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Applied Energy

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

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

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].

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

(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

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

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

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.

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

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

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

particles)

The bed void fraction of the

catalyst

e

e

as AC 1

2ppr2rLL 1 e 2r 1 e 41

m

d

diameter

Effectiveness factor

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.

"

2

ds

h

2 i1=2

d

ds dc Lc 2c

/Asph

gHDAs tanh

/Asph

/Asph VSPP

DeAsph sh

DK

D 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

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].

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:

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

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

H2

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

a 10:313log10 T 460 36 447

API sp141:5

131:5

gr

15:6

186

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

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

0

0U

A0L

HDAs AHDAs AHDAs

constraints)

(inequality constraints)

(inequality constraints)

(inequality constraints)

(inequality constraints)

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

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

the sum of squared errors (SSEs).

process constraints and linear bounds on all

decision variables.

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

constraints)

i

iU

K iL

HDAs 6 K HDAs 6 K HDAs ,

i = 1, 2, 3

(inequality constraints)

(inequality constraints)

(inequality constraints)

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).

187

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].

188

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=7 Mpa

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

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

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

operating conditions.

Table 4

Kinetic parameter values evaluated with two approaches for HDAs model.

m

K iHDAs

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

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

(%)

Conversion

(%)

Absolute

error (%)

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

Conversion (%)

0.1783

0.6666

0.5563

0.9559

85.14

44.45

53.64

20.34

189

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

1.5

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%)

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

Asphalten contenet in

products (wt%)

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%)

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

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.

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

190

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

asphaltene.

10

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

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

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].

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