygen content of lump-i in product (μg g−1)

Ei :

Activation energy of lump-i (kJ mol−1)

ai :

Correction factor for reaction pressure of lump-i

bi :

Correction factor for reaction time of lump-i

di :

Oxygen adsorption self-blocking parameter

ni :

Reaction order

R:

Universal gas constant (kJ mol−1 K−1)

\(\overline{{\mathrm{E}}_{\mathrm{r}}}\) :

The average relative error (%)

SSR:

Sum of Squares due to residuals

\({\mathrm{w}}^{\mathrm{Cal}}\) :

Calculated oxygen content of experimental sample i (μg g−1)

\({\mathrm{w}}^{\mathrm{Exp}}\) :

Experimental oxygen content of experimental sample i (μg g−1)

\({\mathrm{y}}_{\mathrm{i}}^{\mathrm{Cal}}\) :

Calculated deoxidation rate of experimental sample i (%)

\({\mathrm{y}}_{\mathrm{i}}^{\mathrm{Exp}}\) :

Experimental deoxidation rate of experimental sample i (%

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Acknowledgements

We gratefully acknowledge the financial support of the National Natural Science Foundation of China (21978237), Shaanxi Technology Innovation Shaanxi Key Research and Development Plan Project (2018zdxm-gy-161), Natural Science Basic Research Program of Shaanxi (Program No. 2021JLM-19), Natural Science Basic Research Program of Shaanxi (Program No. 2019JLP-03).

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Authors and Affiliations

  1. School of Chemical Engineering, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Northwest University, Xi’an, 710069, Shaanxi, China

    Yijie Wang, Yonghong Zhu, Feng Tian, Huan Dong, Xiaoyong Fan, Chongpeng Du, Louwei Cui, Huaan Zheng & Haipeng Teng

  2. Hydrocarbon High-Efficiency Utilization Technology Research Center, Yanchang Petroleum Co. Ltd., Xi’an, 710075, Shaanxi, China

    Yonghong Zhu

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  1. Yijie Wang
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Contributions

YW: Writing—review & editing, Methodology, Investigation, Writing—original draft. YZ: Software, Validation. FT: Software. HD: Data curation. XF: Formal analysis. CD: Validation. LC: Supervision, Resources. HZ: Project administration. HT: Project administration, Investigation, Resources.

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Correspondence to Haipeng Teng.

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Wang, Y., Zhu, Y., Tian, F. et al. Lumped kinetic model for the hydrodeoxygenation of full-range middle-low temperature coal tar. Reac Kinet Mech Cat 134, 179–198 (2021). https://doi.org/10.1007/s11144-021-02053-1

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