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Improving the Performance of the Naphtha Stabilizer in
the Refinery Plant

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E-ISSN: 2278179X

Engineering & Technology

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

Section C:Engineering & Technology

Research Article

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

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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

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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

1017

Improving...

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.

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.

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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.

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

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Improving...

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)

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)

(5)

L = V +

(F

U W ) V

(6)

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:

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(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<

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

I

Q I = I

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

(18)

(19)

(20)

1021

Improving...

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 =

(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)

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

(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 *

(29)

(30)

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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)

^ |oK

^~ )K

= (o}K

(34)

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)

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

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.

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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

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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

Units

---KW

KW

C

Kg/cm2

Kmole/hr

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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

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...

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

700

600

500

400

300

200

100

0

Liquid

Vapor

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

Stage number

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.

1027

Improving...

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

Reflux Ratio

Reflux Ratio

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

kmole/h

35

30

25

20

15

10

5

0

rate in

kmole/h

0.5 1 1.5 2 2.5 3 3.5 4

Reflux ratio

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

1028

Improving...

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.

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

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...

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.

Kmole/h

a

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

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.

1030

Improving...

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

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

C5+

recovery in

reformate

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

1031

Improving...

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

1032

Improving...

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.

1033

Improving...

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.

Chemical Engineering, Basra University Basrah, Iraq

1034

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