Comparison of Lumping Approaches To Predict The Product Yield in A Dual Bed VGO Hydrocracker

INTERNATIONAL JOURNAL OF CHEMICAL
REACTOR ENGINEERING
Volume 9 2011 Article A4
Comparison of Lumping Approaches to
Predict the Product Yield in a Dual Bed
VGO Hydrocracker
Sepehr Sadighi
Arshad Ahmad
Mansoor Shirvani
Universiti Teknologi Malaysia, sadighi sepehr@yahoo.com
Universiti Teknologi Malaysia, arshad@fkkksa.utm.my
Iran University of Science & Technology, shirvani.m@iust.ac.ir

ISSN 1542-6580
Copyright c 2011 The Berkeley Electronic Press. All rights reserved.
Comparison of Lumping Approaches to Predict the
Product Yield in a Dual Bed VGO Hydrocracker
Sepehr Sadighi, Arshad Ahmad, and Mansoor Shirvani
Abstract
In this research, to predict the product yields of a pilot scale VGO hydroc-
racking reactor charged with mono functional hydrotreating and hydrocracking
catalysts, two different four-lump models are developed. The rst one, called
combined bed model, is a simplex in which there is no boundary between hy-
drotreating and hydrocracking reactions through the reactor. The second one,
called dual bed model, is a rigorous model in which hydrogen consumption and
hydrotreating reactions are included. In this way, the reactor is subdivided into
two different layers, so the effect of hydrotreating reactions on the hydrocrack-
ing section can be considered. Results show that the absolute average deviation
(AAD%) of the yield prediction for the combined bed and the dual bed models are
8.23 percent and 5.87 percent, respectively. The main reason for the lower average
deviation of the dual bed model is its higher accuracy to predict the yield of gas
which is also the major advantage of this approach. However, the simplicity of the
combined bed model can make it more applicable and attractive, especially when
hydrogen consumption as well as sulfur, nitrogen and aromatic specications of
the feed and products are not accessible.
KEYWORDS: hydrotreating, hydrocracking, lump kinetic model, hydrogen con-
sumption, dual bed hydrocracking reactor
1. Introduction
Processing of heavy feedstock into high value products has interested refiners
worldwide due to increasing demand of light oil fractions and decreasing reserves
of low sulfur crude oils. With the consideration of profit margins, hydrocracking
has gained interest because of being an appropriate option for upgrading of heavy
feedstock into various products. Moreover, it is a process in a refinery which
improves the quality and quantity of the refined petroleum products.
Among all the commercially proven technologies for hydrocracking, those
using fixed-bed reactors in series charged with different functionalities are very
favorable. But, the main disadvantage of fixed-bed reactors is the loss of catalyst
activity over time as a result of catalyst deactivation which reduces drastically the
length of run (Alvarez et al., 2008). Typical reactions which occur in
hydrocracking are (i) hydrogenation of polyaromatics, sulfur and nitrogen
containing compounds, and (ii) cracking of higher carbon number (cyclo)-alkanes
to lighter fractions (Balasubramanian & Pushpavanam, 2008). During the
hydrotrating process (HDT) a portion of the hydrogen, dependent to
hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) reactions, is
consumed and most of heavy sulfur and nitrogen compounds are converted to the
light products.
Kinetic modeling of the reactions occurring in a hydrocracker and
estimation of the rate coefficients is a crucial step in its design. An accurate
estimation of the rate coefficients will enable us to optimize and control the
product yield distribution in a hydrocracker. Ideally, the kinetic model should take
into account all elementary reactions which the different components in the
feedstock undergo. 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 (Krambeck, 1991). The major
lumping methods interested in hydrocracking are continuum theory of lumping
and discrete lumping approaches. In the first method, the reactive mixture is
considered to form a continuum mixture with respect to its properties such as
boiling point, molecular weight, carbon number or chemical species (Basak et al.,
2004; Elizalde et al., 2009). But, in the discrete lumping approach, the reaction
network is reduced to the limited number of reactions among the lumped
components. The lumps, based on compound types present in feedstock and
products (e.g., lumps of diesel, kerosene, gasoline, etc.), are often defined by
boiling point ranges. This approach is attractive for kinetic modeling of complex
mixtures because of its simplicity (Ancheyta et al., 2005).
1 Sadighi et al.: Lumping Model for a Dual Bed VGO Hydrocracker
Published by The Berkeley Electronic Press, 2011
However, it should be mentioned that lumped kinetics have the following
major disadvantages: (1) they are strongly dependant to feedstock and catalyst;
(2) they are only valid for the range of studied operating conditions, and also (3) if
bench-scale trickle-bed reactors are used for the experimentation, reaction kinetics
will be affected by hydrodynamics and mass transfer processes. If any of those
parameters is to be changed, then the model must be refitted on the basis of a new
experimental program.
To make the lumped models more accurate, it is possible to choose as
many lumps as possible. However, this may lead to a large number of model
parameters (e.g., rate constants). So, less number of species, especially in the case
of limited number of experiments, can make the model more acceptable.
According to discrete lumping approach, there are many researches in
which hydrocracking models with three-lump (Yui & Sanford, 1989; Callejas &
Martinez, 1999; Aoyagi et al., 2003), four-lump (Aboul-Gheit, 1989; Valavarasu
et al., 2005; Sadighi et al., 2010d), five-lump (Ancheyta et al., 1999; Almeida &
Guirardello, 2005; Singh et al., 2005; Sadighi et al., 2010c) and six-lump (Sadighi
et al., 2010a; Sadighi et al., 2010b) partitions have been developed. Moreover, for
the other processes such as catalytic pyrolysis of heavy oil (Meng et al., 2006) and
fluid catalytic cracking (Chen et al., 2007), eight-lump kinetic models were
presented.
In the present study, two kinds of discrete lumping models for a dual bed
pilot scale hydrocracking plant have been compared together. The first approach
is a simplified model which considers only hydrocracking reactions. So, it is
assumed that the catalytic bed operates like a bi-functional catalyst;
hydrocracking reactions can be occurred uniformly through the bed. The second
one is a rigorous approach which needs complementary data from the hydrogen
consumption as well as sulfur, aromatic and nitrogen contents of the feed and
products. This strategy is according to the previous study (Sadighi et al., 2010d).
But its equations are formulated here in detail to make it more applicable for
being used in a mathematical model. To have a more realistic model and closer to
the industrial scenario, the measured yields for estimating the required parameters
are calculated on the basis of mass flow rate of fresh VGO feed.
2. Experimental
The device, catalyst, feed and operating conditions were described completely in
the previous work (Sadighi et al., 2010d). The reactor was composed of four
sections. The first part, having a length of 100 mm, was packed with inert SiC
particles. This section was used to provide a uniform distribution of gas and
liquid. The two following sections with a length of 355mm and 865 mm were
2 International Journal of Chemical Reactor Engineering Vol. 9 [2011], Article A4
http://www.bepress.com/ijcre/vol9/A4
loaded with 63.5cm
3
hydrotrating and 152 cm
3
hydrocracking catalysts,
respectively. The last section was also contained with 50mm of inert (Figure 1).
Because in the under study process, two mono functional zeolite based
hydrotreating and hydrocracking catalysts were used, the reactor can be called a
dual bed VGO hydrocracker.

Figure 1. Sections of catalytic reactor bed

In this study, two types of commercial hydrotreating and hydrocracking
(zeolite-based) catalysts with the same size of industrial application were applied.
The characteristics of HDT and HDC catalysts are presented in Table 1. Before
charging the feed, both catalysts were heated up to 130
0
C, and also they were held
at this temperature about 6 hr for drying. Then, it is sulfided with an appropriate
agent according to the manual of the catalyst vendor.

Table 1- characteristics of HDT&HDC catalyst
Property HDT HDC
Size & Shape 1/16 & Quadralobe 1/16 & Cylindrical
Color Green Brown
Bulk density (kg/m
3
) 750 850
BET Surface Area (m
2
/g) 186.56 199.46
Langmuir Surface Area(m
2
/g) 259.20 273.71
Average Pore Diam (A
0
) 89.09 69.14
Main Ingredients Mo, Ni, Ti Zr, W, Ni, Si, Al

The hydrocracking feed was prepared by blending of the fresh VGO and
recycle feed (unconverted oil) taken from Isomax unit of a real refinery. The feed
properties are shown in Table 2. Mixing ratio of fresh and recycle feeds were 83.3
vol% and 16.7 vol %, respectively.

Table 2- Properties of fresh VGO and recycle feed
Property Fresh VGO Recycle Feed
SP.GR@15.56C 0.8777 0.8738
Distillation Range (vol%)
ASTM D1160 C C
IBP 329.7 287.8
10% 390.6 390.7
30% 423.2 430.1
50% 445.6 452.9
70% 475.1 478.3
90% 523.7 517.1
End point 567.1 561.3
Nitrogen (ppmwt) 800 200
Sulfur (wt%) 1.4 0.03
Aromatics (wt%) 34 14.5
Asphalt & Resin (wt %) <0.1 <0.1

The pilot scale experiments were carried out under the following process
conditions: (1) H
2
/HC=1357 Nm
3
/Sm
3
; (2) LHSV=0.8, 0.9 and 1.05 hr
-1
; (3)
Temperature=360C, 370C, 380C and 390C, and (4) Pressure =146 bar. The
pressure, the range of LHSV and H
2
/HC were selected according to the
recommendation of the catalyst manufacturer.
3. Modeling approach for the dual bed hydrocracking reactor

This work considers 4-lump mathematical model, i.e., VGO, distillate, naphtha
and gas to match main products (Table 3). The kerosene and diesel, also light and
heavy naphtha are lumped together as distillate and naphtha cuts, respectively.
Additionally, it is assumed that only VGO (as hydrocracking feed) consumes
hydrogen to be cracked to lighter cuts. So, the total consumed hydrogen in
hydrocracking section can be calculated on the basis of cracked VGO. Therefore,
hydrogen can be included in the mass balance equations without creating high
complexity. Figure 2 illustrates the process pathways associated with the
mentioned strategy. Note that if all pathways of reactions are considered, the
model will include twelve kinetic parameters which should be estimated by using
experimental data.

Table 3. Average properties of hydrocracking product (Sadighi et al, 2010d)
Lump Sp.g @15C IBP-FBP (C)
Gas 0.35 40
-

Naphtha 0.75 40-160
Distillate 0.823 161-370
VGO 0.89 370
+

Figure 2. The complete 4-lump kinetic model

The following assumptions are considered in the development of the
present models (Mohanty et al., 1991):

1- Hydrocracking is a first order hydrocracking reaction and since hydrogen
is present in excess, the rate of hydrocracking can be taken to be
independent of the hydrogen concentration.
2- The pilot reactor operates under isothermal conditions.
3- A plug flow pattern exists in the trickle bed reactor.
4- Hydrogen feed is pure.
5- The petroleum feed and the products are in the liquid phase in the reactor.
6- The pilot unit is in steady state operation.
7- Catalyst activity does not change with time; therefore simulation is only
valid for start of run conditions.

For each reaction, the kinetic expression is formulated as the function of
mass concentration and kinetic parameters (
0
k , E ). Based on the mentioned
assumptions, rate constants of the proposed models are as follows:

Vacuum gas oil or Feed ( F ): ) exp(
0
RT
E
k k
Fj
Fj Fj

= (1)

Note that j in Eq. 1 represents distillate ( D), naphtha ( N ) and gas ( G )

Distillate ( D): ) exp(
'
' 0 '
RT
E
k k
Dj
Dj Dj

= (2)

' j in Eq. 2 represents naphtha ( N ) and gas ( G ).

Naphtha ( N ): ) exp(
0
RT
E
k k
NG
NG NG

= (3)
In equations 1 to 3, T and R are the bed temperature and ideal gas constant,
respectively.
From Figure 2, it can be found that for converting VGO to the lighter
products, hydrogen should be consumed for each path. Therefore, the reaction
rates for these products can be described as follows:

Distillate (
D
R ):
=
+ =
G
N j
D Dj F FD D
C k C k R
'
'
) 1 ( o (5)
Naphtha (
N
R ):
NG NG D DN F FN N
C k C k C k R + + = ) 1 ( o (6)

Gas (
G
R ):
N NG D DG F FG G
C k C k C k R + + + = ) 1 ( o (7)

In equations 5 to 7, o shows the consumed unit mass of hydrogen per unit mass
of converted VGO which is added to the molecular structure of products
(distillate, naphtha and gas) during hydrocracking reactions.

3.1. Combined bed model
In this approach, the hydrogen consumption is neglected. It is obvious that during
hydrocracking and hydrotreating reactions, hydrogen molecule is absorbed in the
hydrocarbon structure, but sulfur and nitrogen are removed. According to the
experimental data (Sadighi et al, 2010d), this assumption can create 1% error in
the mass balance which can be considered negligible. So, the o coefficient in
equations 5 to 7 is assumed to be zero.
Additionally, it is assumed that hydrocracking and hydrotreating reactions
are carrying out simultaneously through the reactor bed similar to a bi-functional
hydrocracking catalyst. Therefore, there is no boundary between hydrotrating and
hydrocracking reactions. The scheme of combined bed model is illustrated in
Figure 3(A).

So, the reaction rates (
j
R ) can be formulated as follows:

Vacuum gas oil reaction (
F
R ):
F
G
D j
Fj F
C k R
=
= (4)


Figure 3. Schematic representation of the developed lumping models
(A) Combined bed model (B) Dual bed model

3.2. Dual bed model
In this approach, the reactor is divided into two distinguished layer. In the first
one, after carrying out the hydrotrating reactions (Table 4), the product is entered
to the second layer. Therefore, the second step is only involved of hydrocracking
reactions. The scheme of the dual bed model is illustrated in Figure 3 (B).
Before entering the products of the hydrotrating step into the
hydrocracking one, it is imagined that by using two pseudo streams, H
2
S and NH
3

are extracted from the hydrotrating products. So, they are not involved in the mass
balance equations of hydrocracking section. Because these components are stable
and also their flow rates are negligible, this assumption will not create a
considerable error for the mathematical model. After hydrotrating reactions, to
calculate the mass flow rate of feed, naphtha and distillate, equations 8 to 10 are
formulated. Because the contents of sulfur and nitrogen in the product of the
reactor are less than 50 ppm, they have been neglected.
)) ( 1 (
2
0 0
Af Ap
VGO
H
Nf Sf f fh
X X
Mw
Mw
X X m m = (8)
) 7 .(
.
3 2
0
0
NH H Nc
N
Nf f
Nh
Mw Mw Mw
Mw
X m
m + = (9)
) 2 .(
.
2 2
0
0
S H H Sc
S
Sf f
Dh
Mw Mw Mw
Mw
X m
m + = (10)
In above equations,
0
f
m is the mass flow rate of the fresh VGO;
0
fh
m ,
0
Nh
m ,
0
Dh
m
are the mass flow rate of the purified VGO, naphtha and distillate leaving the
hydrotreating section, respectively;
Sf
X ,
Nf
X ,
Af
X are the mass fraction of
sulfur, nitrogen and aromatics in the fresh feed, respectively;
S H NH H VGO Sc Nc S N
MW MW MW Mw Mw Mw Mw Mw
2 3 2
, , , , , , , are the molecular weight
of nitrogen, sulfur, nitrogen lumped component (quinoline), sulfur lumped
component (4,6-DMBT), VGO feed (420), hydrogen, ammonia and hydrogen
sulfide, respectively.

Table 4. Major reactions in the hydrotreating of VGO (Sadighi et al., 2010d)
Reaction Lumped component Consumed hydrogen Products
Hydrodesulfurization 4,6-DMBT 2 moles per S atom Distillate & H
2
S
Hydrodenitrogenation Quinoline 7 moles per N atom Naphtha & NH
3

Hydrodearomatization di-aromatics 2 moles per arom. molecule VGO

The reactions in the hydrocracking step are according to equations 5 to 7;
but the o coefficient is calculated by the following quadratic polynomial
equation (Sadighi et al., 2010d).

LHSV T LHSV T LHSV T . . . . .
12
2
22
2
11 2 1 0
| | | | | | o + + + + + = (12)

In this equation, T is the reaction temperature (K); LHSV is liquid hourly space
velocity of the reacting stream through the bed (hr
-1
). Also,
0
| is the intercept
coefficient,
1
| and
2
| are the linear terms,
1 1
| and
22
| are the squared terms and
12
| is the interaction term (Table 5).

Table 5. Coefficient values for the hydrogen consumption
Variable
0
|
1
|
2
|
11
|
22
|
12
|
T.LHSV 3441.319 -10.762 -18.906 0.00854 5.452 -0.00858

3.3. Model development and parameter estimation
In order to model the reactor, a cell network is applied. All beds from the inlet to
the outlet are divided into a number (N
l
=200) of well-mixed cells which are
grouped along the flow direction. Mixing only occurs within each cell and back
mixing is not accounted for between the adjacent cells. The accuracy of this
approach for the VGO hydrocracking process in trickle bed regime was confirmed
in the previous work (Sadighi et al., 2010d).
To improve the accuracy of the developed model, the volumetric flow rate
in the reactor (v ) is considered variable, and it is calculated according to the
density of output stream of each cell. Therefore, the mass balance equation for
each cell can be written as follows:

) ( ) ( ) ( ) ( '. . ) 1 ( ) 1 ( i i C i V i R i i C
j cat j j
v c q v = (13)

In Eq. 13, j ranges from the fresh feed ( F ) to the gas ( G ), and a negative sign
indicates reactant (fresh feed or VGO).
l
b
cat
N
V
i V = ) ( (14)
) (
) (
0
i
m
i
G
f j
j
v

=
= (15)
) ( ). (
0
i i C m
j j
v = (16)
=

=
=
G
F j
j
G
F j
j
j
m
m
i

.
) (
1
0
0
(17)
0
) ( ). (
f
l l j
j
m
N N C
Y
v
= (18)
In above equations,
j
is density of lumps (Table 3); i is the number of cells
which ranges from 1 to 200; C is the mass concentration of lumps; q is the
effectiveness factor; ' c is the catalyst volume fraction; ) (i V
cat
is the volume of
hydrocracking catalyst in each cell;
b
V is the volume of the bed; N
l
is the number
of cells (200);
0
f
m is the mass flow rate of fresh feed, and
j
Y is the yield of each
lump in the product stream leaving the reactor. The effectiveness factor for
cylindrical catalyst in trickle bed regime and the bed void fraction are 0.7 (Mills
& Dudukovic) and 0.35, respectively.
For parameter estimation, sum of squared error, SQE , as given below, is
minimized:

2
1
) (
pred
jn
t
N
n
meas
jn
G
F j
Y Y SQE =
=

=
(19)

In Eq.19,
t
N ,
meas
jn
Y and
pred
jn
Y are the number of test runs, the measured and the
predicted yields, respectively.
For the combined bed model, equations 1 to 7 and 13 to 18 should be
solved simultaneously by applying the following boundary conditions:

f
f
m
v
0
) 0 ( = ;
f f
C = ) 0 ( ; 0 ) 0 ( =
D
C ; 0 ) 0 ( =
N
C ; 0 ) 0 ( =
g
C (20)

But, for the dual bed model, equations 1 to 7 and equations 12 to 18
should be solved simultaneously by applying the following boundary conditions:

) 0 (
) 0 (
0
v

=
=
N
f j
jh
m
(21)
=
+ +
=
N
f j
jh N
Nh
N
f j
jh D
Dh
N
f j
jh f
fh
m
m
m
m
m
m
0
0
0
0
0
0
1
) 0 (

(22)
) 0 (
) 0 (
0
v
fh
f
m
C = ;
) 0 (
) 0 (
0
v
Dh
D
m
C = ;
) 0 (
) 0 (
0
v
Nh
N
m
C = ; 0 ) 0 ( =
g
C (23)

To develop the model, Aspen Custom Modeler (ACM) programming
environment (AspenTech, 2004) is used. Then Eq.19 is minimized by sequencing
NL2Sol and Nelder-Mead algorithm which are both existed in Aspen Custom
Modeler software. NL2Sol algorithm is a variation on Newton's method in which
a part of the Hessian matrix is computed exactly and a part of that is
approximated by a secant (quasi-Newton) updating method. To promote
convergence from a poor initial point, a trust-region is used along with a choice of
model Hessian. Hence, the approximate region is found with NL2Sol; then to fine
tune the parameters; Nelder-Mead method is used.
To evaluate the estimated kinetic parameters, absolute average deviation
of predictions ( % AAD ) is calculated by using the following expression.
100
) (
%
1
2
2
=

=

=
t
t
N
n meas
jn
pred
jn
meas
jn
G
F j
N
Y
Y Y
AAD (24)
Moreover, the goodness of fitting of developed models is checked with
analysis of variance (ANOVA) using Fischer test with 99% probability.

4. Results and discussions

At first for the combined bed model, twelve kinetic parameters, frequency factors
and activation energies were estimated by using the experimental data. After
estimating parameters and predicting yields, the AAD% of the model was 8.28%
in comparison to the measured data.
In Table 6, kinetic constants and the rate order of reactions at the mean
operating temperature (375
0
C) to the highest one (k
DN
or distillate to naphtha) are
presented. It is found that for the combined bed model, the rate orders of
converting VGO to naphtha (k
FN
) and distillate to gas (k
DG
) are significantly
lower than the highest value (k
DN
). It means that these reactions can be ignored.
After eliminating the low-reaction-rate pathways and re-estimating the parameters
(Table 7), the AAD% of the reduced model was found to be 8.23%. It can be
concluded that the model reduction can improve the accuracy of the yield
prediction which is the similar scenario with respect to the previous works
(Sadighi et al., 2010a; Sadighi et al., 2010b; Sadighi et al., 2010c).
From Table 7, it is obvious that apparent activation energies of VGO to
middle distillate and gas are 14.97 kcal/mol and 7.32 kcal/mol, respectively. The
reported ones by Aboul-Ghiet (1989) were about 13-17.5 kcal/mol, and 18-19
kcal/mol, respectively. It is thought that the lower estimated activation energy for
hydrocracking of feed to gas in this work is due to the higher hydrocracking
activity of zeolite type catalyst. Additionally, the estimated activation energy
(Botchwey et al., 2004) for formation of naphtha from middle distillate in the low
severity temperature regime (340 to 370
0
C) was about to 8.8 kcal/mol. Moreover
the reported value for hydrocracking of kerosene to heavy naphtha in an industrial
hydrocracking process charged with amorphous catalyst was 7.43 kcal/mol
(Sadighi et al., 2010 a). It can be concluded that the estimated activation energy of
distillate to naphtha in this work (7.11 kcal/mol) is not far from the others.
The simplified reaction-path network for the four-lump combined bed
model is shown in Figure 4.

Table 6. Kinetic parameters for complete network of combined bed model
Frequency Factor
(m
3
.hr
-1
.m
3
total cat
-1
)
Activation Energy
(kcal/mol)
Rate order
k
0FD
3.49E+05 E
FD
15.80 k
FD
0.61
k
0FN
2.44E+07 E
FN
69.30 k
FN
3.79E-17
k
0FG
3.34E-01 E
FG
2.10 k
FG
0.024
k
0DN
900.84 E
DN
7.49 k
DN
1
k
0DG
2.48E+07 E
DG
34.07 k
DG
2.98E-05
k
0NG
1.10E+00 E
NG
0 k
NG
0.41

Table 7. Kinetic parameters for reduced network of combined bed model
Frequency Factor
(m
3
.hr
-1
.m
3
total cat
-1
)
Activation Energy
(kcal/mol)
Rate order
k
0FD
1.82E+05 E
FD
14.97 k
FD
0.62
k
0FN
- E
FN
- k
FN
-
k
0FG
2.29E+01 E
FG
7.32 k
FG
0.03
k
0DN
660.20 E
DN
7.11 k
DN
1
k
0DG
- E
DG
- k
DG
-
k
0NG
8.33E-01 E
NG
- k
NG
0.32

Figure 4. The reduced 4-lump kinetic network for the combined bed model

After following again the described strategy for the dual bed model, it was
found that the AAD% of the complete and reduced approaches were 6.77% and
5.87%, respectively. The apparent kinetic constants of those are presented in
Tables 8 and 9, respectively. Also, the reduced kinetic network of this strategy is
depicted in Figure 5.


Table 8. Kinetic parameters for the complete network of the dual bed model
Frequency Factor
(m
3
.hr
-1
.m
3
HCR cat
-1
)
Activation Energy
(kcal/mol)
Rate order
k
0FD
6.72E+07 E
FD
23.37 k
FD
0.57
k
0FN
1.04E+08 E
FN
24.63 k
FN
0.33
k
0FG
0 E
FG
13.08 k
FG
0
k
0DN
0 E
DN
2.14 k
DN
0
k
0DG
6.90E+03 E
DG
28.15 k
DG
1.43E-06
k
0NG
1.55E+00 E
NG
0 k
NG
1

Table 9. Kinetic parameters for the reduced network of the dual bed model
Frequency Factor
(m
3
.hr
-1
.m
3
HCR cat
-1
)
Activation Energy
(kcal/mol)
Rate order
k
0FD
1.32E+07 E
FD
21.25
k
FD
0.59
k
0FN
1.42E+10 E
FN
31.02
k
FN
0.32
k
0FG
- E
FG
- k
FG
-
k
0DN
- E
DN
- k
DN
-
k
0DG
- E
DG
- k
DG
-
k
0NG
1.514 E
NG
- k
NG
1

Figure 5. The reduced 4-lump kinetic network for the dual bed model

It should be noted that the kinetic constants and the kinetic network of the
combined bed model (Table 7 and Figure 4) show the performance of
hydrotreating and hydrocracking sections together. But the related ones for the
dual bed model (Table 9 and Figure 5) only demonstrate the performance of the
hydrocracking catalyst.
Therefore, it can be understood that in comparison to the combined bed
approach, the dual bed one can predict the yield of hydrocracking reactor with
lower AAD% about 2.36%. The brilliant point in this approach which can be
understood from Table 9 is its requirement to only five kinetic parameters
(frequency factors and activations energies) to predict twelve sets of test runs
(three levels of LHSV and four levels of temperature). But, this approach needs
complete information from hydrogen consumption as well as sulfur, nitrogen and
aromatic contents of the feed and product. In contrast, combined bed model needs
seven parameters to predict the yield of products with AAD % of 8.23. But it is a
simplex in which no hydrotrating or hydrogen consumption data is needed.
In the previous works (Sadighi et al., 2010a), it was reported that the
activation energies for both light and heavy naphtha to gas were about to 9
kcal/mol for a dual-functional amorphous hydrocracking-hydrotreating catalyst.
But, from Tables 7 and 9, it can be concluded that in this range of operating
temperature, the activation energy for hydrocarcking of naptha to gas is
independent to temperature (E
NG
=0). The reason for this phenomenon is supposed
to be higher ability of zeolite type catalysts for hyrocracking (Shimada et al.,
1997). So, gas formation from naphtha may be influenced by the nature of
catalyst, and it is independent to temperature within the operating range.
The AAD percentages for all lumps are presented in Table 10. It can be
concluded that the predictions of the combined and dual bed models are close
together and they are acceptable for all products except to the case of gas for the
combined bed model. Additionally, in the Table 11, the ANOVA of both
strategies has been presented. The positive point in this table is acceptable
difference between the F-critical and the F-test of the proposed models.

Table 10. The AAD% for the different dual bed lumping models
Lump
Combined bed
(Completed)
Combined bed
(Reduced)
Dual bed
(Completed)
Dual bed
(Reduced)
Gas 21.04 20.7 11.00 9.26
Naphtha 4.92 5.34 8.29 7.04
Distillate 5.33 5.11 4.87 4.34
Un.VGO 1.83 1.76 2.90 2.85
Ave. 8.28 8.23 6.77 5.87

Table 11. ANOVA results of the developed models

Combined bed
(complete)
Combined bed
(reduced)
Dual bed
(complete)
Dual bed
(reduced)
DF* of regression 11 6 11 4
DF* of residual 36 41 36 43
R
2
-adjusted (%) 99.944 99.974 99.916 99.976
F-value 1789.69 3865.29 1189.87 4193.26
F-critical (1%) 2.79 3.28 2.79 3.79
*DF is degree of freedom

Figures 6 to 9 show comparisons between the measured yields and the
predicted ones. To evaluate the accuracy of the prediction, the corresponding
deviation plot is also presented. The deviation error reported in these figures was
calculated as follows:

100
Pr
%
=
yield Measured
yield edicted yield Measured
Error (25)

As it was resulted from Table 10, close mappings between the measured
and predicted yields by using both approaches can be understood. Moreover, it
can be found that deviations are acceptably distributed evenly around the zero; but
in the Figure 6, more deviation for the gas lump can be found for the combined
bed model.
Additionally, the deviation plot for the predicted gas by the combined bed
model in the Figure 6 demonstrates that in most of temperatures and LHSVs, the
dual bed model predicts lower yield for the gas lump in comparison to the
measured data. It is supposed that this deviation is because of disregarding the
reactions which can produce gas in the hydrotreating layer. Conversely, for most
of temperatures and LHSVs, the combined bed model predicts higher values for
the yield of gas. It is supposed that the main reason for this deviation is the
consideration of gas producing reactions in all points along the catalytic bed.
Because of lower ability of hydrotreating catalyst to produce gas than that of
hydrocracking one, the model predicts more gas in comparison to the measured
values. Therefore the yield of gas can be laid between the values predicted by the
combined and dual bed models.


Figure 6. Predicted yields (, &), measured yields (, & ) and
deviation plots for the prediction of gas lump


deviation plots for the prediction of naphtha lump


deviation plots for the prediction of distillate lump


deviation plots for the prediction of VGO lump

5. Conclusions

It was demonstrated that the product yields of a pilot scale VGO-hydrocracker
could be predicted with the AAD% of 5.87% by using a four-lump rigorous model
approach, called the dual bed model. This model could predict the yield of gas,
naphtha, diesel and residue with the AAD% of 9.26%, 7.04%, 4.34% and 2.85%,
respectively. These deviations for 12 test runs (48 observations) in three levels of
LHSV and four levels of temperature can be satisfying. But to develop such a
model, the hydrogen consumption of the process was needed. Moreover, sulfur,
nitrogen and aromatic content of the feed and product should be analyzed. In
contrast, there was a simpler four-lump approach, called the combined bed model
which was capable of predicting the yield of products with the AAD% of 8.23%.
This model could predict the yield of gas, naphtha, diesel and residue with the
AAD% of 20.7%, 5.34%, 5.11% and 1.76%, respectively. The enormous deviation
for the gas lump can be the disadvantage of this model. But, the advantage of this
model over the dual bed model was its simplicity because it only required product
yields to tune the model parameters.

6. Nomenclature

6.a Notations

AAD Absolute Average Deviation, %
C
Mass concentration, kg/m
3

D Distillate
E Apparent activation energy, kcal/mol
G
Gas
k
Reaction rate constant, m
3
.hr
-1
.m
3
cat
-1

0
k
Frequency factor, m
3
.hr
-1
.m
3
cat
-1

LHSV
Liquid Hourly Space Velocity, hr
-1

0
m Mass flow rate, kg/hr
Mw
Molecular weight
S
Mw
Molecular weight of sulfur (32)
N
Mw
Molecular weight of nitrogen (14)
N
Naphtha
l
N
Number of cells (200)
t
N
Number of experiments
R
Ideal gas constant, 1.987 kcal.kmol
-1
.K
-1

j
R
Reaction rate of lump j, kg.hr
-1
.m
3
cat
-1

T Temperature, K or R
b
V
Total Volume of bed, m
3

cat
V
Volume of catalyst per cell, m
3

VGO
Vacuum Gas Oil
X Mass fraction of lumps
Y

Yield of products

6.b Greek letters
o Consumed mass of hydrogen per mass of VGO
12 22 11 2 1 0
, , , , , | | | | | | Coefficient values for the hydrogen consumption
' c Catalyst void fraction
q
Effectiveness factor
v Volume flow rate, m
3
/hr

Density, kg/m
3

6.c Subscripts
Af
Aromatic in feed
Ap
Aromatic in product
' Dj
Distillate to lighter lumps
Dh Diesel in the output stream of hydrotrating bed
fh
VGO feed or residue in the output stream of hydrotrating bed
Fj
Feed to lighter lumps
i Cell number
j
Distillate, naphtha and gas lumps
' j
naphtha and gas lumps
2
H Hydrogen
S H
2
Hydrogen sulfide
n Number of experiments
Nc Nitrogen lumped component
Nf
Nitrogen in feed
Nh Naphtha in the output stream of hydrotrating bed
3
NH Ammonia
Sc Sulfur lumped component
Sf
Sulfur in feed

References
Aboul-Gheit K., "Hydrocracking of vacuum gas oil (VGO) for fuels production",
Erdol Erdgas Kohle, 1989, 105, 1278.

Almeida R. M. and Guirardello R., "Hydroconversion kinetics of Marlim vacuum
residue", Catalysis Today, 2005, 109, 104.

Alvarez A. and Ancheyta J., "Modeling residue hydroprocessing in a multi-fixed-
bed reactor system", Applied catalysis A: General, 2005, 351, 148.

Ancheyta J., Sanchez S. and Rodriguez M. A., "Kinetic modeling of
hydrocracking of heavy oil fractions: A review", Catalysis Today, 2005,
109, 76-92.

Ancheyta-Juarez J., Lopez-Isunza F. and Aguilar-Rodriguez E., "5-Lump kinetic
model for gas oil catalytic cracking", Applied Catalysis A: General, 1999,
177, 227.

Aoyagi K., McCaffrey W. C. and Gray M. R., "Kinetics of hydrocracking and
hydrotreating of coker and oilsands gas oils", Petroleum Science
Technolology, 2003, 21, 997.

Basak K., Sau M., Manna U. and Verma R.P., "Industrial hydrocracker model
based on novel continuum lumping approach for optimization in
petroleum refinery", Catalysis Today, 2004, 98, 253.

Balasubramanian P. and Pushpavanam S., "Model discrimination in
hydrocracking of vacuum gas oil using discrete lumped kinetics", Fuel,
2008, 87, 1660.

Botchwey C., Dalai A.K. and Adjaye J., "Kinetics of Bitumen Derived Gas Oil
Upgrading Using a Commercial NiMo/Al
2
O
3
Catalyst", The Canadian
Journal of Chemical Engineering, 2004, 82, 478.

Callejas M. A. and Martinez M. T., "Hydrocracking of a Maya residue, kinetics
and product yield distributions", Industrial Engineering Chemical
Research, 1999, 38, 98.

Chen C., Yang B., Yuan J., Wang Z. and Wang L., "Establishment and solution of
eight-lump kinetic model for FCC gasoline secondary reaction using
particle swarm optimization", Fuel, 2007, 86, 2325.

Elizalde I., Rodrguez M.A. and Ancheyta J., "Application of continuous kinetic
lumping modeling to moderate hydrocracking of heavy oil", Applied
Catalysis A: General, 2009, 365, 237.

Krambeck F.J., "Kinetics and thermodynamics lumping of multicomponent
mixtures", Elsevier, 1991, Amsterdam, 111.
.
Meng X., Xu C., Gao J., Li L., "Catalytic pyrolysis of heavy oils: 8-lump kinetic
model", Applied Catalysis A: General, 2006, 301, 32.

Mills P.L., Dudukovic M.P., "A Dual-Series Solution for the Effectiveness Factor
of Partially Wetted Catalysts in Trickle-Bed Reactors", Ind. Eng. Chem.
Fund., 1979, 18, 2.

Mohanty S., Saraf D. N. and Kunzro D., "Modeling of a hydrocracking reactor",
Fuel Processing Technology, 1991, 29, 1-17.

Sadighi S., Arshad A. and Mohaddecy S. R., "6-Lump Kinetic Model for a
Commercial Vacuum Gas Oil Hydrocracker", International Journal of
Chemical Reactor Engineering, 2010a, 8, A1.

Sadighi S., Arshad A. and Irandoukht A., "Modeling a Pilot Fixed-bed
Hydrocracking Reactor via a Kinetic Base and Neuro-Fuzzy Method",
Journal of Chemical Engineering Japan, 2010b, 43 (2), 174.

Sadighi S., Arshad A. and Irandoukht A., "Kinetic Study on a Commercial
Amorphous Hydrocracking Catalyst by Weighted Lumping Strategy",
International Journal of Chemical Reactor Engineering, 2010c, 8, A60.

Sadighi S., Arshad A. and Rashidzadeh M., "4-Lump kinetic model for vacuum
gas oil hydrocracker involving hydrogen consumption", Korean Journal of
Chemical Engineering, 2010d, 27 (4), 1099.

Shimada H., Yoshitomi S., Sato T., Matsubayashi N., Imamura M., Yoshimura Y.
and Nishijima A., "Dual-functional Ni-Mo sulfide catalysts on zeolite-
alumina supports for hydrotreating and hydrocracking of heavy oils",
Studies in Surface Science and Catalysis Hydrotreatment and
Hydrocracking of Oil Fractions, Proceedings of the 1st International
Symposium/6th European Workshop, 1997, 106, 115-128.

Singh J., Kumar M., Saxena A. K. and Kumar S., "Reaction pathways and product
yields in mild thermal cracking of vacuum residues: A multi-lump kinetic
model", 2005, Chemical Engineering Journal, 108, 239.

Valavarasu G., Bhaskar M. and Sairam B., "A Four Lump Kinetic Model for the
Simulation of the Hydrocracking Process", Petroleum Science
Technology, 2005, 23, 1323.

Yui S. M. and Sanford E. C., "Mild hydrocracking of bitumen-derived coker and
hydrocracker heavy gas oils: kinetics, product yields and product
properties, Industrial Chemical Research, 1989, 28, 319.


Comparison of Lumping Approaches To Predict The Product Yield in A Dual Bed VGO Hydrocracker

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Comparison of Lumping Approaches To Predict The Product Yield in A Dual Bed VGO Hydrocracker

Hochgeladen von

Copyright:

Verfügbare Formate

INTERNATIONAL JOURNAL OF CHEMICAL

Universiti Teknologi Malaysia, sadighi sepehr@yahoo.com

Universiti Teknologi Malaysia, arshad@fkkksa.utm.my

Iran University of Science & Technology, shirvani.m@iust.ac.ir

Das könnte Ihnen auch gefallen