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6Lump Kinetic Model for a Commercial Vacuum Gas Oil Hydrocracker

Article in International Journal of Chemical Reactor Engineering · January 2010

DOI: 10.2202/1542-6580.2164

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 I NTERNATIONAL J OURNAL OF C HEMICAL
R EACTOR E NGINEERING
Volume 8 2010 Article A1

6-Lump Kinetic Model for a Commercial

Vacuum Gas Oil Hydrocracker
Sepehr Sadighi∗ Arshad Ahmad†
S.Reza Seif Mohaddecy‡

∗
Universiti Teknologi Malaysia, sadighi sepehr@yahoo.com
†
Universiti Teknologi Malaysia, arshad@fkkksa.utm.my
‡
mohaddecy@yahoo.com
ISSN 1542-6580
Copyright c 2010 The Berkeley Electronic Press. All rights reserved.
 6-Lump Kinetic Model for a Commercial Vacuum
Gas Oil Hydrocracker
Sepehr Sadighi, Arshad Ahmad, and S.Reza Seif Mohaddecy

Abstract
A 6-lump kinetic model, including a catalyst decay function for hydrocracking
of vacuum gas oil in a commercial plant, is proposed. The model considers vac-
uum gas oil (VGO) and unconverted oil, having boiling point higher than 380-◦ C
(380+◦ C) as one lump. Other lumps are diesel (260-380-◦ C), kerosene (150-260-
◦
C), heavy naphtha (90-150-◦ C), light naphtha (40-90-◦ C) and gases (40-◦ C) as
products. Initially, a kinetic network with thirty coefficients is considered, but fol-
lowing an evaluation using measured data and order of magnitude analysis, mainly
the route passes of converting middle distillates to naphtha lumps are omitted; thus
the number of kinetic coefficients is reduced to eighteen. This result is consistent
with the reported characteristics of amorphous catalyst, which has the tendency
to produce more distillates than naphtha. By using catalyst decay function in the
kinetic model and replacing days on stream with a noble term, called accumulated
feed, the prediction of the final approach during 1.5 years is in good agreement
with the actual commercial data. The average absolute deviation (AAD%) of the
model is less than 5% for all main products. If the residue or unconverted VGO
is considered, the error only increases to 6.94% which is still acceptable for a
commercial model. The results also confirm that the hydrocracking of VGO to
upgraded products is represented better by a second order reaction.

KEYWORDS: vacuum gas oil, hydrocracking, lump kinetic model, catalyst life,
Isomax
Sadighi et al.: 6-Lump Kinetic Model 1

1. Introduction
Hydrocracking is one of the most important processes in a modern refinery to
produce low sulfur diesel. The versatility and flexibility of the process makes it
economically attractive to convert different types of feedstock into various yields
including gas, LPG, naphtha, kerosene and diesel, leading to its widespread
applications. Typical of industrial processes, optimal operation is required to
guarantee profitability and such a task necessitates the use of process models.
These models are used to predict the product yields and qualities so that the effect
of operating parameters such as reactor temperature, pressure, space velocity, as
well as others on product yields and qualities can be understood. The models can
also be used for process optimization and control, design of new units and
selection of suitable hydrocracking catalysts (Valavarasu et al., 2005). However,
the complexity of hydrocracking feed makes it extremely difficult to characterize
and describe its kinetic at a molecular level (Ancheyta et al., 1999). One way of
simplifying the problem is to consider the partition of the species into a few
equivalent classes, the so-called lumps or lumping technique, and then assume
each class is an independent entity (Astarita and Sandler, 1991). This approach is
attractive for kinetic modeling of complex mixtures because of its simplicity
(Ancheyta et al., 2005).
Mosby (1986) reported a model that describes the performance of a residue
hydrotreater using first-order lumped kinetics. The proposed model divides
residue into lumps that are “easy” and “hard” crack. This scheme was used to
determine the kinetic parameters of vacuum gas oil (VGO) hydrocracking. The
first 3-lump model was presented by Yui and Sandford (1989) for gas oil
hydrocracking, performed in a trickle-bed reactor at various different operating
conditions. Then, Callejas and Martinez (1999) studied the kinetics of Maya
residue in a perfectly mixed reactor in the presence of a hydrotreating commercial
catalyst. They used a first-order kinetic model with a 3-lump configuration.
Another 3-lump model with four kinetic constants was presented by Aoyagi et al.
(2003) studied the kinetics of hydrotreating and hydrocracking of conventional
gas oil, coker gas oil and the gas oil derived from Athabasca bitumen. Another 4-
lump model was proposed by Aboul-Gheit (1989) to determine the kinetic
parameters of VGO hydrocracking, expressing composition in molar
concentration. In this kinetic model, VGO was converted to gas, gasoline and
middle distillates. The model had eight kinetic constants that were estimated by
experiments performed in a fixed-bed plug flow micro reactor. Ayasse et al.
(1997) fitted experimental product yields from catalytic hydrocracking of
Athabasca bitumen obtained in a continuous-flow mixed reactor. In this 4-lump
model, all data were obtained at a constant temperature, so the Arrhenius
parameters of the rate constants were only valid in a narrow operating range.

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2 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

Moreover, the model was stoichiometric base, and it was significantly model-
dependent. Because the number of parameters was too large, the approach was not
recommended for more lumps. Anchyeta et al. (1999) proposed a 5-lump kinetic
model for catalytic cracking of gas oil in which the deactivation of catalyst was
considered as an exponential law with one decay parameter depending on the
time-on stream. Almeida et al. (2005) presented a 5-lump kinetic model for
hydroconversion of Marlim vacuum residue in which by utilizing fourteen
experiments in the batch reactor, 26 coefficients were estimated for the kinetic
model. Sanchez et al. (2005) proposed a five-lump kinetic model with 10 kinetic
parameters for moderate hydrocracking of heavy oils. Singh et al. (2005) also
adopted a five-lump modeling strategy in predicting the yield of mild thermal
cracking of vacuum residue.
The complexity of real feedstock suggests that models based on lumping
theory will continue to be used for the study of hydrocracking reaction kinetics.
However, more sophisticated and accurate approaches are required to provide
better understanding and to ensure that the model is a reasonable representation of
heavy oil hydrocracking kinetics (Ancheyta et al., 2005).
Although many research outcomes on hydrocracking have been published,
kinetic aspects with real feed and industrial scale, and deactivation model of the
catalyst have not received much attention. In line with this issue, this paper
proposes a practical kinetic model with 6 lumps that includes of VGO, diesel,
kerosene, light naphtha, heavy naphtha and gases, which calculates the yield of all
products in an industrial hydrocracking unit, taking into account catalyst
deactivation.
The advantage of the presented approach is lumping of middle distillate and
naphtha to four discriminated groups which are diesel and kerosene (as middle
distillate) as well as heavy and light naphtha (as naphtha). Therefore, the
evaluation of the catalyst from operating and economical aspects can be
performed more accurate because each of the intended products has different
worth, usage and finishing process. Moreover, it is the first model including of
decay parameters for all reaction paths to simulate the effect of poisoning agents
like coke and metals. Also, by introducing accumulation term instead of days on
stream in the deactivation function, the accuracy of the hydrocracking model is
improved.

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Sadighi et al.: 6-Lump Kinetic Model 3

2- Hydrocracking kinetic model

Previous works for modeling of hydocracking unit were not successful when six
or seven lumps were used (Ancheyta et al., 2005) and as such, studies on product
distributions did not achieve the desired details.
This work considers six lumps, i.e., VGO (or unconverted oil), diesel,
kerosene, heavy naphtha, light naphtha and gas to match main products in the
refineries. Fig.1 illustrates the process pathways associated with the strategy. Note
that if all pathways of reactions are considered, the model would include of thirty
kinetic parameters and fifteen decay constants for the catalyst deactivation. All
parameters should be estimated using experimental data, and it is laborious. Some
judgments are normally welcome to reduce the model complexity, without
sacrificing the accuracy.

Figure 1. The complete 6-lump kinetic model

Upon close scrutiny of the system under consideration, the model can be
reduced to what is shown in Fig.2 where only sixteen kinetic parameters and eight
constants for catalyst deactivation, totally twenty-four parameters, are estimated.
The reduction of parameters is done according to the order of magnitude of rate
constants in comparison to the highest one in the average process temperature
which will be discussed later.

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4 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

Figure 2. The reduced 6-lump kinetic model

3. Data gathering
3.1 Hydrocracking process
A commercial first stage hydrocracking unit, with the commercial name of
Isomax licensed by UOP Company, was chosen as a case study. The feed of the
hydrocracking reactor was a mixture of fresh vacuum gas oil (Table 1) and
unconverted oil, recycled from the separation section at the end of the process
(Fig.3).
The combined feed (with combined feed ratio or CFR about to 1.5) was
mixed with hydrogen and heated before entering the reactor. Since the strategy for
modeling is lumping of feed and products, hydrogen is neglected in the mass
balance. The hydrocracking reactor had 4 beds with a total amount of loaded
catalyst in the reactor about 69000 kg. The hydrocracking catalyst was an
amorphous type with specifications as displayed in Table.2. The product and feed
samples were analyzed according to the ASTM standard procedures.

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Sadighi et al.: 6-Lump Kinetic Model 5

Figure 3. A simplified scheme of hydrocracking process

Table 1. Properties of fresh vacuum gas oil

Density at 15°C g /cm3 0.91

Density at 50°C g /cm3 0.89
Sulfur wt% 1.9
Total Nitrogen ppmwt 1018
Conradson Carbon wt% 0.04
Refractive index at 20°C - 1.51
Ultimate analysis
C wt% 85.9
H wt% 12.1
Distillation analysis ( ASTM D1160 )
IBP °C 333
10% °C 381.1
30% °C 411.7
50% °C 431.7
70% °C 453.3
90% °C 480.0
FBP °C 505.0

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6 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

Table 2. Catalyst Specifications of hydrocracking process

Shape - Extrude
Diameter mm 2.5
Length mm 6.1
Surface Area m2/g 176
Pore Volume m2/g 0.51
Bulk Density g/ml 0.75
Chemical Properties
MoO3 wt % 10.5
NiO wt % 2.35
P wt % 1.35
Na2O wt % 0.05

3.2 Operating conditions

From the start of run (SOR) to the middle of run (MOR), fourteen set of data
comprising of flow rates, pressure and temperature were gathered from the target
commercial hydrocracking process (see Table 3). The main products of the
process were gases, LPG, light naphtha (LN), Heavy naphtha (HN), kerosene,
diesel and unconverted oil (offtest). Performing mass balance around the unit
showed that the error for all selected experiments was between 1% and 2%,
mainly related to the consumed hydrogen for hydrocracking (HDC) and
hydrodearomatization (HDA) reactions. This error was normalized on all lumps.
The average density and boiling point range of these products from the SOR
to the MOR are presented in Table 4. Based on the gathered data, it was noted that
properties of the offtest or unconverted oil was close to that of VGO feedstock.
Therefore considering them as one lump was a reasonable assumption.

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Sadighi et al.: 6-Lump Kinetic Model 7

Table 3. Feed flowrate and reactor operating condition

Fresh Feed Recycle Feed WABT PH2

Day
(kg/hr) (kg/hr) (°C) (Mpa)
0 48545.5 32364.3 397.4 15
31 48515.4 32344.2 397.7 15
60 48515.4 32344.2 397.7 15
61 48515.4 32344.2 397.9 15
92 49445.8 32965.2 397.7 15
122 39245.2 26162.8 378.0 15
184 48567.6 32378.4 398.3 15
213 48567.6 32378.4 398.3 15
244 51139.9 34092.6 399.1 15
305 50038.6 33359.1 399.5 15
336 49841.7 33226.5 399.7 15
395 48722.3 32480.9 399.8 15
425 49940.2 33294.8 399.9 15
456 49867.8 33244.5 399.5 15

Table 4. Average properties of hydrocracking product

IBP-FBP IBP-FBP
Sp.gr Actual Model
(°C) (°C)
LPG 0.35 40- 40
LN 0.684 37-89 40-90
HN 0.744 86-146 90-150
Kerosene 0.796 148-267 150-260
Diesel 0.823 266-378 260-380
Offtest 0.915 313-484 380+

4. Industrial fixed-bed hydrocracking reactor model

Mathematical models for a trickle-bed catalytic reactor can be complex due to the
many microscopic and macroscopic effects occurring inside the reactor; flow
patterns of both phases, size and shape of a catalyst particles, wetting of the
catalyst pores with liquid phase, pressure drop, intraparticle gradients, thermal
effects and, of course, kinetics on the catalyst surface (Sertic-Bionda et al., 2005).
In pilot or laboratory fixed–bed reactors these non-idealities made researchers to
obey from some rules to assume the reactor in a plug flow regime (Klinken et al.,
1980; Bej et al., 2000). But a commercial hydrocracking can be virtually plug

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8 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

flow (Mederos et al., 2009; Mary et al., 2009) which increases the accuracy of the
yield prediction and reliability of the estimated kinetic parameters. Therefore, all
phenomena which create non idealities can be neglected.

4.1 Kinetic expression

For each reaction, a kinetic expression ( R ) is formulated as the function of mass
concentration ( C ), deactivation function ( ϕ ) and kinetic parameters ( k 0 and E ).
The reaction of VGO hydrocracking to yield products is considered as either first
order or second order, to be confirmed by kinetic estimation using gathered data.
It is well known that the deactivation of a catalyst is caused by its surface coke.
So it is supposed that catalyst’s deactivation is a time function. The exponential
law is assumed for catalyst decay ( ϕ ), which depends on deactivation constant
( α ) and time-on-stream ( t c ) or accumulated feed term ( AF ), discussed later.
The previous researchers (Ancheyta et al., 1999; Forissier et al., 1991) used
one or two decay parameters to simplify the overall kinetic model and parameter
estimation. This assumption was also used in other works in the modeling of
catalytic reformers (Padmavati and Chaudhuri, 1997) and fluid catalytic crackers
(Hongjun et al., 2006). In these works, a non-selective deactivation model, based
on the hypothesis that ( ϕ ) was the same for all reactions was used to simplify the
overall kinetic model and parameter estimation. But, in this research, a selective
deactivation is applied in which different decay parameters are used for all
possible reaction paths. This kind of selective models can approximate more the
reality and would give better results (Corella et al., 1988).
According to above assumptions, kinetic constants of the model are
expressed as:

− EFj
Vacuum gas oil or Feed ( F ): k Fj = ϕ Fj k0 Fj exp( ) (1)
RT

Note that j in Eq.1 represents diesel ( D ), kerosene ( K ), heavy naphtha ( HN ),

light naphtha ( LN ) and gas ( G ) lumps.

− EDj '
Diesel ( D ): k Dj ' = ϕ Dj ' k0 Dj ' exp( ) (2)
RT

j ' in Eq.2 represents kerosene ( K ), heavy naphtha ( HN ), light naphtha ( LN )

and gas ( G ) lumps.

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Sadighi et al.: 6-Lump Kinetic Model 9

− EKj ''
Kerosene ( K ): k Kj '' = ϕ Kj '' k0 Kj '' exp( ) (3)
RT

j ' ' in Eq.3 are heavy naphtha ( HN ), light naphtha ( LN ) and gas ( G ) lumps.

− EHNj '''
Heavy Naphtha ( HN ): k HNj ''' = ϕ HNj ''' k 0 HNj ''' exp( ) (4)
RT

j ' ' ' in Eq.4 are light naphtha ( LN ) and gas ( G ) lumps.

− ELNG
Light Naphtha ( LN ): k LNG = ϕ LNG k0 LNG exp( ) (5)
RT

In equations 1 to 5, the T and R are the absolute value of weight average bed
temperature ( WABT ) and ideal gas constant, respectively. The decay function
( ϕ ) in these equations is formulated as the following (Levenspiel, 2001):

Decay function ( ϕ ): ϕij = exp(−α ij × Life) (6)

In Eq.6, α ij shows the deactivation constant for converting i lump to j one in

hydrocracking process. They are estimated from actual data as model parameters
to simulate the effect of coke deposition on the rate of hydrocracking reactions.
Also, note that Life value in this equation can be expressed in days-on-stream ( tc )
or accumulated feed ( AF ), discussed later.
Thus the reaction rates ( R ) can be formulated as the following:

G
n
Vacuum gas oil reaction ( RF ): RF = ( ∑ ϕ Fj k Fj )C F (7)
j=D

C F in Eq.7 is the mass concentration of VGO and n is the order of reaction which
can be 1 or 2.
G
n
Diesel ( RD ): RD = ϕ FD k FD C F − ∑ ϕ Dj ' k Dj 'C D (8)
j '= K
G
n
Kerosene ( RK ): RK = ϕ FK k FK C F + ϕ DK k DK C D − ∑ϕ
j ''= HN
k CK
Kj ' Kj ' (9)

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10 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

Heavy Naphtha ( RHN ):

G
n
RHN = ϕ FHN k FHN CF + ϕ DHN k DHN CD + ϕ KHN k KHN C K − ∑ϕ
j ' ' = LN
k C HN
HNj ' ' HNj '' (10)

Light Naphtha ( RLN ):

n
RLN = ϕ FLN k FLN C F + ϕ DLN k DLN C D + ϕ KLN k KLN C K + ϕ HNLN k HNLN C HN − ϕ LNG k LNG C LN (11)

Gas ( RG ):
n
RG = ϕ FG k FG C F + ϕ DG k DG C D + ϕ KG k KG C K + ϕ HNG k HNG C HN + ϕ LNG k LNG C LN (12)

4.2 Mass balance

In the interest of improving the accuracy of the developed model, the volumetric
flow rate in the reactor ( υ ) is considered variable; it is calculated according to the
density of the output stream (Eq.17). Thus equations 13 to 17 for the catalyst bed
should be solved simultaneously.

∂ (υC j )
± Rj = 0 (13)
∂ω

In Eq.13, j is from feed lump ( F ) to gas ( G ); C is mass concentration of lump;

ω is weight of catalyst, and "−" sign is for reactant (feed or VGO), as well as "+"
sign is for products.

∂ ( ρν )
=0 (14)
∂ω

G
Fm = ∑ C jυ (15)
j =F

C j .ν
Xj = (16)
F

G
ρ = ∑ X jρj (17)
j =F

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Sadighi et al.: 6-Lump Kinetic Model 11

In equations 14 to 17, ρ and ν are density of stream and volume flow rate
through reactor, respectively; Fm is the mass flow rate of stream passing through
the bed; X and ρ j are mass fraction and density of lumps (Table 4), respectively.
After calculating the mass concentration and volume flow rate of each lump in the
effluent stream of the reactor, the product yields can be found as the following:

C j .υ .(1 − Rs j )
Yj = (18)
Ff

In equation 18, Rs and F f are recycle fraction and mass flow rate of fresh VGO,
respectively. It is obvious that the former parameter for all lumps, except to
unconverted oil, is zero.
Finally, for parameter estimation, sum of squared error, SQE , as given
below, is minimized (Ancheyta, 1999):

Nt G
meas pred 2
SQE = ∑ ∑ (Y jk − Y jk ) (19)
k =1 j = F

meas pred
In Eq.19, N t , Y j and Y j are the number of test runs, measured product yield
and the predicted by model, respectively.
The hydrocracking reaction model according to equations 1 to 19 is coded
and solved in Aspen Custom Modeler (Aspen Tech) programming environment.
In order to estimate kinetic parameters, the objective function presented in Eq.19
is minimized by Nelder-Mead method.
The estimated parameters and the adequacy of regression are checked with
analysis of variance (ANOVA) using R-adjusted and Fischer test with 95%
probability [Clarke and Kempson, 1997; Montgomery, 2001]. The ANOVA of all
discussed strategies in the next section are studied and the adequacy of them is
tested using static Fischer ( F ) with 5% critical level. Also, to compare the
simulated and measured product values, absolute average error ( AAE ) and
absolute average deviation ( AAD ) (Marafi et al., 2008) were calculated by the
following equations:

meas pred
abs (Yk − Yk )
AAE % = 100 (20)
Nt

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12 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

Nt meas pred 2
(Yk − Yk )
∑ meas 2
k =1 Yk
AAD% = 100 % (21)
Nt

5. Results and discussions

5.1 Model without Decay Function
The thirty kinetic parameters for the assumed model (Fig.1), without decay
functions, were estimated, using measured industrial data, presented in Table 5.
All reactions were considered first order (Mohanty et al., 1991). In this table, the
ratio of magnitude of all rate constants to the highest one (kKHN or kerosene to
heavy naphtha) were calculated.
After parameter estimation and simulation, the AAE % and AAD % for the
first strategy, called complete model, were 0.502% and 8.16%, respectively in
comparison to measured data. In Table 6, the value of F = 816.95 for this
approach is enough higher than Fcrit (29,54,0.05) = 1.65 , demonstrated that the
regressed model fitted well the observed values.
Estimated parameters in Table 5 reveals that the rate constant of reactions in
the average WABT (397.18 0C) for kFG, kDHN, kDLN, kDG, kKLN, kKG and kHNLN are
significantly lower compared to highest value (kKHN). It means that these
reactions, which are related to conversion of feed to gas (kFG), middle distillates to
naphtha cuts (kDHN, kDLN and kKLN), middle distillates to gas (kDG and kKG) and
heavy to light naphtha (kHNLN) have much lower selectivity so that they can be
omitted. This phenomenon is consistent with the literatures (Scherzer and Gruia,
1996; Ali et al., 2002) that reported amorphous catalysts having tendency to
produce higher amounts of middle distillates and lower amounts of naphtha
fractions, thus explaining the reasons for the low rate constants of kDHN, kDLN,
kDG, kKLN and kKG and higher rates of feed to middle distillates (kFD and kFK) than
feed to naphtha cuts (kFHN and kFLN). Also, we suppose that low rate constants for
converting VGO, diesel and kerosene to gas are rational because lighter products
have more tendencies to be cracked to gas in hydrocracking unit and for cracking
heavier chains like VGO, diesel and kerosene more severity is needed. Because
diesel has low tendency to be converted to light products, its yield is higher than
kerosene. Moreover, the high value of kKHN can be a good reason for tendency of
process to produce more heavy naphtha than light naphtha.
After eliminating the low rate reaction paths (<6E-6) and estimating the
parameters again, the AAE % and AAD % of resulted reduced model were found
to be 0.496% and 8.11%, respectively which can be considered acceptable thus

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Sadighi et al.: 6-Lump Kinetic Model 13

justifying the removal of the less important reactions. The value of F = 2013.5
for this strategy, presented in Table 6, was higher than Fcrit (15,68,0.05) = 1.8 ,
confirmed that the regressed model fitted well the observed values.

Table 5. Kinetic parameters for the complete model

Frequency Factor Activation Energy Rate constant
Order
(hr-1) (kcal/mol) (hr-1)
k0FD 4.84 EFD 12.06 kFD 5.62E-04 0.67
k0FK 14.21 EFK 13.65 kFK 5.01E-04 0.60
k0FHN 6010.61 EFHN 25.37 kFHN 3.19E-05 0.04
k0FLN 14.955 EFLN 16.29 kFLN 7.25E-05 0.09
k0FG 1.0552 EFG 57.13 kFG 2.45E-19 3.E-16
k0DK 9503.7 EDK 23.58 kDK 1.93E-04 0.23
k0DHN 0.003 EDHN 24.19 kDHN 3.79E-11 4.54E-08
k0DLN 0.739 EDLN 30.93 kDLN 6.02E-11 7.21E-08
k0DG 1.274 EDG 33.96 kDG 1.07E-11 1.28E-08
k0KHN 0.223 EKHN 7.44 kKHN 8.35E-04 1
k0KLN 0.879 EKLN 49.72 kKLN 5.31E-17 6.36E-14
k0KG 0.002 EKG 17.07 kKG 4.30E-09 5.2E-06
k0HNLN 0.227 EHNLN 93.96 kHNLN 5.10E-32 6.11E-29
k0HNG 0.304 EHNG 8.71 kHNG 4.39E-04 0.5
k0LNG 0.044 ELNG 8.28 kLNG 8.76E-05 0.10
Table 6. Analysis of variance for different modeling approaches
Complete Reduced Decay Accumulated Final
model model model model model
R-adjusted 99.77 99.95 99.92 99.92 99.94
DF* of regression 29 15 23 23 23
DF* of residual 54 68 60 60 60
F-test 816.95 2013.50 1228.38 1229.02 1574.33
F-critical 1.65 1.8 1.71 1.71 1.71
*DF is degree of freedom

5.2 Model with Decay Function

Attempting to make the model closer to actual industrial scenario, a catalyst decay
function ( ϕ ) was introduced (Eq.6). This function multiplied to rate constants
(Eqs.1 to 5) to show decreasing of hydrocracking capability with time. The
deactivation parameters ( α ij ) were estimated like kinetic parameters to minimize

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14 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

the sum of square errors. At this step, tc, in the decay function was time-on-stream
(day). The estimated deactivation and kinetic parameters are presented in Table 7.
After implementing the deactivation model, the AAE % and AAD % of the model
reduced to 0.485% and 8.06%, respectively. For this strategy, called decay model,
the value of F = 1228.38 was higher than Fcrit (23,60,0.05) = 1.71 , approved that
the regressed model fitted well the observed values (Table 6).
Decay constants in Table 7 show that all reactions were affected by the
deactivation of the catalyst which was unfavorable to yield main products. It can
be concluded that decay constants for converting feed to naphtha cuts ( α FHN and
α FLN ) were higher than those for middle distillates ( α FD and α FK ) ; thus the
former were the most impressed desirable reactions. These phenomena can justify
the necessity for increasing the bed temperature by the time in Isomax process
from SOR to EOR (end of run) to maintain the ability of the catalyst to yield main
products, especially heavy naphtha.
To have a better view from WHSV during the process, the diagram
demonstrating the WHSV versus time was shown in Fig.4. Here, it can be noted
that there is a discrepancy in the data trend, especially for the 122th day of life. It
demonstrates that the catalyst did not follow a uniform passage of feed. Therefore,
using days on stream as life in decay function could increase the error.

To further improve the model, a new term called accumulated feed ( AF) was
used to be replaced with tc . This term was estimated using the following
relationship:
i

AF =
∑ time=0
( Fi × tc i )
(22)
Wcat
AF , is a dimensionless term representing the total amount of feed (kg) passed on
total catalyst weight at specific life time.

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Sadighi et al.: 6-Lump Kinetic Model 15

Table 7. Kinetic and deactivation parameter for the model with decay function
Frequency Factor Activation Energy Decay constants
(hr-1) (kcal/mol) (hr-1)
k0FD 5.67 EFD 12.27 α FD 6.45E-05
k0FK 16.72 EFK 13.93 α FK 1.16E-09
k0FHN 15327.9 EFHN 26.01 α FHN 1.28E-04
k0FLN 12.111 EFLN 15.82 α FLN 1.10E-04
k0FG - EFG - α FG -
k0DK 7360.7 EDK 23.21 α DK 6.11E-04
k0DHN - EDHN - α DHN -
k0DLN - EDLN - α DLN -
k0DG - EDG - α DG -
k0KHN 0.193 EKHN 7.43 α KHN 1.66E-04
k0KLN - EKLN - α KLN -
k0KG - EKG - α KG -
k0HNLN - EHNLN - α HNLN -
k0HNG 0.163 EHNG 8.59 α HNG 4.11E-05
k0LNG 0.365 ELNG 9.10 α LNG 2.47E-04

Figure 4. WHSV of the reactor vs. Catalyst life

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16 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

Following the replacement of tc with AF, the decay and kinetic parameters
were estimated again and they were presented in Table 8. Now, the AAE % and
AAD % of the predicted yields in comparison with measured data reduced to
0.48% and 7.94%, slightly better than the previous results. The value of
F = 1229.02 according to Table 6 for accumulated model was higher than
Fcrit (23,60,0.05) = 1.71 , approved that the regressed model fitted well the
observed values in this strategy.

Table 8. Kinetic and deactivation parameter for the model with accumulated decay function
Frequency Factor Activation Energy Decay constants
(hr-1) (kcal/mol)
k0FD 3.898 EFD 11.81 α FD 8.56E-07
k0FK 15.656 EFK 15.66 α FK 2.45E-06
k0FHN 46841.4 EFHN 27.11 α FHN 1.83E-06
k0FLN 52.270 EFLN 17.96 α FLN 5.21E-06
k0FG - EFG - α FG -
k0DK 1193.9 EDK 21.55 α DK 5.30E-07
k0DHN - EDHN - α DHN -
k0DLN - EDLN - α DLN -
k0DG - EDG - α DG -
k0KHN 0.019 EKHN 4.43 α KHN 6.09E-06
k0KLN - EKLN - α KLN -
k0KG - EKG - α KG -
k0HNLN - EHNLN - α HNLN -
k0HNG 0.009 EHNG 4.03 α HNG 9.05E-09
k0LNG 0.221 ELNG 9.47 α LNG 1.48E-03

As followed in literatures (Ancheyta et al., 1999; Trejo and Ancheyta, 2005),

improving the model accuracy may be achieved in catalytic cracking of VGO and
hydrotreating of asphaltenes by considering the reaction of feed as second order.
Taking this approach and again subjecting the model to be fitted by the industrial
data, the estimated kinetic parameters were obtained and presented in Table 9.
The AAE % and AAD % of the model were 0.426% and 6.94%, confirming that
this assumption is also applicable for hydrocracking of VGO. According to the
last column of Table 6, the value of Fcrit (23,60,0.05) was 1.71 for the final
estimating approach, called final model, which was enough lower than

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Sadighi et al.: 6-Lump Kinetic Model 17

F = 1574.33 to confirm the agreement of predicted yields by model with the

actual ones gathered from Isomax plant.

Table 9. Kinetic and deactivation parameter for the model with second order
Frequency Factor Activation Energy Decay constants
(hr-1) (kcal/mol)
k0FD 0.029 EFD 13.72 α FD 2.59E-06
k0FK 0.142 EFK 15.87 α FK 2.76E-06
k0FHN 829.0 EFHN 29.88 α FHN 3.94E-10
k0FLN 0.091 EFLN 17.88 α FLN 4.25E-06
k0FG - EFG - α FG -
k0DK 1427.4 EDK 22.31 α DK 1.75E-03
k0DHN - EDHN - α DHN -
k0DLN - EDLN - α DLN -
k0DG - EDG - α DG -
k0KHN 0.007 EKHN 3.376 α KHN 1.06E-05
k0KLN - EKLN - α KLN -
k0KG - EKG - α KG -
k0HNLN - EHNLN - α HNLN -
k0HNG 0.008 EHNG 3.94 α HNG 1.72E-08
k0LNG 0.919 ELNG 11.59 α LNG 1.50E-03

From Table 9, it is obvious that apparent activation energy of VGO

hydrocracking to middle distillate and naphtha are about 13-15.9 kcal/mol and 17-
28 kcal/mol, respectively. The reported ones by Aboul-Ghiet (1989) for
hydrocracking of VGO to middle distillate and naphtha were about 13-17.5
kcal/mol and 22-24 kcal/mol, respectively, not far from this research.
Furthermore, the activation energy of catalytic cracking of naphtha to gas,
reported by Ancheyta et al. (1999) was 9-9.92 kcal/mol, close to the reported one
in this work. All estimated activation energies in this paper are lower than
reported values by Sanchez et al. (2005) for a 5-lump model. It seems because
VGO feed in Sanchez work was the product of heavy residue, its cracking to
lighter lumps needs higher activation energy than the lighter VGO used in this
current work.
The average values of activation energy presented by Singh (2005) for mild
thermal cracking of VGO to distillate and naphtha as well as distillate to naphtha

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18 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

were 25 kcal/mol and 30.88 kcal/mol, respectively. It is obvious that the value
presented in this current work is lower than thermal cracking process because of
existing catalyst and hydrogen. Because this investigation is the first lumping
approach in which light and heavy naphtha as well as diesel and kerosene are
characterized separately, the apparent activation energies of converting middle
distillate and naphtha lumps to each other cannot be compared to others.
The final reaction scheme for 6-lump VGO hydrocracking is shown in the
Figure 2 with the title of reduced model. Figures 5 to 9 show comparisons
between measured product yields from industrial hydrocracking reactor and the
model predictions. It can be concluded that the predicted yields by model are in
good agreement with the measured values from Isomax unit.

Figure 5. Comparison of predicted diesel yield of model with measured data

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Sadighi et al.: 6-Lump Kinetic Model 19

Figure 6. Comparison of predicted kerosene yield of model with measured data

Figure 7. Comparison of predicted H.Naphtha yield of model with measured data

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20 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

Figure 8. Comparison of predicted L.Naphtha yield of model with measured data

Figure 9. Comparison of predicted Gas yield of model with measured data

The AAE % and AAD % of residue, diesel, kerosene, heavy naphtha, light
naphtha and gas are presented in Table 10. The prediction of final modeling
approach including of sixteen rate parameters and eight deactivation constants,
estimated from eighty-four observations, for all products, except residue, was
acceptable. The AAD % of model prediction in comparison to measured data for
all products is less than 5%, supposed to be acceptable for a lumping strategy

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Sadighi et al.: 6-Lump Kinetic Model 21

according to similar researches (Ancheyta et al., 1999; Trejo and Ancheyta, 2005;
Sing et al., 2005; Marafi et al., 2008). We thought that the flagrant error for the
residue is because of its swinging with diesel, concluded from Table 4, as if the
initial cuts of them cannot be separated completely in the separation unit of
Isomax. Therefore, it tremendously impressed the accuracy of the model for
prediction of offtest or residue. Because it is not the main product of Isomax and
its yield is quite low, it cannot affect the application of the model to predict the
yield of precious and strategic products such as naphtha, kerosene and diesel.

Table 10 . AAE% and AAD% of model prediction in comparison to measured data

AAE% AAD%
Residue 0.610 27.66
Diesel 0.695 1.63
Kerosene 0.583 1.79
H.Naphthaa 0.325 2.38
L.Naphtha 0.260 4.37
Gas 0.083 3.83
Ave% 0.426 6.94

6. Conclusions
In this research, a 6-lump kinetic model for hydrocracking of vacuum gas oil
(VGO) was proposed. The model includes gas, light naphtha, heavy naphtha,
kerosene, diesel and unconverted VGO or off test as lumps and sixteen kinetic
parameters as well as eight decay constants for the catalyst deactivation. The
advantage of this model over the previous works was its capability to predict the
light and heavy naphtha as well as diesel and kerosene separately from other
lumps, important to better economically evaluation of the hydrocracking process.
Fourteen test runs were gathered during 1.5 years from a commercial
hydrocracking unit and they were used to tune the model constants. The estimated
parameters showed that the tendency of the catalyst to crack VGO and diesel to
gas and naphtha was negligible, compatible with the nature of amorphous
catalysts. After omitting these reactions and using a selective decay function to
consider the life of the catalyst in the model, the absolute average deviation of the
model decreased from 8.06% to 7.94%. To improve the prediction of the model,
the days on stream in the decay function was replaced with a new dimensionless
term, called accumulated feed and the hydrocracking of VGO to all lighter
products was assumed as second order reaction. Product yields predicted after

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22 International Journal of Chemical Reactor Engineering Vol. 8 [2010], Article A1

applying these strategies showed an acceptable agreement with absolute average

deviation of 6.04%. But, the error for main products including of gas, light and
heavy naphtha, kerosene and diesel was less than 5%, supposed to be acceptable
for a commercial hydrocracking model.

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