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Applied Energy 94 (2012) 182191

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Improving fuel quality by whole crude oil hydrotreating: A kinetic model


for hydrodeasphaltenization in a trickle bed reactor
A.T. Jarullah, I.M. Mujtaba , A.S. Wood
School of Engineering, Design and Technology, University of Bradford, Bradford BD7 1DP, UK

a r t i c l e

i n f o

Article history:
Received 20 September 2011
Received in revised form 11 January 2012
Accepted 15 January 2012
Available online 16 February 2012
Keywords:
Hydrodeasphaltenization
Trickle-bed reactor
Three-phase heterogeneous model
Kinetic parameters
Simulation and optimization

a b s t r a c t
Fossil fuel is still a predominant source of the global energy requirement. Hydrotreating of whole crude
oil has the ability to increase the productivity of middle distillate fractions and improve the fuel quality
by simultaneously reducing contaminants such as sulfur, nitrogen, vanadium, nickel and asphaltene to
the levels required by the regulatory bodies. Hydrotreating is usually carried out in a trickle bed reactor
(TBR) where hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM) and
hydrodeasphaltenization (HDAs) reactions take place simultaneously. To develop a detailed and a validated TBR process model which can be used for design and optimization of the hydrotreating process,
it is essential to develop kinetic models for each of these reactions. Most recently, the authors have developed kinetic models for all of these chemical reactions except that of HDAs. In this work, a kinetic model
(in terms of kinetic parameters) for the HDAs reaction in the TBR is developed.
A three phase TBR process model incorporating the HDAs reactions with unknown kinetic parameters
is developed. Also, a series of experiments has been conducted in an isothermal TBR under different operating conditions affecting the removal of asphaltene. The unknown kinetic parameters are then obtained
by applying a parameter estimation technique based on minimization of the sum of square errors (SSEs)
between the experimental and predicted concentrations of asphaltene compound in the crude oil.
The full model with the estimated kinetic parameters is then applied to evaluate the removal of asphaltene (thus affecting fuel quality) under different operating conditions (than those used in experiments).
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Trickle-bed reactors (TBRs) have been largely employed in hydrodesulfurization (HDS) and hydrocracking (HDC) of heavy oil
feedstocks, and in other hydrotreating processes such as hydrodenitrogenation (HDN), hydrodemetallization (HDM) or hydrodeasphaltenization [1] of oil-fractions or their derivatives obtained
from the crude distillation unit (CDU). Hydrotreating is carried
out to improve the fuel quality by removing the contaminants,
such as sulfur, nitrogen, metals, aromatics and asphaltenes form
the oil fractions. However, with the hydrotreatment followed by
CDU, a signicant amount of these contaminants will remain at
the bottom of the atmospheric and vacuum distillation column
[2,3]. Our recent experimental study shows for the rst time that
hydrotreating of whole crude oil does not only increase the productivity of middle distillate fractions but also improves the fuel
quality by simultaneously reducing the contents of impurities
(such as sulfur, nitrogen, vanadium, nickel and asphaltene) [4].
Asphaltenes can be dened as the heaviest compounds of hydrocarbon sources (with a density of between 1.13 and 1.20 g/ml at
Corresponding author.
E-mail address: I.M.Mujtaba@bradford.ac.uk (I.M. Mujtaba).
0306-2619/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2012.01.044

room conditions) that are insoluble in parafns such as normal


pentane, normal heptane, normal hexane, etc. and are soluble in
an excess quantity of aromatic compounds such as benzene or toluene [59].
Asphaltenes are well known to be coke precursors, as they are
the most complex molecules present in petroleum. They are a complex mixture of high boiling point, high molecular weight compounds consisting of condensed polynuclear aromatics carrying
alkyl, cycloalkyl, and highly undesirable compounds [1013].
Asphaltenes are mainly responsible for catalyst deactivation during catalytic hydrotreating or hydrocracking of heavy oils, and residues (owing to their tendency to form coke). In the hydrotreating
(HDT) process of heavy oils, asphaltenes affect the overall rate of
HDT reactions; they precipitate on the catalyst surface and close
the pore mouths, acting as a coke precursor that leads to the deactivation of the catalyst and cause many troubles throughout the
petroleum renery [7,1416]. The presence of polar chemical functions of asphaltenes in oil formations probably limits the hydrocarbon production. Asphaltene compounds are responsible for the
high density and viscosity of crude oils and heavy oils, which lead
to transport problems [7,17]. Removing the aliphatic side chains of
the asphaltenes or hydrotreating the oil can change the asphaltenes to become less soluble during hydrotreatment [18].

A.T. Jarullah et al. / Applied Energy 94 (2012) 182191

183

Nomenclature
a
aL
aS
AC
A0HDAs
API
CDU
C LH2
C LAsph
C SH2
C LAsph
DeAsph
dc
DLH2
DK
DLAsph
DR
ds
EAHDAs
GL
HDAs
hH2
KHDAs
K LH2
K SH2
K SAsph
L
Lc
LHSV
m
NL/L
n
Mw
p
PGH2
r
rg
rHDAs
R
Sg
Sp
SSEs

dimensionless number
gasliquid interfacial area (cm1)
liquidsolid interfacial area (cm1)
surface area (cm2)
pre-exponential factor (mol/cm3)1n (cm3/g s)
(mol/cm3)m
American Petroleum Institute
crude distillation unit
concentration of hydrogen in the liquid phase
(mol/cm3)
concentration of asphaltene compound in the liquid
phase (mol/cm3)
concentration of H2 in the solid phase (mol/cm3)
concentration of asphaltene compound in the solid
phase (mol/cm3)
effective diffusivity of asphaltene in the pores of catalyst
(cm2/s)
diameter of cylindrical catalyst particle (cm)
molecular diffusivity of H2 in the liquid (cm2/s)
knudsen diffusivity (cm2/s)
molecular diffusivity of asphaltene in the liquid (cm2/s)
reactor diameter (cm)
diameter of spherical catalyst particle (cm)
activation energy for HDAs process (J/mol)
liquid mass velocity (g/cm2 s)
hydrodeasphaltenization
Henrys coefcient for hydrogen (MPa cm3/mol)
reaction rate constant for HDAs reaction (mol/cm3)1n
(cm3/g s) (mol/cm3)m
gasliquid mass transfer coefcient for hydrogen (cm/s)
liquidsolid mass transfer coefcient for H2 (cm/s)
liquidsolid mass transfer coefcient for asphaltene
(cm/s)
length of particle (cm)
length of cylindrical catalyst particle (cm)
liquid hourly space velocity (h1)
order of reaction of hydrogen
normal litre/litre
order of reaction of Asphaltene
molecular weight
reactor total pressure (psia)
partial pressure of hydrogen (MPa)
particle radius (cm)
pore radius (cm)
chemical reaction rate of HDAs process per unit mass of
the catalyst (mol g1 s1)
universal gas constant (J/mol K)
specic surface area of particle (cm2/g)
total geometric external area of particle (cm2)
sum of square errors

Crude oil hydrotreating in the presence of the asphaltenes


(which close active sites of the catalyst) is a very difcult task.
A better knowledge of kinetics in addition to the effects of catalyst properties on diffusion limitations and other concepts (mass
and heat transfer, thermodynamics, transport phenomena, etc.)
permits the design of reactors not only for asphaltene conversion
or removal but also for any catalytic hydrotreating reaction in
which heavy oil cuts are included. Catalyst selectivity does not only
depend on the kinetics of each reaction but also on the relative diffusivities of the reacting molecules, when diffusion limitations exist. Kinetics can help in making a better selection of suitable
catalysts [15].

Sp gr15.6
TmeABP
TBR
ug
uL
v
Vg
V H2
Vp
z

specic gravity of oil at 15.6 C


mean average boiling point (R)
trickle bed reactor
velocity of the gas (cm/s)
velocity of the liquid (cm/s)
volume (cm3)
pore volume per unit mass of catalyst (cm3/g)
molar gas volume of H2 at standard conditions (Nl/mol)
total geometric volume of catalyst (cm3)
reactor bed length (cm)

Greek letters
qB
bulk density of the catalyst particles (g/cm3)
qL
liquid density at process conditions (lb/ft3)
q15.6
specic gravity of oil at 15.6 C
q20
density of the oil at 20 C (g/cm3)
q0
density of oil at 15.6 C and 101.3 kPa (lb/ft3)
qp
particle density (g/cm3)
g
catalyst effectiveness factor
gHDAs
catalyst effectiveness factor for HDAs process
e
void fraction of the catalyst bed
lL
liquid viscosity at process conditions (mPa s)
tLC
critical specic volume of liquid feedstock (ft3/mol)
H2
tC
critical specic volume of H2 (cm3/mol)
tL
molar volume of liquid feedstock (cm3/mol)
tH2
molar volume of H2 (cm3/mol)
tAsph
molar volume of asphaltene (cm3/mol)
kH2
solubility coefcient of H2 (Nl kg1 MPa1)
DqP
pressure dependence of liquid density (lb/ft3)
DqT
temperature correction of liquid density (lb/ft3)
u
thiele modulus
h
particle porosity
s
tortuosity factor
Superscripts

degree
G
gas phase
H2
hydrogen
L
liquid phase or gasliquid interface
S
solid phase or liquidsolid interface
Subscripts
0
at the rst reactor length
c
cylindrical
f
at the nal reactor length
g
gas
H2
hydrogen
L
liquid
s
spherical
Asph
asphaltene

In our recent studies, the effect of sulfur, nitrogen, vanadium


and nickel on crude oil hydrotreating with their kinetic models
have been studied [2,3]. This work focuses on obtaining an accurate kinetic model of hydrodeasphaltenization (HDAs) reactions
in a TBR based on experimental data and optimization techniques.
The experiments are carried out in a continuous ow, trickle bed
hydrotreating pilot plant reactor. The operating reaction temperature (T), hydrogen pressure (P), liquid hourly space velocity (LHSV)
are varied between 335400 C, 410 MPa, 0.51.5 h1, respectively, with constant (H2/Oil) ratio of 250 NL/L. The main challenge
in developing an accurate process model is to determine accurately
the kinetic parameters of the chemical reactions involved in the

184

A.T. Jarullah et al. / Applied Energy 94 (2012) 182191

process. For hydrodeasphaltenization reactions, the development


of such kinetic models is even a more challenging task due to the
complex physical and chemical changes that the feed undergoes,
along with the mass transfer phenomena in the reaction system.
The ultimate objective of this work is to develop a threephase
heterogeneous TBR model (involving the hydrodeasphaltenization
reactions) so that the model can be used for the design and optimization of the whole crude oil hydrotreating process with the objective of providing quality energy sources.

2. Reactor model description for HDAs reaction


Mathematical models are utilized particularly in the natural
sciences and engineering disciplines (such as physics, biology, electrical engineering) but also in the social sciences (such as economics, sociology and political science). Process models are commonly
employed for the optimization of chemical operations because
they allow for an estimate of the optimum operating conditions
without making changes to the actual process. A process model
plays a vital role in the optimization of chemical operations in
the chemical process industry. A typical chemical engineering
model involves the mass and energy balances, physical property
correlations, chemical kinetics, etc. and can be described by a set
of algebraic and differential equations for both steady state and
dynamic processes. A steady state model ignores the changes in
process variables with time while dynamic models consider
dynamic characteristics [19,20].
In this work, efforts are made in order to develop an adequate
mathematical model that can account for the hydrodeasphaltenization of crude oil in a trickle bed reactor. The mathematical model
is based upon two-lm theory and includes mass transfer phenomena at the gasliquid and liquidsolid interfaces and correlations to
evaluate gasliquid and liquidsolid masstransfer coefcients, oil
viscosity, oil density, hydrogen solubility, diffusivity, molar volume, specic surface area, etc. at process conditions, utilizing
information stated in the literature [2,3,21,22].
Three phases are considered in the reactor system, catalyst particles (solid phase), hydrogen (gas phase) and oil feedstock (liquid
phase). For the reactions to happen, hydrogen being the major

constituent of the gasphase, has to be transferred to the liquid


phase and then to the catalyst surface in order to react with other
reactants.
The mathematical model has been developed with the following assumptions: There is no radial concentration prole within
the reactor, the reactor operates isothermally under steady-state
conditions, one-dimensional heterogeneous model, and the phase
change of light cuts is negligible.
The assumptions for the reactor kinetic model of hydrodeasphaltenization of crude oil with the required data and available
tools are presented in Fig. 1.
2.1. Mass balance equations
Mass balance equations in the TBR for co-current operations can
be divided into three phases as follows:
 Gas phase
G

Hydrogen:

PGH2
RT L
 C LH2
 kH2 aL
ug
dz
hH2

dPH2

!
1

 Liquid phase
L

Hydrogen:

dC H2

dz"
#
!
PGH2
1 L
S
kH2 aL
 C LH2  kH2 aS C LH2  C SH2

ul
hH2


dC Asph
1 S
 kAsph aS C LAsph  C SAsph
ul
dz
L

Asphaltene:

 Solid phase



S
Hydrogen: kH2 aS C LH2  C SH2 qB gHDAs r HDAs



S
Asphaltene: kAsph aS C LAsph  C SAsph qB gHDAs r HDAs

Fig. 1. Assumptions for modeling and simulation of HDAs reaction with the required data and available tools.

185

A.T. Jarullah et al. / Applied Energy 94 (2012) 182191

Eqs. (4) and (5) determine the amount of hydrogen involved in


HDAs reaction (only total H2 input to the reactor). In reality, H2 will
also be consumed for other HDT reactions such as HDS, HDN and
HDM (Jarullah et al. [2,3]). The actual H2 exiting from the TBR will
be lower than those predicted by the Eq. (1). However, this will not
affect the determination of the kinetic parameters presented in this
work (a sensitivity analysis of the kinetic parameters is included in
this work to demonstrate this).

Table 2
Characteristics of the catalyst used in the model equations.
Parameter

Equation

Surface area (for cylinder


particles)
The bed void fraction of the
catalyst

e
e
as AC 1
2ppr2rLL 1  e 2r 1  e 41
m
d

The equivalent spherical


diameter
Effectiveness factor

2.1.1. Model initial conditions


Since the mathematical model presented above consists of a set
of differential equations in the gas and liquid phases along the
reactor bed length, it is necessary to dene initial conditions for
the gas and liquid phases.

"

C LH2 z 0 C LH2 initial

C LAsph z 0 C LAsph initial

2

ds

h
 2 i1=2
d
ds dc Lc 2c
/Asph
gHDAs tanh
/Asph

/Asph VSPP
DeAsph sh
DK

PGH2 z 0 PGH2 initial

D 2 #

e 0:38 0:073 1 dsDR 2

n1

sn1

K HDAs C Asph

!
1

qP

 0:5

DeAsph

1
D1

DL
Asph


T 0:5
9700r g Mw
2h

r g Sg q
P
qB
h qP V g = V g 1
e

2.3. Gas and liquid properties and process coefcients


The correlations used for trickle bed reactor model are taken
from the literature to estimate several parameters, which are summarized in Table 1 [23,2433].

2.2. Reaction kinetics


Crude oil contains many compounds of asphaltenes and the
overall hydrodeasphaltenization reaction is generally represented
by a practical and largely accepted generalized equation [22]. Modeling of such reactions is a hard task due to the large numbers of
components of crude oil. Asphaltenes are found in more than one
form in crude oil. Each form is described by its own reactivity
and complex reaction ways, which are specic to each feed. Therefore, the reaction rate equation for such a complex feed is generally
lumped into a single power law reaction [23]. The HDAs reactions
are modeled by power law models of nth orders of asphaltene and
mth orders power law model for hydrogen as follows:

r HDAs K HDAs C SAsph n C SH2 m

2.4. Characteristics of the catalyst


The correlations used for the characteristics of the catalyst bed
have been taken from the literature [1,26,30,3440]. These correlations are shown in Table 2.
2.5. Kinetic parameters of the mathematical model
It is required to generate a useful model that can be used condently to describe the reactor performance, design and operation
optimization, and accuracy in the calculations of kinetic parameters of the relevant reaction system. In this work, the asphaltene
order (n), hydrogen order (m), reaction rate constants (KHDAs), activation energy (EAHDAs) and pre-exponential factor (A0HDAs ) parameters of Eqs. (9) and (10) are signicant parameters for the HDAs
process. This paper is mainly focused upon the accurate calculation
of these parameters to be used in the process model for simulation
studies.

The reaction rate constant for HDAs reactions (KHDAs) are evaluated by employing the Arrhenius equation as follows:



EAHDAs
K HDAs A0HDAs exp 
RT

10

Table 1
Gasliquid properties and process coefcients used in the model equations.
Parameter

Equation

Gasliquid mass transfer coefcient

K LH aL
DLH

0:5
 0:4 
lL
7 GL
l
q DL

K Si
DLi aS

1=3

0:5 
lL
1:8 aGS lL
q DL

Liquidsolid mass transfer coefcients (i = H2, Asph)

H2

Molecular diffusivity (i = H2, Asph)

DLi 8:93  108 tL0:433 lT

Molar volume (i = H2, crude oil)

tL 0:285tiC 1:048
tcrude
7:5214  103 T meABP 0:2896 q15:6 0:7666 Mw
C

Henrys coefcient

hH2 kH q2
2 L

t0:267
i

H2 solubility
Oil density

VH

 


kH2 0:559729  0:42947  103 T 3:07539  103 qT 1:94593  106 T2 0:835783
q20 2
20
qL q0 DqP  DqT
 P 
 P 2
 0:01  0:299 263  100:0603q0   1000
DqP 0:167 16:181  100:0425q0   1000

DqT 0:0133 152:4q0 DqP 2:45   T  520  8:1  106  0:0622  100:764q0 DqP   T  5202
Oil viscosity

lL 3:141  1010 T  4603:444 log10 APIa


a 10:313log10 T  460  36  447
API sp141:5
 131:5
gr
15:6

186

A.T. Jarullah et al. / Applied Energy 94 (2012) 182191

3. Parameter estimation approaches

Min
n, m,
_ u(z), v) = 0, [z0,
s.t f(z, x(z), x,
zf]
nL 6 n 6 nU
mL 6 m 6 mU

Different parameter estimation techniques have been reported


elsewhere [2,3]. In the present study, two approaches have been
used in order to determine the best values of kinetic parameters
based upon the concentration of asphaltene in hydrodeasphaltenized products under various process conditions, which are:
A1. Non-linear regression to simultaneously determine the reaction orders of asphaltene compound (n), hydrogen compound
order (m) and reaction rate constants (KHDAs), then linear regression with the Arrhenius equation to calculate activation energy
(EAHDAs) and pre-exponential factor (A0HDAs ).
A2. Non-linear regression to estimate n, m, EAHDAs and A0HDAs
simultaneously.
Both approaches utilize the minimization of the following
objective function which is the sum of squared errors (SSEs) between the concentrations measured experimentally of asphaltene
cal
compound (C exp
Asph;i ) and predicted (C Asph;i ), in the products:

SSE

N
Data
X

cal
C exp
Asph;i  C Asph;i

i2

11

SSE
EAHDAs, A0HDAs

EALHDAs  EAHDAs  EAUHDAs


0
0U
A0L
HDAs  AHDAs  AHDAs

(process model, equality


constraints)
(inequality constraints)
(inequality constraints)
(inequality constraints)
(inequality constraints)

_ u(z), v) = 0 is the process model, x_ is the derivative of


f(z, x(z), x,
differential variables with respect to length of the bed reactor, z is
the length of the bed reactor (independent variable), x(z) is the
system of all differential and algebraic variables, u(z) is the control
variables, and v represents the length independent constant
parameters (the design variables). The optimization problem is
posed as a Non-linear Programming (NLP) problem and is solved
utilizing a Successive Quadratic Programming (SQP) method
within gPROMS package [41].
4. Experimental studies with pilot-plant TBR

i1

4.1. Equipment
3.1. Optimization problem formulation for parameter estimation
The parameter estimation problem formulation can be stated as
follows:
Given

Obtain

the crude oil feedstock, the reactor


conguration, the catalyst, reaction
temperature, hydrogen pressure and liquid
hourly space velocity.
for the rst approach (A1): the reaction orders
of asphaltene compound (n), hydrogen
compound (m) and reaction rate constants
(K 1HDAs ; K 2HDAs ; K 3HDAs ) at different temperatures
(335 C, 370 C, 400 C, respectively).
for the second approach (A2): the reaction
orders of asphaltene compound (n), hydrogen
compound (m), the activation energy (EAHDAs)

So as to
minimize
Subject to

and pre-exponential factor (A0HDAs ).


the sum of squared errors (SSEs).
process constraints and linear bounds on all
decision variables.

Mathematically, using the rst approach (A1), the problem can


be described as:
Min
n, m, KHDAs

SSE

_ u(z), v) = 0, [z0,
s.t f(z, x(z), x,
zf]
nL 6 n 6 nU
mL 6 m 6 mU

(process model, equality


constraints)

i
iU
K iL
HDAs 6 K HDAs 6 K HDAs ,
i = 1, 2, 3

(inequality constraints)
(inequality constraints)
(inequality constraints)

Using the second approach (A2), the problem can be presented


as:

Experiments were carried out in a continuous trickle bed reactor-pilot plant unit. Fig. 2 shows a schematic diagram of the hydrotreating pilot plant. The reactor is designed as a tube with an inside
diameter of 2 cm and a length of 65 cm. The length of the reactor is
divided into three parts. The rst part, of length of 20 cm, is lled
with inert particles. The second part of the reactor with a length
of 27.8 cm contained a packing of 60.3 g catalyst. The bottom section is also packed with inert particles of length of 17.2 cm. The
top part of the reactor is used to heat up the mixture to the required
temperature and ensuring homogeneous ow distribution of gas
and liquid in addition to avoid end effects, whereas the bottom part
is employed to serve as disengaging section. The reactor is operated
in isothermal mode by ve zone electric furnaces that provide an
isothermal temperature along the active reactor section. Before
the actual experiments, the catalyst was transformed into the active
sulde form by a solution of 0.6 vol.% of CS2 in a commercial gas oil.
4.2. Materials
Iraqi crude oil was employed as a feedstock for the pilot plant
HDT studies. The specications of the feedstock used in the present
work are presented in Table 3. The catalyst employed for the HDAs
process is a commercial cobaltmolybdenum on alumina (CoMo/
c-Al2O3) type catalyst. It has a diameter of 1.8 mm, a length of
4 mm, and a bulk density of 0.67 g/cm3. The catalyst used was
extruded with a cylindrical shape. The surface area and pore
volume of the catalyst are 180 m2/g and 0.5 cm3/g, respectively.
4.3. Experimental runs
While carrying out experiments, the following processes were
considered during crude oil hydrotreating:

Hydrodesulfurization (HDS).
Hydrodeasphaltenization (HDAs).
Hydrodenitrogenation (HDN).
Hydrodemetallization (HDM), involves
i. Hydrodevanadization (HDV).
ii. Hydrodenickelation (HDNi).

A.T. Jarullah et al. / Applied Energy 94 (2012) 182191

187

Fig. 2. Schematic diagram of the hydrotreating pilot-plant unit.

Table 3
Specications of the feedstock.
Sp gr @ 15.6 C
API
Pour point
Viscosity @ 37.8 C
Sulfur content
CCR
Nickel content
Nitrogen content
Vanadium content
Asphaltenes content

0.8558
33.84237
36 (C)
5.7 (cSt)
2.0 (wt%)
5.1 (wt%)
17 (ppm)
0.1 (wt%)
26.5 (ppm)
1.2 (wt%)

The major focus of this paper during hydrotreating is asphaltene content (HDAs). However, the effects of other impurities (sulfur,
nitrogen, vanadium and nickel) have not been neglected, but they
are addressed elsewhere [2,3].
The main hydrotreating reactions in this study are hydrodeasphaltenization (HDAs) reactions. The measured data from these
experiments are used to estimate the kinetic parameters of the
model that can be used to describe the HDAs reactions and to validate the model at various operating conditions. The pilot plant has
four main sections, which are:





Feed section
Reactor section
Products sections
Gases section

The feed section includes a gas and liquid feed. The gas supply
module (hydrogen) is fed to the reactor by a heated high-pressure
line and the unit was supplied with an electrical gas inlet ow
sensor and hydrogen ow rate. The feed supply module primarily
consists of a liquid feed tank and a feed pump. The feed tank is
cylindrical with a capacity of 2 L. The unit was supplied with a
high-pressure dosing pump to provide the feed oil into the reactor.
The feedstock and hydrogen pass through the reactor in a co-current ow mode. The reactor section is mentioned in Section 4.1.
The product section involves low and high pressure gasliquid separators and products storage tanks. The reactor outlet leads to these
separators (where the liquid and gas are separated). Eventually, the

gas section includes a gas ow meter through which the exiting gas
is passed before being released. Further details of the experimental
pilot plant employed in this work, (reactor, equipment and procedure, catalyst loading, catalyst presulding) can be found in Jarullah
et al. [4].
5. Results and discussions
5.1. Experimental results
A set of experiments has been conducted for crude oil hydrodeasphaltenization using the following operating conditions: the
reactor temperature was varied from 335 to 400 C, the liquid
hourly space velocity (LHSV) from 0.5 to 1.5 h1, the hydrogen
pressure from 4 to10 MPa but hydrogen to oil ratio (H2/Oil) was
kept constant at 250 NL/L.
The effect of operating conditions (reaction temperature, pressure and liquid hourly space velocity) on the asphaltene concentrations in products is presented in Fig. 3 (also in Table 5, and Fig. 6
with model predictions). The experimental observations showed
that the asphaltene content in the hydrotreated crude oil decreased
with decreasing liquid hourly space velocity and with increasing
temperature and pressure. These observations have been noted
by several investigators utilizing various oil feedstocks (i.e. oil fractions following distillation), but not the whole crude oil [23,42].
Signicant reduction in asphaltene content at high temperatures can be attributed to several factors: at high reaction temperature, the large molecules will be decomposed into smaller
molecules, which can diffuse more easily inside the catalyst pores
and reach the inner active sites where the HDAs reactions happen.
Also at high temperature, the oil viscosity will decrease leading to
high diffusion through the catalyst pores. Furthermore, the activation energy is raised by being increasing the temperature leading
to increase in the number of particles of these compounds interacted [14,43]. Deasphaltenization increases by decreasing liquid
hourly space velocity because of the contact time (residence time)
increases between the molecules of reactants and catalyst, and
provide sufcient time for the reaction process [23,44]. The reason
for increase in deasphaltenization by increasing hydrogen pressure
is related to the contact between the hydrogen and hydrocarbons
and the catalyst [42].

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A.T. Jarullah et al. / Applied Energy 94 (2012) 182191

5.2. Kinetic parameter estimation

Asphalten in products (wt%)

1.2
1
0.8
0.6
0.4
0.2
0
600

610

620

630

640

650

660

670

680

Temperature (K)
LHSV=0.5 (1/hr), P=4 Mpa
LHSV=0.5 (1/hr), P=7 Mpa
LHSV=0.5 (1/hr), P=10 Mpa

LHSV=1.0 (1/hr), P=4 Mpa


LHSV=1.0 (1/hr), P=7 Mpa
LHSV=1.0 (1/hr), P=10 Mpa

LHSV=1.5 (1/hr), P=4 Mpa


LHSV=1.5 (1/hr), P=7 Mpa
LHSV=1.5 (1/hr), P=10 Mpa

Fig. 3. Experimental results variation of outlet asphaltene content at different


operating conditions.

Table 4
Kinetic parameter values evaluated with two approaches for HDAs model.
m

K iHDAs

First approach (linear)


0.283440 (i = 1)
0.754769 (i = 2) 0.3039
1.857120 (i = 3)

EAHDAs

A0HDAs

SSE

1.449

98030.374

73221525.5

6.5  104

104481

2.56134  108

6.3  104

Second approach (non-linear)


0.3068 1.452

In this work, the kinetic parameters estimation for hydrodeasphaltenization of crude oil is carried out based upon the experimental information and the mathematical model of the trickle
bed reactor.
In the rst approach, the asphaltene order (n), hydrogen order
(m) and reaction rate constants (K iHDAs , i = 1, 2, 3) were calculated
simultaneously. A linearization approach is then used for determining the activation energy (EAHDAs) and the pre-exponential factor
(A0HDAs ). The Arrhenius equation (Eq. (10)) is utilized for calculating
the activation energy and the pre-exponential factor. The Arrhenius-based dependence of the kinetic model is illustrated in
Fig. 4. Plot of ln KHDAs versus 1/T gives a straight line with a slope
equal to EAHDAs/R and intercept equal to ln A0HDAs .
The activation energy (EAHDAs), pre-exponential factor (A0HDAs ),
asphaltene order (n) and hydrogen order (m) have been estimated
simultaneously using the second approach. The kinetic parameters
generated using both approaches are demonstrated in Table 4. It
can be seen from Table 4 that the rst approach gives a sum of
squared errors (SSEs) higher than the second approach, which gives
a clear indication that the kinetic parameters calculated with the
second approach are more accurate based upon the sum of squared
errors (the objective function). On the other hand, the calculation
of activation energy and pre-exponential factor by linearization
of the Arrhenius equation gives a higher error in comparison to
the kinetic parameters estimation by non-linear regression simultaneously. Therefore, a non-linear approach is applied for describing the performance of pilot plant TBR. The reaction order of
asphaltene is 1.452 and 0.3068 for hydrogen, which is typical for

Table 5
Simulation results of the pilot plant-TBR using linear and non-linear regression versus experimental results for crude oil hydrodeasphaltenization.
Operating conditions

Experimental results

Simulated results

LHSV
(h1)

P
(MPa)

T
(C)

Asphaltene
(wt%)

Conversion
(%)

Asphaltene (wt%)-Nonlinear regression

Conversion
(%)

Absolute
error (%)

Asphaltene (wt%)Linear regression

Conversion
(%)

Absolut
error (%)

0.5
1
1.5
0.5
1
1.5
0.5
1
1.5
0.5
1
1.5
0.5
1
1.5
0.5
1
1.5
0.5
1
1.5
0.5
1
1.5
0.5
1
1.5

4
4
4
4
4
4
4
4
4
7
7
7
7
7
7
7
7
7
10
10
10
10
10
10
10
10
10

335
335
335
370
370
370
400
400
400
335
335
335
370
370
370
400
400
400
335
335
335
370
370
370
400
400
400

0.639
0.868
0.966
0.335
0.610
0.760
0.153
0.355
0.510
0.560
0.790
0.910
0.262
0.512
0.660
0.116
0.295
0.440
0.520
0.750
0.860
0.236
0.475
0.620
0.089
0.255
0.398

46.75
27.67
19.50
72.08
49.17
36.67
87.25
70.42
57.50
53.33
34.17
24.17
78.16
57.33
45.00
90.33
75.42
63.33
56.67
37.50
28.33
80.33
60.42
48.33
92.58
78.75
66.83

0.6406
0.8611
0.9575
0.3244
0.5843
0.7300
0.1470
0.3618
0.5174
0.5778
0.8124
0.9195
0.2669
0.5189
0.6702
0.1107
0.3004
0.4508
0.5365
0.7788
0.8927
0.2331
0.4767
0.6303
0.0912
0.2636
0.4087

46.62
28.24
20.21
72.97
51.31
39.17
87.75
69.85
56.88
51.85
32.30
23.37
77.76
56.76
44.15
90.77
74.97
62.43
55.29
35.10
25.61
80.57
60.27
47.47
92.40
78.03
65.94

0.25
0.70
0.88
3.16
4.21
3.95
3.92
1.91
1.45
3.18
2.83
1.04
1.87
1.35
1.54
4.57
1.83
2.45
3.17
3.84
3.80
1.23
0.36
1.66
2.47
3.37
2.69

0.6173
0.8437
0.9441
0.3192
0.5789
0.7251
0.1504
0.3668
0.5226
0.5541
0.7938
0.9048
0.2627
0.5139
0.6657
0.1139
0.3057
0.4566
0.5131
0.7595
0.8772
0.2294
0.4721
0.6259
0.0942
0.2690
0.4148

48.56
29.69
21.32
73.40
51.76
39.57
87.47
69.43
56.45
53.82
33.85
24.60
78.11
57.17
44.52
90.51
74.52
61.95
57.24
39.71
26.90
80.88
60.66
47.84
92.15
77.58
65.43

3.39
2.80
2.27
4.72
5.10
4.59
1.70
3.32
2.47
1.05
0.48
0.57
0.27
0.37
0.86
1.81
3.63
3.77
1.33
1.27
2.00
2.80
0.61
0.95
5.84
5.49
4.22

Model prediction
0.75
1.25
1.25
1.5

10
4
5.5
5.5

400
370
385
335

Asphaltene content-wt% (using 2nd approach)

Conversion (%)

0.1783
0.6666
0.5563
0.9559

85.14
44.45
53.64
20.34

189

A.T. Jarullah et al. / Applied Energy 94 (2012) 182191

7.63E-03

0.6
n

0.5

-1

Ea

A0

6.63E-03
5.63E-03

-0.5
0

SSE

lnk HDAs

0.4

3.63E-03

0.2

y = -11.791x + 18.109
R2 = 0.9976

2.63E-03

0.1

0.5
1
1.66 1.64 1.62

4.63E-03
0.3

1.63E-03

0
-15.0% -10.0%
1.6

1.58 1.56 1.54 1.52

1.5

SSE

-1.5

-5.0%

1.48 1.46

0.0%

5.0%

10.0%

6.30E-04
15.0%

Perturbation

1000/T (K)
Fig. 5. Sensitivity analysis of evaluated kinetic parameters.

1.2
1

(a)

0.8
0.6
0.4
608 K
643 K
673 K

0.2
0
0.4

0.6

0.8

1.2

Simulated
Simulated
Simulated

1.4

1.6

Asphalten contenet in
products (wt%)

LHSV (hr -1)


1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0.4

(b)

608 K
643 K
673 K

0.6

0.8

1.2

Simulated
Simulated
Simulated

1.4

1.6

LHSV (hr -1)


Asphalten contenet in
products (wt%)

lumped kinetics. Jarullah et al. [2,3] had a similar observation in


estimating kinetic parameters for hydrodesulfurization, hydrodenitrogenation and hydrodemetallization of crude oil.
For the purpose of assessing the kinetic parameters and providing enough evidence to ensure that values of kinetic parameter estimated correspond to the global minimum of the objective function
(so that the developed process model is accurate), sensitivity analyses for n, m, EAHDAs and A0HDAs values were performed. The information obtained from parametric sensitivity analysis is very useful for
optimization and parameter calculation. It gives us a clear indication which parameter has the biggest inuence on the accuracy of
the kinetic model. The sensitivity of the parameters to the system
behavior is obtained by varying the parameter around the optimal
values of the selected parameter and estimating the corresponding
change in the objective function [45]. Sensitivity analysis is done by
perturbation of each calculated parameters and is preferably in the
range of 10% with keeping the other parameters in their original
values [46,47]. The objective function for each perturbation in the
parameter values is re-estimated. Then for each parameter, the perturbation value is drawn versus the corresponding value of the
objective function as illustrated in Fig. 5 (for each parameter). If
all perturbations in all the parameters give the same value of the
objective function as with their original values (0% perturbation),
then the global minimum has been achieved. In other words, when
at least one parameter does not give the same value as the others at
0% perturbation, this means that the values of this parameter need
to be re-determined due to poor parameter calculation. It is observed from Fig. 5 that the calculated kinetic parameters are the
optimum because the perturbations in n, m, EAHDAs and A0HDAs give
the same minimum of the objective function (SSE) with their original values at 0% perturbation, which give a clear indication that the
global minimum has been achieved. It has also been noticed from
Fig. 5, n and EAHDAs have the biggest impact on HDAs kinetic model
compared to m, and A0HDAs .
A comparison between experimental results and model predictions for crude oil hydrodeasphaltenization for both approaches is
shown in Table 5, and plotted in Fig. 6 (using the second approach).
It has been noticed from the results, the model predicts the asphaltene content very well (in the range of operating conditions used in
this work) with average absolute error less than 5% (between both
concentrations) by using second approach and maximum error
5.84 using the rst approach. It has also been observed (Fig. 6) that
the asphaltene content decreases with increasing temperature,
pressure and decreasing liquid hourly space velocity. These decreases can be attributed to the kinetics parameters used to describe HDAs reactions in this model are impacted by the process

Asphalten contenet in
products (wt%)

Fig. 4. Linear representation of Arrhenius equation for crude oil hydrodeasphaltenization.

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0.4

(c)

608 K
643 K
673 K

0.6

0.8

1.2

Simulated
Simulated
Simulated

1.4

1.6

LHSV (hr -1)


Fig. 6. Predicted (lines) and experimental results (points) variation of outlet
asphaltene content vs. liquid hourly space velocity at different reactor temperature
and at pressure (a) 4 MPa, (b) 7 MPa, (c) 10 MPa.

conditions. The reaction temperature of the reactor inuences


the diffusivities of the components, mass velocity of the gases
and liquids, solubility and Henrys coefcients of hydrogen, mass
transfer coefcient at the gasliquid and at the liquidsolid interfaces in addition to viscosity and density of the compounds.
The reaction temperature affects the rate constant of hydrodeasphaltenization reaction. The reaction rate constants described

A.T. Jarullah et al. / Applied Energy 94 (2012) 182191

Asphaltene concentration (mol/cm3)

190

Asphaltene (wt%) -Predicted

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

0.2

0.4

0.6

0.8

4.00E-05
3.50E-05

Liquid phase
Silid phase

3.00E-05
2.50E-05
2.00E-05
1.50E-05
1.00E-05
5.00E-06
0.00E+00
0

by the Arrhenius equations increase with increasing reaction temperature, leading to an increase in the reaction rates of HDAs.
These results supported the fact that reaction temperature is very
important to enhance the degree of deasphaltenization.
The partial pressure of hydrogen inuences the HDAs reactions.
The mechanisms utilized to describe the HDAs reactions used a kinetic equation with the order of the hydrogen concentration less
than 1.0 at the catalyst surface. Hence, asphaltene conversion will
increase with pressure. The impact of pressure above 10 MPa can
be neglected according to the literature because the viscosity of
the oil feedstock will increase with increasing pressure. The diffusivity and mass transfer coefcient as a result will decrease with
pressure. Thus, at high operating pressures, the pressure effect
upon asphaltene conversion becomes less important [27,28,48].
Liquid hourly space velocity (LHSV) is also an important operating condition, which calculates the severity of reaction and the efciency of the hydrotreating process. Increasing the residence time
means a decrease in liquid hourly space velocity described by liquid velocity, and therefore the reaction severity will increase.
On the other hand, the quantity of the reactions rates becomes
important whenever the liquid hourly space velocity is decreased,
[13,14,28,48].
Fig. 7 illustrates a parity plot of the model for HDAs reactions
presented in this study. The plot between the experimental results
and simulated asphaltene concentrations in all products appears to
be straight line with a slope close to 1.0, indicating very good
agreement between the experimentally measured results and the
theoretical data obtained via the model presented in this work.
The model can be employed to predict the asphaltene contents under various operating conditions for which experimental data are
not available as shown in Table 5.
5.3. Simulation of the pilot plant reactor system
The model developed can now be employed to describe the
behavior of the pilot plant trickle bed reactor used for crude oil
hydrodeasphaltenization. Fig. 8 shows the molar concentration
proles of asphaltene along the catalyst bed length in the liquid
and solid phase at maximum temperature (T = 400 C) and pressure (P = 10 MPa) and minimum liquid hourly space velocity
(LHSV = 0.5 h1). It has been observed from this Figure that the
concentration prole of asphaltene in both liquid phase and solid
phase reduces along the catalyst bed length. It is also noted that
there is a concentration gradient between both phases. This gradient is governed by liquidsolid mass transfer rate calculated from
the correlations employed in the model presented, which depends
on the physical properties of the liquid, such as density and

15

20

25

30

Fig. 8. Concentration proles of asphaltene in liquid and solid phase along the
reactor bed length.

0.9

Effectiveness Factor

Fig. 7. Comparative results between experimental and predicted concentrations of


asphaltene.

10

Reactor bed length (cm)

Asphaltene (wt%) - Experimental

0.5 (1/hr)

0.8
P

0.7

P
4M

Pa

0.6

1.0 (1/hr)

1.5 (1/hr)
P

7M

Pa

10

Pa

0.5
0.4
0.3
0.2
0.1
0
608 643 673

608 643 673

608 643 673

Temperature (K)
Fig. 9. Catalyst effectiveness factor at different operating conditions.

viscosity, and liquid mass velocity. Hence, the feedstock will become lighter and thus physical properties will be improved and
mass transfer of liquidsolid is enhanced reducing this concentration gradient [23,28].
Interior diffusion of the catalyst particle depends basically on
the porosity of the catalyst particle and on the molecules size being
diffused through the pores. In order to compare the impact of operating conditions upon internal gradients, effectiveness factor were
calculated and illustrated in Fig. 9 at different reactor temperature,
pressure and liquid hourly space velocity (LHSV). From the results
presented in this Figure, it is noticed that the effectiveness factor
decreases as the reaction temperature is increased due to the reaction rate constants that depends upon the reaction temperature
more strongly than the diffusivity leading to smaller effectiveness
factor [49]. With respect to reactor pressure and LHSV, it has been
observed that an increase in reactor pressure and decrease in LHSV
provokes a marginal reduction in the effectiveness factor compared
with the reaction temperature. This indication means that the
internal diffusion does not depend signicantly of these factors
(LHSV and pressure) due to the external diffusion that in fact is
function of these factors [30].
6. Conclusions
Contaminant-free high-quality energy sources are more in demand than ever due to legislation on environmental impact. Our
recent experimental study shows that the hydrotreating of whole
crude oil has the potential for meeting this demand. Asphaltene

A.T. Jarullah et al. / Applied Energy 94 (2012) 182191

is one of the important contaminants which must be removed to a


large extent from the fuel to meet the regulatory demand. Hydrodeasphaltenization (HDAs) of the whole crude oil directly is one of
the toughest and most challenging tasks in the petroleum rening
industry but no information regarding this is available in the public
domain. To assess the effectiveness of such process and to design
an efcient process, model based techniques are of great importance as they are comparatively much cheaper than the experimental based option. However, a reliable process model requires
an accurate estimation of the kinetic parameters of the asphaltenization reaction scheme in the trickle bed reactor which has been
the focus of this study. A rigorous process model of a TBR is developed in this work and the kinetic parameters for HDAs process
have been estimated in via minimization of the sum of square errors (SSEs) between the experimental data of asphaltene and the
model predictions. A series of experimental data were conducted
in a pilot plant trickle bed reactor in order to evaluate the effect
of operating conditions on HDAs reactions and to estimate the kinetic parameters of the reactions involved. Two approaches (linear
and non-linear regression) were employed to calculate the best kinetic parameters Based on the value of SSE, the kinetic parameters
calculated using non-linear regression is found to be more accurate
and gives lower error.
The model incorporating the estimated kinetic parameters is
then used for simulating the behavior of the pilot plant TBR system, which provides further insight of the process. The inuences
of operating conditions in crude oil hydrodeasphaltenization process are also reported.
Finally we note that sulfur, nitrogen, vanadium and nickel are
also regarded as important impurities in crude oil. Studying the effects of these contaminants was beyond the scope of this paper,
but has been reported in [2] and [3].
References
[1] Sattereld CN. Trickle-bed reactors. AIChE J 1975;21:20928.
[2] Jarullah AT, Mujtaba IM, Wood AS. Kinetic parameter estimation and
simulation of trickle-bed reactor for hydrodesulfurization of crude oil. Chem
Eng Sci 2011;66:85171.
[3] Jarullah AT, Mujtaba IM, Wood AS. Kinetic model development and simulation
of simultaneous hydrodenitrogenation and hydrodemetallization of crude oil
in a trickle-bed reactor. Fuel 2011;90:216581.
[4] Jarullah AT, Mujtaba IM, Wood AS. Improvement of the middle distillate yields
during crude oil hydrotreatment in a trickle-bed reactor. Energy Fuels
2011;25:77381.
[5] Hirschberg A, DeJong LNJ, Schipper BA, Meijer JG. Inuence of temperature and
pressure on asphaltene occulation. Soc Petroleum Eng J 1984;24:28393.
[6] Wang JX. Predicting asphaltene occulation in crude oils, PhD thesis. Socorro:
NMIMT; 2000.
[7] Wauquier JP. Crude oil petroleum products process owsheets. Paris: Institute
Francais du Petrole; 1995.
[8] Wiehe IA. Two-dimensional solubility parameter mapping of heavy oils. Fuel
Sci Technol Int 1996;14:289312.
[9] Mohammadi AH, Richon D. A monodisperse thermodynamic model for
estimating asphaltene precipitation. AIChE J 2007;53:29407.
[10] Abdul-Halim AM, Abdullah A, Ayad A, Abdul-Salam M. Catalytic hydrotreatment of petroleum residue. Fuel Sci Technol Int 1987;5:65575.
[11] Benito AM, Callejas MA, Martnez MT. Kinetics of asphaltene hydroconversion:
2. Catalytic hydrocracking of a coal residue. Fuel 1997;76:90711.
[12] Callejas MA, Martnez MT. Hydroprocessing of a maya residue. 1. Intrinsic
kinetics of asphaltene removal reactions. Energy Fuel 2000;14:13048.
[13] Areff HA. The effect of operating conditions on vacuum gas oil hydrotreating
on sulfur and aromatics content, MSc thesis. Iraq: University of Tikrit; 2001.
[14] Abbas AS. Low sulfur feedstock from basrah reduced crude oil for coke
production, MSc thesis. Iraq: University of Baghdad; 1999.
[15] Trejo F, Ancheyta J. Kinetics of asphaltenes conversion during hydrotreating of
Maya crude. Catal Today 2005;109:99103.

191

[16] Calemma V, Rausa R, DAntona P, Montanari L. Characterization of asphaltenes


molecular structure. Energy Fuel 1998;12:4228.
[17] Ting PD, Hirasaki GJ, Chapman WG. Modeling of asphaltene phase behavior
with the SAFT equation of state. Petrol Sci Technol 2003;21:64761.
[18] Bartholdy J, Andersen SI. Changes in asphaltene stability during hydrotreating.
Energy Fuel 2000;14:525.
[19] Leo MR, Rassadin B. Mathematical modelling of chemical processes. University
of Michigan: Mir Publishers; 1992.
[20] Khalfhallah HA. Modelling and optimization of oxidative desulfurization
process for model sulfur compounds and heavy gas oil, PhD thesis. UK:
Bradford University; 2009.
[21] Jimenez F, Nunez M, Kafarov V. Modeling of industrial reactor for
hydrotreating of vacuum gas oils Simultaneous hydrodesulfurization,
hydrodenitrogenation and hydrodearomatization reactions. Chem Eng J
2007;134:2008.
[22] Abbasi R, Fatemi Sh. Mathematical modeling of gas oil HDS and optimization
of operational conditions in trickle bed reactor by genetic algorithm. Int J
Chem React Eng 2009;7:127.
[23] Alvarez A, Ancheyta J. Modeling residue hydroprocessing in a multi-xed-bed
reactor system. Appl Catal A: General 2008;351:14858.
[24] Raid RC, Prausnitz JM, Poling BE. The properties of gases and liquids. 4th
ed. New York: McGraw-Hill; 1987.
[25] Ahmed T. Hydrocarbon phase behaviour. Houston: Gulf Publishing; 1989.
[26] Froment GF, Bischoff KB. Chemical reactor analysis and design. 2nd ed. New
York: Wiley; 1990.
[27] Korsten H, Hoffmann U. Three-phase reactor model pilot trickle-bed for
hydrotreating in reactors. AIChE J 1996;42:135060.
[28] Bhaskar M, Valavarasu G, Meenakshisundaram A, Balaraman S. Application of
a three phase heterogeneous model to analyse the performance of a pilot plant
trickle bed reactor. Petrol Sci Technol 2002;20:25168.
[29] Dudukovic MP, Larachi F, Mills PL. Multiphase catalytic reactors: a perspective
on current knowledge and future trends. Catal Rev 2002;44:123246.
[30] Macas MJ, Ancheyta J. Simulation of an isothermal hydrodesulfurization small
reactor with different catalyst particle shapes. Catal Today 2004;98:24352.
[31] Mederos FS, Rodrguez MA, Ancheyta J, Arce E. Dynamic modelling and
simulation of catalytic hydrotreating reactors. Energy Fuels 2006;20:93645.
[32] Shokri S, Zarrinpashne S. A mathematical model for calculation of effectiveness
factor in catalyst pellets of hydrotreating process. Petrol Coal 2006;48:2733.
[33] Mederos FS, Ancheyta J. Mathematical modeling and simulation of
hydrotreating reactors: cocurrent versus countercurrent operations. Appl
Catal A: General 2007;332:821.
[34] Mears DE. The role of axial dispersion in trickle-ow laboratory reactors. Chem
Eng Sci 1971;26:13616.
[35] Carberry JJ. Chemical and catalytic reaction engineering. New York: McGrawHill; 1976.
[36] Scamangas A, Marangozis N. Catalytic hydrodesulfurization of a petroleum
residue. Chem Eng Sci 1982;37:812.
[37] Shah YT. Gaslquidsolid reactor design. USA: McGraw-Hill Inc.; 1979.
[38] Li C, Chen W, Tsai C. Highly restrictive diffusion under hydrotreating reactions
of heavy residue oils. Ind Eng Chem Res 1995;34:898905.
[39] Chang J, Liu J, Li D. Kinetics of resid hydrotreating reactions. Catal Today
1998;43:2339.
[40] Marroquin G, Ancheyta J, Esteban C. A batch reactor study to determine
effectiveness factors of commercial HDS catalyst. Catal Today 2005;104:705.
[41] gPROMS. Introductory user guide. Process System Enterprise Ltd. (PSE); 2005.
<http://www.psenterprise.com/gproms/>.
[42] Ancheyta J, Rivera GB, Sanchez GM, Arellano AMP, Maity SK, Cortez MT, et al.
An exploratory study for obtaining synthetic crudes from heavy crude oils via
hydrotreating. Energy Fuels 2001;15:1207.
[43] Isoda T, Kusakabe K, Morooka Sh, Mochida I. Reactivity and selectivity for the
hydrocracking of vacuum gas oil over metal-loaded and dealuminated Yzeolites. Energy Fuels 1998;12:493502.
[44] Kim LK, Choi KS. Hydrodesulfurization over hydrotreating catalysts. Int Chem
Eng 1987;27:34057.
[45] Rao SK, Imam R, Ramanathan K, Pushpavanam S. Sensitivity analysis and
kinetic parameter estimation in a three way catalytic converter. Ind Eng Chem
Res 2009;48:377990.
[46] Resendiz E, Ancheyta J, Rosales-Quintero A, Marroquin G. Estimation of
activation energies during hydrodesulfurization of middle distillates. Fuel
2007;86:124753.
[47] Alcazar LA, Ancheyta J. Sensitivity analysis based methodology to estimate the
best set of parameters for heterogeneous kinetic models. Chem Eng J
2007;128:8593.
[48] Al-Humaidan FS. Modelling hydrocracking of atmospheric residue by discrete
and continuous lumping, MSc thesis. Kumait: Kuwait University; 2004.
[49] Shichi A, Satsuma A, Iwase M, Shimizu K, Komai Sh, Hattori T. Catalyst
effectiveness factor of cobalt-exchanged mordenites for the selective catalytic
reduction of NO with hydrocarbons. Appl Catal B: Environ 1998;17:10713.