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Kinetic parameter estimation and reactor simulation of full-range low temperature coal tar during hydrodeasphaltenization over Ni–Mo/γ-Al2O3

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Abstract

In this study, the whole fraction low temperature coal tar (LTCT) was used as raw material, a series of hydrodeasphaltenization (HDAs) experiments were conducted in an isothermal trickle bed reactor, then the kinetic equation of the reaction was established in gPROMS software and the parameters were estimated. The trickle bed reactor model was established and the effects of operating conditions on HDAs reaction and catalyst effective factors were analyzed. The reactor temperature was varied from 623 to 683 K, the hydrogen pressure from 6 to 12 MPa, keeping constant hydrogen-to-oil volume ratio at 1000:1, liquid hourly space velocity at 0.5 h−1. The results showed that the relative error between the experimental and the simulated results were less than ± 5%, which proved that the model had good applicability; the activation energy was 149.8 kJ mol−1, the pre-exponential factor was 633,832, the reaction order was 1.347, and the order of hydrogen was 2.33. The higher activation energy indicated that the HDAs was difficult to occur compared with the reaction in crude oil. And the high hydrogen order indicated that the pressure had a significant influence on the reaction rate. However, the high temperature and low pressure would reduce the effective factor of the catalyst. The reason may be that the large diffusion limitation and reaction heat of asphaltenes lead to a large difference in reaction rates between the catalyst surface and the tunnel of pores under high temperature. This study could contribute to a more in-depth understanding of the features and rules of LTCT HDAs, and also provide a useful model for reactor design, operation and control.

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Abbreviations

LTCT:

Low temperature coal tar

HDAs:

Hydrpdeasphaltenezation

n :

Reaction order of asphaltenes

m :

Reaction order of hydrogen

r :

Chemical reaction rate (mol g−1 s−1)

K HDAs :

Reaction rate coefficient

A 0 :

Pre-exponential factor

EA HDAs :

Activation energy (kJ mol−1)

R :

Universal gas constant

T :

Temperature (K)

u g :

Velocity of the gas (cm s−1)

\(K_{{H_{2} }}^{L}\) :

Gas–liquid mass transfer coefficient for H2 (cm s−1)

a L :

Specific surface area, gas–liquid interface (cm−1)

a S :

Specific surface area, liquid–solid interface (cm−1)

P :

Pressure (MPa)

h :

Henry’s coefficient for H2 (MPa cm3 mol−1)

z :

Reactor bed length (cm)

\(u_{l}\) :

Velocity of the liquid (cm s−1)

\(K_{{H_{2} }}^{s}\) :

Liquid–solid mass transfer coefficient for H2 (cm s−1)

\(K_{Asph}^{s}\) :

Liquid–solid mass transfer coefficient for asphaltenes (cm s−1)

\(C_{{H_{2} }}^{L}\) :

Concentration of H2 in the liquid phase (mol cm−3)

\(C_{Asph}^{L}\) :

Concentration of asphaltenes in the liquid phase (mol cm−3)

\(C_{{H_{2} }}^{S}\) :

Concentration of H2 in the solid phase (mol cm−3)

\(C_{Asph}^{S}\) :

Concentration of asphaltenes in the solid phase (mol cm−3)

L p :

Particle size (cm)

V p :

Total geometric volume of catalyst (cm3)

S p :

Total geometric external area of catalyst (cm2)

r c :

Radius of cylinder (cm)

N :

The number of lobes

L :

Particle length (cm)

A 1 :

The lateral area of the geometric shape between lobes (cm2)

A 2 :

The common area between each cylinder (cm2)

d p :

Particle diameter (cm)

\(D_{{H_{2} }}^{L}\) :

Molecular diffusivity of H2 in the liquid (cm2 s−1)

\(D_{Asph}^{L}\) :

Molecular diffusivity of asphaltenes in the liquid (cm2 s−1)

D K :

Knudsen diffusivity (cm2 s−1)

De :

Effective diffusivity of asphaltenes in the pores of catalyst (cm2 s−1)

Ds :

Diameter of spherical catalyst particle (cm)

D R :

Reactor diameter (cm)

d c :

Diameter of catalyst particle (cm)

G L :

Liquid mass velocity (g cm−2 s−1)

T meABP :

Mean average boiling point (0R)

Mw :

Molecular weight (g mol−1)

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Acknowledgements

The financial supports of this work are provided by the National Natural Science Foundation of China (21646009), Shaanxi Province Department of Education Industrialization Training Project (14JF026; 15JF031), Shaanxi Province Science and Technology Co-ordination Innovation Project Planned Program (2016KTZDGY08-03), Young Science and Technology Star Project of Shaanxi Province (2016KJXX-32) and Northwest University Graduate Innovation and Creativity Funds (YZZ17141).

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Authors and Affiliations

  1. School of Chemical Engineering, Northwest University, 229#, Taibai Road, Xi’an, 710069, China

    Huan Dong, An Fan, Dong Li, Yucheng Tian, Yong Dan, Xian Feng, Xiaoyong Fan & Wenhong Li

  2. The Research Center of Chemical Engineering Applying Technology for Resource of Shaanxi, Xi’an, 710069, China

    Huan Dong, An Fan, Dong Li, Yucheng Tian, Yong Dan, Xian Feng, Xiaoyong Fan & Wenhong Li

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  1. Huan Dong
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Dong, H., Fan, A., Li, D. et al. Kinetic parameter estimation and reactor simulation of full-range low temperature coal tar during hydrodeasphaltenization over Ni–Mo/γ-Al2O3. Reac Kinet Mech Cat 129, 899–923 (2020). https://doi.org/10.1007/s11144-020-01745-4

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