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KINETIC MODELLING OF INDUSTRIAL VGO

HYDROCRACKING IN A LIFE TERM OF
CATALYST

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 KINETIC MODELLING OF INDUSTRIAL VGO HYDROCRACKING
IN A LIFE TERM OF CATALYST

Azita Barkhordari, Shohreh Fatemi, Mahdi Daneshpayeh

School of Chemical Engineering, Faculty of Engineering, University of Tehran, Iran

Abstract: Hydrocracking is widely practiced by the refiners to convert vacuum gas oil into
the light fuels. A major issue encountered in hydrocracking reactions, is the decrease of
catalytic activity with time on stream. To compensate catalyst deactivation, it is required to
increase the process temperature until the yield of products being constant. For modeling and
simulation the industrial scale hydrocracking process, two types of kinetic modeling was
studied in this research; continuous and discrete kinetic lump model, and more agreement to
the pilot scale data was found for the discrete model. Genetic algorithm has been carried out
for optimization and tuning the kinetic parameters. The discrete lump model with five lumps
of LPG, naphtha, kerosene, diesel and VGO model was employed to simulate the industrial
VGO hydrocracking process of Bandar-Abbas refinery. The activity function was adjusted
with real outlet yields as the time dependent function for 20 days of operation. As a result,
refinery test runs spanning over three and half years of operation were gathered and used to
validate the model and interpret the simulation results. Good agreement between the
calculated and experimental data with average absolute relative deviation of 8.5% was
observed.

Keywords: hydrocracking, activity function, discrete model, genetic algorithm.

1. INTRODUCTION
Modelling of the complex hydrocracking kinetics has been necessary since the process began being used in the
petroleum refining industry. It is necessary to develop kinetic models which can accurately predict the product
distributions under hydrocracking conditions. Lumping models have been classified as: models based on continuous
mixture and models based on discrete lumps (Ancheyta, et al., 2005). Among all the commercially proven
technologies for heavy fraction hydroprocessing, those using fixed-bed reactors in series loaded with catalysts with
different functionalities are the most used process configurations (Furimsky, , 1998). The main disadvantage of
fixed-bed reactors is the loss of catalyst activity over time as a result of premature catalyst deactivation which
reduces drastically the length of run (Sie, et al., 2001). In the hydrocracking process, the catalyst is known to
deactivate during normal operations (Spare. et al., 1997). To design and predict the expected behavior of heavy oil
upgrading processes at commercial scale, adequate reactor modeling tools are required. It is the objective of this
work to develop a kinetic model based on detailed experimental data, which accounts for major VGO hydrocracking
reactions including deactivation of the catalyst by coking, capable of describing the behavior of both pilot and
industrial scale reactors.

In this work, the two models, continuous and discrete lumping are studied and compared using pilot scale data to
find out the best model fitted to the actual results, then the preferred model would be chosen for the industrial scale
modelling of Bandar-Abbas hydrocracking unit.

2. MODELLING
2.1 Continuous lumping

The continuous lumping model used in this study is that proposed by Laxminarasimhan et al., 1996 which is
described elsewhere. An optimization by genetic algorithm was used for the estimation of the model parameters in

1
which an objective function was formulated as the sum of square deviations between predicted and experimental
concentration of each boiling fraction in the products including cuts of L.P.G, Naphtha, Kerosene, Diesel and
residual VGO.

2.2 Discrete lumping

The second kind model is discrete lumping that contains four parallel first order reactions, in this work, containing
four kinetic parameters in each temperature.
LPG
k1
k2 Naphtha
Feed
k3
k4 Kerosene

Diesel

Fig 1. Kinetic model for discrete lumping

The mass balance of each pseudo-component in the packed bed reactor is written by the plug flow assumption. The
kinetic model was applied to predict the yield of each lump at four space times, and three various temperatures. The
kinetic parameters were optimized by minimization the square of difference between the yields of the model and
pilot experiments.

2.3 Catalyst Deactivation

Hydrocracking catalyst deactivates during the operation because of coke formation, poison deposition and solid state
transformation. Coke seems to have a strong effect on the hydrogenation and has a much stronger effect than others
on the cracking activity (Furimsky. et al., 1998). In the hydrocracking process, the catalyst is known to deactivate
during normal operations. To compensate catalyst deactivation, it is required to increase the process temperature
until the yields of product being constant. On the other hand, the rate of deactivation depends on temperature run
conditions. Coking affects the main kinetic reactions by an activity function. The industrial data and other studies
show that deactivation show an exponential behavior with time (Ancheyta-Juarez. et al., 2000). In this work an
exponential function is used to represent the catalyst activity decay with time:
φ = exp(-kd tc) (1)
Equation 1 has a parameter (kd) other than kinetic parameters which should be predicted. This parameter should be
derived from the industrial data running for a long time.

3. EXPERIMENTAL
3.1 Pilot plant data

The experimental data used for kinetic parameter estimation and comparison of two models (continuous and
discrete) were taken from pilot plant experiments (Fyel-Kady, 1979) in which hydrocracking of vacuum gas oil was
carried out in an isothermal tubular packed bed reactor working at a wide range of operating conditions, such as
reaction temperature of 390, 410 and 430˚C, LHSV (liquid hourly space velocity) of 0.4, 0.667, 1 and 2 hr -1 at a
constant pressure of 10.3 Mpa. The reaction was conducted using a bifunctional Mo-Ni/silica-alumina catalyst,
which was replaced by fresh catalyst after a few operations. With catalyst replacement, the authors were assured it
works in a regime in which catalyst deactivation can be neglected. A more detailed description of the experiments is
given elsewhere. After tuning the kinetic parameters and choosing the best fitted model, continuous or discrete,
simulation of the industrial hydrocracking process would be performed.

3.2 Industrial plant data

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The industrial plant data was received from Isomax unit of Bandar Abbas oil refinery during three and a half years
of operation. In this plant there are two reactors in series, and each reactor is injected by hydrogen make up to keep
hydrogen at excess ratio and to delay catalyst coking. Each reactor is divided into two sections; the first section of
the first reactor is filled with Ni-Mo and the other sections filled with Ni-W on silica-alumina catalysts. It is found
that Ni-Mo was relatively similar activity to Ni-W (Walid., 2004). As the reactors operate at adiabatic condition, the
bed temperature varies from 400 to 425˚C, top to the bottom. We utilized WABT (weight average bed temperature)
in the simulation that would be considered as a constant working temperature for isothermal conditions. The overall
space time of the process is constant and equal to 1.877 hr. The outlet product was split to five lumps of LPG,
naphtha, kerosene, diesel, and VGO, which were considered for validation of the model in industrial scale. The feed,
and reactor specifications, the yield of lump products at initial time (WABT= 400˚C) and final time (WABT=432˚C)
of the process are listed in Tables 1, 2 and 3, respectively.

Table 1. Physical and chemical properties of the feedstock

Property VGO
Sp. Gr. 0.893
Viscosity @ 100˚C 4.8
S, wt% 1.57
Lumps of feed Diesel %10
comp.
VGO %90
(weight fraction)
3
Flow rate (m /hr) 93.27

Table 2. Reactor conditions

Number of reactors 2
Initial inlet temperature(˚C ) 375
Final inlet temperature(˚C ) 395
Reactor inlet pressure (Mpa) 20-21
diameter (3.6 m)
Bed 1
Length (2.115 m)
diameter (3.6 m)
Bed 2
Length (15.185 m)

Table 3. The yield of the lump products at initial and final time of the process, reactor outlet

Products LPG Naphtha Kerosene Diesel Feed

Yield (initial, WABT= 400˚C ) 2.35 18.23 23.18 55 1.23

Yield (final, WABT= 423˚C) 3.15 28.29 18.36 50 0.2

4. RESULTS AND DISCUSSION

In the pilot scale, the twenty data of five lumps at four space times (0.4, 0.667, 1 and 2 hr) were used to estimate the
kinetic parameters at the constant temperature. Since the bed temperature of the industrial reactor may vary from
390 to 430˚C, initial to final step, we have analyzed the pilot data at different temperatures of 390, 410 and 430˚C
for kinetic parameters prediction. The kinetic parameters are independent of time but dependent to the temperature
by Arrhenius equation. The parameters were estimated and optimized by genetic algorithm using the fitness function
of sum of squared error between experimental and predicted yields of the product lumps. The results of continuous
and discrete lumping model are discussed in the following section.

3
4.1 Continuous lumping

There are five kinetic parameters obtained for the continuous model at each temperature. These parameters
increased to ten to predict yields of products at all temperatures. The parity plots of the model and experimental data
at various space times and all temperatures (390, 410 and 430˚C) are presented in Fig 2 after optimization.

90
80
70

Predicted Yeild Wt.%

60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90
Experimental Yeild Wt.%

Fig 2. Yield of products at T=390˚C, 410˚C and 430˚C and space time=0.4, 0.667, 1 and 2 hr for continuous
lumping model.

4.2 Discrete lumping

There are four kinetic parameters in the discrete model which are optimized in each temperature and reported in
Table 4. The constants of Arrhenius equation are derived and reported in Table 4. The parity plots of the product
yields obtained from model and experiments for space times of 0.4, 0.667, 1 and 2 hr. and all temperatures (390, 410
and 430˚C) are shown in Fig 3.

Table 4. Optimized kinetic parameters of discrete model for hydrocracking at each temperature

Temperature(˚C) k1 k2 k3 k4
390 0.1325 0.1005 0.0321 0.0353
410 0.2100 0.1707 0.0876 0.0690
430 0.3116 0.2523 0.2386 0.1383

90
80
70
Predicted Yeild Wt.%

60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90
Experimental Yeild Wt.%

Fig 3. Yield of products at T=390˚C, 410˚C, 430˚C and time=0.4, 0.667, 1 and 2 hr for discrete lumping model.

As can be observed, discrete lumping has a better fit than continuous lumping. The average absolute relative
deviations are determined all temperature for the discrete and continuous lumping model and presented in Table 5.

4
 Table 5. Comparison of relative errors for two models

Model Number of parameters AARD* (%wt)

Discrete 8 5.97
Continuous 10 9.16

1 N
yexpi ym od
* AARD i
100 , N 60
N i 1 yexp i

4.3 Catalyst deactivation

Due to the high precision of discrete lumping, this model was selected and accompanied with catalyst deactivation
for industrial hydrocracking modeling. The optimized activation energies proposed in discrete model were employed
directly into the industrial scale modeling. The other kinetic parameters; pre-exponential terms of Arrhenous eq. as
well as the parameter of deactivation function, were tuned by Genetic Algorithm for well prediction of the yields of
LPG, Naphtha, Kerosene, Diesel and activity coefficient of industrial hydrocracking. The rate of catalyst
deactivation depends on run time. We used the first run temperature for the fresh catalyst to obtain all the pre-
exponential kinetic parameters, and the WABT of the first 20 days (80 data) were used to derive the coefficient of
deactivation. These parameters are reported in table 6. Due to the outlet analysis during the rest of three and a half
year operation of industrial scale, the data were used to validate the simulation results.

Table 6. The pre- exponential kinetic parameters for industrial scale.

Pre- exponential kinetic parameters (hr-1) Activation Energies (Ei/R,˚K)

k01 5.67×106 9.969×103
k02 9.26×107 1.074×104
k03 1.48×1013 2.369×104
k04 2.00×109 1.59×104
kd 3.99×10-4 --

Comparison of experimental and predicted values of the product yields was examined for validation of the model
during the rest of three and a half years operating time, and is observed in Fig. 4. As it is observed, this model shows
a good fit on industrial data.

60

AARD (%wt) = 8.25

50
Predicted Yeild Wt.%

40

30

20 LPG
Naphtha
10 Kerosene
Diesel
0
0 10 20 30 40 50 60
Experimental Yeild Wt.%

Fig 4. Comparison of experiment and model during the three and a half years.

5. CONCLUSION

In this study a discrete five-lump model with four kinetic parameters accompanied with time dependent deactivation
coefficient was developed for modelling of the industrial VGO hydrocracking process. In this study the process of
VGO hydrocracker of Bandar-Abbas Refinery was simulated for a total operation of three and a half year. The

5
 lumps of pseudo-components were LPG, Naphtha, diesel, kerosene and VGO. The model has four temperature
dependent kinetic parameters and a time dependent deactivation coefficient. The proposed discrete lump model was
validated using the actual yields during the left three and a half year period of the reaction to achieve to the ultimate
time to shutting down the process.

100 35

90 LPG Kerosene Diesel Naphtha

30
80

70 25

Product Yeild Wt.%

60
20
50
15
40

30 10
20
5
10

0 0
0 200 400 600 800 1000 1200
Stream Time (hr)

Fig 5. Effect of the stream time on product yield. The curves are derived by the model. The dot plot is presented
from the industrial plant.
1 425

0.9 420

Temperature ( C)
0.8 415
φ & Yeild

0.7 410

0.6 405

0.5 400
deact.coe. Yeild WABT

0.4 395
0 150 300 450 600 750 900 1050 1200
Stream Time (days)

Fig 6. Trend of WABT, φ and liquid yield of VGO versus the time of stream. WABT is presented from the real
operational condition, deactivity and conversion is predicted by the model.

REFERENCES

A.V.Spare (1997), Catalyst Deactivation kinetics from Variable Space-Velocity Experiments, Chemical Engineering
Science, Vol.52, No.24, 4615-4623.
E. Furimsky (1998), Appl. Catal. A 171, 177–206.
Fyel-Kady (1979), Hydrocracking of Vacuum Distillate Fraction over Bifunctional Molybdenum-Nickel / Silica–
Alumina Catalyst, Indian Journal of Technology, Vol 17, 176-183
Jorge Ancheyta, Sergio Sa´nchez, Miguel A. Rodrı´guez (2005), Kinetic modeling of hydrocracking of heavy oil
fractions: A review, Catalysis Today 109 (2005) 76–92
Jorge Ancheyta-Juarez and Rogelio Sotelo-Boyas (2000), Estimation of Kinetic Constants of a Five-Lump Model
for Fluid Catalytic Cracking Process Using Simpler Sub-models, Energy & fuels, 14, 1226-1231
Laxminarasimhan, C. S., Verma, R. P. and Ramachandran (1996), P. A., AICHE J., 1996, 42, 2645
Sie (2001), Appl. Catal. A 212, 129–151.
Walid A.Al-Naeem (2004), Hydrocracking Catalysts for Vacuum Gas Oil and De-Metallized Oil Blend, thesis.

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