JECET; March 2014-May 2014; Vol.3.No.2, 1015-1034.

E-ISSN: 2278179X

Journal of Environmental Science, Computer Science and

Engineering & Technology
An International Peer Review E-3 Journal of Sciences and Technology

Available online at www.jecet.org

Section C:Engineering & Technology
Research Article

Improving the Performance of the Naphtha Stabilizer in

the Refinery Plant
*Ahmed Raheem Hashim and Alaa Abdulrazaq Jassim
*Department of Chemical Engineering, Basra University Basrah, Iraq
Department of Chemical Engineering, Basra University Basrah, Iraq
Received: 18 March 2014; Revised: 04 April 2014; Accepted: 12 April 2014

Abstract: In this study, theoretical investigations have been made concerning naphtha
stabilizer column at the Basra refinery. The main objective of the naphtha stabilizer
distillation is to separate the light ends and LPG product from the reformate product. The
naphtha stabilizer was subjected to simulation and optimization to find the optimum
operating conditions by using Aspen HYSYS V7.1 and MATLAB (R2008a) program. A
steady state simulation model is utilized to study the behavior of multi-component nonideal mixture in the naphtha stabilizer distillation. A procedure has been introduced to
build up a mathematical model and simulation for a naphtha stabilizer based on the
MESH equations. The set of algebraic equations are solved by using tridiagonal matrix
method. The simulation model was subjected to the validity test by comparing the
simulation results with the HYSYS simulation results. The validity test shows a great
similarity and reliability for simulation model where it was highly accurate and very
close to HYSYS simulation results, where the ABS deviation was(<0.014). Optimization
results shows that, its possible to increase the recovery of C5+ in the reformate from
97 % in actual unit to 99.6 %, also the reformate production increases about (2.383%)
from the actual reformate production by changing the design variables and operating
conditions. HYSYS process modeling software was used to analyze the effect of reflux
ratio, feed temperature, column pressure, column efficiency, condenser cooling duty and
reboiler heating duty on the recovery of C5+ in the reformate and the reformate
production naphtha stabilizer distillation column.
Keywords: Refinery Plant, Naphtha stabilizer, Modeling, Simulation, Optimization,
HYSYS.
JECET; March 2014-May 2014; Vol.3.No.2, Sec. C; 1015-1034.

1015

Improving...

Hashim and Jassim.

INTRODUCTION
Naphtha is transformed into reformate by catalytic reforming. This process involves the
reconstruction of low-octane hydrocarbons in the naphtha into more valuable high-octane gasoline
components without changing the boiling point range. Naphtha and reformate are complex mixtures
of paraffins, naphthenes, and aromatics in the C5C12 range. The purpose of catalytic reforming is
primarily to increase the octane number of the naphtha feedstock to a level that makes the reformate
product suitable as a gasoline blend stock. The octane number represents the ability of a gasoline to
resist knocking during combustion of the airgasoline mixture in the engine cylinder. Stabilizing the
reformates in the naphtha stabilizer lead to increase RON, and this is done by eliminating the
impurities in the reformate (impurities like Hydrogen, Sulfur, light gases and LPG). A stabilizer is
essentially a distillation column intended to remove what is normally a relatively small amount of
"light ends" from a product. The general objective of distillation is the separation of substances that
have different vapor pressures at any given temperature. The word distillation as used here refers to
the physical separation of a mixture into two or more fractions that have different boiling points1.
Separation technology plays an important role in the process engineering. The typical separation
techniques are such as distillation, absorption, extraction and so on. On account of the complexities of
feeds, products and by-products as well as various additives, multi-component multi-stage separation
is especially important and widely used, so the development of the proper algorithm for simulating
such processes is critically important2. Simulation is a key step in distillation column optimization
problems. Accuracy, speed and convergence properties are three important factors in selection of
proper simulation method. Accuracy depends mainly on the distillation column modeling assumptions
followed by the termination criteria in simulation steps.
Simulation of such complex process has been paid much attention and several procedures have been
developed since the last decades. The equations that describe the multi-component multi-stage
separation process operating at steady state, while appearing to be simple, are in fact highly nonlinear
and interdependent. Hence, the solution of these equations is intrinsically iterative, complex and hard
to convergence3. Amundson and Pontinen4 for the first time proposed a set of nonlinear simultaneous
equations for the multi-component and multi-stage separation process resolved by the matrix method,
in which the S (Summation) equations and the H (Enthalpy) equations are solved separately for
obtaining the tray temperature and the flow rate. It is effective for simulating the distillation
separation, but not suitable for absorption or extraction processes because of wide boiling feed.
Wang and Henke5 modified Amundson's algorithm and proposed the tri-diagonal matrix method,
which eliminated the inversion of huge matrices and reduced calculation time. Kumar et al6
developed steady state, multicomponent distillation model for fractionation of crude oil based on
equilibrium stage relations. The model equations for an ordinary equilibrium stage of a simple
distillation column, commonly known as Mass balance, Equilibrium, Summation and Enthalpy
balance (MESH) equations. The set of nonlinear algebraic equations is solved using the Newton
Raphson method. Computation of equilibrium constants and enthalpies of different streams as
functions of temperature and composition are based on the cubic equation of state proposed by
PengRobinson. The results obtained from this simulation was compared and validated with Aspen
Plus simulation software. It is found that the proposed model have good match with the data published
in literature as well as given by the commercial simulator. Bhutani et al.7 subjected a separation
distillation column of styrene production plant to the modeling and simulation. Fortran 90 program
used for simulation the distillation column. The shortcut method, commonly known as FenskeUnderwood-Gilliland (FUG) method is employed for calculation of actual number of theoretical
stages, reflux ratio, condenser and reboiler duty in F90.The simulation results obtained using Hysys
JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1016

Improving...

Hashim and Jassim.

and F90 simulation program are very close and the minor differences are due to differences in
physical properties. The predicted results are also comparable to the industrial data. Shan et al.8
presented a flexible model and a robust algorithm for simulation of multi-stage multi-component
separation processes of a twenty-component paraffin mixture from n-C3H8 to n-C20H42. An efficient
algorithm was proposed to solve the approximate tri-diagonal matrix derived from the MESH
equations. The target variables for the multicomponent distillation column was total flow rate, reflux
ratio, the concentration of key components, the draw amount of the key components and the liquid
flowrate of the column inter-stage, while the independent variables was the duty of condenser, the
duty of reboiler, the vapor draw flowrate of the main column, the liquid draw flowrate of the main
column, the draw flowrate of the side stripper column, the recycle flowrate of the inter-stage, the duty
of a stage, the side draw flowrate of the main column. The simulation showed that the results are
comparable with that of the InsideOut algorithm. The proposed algorithm shows good stability and
fast convergence with different initial values. Ramesh et al.9 modeled the continuous distillation
column by using two different models, equilibrium model and rate-based model. A comparison
between the two approaches was made, where concluded that the inclusion of liquid and vapor phase
non-ideality calculation has increased the accuracy of the equilibrium model. The steady-state and
dynamic simulation results have shown that the deviation between these two models is less than 4%.
The distillation column was modeled based on MESH equations which are solved to give product
distributions, flow rates, temperatures, and so on. UNIFAC method has been chosen for calculating
activity coefficient. The virial equation was used to calculate the fugacity coefficients. Mustapha et
al10 modeled a high pressure distillation column by using MESH equations , where the column is
designed to separate the load made up of (methane , ethane, propane, iso-butane ,n-butane, isopentane, n-pentane) into a distillate rich in propane and a residue fairly rich in n-butane and isobutane. The simulation of the distillation tower was done by using Fortran code. The rigorous method
was used based on the bubble point calculation without definition of the light and heavier keys in the
column, where the Thomas numerical method used to solve the matrix. The model was validated by
comparing the results of simulation with those obtained experimentally, the results obtained showed
an extremely low discrepancy (<2%). Behera11 modeled a steady state distillation column by using
equilibrium stage model using MESH equations, in which the equations solved by using NewtonRaphson method. The activity coefficient calculated by using UNIFAC group contribution method.
The average percentage of error in determining the activity coefficient by UNIFAC group contribution
method varies from 9- 15% with respect to the experimental values. So with this much percentage of
error the vapor-liquid equilibrium data generated by UNIFAC can be successfully implemented in
designing separation processes. Mosorinac and Stevanovic12 presented an integrated modelling
method for continuous multistage multicomponent distillation column using MESH equations. The
required specification for the modeling and simulation are: 1) number of plates in each section of the
column, 2) quantity, composition and thermal condition of the feed, 3) column pressure, 4) type of
overhead condenser, total or partial, 5) reflux ratio. Computation procedure which was used the
constant molar overflow is assumed and the material balance and equilibrium relationship equations
are solved stage by stage starting at the top or bottom of the column. Nasri and Binous13 used
Mathematica , the famous computer algebra to perform steady-state and dynamic simulations of a
multi-component distillation column . Soave RedlichKwong equation of state (SRK EOS) was used
in order to calculate the vapor-liquid equilibrium (VLE) relationships and to compute the vapor- and
liquid-phase enthalpies. Rigorous modeling was performed; where both mass and energy balance
(MESH) equations are solved. All of steady-state results of the column simulations were agree very
well with those obtained using HYSYS. Akpa and Umuze14 developed a steady state models for a
multi-component crude distillation column from the MESH equations, where the equilibrium based

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1017

Improving...

Hashim and Jassim.

models are developed for the distillation with an improved computational algorithm. In these models,
the non-linear equation sets are solved by using Newton-Raphson method. These equations were
transformed into a matrix and solve by matrix inversion using the Matlab solver. The model results of
the concentrations and temperatures for five components compared favorably with output values from
the distillation unit with maximum deviations of 8.33% and 6.62% respectively.
In this work the equilibrium stage model was used and the set of non-linear equations governing the
column (MESH) equations used for the mathematical modeling of the multicomponent distillation to
model the naphtha stabilizer from the catalytic reforming unit in the Basra refinery and the solution
procedure is the tridiagonal matrix method. The algorithm used for the model solution is Wang-Henke
algorithm, the program used to solve the set of equations is MATLAB software.
Commercial Simulation Software (HYSYS): HYSYS is an advance process simulation
environment for the process industries developed by Hyprotech. HYSYS is one of the software which
is widely accepted and used for refinery simulation. It performs the oil distillation calculation through
detail plate by plate calculation. It is a market leading process modeling tool for conceptual design,
optimization, business planning, asset management and performance monitoring for oil and gas
processing, petroleum refining, and air separation industries.
Process Description: Naphtha stabilizer column located in catalytic reforming unit in Basra
refinery/Iraq, the unstabilized naphtha consists of the fuel gas, LPG and naphtha reformate after being
reconstructed in the catalytic reformers is pumped to naphtha stabilizer at 176 Co and 14 Kg/cm2 after
preheating in the stabilizer feed/bottom exchanger as shown below in the figure 1.

Figure 1: Schematic diagram for a catalytic reformer unit.

Stabilizer column has 30 trays with feed entering on the 16th tray. Fuel gas, fuel oil and H.P steam are
utilized as reboiling medium for the stabilizer. Stabilizer reboiler is a furnace reboiler.
The overhead products are partially condensed in the stabilizer overhead condenser. The LPG and Off
Gas are cooled down to 45 Co before routing to stabilizer reflux drum. Stabilizer reflux is pumped by
stabilizer reflux pumps. Reflux is fed on tray no. 1 of stabilizer column. Stabilized naphtha product
from stabilizer bottom exits with 223 Co and exchanges heat with the feed in the heat exchanger
before being routed under its own pressure to gasoline pool.

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1018

Improving...

Hashim and Jassim.

Naphtha Stabilizer Modeling: Mathematical model of any process is a set of equations including the
necessary input data to solve the equations, whose solution gives a specified data representative of the
process to a corresponding set input that allows us to predict the behavior of chemical process
system15. In the refineries the crude oil feedstock is a complex multi-component mixture which has to
be separated into groups of compounds. The complexities of feeds and products made the
development of the proper algorithm for simulating such processes is important. Modeling methods
for distillation columns are divided into three methods according to the assumptions made in the
development of the model as: approximate, equilibrium and rate based methods. The equilibrium
based methods are the most commonly used method and is based on the equilibrium assumption
between leaving vapor and liquid flows for each stage9 as shown below in the figure 2. A complete
separation process of naphtha stabilizer is modeled as a sequence of N of these equilibrium stages. In
this method the model equations of the column called MESH (Material balance equation, Equilibrium
phase equations, Summation equations and Heat balance equations) are solved. The set of non-linear
model (MESH) equations that describe multi-component separation processes are solved iteratively
by using matrix method.

Figure 2: Schematic diagram of an equilibrium stage.

Model assumptions: The complexity of Model depends on the types of assumption considered the
mathematical and computational difficulties occurring in solving the model equations (computing
time, store location) are reasons for the model simplifications required in the majority of cases. It also
leads to appropriate type of modeling techniques. Together with the assumptions, the specific column
simulated will be assumed to have the conditions and configurations listed in the following:
1. Steady state.
2. Liquid and vapour phases are perfectly mixed for the equilibrium stages including the
condenser and reboiler.
3. Partial condensation in the condenser and partial evaporation in the reboiler.
4. Liquid and vapors phases leave each stage at thermal equilibrium (same temperature and
pressure).
5. Neglect vapor and liquid holdup in all stages including the condenser and reboiler.
6. Physical properties can be determined by using different thermodynamic packages.
7. No heat is lost from any tray (adiabatic) .
8. Column pressure is constant.
JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1019

Improving...

Hashim and Jassim.

9. Stage efficiency is 100%.

10. Heat of mixing is zero.
Model Equations: The equations that model equilibrium stages are termed the MESH equations,
MESH being an acronym referring to the different types of equations that form the mathematical
model. The M equations are the Material balance equations:
Total material balance is:
L + V + F L V U W = 0

(1)

Mass balance for component i:

L x, + V y, + F z, (L + U )x, (V +W )y, = 0

(2)

The E equations are the phase equilibrium relations for each component:
E, = y, K , x, = 0

(3)

Where K , is the phase equilibrium ratio for species i on stage j. The estimation of the K-values from
fugacity and activity coefficients.
The S equations are summation equations:
(S ) =  y, 1.0 = 0

(4)

(S ) =  x, 1.0 = 0

(5)

The liquid flow rate at each stage can be calculated as following:



L = V +

(F

U W ) V

(6)

And the H equations are the heat balance equations:

L H"#$% + V H&#'% + F H(# )L + U *H"# )V + W *H&# Q  = 0

(7)

Where H(# , H&# H"# are the feed, vapor and liquid enthalpy respectively at the tray j. yi.j and xi,j are
the mole fractions of vapor and liquid streams.
Solution procedure: To solve the above equations a tridiagonal matrix algorithm used, which results
from the equation (2). Proceeding by elimination of L and y, , by substituting equation (6) and
equation (3) into equation (2) . Thus, equations for calculating y and L are partitioned from the other
equations. The result for each component and each stage is as follows where the i subscripts have
been deleted from the B, C and D terms. The mathematical model equations for a column of N trays
can be reduced according to Thomas algorithm to:
A x, + B x, + C x, = D

(8)

Where:

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1020

Improving...

Hashim and Jassim.


(F

A = V +

B =-1V +

(F

W U ) V

2j

W U ) V + U + (V + W )K , 2

C = V K ,
D = F z,

2j

(9)
(10)

1 j 1

(11)

1j

(12)

With m refers to number of the trays. Equation (8) can be solved for N x C equations, where the
unknowns are the compositionsx, . For each component, the Thomas numerical method can be used
to solve the matrix form Equation (13) in order to determine the composition profiles as function of
the tray position.

5
4
4
4
4
4
4
4
4
4
3

6 7 .. ..
89 69 79 .. ..
0 8: 6: 7: . . ..
. . .
. . .
8; 6; 7;
. . .
. . .
0
.. .. 8<9 6<9 7<9 0
0
..
0 8< 6< 7<
0

0 8<
6<

[ABC] [AB,; ] = [C; ]

AB,
C
@5 A @ 5 C @
B,9
?4 A ? 4 9 ?
C
B,:
?4 ? 4 : ?
..
?4
? 4 .. ?
?4
?
? 4
A
? 4 B,; ?=4 C; ?
?4 ? 4 .. ?
?4 ? 4 .. ?
? 4AB,<9 ? 4C<9 ?
? 4AB,< ? 4C< ?
> 3 AB,< > 3 C< >

for 1 i C

(13)

(14)

Constants B and C for each component depend only on tear variables T and V provided that K-values
are composition independent. If not, compositions from the previous iteration may be used to estimate
the K-values. A new set of V tear variables is computed by applying the following modified heat
balance equations , which is obtained by substitution of equation (6) in to equation (7) twice to
eliminate L and L . The equations can be written after rearrangement as follows:
 V +  V = 

(15)

Where:
 = H"#$% H&#

(16)

 = H&#'% H"#

(17)


(F

 = 1

W U ) V 2 GH"# H"#$% H + F GH"# H(# H + W GH&# H"# H + Q 

I
Q I = I
 GF H(# U H"# W H&# H  Q  V H&% LI H"J

Q = V9 H&K + F H(% (L U )H"% (V + W )H&%

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

(18)

(19)
(20)

1021

Improving...

Hashim and Jassim.

The vapor and liquid enthalpies are evaluated at the stage temperatures last computed rather than at
those used to initiate the iteration. Written in diagonal matrix form (15) applied over stages 2 to N-1
is:
9 0 0 0
0
V:
9 9 V9
5 0 0
@
0 @ 5 VL @ 5
:
:
:
4
? 4
? 4
?
L
0 ? VN
4 0 L L 0
4
? 4
?

4
?.4 ? = 4
?

?
4
? 4 ? 4
0 I: I: 0 0 ? 4VI9 ? 4 I: ?
4
0 0 I9 I9 0 ? 4VI ? 4 I9 ?
4
0 0
0 I I > 3 VI > 3 I >
3

(21)

Matrix equation (21) is readily solved one equation at a time by starting at the top where V9 known
and working down recursively is. Thus
V =

O#$% P#$% &#$%

(22)

Q#$%

And so on. Corresponding liquid flow rates are obtained from equation (6).
K-values calculation: To solve equations by the Thomas method, Ki,j values are required. When they
are composition dependent, initial assumptions for all x, and y, values are needed. K-values are
computed from:
RST
H
RSU

K = G

(23)

Where " , & vapor and liquid fugacity coefficients which can be calculated by using equation of
state16.
^ 9^`.a

S
 = exp Y(Z 1) [S ln(Z B) [ _ ^`.a
[Sb ln G

c[
Hd
c

(24)

Constants A , B , A and B depend on TfS , PfS and  . for pure species

m nS

A = 0.42747 a o
m nS

B = 0.08664 o

nS

(25)

nS

(26)
9

ai = r1 + mi(1 Tft.N )u

mi = 0.48 + 1.574 i + 0.176 i9

(27)
(28)

Where acentric factor, Z compressibility factor, Pr reduced pressure and Tr reduced temperature.
For vapour mixtures:
A = w w y y A
t.N

A = )A A *

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

(29)
(30)
1022

Improving...

Hashim and Jassim.

B = w y B

(31)

Enthalpy Calculation:
The ideal vapor enthalpy can be calculated:
x
)
H& = (y H&

(32)

Liquid enthalpy for ideal solution is obtained from the following equation16:
x
H" =  x yH&
 {

(33)

Where is molal heat of vaporization, which can be obtained from16:

^ |oK
^~ )K

= (o}K

(34)

Where T  in F x (T(Fo)=1.8T(Co)+32) and T is absolute temperature , A2 and A3 are Antoine equation

constants.
For nonideal behavior:
For vapor phase16:
x
) + RT 1Z& 1
H& = w(y H&

:^K
9[

ln G1 + c H2

:^K
9[

ln G1 + c H2

[m

(35)

[m

(36)

For liquid phase16:

x
) + RT 1Z" 1
H" = w(x H&

x
Where H&
is function of temperature and can be calculated from
o

x
H&
= o CmxU dT = a + a9 T + a: T 9 + aL T: dT , where a1,a2,a3,a4 are constants. R is the

universal gas constant (8.314 Kj/kmol.K)

Validation of the column model: In order to analyse the impact of the various operating parameters
on the Naphtha stabilizer, the model was subjected first to validity test to verify the model validity and
its reliability to demonstrate the actual naphtha stabilizer tower. The column is designed to separate
the load made up of H2/ C1 / C2 / and traces of C3 and C4 as Off gas and iso-C4/n-C4/iso-C5/n-C5 as
LPG distillate and a residue (Reformate) rich in C5+. Comparing the results obtained from MATLAB
program with that obtained from HYSYS simulator, the results obtained show an extremely low
absolute deviation (<0.014).
Optimization of a Distillation Column with HYSYS: At the end of model development and
simulation, the model was thereafter optimized using the optimization section of model analysis tools
of Aspen HYSYS by incorporating an optimizer into the flowsheet as depicted in figure 3. The
manipulated variables of the optimization were the reflux ratio and the reboiler and the condenser
temperatures of the column while the objective function was the maximization of the reformate
production in the bottom product of the column. The ranges of the manipulated variables used for the
optimizations are as shown in Table 1.

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1023

Improving...

Hashim and Jassim.

Figure 3: Aspen HYSYS distillation optimization flowsheet

Table-1: The limits of the manipulated variables of the process.
Parameter
Reflux ratio
Condenser temperature (Co)
Reboiler temperature (Co)

Low bound
1
35
220

High bound
4
55
230

Hysys contains a multi-variable steady-state optimizer. Once the flowsheet has been built and a
converged solution has been obtained, the optimizer could be utilized to find the operating conditions
which minimize (or maximize) an objective function. The following terminology is used in describing
the HYSYS optimizer:

Primary variables which are imported from the flowsheet whose values are manipulated in
order to minimize (or maximize) the objective function.

Objective function is the function which should be minimized or maximized.

Constraint functions are defined in three ways. Inequality and equality constraint functions
which may be defined in the optimizer spreadsheet.
In this work, for the optimization purposes an objective function was adopted in such a way that it
would maximize the productivity of the reformate.
RESULTS AND DISCUSSION
Simulation Results: The model equations utilized for the operation type of a distillation column were
applied to a multicomponent mixture, which were referred to as components shown in the
appendix(3). The model equations were solved using MATLAB program. An algorithm for solving
the operation type of multicomponent distillation problem is shown in appendix (1). The process flow
sheet used in the simulation of the naphtha stabilizer is shown below in Figure 4. The input data are
shown in appendix (2). In the application of the proposed method, a feed of 390. 34 kg mol/h
containing the composition as shown in appendix (3) is to be fractionated in a distillation
column(naphtha stabilizer) operating at a pressure of 14 kg/cm2 ,feed stage is 16, the distillate off gas
rate is 31.19 kg mol/h , while LPG rate is 34.37 kg mole/h and the reflux ratio is 2.05. The total
number of theoretical stages in the column is 30. The parameters used in obtaining simulated results
are as follows: the top and bottom temperatures and the reflux ratio. In Figure 5 the temperature
profile shows how the temperature changes in the column. In the first stage where the temperature is
about 45 C, where the lowest temperature of the condenser is the temperature where the vapours are
partially condensed and that temperature is the bubble point temperature.
JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1024

Improving...

Hashim and Jassim.

Appendix 1: Algorithm for the computational procedure for Distillation Column.

Appendix-2: Normal operating conditions for the naphtha stabilizer feed stock.
No.
1
2
3
4
5
6

Discretion
Reflux ration
Reboiler heat duty
Condenser heat duty
Feed temperature
Feed pressure
Feed flow rate

Value
2.05
1759.192
-1044.766
176
14
390.34

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

Units
---KW
KW
C
Kg/cm2
Kmole/hr

1025

Improving...

Hashim and Jassim.

Appendix-3: Feed composition for the naphtha stabilizer feed stock.

S/N
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72

Component
hydrogen
methane
ethane
ethylene
Propene
Propane
i-Butane
Butene-1
Isobutene
n-Butane
t-Butene-2
c-Butene-2
3-Methylbutene-1
i-Pentane(2methylbutane)
Pentene-1
2-Methylbutene-1
n-Pentane
t-Pentene-2
c-Pentene-2
2-Methylbutene-2
2,2-Dimethylbutane
Cyclopentene
Cyclopentane
2,3-Dimethylbutane
2,2,4-Trimethylpentane
n-Heptane
1c,2-Dimethylcyclopentane
Methylcyclohexane
Ethylcyclopentane
2,5-Dimethylhexane
2,4-Dimethylhexane
3,3-Dimethylhexane
2,3,4-Trimethylpentane
Toluene
2,3-Dimethylhexane
2-Methyl-3-ethylpentane
2-Methylheptane
4-Methylheptane
3-Methyl-3-ethylpentane
3,4-Dimethylhexane
1c,3-Dimethylcyclohexane
3-Methylheptane
3-Ethylhexane
1t,4-Dimethylcyclohexane
1,1-Dimethylcyclohexane
2,2,5-Trimethylhexane
n-Octane
1c,2-Dimethylcyclohexane

composition%
1.698
0.613
2.176
0.157
0.213
4.423
1.677
0.039
0.039
3.355
0.044
0.025
0.011
3.472
0.019
0.077
3.16
0.064
0.033
0.172
0.147
0.007
0.163
0.526
0.016
5.474
0.097
0.084
0.209
0.356
0.623
0.079
0.038
10.919
0.446
0.145
1.89
0.856
0.102
0.125
0.049
2.111
0.586
0.063
0.02
0.081
2.858
0.247

S/N
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95

Component
4-Methyl-t-pentene-2
2-Methylpentane
2-Methyl-2-pentene
3-Methylpentane
Hexene-1
c-Hexene-2
t-Hexene-2
c-Hexene-3
t-Hexene-3
n-Hexane
3-Methyl-c-pentene-2
2,2-Dimethylpentane
Methylcyclopentane
2,4-Dimethylpentane
2,2,3-Trimethylbutane
Benzene
3,3-Dimethylpentane
Cyclohexane
2-Methylhexane
2,3-Dimethylpentane
1,1-Dimethylcyclopentane
3-Methylhexane
3-Ethylpentane
1t,2-Dimethylcyclopentane
Ethylcyclohexane
Ethylbenzene
o-Xylene
m-Xylene
p-Xylene
Nonene-1
n-Nonane
i-Propylbenzene
n-Propylbenzene
1-Methyl-3-ethylbenzene
1-Methyl-4-ethylbenzene
1,3,5-Trimethylbenzene
1-Methyl-2-ethylbenzene
1,2,4-Trimethylbenzene
sec-Butylbenzene
n-Decane
1,2,3-Trimethylbenzene
1-Methyl-3-i-propylbenzene

n-Undecane
1,2,4,5-Tetramethylbenzene

1-Methylnaphthalene
2-Methylnaphthalene
n-Tetradecane

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

composition%
0.006
1.5
1.577
2.453
0.013
0.022
0.048
0.015
0.038
4.175
0.133
0.147
0.898
0.458
0.011
2.085
0.163
0.228
3.411
1.118
0.116
4.394
0.47
0.363
0.283
2.79
3.598
6.789
2.915
0.013
0.909
0.147
0.546
2.049
0.932
0.917
0.76
2.829
0.012
0.031
0.532
0.045
0.095
0.149
0.009
0.014
0.01

1026

Improving...

Hashim and Jassim.

Figure 4: Process flowsheet for the Naphtha stabilizer.

Temperature in C

Temperature profile
250
200
150
100
50
0

Temperature
profile
1 4 7 10 13 16 19 22 25 28 31
Stage Number

Molar Flow kmol/h

Figure 5: Distillation Column Temperature Profile.

700
600
500
400
300
200
100
0

Molar Flow Profile

Liquid
Vapor

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31
Stage number

Figure 6: Column Molar Flow Profile.

There is a temperature augmentation on the second stage, because of the reflux introduction to the
column. The temperature continue increasing as the stages go down till the feed stage where the feed
is entering in high temperature in 176 Co. Near to the reboiler the temperature increases dramatically
because of the reboilers heat duty where high temperature needed to vaporize all the components in
the reboiler and that temperature is the dew point temperature.

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1027

Improving...

Hashim and Jassim.

In Figure 6 the molar liquid and vapour flows are exposed. As feed is introduced in the liquid phase,
there is an increase on the liquid molar flow on stage 16; a decrease of the flow rate is noticed due to
the high temperature which reigns at the bottom of columns. The vapour flow tends to be constant in
the column, except on stages 2 and 16, this may happen because the reflux temperature is low and
condensates some of heavy components in the vapour phase, while in the stage 16 the feed
temperature is very high and vaporizes some of the heavy components and traces of light gases in the
liquid phase. For trays( >17) the vapour slowly increases that is due to the more volatile components
that are existed in the feed as well as the amount of the vapours which result in evaporating the liquid
that comes down to the reboiler .
The Effect of Decision Variables: There are several of decision variables that can effect on the
operation of naphtha stabilizer specifically on the recovery of C5+ in the reformate and on the heating
and cooling duty.
Reflux ratio effect: Figure 7.(a,b,c,d) below shows the effect of various values of reflux ratio on the
recovery of C5+ in the reformate, reboiler and condenser duty, reformate flow rate and off gas flow
rate. As seen from figure (7) below after reflux ratio of 3 there are no effect on the recovery of C5+ ,
reformate and off gas flow rates, while the condenser and reboiler duty keep rising up with increasing
in reflux ratio.

3000

1
0.98
0.96
0.94
0.92
0.9
0.88
0.86

2500

C5+
recovery in
reformate

Heating Duty

C5+ recovery

C5+ recovery in
reformate

2000
1500

Condenser
Duty (KW)

1000

Reboiler
Duty (KW)

500
0

0.5 1 1.5 2 2.5 3 3.5 4

Reflux Ratio

Reflux Ratio

Reformate flow rate in

Kmole/h
330
325
320
315
310
305
300
295

Reformate
flow rate in
Kmole/h
0.5 1 1.5 2 2.5 3 3.5 4
Reflux ratio

Off gas flow rate in

kmole/h

35
30
25
20
15
10
5
0

Off gas flow

rate in
kmole/h
0.5 1 1.5 2 2.5 3 3.5 4
Reflux ratio

Figure 7: Influence of the reflux ratio on the various parameters.

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1028

Improving...

Hashim and Jassim.

Condenser heat duty effect: The effect of the condenser cooling duty on the recovery of C5+,
reboiler duty, off gas and reformate flow rates for naphtha stabilizer is shown in the figure 8(a,b,c,d)
below . From the figure (8a) below it is being noticed that increasing in the condenser duty will
increase the amount of the off gas product, the reformate production slightly increases with the
increasing in condenser duty as shown in figure (8b). The increasing in the condenser duty increases
the reboiler duty and vice versa as shown in figure (8c) . Finally the effect of the condenser duty on
the recovery of C5+ in the reformate is shown in figure (8d), which is as expected it will increases
when the condenser duty increases.

Off gas rate in Kmole/h

33
32.5
32
31.5
31
30.5
30
29.5

Reformate rate in
Kmole/h

326
325.5
325
Off gas rate
in Kmole/h

Reformate
rate in
Kmole/h

324.5
324
323.5

Condenser duty in KW

Condenser duty in KW

Reboiler duty in KW
3000

2500
2000
1500
1000

Reboiler duty
in KW

500
0

0.978
0.976
0.974
0.972
0.97
0.968
0.966
0.964
0.962

C5+ recovery in
reformate

C5+
recovery in
reformate

Condenser duty in KW
Condenser duty in KW

Figure 8: Influence of the condenser duty on the various parameters.

Reboiler heat duty effect: The effect of reboiler duty on the reformate production and the condenser
duty of the naphtha stabilizer was studied as shown in figures 9(a,b,c,d) below. In Figure (9a) the
reformate production decreases with the increasing of the reboiler duty.
With the temperature increasing in the bottom of the tower, the heat transfer to the distillation tower
increases which made the liquid boiled up and increasing in vapours over the liquid inside the tower
where in this case the recovery of the C5+ in the reformate decreases as well due to the huge amount
of the heavy component which in results will be evaporated from the bottom as shown in Figure (9b).
Reboiler duty has a major effect on the top of the tower, where the condenser duty increases
JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1029

Improving...

Hashim and Jassim.

proportionally with reboiler duty as shown in figure (9c) due to the vapours increasing. Increasing the
reboiler duty led to the increasing in the vapours evaporated which is rich in the C5+ components
within the distillation , thats lead to the increasing in the production of LPG product due to the heavy
components increasing while slightly decreasing in the Off gas product, as shown in the figure(9d)
below.

Reformate Flow rate in

Kmole/h
a

C5+ recovery in the

reformate

340
330
320
310
300
290
280
270
260

0.95
Reformate
Flow rate in
Kmole/h

C5+ recovery in
the reformate

0.9
0.85
0.8
0.75

Reboiler Duty in MW

Reboiler Duty in MW

Condenser Duty in MW
4
3.5
3
2.5
2
1.5
1
0.5
0

Condenser
Duty in KW

100
90
80
70
60
50
40
30
20
10
0

Reboiler Duty in MW

d
Off gas rate
in Kmole/h
LPG rate
Kmole/h

Reboiler Duty in MW

Figure 9: Influence of the reboiler duty on the various parameters.

Feed temperature effect: Feed temperature contributes to the overall column temperature and tray
stage temperatures. Figures 10 (a, b) depicts the response of C5+ recovery in the reformate, reboiler
and condenser heat duty to feed temperatures respectively.
This variable is not dramatically influent in the reformate C5+ recovery for temperatures below the
operation, while it decreases with increasing in feed temperature above the normal operation
temperature as shown in Figure (10a).
As shown in Figure (10b) below if the feed is fed at a higher temperature, the reboiler duty decreases
significantly, while the condenser duty slightly increases.

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1030

Improving...

Hashim and Jassim.

If the feed is fed at low temperatures, more energy is needed in the reboiler to evaporate part of the
liquid in the column. The condenser duty is higher when the feed is introduced to the column at high
temperatures

C5+ recovery

0.978
0.976
0.974
0.972
0.97
0.968
0.966
0.964
0.962
0.96

4000
3500

3000

C5+
recovery in
reformate

Heating Duty

C5+ recovery in
reformate

2500
Condenser
Duty (KW)

2000
1500

Reboiler
Duty (KW)

1000
500
0

Feed Temperature in C

Feed Temperature in C

Figure 10: Influence of the feed temperature on the various parameters.

Feed flow rate effect: The flow rate was varied from 225 to 425 kmole/hr. The curve relating the
flow rate, condenser and reboiler duty indicated an increase of both the dependent and independent
variables. The increase in the feed stream gives more work (load) to the reboiler and the condenser
duty, as shown in Figure (11a) below.
With the increase in flow rate; reboiler and condenser duty increase but there is no effect on the
product purity as seen in Figure (11b) below.

2500

C5+ recovery in
reformate

a
Heating flow in KW

2000
1500
Condenser
duty (KW)

1000

Reboiler duty
(KW)

500
0

1
0.99
0.98
0.97
0.96
0.95
0.94
0.93
0.92
0.91
0.9

Feed flow in kmole/h

C5+
recovery in
reformate

Feed flow in kmole/h

Figure 11: influence of the feed flow rate on the various parameters.

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1031

Improving...

Hashim and Jassim.

Operation pressure effect: Pressure is a critical factor in normal distillation. As the pressure is
increased, the temperatures throughout the column will also increase and vice versa. Maintaining
proper pressure can play a crucial role in the stable operation of a distillation column. Pressure
fluctuations make control more difficult and reduce unit performance.
Pressure variations alter column vapours loads and temperature profiles, as shown in figures(12a,12b)
below.

800

Vapor profile

700

V profile at
P=10

600

V profile at
P=11

500

V profile at
P=12

400

V profile at
P=13

300

250

Temperature profile

T profile at
P=10

200

T profile at
P=11

150

T profile at
P=12

100

T profile at
P=13

V profile at
P=14

200
100

V profile at
P=15

V profile at
P=16

Stage number

T profile at
P=14

50

T profile at
P=15

V=(kmole/h)
P= (kg/cm2)

Stage number

T= (C)
P=(kg/cm2)

Figure 12: Influence of the operating pressure on the vapor and temperature profiles.
The pressure in a distillation column has an effect on the vapours flow within the distillation column,
as the pressure increases the vapours flow decreases, as shown in the figure (13a) below where the
effect of the operation pressure versus top and bottom products studied. While the condenser and the
reboiler temperature increase as pressure increases, where the latent heat decreases with increasing
pressure; this would have the effect of decreasing the reboiler and the condenser duty as pressure
increases, as shown in the figure(13b) below.
400

350
300
250
200
150
100
50
0

6000

5000
Off gas rate
in kmole/h
LPG rate in
kmole/h
reformate
rate in
kmole/h

4000
3000

CondenserDuty
in KW

2000

Reboiler Duty in
KW

1000
0

10 11 12 13 14 15 16
Column operating pressure in kg/cm2

10 11 12 13 14 15 16
Column operating pressure in kg/cm2

Figure 13: Effect of operation pressure on Top and Bottom products and the energy duty

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1032

Improving...

Hashim and Jassim.

CONCLUSION
Naphtha stabilizer in Al-Basra refinery is successfully modelled using a simple unit model structure
based on the MESH equations. The model equations are solved using 19 iterations by using MATLAB
(R2008a) software. A powerful equation of state (SRK) can be applied to predict the required pure
component properties, such as the fugacity, K-values, compressibility factor and enthalpies for the
different phases at given conditions (temperature, pressure, composition). The predicted equilibrium
stage model agrees very well with HYSYS software results obtained by simulating the data that has
been taken from Al-Basra refinery/ naphtha reforming unit/ naphtha stabilizer, where it was highly
accurate and very close to HYSYS simulation results, where the ABS deviation was(<0.014). An
efficient and reliable algorithm is proposed to calculate the multi-component multi-stage separation
process as seen in appendix (1). A simulation analysis by using HYSYS was used to estimate the
effect of the process parameters on the reformate product quantity, the recovery of C5+, top products
and energy duties of the naphtha stabilizer. The profiles for the flow rates and temperature were
obtained. The temperature profile ranged from 45C at the condenser to 223C at the reboiler. The
optimization was carried out under the condition of constant pressure across the column. The
optimum conditions for the purity of the reformate production and the recovery of C5+ were achieved
using Aspen HYSYS software. At the optimum values of the process parameters, the bottom product
is 99.6% pure. The influence of column feed was investigated. An increase was seen when fresh feed
flow rate was varied between 225 and 425 K mole/hr. Variation of reflux ratio depicted multiplicity
effects between 0.5 to 3. The reformate production and C5+ concentration began to increase at
increasing in the reflux ratio. It is possible to get high purity of reformate for reflux ratio 3. Feed
temperature was varied from 125C to 195C showed a variation of reboiler duty from 3.59MW to
1.36MW (62.11% difference).
REFERENCES
1. C .D. Holand, fundamentals and modeling of separation processes prentice-hall, inc
Englewood cliffs, new jersey, 1975.
2. L.N. Sridhar and A. Lucia Tearing Algorithms for Separation Process Simulation [J].
Comput. Chem. Eng. 1990, 14(8): 901905.
3. J. Jaroslav, V. Hlavacek, and M. Kubicek, Calculation of Multistage Countercurrent
Separation Processes-I. Multi-component Multi-stage Rectification by Differentiation with
Respect to an Actual Parameter (J), Chem. Eng. Sci. 1973, 28 (10), 1555-1563.
4. N. R. Amundson and A. J. Pontinen Multicomponent Distillation Calculations on a Large
Scale Computer [J]. Ind. Eng. Chem., 1958, 50: 730738.
5. J.C. Wang and G. E. Henke Tridiagonal Matrix for the Distillation [J]. Hydrocarbon
Process, 1966, 45(8): 155163.
6. V. Kumar, A. Sharma, I. R. Chowdhury, S. Ganguly and D.N. Saraf A crude distillation unit
model suitable for online applications, Fuel Processing Technology, 2001, 73,121.
7. N. Bhutani, A. Tarafder, A. K. Ray and G. P. Rangaiah, Multi-objective Optimization of
Industrial Styrene Production Using A Process Simulator and A Genetic Algorithm , AIChE,
Prepared for Poster Presentation at the 2004 Annual Meeting, Austin, TX, Nov 7-12.
8. L. Shan, Z. X. Ping, Z. S. Jiang, T.X. Shun and X.S. Guang Simulation of Multi-component
Multi-stage Separation Process-An Improved Algorithm and Application, The Chinese
Journal of Process Engineering, 2006, 6, 2, 248-254.

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1033

Improving...

Hashim and Jassim.

9. K. Ramesh, N. Aziz, SR Abd Shukor and M. Ramasamy" Dynamic Rate-Based and

Equilibrium Model Approaches for Continuous Tray Distillation Column", Journal of Applied
Sciences Research, 2007, 3(12): 2030-2041.
10. D. Mustapha, O. Fatima and T.Sabria Distillation of a Complex Mixture. Part I: High
Pressure Distillation Column Analysis: Modeling and Simulation", Entropy, 2007, 9, 58-72.
11. M. Behera Vapour Liquid Equillibrium Modeling Using UNIFAC Group Contribution
Method and Its Application in Distillation Column Design and Steady State Simulation , Bsc
thesis, Department of Chemical Engineering National Institute of Technology, Rourkela ,
2010.
12. T. Mosorinac and J. S. Stevanovic A multistage, multiphase and multicomponent process
system modeling, International Journal of Mathematical Models and Methods in Applied
Sciences , 2012, 1, 5.
13. Z. Nasri and H. Binous, Rigorous distillation dynamics simulations using a computer
algebra Computer Applications in Engineering Education, 2012, 20, 2, 193202.
14. J.AKPA and O. UMUZE Simulation of a Multi-component Crude Distillation Column,
American Journal of Scientific and Industrial Research, 2013, 4(4): 366-377.
15. B. Wayne, "Process Dynamics Modeling, Analysis and Simulation", Prentic- Hall PTR, New
Jersey, 1998.
16. E. J. Henley & J. D. Seader, "Equilibrium-stage separation operations in chemical
engineering", New York NY, Wiley, 1981.

*Corresponding author: Ahmed Raheem Hashim; Department of

Chemical Engineering, Basra University Basrah, Iraq

JECET; March 2014-May 2014; Vol.3.No.2, Sec. C;1015-1034

1034