Petroleum Science and Technology, 23:1323–1332, 2005

Copyright © Taylor & Francis Inc.

ISSN: 1091-6466 print/1532-2459 online
DOI: 10.1081/LFT-200038172

A Four Lump Kinetic Model for the Simulation of

the Hydrocracking Process

G. Valavarasu, M. Bhaskar, and B. Sairam

Research and Development Centre, Chennai Petroleum Corporation Limited,
Manali, Chennai, India

K. S. Balaraman
Centre for High Technology, New Delhi, India

K. Balu
Chemical Engineering Department, A. C. College of Technology,
Anna University, Chennai, India

Abstract: Hydrocracking is a very important secondary refining process used to con-

vert low value vacuum gas oils into high value fuels. The chemistry of the hydrocrack-
ing process is very complex due to the involvement of high molecular weight complex
hydrocarbons in the reactions. Process modeling and simulation of the hydrocracking
unit is very challenging due to the complexities of chemistry and the process. In the
present work, a mathematical model is described to analyze the performance of the
hydrocracking process in terms of product yields. A four lump discrete lumping ap-
proach is employed with a hydrocracking reaction scheme involving six reactions. The
kinetic constants for the reactions were estimated by minimizing the error between
the experimental and predicted yields of kinetic lumps. Experimental data reported
by Ali et al. (2002) were used to validate the proposed model. The model predictions
were found to agree well with the experimental data. The proposed model can be used
to simulate the performance of commercial hydrocrackers using kinetic parameters
estimated from pilot plant experiments.

Keywords: hydrocracking, discrete lumping, simulation, kinetics

Received 4 March 2004; accepted 8 July 2004.

Address correspondence to G. Valavarasu, Research and Development Centre,
Chennai Petroleum Corporation Limited, Manali, Chennai 600 068, India. E-mail:
gvalavarasu@yahoo.com

1323
1324 G. Valavarasu et al.

INTRODUCTION

The environmental regulations to improve the quality of petroleum fuels led

to the development of hydrocracking as a major refining process. Hydro-
cracking units produce very clean middle distillate products with minimum
impurities, such as sulfur, aromatics, etc. The versatility and flexibility of
the process makes it economically attractive to process different types of
feedstocks to yield various product slates. Hydrocracking units can take up
feedstocks ranging from naphtha to heavy residues and produce products
like LPG, gasoline, jet fuel, or diesel. A typical process flow diagram of the
hydrocracking unit is given in Figure 1.
Hydrocracking employs a dual function catalyst with both cracking and
hydrogenation components. Generally, the cracking components include sil-
ica/ alumina or zeolite, and the hydrogenation components include noble
metals like Pt, Pd, etc., and non-noble metals like Ni, W, Co, Mo, etc. The
hydrocracking of petroleum fractions involves complex chemistry, includ-
ing various reactions, such as hydrogenation-dehydrogenation, isomerization,
C−C bond scission, hydrogen transfer, disproportionation, paring reaction
and ring saturation, ring opening, and dealkylation.
Modeling and simulation of hydrocracking units is a difficult task due to
the complex hydrocracking reaction kinetics. Because hydrocracking is be-
coming a prominent refining process of choice in modern petroleum refineries,
it becomes essential to develop process models to simulate the performance
of hydrocrackers. These models can be used to predict the individual prod-
uct yields and product qualities and for sensitivity analysis, like studying the
effect of operating parameters such as reactor temperature, pressure, space

Figure 1. Process flow diagram of once-through hydrocracking process.

Four Lump Kinetic Model for the Hydrocracking Process 1325

velocity, etc., on product yields and qualities. The models can also be used
for process optimization and control, design of new units, and selection of
suitable hydrocracking catalysts. Because the hydrocracking process involves
various reactions and components, it is not possible to keep track of all
the possible reactions and reaction mechanisms occurring simultaneously in
the reactor.
To simplify the hydrocracking process and to develop simple models,
researchers have studied the hydrocracking process with different modeling
approaches. Some researchers viewed hydrocracking chemistry of petroleum
fractions with respect to the hydrocracking of a set of model compounds or
pseudo compounds. Various experimental yield distribution data on hydro-
cracking of several model compounds have been generated and used as guid-
ing factors for analyzing the chemistry of hydrocracking (Sullivan et al.,
1964). Based on the product distribution patterns generated, the discrete lump-
ing approach was developed initially to describe the hydrocracking chem-
istry and kinetics. Several approaches, like sophisticated model compounds,
structure-oriented lumping, and continuous lumping, have been developed
over the past few decades.
Strangeland and Kittrell (1972) developed different hydrocracker models
based on the discrete lumping approach. They developed models based on
some form of lumping of the compound types present in the feedstock and
products (e.g., lumps of LPG, naphtha, jet fuel, diesel, etc.) and devised
various series and parallel reactions for the hydrocracking reaction scheme. In
all the discrete lumping models, the various individual reactions involved have
been lumped and viewed as an overall hydrocracking reaction, which results
in the distribution of a particular lump of a heavier petroleum fraction into
lighter lumps. The accuracy of discrete lumping models lies in the number
of kinetic lumps chosen to analyze the reactions.
Strangeland (1974) suggested a better and simpler approach for modeling
hydrocracking kinetics, which used analogy of cracking with comminution of
particles to develop a correlative method for predicting the entire TBP curve
of the product for a specified set of operating conditions. Krishna and Sax-
ena (1989) suggested a different approach, one that considers hydrocracking
analogous to axial dispersion. This is a simplistic model with a minimum
number of parameters.
Lakshminarasimhan et al. (1996) developed a mathematical model to
represent the hydrocracking process based on continuous lumping approach.
They used TBP of the reaction mixture as a characterization parameter and
reformulated the mass balance equations in terms of rate constant as a contin-
uous variable. They used a novel distribution function to determine the frac-
tional yield distribution of species and formulated integrodifferential equa-
tions to obtain yields of various fractions as a function of reactor residence
time. This model requires complex mathematical procedures to solve the
resulting integrodifferential equations.
1326 G. Valavarasu et al.

MODEL FORMULATION

In the present work, a four lump mathematical model was formulated with six
significant reactions among them. The proposed model takes the following
kinetic lumps into consideration:

1. Gas (0–32◦ C)
2. Naphtha (32–150◦ C)
3. Middle Distillates (150–343◦ C)
4. VGO Feed (343◦ C+)

The kerosene and diesel fractions were lumped together as middle dis-
tillates. These four lumps are considered to undergo six reactions to yield
different product yield patterns. The proposed reaction scheme for the hydro-
cracker model is represented as follows:

This reaction scheme was developed based on the available information on

the chemistry and kinetics of the hydrocracking process. This reaction scheme
takes into account the reactions of the feedstock, middle distillates, and naph-
tha. In the present work, any given lump reacts to give all the products boiling
below it.
The structure of the mathematical description of the hydrocracking pro-
cess in accordance with the preceding reaction scheme, for the case of plug
flow, can be written as follows:

dCF
= −(k1 + k2 + k3 )CF (1)
dt

dCMD
= k1 CF − k4 CMD − k5 CMD (2)
dt

dCN
= k2 CF + k4 CMD − k6 CN (3)
dt

dCG
= k3 CF + k5 CMD + k6 CN (4)
dt
Four Lump Kinetic Model for the Hydrocracking Process 1327

There are four differential equations to describe the conversion of each

of the kinetic lumps with six kinetic constants. Solving these equations with
the initial product distribution as boundary conditions will yield the product
distribution at various reaction times.
The hydrocracking reactions are considered to be isothermal. The flow
inside the reactor is assumed to follow plug flow pattern. The axial dispersion
and mass transfer effects are neglected in the present work. It is assumed that
a particular lump yields all the products boiling below it.

MODEL ANALYSIS

In recent years, Ali et al. (2002) have generated extensive data on the hydro-
cracking of heavy vacuum gas oil using amorphous silica-alumina and zeo-
lites as catalyst supports. The experimental data reported by Ali et al. (2002)
for the USY-ASA/NiMo catalyst at three different temperatures was used
to validate the proposed model in the present work. The vacuum gas oil
(VGO) feedstock used in the work of Ali et al. (2002) has 91.1 wt% of VGO
(343◦ C+) and 8.9 wt% of middle distillates (150–343◦ C).
The kinetic constants for the model were estimated by minimizing the
error between experimental data and predicted values of product yields. The
error function defined to estimate these parameters, (Y exp −Y pred)2 , was
minimized using a standard optimization procedure. The estimated kinetic
constants are presented in Table 1. Then the model differential equations
were solved to obtain product yield distributions at various residence times
in the reactor using the estimated kinetic parameters. The model equations
were solved to generate data on the effect of reaction time (inverse of liquid
hourly space velocity) and temperature on product yields. The data generated
for the effect of operating temperature on the product yields at a constant
space velocity of 1.0 h−1 are presented in Table 2 and Figure 2. The effect of
reaction time on the product yields for various temperatures (380◦ C, 395◦ C,
and 410◦ C) are shown in Figures 3, 4, and 5.

Table 1. Kinetic parameters for the proposed hydrocracking reactions

Kinetic
parameter
(h−1 ) Kinetic expression k at 410◦ C

k1 1.6665 × 1012 Exp(−3.9366 × 104 /RT ) 0.4462

k2 4.6868 × 1017 Exp(−5.7755 × 104 /RT ) 0.1577
k3 1.3508 × 1014 Exp(−4.9559 × 104 /RT ) 0.0193
k4 4.4232 × 1012 Exp(−4.4285 × 104 /RT ) 0.0333
k5 1.2094 × 1013 Exp(−4.5902 × 104 /RT ) 0.0236
k6 85.1715 Exp(−1.1627 × 104 /RT ) 0.0160
1328 G. Valavarasu et al.

Table 2. Effect of temperature on product yields at a constant

LHSV of 1.0 h−1

Product yield (wt%)

Temperature
(◦ C) Feed Middle distillates Naphtha Gas

350 88.50 11.20 0.24 0.06

370 83.89 14.89 1.00 0.21
390 72.73 22.93 3.66 0.68
410 50.20 36.55 11.27 1.99
430 19.59 48.84 26.51 5.06
450 1.89 43.65 43.98 10.48

From the kinetic parameters, it is observed that the conversion of feed

into naphtha and gas is more temperature sensitive compared to the conversion
into middle distillates. The conversion of middle distillates into naphtha and
gas is also more temperature sensitive.

Effect of Temperature Product Yields

The effect of temperature on the yields of various products was studied at a

constant LHSV of 1.0 h−1 using the model. The yield of the VGO feedstock
was found to reduce as the temperature increased from 350–450◦ C. The yield
of middle distillates increased with increasing temperature from 350–430◦ C
and then dropped above the temperature of 430◦ C. This is due to the increased

Figure 2. Effect of temperature on product yields.

Four Lump Kinetic Model for the Hydrocracking Process 1329

Figure 3. Effect of reaction time at 380◦ C on product yields.

rate of secondary cracking reactions of middle distillate fractions above this

temperature, i.e., at higher reaction severities. The yield of naphtha and gas
increased sharply with increasing temperature. The increase in the yield of
naphtha and gas was lower at lower temperatures. At higher temperatures the
yields of these products was very high, indicating high temperature sensitivity
of these reactions. The predictions of the model were consistent with the
general chemistry of hydrocracking reactions.

Figure 4. Effect of reaction time at 395◦ C on product yields.

1330 G. Valavarasu et al.

Figure 5. Effect of reaction time at 410◦ C on product yields.

Effect of Reaction Time on Product Yields

The effect of reaction time on the product yield pattern was predicted based
on the model output at three different temperatures of 380◦ C, 395◦ C, and
410◦ C. The yield of VGO feedstock decreased with increasing residence
time, while the yields of other products, such as middle distillates, naphtha,
and gas, increased gradually. Similar trends were observed for 380◦ C and
395◦ C. At 410◦ C, the yield of VGO decreased, while the yield of middle
distillates increased sharply initially and then showed a steady value at higher
reaction times. The yields of naphtha and gas were found to increase steadily
with residence time. This also follows the general trend of hydrocracking
reactions.
The model predictions were compared with the experimental data used
in the present work and shown in Table 3. The parity data of the model
predictions vs. experimental data is presented in Figure 6. The proposed

Table 3. Experimental vs. predicted yields for the data of Ali et al. (2002)

Temperature (◦ C) 380 395 410 410

LHSV (h−1 ) 0.97 0.96 1.11 1.05
Reaction time (h) 1.0309 1.0417 0.9009 0.9524

Product yields (wt%) Exp. Pred. Exp. Pred. Exp. Pred. Exp. Pred.

Gas 0.4 0.4 0.9 0.9 1.8 1.8 2.2 1.9

Naphtha 1.9 2.0 4.7 5.1 10.3 10.4 12.2 10.9
Middle distillates 19.0 18.5 24.8 26.5 35.8 34.6 37.3 35.6
Feed 78.7 79.1 69.6 67.5 52.1 53.3 48.3 51.6
Four Lump Kinetic Model for the Hydrocracking Process 1331

Figure 6. Parity plot for the data of Ali et al. (2002).

model was found to represent experimental data satisfactorily with the specific
catalyst and feed system in the range of operating conditions studied. The
model can also be used for any catalyst and feed system, provided kinetic
parameters are estimated from pilot plant experiments.

CONCLUSIONS

A model for the hydrocracking process was developed based on a discrete

lumping approach. The model was validated with the data of Ali et al. (2002)
and found to fit well with the experimental data in the range of operating
conditions studied. The model predictions followed the general trend of the
hydrocracking process. The yield of VGO feed decreased continuously as the
reaction time increased, while the yields of naphtha and gas increased. The
yield of middle distillates initially increased with residence time and then
decreased due to secondary cracking mechanisms. The effect of temperature
on product yields was studied using the model and found to represent the
hydrocracking process. The model can be used for predicting the performance
of commercial hydrocrackers, provided kinetic parameters are determined
from pilot plant experiments.

ACKNOWLEDGMENT

The authors thank the management of Chennai Petroleum Corporation Lim-

ited for allowing us to publish this paper.
1332 G. Valavarasu et al.

NOMENCLATURE

F Feedstock VGO
MD Middle distillates
N Naphtha
G Gas
CF , CMD , CN , CG Concentrations of feedstock, middle distillates,
naphtha, gas, respectively, at time t, wt%
LHSV Liquid hourly space velocity, h−1
k1 , k2 , k3 , k4 , k 5 , k6 First order reaction rate constants for the proposed
reactions, h−1
t Reaction time, h

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hydrocracking catalysts using amorphous silica-alumina and zeolites as
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kinetic description of hydrocracking. Chem. Eng. Sci. 44:703.
Lakshminarasimhan, C. S., Verma, R. P., and Ramachandran, P. A. (1996).
Continuous lumping model for simulation of hydrocracking. AIChE Jour-
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cracking. Ind. Eng. Chem. Proc. Des. Dev. 11(1):15–20.
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