18th European Symposium on Computer Aided Process Engineering – ESCAPE 18

Bertrand Braunschweig and Xavier Joulia (Editors)

© 2008 Elsevier B.V./Ltd. All rights reserved.

Calculation of Critical Points in Reactive Mixtures

using a Global Optimization Approach
Francisco Sanchéz-Mares a, Adrián Bonilla-Petriciolet a, Juan Gabriel Segovia-
Hernández b, Juan Carlos Tapia-Picazo a, Antonin Ponsich c
a
Instituto Tecnológico de Aguascalientes, Av. López Mateos 1801, Ags., 20256, México
b
Universidad de Guanajuato, Noria Alta s/n, Guanajuato, 36050, México
c
Instituto Tecnológico Autónomo de México, Río Hondo 1, México D.F., 01080, México

Abstract
This work reports the application of a stochastic optimization method for the calculation
of critical properties in systems subject to chemical reactions. Specifically, we have
used the Simulated Annealing method to solve robustly the criterion of Heidemann and
Khalil (1980), which has also been coupled with the thermodynamic framework of Ung
and Doherty (1995) to determine the critical states in reactive mixtures. Our numerical
experience with the proposed method using cubic EoS shows that it is suitable to
perform this type of thermodynamic calculations in systems with chemical equilibrium.
In general, this method can locate the criticial conditions in reactive systems with
reliability; it can be applied with any thermodynamic model without problem
reformulations and shows a reasonable computational time.

Keywords: Critical point, reactive mixtures, global optimization

1. Introduction
The determination of critical points in reactive and non-reactive mixtures is important
for both theoretical and experimental issues in the context of Chemical Engineering.
During the last years, the study of critical phenomenon in systems with and without
chemical reactions has received an increasing attention due to growing interest in
chemical processing operations and technologies based on supercritical fluids. In
particular, the application of supercritical fluids in reactive mixtures offers several
advantages. For example, the reaction yields can be increased by adjusting the pressure
of the system (Hou et al., 2001; Platt et al., 2006). Until now, some experimental
studies have been performed to determine the critical properties in reactive systems that
have a current interest for the industry (Hou et al., 2001). However, in comparison to
nonreactive mixtures, few numerical strategies have been proposed for the calculation
of critical points in systems subject to chemical equilibrium (Platt et al., 2006).
Generally, the available methods use local solvers to find the critical equilibrium. But,
due to the mathematical nature of the critical point problem, these methods may face
numerical difficulties such as initialization dependence, divergence and slow
convergence. Moreover, the presence of chemical equilibrium increases its
mathematical and dimensional complexity. A suitable choice to reduce the problem
dimension and favor the numerical behavior of solving strategies implies the application
of variable transformation approaches (Ung and Doherty, 1995). These approaches in
combination with global solving strategies, for instance the stochastic optimization
methods, can be used to develop reliable strategies for the calculation of critical
conditions in reactive systems. Therefore, in this work we report the first attempt for the
2 F. Sánchez-Mares et al.

application of a stochastic optimization method in critical point calculations for

mixtures subject to chemical equilibrium.

2. Problem statement
2.1. Thermodynamic conditions for the calculation of critical points in reactive mixtures
For nonreactive mixtures, the most widely used criteria for critical point calculations
was established by Heidemann and Khalil (1980). This criteria is based on the stability
of homogeneous phases using a Taylor expansion of the Helmholtz energy and it is
given by
→
Q ∆n = 0 (1)

c c c
∑ ∑ ∑ Aijk ∆ni ∆n j ∆nk =0 (2)
i =1 j =1 k =1

where
⎡ ∂2 A ⎤
Qij = Aij = ⎢ ⎥ (3)
⎢⎣ ∂ni ∂n j ⎥⎦ T ,V

⎡ ∂3 A ⎤
Aijk = ⎢ ⎥ (4)
⎣⎢ ∂ni ∂n j ∂nk ⎥⎦ T ,V
subject to the following restriction
→T →
∆n ∆n − 1 = 0 (5)
being A the Helmholtz energy, V is the total volume, T is the absolute temperature, c is
the overall number of components in the mixture, n i is the mole number of component i
→
and ∆n = (∆n1 ,..., ∆n c ) T , respectively. These equations form a c + 2 nonlinear system
that must be solved to find the critical states of a multicomponent mixture, where the
unknowns are the critical temperature Tc, the critical volume Vc and the components of
→
vector ∆n . To extend this criterion for the calculation of critical conditions in reactive
systems, we must consider the presence of the chemical equilibrium
c
= ∏ aivi
r
r
K eq r = 1,..., R (6)
i =1

r
where K eq is the chemical equilibrium constant of reaction r, ai is the activity of
component i and vir is the stoichiometric coefficient of component i in the reaction r,
respectively. In this work, the effect of chemical reactions on the location of critical
conditions has been considered using the thermodynamic approach developed by Ung
and Doherty (1995). These authors proposed the use of transformed composition
variables to provide a simpler thermodynamic framework for modeling reactive sytems.
Calculation of critical points in reactive mixtures using a global optimization approach 3

These transformed variables depend only on the initial composition of each independent
chemical species and are constant as the reactions proceed. They restrict the solution
space to the compositions that satisfy stoichiometry requirements and reduce the
dimension of the composition space by the number of independent reactions. So, the
transfomed variables for a mixture of c components subject to R independent chemical
reactions, in mole fraction units, are defined as
→ →
xi − vi N −1 xref
Xi = → →
i = 1,..., c − R (7)
1 − vTOT N −1 xref
→
where X i is the transformed mole fraction of component i, xref is the column vector
→
of R reference component mole fractions, v i is the row vector of stoichiometric
→
coefficients of component i for each reaction, vTOT is a row vector where each element
corresponds to the sum of the stoichiometric coefficients for all components that
participate in reaction r, and N is a square matrix formed from the stoichiometric
coefficients of the reference components in the R reactions (Ung and Doherty, 1995). It
is important to note that these variables satisfy the restriction ∑ X i = 1 for
i = 1,..., c − R where X i may have positive or negative values (even greater than unity)
depending on the reaction type. Consequently, these characteristics of transformed
variables allow that all of the procedures used to obtain thermodynamic properties of
nonreactive mixtues can be extended to reactive ones. Based on this fact, we have
coupled these transformed variables with the formulation of Heidemann and Khalil to
develop an alternative technique for the calculation of critical properties in reactive
mixtures. It is convenient to mention that a similar approach has been proposed by Platt
et al. (2006). However, these authors used a nested method employing a local search
technique to find the critical conditions. Due to highly non-linear nature of this
thermodynamic problem, their algorithm may fail to find the critical states in difficult
systems. In this work, to overcome these difficulties and to develop an improved
method, we use a global solving strategy to determine the critical conditions in reactive
systems. In the following section, we describe the proposed strategy.

2.2. Description of solution approach

As indicated by Stradi et al. (2001), the non-linear equations system that defines the
Heidemann and Khalil formulation may have none, one or several solutions (critical
states). Under this context, local solvers are not suitable to solve this problem and, by
consequence, a reliable numerical strategy must be used. In this work we use an
optimization approach for finding the critical conditions in reactive mixtures. As
indicated by Henderson et al. (2004), the formulation of the critical point calculation as
an optimization problem offers some advantages such as: a) the use of a direct
optimization method which only requires the values of the objective function avoiding
calculation of function derivatives, and b) the application of any thermodynamic model
without problem reformulations. So, we have used the following objective function for
the calculation of critical properties
4 F. Sánchez-Mares et al.

c+2
Fobj = ∑ fi2 (8)
i =1

where f i represents the nonlinear equations of the Heidemann and Khalil’s criterion. If
a mixture shows one or several critical points, this objective function will have one or
several global optimums where Fobj = 0 . In this work, the stochastic optimization
method Simulated Annealing (SA) is used to minimize this objective function. SA
method is inspired in the thermodynamic process of cooling of molten metals to achieve
the lowest free energy state. It is a robust numerical tool that presents a reasonable
computational effort in the optimization of multivariable functions; it is applicable to
ill-structure or unknown structure problems, it requires only calculations of the
objective function and can be used with all thermodynamic models. This method is
considered as a good optimization strategy if is properly implemented. In the field of
Chemical Engineering, it is one of the most used optimization methods and have been
applied in several thermodynamic calculations, including the determination of critical
conditions in nonreactive mixtures (Henderson et al., 2004; Sánchez-Mares and
Bonilla-Petriciolet, 2006). To the best of the author’s knowledge, this method has not
been applied to locate the critical states in systems with chemical equilibrium. In the
Figure 1 we show the algorithm proposed to determine the critical coordinates in
reactive systems using SA method. Specifically, for a particular mixture with a
transformed composition X, the objective function is minimized with respect to the
unknowns of the formulation of Heidemann and Khalil. Thus, this function is
minimized inside arbitrary intervals defined for (Tc, Vc) and taking into account that
∆n1 ∈ (0, 1) and ∆ni ≠1 ∈ (−1, 1) . To satisfy the restriction imposed by Equation (5), we
have used the following normalization
∆ni
∆ni = (9)
c
∑ ∆ni2
i =1

Equation (9) allows that all proposed solutions are feasible. Based on our numerical
experience with SA method and some preliminary calculations, we have defined that the
SA algorithm developed by Corana et al. (1987) using the cooling schedule reported by
Sánchez-Mares and Bonilla-Petriciolet (2006) works well for the calculation of critical
conditions in reactive mixtures.

3. Case of study
With illustrative purposes, in this work we have considered the calculation of the critical
properties of the reaction for MTBE production. MTBE is an important industrial
chemical and has been used an anti-knock agent to replace tetra-ethyl lead in gasoline.
This reaction is given by: isobutene (1) + methanol (2) ↔ methyl-tert-butyl ether (3)
with n-butane (4) as inert. We have selected MTBE as reference component and the
transformed mole fractions are defined as
x1 + x3
X1 = (10)
1 + x3
Calculation of critical points in reactive mixtures using a global optimization approach 5

x 2 + x3
X2 = (11)
1 + x3

x4
X4 = = 1 − X1 − X 2 (12)
1 + x3

where X i ∈ (0, 1) for i = 1,..., c − R . The thermodynamic properties of this mixture has
been calculated using the SRK EoS with conventional mixing rules. The binary-
interaction coefficients kij for the SRK EoS were calculated with the following
expression

⎡ 8 VciVc j ⎤
k ij = 1.0 − ⎢ 1/ 3 ⎥ (13)
⎢ (Vci + Vc1j / 3 ) 3 ⎥
⎣ ⎦
being Vci the critical volume of pure component i. On the other hand, Stradi et al.
(2001) have reported the analytical expressions to evaluate the conditions of Heidemann
and Khalil (1980) for a generalized cubic equation of state (EoS). These expressions
were used in this work to evaluate Equations (1)-(4) for the case of SRK EoS. Finally,
the objective function was optimized inside the intervals: Tc ∈ [400, 600] kelvin,
Vc ∈ [100, 400] cm3/mol, ∆n1 ∈ (0, 1) and ∆ni ≠1 ∈ ( −1, 1) for i = 1,..., c .

1. Define X for the reactive mixture and model parameters.

→
2. Guess initial values for (Tc ,Vc , ∆n) .
→
3. Normalize ∆ n using Eq. (9).
4. Find Pc with the EoS.
5. Do the transformation procedure X - x using Equations (6) and (7).
6. Evaluate the formulation of Heidemann and Khalil (1980) using Equations (1)-(4)
and calculate the objective function Fobj.
→
7. Check for minimum; proceed with SA method with new values of (Tc ,Vc , ∆n)
and repeat steps 3-7 until satisfy the convergence criterion of Simulated Annealing
method.
8. If the global optimum of Fobj is ≤ 1.0E-10, then we have a critical point. Finally,
do a phase stability analysis of the calculated critical state.

Figure 1. Overall algorithm for the calculation of critical points in reactive mixtures using the
Simulated Annealing optimization method and the Heidemann and Khalil’s criterion.

4. Results and Discussion

In Table 1 we report the calculated critical conditions for some arbitrary transformed
mole fractions of the reactive mixture used as case of study. For all calculations
6 F. Sánchez-Mares et al.

performed, we have considered an equilibrium constant independent on the temperature

where K eq = 0.5 . In general, the SA method is suitable to find the critical properties in
this mixture and its reliability is almost insensitive to the initial values of optimization
variables. In fact, we have obtained a succes rate of 100% in the calculation of the
critical properties for this reactive system using random initial values for SA method.
With respect to the computational effort, the proposed strategy requires around 22
seconds to reach the convergence using a Processor Intel Celeron M 1.50 GHz with 240
MB of RAM. On the other hand, our numerical experience with the proposed method in
others reactive mixtures show that it is robust for finding its critical properties and
shows a better performance than that obtained for a local solver. For example, we
solved our case of study using a Newton method with random initial values but it
showed several failures in the location of the critical states. Finally, the results of phase
stability analysis performed for the calculated critical states indicate that they are stable.

Table 1. Calculated critical properties for the reactive mixture isobutene (1) + methanol (2) ↔
methyl-tert-butyl ether (3) with n-butane (4) as inert. K eq = 0.5 and SRK EoS. 1
Critical properties

X Tc, kelvin Pc, bar

(0.1, 0.1, 0.8) 430.78 40.49
(0.5, 0.1, 0.4) 429.06 41.18
(0.7, 0.1, 0.2) 428.05 41.56
1
Reference component: MTBE

5. Conclusions/Remarks/Future work
In this work we report an improved method, based on the application of a stochastic
optimization method, for the calculation of critical properties in reactive mixtures.
Specifically, we have used the Simulated Annealing optimization method to solve the
formulation of Heidemann and Khalil in combination with the thermodynamic
framework of Ung and Doherty (1995). In general, the proposed method is a suitable
strategy to find the critical equilibrium in reactive systems, it can be applied with any
thermodynamic model and reaction type, and its computational time is reasonable. In
future work, we will focus on increasing the efficiency of this numerical strategy.

6. Acknowledgements
Authors acknowledge financial support from CONACYT, ITA, U. de Gto. and ITAM.

7. References
A. Corana, M. Marchesi, C. Martini, S. Ridella, 1987, ACM Transactions on Mathematical
Software, 13, 3, 262-280.
R.A. Heidemann, A.M. Khalil, 1980, AIChE Journal, 26, 5, 769-779.
N. Henderson, L. Freitas, G.M. Platt, 2004, AIChE Journal, 50, 6, 1300-1314.
Z. Hou, B. Han, X. Zhang, H. Zhang, Z. Liu, 2001, Journal of Physical Chemistry B, 105, 19,
4510-4513.
G.M. Platt, N. Henderson, J.L. de Medeiros, 2006, Brazilian Journal of Chemical Engineering,
23, 3, 359-364.
F. Sanchez-Mares, A. Bonilla-Petriciolet, 2006, Afinidad, 63, 525, 396-403.
B.A. Stradi, J.F. Brennecke, J.P. Khon, M.A. Stadtherr, 2001, AIChE Journal, 47, 1, 212-221.
S. Ung, M.F. Doherty, 1995, Chemical Engineering Science, 50, 20, 3201-3216.