Chemical Product and Process

Modeling
Volume 6, Issue 2

2011

Article 3

CAPE FORUM 2011

Modelling and Optimization of Crude Oil

Hydrotreating Process in Trickle Bed Reactor:
Energy Consumption and Recovery Issues
Aysar T. Jarullah, University of Bradford
Iqbal M. Mujtaba, University of Bradford
Alastair S. Wood, University of Bradford

Recommended Citation:
Jarullah, Aysar T.; Mujtaba, Iqbal M.; and Wood, Alastair S. (2011) "Modelling and
Optimization of Crude Oil Hydrotreating Process in Trickle Bed Reactor: Energy Consumption
and Recovery Issues," Chemical Product and Process Modeling: Vol. 6: Iss. 2, Article 3.
DOI: 10.2202/1934-2659.1600

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Modelling and Optimization of Crude Oil

Hydrotreating Process in Trickle Bed Reactor:
Energy Consumption and Recovery Issues
Aysar T. Jarullah, Iqbal M. Mujtaba, and Alastair S. Wood

Abstract
Energy consumption is a very important consideration for reducing environmental impact and
maximizing the profitability of operations. Since high temperatures are employed in hydrotreating
(HDT) processes, hot effluents can be used to heat other cold process streams. The aim of the
present paper is to describe and analyze the heat integration (during hydrotreating of crude oil in
trickle bed reactor) of a hydrotreating plants process based upon experimental work.
In this work, crude oil is hydrotreated upon a commercial cobalt-molybdenum on alumina
catalyst presulfided at specified conditions. Detailed pilot plant experiments are conducted in a
continuous flow isothermal trickle bed reactor (TBR) in which the main hydrotreating reactions,
are hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeasphaltenization (HDAs)
and hydrodemetallization (HDM). The latter includes hydrodevanadization (HDV) and
hydrodenickelation (HDNi). The reaction temperature, the hydrogen pressure, and the liquid
hourly space velocity (LHSV) are varied within certain ranges, with constant hydrogen to oil ratio
(H2/Oil).
Experimental information obtained from a pilot plant, together with kinetics and reactor
modeling tools,and a commercial process data are employed for heat integration process model.
The optimization problem to minimize the overall annual cost is formulated as a Non-Linear
Programming (NLP) problem, which is solved using Successive Quadratic Programming (SQP)
within gPROMS.
KEYWORDS: hydrotreating, trickle-bed reactor, integrated process, energy recovery

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Jarullah et al.: Optimization of Crude Oil Hydrotreating

1. Introduction
One of the tasks with which chemical engineers are continually addressing
included is the scale up of laboratory experiments to full-scale production. Due to
the high cost of a pilot plant study, this step is starting to be surpassed in several
instances via designing the full scale unit based on the process of a bench scale
plant called a microplant. In order to make this jump successfully, a thorough
understanding of the chemical kinetics and transport limitations is required.
However, energy conservation is significant in operation design. The estimation
of the minimum cooling and heating requirements reveal important energy
savings. For instance, Union Carbide in the USA and Imperial Chemical
Industries in the UK have both reported the results of numerous case
investigations that reference 30% to 50% energy savings in comparison to
conventional practice (Douglas, 1988).
Concentrations of carbon dioxide (CO2) in the atmosphere have increased
from 270 ppm before the industrial age to 380 ppm by 2006: a 31% increase since
1870 and a 41% increase over preindustrial values. The primary human source of
carbon dioxide in the atmosphere is from the burning of fossil fuels towards
energy production and transport. To avoid or reduce global warming, dramatic
cuts in all carbon dioxide emissions must be achieved, 25% to 40% below 1990
levels by 2020, and 80% to 95% below 1990 levels by 2050
(www.greenpeace.org). However, more efficient utilization of energy
consumption results in the reduction of the negative effects of carbon dioxide
emissions. Thus, process integration is an efficient design methodology, which
addresses cases related to energy efficiency, waste minimization and an efficient
utilization of raw materials.
Operation units, oil refineries, petrochemical complexes and gas units all
generate big amounts of low grade heat. This energy is usually rejected to the
atmosphere utilizing either air or cooling water systems. However, there are
opportunities for recovering some of this energy, and using it either as part of an
operation integration scheme or to heat in domestic and industrial specifications
by the installation of a hot water system. Energy integration is a very beneficial
tool and is a significant phase in estimating the cost of preliminary design, where
recovery of waste heat provides both financial and environmental benefits to
process unit operators. From an energy saving point view the significant field of
energy use improvement are the heat exchange retrofit projects for maximizing
the existing heat recovery (Khalfalla, 2009).
Traditional design methods begin by designing the reactor, the separation
system, the heat exchanger and finally end by utilizing utilities for supplying
residual needs (Douglas, 1988). The utility includes hot and cold utility units.
Typically, hot utility units are furnaces, turbines, generators, boilers and motors
1

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Chemical Product and Process Modeling, Vol. 6 [2011], Iss. 2, Art. 3

providing the necessary power, hot water and steam. Cold water from external
sources is employed as the cold utility, which provides the required cooling in the
operations. In the recovery system, the process streams exchange heat so as to
reduce the cold and hot utility requirements. The heat exchangers are the only
units in a heat recovery system (Khalfalla, 2009).
The main focus of this paper is to maximize heat recovery within the
crude oil hydrotreating process in a trickle bed reactor based, upon experimental
work and analysis the heat integration process.

2. Experimental Work
Briefly, hydrotreating experiments were conducted in an isothermal pilot-plant
continuous flow trickle bed reactor (TBR). The reactor tube was made from
stainless steel with an inside diameter of 2 cm and a length of 65 cm. The
temperature of the reactor was maintained at the desired value by utilizing
independent temperature control of five zone electric furnaces that provide an
isothermal temperature along the active reactor section. A commercial cobaltmolybdenum on alumina (Co-Mo/-Al2O3) catalyst was used for all experiments.
60.3 g of the fresh catalyst was charged to the HDT reactor and in situ activated
by a solution of 0.6 vol% of CS2 in commercial gas oil. Iraqi crude oil was
employed as a feed for the pilot plant hydrotreating studies. The main properties
of the feedstock and the catalyst used in this work are shown in Tables 1and 2,
respectively. The main hydrotreating reactions considered in this study are HDS,
HDN, HDAs and HDM, which involves HDV and HDNi. The experimental
studies were carried out by varying the temperature (335-400 C), the pressure 410 MPa and the liquid hourly space velocity (LHSV) 0.5-1.5 hr-1, maintaining
constant H2/Oil ratio at 250 L/L. Further details of the experimental pilot plant,
reactor, equipment and procedure, experimental runs, catalyst loading and catalyst
presulfiding used in this study can be found in Jarullah et al. (2011a,b,c,d).
Table 1: Feedstock specifications
Specific Gravity at 15.6 C
0.8558
Viscosity at 37.8 C
5.7 cSt
Pour point
-36 C
Sulfur content
2.0 wt %
Nitrogen content
0.1 wt %
Asphaltenes content
1.2 wt %
Vanadium content
26.5
Nickel content
17 ppm

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Jarullah et al.: Optimization of Crude Oil Hydrotreating

Table 2: Catalyst commercial specifications (Co-Mo/-Al2O3)

Chemical properties
MoO3
NiO
SiO2
Na2O
Fe
SO2
Al2O3
Physical properties
Form
Pore volume
Surface area
Mean particle length
Bulk density
Mean particle diameter

15 wt %
3 wt %
1.1 wt %
0.07 wt %
0.04 wt %
2 wt %
Balance
Extrude
0.5 cm3/g
180 m2/g
4 mm
0.67 g/cm3
1.8 mm

3. Energy Consumption and Recovery Issues

Pilot plant trickle bed reactor experiments show that conversion in hydrotreating
reactions is better at high reaction temperatures. Energy consumption for the pilot
plant scale was negligible and natural cooling after the reaction was sufficient (no
additional utility was required as the amounts reactants and products were small at
pilot plant scale), thus heat recovery was not taken into consideration. On the
other hand, heat recovery was not an issue in the pilot plant scale process. In
industrial processes, energy consumption will be a large issue and heat recovery
must be taken into account, especially when the type of reactions are exothermic.
Therefore, scaling up a heat integrated hydrotreating process was considered for
reducing overall energy consumption (hence reducing environmental effect).
However, this leads to the addition of a number of exchangers in the system,
requiring capital investment. The objective is to calculate a retrofit design, which
can reduce the energy consumption, maximize energy recovery and consequently
minimize capital investment.
Generally heat exchangers operate in series with a heater and a cooler. The
heater regulates the final temperature of the cold fluid to the required reaction
temperature, and the cooler adjusts the final temperature of the hot fluid to
requirements of the next step of the process. The exchangers, heaters and coolers
used for heat integration and energy consumption in this study are shown in
Figure 1.

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Chemical Product and Process Modeling, Vol. 6 [2011], Iss. 2, Art. 3

Figure 1: Process of heat integrated reaction system

As depicted in Figure 1, the crude oil feedstock (cold stream) is pumped

by P1 before preheating from TC0 to TC1 in heat exchanger H.E1. Then, the crude
oil is fed into furnace F1 in order to preheat from TC1 to the reaction temperature
(TR). The second main feedstock, which is hydrogen (cold stream) is fed into heat
exchanger H.E2 to preheat from TH0 to TH1. After this, its temperature rises from
TH1 to the reaction temperature (TR) by the furnace F1. The product stream
leaving the reactor (hot stream) is cooled from TP1 to TP2 by contacting with the
main crude oil feedstock in heat exchanger H.E1. Due to high reaction products
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Jarullah et al.: Optimization of Crude Oil Hydrotreating

temperature, the products stream is cooled again from TP2 to TP by in contact with
hydrogen feed in heat exchanger H.E2, then its temperature is reduced from TP to
the final product temperature (target temperature) TFP in cooler CO1 by using cold
water at TW1.

4. Model Equations
The major focus of this paper is to minimize energy consumption and maximize
heat recovery during crude oil hydrotreating. The main mass balance equations,
energy balance and reaction rate equations for all processes (HDS, HDN, HDAs,
HDV and HDN) are presented in Table 3. Other correlations for estimating gas
and liquid properties and characteristics of the catalyst bed used at process
conditions can be found in Jarullah et al. (2011b,c,d). Also, all the parameters
required for the industrial trickle bed reactor are estimated based on the
information presented in the literatures (Tarhan, 1983; Wauquier, 1995;
Rodriguez and Ancheyta, 2004; Bhaskar et al., 2004; Mederos and Ancheyta,
2007; Alvarez et al., 2009; Chen et al., 2010).
a) Heat Exchanger (H.E1)
The products stream that leaves the reactor is used for preheating the crude oil
feedstock from TC0 to TC1 through H.E1 and at the same time is cooled from TP1 to
TP2. The heat duties for these streams are described as follows:
Q1HE1 (VL c pL L ) (TC1 TC 0 )

(1)

Q2 HE1 (V L c pL L VG c Gp G ) (TP 2 TP1 )

(2)

Q2 HE1 Q1HE1
Q1HE1
AHE1
U HE1 Tlm1
T T2
Tlm1 1
T
ln 1
T2

(3)

T1 TP1 TC1
T2 TP 2 TC 0

(6)
(7)

(4)
(5)

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Chemical Product and Process Modeling, Vol. 6 [2011], Iss. 2, Art. 3

Table 3: Mass balances and reaction rate equations (Jarullah et al., 2011b,c,d)
Mass balance equations
Gases compounds (H2, H2S) in

dPi G
RT L Pi G

C iL
k i a L
gas phase

dz

ug

Gases compounds (H2, H2S) in

liquid phase

hi

L
G

dC i
1
k iL a L i C iL k iS a S C iL C iS
dz
u l

hi

Liquid compounds (S, N, Asph, V

and Ni) in liquid phase

dC iL
1
k iS a S C iL C iS
dz
uL

H2 in solid phase (j =HDS, HDN,

HDAs, HDV and HDNi)
H2S in solid phase

k HS 2

S, N, Asph, V and Ni in solid

phase (j =HDS, HDN, HDAs,
HDV and HDNi)
Energy balance equationa

k iS

a C C r
a C C
a C C r
L
H2

k HS 2 S

L
H 2S

S
H2

L
i

j j

S
H 2S

S
i

HDS HDS

j j

l
dT
H R r j B j
G
dz
u g G c p g u L L c pL l

Chemical reaction rates

rHDS K HDS

HDS

C C
S n
sul

1 K
C C

H 2S

S m
H2

C HS 2 S

HDN, HDAs, HDV and HDNi

rj K j

HDS , HDN, HDAs, HDV and

HDNi

EA j

K j A 0j exp
RT

H2S

2761
K H 2 S 41769 8411 exp

RT

S nj
i

S mj
H2

taken from Tarhan (1983)

Q1HE1 and Q2HE1 are heat duties of H.E1, TC0 is the inlet temperature of the
cold fluid, TC1 is the outlet temperature of the cold fluid, TP1 is the inlet
temperature of the hot products mixture, TP2 is the outlet temperature of the hot
products mixture, VL is the volumetric flow rate of crude oil, VG is the volumetric
flow rate of hydrogen (includes the main hydrogen feed plus quench feeds), L is
the liquid density, G is the gas density (includes all reacting gases), cpG is the
specific heat capacity of gas (involves all gases (reactants and products)), cpL is
the specific heat capacity of liquid, AHE1 is the heat transfer area of H.E1, UHE1 is

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Jarullah et al.: Optimization of Crude Oil Hydrotreating

the overall heat transfer coefficient for H.E1 and Tlm1 is the log mean
temperature difference for H.E1.
b) Heat Exchanger (H.E2)

The main hydrogen feedstock is heated from TH0 to TH1 in H.E2 by contact with
the products stream that leaves H.E1, which is cooled at the same time from TP2 to
TP in H.E2. The model equations for H.E2 are:
Q1HE 2 (VH 2 c Hp 2 G ) (TH 1 TH 0 )

(8)

Q2 HE 2 (VL c L VG c G ) (TP TP 2 )

(9)

L
p

G
p

Q2 HE 2 Q1HE 2
Q1HE 2
AHE 2
U HE 2 Tlm 2
T T4
Tlm 2 3
T
ln 3
T4

(10)

T3 TP 2 TH 1
T4 TP TH 0

(13)
(14)

(11)
(12)

Q1HE2 and Q2HE2 are heat duties of H.E2, TH0 is the inlet temperature of the
cold fluid, TH1 is the outlet temperature of the cold fluid, TP2 is the inlet
temperature of the hot products mixture, TP is the outlet temperature of the hot
products mixture, VH2 is the volumetric flow rate of hydrogen (without quench
feeds), cpH2 is the specific heat capacity of hydrogen, AHE2 is the heat transfer area
of H.E2, UHE2 is the overall heat transfer coefficient for H.E2 and Tlm2 is the log
mean temperature difference for H.E2.
c) Cooler (CO1)

The product stream that leaves H.E2 is cooled from TP to the final product
temperature TFP in the cooler by using water at TW1. The model equations for CO1
are shown below:
Q1CO1 mW cp w (TW 2 TW 1 )

(15)

Q2CO1 (VL c L VG c G ) (TFP TP )

(16)

Q2CO1 Q1CO1

(17)

L
p

G
p

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Chemical Product and Process Modeling, Vol. 6 [2011], Iss. 2, Art. 3

Q1CO1
U CO1 Tlmc
T T6
5
T
ln 5
T6

ACO1

(18)

Tlmc

(19)

T5 TP TW 2
T6 TFP TW 1

(20)
(21)

Q1CO1 and Q2 CO1 are heat duties of CO1, TW1 and TW2 are the inlet and
outlet temperature of the cooled water, TFP is the final products temperature, ACO1
is the heat transfer area of CO1, UCO1 is the overall heat transfer coefficient for
CO1, Tlmc is the log mean temperature difference for CO1, cpw is the heat
capacity of water and mw is the mass flow rate of cooling water.
The total heat transfer area (At) is given in the following equation:
At AHE1 AHE 2 ACO1

(22)

d) Furnace (F1)

The main feedstocks, crude oil and hydrogen are fed into furnace F1 separately in
order to preheat from TC1 to the reaction temperature (TR) for crude oil and from
TH1 to TR for hydrogen. The heat equations for F1 can be written as follows:
QH 2 (VH 2 c Hp 2 G ) (TR TH 1 )

(23)

QCrude (VL c Lp L ) (TR TC1 )

(24)

QF QH 2 QCrude

(25)

Note, all the physical properties of gases and liquid (such as gas and liquid
density, heat capacity of gas and liquid, gas compressibility factor) are estimated
at average temperature (Tav) for each equipment using the following equation:
Tav

Tin Tout
2

(26)

Tin and Tout are the inlet and outlet temperatures for item of each equipment.

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Jarullah et al.: Optimization of Crude Oil Hydrotreating

5. Optimization Problem Formulation

The optimization problem can be stated as follows:
Given

Optimize

inlet temperature of crude oil (TC0) and hydrogen (TH0),

outlet temperature of products mixture (TP1), reaction
temperature (TR), inlet water temperature(TW1), volumetric
flow rate of liquid (VL) and gas (VH2 and VG).
TP2, TH1, TW2

So as to minimize the total annual cost of the process (Ct).

Subject to

process constraints and linear bounds on all decision

variables.

Mathematically, the optimization problem can be presented as:

Min
Ct
TP2, TH1, TW2
s.t
f(x(z), u(z), v) = 0
TP2L TP2 TP2U
TH1L TH1 TH1U
TW2 L TW2 TW2 U
TF L TF TFU
TW L TW TW U
TR = TR*
TFP = TFP*

(model, equality constraints)

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

TW and TF are the temperature differences between the inlet and outlet
temperatures of water in the cooler and liquid crude oil in the furnace,
respectively. TR* is the required reaction temperature (which is 400C) and TFP* is
the target final temperature of product (which is 26C). Note, in practice, that the
best temperature difference between inlet and outlet water in the cooler is within
5-20C, and between inlet and outlet crude oil in the furnace within 100-130C,
which are quite practical. U and L are the upper and lower bounds.

5.1 Cost Function

The objective function is the overall annual process cost (Ct), which can be
calculated using the following expression:

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Chemical Product and Process Modeling, Vol. 6 [2011], Iss. 2, Art. 3

Ct ($/yr) = Annualized Capital Cost ($/yr) + Operating Cost ($/yr)

(27)

To calculate the annualized capital cost (ACC) from capital cost (CC), the
following equation is used (Smith, 2005):
ACC CC

i (1 i ) n
(1 i ) n 1

(28)

n is number of years and i is the fractional interest per year; n = 10 years, i = 5%

(Smith, 2005).
Capital Cost (CC, $) = Reactor Cost (CR) + Compressor Cost (CComp) + Heat
Exchanger Cost (CHE) + Pump Cost (CP) + Furnace Cost (CF)
(29)

The operating cost is calculated as shown below:

Operating Cost ($/yr) = Heating Cost (CH) + Compression Cost (CCmpr) +
Pumping Cost (CPU) + Cooling Cost (CCol)
(30)

The capital costs of equipment can be estimated using the following

equations (Douglas, 1988; Smith, 2005; Quintero and Villamil, 2009):
a) Reactor Cost (CR)

M &S
1.066 0.802
C R ($)
101.9 DR LR (2.18 FC )
280
FC Fm F p

(31)
(32)

b) Compressor Cost (CComp)

M &S
0.82
C Comp ($)
(517.5)(bhp) (2.11 Fd )
280

hp
bhp

ise

P
3.03 10 5
Pin Qin out
hp

Pin

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(33)
(34)
(35)

10

Jarullah et al.: Optimization of Crude Oil Hydrotreating

cp H 2

H 1
2
cv

H2
cp
H
2
cv

(36)

cv G cp G R

(37)

c) Heat Exchanger Cost (CHE)

M &S
0.65
C HE ($)
210.78 At (2.29 FC )
280

FC ( Fd F p ) Fm

(38)

(39)

d) Pump Cost (CP)

Q
M &S
3
C P ($)
9.84 10 FC P
280
4
FC Fm F p FT

0.55

(40)
(41)

e) Furnace Cost (CF)

M &S
3
0.85
C F ($)
5.52 10 QF (1.27 FC )
280

FC Fd Fm F p

(42)
(43)

M&S is the Marshall and Swift index for cost escalation (M&S = 1468.6
(chemical engineering, 2010)), bhp is the brake horsepower required in the
compressor motor, hp is the compressor horsepower,ise is isentropic efficiency,
is the specific heat ratio, Qin is the volumetric flow rate at compressor suction, cvG
is the specific heat capacity at constant volume and Pin and Pout are the pressure in
the compressor inlet and outlet, respectively. ise ranges between 70-90% (here it
is assumed to be 80%) (Douglas, 1988). Qp is the pump power, QF is the heat duty
of the furnace, LR is the reactor length, DR is the reactor diameter and FC, Fm, Fp,
FT and Fd are the dimensionless factors that are functions of the construction
material, operating pressure and temperature, and design type.

11

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Chemical Product and Process Modeling, Vol. 6 [2011], Iss. 2, Art. 3

The operating cost is calculated using the following expressions:

a) Heating Cost (CH)

0.062$ 24h 340day

C H ($ / yr ) QF (kW )

kWh 1day 1yr

(44)

b) Compression Cost (CCmpr)

bhp(hp) 1kW 0.062$ 24h 340day

C Cmpr ($ / yr )

0.9 1.341hp kWh 1day 1yr

(45)

c) Pumping Cost (CPU)

0.062$ 24h 340day

C PU ($ / yr ) QP (kW )

kWh 1day 1yr

(46)

d) Cooling Cost (CCol)

kg f $ 24h 340day

C Col ($ / yr ) mw w

h kg 1day 1yr

(47)

fw is the price of cooling water, which is 0.0305 $ per ton (Khalfallah, 2009). The
compression cost is based upon a motor efficiency of 90% (Bouton and Luyben,
2008) and an average power price of 0.062$/kWh (Alvarez et al., 2009).

6. Results and Discussion

The industrial trickle bed reactor (TBR) in this study has a processing capacity of
10000 bbl/day. The reactor is assumed to operate for 340 days/yr. In our previous
study (Jarullah et al., 2011a), it has been found that the crude oil hydrotreatment
process (from experimental data) achieved maximum conversion of the impurities
(sulfur, nitrogen, vanadium, nickel and asphaltene) at reaction temperature 400
C, liquid hourly space velocity (LHSV) 0.5 hr-1 and hydrogen pressure 10 MPa.
These conditions are utilized as a typical operating condition for the industrial
trickle bed reactor (TBR).
The values of constant parameters with factors and coefficients used in
this work (Douglas, 1988; Sinnott, 2005; Smith, 2005) are listed in Table 4.

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Jarullah et al.: Optimization of Crude Oil Hydrotreating

Table 4: Values of constant parameters, factors and coefficients used in this work
Parameter
Unit
Value
C
28.00
TC0
C
70.00
TH0
C
406.02
TP1
C
20.00
TW1
kJ/kg K
4.189
Cpw
W/m2 K
250
UHE1
W/m2 K
113
UHE2
2
W/m K
400
UCO1
Dimensionless Factors
Fm
Fp
Fd
FT
3.67
3.93
0.0
0.0
Reactor
0.0
1.0
0.0
0.0
Compressor
0.75
0.15
1.0
0.0
Furnace
1.0
1.9
0.0
1.0
Pump
3.75
0.625
1.0
0.0
Heat Exchanger

6.1 Kinetic Parameters Estimation

The optimal set of kinetic parameters for crude oil hydrotreating reactions
(involve HDS, HDN, HDAs, HDV and HDNi) have been evaluated based upon
minimizing the sum of squared error between experimental and estimated results.
These kinetic parameters were validated against pilot plant experiments reported
elsewhere (Jarullah et al., 2011b,c,d). Such kinetic parameters (summarized in
Table 5) used for HDS, HDAs, HDN, HDV and HDNi have been developed
accurately among all results for all reactions with average absolute error less than
5%, which can be confidently applied for reactor design, operation and control.
Table 5: Kinetic parameters of hydroprocessing reactions (Jarullah et al., 2011b,c,d)
Reactions
Reaction Hydrogen Activation
Pre-exponential factor (A0)
(mol/cm3)1-n.(cm3/g.sec).
order (n) order (m) energy (EA)
(J/mol)
(mol/cm3)-m
1.147
0.4709
50264.10
2026.23
HDS
1.672
0.3555
71775.5
2.85107
HDN
1.452
0.3068
104481
2.56134108
HDAs
1.251
0.6337
46181.6
126566
HDV
1.688
0.5667
37678.3
1.045108
HDNi
Note: these parameters are used in the model equations presented in Table 3.

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Chemical Product and Process Modeling, Vol. 6 [2011], Iss. 2, Art. 3

Table 6: Results of optimization problem for heat integration process

Variables
Without heat
With heat
Decision
Optimized
integration
integration
variable type value
At (m2)
475.3148
1033.207
202.99
TP2 (C)
Ct ($/yr)
9744870.8
4310909.8
200.57
TH1 (C)
CS (%)
------55.76
40.00
TW2 (C)
mw (kg/hr)
711873.9
272716.56
400.00
TR (C)
Qt (kJ)
1386189676.8
496317300.5
110.25
TF (C)
QC (kJ)
1431379037
548357040
20.00
TW (C)
QHE1 (kJ)
------784918598.4
26.00
TFP (C)
QHE2 (kJ)
------104953777.9
------------Qr (kJ)
------889872376.3
------------ES (%)
0.0
64.2
------------CS = Cost saving, ES = Energy saving, Qr = Heat recovery, Qt = Total heating, QC = Heat
duty of cooler, QHE = Heat duty of exchanger1,2.

6.2 Optimization Results

The optimization results, which are summarized in Table 6, show that the
minimum total cost (Ct) and cooling water amounts with heat integration of the
hydrotreating process are less than those without the heat integration at specified
variables. The cost saving is around 56% in comparison with the cost obtained
without heat integration to achieve the reaction temperature (400C) and to reduce
the final product temperature up to 26C. Also, the amount of cooling water
required for reaching the final product temperature is greater than that with heat
integration due to the heat recovery, and consequently the cost of the cold utility
in addition to capital cost of cooler will decrease.
The results also show that the minimum energy requirement was reduced
by 64.2%. Therefore, the CO2 emissions will be reduced by 64.2%, which has the
added benefit of significantly reducing environmental impact.

7. Conclusions
Heat integration and energy consumption in a hydrotreating process were
investigated. It has been observed that the energy consumption and heat recovery
is considered a big issue that should be taken into account in industrial operations
particularly when the type of reactions are exothermic, the recovery of which is
very significant for maximizing profitability of process. Optimization problem
was formulated in order to optimize some of the design and operating parameters
of integrated process while minimizing an objective function, which is a coupled
function of capital and operating costs including design parameters. Optimal

DOI: 10.2202/1934-2659.1600

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Jarullah et al.: Optimization of Crude Oil Hydrotreating

minimum energy requirements, heat recovery and cost saving were obtained
utilizing optimization process. The results show that the cost saving are 55.76%
and the energy saving is 64.2% in comparison to the process without heat
integration. This saving in the energy consumption provides better minimum
energy requirement, hence reducing environmental effect and maximum heat
recovery.

Nomenclature
aL

Gasliquid interfacial area, cm-1

aS
ACC
ACO1
AHE1
AHE2
At
A0 j
HDAs
HDM
HDN
HDNi
HDS
HDT
HDV
CF

Liquidsolid interfacial area, cm-1

Annualized capital cost, $/yr
Heat transfer area of CO1, m2
Heat transfer area of H.E1, m2
Heat transfer area of H.E2, m2
Total heat transfer area, m2
Pre-exponential factor for reaction j, (mol/cm3)1-n(cm3/g.sec)(mol/cm3)-m
Hydrpdeasphaltenezation
Hydrodemetalization
Hydrodenitrogenation
Hydrodenickelation
Hydrodesulfurization
Hydrotreating
Hydrodevanadization
Furnace cost, $

CH
CHE

C iL

Heating cost, $/yr

Heat exchanger cost, $
Concentration of i compound in the liquid phase, mol/cm3

C iS

Concentration of i compound in the solid phase, mol/cm3

CP

CPU
CR
Ct
cpw
cv
DR
EA j

Pump cost, $
Specific heat capacity, J/g.K
Pumping cost, $/yr
Capital cost of the reactor, $
Overall annual process cost, $/yr
Heat capacity of water, J/g.K
Specific heat capacity at constant volume, J/g.K
Reactor diameter, cm
Activation energy for j process, J/mol

hi

Henrys coefficient, MPa.cm3/mol

hp

Compressor horsepower

cp

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Chemical Product and Process Modeling, Vol. 6 [2011], Iss. 2, Art. 3

Kj

Reaction rate constant for j reaction, (mol/cm3)1-n(cm3/g.sec)(mol/cm3)-m

K H 2S

Adsorption equilibrium constant of H2S, cm3/mol

k iL

Gasliquid mass transfer coefficient for i compound, cm/sec

k iS

liquidsolid mass transfer coefficient for i compound, cm/sec

LR
mj

Length of reactor bed, cm

Order of reaction of hydrogen in reaction j

mw
nj
M&S
N
Ni
P1
Pi G
Pin
Pout
q
Qi
Qin
Qp
rj
R
S
T
TBRs
TC0
TC1
TFP

Mass flow rate of cooling water, g/sec

Order of reaction of i compound in reaction j
Marshall and Swift index for cost escalation
Nitrogen
Nickel
Pumps1
Partial pressure, MPa
Inlet pressure, Ib/ft3
Outlet pressure, Ib/ft3
Quench mass flow rate, g/sec
Heat duties of H.E1,2, CO1, C1 and F1, J/sec
Volumetric flow rate at compressor section, ft3/min
Power pump, kW
Chemical reaction rate of j reaction per unit mass of catalyst, mol/g.sec-1
Universal gas constant, J/mol.K
Sulfur
Temperature
Trickle Bed Reactors
Inlet temperature of the cold fluid to H.E1, K
Outlet temperature of the cold fluid from H.E1, K
Outlet product temperature from CO1, K

TH0
TH1
TP
TP1
TP2
TR
Tw1
Tw2
UCO1
UHE1

Inlet temperature of the cold fluid to H.E2, K

Outlet temperature of the cold fluid from H.E2, K
Outlet temperature of the hot products mixture from H.E2, K
Inlet temperature of the hot products mixture to H.E1, K
Outlet temperature of the hot products mixture from H.E1, K
Inlet reactor temperature, K
Inlet water temperature to CO1, K
Outlet water temperature from CO1, K
Overall heat transfer coefficient for CO1, W/m2 K
Overall heat transfer coefficient for H.E1, W/m2 K

UHE2

Overall heat transfer coefficient for H.E2, W/m2 K

ug
uL

Velocity of the gas, cm/sec

Velocity of the liquid, cm/sec

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Jarullah et al.: Optimization of Crude Oil Hydrotreating

V
VG
VH2
VL
z

Vanadium
Volumetric flow rate of gas, cm3/sec
Volumetric flow rate of hydrogen, cm3/sec
Volumetric flow rate of crude oil, cm3/sec
Axial position along the catalyst bed, cm

Greek letters
HR

Overall heat of reaction, J/mol

Bulk density of the catalyst particles, g/cm3

B
L
G
j

Liquid density at process conditions, g/cm3

Gas density, g/cm3
Catalyst effectiveness factor for j reaction

ise
g
l

Isentropic efficiency

Tlm

log mean temperature difference

Gas phase fraction

Liquid phase fraction
Specific heat ratio

Superscripts
G
H2
L

Gas phase
Hydrogen
Liquid phase or gas-liquid interface

Solid phase or liquid-solid interface

Subscripts
B
F
g

Bulk
Furnace
Gas

G
H2

Gases
Hydrogen

H2S

Hydrogen sulphide

Liquid

R
sul

Reactor
Sulfur

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Chemical Product and Process Modeling, Vol. 6 [2011], Iss. 2, Art. 3

References
Alvarez, A and Ancheyta, J. (2009). Effect of Liquid Quenching on
Hydroprocessing of Heavy Crude Oils in a Fixed-Bed Reactor System.
Ind. Eng. Chem. Res, 48, pp 1228.
Bhaskar, M., Valavarasu, G., Sairam, B., Balaraman, K.S. and Balu, K. (2004).
Three-Phase Reactor Model to Simulate the Performance of Pilot-Plant
and Industrial Trickle-Bed Reactors Sustaining Hydrotreating Reactions.
Ind. Eng. Chem. Res., 43, pp 6654.
Bouton, G.R. and Luyben, W.L. (2008). Optimum Economic Design and Control
of a Gas Permeation Membrane Coupled with the Hydrotreating (HAD)
Process. Ind. Eng. Chem. Res., 47, pp 1221.
Chemical Engineering. (2010). Economic Indicators. www.che.com [Accessed
January 16, 2010].
Chen, H., Zheng, J., Xu, P., Li, L., Liu, Y. and Bie, H. (2010). Study on real-gas
equations of high pressure hydrogen. International Journal of Hydrogen
Energy, 35, pp 3100.
Douglas, J.M. (1988). Conceptual Design Chemical Processes. New York,
McGraw- Hill.
Jarullah, A.T., Mujtaba, I.M., Wood A.S. (2011a). Improvement of the Middle
Distillate Yields during Crude Oil Hydrotreatment in a Trickle-Bed
Reactor. Energy and Fuels, 25, pp 773.
Jarullah, A.T., Mujtaba, I.M., Wood A.S. (2011b). Kinetic parameter estimation
and simulation of trickle-bed reactor for hydrodesulfurization of crude oil.
Chemical Engineering Science, 66, pp 859.
Jarullah, A.T., Mujtaba, I.M., Wood A.S. (2011c). Kinetic Model Development
and
Simulation
of
Simultaneous
Hydrodenitrogentaion
and
Hyhdrodemetallization of Crude Oil in a Trickle-Bed Reactor. Fuel, 90,
pp 2165.
Jarullah, A.T., Mujtaba, I.M., Wood A.S. (2011d). Hydrodeasphaltenization of
Crude Oil in a Trickle Bed Reactor: Kinetic Model Development and
Process Simulation. Submitted to Chemical Engineering Science.
Khalfhallah, H.A. (2009). Modelling and optimization of Oxidative
Desulfurization Process for Model Sulfur Compounds and Heavy Gas Oil.
PhD Thesis, University of Bradford.
Mederos, F.S. and Ancheyta, J. (2007). Mathematical modeling and simulation of
hydrotreating reactors: Cocurrent versus countercurrent operations.
Applied Catalysis A: General, 332, pp 8.
Quintero, A.R. and Villamil, V.F.D. (2009). On the Multiplicities of a Catalytic
Distillation Column for the Deep Hydrodesulfurization of Light Gas Oil.
Ind. Eng. Chem. Res., 48, pp 1259.
DOI: 10.2202/1934-2659.1600

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Jarullah et al.: Optimization of Crude Oil Hydrotreating

Rodriguez, M.A. and Ancheyta, J. (2004). Modeling of Hydrodesulfurization

(HDS), Hydrodenitrogenation (HDN), and the Hydrogenation of
Aromatics (HDA) in a Vacuum Gas Oil Hydrotreater. Energy Fuels, 18,
pp 789.
Sinnott, R.K. (2005). Chemical Engineering, Volume 6: Chemical Engineering
Design. 4th ed. UK, Elsevier Butterworth-Heinemann.
Smith, R. (2005). Chemical Process Design and Integration. UK, John Wiley &
Sons.
Tarhan, O.M. (1983). Catalytic Reactor Design. New York, McGraw-Hill.
Wauquier, J.P. (1995). Crude Oil: Petroleum Products; Process Flowsheets.
Paris, Editions Technip.

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