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Contents lists available at ScienceDirect

**Fluid Phase Equilibria
**

journal homepage: www.elsevier.com/locate/fluid

**Application of a global optimization algorithm to phase stability
**

and liquid–liquid equilibrium calculations

Stanislaw K. Wasylkiewicz a,∗ , Yau Kun Li a , Marco A. Satyro a,b ,

Monika J. Wasylkiewicz a,b,1

a

Virtual Materials Group Inc., Calgary, Alberta, Canada

b

The Schulich School of Engineering, University of Calgary, Calgary, Alberta, Canada

a r t i c l e i n f o a b s t r a c t

Article history: A global optimization algorithm was developed for ﬁnding all singular points (minima, maxima and

Received 29 May 2013 saddles) of an objective function by exploring the natural connectedness that exists between their singular

Received in revised form 19 August 2013 points. The idea of following ridges and valleys using information gathered along the way was signiﬁcantly

Accepted 25 August 2013

enhanced by applying the arc length continuation method. The algorithm was applied to the Gibbs tangent

Available online 8 September 2013

plane stability test for multiphase liquid mixtures. The global optimization algorithm gives an efﬁcient

and robust scheme for locating all stationary points of the tangent plane distance function predicted by

Keywords:

any thermodynamic model. Since it provides very good initial estimates for the liquid–liquid equilibrium

Global optimization

Gibbs tangent plane stability test

calculations, it became an integral part of a combined phase equilibrium and stability algorithm. The

Liquid–liquid equilibrium combined algorithm is self-starting and signiﬁcantly improves reliability and robustness of multiphase

Arc length continuation equilibrium calculations. It was successfully tested on a variety of problems and is applicable to any

component’s mixtures and any number of liquid phases. Solutions have been found for the entire phase

diagram.

© 2013 Elsevier B.V. All rights reserved.

**1. Introduction various methods for ﬁnding one or more solutions resulting from
**

model equations, but they do not guarantee that the solution corre-

Geometric methods based on residue curve map (RCM) technol- sponds to a tangible physical criterion such as minimum free energy

ogy are efﬁcient tools for distillation process synthesis and design or that all solutions have been found. This can be of paramount

[1,2]. In modern process simulators, designers need tools for gen- importance for some modeling problems of physical systems. For

eration of RCMs and liquid–liquid equilibrium (LLE) diagrams to example in liquid phase stability analysis, we have to ﬁnd all sta-

help visualize the phase behavior from the global thermodynamic tionary points of a tangent plane to the Gibbs free energy surface

space perspective. Unfortunately, most of these tools fail if more to determine whether the examined liquid is stable or not.

than two liquid phases are present at equilibrium [3]. Even if such In this paper, we describe a general approach for ﬁnding all

phenomena are not observable in reality, it is important to cal- singular points of mathematical models by exploring the natural

culate a stable LLE solution, as predicted by the thermodynamic connectedness that exists between singular points of an objective

model. Incorrect single liquid solutions or unstable liquid phases function. The idea of following ridges and valleys using informa-

may result in program failures or erroneous results. To ﬁnd a glob- tion gathered along the way is not new and was used in many of the

ally stable equilibrium solution, a stability test in terms of the hill climbing or direct search optimization techniques developed in

tangent plane criterion [4–8] is commonly performed using global the 1960s [18]. However, since these optimization techniques do

optimization techniques [9–17]. not use derivative information to determine the search direction,

Finding all solutions of mathematical models is still a challeng- they have difﬁculties tracking strong curvature and are not useful

ing problem in many areas of science and engineering. There are for large-scale problems. They are generally considered to be less

efﬁcient than derivative-based methods.

Van Dongen and Doherty [18] used ideas from differential

geometry and the theory of differential equations to describe the

∗ Corresponding author. Present address: Computer Modelling Group Ltd., 150, dynamics of distillation processes. They deﬁned a ridge on a topo-

3553 – 31 Street NW, Calgary, Alberta T2L 2K7, Canada. Tel.: +1 403 531 1307. graphic map of a boiling temperature surface that contains contour

E-mail addresses: stan.wasylkiewicz@cmgl.ca, stan.wasylkiewicz@gmail.com

lines for different temperature values as a location where the con-

(S.K. Wasylkiewicz).

1

Current address: Department of Chemical and Materials Engineering, University

tour lines exhibit maximum curvature. They gave also another

of Alberta, Edmonton, Alberta, Canada. deﬁnition for ridges (valleys) as maxima (minima) of an objective

**0378-3812/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
**

http://dx.doi.org/10.1016/j.ﬂuid.2013.08.030

Superscripts The necessary and sufﬁcient condition for phase stability is given k liquid phase index by theorems 3 and 4 of Baker et al. During branch tracking we look for bifurcation points. ˛ij binary interaction parameter in NRTL model i activity coefﬁcient of component i ıij Kronecker delta function 2.K. Tangent plane stability test tuning factor in pseudo arc length equation Lagrange multiplier Gibbs [4. [6]. J/mol hill. The Nsad odd number of odd saddles algorithm relies on a new arc length continuation method that gives Ntng number of tangent nodes a robust scheme for locating all stationary points of the tangent MAX maximum plane distance function predicted by a thermodynamic model. z)≥0 ∀x (1) old branch 0 derivative computed at the bifurcation point for the The tangent plane distance function F(x) is the distance from the new branch Gibbs free energy surface to the tangent plane at z. This was later proved up aij . s) pseudo arc length equation. N = Nc − 1 conditions. First we created the Lagrangian func- Eq. . K or to R3 by Cheng-Dong and Xiao-Xia [20]. z) tangent plane to the Gibbs energy surface at com. bij binary interaction parameter in the VLE model.21]. [13. Wasylkiewicz et al. i chemical potential of component i. cal/mol Valleys and ridges of the least-squares landscape are speciﬁc c contour line value of the potential function. equation-solving computations and uphill. ˚p ) Rachford–Rice equation. . . which consists of a series of down- g(x) molar Gibbs free energy. In x mole fractions of the liquid phase this article we show examples of three different mixtures.. K liquid phases. The mixture is stable if and T transposed vector or matrix only if the tangent plane distance function F(x) is non-negative at all stationary points. The algorithm locates all the g(z) = zi i (z) (3) stationary points of the tangent plane distance function by tracking i=1 . kPa oped technique was successfully tested on a variety of problems. Np number of liquid phases We applied this new global optimization algorithm to the Gibbs Nsad even number of even saddles tangent plane stability test for multiphase liquid mixtures. together with gradient system prop. . evaluated at a composition x. This can be expressed mathematically as follows Subscripts i component index b derivative computed at the bifurcation point for the F(x) ≡ g(x) − L(x. (20) calculations. is self-starting and signiﬁcantly improves reliability t continuation parameter and robustness of multiphase equilibrium calculations. by a thermodynamic model.5) because they are inherently poorly scaled. J/mol K gies can be calculated and it is a simple matter to determine the SA saddle point that corresponds to the most stable solution. t. z) tangent to the surface at the composition z. F(x) integral curves of the gradient vector ﬁeld and have been deﬁned F(x) tangent plane distance function by Lucia and Feng [21] as a collection of constrained extrema over ∇ F( x) gradient of the potential function F(x) a set of level curves. . from Nmin number of minima which additional branches are later started in eigendirections [23]. Eq. [22] position z to ﬁnd all homogeneous and heterogeneous azeotropes predicted L( x. They conjectured that the ridges and val- List of symbols leys of F(x) are all connected to each other and that this connected domain contains all the stationary points. components as follows erties. based on a method originally developed by Wasylkiewicz et al. ) Lagrangian function for the optimization problem. (17) tion for the optimization problem and applied the Kuhn–Tucker N dimension of the optimization problem. ranging z overall composition of the liquid mixture from a ternary system with three liquid phases to a ﬁve component system with two liquid phases. (19) called “global terrain method”. at a ﬁxed temperature T and pressure p. The algorithm s arc length can be applied to any component’s mixtures and any number of T temperature. we developed a new arc length continuation method that is L(x. Based on this deﬁnition they developed a so G(x. J/mol a necessary and sufﬁcient condition for absolute stability of a mix- time ture of overall composition z is that the Gibbs free energy surface ˚ liquid phase fraction g(x) be at no point below the plane L(x. They noticed that the nonlinear optimization prob- H Hessian matrix lems used to deﬁne valleys and ridges can be quite difﬁcult to solve Hj (˚2 . With MIN minimum all stationary points located the corresponding Gibbs free ener- R gas constant. S. predictor–corrector g(x. The devel- p pressure. s) augmented homotopy function. Then we added an additional equation deﬁning the arc Nc number of components length to the system of original equations to form an augmented Nmax number of maxima system. LLE and VLLE solutions have been Greek symbols successfully found for the entire phase diagrams. The second deﬁnition. J Jacobian matrix To overcome the difﬁculties with tracking of ridges and valleys K liquid–liquid equilibrium constant [13. The molar Gibbs free energy of a mixture of overall composi- function F(x) taken in the constraint plane normal to the ridge-top tion z can be expressed in terms of chemical potentials i ( z) of all locus. Eq. was used by Wasylkiewicz et al. Eq.19] to develop a robust global algorithm for implementation of the Gibbs tangent plane Nc analysis for complex liquid mixtures. t. / Fluid Phase Equilibria 358 (2013) 304–318 305 its ridges and valleys.5] showed that. (A.

categories: Nc −1 ∂F(x) ∂i (x) ∂Nc (x) ∂Nc (x) = j (x) − Nc (x) − j (z) + Nc (z) + xi − + = j (x) − Nc (x) − j (z) + Nc (z) ∂xj ∂xj ∂xj ∂xj i=1 ∂ (x) Nc −1 Nc −1 ∂Nc (x) ∂ (x) Nc i i + xi + 1− xi = j (x) − Nc (x) − j (z) + Nc (z) + xi j = 1. (13): Nc −1 Nc −1 Nc ∂F(x) ∂i (x) ∂Nc (x) + i (z)(xi − zi ) − Nc (z) (xi − zi ) = zi i (z) J [∇ F(x)] = H [F(x)] = = − = H [g(x)] ∂xi ∂xj ∂xj ∂xj i=1 i=1 i=1 (13) Nc −1 Nc + i (z)(xi − zi ) + Nc (z)(xNc − zNc ) = xi i (z) (6) ∂F(x) ∂ xi i (x) i=1 i=1 = RT ln ∂xi ∂xj ∂xj xNc Nc (x) Finally. Nc − 1 We have Nc Nc −1 Nc The linear term L(x. the Hessian matrix of F(x) and g(x) are i=1 i=1 i=1 identical [25]. Eq. z) = zi i (z) + [i (z) − Nc (z)] (xi − zi ) = zi i (z) derivative of F(x). Numerical solution strategies used for Differentiation of F(x) with respect to the Nc – 1 independent global optimization [28] can be grouped into the following three mole fractions gives Eq. (7). . (8) and substituted into Eq. smooth derivatives close to composition boundaries and compo- Nc nent vertices. . Modern mathemat- i = 1. i ( z) is calculated at the overall composition z and i ( x) at any NRTL. (11). . . . (7) giving to the solutions [27] if the proper method is selected for a particular prob- following expression for the tangent plane distance function. . inner and outer approximation. UNIQUAC. z) = g(z) + (xi − zi ) (4) = j (x) − Nc (x) − j (z) + Nc (z) ∂xi ∂xj i=1 x=z By applying the Bakhuis–Rooseboom equation [24] xj j (x) zNc Nc (z) = RT ln =0 (12) xNc Nc (x) zj j (z) ∂g(x) = i (x) − Nc (x) (5) ∂xi j = 1. Nc − 1) vanish. Nc . . . For some optimization problems. .p. The mole fraction of component c can be ical optimization methods can deliver adequate globally optimal calculated from Eq. Finding the global (9) minimum of a function that has a large number of local minima and maxima is far more difﬁcult.g. . ∂g(x) Nc −1 ∂F(x) L(x. / Fluid Phase Equilibria 358 (2013) 304–318 The equation of the plane tangent at z to the Gibbs energy surface yields the stationary conditions. Global optimization in process design Michelsen [7. interval xi =0 (11) ∂xj methods [17]. the expression for the tangent plane distance function ıij ∂ ln i (x) 1 ∂ ln Nc (x) in terms of chemical potential can be written as Eq. Nc • Deterministic methods (e. global optimization can be extremely difﬁcult and frequently engineers are forced to set- i=1 i=1 tle for solutions that are “good enough” because ﬁnding the best Nc −1 solution could be prohibitively expensive. . written assuming the use is given by of an activity coefﬁcient model. lem. (9). (10).. Nc − 1 (10) ∂xj ∂xj ∂xj i=1 i=1 i=1 along with the use of the Gibbs–Duhem equation at constant tem- perature and pressure. (8). xi = 1 (8) i=1 3. (9) are calculated analyti- where the chemical potential of the i-th component of the mixture cally or numerically for any suitable activity coefﬁcient model (e.. . etc. xi ≥0 i = 1. (12). Eq. Therefore. The objective of global optimization is to ﬁnd the best solution of highly nonlinear models that may have a number of locally optimal Nc −1 Nc −1 F(x) = xi [i (x) − i (z)] + 1− xi [Nc (x) − Nc (z)] solutions.. Optimization is also progressively its derivatives with respect to all of the independent variables (xi becoming more important in plant operations. (1) does not inﬂuence the second L(x.x differential geometry [13. The partial derivatives of i=1 activity coefﬁcients ∂ln j (x)/∂xj in Eq.. F(x) will be Optimization methods are now routinely applied at each level non-negative if it is non-negative at all stationary points where of system and process design. Therefore.g. = RT + + − (14) xi ∂xj xNc ∂xj Nc F(x) = xi [i (x) − i (z)] (7) ␦ij is the Kronecker delta function. z) in Eq. methods based on i=1 T.) using a routine [26] specially designed to give point from the composition space. branch and bound methods [12]. = xi [i (x) − Nc (x) − i (z) + Nc (z)] + Nc (x) − Nc (z) Finding an arbitrary local minimum is relatively straightforward i=1 by using classical local minimization methods. homotopy continuation [16].306 S. Eq. Eq.8] noted that all of the minima in F(x) are located in the interior of the permissible region. . cut- ∂i (x) ting plane methods. Eq.21]).K. Wasylkiewicz et al.

advantage viz. diverge from unstable manifolds. opt ∇ F(x)T ∇ F(x) (16) x mance [39. Using locally instead of globally optimal these deﬁnitions can be expressed as the following constrained parameters for thermodynamic models are potential sources of optimization problem [21. traditional phase stability algorithms. ) = F(x) − c = 0 • The singular points of Eq. tion F(x) taken in the constraint planes normal to the ridge-top The stochastic and heuristic global optimization methods are (valleys-bottom) locus [18]. The contour line value is then an and valleys correspond to the stable manifolds.) for the optimization problem described by Eq. ) = ∇ F(x)T ∇ F(x) + [F(x) − c] (17) d deﬁned by the gradient ∇ F( x) of a potential function F(x) where we can get Eq. Dongen and Doherty [18] as a locus on a topographic map where the ods should be used. Failure to ﬁnd the globally optimal solutions in phase stability s. • Heuristic strategies that search the optimization domain in a • The ﬂow of trajectories is always downhill (i. these methods may offer the best compromise between rithm.t. xN . stochastic or heuristic global optimization methods are the only reasonable choice.-a-viz. (15) converge toward stable manifolds and sampling. librium modeling [34]. Some properties of this type of functions are essential for our exploring the problem domain not by random guesses but rather by global optimization algorithm and are summarized in this para- systematic movement along ridges and valleys. (15). tour lines for different elevations exhibit maximum curvature at putational effort even for moderate size problems. (16) dx = −∇ F(x) (15) L(x. differential • Ridge-top and valleys-bottom trajectories are tangent to eigendi- evolution [34]. Mathematically. cuckoo search [36]). Lx (x. harmony search [35]. F(x) decreases more or less intelligent way (e. F(x) = c calculations can have even more serious consequences in subse- where F(x) is the gradient of the potential function F(x) at point quent process calculations. (18) F(x): RN → R and F(x) ∈ C∞ . of constrained extrema over a set of level curves. rections of the Jacobian J[F(x)] or Hessian H[F(x)] matrix at the stationary points. Wasylkiewicz et al.e. if the objective function Ridges and valleys of a potential function F(x) are speciﬁc inte- calculation is quick and partial derivates can be easily calculated gral curves of the gradient vector ﬁeld and have been deﬁned by Van analytically or numerically. They can locate good connected domain contains all the stationary points [20]. or switching between them dur- function F(x). Especially if calculations of a single point of an objective function is very time consuming (e.23]. contour lines for different elevations exhibit maximum curvature. ing distillation column simulation. For any given contour line at a speciﬁed value of c. genetic algorithms [31. Using an erroneous VLE solution instead x and c is any given value (or level. parameter c and solving Eq. colony optimization. Eq.g. for some ridges and valleys of F(x). in reservoir modeling and optimization 5. (15) occur at stationary points in F(x) and vice versa. S. and saddle points occur at saddles in F(x).. Ridges and valleys of a potential function [38]). x2 . ideal continuation parameter for this global optimization problem. valleys of the potential function. ridge-tops can be tracked by gradually increasing or decreasing • Ridges in F(x) correspond to the unstable manifolds of Eq. or vice versa.. and Lagrange multiplier ) and one parameter (contour • Unstable nodes occur at maxima in F(x). A current branch that follows valley-bottoms or minima in F(x). On the other hand.K.. easy to implement and use. If it is acceptable for a particular optimization potential function is essential for our global optimization algo- problem. problem reformulation is needed depending on the ther. 4. Stationary points of a potential function Cheng-Dong and Xiao-Xia [20] showed that all stationary points of a potential function F(x) are connected by a network of ridges and The tangent plane distance function (Eq. swarm-based optimization algorithms [33]. stochastic tunneling [30]. Unfortunately. / Fluid Phase Equilibria 358 (2013) 304–318 307 • Stochastic methods (e. ant curves of F(x). (15). Heuristic global optimization methods have been frequently Later. to the global solution..32]. evo.. We explore this connectedness by following ridges and quality of solution and efﬁciency for multivariable optimization. reactive search optimization. Also. (18) contains N + 1 unknowns (independent variables x1 . (15): function L(x. A gradient system in RN is an autonomous ordinary differential By applying the Kuhn–Tucker conditions [41] to the Lagrangian equation. (18). Eq.g. • Ridges (valleys) are maxima (minima) of the potential func- modynamic model being used [9–12].g. resulting in errors and uncertainties in equipment design and erroneous model perfor. Eq. stable nodes occur at line value c). This is an important graph. the more reliable deterministic meth. Therefore we can quickly ﬁnd all the stationary points by tion. methods. are independent of a model and can • Ridges and valleys of F(x) are all connected to each other and this handle large number of decision variables. (16). The collection of these optima for all level values contains all of the ridges-tops and valleys-bottoms. problem described by Eq. Lucia and Feng [21] deﬁned ridges and valleys as a collection used for solving parameter estimation problems in phase equi. most current deterministic • Level curves of F(x) on a topographic map that contains con- global optimization methods are too expensive in terms of com. The deterministic methods theoretically guarantee convergence • There are no periodic solutions of Eq. (16): problems for design of separation processes. can cause convergence failure we can ﬁnd a point on the line that corresponds to a local opti- in the column or give erroneous conclusions about simulated plant mum in the gradient norm by solving the constrained optimization performance. solutions within a reasonable CPU time although they often face difﬁculties in ﬁnding the global solution [37] and do not guarantee The connectedness that exists between singular points of the the global optimality. (7)) is a potential func- valleys. • The Jacobian is a symmetric matrix and has all real eigenvalues. ) = 2H[F(x)]T ∇ F(x) + ∇ F(x) = 0 (18) The gradient system has the following useful properties: L (x. . or elevation) of the potential of a correct VLLE one. parallel tempering). along every solution curve) and is perpendicular to the level lution strategies.40]. simulated annealing [29]. Monte-Carlo • Trajectories of Eq.

One can attempt to track a routine [43] specially designed to give smooth derivatives close the branches of Eq. the arc length (s). While tracking the continuation branches. at ﬁrst. If it changes sign between two consecutive points on the branch. (19). by gradually increasing parameter s and solving Eq. from the following equation. The algorithm starts from any stationary point inside the Lx (x. dt(sk )/ds] can be approxi. Eq. cation point for the old branch and the subscript 0 for the new ity and efﬁciency of the algorithm we developed a new arc length branch. s) deﬁning the arc length has been added to the stationary points inside the problem domain is summarized as fol- system of Eq. . (18) starting from any stationary point of F(x). The direction of the sec- ond branch that intersects the current brunch at this bifurcation Without good initial estimates for the number of liquid phases point is then calculated from the Keller’s [42] approximation of the and their compositions. Check the topological criterion (see Appendix B) for all stationary xi (sk ). x2 . the number ⎡ ⎤ of liquid phases in equilibrium cannot be determined on the basis ⎡ ⎤ dx0 Lxx (x. s). Calculate the Hessian matrix H[F(x)] at the stationary point. xN . we choose ities where the continuation parameter must start to decrease or two points close to the vertex. calculate two derivatives and then increase to follow the branch. (22) is calculated numerically using cess of the global optimization method. t) ∇ F(x) 0 of tangent plane analysis alone. . t) and one 2. The current branch can be tracked then its eigenvalues and eigenvectors. . matrix. For that reasons. Instead of gradually increasing or decreasing the value of the continuation switching suddenly from the forward to the backward difference parameter t and using the most recently calculated point as an ini. this type of use a difference formula that does this gradually.. the liquid–liquid equilibrium calculations algebraic bifurcation equation can easily fail to converge to a stable solution. (19). where an additional The algorithm for tracking of continuation branches to ﬁnd all equation g(x. . we adopted branches to be started from. In a corrector step. Since very close parameter continuation can fail at turning points or other singular. . Add new stationary point to the set of found stationary points continuation parameter t is one of the unknowns it can increase or (SFSP). . 8. The Jacobian matrix in Eq. t. the continuation parameter. However. The reliability and efﬁciency of the algorithm is crucial for the mated by the secant vector connecting points k − 1 and k. we monitor the determinant of the Jacobian matrix of Eq.21] to follow where the subscript b indicates derivatives computed at the bifur- ridges and valleys of the potential function. .. where is a tuning factor selected close to 0. Therefore success of the search for all stationary points of the tangent plane Eq. (19) contains N + 2 unknowns (x1 .K. 4. s) F(z) = 0. / Fluid Phase Equilibria 358 (2013) 304–318 Various algorithms were previously used [13. Take one point from SIC and start a new branch in one of the eigendirections. (20) is linear with regard to the independent variables xi and distance function F(x). Eq. (19). For uphill movement. formula just before independent variable reaches the boundary. decrease. to the composition boundaries and component vertices. Combined phase equilibrium and stability algorithm calculate a new bifurcation point [22]. t. . For the tangent plane distance function. (sk ) and t(sk ) are known from the previously calculated points from SFSP. s) = ⎣ L (x. b db dtb ⎣ ⎦ (1 − ) dt0 the combined phase equilibrium and stability algorithm should be ds ds ds ds used. and parameter. t) ⎦=0 (19) composition of the original mixture z is usually selected as the starting point for the algorithm since at this point F(z) = 0 and g(x. ric distortion on the objective function [21]. To resolve these problems. we explore only directions that correspond to dominant geomet- dictor step during branch tracking. Since the 3. The vector tangent to the continuation path at this point [dxT (sk )/ds. add the dt(sk ) bifurcation point coordinates and corresponding eigenvectors to + 1 − [t − t(sk )] − (s − sk ) (20) SIC for later exploration. Also. to a vertex this difference formula cannot be applied. Add new stationary point coordinates and corresponding eigen- Since the arc length is a nonlinear function of the independent vectors to the set of initial conditions (SIC) for subsequent variables [22]. lows.99 to place more emphasis on the original problem independent variables than on 7. initial conditions are explored. t. we 7. go to step 5. and continuation parameter t. t) = 2J H[F(x)]T ∇ F(x) + H [F(x)] (22) Efﬁcient tracking of continuation branches is crucial for the suc. the pseudo arc length equation deﬁned by Keller [42] 5. If a bifurcation has been detected. If there are some unused initial conditions in SIC. Fortunately. (18) to form the following augmented system. The arc step size (s − sk ) is set initially to 0. the ⎢ ⎥ G(x. ds 6. point k for an arc length sk . other directions from the set of from bifurcation points. d(sk )/ds.01 and then reduced If after exploring all dominant geometric distortion directions the for strongly nonlinear paths or enlarged for nearly linear ones far topological criterion is not fulﬁlled. . Follow the branch up to a new stationary point N dxi (sk ) d(sk ) g(x. (22). s) = [xi − xi (sk )] + [ − (sk )] or to a boundary of the domain. t. a mod. iﬁed arc length continuation was used [22]. while the arc length always increases. It is summarized as follows. ⎡ ⎤ 1. for the arc length relationship g(x. To speed up the branch tracking. (19) by the Newton–Raphson method. extrapolate them to the original point. t) problem domain. . Check for bifurcations along the i=1 ds ds continuation branch. it provides ⎣ dxT ⎦ ⎢ ds ⎥ good initial estimates for the LLE calculations.18. We optimize the Newton it corresponds to the smallest positive eigenvalue of the Hessian step length and take the problem constraints into account.. 6. Tracking continuation branches Lxx (x. we tial guess for the next one on the branch. The stability test usually does not ⎢ ds ⎥ ⎢ ⎥⎢ ⎥ deliver the exact compositions of phases in equilibrium and some- ⎢ ∇ F(x)T 0 −1 ⎥ ⎢ d0 ⎥ ⎢ ⎥⎢ ⎥=0 (21) times predicts incorrect number of phases. Eq.. we solve Eq. Wasylkiewicz et al.308 S. go to step 2. To enhance reliabil. for downhill movement to the most negative eigenvalue. . The top left part of the above matrix can be calculated [23] continuation method described in details in the next paragraph. This secant vector is used in a pre. t. If a newly found stationary point is not in SFSP.

One eigenvalue at this stationary point is positive. z)/RT calculated for the overall composition z = [0. Wasylkiewicz et al.48 K. All selected com. Since the topological criterion is satisﬁed initial guesses for LLE ﬂash calculations (see Table 3 and Fig. as in Fig. z = [0. The Table 1 NRTL/Ideal/Chemical binary parameters for the mixture of ethanol (1). at temperature T and pressure p. i bi1 bi2 bi3 ˛i1 ˛i2 ˛i3 1 – −71. 1. In this example.325 kPa was calculated by NRTL/Ideal/Chemical model using the chemical process simula- tor VMGSim [44].4] at a saturation temperature of 338.2.30000 – . If the calculated equilibrium is globally stable.22474 2 683. save the coordinates of all minima of F(x) and go to step 3. An important part of VLLE calculations is the liquid stability test and LLE ﬂash calculations. z)/RT.4.48 K.22474 0.48 K. 3. We use our stability 0.1.4. 5. A.03325.4] as shown in Table 2 and Fig. If one or more of the phase fractions converge to zero. 6. 4. and branches correctly calculating the LLE for the overall composition z = [0. S.29814 0. For a liquid of an overall composition z. water and benzene Vapor–liquid–liquid equilibrium (VLLE) for the mixture of ethanol. The nonzero binary interaction parameters are shown in Table 1. Binary interaction parameters bij are in K. eliminate the corresponding liquid phases from the solution. 0. Initial (LLEStrtPnt) and ﬁnal (LLE) tie lines for LLE calculations. In the following paragraph. ﬁnd all stationary points of the tangent plane dis- tance function F(x) using algorithm described in the previous paragraph and check the stability of the liquid. tion F(x. then end. 2).40577 – 1690. our rigorous LLE ﬂash calculation routine described in Appendix the other one is negative. 2. / Fluid Phase Equilibria 358 (2013) 304–318 309 1.40053 1357. To create a VLLE diagram. we show a comprehensive procedure for Fig.36832 82. we show in details all steps of the combined phase equilibrium and stability algorithm applied to Fig.67004 0. z)/RT calculated to test stability of one liquid phase L1 = [0. 1. The dimensionless interaction parameters ij in the NRTL model are related to the interaction energy parameters gij and deﬁned as ij = gij /RT = aij + bij /T + cij ln(T). which are imbedded in the search for a correct bubble point temperature for a particular mixture. for tracking ridges and valleys of the dimensionless tangent plane distance func- tion F(x.K. From all stationary points found in the previous stability test two other stationary points (minima) have been found in the step (Table 2) we select both minima which compositions are good entire composition space. save the coordinates of all minima of F(x) found dur- ing the last stability test calculations and go to step 3. 8. Otherwise. Ternary mixture of ethanol.29814 – 0.2. the overall dle point on the dimensionless tangent plane distance function composition z represents an unstable liquid. They were calculated using experimental data from [45.46]. Examples 8. then end. Branches for tracking ridges and valleys of the dimensionless tangent plane one ﬁve-component and two ternary mixtures.2. Use the coordinates of the minima of F(x) (up to the limit allowed by the phase rule) as an initial guess in calculations of the liq- uid phases in equilibrium.21198 – 0. Now we switch to F(x. Notice that for the two examples of liquid–liquid–liquid equilibrium the ﬁnal stable three phase equilibrium was found after previously ﬁnding unstable two liquid phase equilibrium. 0. we conclude that all stationary points in this case We start with the stability test for the overall composition have been found. (see Appendix B). distance function F(x. 0.85914] at temperature 338.4] positions were unstable and end up at two or three liquid phase at temperature 338. water (2) and benzene (3).10761. In this case the Since values of the dimensionless tangent plane distance func- starting point for branch tracking (overall composition z) is a sad.33937 – 0. 0. 4. water and benzene at pressure 101. If the liquid is globally stable. 0. Using our global optimization routine. z)/RT are negative at both minima (Table 2).30000 3 571. equilibria. test several times along with rigorous LLE ﬂash calculations to make sure that the LLE is correct and all liquid phases in equilibrium are stable. 0. we repeatedly applied bub- ble point calculations to cover all possible heterogeneous regions in the composition space. Otherwise. 2. Check the global stability of one of the liquid phases present in the LLE calculation solution. Make use of the rigorous LLE ﬂash calculation routine described in Appendix A. 0.4.

0E-06) at all stationary points.85914 20.54716 0.85914 0. z)/RT are tine.03325.4499 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 2) Number of minima Nmin = 3 Number of odd saddles Nsad odd = 2 calculation routine converges quickly to the two-phase LLE solution mixture and then compare to the value calculated for the overall shown in Table 3.38052 L2 at LLE 0. liquid L1 is unstable.83048 12.52356 0.25762 0.48 K.16840 0. Temperature 338. composition space.05908 0.5054 MIN 1 −6.03325 0. Since the value for the mixture is lower than that uid phases (L1 and L2) and their mixture.310 S. (within assumed tolerance 1.28444 0.0048 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 2) Number of minima Nmin = 2 Number of odd saddles Nsad odd = 1 Table 3 NEWTON LLFLSH calculations for the mixture of ethanol (1).29063 0.19063 L2 at LLE 0.17452 L1 at LLE 0. NRTL/Ideal/Chemical model.98595 SA −1 7. z)/RT x1 x2 x3 Eigenvalues MIN 1 0. / Fluid Phase Equilibria 358 (2013) 304–318 Table 2 Results of the search for all stationary points for the mixture of ethanol (1).28778 Table 4 Results of the search for all stationary points for the mixture of ethanol (1).93217 Starting point L2 0.38409 −0. Now we liquid mixture in Table 5.00694 L1 at LLE 0.4 0.72213 MIN 1 −6.18094 0.54716 0. 0. 0. and values of all stationary Table 5 NEWTON LLFLSH calculations for the mixture of ethanol (1).4].00694 4. L2 and L3) and their In other words.23057 39.03763 0. four other stationary points have been found in the whole negative at both minima. locations.36548 −0. Temperature 338.16898 0. water (2) and benzene (3).4. z)/RT are non-negative Now we switch again to our rigorous LLE ﬂash calculation rou. z = [0.85914 0. z = [0.10761 0. We perform the stability test for one liquid phase (e.49665 4.04733 10. L2 and L3.01617 0.45715 Starting point L2 0.05166 0.62871 0.61591 −0.17381 0.85742 MIN 1 −0. The compositions of three minima found in the previous L1 is stable.62871 0.25762 0. We calculate the Gibbs free energies for both liq.05590 6.26525 Starting point L1 0.03763 0.22844 0. Wasylkiewicz et al.0 0.77769 0.78856 0.4 0.4.11367 −0.03347 0.07999 0. 0.48 K. we conclude that the liquid z will pos- value calculated for the overall composition z.4 −0.4 −0.28444 0. 0.06755 0. 0. Gibbs free energies for all liquid phases (L1.05908 0. Now we check if the liquids L1. In this case the starting point for branch tion (see Table 4).41589 −0. 0.16840 0.11367 0. water (2) and benzene (3).2. the two-liquid mixture in Table 3 is higher than that for the three- clude that the liquid z will possibly split into L1 and L2. Type Index F(x. 2).85826 0. the number.2 0.54572 4. composition z.28794 .01617 0.K.21863 −0.7859 MIN 1 −0.03325 0.10761. x1 x2 x3 ˚k g(x)/RT Overall composition z 0.92E-08 0.10761 0.78856 0. In this case the starting point for branch tracking tion. NRTL/Ideal/Chemical model.36833 Starting point L3 0.4]. Since values of F(x.2. Type Index F(x. z)/RT x1 x2 x3 Eigenvalues SA −1 0. water (2) and benzene (3). perform the stability test. NRTL/Ideal/Chemical model.19130 L3 at LLE 0.79E-04 0. water (2) and benzene (3).2 0. There is no need to check stability of the other two liquid stability test step (Table 4) are very good initial guesses for LLE ﬂash phases in equilibrium (L2 and L3 from Table 5) since the points rep- calculations (see Table 5).60258 −0. and then compare to the for the overall composition.2 0. We calculate the Gibbs free energy surface (necessary conditions for equilibrium). NRTL/Ideal/Chemical model. are stable. Temperature 338.17381 0.03325 0.34836 Mixture of L1 and L2 −0. L2 and L3 have to check if the liquids L1 and L2 are stable.18581 0.g.66389 SA −1 1. x1 x2 x3 ˚k g(x)/RT Overall composition z 0. 0. liquid L1 from Table 5) and is a minimum on the dimensionless tangent plane distance func. four other tracking is a minimum on the dimensionless tangent plane distance stationary points (minima and saddle points) have been found in function (see Table 6 and Fig.4].0 0. we con. z = [0.27339 Mixture of L1.93398 0.10761 0.93398 0. Since the value for sibly split into L1.4 0.04137 0. Temperature 338.g. 0.4 −0. Since values of F(x.26525 Starting point L1 0.4.2. Using our global optimization routine. L2 and L3 −0.77E-03 0.93217 46. we choose one liquid phase (e. Now the calculation routine converges resenting these liquids must have a common tangent plane to the to the three-phase LLE solution shown in Table 5. Notice that the Gibbs free energy for the mixture is lower than that for the overall composition.5528 2.85914].48 K.48 K.10827 0. liquid To be sure that we have found a stable three liquid phase solu- L1 from Table 3).05166 0. liquid tine. 3).44E-05 0.78161 264. Using our global optimization rou- the whole composition space (Fig. z = [0.

97733 SA −1 3. The UNIQUAC model was used for calculations. in the opposite direction (branch 2) up to a stationary point. 8). compositions satisfying the LLE is sufﬁcient [13]. z)/RT is crucial for the success of our global optimization The ethylene glycol – lauryl alcohol – nitromethane system is method.06444 13. The system was investigated and follow the valley up to the lauryl alcohol vertex using the con- by several researchers [9. 0.50] are presented in Table 7. 0. z = [0.33974 MIN 1 −3. LLLE calculation results. branch tracking until all starting points have been examined and Fig. 0.16635 35. 7.04137 0.66400 0. We start at an overall composition z (trivial solution for known to have three liquid phases in equilibrium in part of the the tangent plane stability problem) in a dominant eigendirection composition space (see e.54349 4.02E-07 0. Ternary mixture of ethylene glycol.09308 −0. We store this point as another starting point on data from [9.22859 0. The dimensionless for branch tracking and calculate all eigenvalues and eigenvectors interaction parameters ij in the UNIQUAC equation are related necessary for determination of the type of the stationary point to the interaction energy parameters uij as ij = exp(− uij /RT).18095 0.85E-07 0.48 K. .29063.03347 0.18581] at temperature 338. z)/RT x1 x2 x3 Eigenvalues MIN 1 0. 0. Then we follow the valley number of mixture compositions using various calculation meth.09429 5. z)/RT calculated for the overall composition z = [0.47302. S.07E-04 0.27175 SA −1 7. lauryl alcohol and and pure component parameters are shown in Table 7. 0. Type Index F(x.52356 0.73123 MIN 1 −2. The binary 8. / Fluid Phase Equilibria 358 (2013) 304–318 311 Table 6 Results of the search for all stationary points for the mixture of ethanol (1). nitromethane Efﬁcient tracking of ridges and valleys of the potential func- tion F(x.85826 20.2.25620] at temperature 295 K are shown in Fig.47–51].18581 0.0 0. 3.93791 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 2) Number of minima Nmin = 3 Number of odd saddles Nsad odd = 2 points of tangent plane distance function must be the same for each Contour lines of the dimensionless tangent plane distance func- liquid phase in equilibrium and a stability test for any one of the tion F(x. 6 and Fig. z)/RT calculated to test stability of one liquid phase L1 = [0.60348 −0. They tested phase stability for a tinuation method (see branch 1 in Fig.9858 cal/(mol K).27078. NRTL/Ideal/Chemical model. 5). as well as possible directions to start new branches. and branches for tracking ridges and valleys of the dimensionless tangent plane distance function F(x. water (2) and benzene (3). 0.10827 0.24292 0.52356.18581]. The pure component and binary parameters calculated based case a saddle point. Wasylkiewicz et al.K. Fig.29063. Temperature 338.40576 2.52356. We continue where R = 1. in this ods.48 K.g.77768 0.29063 0.57E-03 0.16793 0.

z = [0. i ui1 ui2 ui3 ri qi 1 – 490.0 0.51748 VMGSim [44] with the binary interaction parameters shown in 3 −140. Temperature 295 K.01366 0.08044 72.92990 SA −1 0.01689 0.47302.96906 3.0086 1.01885 7. Using our global optimization routine. two all liquid phases in equilibrium are stable. other (nontrivial) stationary points (minima) have been found in the whole composition space. Vapor–liquid–liquid equilibrium for the mixture of ethanol.4] at a temperature of 295 K.4. We use our stability test eigenvalue at this stationary point (trivial solution z) is positive.80981 SA −1 0.01731 0.868 Table 8 Results of the search for all stationary points for the mixture of ethylene glycol (1).00200 0.2. 7 and Fig. / Fluid Phase Equilibria 358 (2013) 304–318 Table 7 UNIQUAC binary and pure component parameters for the mixture of ethylene glycol (1). z)/RT.90590 0.25308 72. 9). and nitromethane at temperature 295 K. water and ben.00167 0. Type Index F(x. 0. Wasylkiewicz et al. One z = [0. lauryl alcohol (2) and nitromethane (3).8898 108. and LLE ﬂash calculations to make sure that the LLE is correct and the other is negative.1161 264. more minima and one more saddle point (see Fig. 5) was calculated by UNIQUAC/Ideal/Chemical model using 2 −162.18824 0.325 kPa.8495 7.7016 8.02522 0.3081 −0.977 1.53802 0. Since the topological criterion is sat- isﬁed (see Table 10).47302 0.35228 (Fig.12370 MIN 1 0.27078 0.372 3 929. Liquid–liquid equilibrium for the mixture of ethylene glycol. lauryl alcohol and nitromethane at a temperature of 295 K 1 – −118. z = [0. z)/RT x1 x2 x3 Eigenvalues MIN 1 0.46383 26. 4. Binary interaction parameters uij are in cal/mol. The dimensionless interaction parameters ij in the UNI- QUAC equation are related to the interaction energy parameters We start with the stability test for the overall composition uij and deﬁned as ln( ij ) = − uij /RT = aij + bij /T + cij ln(T). Fig. 0.9342 3.55850 – −516. lauryl alcohol (2) and nitromethane (3).6252 2.4088 2. 0.4.4887 – 2. Binary interaction parameters bij are in K. .25620].K. i bi1 bi2 bi3 col.27078. In this case the starting point In the following few tables.27374 −0.01677 0.4] (see Table 10).312 S.90359 MIN 1 −0. All lauryl alcohol (2) and nitromethane (3). Fig. 0. In this case we have found two Table 9 UNIQUAC/Ideal/Chemical binary parameters for the mixture of ethylene glycol (1). 0.24249 0.59988 – Table 9.48063 −478.75584 530. Liquid–liquid equilibrium (LLE) for the mixture of ethylene gly.248 2 138. 0. we conclude that all stationary points in this case have been found.2.3904 – 606. we show an example of the detailed for branch tracking (overall composition z) is a saddle point on procedure for correct calculations of LLE for the overall composition the dimensionless tangent plane distance function F(x.25620 1. stationary points found in the process are summarized in Table 8. UNIQUAC model. 5. lauryl alcohol zene at pressure 101.48015 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 2) Number of maxima Nmax = 0 Number of minima Nmin = 3 Number of even saddles Nsad even = 0 Number of odd saddles Nsad odd = 2 Number of tangent nodes Ntng = 0 the topological criterion is fulﬁlled.51886 0.

7.14696 Starting point L1 0.00711 0. In this case the starting point for branch tracking is a saddle point on the dimensionless tangent plane distance function (see Table 12).00445 0. Fig.21198 0. two other sta- tionary points (minima) have been found in the whole composition space. Using our global optimization routine.22162 L2 at LLE 0.47273 MIN 1 −0.0 0. Contour lines of the dimensionless tangent plane distance function F(x. 0.00631 0. z)/RT calculated for the overall composition z = [0.2 0. / Fluid Phase Equilibria 358 (2013) 304–318 313 Table 10 Results of the search for all stationary points for the mixture of ethylene glycol (1). UNIQUAC/Ideal/Chemical model.2.47302.17560 Since values of dimensionless tangent plane distance function F(x. S. Wasylkiewicz et al.26469 0.K. z)/RT Fig.00445 0. z)/RT are negative at both minima. The compo- sitions of minima found in the previous stability test step (Table 10) are good initial guesses for LLE ﬂash calculations (see Table 11). 8. Since the value for the mixture is lower than that for the overall composition.03226 0.4 −0.g.4].4.47302.47302.96063 0.97101 0.20268 0. 0.10520 0. Now we switch to our rigorous LLE ﬂash calculation routine (see Appendix A).4 0. 0.69212 0.1294 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 2) Number of minima Nmin = 2 Number of odd saddles Nsad odd = 1 Table 11 NEWTON LLFLSH calculations for the mixture of ethylene glycol (1). z)/RT calculated for the overall composition z = [0. the overall com- position z represents an unstable liquid.4 0.10520 0. Since values of F(x. z)/RT x1 x2 x3 Eigenvalues SA −1 0.02454 244. 0. . Temperature 295 K.02454 0. We perform the stability test for one liquid phase (e. 6.25620] at temperature 295 K. x1 x2 x3 ˚k g(x)/RT Overall composition z 0. Branches for tracking ridges and valleys of the dimensionless tangent plane calculated for the overall composition z = [0. Lower part of the composition space. ture 295 K. UNIQUAC/Ideal/Chemical model.348 23.27078. The NEWTON LLFLSH routine converges to two-phase LLE solution shown in Table 11. we conclude that the liquid z will possibly split into L1 and L2. Contour lines of the dimensionless tangent plane distance function F(x. distance function F(x.4. We calculate the Gibbs free energies for both liquid phases (L1 and L2) and their mixture and then compare to the value calculated for the overall composition z. Type Index F(x.51755 −0.15559 0. 0.69212 4. z)/RT are negative at both minima (Table 10). z = [0. 0.26617 L1 at LLE 0. Temperature 295 K. lauryl alcohol (2) and nitromethane (3).52333 0.2.2 0. liquid L1 from Table 11). 0.25115 −0. Fig. 0. 0.25620] at tempera- ture 295 K.4].27078.03840 Mixture of L1 and L2 −0. 0.31620 1. Now we check if the liquids L1 and L2 are stable.14639 MIN 1 −0.27078.20268 0.97101 0.73383 Starting point L2 0.74885 −0. L1 is unstable. z = [0.4 0. lauryl alcohol (2) and nitromethane (3).25620] at tempera.

lauryl alcohol (2) and nitromethane (3). Notice that Gibbs free energy for ﬂash calculations (see Table 13).47302. UNIQUAC/Ideal/Chemical model.28926 L3 at LLE 0. Temperature 295 K. UNIQUAC/Ideal/Chemical model.83e-8 0. Wasylkiewicz et al. / Fluid Phase Equilibria 358 (2013) 304–318 Table 12 Results of the search for all stationary points for the mixture of ethylene glycol (1). Using our global Fig.24334 0.18771 L2 at LLE 0.0 0. L1 is stable. 0. z)/RT. 12684.2. 0. z)/RT x1 x2 x3 Eigenvalues MIN 1 0. L2 and L3) L2 and L3 are stable.2. Type Index F(x.22688 0. 0.46722 0. In this case the starting point for branch tracking is a minimum on the dimensionless tangent plane distance function (see Table 14).96063 0. been found in the whole composition space.25923 −0. lauryl alcohol (2) and nitromethane (3).2. We perform the stability test for one liquid phase (e.30627 −0.48585 −0. calculate the Gibbs free energies for all liquid phases (L1.22381 2.4 0.26307 L1 at LLE 0.22991 1.2.28944 0.12684 0.2 0.14699 0. Lower part of the composition space. In this case the starting point for branch tracking (overall composition z) is a saddle point on the dimensionless tangent plane distance function F(x.14699 0. Branches for tracking ridges and valleys of the dimensionless tangent plane distance function F(x.00691 0.28617 0. 0. Temperature 295 K. benzene (2).11368 2.13711 0. cyclohexane (4) and water (5). z)/RT are non-negative at all stationary points.4 −0.12684 0. 72989].54342 SA −1 6.48392 0.22991 0.72989 1. z)/RT calculated for the overall composition z = [0.4. the two-liquid mixture in Table 11 is higher than that for the three- tine converges to three-phase LLE solution shown in Table 13. z)/RT x1 x2 x3 Eigenvalues SA −1 0.28727 0.2. 0. UNIQUAC/Ideal/Chemical model. Now the NEWTON LLFLSH rou.52] are presented in Table 15. 0.24902 MIN 1 3.03829 Mixture of L1. lauryl alcohol (2) and nitromethane (3). liquid L1 from Table 13).03215 0. we conclude that the liquid z will Table 11 (not tested for stability) are good initial guesses for LLE possibly split into L1.35732 4. and their mixture and then compare to the value calculated for the The compositions of minima found in the previous stability test overall composition z.21198. 0.46722 0.68808 2. L2 and L3 −0. 0.00330 0.28944 0.29993 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 2) Number of minima Nmin = 2 Number of odd saddles Nsad odd = 1 Table 13 NEWTON LLFLSH calculations for the mixture of ethylene glycol (1). two other stationary points (minima) have 0.14327 0. z = [0. the other eigenvalues are positive.21198 0.03226 0.48297 MIN 1 −0. Type Index F(x. We liquid mixture in Table 13.01025 0.00711 0. Since the value for the mixture is lower than step (Table 12) combined with the composition of liquid L2 from that for the overall composition. Since the topological .K. z = [0.14327 0. One eigenvalue at this stationary point is negative. z = [0.52333]. L2 and L3.71590 1. Now we have to check if the liquids L1. 0.43450 −0.g. 9. The binary and pure component parame- ters taken from [49. Temperature 295 K.0 0.96094 0.3. furfural (3).27995 Starting point L3 0. The UNIQUAC model is used.74497 4. we start with the stability test (see Table 16). two other stationary points have been found in the whole composition space.20e-3 0. Five-component mixture This example involves the ﬁve-component mixture of acetic acid (1).14696 Starting point L1 0. 8. 0.314 S.45698 Starting point L2 0.72989 0.13711 0.37591 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 2) Number of minima Nmin = 2 Number of odd saddles Nsad odd = 1 Now we switch again to our LLE ﬂash calculation routine.4].71590 0. 14327. x1 x2 x3 ˚k g(x)/RT Overall composition z 0.25620] at temperature 295 K. Since values of F(x. To calculate LLE for the overall composition z = [0.48393 0.74535 MIN 1 −0.52333 −0.66599 2. 0.28617 0.24334 1. Using our global optimization routine.27078.26469. optimization routine.2] at a temperature of 295 K.18008 Table 14 Results of the search for all stationary points for the mixture of ethylene glycol (1).26469 0.

The routine converges very quickly to two-phase calculate the Gibbs free energies for both liquid phases (L1 and L2) LLE solution shown in Table 21.48.1313 151. has been signiﬁcantly enhanced. The NEWTON LLFLSH repeat the LLE ﬂash calculations using the two remaining phases as routine converges to two-phase LLE solution shown in Table 17. z)/RT are non-negative (within assumed L1 is stable. Type Index F(x. 8. In this case the starting point for branch tangent plane stability test for multiphase liquid mixtures. S.8012 784.22E-16 0. step (Table 19) as the initial guess for the calculations. In this case the starting point for branch tracking is and perform stability test.2.4. two other function (see Table 22). We points in this case have been found. use the compositions of minima found in the previous stability test Since values of the dimensionless tangent plane distance func. we conclude that all stationary Now we switch to our rigorous LLE ﬂash calculation routine.466 94. UNIQUAC model. L1 and L2 are stable.577 3. z)/RT are non-negative at all stationary points. z)/RT.16405 – −11.2 0. liquid L1 from Table 21) from Table 17). described in paragraph 7. We start with stability test for the overall composition z = [0.0E-06) at all stationary points.53290 0. The algo- optimization routine.240 5 −523. applied to ﬁnd correct number of liquid phases in equilibrium.1669 MIN 1 −2.2]. of minima found in the previous stability test step (Table 16) are Now we eliminate the liquid phase L1 from the solution and good initial guesses for LLE ﬂash calculations. the liquid L1 is stable. Since the that for the overall composition.03603 14. It gives an efﬁcient and robust scheme for ﬁnding all sin- liquid region. z)/RT technique was tested on three different mixtures. tolerance 1. ranging from a are negative at all minima.175 4. Since robustness of multiphase equilibrium calculations. water and benzene.810 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 4) Number of minima Nmin = 2 Number of odd saddles Nsad odd = 1 criterion is satisﬁed (see Table 16). The We developed a new arc length continuation method to overcome overall composition is in the two-liquid region (see Fig. function. Temperature 295 K. Using our global optimization routine.0370 7. Since values of F(x. An overall composition z = [0. space. The developed values of dimensionless tangent plane distance function F(x. Using our global distance function predicted by a thermodynamic model.9283 – 0. The gular points of a mathematical model by exploring the natural NRTL/Ideal/Chemical model is used with the binary interaction connectedness that exists between singular points of an objective parameters shown in Table 1.9200 1. Wasylkiewicz et al. the overall composition z represents an ternary system with three liquid phases to a ﬁve component system unstable liquid.484 4 409.g. The LLE ﬂash tion F(x.1187 −1. furfural (3). four stationary points have been found in the whole composition space. Using our global optimization routine. z)/RT are negative at both minima (Table 16) the overall calculation routine does not converge to a three-phase solution but composition z represents an unstable liquid.75E-02 0. i ai1 ai2 ai3 ai4 ai5 ri qi 1 – −137.8843 1. four other stationary points (minima and sad.1878 2.2024 2. Binary interaction parameters aij are in cal/mol. 4).26305 0.07430 0.2.1499 – 1421.23356 0.41648 5.2505 137. 0. was climbing optimization techniques. 0.4159 MIN 1 −2.1. Now we have to check if the liquids we conclude that the liquid z will possibly split into L1 and L2. The idea of following ridges and valleys using informa- 0. the same as in example 8. 0. z = [0.836 66. Conclusions This example involves the three-component mixture of A general approach has been developed for ﬁnding all sin- ethanol. furfural (3).200 4.28.1680 2. z)/RT x1 x2 x3 x4 x5 Eigenvalues SA −1 −6.28. We the initial guess.24] (see Table 19). we conclude that the liquid z will value for the mixture is lower than that for the overall composition. The global optimization algorithm has been applied to the Gibbs 0.5019 3. benzene (2). It is the difﬁculties with tracking of ridges and valleys of an objective very close to the three-liquid region as well as to the homogeneous function.64E-02 0. To be sure that we have found a stable two liquid phase solu- We perform the stability test for one liquid phase (e. liquid L1 tion. The tracking (overall composition z) is a saddle point on the dimen.1192 −53. / Fluid Phase Equilibria 358 (2013) 304–318 315 Table 15 UNIQUAC binary and pure component parameters for the mixture of acetic acid (1). algorithm quickly ﬁnds all stationary points of the tangent plane sionless tangent plane distance function F(x. The compositions liquid phase L1 converged to zero.771 216.01925 0.39649 294. 0. Since the value for the mixture is lower than pare to the value calculated for the overall composition z.2 0.0464 3. cyclohexane (4) and water (5). possibly split into L1 and L2.3246 5.48. Ternary mixture close to liquid region boundaries 9. Now we switch to our stops at the boundary shown in Table 20.456 2. we choose one liquid phase (e.2.07903 1382.2 0.09356 0.400 Table 16 Results of the search for all stationary points for the mixture of acetic acid (1).8886 – 22.2. In this case the starting point for branch a minimum on the dimensionless tangent plane distance function tracking is a minimum on the dimensionless tangent plane distance (see Table 18).26321 0. The phase fraction ˚1 for LLE ﬂash calculation routine (NEWTON LLFLSH).585 7.068 −711. gular points of a mathematical model.K. 0. We calculate Gibbs free energy for and their mixture and then compare to the value calculated for the both liquid phases at equilibrium and their mixture and then com- overall composition z. other stationary points have been found in the whole composition Since values of F(x.24] was chosen to illustrate how the step 4 of the combined phase tion gathered along the way. benzene (2).g.06767 0.6783 16. rithm is self-starting and signiﬁcantly improves reliability and dle points) have been found in the whole composition space.082 1172. 0.2 33.072 2 0.400 3 674. cyclohexane (4) and water (5).9320 37.2 0.8131 957. which was previously used in the hill equilibrium and stability algorithm.32388 −255. with two liquid phases. .

85772 20.44E-02 0.02160 0.44457 0.60412 −0.06212 15.03333 0.28.03333 0.2 0.57E-04 0.10850 0.20694 0.85817 L1 at LLE 0. NRTL/Ideal/Chemical model. Temperature 338.12952 0.10868 0.3976 −0.11129 0.316 S.23356 0.09356 0. water (2) and benzene (3). z = [0.10868 0.77977 0.48.2.03360 0.05504 10.9641 0.43731 −1.31266].18001 0.24].25477 0.88717 28.45E-03 0. cyclohexane (4) and water (5).29302.27499 0.28.38279 L2 at LLE 0.16724 0.41648 0.89E-08 0. furfural (3).76894 0. 0.84230 74. 0. 0.61574 Starting point Liquid 2 0.29849 0. 0. x1 x2 x3 ˚k g(x)/RT Overall composition z 0. 0.03360 0.28186 0. Type Index F(x.19307]. z)/RT x1 x2 x3 Eigenvalues SA −1 0.26894.16810 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 2) Number of minima Nmin = 3 Number of odd saddles Nsad odd = 2 Table 20 NEWTON LLFLSH calculations for the mixture of ethanol (1). 0.2 0.02500 0.51726 0.19018 Starting point L2 0.08287 −0.35109 0.24].28.07430 0. z = [0.2 −1.07677 Table 21 NEWTON LLFLSH calculations for the mixture of ethanol (1).85817 0.02E-04 0.72136 MIN 1 −2.16729 35.24]. Temperature 295 K.37392 −0. Temperature 295 K.30751 SA −1 3.29302 0.05504 0.31344 2.K. Type Index F(x.2 0. water (2) and benzene (3). benzene (2).08783 0.01925 0.26321 0.08783 0.56269 −2.28186 0.131 3.2.10850 0.0 L2 at boundary 0.0122 4.27E-05 0. 0.12266 32.84847 0. 0.85772 0.31266 0.22591 Mixture of L1 and L2 −1.51391 0. UNIQUAC model.0370 MIN 1 9. Type Index F(x.0 0.48 K. 0. / Fluid Phase Equilibria 358 (2013) 304–318 Table 17 NEWTON LLFLSH calculations for the mixture of acetic acid (1).12346 0.29849 0.06767 0. z = [0.48.6419 98. furfural (3). NRTL/Ideal/Chemical model.77476 MIN 1 −7.21286 0.19307 0.27357 Starting point L3 0.5109 7.28 0.92323 L3 at boundary 0.00947 4.03929 3.07061 −0.51391 0.93841 MIN 1 −2.11061 5.19171 Mixture of L1 and L2 −0.2.72454 Table 18 Results of the search for all stationary points for the mixture of acetic acid (1).32635 SA −1 7.22864 0.73339 SA −1 5.28 0.31266 5.71021 Starting point Liquid 1 0.28E-06 0.12993 0. z)/RT x1 x2 x3 x4 x5 Eigenvalues MIN 1 0.38426 Liquid 1 at LLE 0.23380 0.18653 0.12346 0.24 −0.18E-03 0.8570 20.07E-03 0. 0.04017 0. 0.90827 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 2) Number of minima Nmin = 3 Number of odd saddles Nsad odd = 2 .29256 0.92939 −0. water (2) and benzene (3). z = [0.40566 0.12953 0.53290 0.19018 0.11206 Liquid 2 at LLE 0. Temperature 338. UNIQUAC model. z = [0. NRTL/Ideal/Chemical model.6471 Topological criterion: Nmax + (−1)N Nmin + Nsad even − Nsad odd = (−1)N is satisﬁed (N = 4) Number of minima Nmin = 2 Number of odd saddles Nsad odd = 1 Table 19 Results of the search for all stationary points for the mixture of ethanol (1). Wasylkiewicz et al.51726 0.48 0.51391.34030 MIN 1 3.48.24 −0. z = [0.68295 0. z)/RT x1 x2 x3 Eigenvalues MIN 1 0.02160 Starting point L2 0.40565 0.8035 2.27357 0.26894 0.02500 0.03603 0. 0.11129 0.36930 Table 22 Results of the search for all stationary points for the mixture of ethanol (1).0040 5.54250 4. 0.2215 15.48 0.44457 0. benzene (2).06E-07 0.04022 0.04017.26305 0.88717 L1 at boundary 0.23418 0.29302 0.12993 0.26894 0.48 K. Temperature 338. Temperature 338.0 0. 0.2 0.04453 0.48 K.29256 0. cyclohexane (4) and water (5).1064 SA −1 7.36836 Starting point L1 0.73831 MIN 1 -5. x1 x2 x3 x4 x5 ˚k g(x)/RT Overall composition z 0.2. NRTL/Ideal/Chemical model.12346. 0.17911 0.19307 0. 0.25477 0. water (2) and benzene (3).48 K.0 0. x1 x2 x3 ˚k Starting point L1 0.40719 5.04017 0.25477.2].84847 0.

i=1 i=1 rium (Np ≥ 2) is a follows [26.7) and solve the set of equations Virtual Materials Group Inc. 4) inside the outer loop NR solver (for mole fraction calculations) for the Material balances LLE problems with more than two liquid phases.4) k=1 Nc −1 Nc −1 KNk c 1− xi1 zi + xik − 1 = 0 k = 2.1).. . Even for this simplest case there (2 ≤ Np ≤ Nc ) have to be calculated. . existence of vertical asymptotes splits the equation domain into Equilibrium equations a set of Nc − 1 regions. using a one-variable solver that is usually faster and more robust . i = 1. zi x¯ i1 = Np i = 1. . .. k . 6. . The equations has to be solved.8) Appendix A. Np (A. . . . Eq..11) for the last component Nc . including utilizing proper function transformation to make the transformed problem as linear as pos- Summation equations sible [54]. .. . . Nc . .1) to get c 3. Wasylkiewicz et al. . using Eq. k = 1. p) using the Newton–Raphson method.2). We also check global consistency of each tangent tions plane stability test. ..9) Summation equation for phase fractions k=2 Np xik − Kik xi1 = 0 i = 1. . Topological criterion for the tangent plane distance function for liquid phase fractions ˚k (k = 2. In this case it can be solved and overall composition z. (Nc − 1) Np (A. . .. .11) The Rachford–Rice [53] formulation is commonly used to solve this problem.4) has been rearranged as follows [19]. The calculations are especially efﬁcient when Nc j Nc j (Ki − 1)zi a good initial estimate is provided from a rigorous Gibbs tangent Hj (˚2 . . .. The mole fractions (xi k . the set of (Nc − 1) Np + Np − 1 equations (A. . . . To this end. Nc (A.. . k = 1.3) Np k=1 xi1 − ˚k (xik − xi1 ) − zi = 0 i = 1.. For the tangent plane distance function F(x). . i = 1. Nc . using Eq. . . (B. . . Calculate and normalize new mole fractions in the reference tories is always into the permissible region.1). . .. The liquid phase 1. .23].54].10) ˚k = 1 (A. . (A. . k = 1. . 4. . . (A.9)–(A. xik = 1 k = 1. . . . . applying some special function classes [55].5) Appendix B. . ..9). . the following set of are two issues when solving these types of equations [55]. k = 1. Nc − 1 (A. . . .1) ik to overcome these problems. . Np ) and Eq.. . . (A. N . i = 1. S.. Nc (A. .2). k = 1. fj = 0 j = 1. . Nc − 1 k = 1. This special property phase 1 combined with the common properties of gradient systems (15) allowed developing the topological criterion [13]. Nc ) in librium cannot be determined on the basis of tangent plane analysis all other phases (k = 2. the ﬂow of trajec- 5. Np . i=1 i=1 1 + k=2 (Kik − 1)˚k = 0 j = 2. Calculation of liquid–liquid equilibrium Using the Newton–Raphson (NR) method. .6) Nmax + (−1)N Nmin + Nsad − Nsad = (−1)N (B.. . . Then we modiﬁed Eq. Np (A.K. . . ...10) for all independent mole fractions (xi k . (A.1) even odd 1+ k=2 (Kik − 1)˚k .54] First we eliminated xN k (k = 1. Also.. . . and using the block-algebra approach [56] or various initialization schemes Nc [57]. summation and material balance equations. Guess xik . . . . . at a speciﬁed temperature and pressure.3) to get Eq. . . i = 1. bining equilibrium. 4).2) To overcome numerical problems with the imbedding inner i=1 loop NR solver (for phase fraction calculations in point No. Rachford–Rice equation (in point No. . Np ) for all Np liquid phases than multi-variable NR method. conventional solution meth- i1 ods often exhibit slow convergence. Calculate and normalize new mole fractions x¯ ik (i = 1. Np (A. The algorithm to calculate multiple-liquid equilib.4).. Np (A. . fj ≡ xik − x¯ ik i = 1.. . Eq. . The algorithm is efﬁcient at solving the LLE problems for two Let us consider the liquid–liquid equilibrium (LLE) problem for a liquid phases [26. Calculate differences between guessed and calculated mole frac- should be used. N ) from the set of independent c p variables using summation equations Eq. Calculate Kik . ˚p ) = (xi − xi1 ) = Np plane analysis [13. Now. and Eq. . .. the set of Eqs. / Fluid Phase Equilibria 358 (2013) 304–318 317 In the paper we show that the number of liquid phases in equi.. A lot of efforts have been made xik = xi1 = Kik xi1 i = 1. fraction for the reference phase ˚1 was also eliminated using Eq. . (A.1). Nc − 1. Np ) using Eq.. . (A.1)–(A. (A.. is gratefully acknowledged for ﬁnancial support of the project. k = 1. alone and the combined phase equilibrium and stability algorithm 7.11) can be solved simultaneously to get all phase fractions and phase composi- tions at equilibrium. (A. . Nc − 1. Np ) and phase fractions (˚k . Np (A. Calculate xN p (A.. Np Acknowledgment j = 1. .. .. . . ... . 2. (A. Nc k = 2. . Nc − 1 k = 2. zi = ˚k xik i = 1.. Np (A. where the algorithm reduces to only one mixture of Nc components. . (Nc − 1)p (A. . . Solve the set of p − 1 Rachford–Rice equations obtained by com. . Each one contains a different solution but only one has physical meaning. Np .

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