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Kinetic parameter estimation and simulation of the second reactor for hydrodesulfurization of diesel

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Abstract

Using NiMo/γ-Al2O3 catalyst and a pilot-scale unit, a kinetic model was developed for the second reactor of the two-stage hydrogenation process to describe the HDS behavior of diesel in sulfur content lower than 10 μg g−1. The HDS reaction happened in the second reactor was simulated by combining the mass transfer, kinetics model and physical property data of diesel, the results show that the simulated values of sulfur content were within an error range of 10%. Meanwhile, it is found that high temperature, high pressure, high H2/oil volume ratio and removal of H2S from the exit stream of the first reactor improve the sulfur conversion in the second reactor. What is more, the influence of different process parameters on the catalyst effectiveness factor was further analyzed, the results indicate that the increase of temperature, pressure and H2/oil volume ratio can all cause the decrease of the effectiveness factor. These results contribute to a more in-depth understanding of the features and rules in the second HDS reactor, and can also give us some valuable guidance for industrial reactor simulation.

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Abbreviations

DBT:

Dibenzothiophene

4,6-DMDBT:

4,6-Dimethyldibenzothiophene

GC-SCD:

Gas chromatography with sulfur chemiluminescence detector

UDHDS:

Ultra-deep hydrodesulfurization

L–H:

Langmuir–Hinshelwood

LHSV:

Liquid hourly space velocity

PAHs:

Polycyclic aromatic hydrocarbons

IBP:

Initial boiling point

FBP:

Final boiling point

HDT:

Hydrogenation

\({w}_{sul}\) :

Mass fraction of sulfur (μg g−1)

\(LHSV\) :

Liquid hourly space velocity (h−1)

\(A\) :

Pre-exponential factor (mol cm−3)1−n

\(n\) :

Reaction order

\(m\) :

Reaction order of pressure

β :

Reaction order of H2/oil volume ratio

\({K}_{{H}_{2}S}\) :

Adsorption equilibrium constant of H2S component

\(P\) :

Pressure (MPa)

\({\mathrm{H}}_{2}/Oil\) :

H2 to oil volume ratio (v/v)

\(R\) :

Universal gas constant (J mol k−1)

\(T\) :

Reaction temperature (K)

\({w}_{Sul}^{L}\) :

Mass fraction of total sulfur compound (μg g−1)

\({H}_{2}S\) :

Hydrogen sulfide

\({a}_{L}\) :

Gas–liquid interfacial area (cm−1)

\(z\) :

Reactor bed length (cm)

\({u}_{L}\) :

Velocity of the liquid (cm s−1)

\({a}_{S}\) :

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

\({k}_{Sul}^{S}\) :

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

\({c}_{Sul}^{L}\) :

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

\({c}_{Sul}^{S}\) :

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

\({\rho }_{b}\) :

Bulk density of the catalyst particles (g cm−3)

\({\eta }_{HDS}\) :

Catalyst effectiveness factor for HDS reaction

\({r}_{Sul}\) :

Reaction rate for total sulfur

\({\rho }_{1}\) :

Liquid density (g cm−3)

Mw :

Molecular weight (g mol−1)

\({\mu }_{L}\) :

Liquid viscosity (mPa s−1)

\({G}_{L}\) :

Liquid mass velocity (g cm−2 s−1)

\({D}_{sul}^{L}\) :

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

\(v\) :

Molar volume (cm3 mol−1)

\({v}_{L}\) :

Molar volume of liquid feedstock (cm3 mol−1)

\({T}_{meABP}\) :

Mean average boiling point (0R)

NE :

The number of experiments

\({A}_{c}\) :

Surface area (cm2)

\(\varepsilon \) :

Void fraction of the catalyst bed

\(v\) :

Volume (cm3)

\(\mathrm{r}\) :

Particle radius (cm)

\({d}_{L}\) :

Length of particle (cm)

\({D}_{R}\) :

Reactor diameter (cm)

\({d}_{s}\) :

Diameter of spherical catalyst particle (cm)

\({d}_{c}\) :

Diameter of catalyst particle (cm)

\({V}_{l}\) :

Molar gas volume of l compound at standard conditions (NL mol−1)

\({\phi }_{Sul}\) :

Thiele modulus

\({V}_{P}\) :

Total geometric volume of catalyst (cm−3)

\({S}_{P}\) :

Total geometric external area of catalyst (cm2)

\({K}_{Sul}\) :

Reaction rate coefficient of Sulfur compound

\(De\) :

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

\(\theta \) :

Particle porosity

\(\tau \) :

Tortuosity factor

\({V}_{g}\) :

Pore volume per unit mass of catalyst (cm3 g−1)

\({D}_{k}\) :

Knudsen diffusivity (cm2 s−1)

\({s}_{g}\) :

Specific surface area of particle (cm2 g−1)

\(SSE\) :

Sum of square errors

exp :

Experiment

cal :

Calculation

\(f\) :

Feedstock

L :

Liquid phase

S :

Solid phase

L :

Liquid phase

S :

Solid phase

exp:

Experimental data

cal:

The data calculated by the model

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Funding

We thank the financial support of China Petrochemical Corporation (Sinopec Group, 120051-1) for financial support.

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Authors and Affiliations

  1. Research Institute of Petroleum Processing, SINOPEC, Beijing, 100083, China

    Zhen Huang, Xueyan Ju, Hong Nie, Yuanbing Xi & Shi Ding

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Huang, Z., Ju, X., Nie, H. et al. Kinetic parameter estimation and simulation of the second reactor for hydrodesulfurization of diesel. Reac Kinet Mech Cat 136, 23–45 (2023). https://doi.org/10.1007/s11144-023-02361-8

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