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Development of a modified kinetic model for residual oil hydroprocessing

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Abstract

A basic conversion model for hydrodesulfurization (HDS) is developed according to corresponding reaction process. Further improvement is conducted on the model considering the HDS characteristics and industrial demand. The model can quantitatively describe the effect of operational conditions, deactivation behavior and residual properties on HDS. By comparison with the experimental data, the calculated conversions are all found to have a total average relative deviation of less than 5%, presenting a good fit in relation to the experimental data. Moreover, the model can also accurately predict the performance of hydrodecarbonresidue and hydrodemetallization. Results indicate that the model has a high universality and practicability.

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Abbreviations

\(C_S\) :

Contention of representative S compound (wt%)

\(C_{{S_{0} }}\) :

Initial contention of representative S compound (wt%)

\(Cz\) :

The contents of Catalyst surface active sites (mol/m2)

\(C_{M}\) :

Adsorbent concentration (mol/m2)

\(C_{{M_{0} }}\) :

Initial contention of representative metal compound (mg/kg)

\(C_{{C_{0} }}\) :

Initial contention of representative carbon residue compound (wt%)

\(C_{H}\) :

The contents of hydrogen atom (mol/m2)

\(C_{L}\) :

Bituminous concentration (wt%)

\(R\) :

Gas constant (8.314 J mol−1 K−1)

\(E_{1}\) :

Activation energy of first step reaction (kJ/mol)

\(E_{2}\) :

Activation energy of second step reaction (kJ/mol)

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

Hydrogen gas concentration (mol/m3)

\(C_{{H_{20} }}\) :

Initial hydrogen gas concentration (mol/m3)

\(\alpha_{1}\) and \(\alpha_{2}\) :

Average weights

\(\tau\) :

Reaction time (h)

\(T\) :

Reaction temperature (°C)

\(E_{a}\) :

Relative apparent activation energy

\(E_{a}^{'}\) :

Apparent activation energy (kJ/mol)

\(\pi_{c}\) :

Active retention factor

\(k_{d}\) :

Deactivation rate constant of covering

\(t\) :

Running time (h or day)

\(n_{0}\) :

The parameter of deactivation curve shape

\(\omega\) :

The parameter of initial hydrogen concentration

\(m_{0}\) :

The index of reaction time

\(m_{1}\) :

The index of reaction time

\(k_{0}^{{}}\) :

Pre-exponential factors (related)

\(k_{0}^{'}\) :

The pre-exponential factor when t = 0

\(\eta\) :

Internal diffusion efficient factor

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

Rate coefficient when \(\eta\) = 1

\(k\) :

Rate coefficient

\(D_{e}^{{}}\) :

Effective diffusion coefficient

\(\eta_{0}\) :

Coefficient

\(N\) :

The parameter of internal diffusion resistance

\(r_{0}\) :

The mesoporous radius of fresh catalyst (nm)

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

The channel reduction deactivation factor of catalyst

\(n_{0}^{'}\) :

The shape parameter of deactivation curve

\(V_{cat}\) :

Catalyst bed volume (m3)

\(\lambda\) :

Hydrogen oil volume ratio (V/V)

\(F_{oil}\) :

Flow of liquid oil into the reactor (ton/h)

\(C_{20}\) :

Initial concentration of H2

\(P\) :

Operation pressure (MPa)

\(K_{H}\) :

Dissociation adsorption constant of H2

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (21703179, 21773194 and 21473143) and the Fundamental Research Funds for the Central Universities of China (20720170103).

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Authors and Affiliations

  1. National Engineering Laboratory for Green Chemical Productions of Alcohols-ethers-esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Xinyuan Li, Zhou Yang, Weikun Lai, Xiaodong Yi & Weiping Fang

  2. SINOPEC Dalian Research Institute of Petroleum and Petrochemicals, Dalian, 116041, China

    Shenghua Yuan, Yanbo Weng & Xinguo Geng

Authors
  1. Xinyuan Li
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  2. Zhou Yang
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  3. Shenghua Yuan
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  4. Yanbo Weng
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  5. Xinguo Geng
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  6. Weikun Lai
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  7. Xiaodong Yi
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Correspondence to Weikun Lai.

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Li, X., Yang, Z., Yuan, S. et al. Development of a modified kinetic model for residual oil hydroprocessing. Reac Kinet Mech Cat 126, 921–937 (2019). https://doi.org/10.1007/s11144-019-01556-2

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