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Residue curve map calculation of a ternary mixture

Article · October 2006

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 RESIDUE CURVE MAP CALCULATION OF A TERNARY MIXTURE

Housam Binous*, Aïda Wakad and Saïda Ben Achour
National Institute of Applied Sciences and Technology
BP 676 Centre Urbain Nord, 1080 Tunis, Tunisia
*corresponding author: [email protected]

Abstract The governing equation[1] that links the liquid

mole fraction in the boiler xi to the
In the present paper, the residue curve map corresponding vapor mole fraction yi can be
(RMC) for the ternary system chloroform - derived from the Rayleigh equation, and has the
methanol - acetone is computed with the help of following final form:
Mathematicausing two methods. The first
method uses the built-in function of dxi
 xi  y i (1)
MathematicaFindRoot, to get the vapor mole d
fractions, and Euler's method to integrate the
governing differential equations. The second where is a warped time variable. From
method solves the differential algebraic equation (1), it appears that pure components
equations (DAEs) using the built-in function of and azeotropes are extreme points in the residue
MathematicaNDSolve. In addition, we show curve map since they satisfy the following
how one can find all binary and ternary equation:
azeotropes of this mixture using FindRoot.
These pedagogic problems are currently being xi  y i (2)
used to describe simple methods to solve DAEs
in the applied math course taught at the If we assume that the deviation from ideal
Chemical Engineering Department of the behavior is only in the liquid phase (low total
National Institute of Applied Sciences and pressure), we can relate the liquid and vapor
Technology in Tunis. They serve also to mole fractions using the modified Raoult's law,
introduce students to the conceptual design of
distillation columns in the process design Pyi  xi Pi sat i (3)
course.
where  i , the activity coefficient obtained using
Keywords: Residue curve map, Differential Wilson's model[2] for multi-component
algebraic equation, Wilson model, ternary mixtures,
systems, azeotropes
 m  m
xA
Introduction ln  k   ln  x j Akj   1   m i ik . (4)
 j 1  i 1
 x j Aij
Residue curve maps are very useful for the j 1

understanding of the behavior of ternary

mixtures and the design of distillation systems. In equation (4), Aij is the binary interaction
In addition, computing residue curve maps parameter which depends on the molar volumes
allows one to find azeotropes as stable nodes, ( vi and v j ) and the energy terms ii and ij ,
unstable nodes or saddle points.
vj  ij  ii 
Aij  exp   . (5)
vi  RT 

32 COMPUTERS IN EDUCATION JOURNAL

 The vapor pressure Pi sat is obtained using The composition and boiling temperature of
Antoine's equation, the different azeotropes is given in Table (2).
Total pressure was taken equal to 760 mmHg.
Bi Az1 is the ternary azeotrope and all other are
ln Pi sat  Ai  . (6) binary azeotropes.
Ci  T
RCMs using FindRoot and
For the ternary system acetone (1) - Euler's method
chloroform (2) - methanol (3), Antoine's
constants are given in Table (1). The following Mathematica command
computes the residue curve from an initial
Values of molar volumes[3] (expressed in starting point using a while loop where
cm3/mol) and energy parameters[3] (expressed FindRoot and Euler's method are invoked:
in kcal/kmol) are:
While[i<200,{T=FindRoot[ P = = Evaluate[x1[i]
λ12 = 116.1171 ; λ21 = -506.8519 ;
PS1[i] GAM1[i]+x2[i] PS2[i] GAM2[i]+x3[i] PS3[i]
λ13 = -114.4047 ; λ31 = 545.2942 ;
λ23 = -361.7944 ; λ32 = 1694.0241 ; GAM3[i]],{T,100}][[1,2]],
v1 = 74.05; v 2 = 80.67; and v3 = 40.73. y1[i]=x1[i] PS1[i] GAM1[i]/P,y2[i]=x2[i] PS2[i]
GAM2[i]/P,
Computing the azeotropes of y3[i]=x3[i] PS3[i] GAM3[i]/P,x1[i+1]=x1[i]-h (x1[i]-
the ternary system y1[i]),

The FindRoot command is used to solve the x2[i+1]=x2[i]-h (x2[i]-y2[i]),x3[i+1]=x3[i]-h (x3[i]-

system of nonlinear algebraic equations that y3[i]),i++}];
defines the azeotropes. To get all three binary
azeotropes as well as the ternary azeotrope, the
FindRoot allows one to compute the bubble
initial guess of the FindRoot function must be
point using the liquid mole fractions, the vapor
changed by the user.
mole fractions are then calculated using
modified Raoult's law. Finally, Euler's method
FindRoot[{Y1X1,Y2X2,
P==X1*PS1*GAM1+X2*PS2*GAM2+X3*PS3*GAM3}, enables one to obtain the next point in the
{X1,0.3},{X2,0.4},{T,40}] residue curve.

A B C
Acetone (1) 7.11714 1210.595 229.664
Chloroform (2) 6.95465 1170.966 226.232
Methanol (3) 8.08097 1582.271 239.726

Table 1 - Antoine's constants[3].

x1 x2 x3 Teb (°C)
Az1 0.3231 0.2303 0,4465 57.3763
Az2 0 0.6547 0,3372 53.896
Az3 0.7895 0 0,2104 55.3768
Az4 0.3372 0.6627 0 64.5366

Tableau 2: Azeotropes of the ternary system.

COMPUTERS IN EDUCATION JOURNAL 33

 If all residue curves, starting from different The first three equations are the differential
initial points, are plotted, one obtains the RCM governing equations (see equation 1) written for
shown in Figure 1 and obtained with all three components (acetone, chloroform and
Mathematica. We clearly see that the methanol; respectively) while the fourth
azeotropes and pure components are extreme equation is the algebraic equation giving the
points in this RMC. dT
bubble point temperature. Since is finite
dt
RCMs using NDSolve to solve a DAE and 10 7 is very large, we must have the
following algebraic relation:
The following Mathematica command
computes the residue curve from an initial P  x1 P1sat  1  x 2 P2sat  2  x3 P3sat  3 (7)
starting point using NDSolve.
The second approach gives the same result as
sol1=NDSolve[{D[x1[t],{t,1}]= =y1[t]-x1[t],
D[x2[t],{t,1}]= =y2[t]-x2[t],D[x3[t],{t,1}]= =y3[t]- shown in Figure 1. The first method presented
x3[t], requires more computational time.
D[T[t],{t,1}]= =10^7 (x1[t] PS1[t] GAM1[t]+
x2[t] PS2[t] GAM2[t]+x3[t] PS3[t] GAM3[t]-P), Conclusions
T[0]= =57.5898 ,x1[0]= =0.2,x2[0]= =0.2,x3[0]=
=0.6},{x1,x2,x3,T},{t,0,40},
AccuracyGoal->Infinity,MaxSteps->Infinity, Mathematica graphical and numerical
StartingStepSize->0.0001, MaxStepSize-> 0.0001] features can be very helpful in computing
RCM's for different ternary mixtures using all

Chloroform
1

0.8

0.6

0.4

0.2

-0.2 0.2 0.4 0.6 0.8 1

Methanol Acetone
-0.2

Figure 1: RMC of the ternary mixture.

34 COMPUTERS IN EDUCATION JOURNAL

 kind of thermodynamic models and conditions. Biographical Information
In fact, one can easily extend this work to other
thermodynamic models such as NRTL, to other Dr. Housam Binous is a full time faculty
ternary mixtures or to higher total pressures member at the National Institute of Applied
where deviation from ideality in the gas phase Sciences and Technology in Tunis. He earned a
must be taken into account. The author will Diplôme d'ingénieur from the Ecole des Mines
show in a future paper that similar ideas can be de Paris and a Ph.D. from the University of
used to compute RCMs when reactions between California at Davis.
components are taking place such as in the case
of the methyl acetate and isopropyl acetate Aïda Wakad and Saïda Ben Achour are
chemistries. These classic problems are junior students in the Masters program at the National
and senior level study material at the National Institute of Applied Sciences and Technology in
Institute of Applied Sciences and Technology in Tunis. They performed the RCM calculations,
Tunis. The students excel in these types of as a partial requirement to obtain their
problems despite the fact that they do not have engineering degree, under the supervision of Dr.
prior knowledge of Mathematica. The Housam Binous.
notebooks are available from the corresponding
author upon request or at Wolfram Research.[4]
The authors have also computed the same
residue curve map using Matlab and
Simulink.[5]

References

1. Doherty, M. F., and M. F. Malone,

Conceptual Design of Distillation Systems,
McGraw-Hill, New York, 2001.

2. Tester, J. W., and M. Modell,

Thermodynamics and Its applications,
Prentice Hall, Upper Saddle River, 3rd
Edition, 1996.

3. Perry, R. H., Green, D. W. and J. O.

Maloney (Eds.), Perry's Chemical
th
Engineers' Handbook, 6 Edition, McGraw-
Hill, New York, 1984.

4. http://library.wolfram.com/infocenter/search
/?search_results=1;search_person_id=1536.

5. http://www.mathworks.com/matlabcentral/fi
leexchange/loadAuthor.do?objectType=auth
or&objectId=1093893.

COMPUTERS IN EDUCATION JOURNAL 35

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