Application of Modified NRTL Models For Binary

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Thermodynamics, Transport, and Fluid Mechanics

Application of modified NRTL models for binary LLE phase characterization
Younas Dadmohammadi, Solomon Gebreyohannes, Brian J Neely, and Khaled A M Gasem
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b00683 • Publication Date (Web): 25 Apr 2018
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Page 1 of 21 Industrial & Engineering Chemistry Research
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9 Application of modified NRTL models for binary
10 LLE phase characterization
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Younas Dadmohammadi
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22 Solomon Gebreyohannes
23 Brian J. Neely
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30 Oklahoma State University
31 School of Chemical Engineering
32 Stillwater, OK 74078-0537
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Khaled A. M. Gasem*
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43 University of Wyoming
44 Department of Chemical & Petroleum Engineering
45 Laramie, WY 82071
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52 * email: gasem@uwyo.edu
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54 Phone: 405-766-2845
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Industrial & Engineering Chemistry Research Page 2 of 21
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3 Abstract
4
5 Phase characterization of liquid-liquid mixtures is required in numerous chemical process
6 calculations. The original non-random two-liquid (NRTL) model is used widely in describing
7 liquid-liquid equilibria (LLE). Application of this model, however, is affected by (a) lack of reliable
8 parameters, (b) a wide range of acceptable parameter values, and (c) highly correlated
9 parameters. Recent modifications of the NRTL model, the two-parameter modified NRTL,
10 “mNRTL2”, and the one-parameter NRTL, “mNRTL1”, address these issues and show
11 promising results for characterizing LLE systems. The accuracy of these two modifications was
12 tested in our previous studies using a comprehensive vapor-liquid equilibria (VLE) experimental
13 database [1] and a representative LLE database [2].
14
15 In the current study, the efficacy of these modified NRTL models is assessed for the proper
16
characterization of LLE phase conditions and attributes, including phase stability, miscibility, and
17
consolute point coordinates. For the systems considered, the modified NRTL models produce
18
19
good LLE characterization results in comparison to those of the original NRTL; albeit, the results
20 from the mNRTL2 model are more precise than those of the mNRTL1 model
21
22 Key words: liquid-liquid phase equilibria; modified NRTL model; stability; miscibility; consolute
23 point coordinates
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3 1. Introduction
4
5 Characterization of phase equilibria of liquid mixtures is important in numerous industries where
6 practitioners are concerned with separation of fluid mixtures. In handling liquid-liquid equilibria
7 (LLE) of a given mixture, interest exists in determining the number of coexisting phases, the
8 stability of phases present, the composition of each phase, and the critical (consolute)
9 coordinate(s) for the mixture investigated. These concerns in LLE modeling have been the
10 subject of intensive investigation for the past two decades. Research in this area intensified
11 gradually to meet demands for higher process efficiency, lower operational costs, and handling
12 process bottlenecks [3].
13
14 Numerous LLE modelling studies appear in the literature [see, e.g., [4-9]]. In many of these
15 studies, the non-random two-liquid (NRTL) and universal quasichemical (UNIQUAC) models
16 were used to correlate the experimental mutual solubilities of a variety of LLE systems. The
17 models are also routinely used to characterize the LLE immiscibility, and determine the critical
18 solution temperature for targeted systems.
19
20
Equation of states are also used in LLE characterization. For example, Fotouh et al. [5] studied
21 the perturbation theory and van der Waals one-fluid theory for predicting the liquid-liquid
22 immiscibility for highly asymmetric mixtures. Similarly, Boshkov et al. [10] studied closed-loops
23 of liquid-liquid immiscibility in binary mixtures, as predicted by the Redlich-Kwong (RK) equation
24 of state (EOS). They reported that liquid-liquid phase behavior is highly sensitive to molecular
25 interactions as indicated by the required interaction parameters.
26 Other research has focused on developing algorithms for characterizing the phase behavior of
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LLE systems using activity coefficient and EOS models. For example, Yushan et al. [11]
28
developed an algorithm to determine LLE compositions using the tangent-plane distance
29
function approach for stability analysis. The NRTL and UNIQUAC activity coefficient models
30
31 were used to express the Gibbs free energy functions for the LLE systems investigated.
32 Similarly, Sofyan and coworkers [12] developed three different algorithms combining the
33 methodology of Gibbs energy minimization and the iteration function method with an extended
34 phase-check procedure were used for multiphase equilibrium calculations. The Peng-Robinson
35 EOS was successfully employed in those studies.
36 In spite of its practical importance, LLE has not been studied as extensively in the literature as
37 vapor-liquid equilibria (VLE). The disproportionate need for VLE measurements and models,
38
and difficulties in developing generalized models for LLE property predictions are key reasons in
39
this regard. Further, the experimental determination of LLE compositions can often be carried
40
41
out on an ad hoc basis, which produces large experimental uncertainties and weakens the
42 incentive for data correlation [13].
43 The current study focuses on the application of the NRTL model and two recent modifications of
44 the NRTL model (two-parameter modified NRTL (mNRTL2) and one-parameter modified NRTL
45 (mNRTL1)) to a variety of LLE systems. The accuracy of these two modifications were
46 evaluated in previous studies using a comprehensive VLE database [1] and a representative
47 LLE database [2]. Our primary objective is to examine the efficacy of these models in
48
determining the LLE phase conditions and attributes of binary mixtures, including phase
49
stability, miscibility, and consulate point coordinates. The current work is a continuation of
50
51
recent efforts by the Thermodynamics Group at Oklahoma State University to develop reliable
52 parameter generalizations for the NRTL model [14].
53 2. Phase equilibrium models
54
55 The Gibbs equilibrium criteria for a closed system require that:
56
57
58
59 3
1
2
3 = (1)
4
5 = (2)
= = 1,
6
7
(3)
8 subject to mass balance constraints. Where T and P are the system temperature and pressure,
9 respectively, and is component partial fugacity. Here, the superscripts “I” and “II” denote the
10 liquid coexisting phases, the subscript “i" signifies the component index, and N is number of
11
components in the mixture. To determine the conditions that satisfy the above equalities, a
12
model is required to evaluate the partial fugacity of each component in each phase. Following
13
14 the split approach formulation, Equation 3 is rewritten in terms accessible variables:
15 = = 1, (4)
16
17 where is the liquid activity coefficient, and is the liquid mole fraction for phases ′ and ′′,
18 respectively.
19 Numerous activity coefficient models have been presented in the literature based on different
20
theories and derivations of the excess Gibbs energy. Local-composition models like the NRTL
21
have proven superior to other models for characterizing the binary liquid-liquid equilibria with
22
sufficient accuracy for design purposes. In this work, we examine the efficacy of the NRTL
23
24 model and its modifications in determining the LLE phase conditions and attributes of binary
25 mixtures, including phase stability, miscibility, and consolute point coordinates.
26 2.1. Non-Random Two-Liquid (NRTL) model
27
28 Wilson’s local-composition concept [15] and Scott’s two-liquid solution theory formed some of
29 the basis for developing the NRTL model by Renon and Prausnitz [16]. Unlike the original
30 Wilson’s model, the NRTL is applicable to partially miscible as well as completely miscible
31 systems [17]. Further, the model resulted in higher precision in representing stability,
32 immiscibility, and consolute coordinates of LLE systems compared with other literature models
33 [6, 8, 9, 11, 18, 19].
34
35
The original NRTL excess Gibbs energy model for a binary system is as follows:

= + $
36
(5)
37 ! "! ! "!
where the model parameters % and & are defined as:
38
39
40 % = exp*−, & - & % = exp *−, & - (6)
41
42 and
/ 0 / 0
43 & = = & & = = (7)
44
45 where R is the universal gas constant, 2 is an energy parameter characterizing interactions
46 between molecules 1 and 2, and , is the non-randomness factor in the mixture. To be
47 consistent with the DECHEMA database [20], the non-randomness factor, , , was kept
48 constant as 0.2 for all binary systems in this work. Further, in our previous work [14], we found
variations in , to have a limited effect on VLE and LLE property predictions and in reducing
49
50
overall prediction errors [14]. Therefore, in this study the original NRTL model was limited to two
interaction parameters (3 and 3 ) to be regressed from mutual solubility data [1].
51
52
53 The interaction parameters of the original NRTL are highly correlated. In the following sections,
54 we present our recent modifications of the NRTL model [1]. The first model (mNRTL2) recasts
55 the original NRTL model parameters in a manner that decreases the correlation between the
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58
59 4
1
2
3 parameters and narrows the range of acceptable parameter values. In the second model
4 (mNRTL1), pure-component properties are used to generalize one of the parameters of the
5 proposed model for LLE systems; thus, we obtain a one-parameter model which eliminates the
6
parameter correlation problem.
7
8 2.2. Modified Non-Random Two-Liquid: mNRTL2 and mNRTL1
9
10
Typically, in applying the NRTL model, three parameters are determined through regression of
11 experimental data for a specific binary system. In a binary system, the NRTL model parameters
12 are designed to account simultaneously for pure-component liquid interactions, g11, and g22, and
13 mixed-component liquid interactions, g12 and g21.
14 As stated earlier, the main disadvantages of the NRTL model are the strong parameter
15 correlation between the two parameters a12 and a21 and wide range of acceptable values. To
16
reduce the parameter correlation and narrow down the range of acceptable values in the NRTL
17
model parameters, two modified NRTL models, mNRTL1 and mNRTL2, were developed in our
18
19
previous work [21, 22]. Equations 8 and 9 present the model parameters for the modified NRTL:
88
20 34 = 524 − 244 6 = 24 71 − : = 24 51 − ;4 6 = 24 <4 (8)
98
21
22

23 <4 = (9)
89
24
25
26 Where for mNRTL2, both gij and Rij are regressed, and for mNRTL1 only gij is regressed and Rij
27 is defined as:
28
> ?
29
<4 = = 8$ 7 @9 :A (10)
30 > ? 9 @8
31
32 Here, B is the acentric factor, C is the critical pressure and, i and j subscripts are molecules i
33 and j, respectively.
34
35 It was shown that the mNRTL2 model, is suitable for most VLE and LLE properties calculation.
36 The effectiveness of the model has been evaluated and compared by our research group with
37 the original NRTL model and resulted in comparable representations of phase equilibria
38
properties to literature models [22, 23]. Further, it was observed that the new proposed
parameters, 24 and <4 , are less correlated than the original NRTL parameters 3 and 3
39
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41 [21, 22]. The interaction ratio, <4 , in the proposed mNRTL2 model was generalized in terms of
42 pure-fluid properties, acentric factor and critical pressure, to develop the one-parameter NRTL
43 model (mNRTL1) [3]. Pertinent equations and derivatives of the original NRTL and modified
44 NRTL models are presented in the supplemental material (Appendices A and B).
45
3. Thermodynamic stability check
46
47 Stability analysis is applied to distinguish between unstable, metastable, and stable phases.
48 This problem was introduced theoretically more than 100 years ago. Then “Gibbs (1876)
49 showed that a necessary and sufficient condition for absolute stability of a mixture at a fixed
50 temperature, pressure, and overall composition is that the Gibbs energy surface be at no point
51 below the plane tangent to the surface at the given overall composition” [4].
52 For a binary system, a state of equilibrium is established by having a minimum Gibbs energy at
53
a given T, P, and an overall composition. This mathematically requires that:
54
55 *∆%E!F - ,? ≤ 0 (11)
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57
58
59 5
1
2
3 In contrast, the condition for instability for such a mixture is realized when:
4
I J9KL I
5 I!
$ < 0 O; $
I! ,?
+ < ! + /! $ < 0 (12)
6 ,M
7
A negative value of the above derivatives implies that the single phase state is unstable at the
corresponding overall composition, , and the introduction of an additional phase is required to
8
9
10 make the system stable or metastable. The locus of the limits of material stability extends to the
11 critical point of the two-phase region.
12 Following Prausnitz [17], the upper portion of Figure 1 presents a plot for gmixt as function of
13 mole fraction. Two types of phase behavior can be distinguished; the solid line curve illustrates
14 the lowest Gibbs energy and complete miscibility (a single phase) and the dashed line presents
15
the partial liquid miscibility. For the dashed curve, at the maximum point, a liquid mixture exists
16
with a higher Gibbs energy; thus, it has a high potential to separate into two different liquid
17
phases, as shown for T1. The formation of the second liquid phase, however, will occur only if
18
19 the Gibbs free energy curve of the mixture is partially concave with respect to composition [16,
20 17].
21 Here, the liquid mixture at T1 achieves a lower Gibbs energy and splits into two separate phases
22 as shown by points 1 and 4 of Figure 1. The corresponding binodal curve in the same figure
23 represents a boundary between the one-phase and two-phase regions. The distinguishing
24 feature of this state is that the equilibrium composition of each component in two phases can be
25
assessed. These two points are called double tangency or binodal points (′ , ′′). Also,
26
depicted in Figure 1 is point 6, which represents one of the local minima in the Gibbs function.
27
28 4. Consolute point coordinates (PQ , RQ )
29
30 The point between stability and instability of a liquid mixture is called incipient instability, which
31 occurs when the two points of the inflection on the spinodal curve of Figure 1 merge into a
32 single point called the consolute (critical) point [17]. As such, the incipient instability is
33 characterized by the two equations:
34 I J9KL
$ =0 (13)
35 I! ,?
36
37 and
38 IS J9KL
39 $ =0 (14)
I!S ,?
40
41 Therefore, we can calculate the incipient point of a mixture or consolute coordinates (C , C ) for a
42 given set of model parameters by solving these two equations simultaneously.
43
44 5. Miscibility coordinates
45 Two methods are used to characterize the state of equilibrium of coexisting phase in
46 multicomponent systems. The equal-fugacity approach and the global Gibbs free energy
47
minimization method aided by the double tangency technique are applied here. While the global
48
Gibbs free energy minimization method is more rigorous and provides the required
49
mathematical sufficiency; the relative simplicity of the equal-fugacity approach makes it
50
51
attractive to practitioners. In the next two sections, these two approaches are briefly presented,
52 as they apply to LLE calculations.
53 6. Equal-fugacity approach
54
55 The equal-fugacity approach asserts that a binary LLE system of known overall composition at a
56 fixed temperature and pressure meets the following criteria subject to mass balance constraints:
57
58
59 6
1
2
3 = (15)
4
5 = (16)
6
where and are the activity coefficients of component i in phases ′ and ″, respectively.
7
8 Given the experimental phase compositions, Equations 15 and 16 can be solved directly for the
9 two binary parameter values needed to fit the mutual solubility data. Specifically, by having gE
10 functions, like Equation 5, the miscibility coordinates can be determined by solving Equations 15
11 and 16 simultaneously. This approach provides a necessary, but not a sufficient condition for
12 the existence of a stable LLE system. Ascertaining that the Gibbs free energy is at a minimum is
13 required to confirm the validity of the miscibility limit ( , ) calculation. This requirement
14 becomes strict when the number of phases is unknown a priori.
15
16
17
18
19
20
21
22
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26
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57
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59 7
1
2
3
T2 2V W
1, 4: $ IJ9KL
4 X 0 and $ <0
T1 I! ,?
5 ,
6 T2 2V W
2: $ IJ9KL
7 = 0 and $ X0
T1 2 I! ,?
8 ,
T2 2V W
3: $
9 IJ9KL
10 = 0 and $ <0
T1 2 I! ,?
,
11
T2 2V W
5: $ IJ9KL
< 0 and $ =0
12
13 T1 I! ,?
,
14
T2 2V W
6: $ IJ9KL
15 X 0 and $ =0
T1 I! ,?
16 ,
17
18
19 5
20 0
T1
21
22 2
23
24
1
gmixt
25 Partial
3 Miscibility
26
27
28
29 4 6
30
31
32 Complete
T2
33 Miscibility
34
35
T2
36 Consolute
37 c
One Phase
T Point
38
39 Binodal
40 Curve
41
42
Temperature
43
44
45 Spinodal
T1 Curve
46
47
Unstable
48
Metastable Region
49
Region
50
51 Two Phases
52
53 0 R′Y Composition, x1 R′′Y 1
54
55
56 Figure 1: Molar Gibbs energy of mixing and T-x diagram of mixture at constant pressure
57
58
59 8
1
2
3 6.1. Global Gibbs minimization and tangent-plane technique
4
5 Although the equal-fugacity approach is the more common method of solution for phase
6 behavior property calculations, it does not guarantee the attainment of global Gibbs energy.
7 Minimization of the global Gibbs free energy can be equivalently codified as the stability test or
8 the tangent-plane technique. As stated earlier, Gibbs asserted that a necessary and sufficient
9 condition for the stability of a binary mixture at a fixed temperature, pressure, and overall
10 composition is having the Gibbs energy surface above the plane tangent to the surface at the
11 given overall composition [24]. Therefore, the concept of tangent-plane analysis can be applied
12 for determination of phase stability and miscibility limit [25]. In the last 20 years, many
13 algorithms have been developed to numerically implement this approach [7, 11, 12, 24, 26].
14
15 Herein, we illustrate the abilities of the original and modified NRTL models to characterize LLE
16
systems by graphical representation of the tangent-plane test. For calculating the double-
17
tangency points, the equations are defined as follows:
18
\ \\ \
J9KL / J9KL I J9KL
=
19
\ \\ (17)
20 ! /! I!\
21
and
22
\ \\ \\
J9KL / J9KL I J9KL
=
23
\ \\
! /! I!\\
(18)
24
25
26
27
28
29
30
31
32
33
34
35
36
2E!F /<
37
38
39
40
41
42
43
44
45
46
47
48
49 [
50 Figure 2: A typical Gibbs energy plot that shows four double tangents
51
52 Equations 17 and 18 show the equality of the slope at the miscibility limits. Therefore, by solving
53 these equations simultaneously, the double-tangency points are obtained. Using this method by
54 itself, however, entails the risk of identifying local minima instead of the global minimum, since
55 the solution is sensitive to the initial estimates of mole fractions in each phase [26]. Figure 2
56 shows four possibilities of double tangents for a typical 2E!F ⁄< - composition plot for a binary
57
58
59 9
1
2
3 system. Only the solid line represents the tangent-plane for a stable equilibrium for the feed
4 composition specified (z1 = 0.7).
5
6
7
7. Flowchart for LLE characterization
8 Figure 3 presents a flowchart that summarizes the mathematical requirements for LLE
9 characterization. The steps outlined are used to investigate the efficacy of two modified NRTL
10 models in comparison to the original NRTL model. For all three models, the flowchart starts with
11 the model selection and related parameters, which are obtained using the equal-fugacity
12 approach as implemented by the in-house software, Generalized Equation of State (GEOS)
13
[27], based on available experimental data.
14
15 In the following case studies, the stability of the mixture is assessed to meet the sufficiency
16 condition. As stated earlier, the 2nd derivative of gmixt is a reliable tool for the stability check. A
17 negative value represents instability and a positive value indicates stability. Further, the roots of
18 the 1st derivative of gmixt, Equation (A-4) for original NRTL and Equation (B-4) for mNRTL1 and
19 mNRTL2, can be used to find the miscibility limits. This information are presented in
20 supplementary appendices. For the instability path, by equating the 1st derivative of gmixt to zero,
21
if more than one root exists, the system has partial miscibility or liquid-liquid equilibrium exists.
22
In this case, we are dealing with two local minima and one maximum. As such, the miscibility
23
24
coordinates can be calculated. For the stability path, by equating the 1st derivative of gmixt to
25 zero, we can identify the condition of complete miscibility. In addition, the consolute coordinates
26 can by calculated by equating the 2nd and 3rd derivatives of gmixt to zero and solving the
27 corresponding equations, simultaneously. All the required equations for these analyses, for both
28 the original and modified NRTL models, are presented in the supplemental material,
29 Appendices A and B, respectively.
30
8. Results and discussion
31
32 In this study, the applicability of recent modifications to the NRTL model for characterization of
33 liquid-liquid phase equilibria was tested on a wide range of molecules. A LLE equilibrium data
34 set consisting of 20 binary LLE systems with more than 150 data points was assembled from
35 DECHEMA [20]. Herein, a case study is presented in details to highlight the characterization
36 methodology presented above. Further detailed case studies are provided in the supplemental
37 material, Appendices C and D. In addition, consolute coordinate values are presented in
38 Appendix 1 for 20 LLE systems using the original and modified NRTL models.
39
40 8.1. Case study I: nitromethane + cyclohexane
41
In this case, we investigate the LLE behavior characterization of the nitromethane +
42
cyclohexane system at 313.15 K and feed composition of x1= 0.5051. The experimental data for
43
44 this system are presented in Table 1. The characterization for the system is investigated for a
45 specific isotherm, 313.15 K. For other isotherms, a similar procedure is applied. The optimized
46 parameters for the original NRTL model, (3 , 3 ), mNRTL2, (2 , < ), and mNRTL1, (< ), are
47 also presented in Table 1. The in-house software GEOS [27] was used in the regression and
48 pre-evaluation of the model parameters.
49
50
51
52
53
54
55
56
57
58
59 10
1
2
3
4
5
Start
6
7
8
9 Modified
Original Model
(mNRTL2-
10 (NRTL) selection
mNRTL1)
11
12
13
14
15 a12, a21, T, P, , α g12, T, P, R12, , α
16
17
18
19
20
0< T 2E!F <0
21 ^ _
Stability Instability
22 T ,?
23
24
25
T2E!F =0 T2E!F
26 7 : =0 7 : =0
T ,? T ,?
27
T ` 2E!F
28 ^ _ = 0
T ` ,?
29 More than 1 root
1 Root
30
31
32 Complete Some partial
33 miscibility Find the consolute miscibility
34 coordinates
35
36 Check for at least
37 2 local minima &
38 one maximum
39
40
41 Find LLE miscibility
42 coordinates
43
44
45
46
Figure 3: Flowchart for LLE mixture characterization based on the original NRTL and modified
47
NRTL models
48
49
50
51
52
53
54
55
56
57
58
59 11
1
2
3 Table 1: Nitromethane + cyclohexane LLE data and model parameters for the original NRTL,
4 mNRTL2, and mNRTL1 models
5
6 T= 313.15 K, P= 10.01 bar
7
8 RY =0.0581 , R
Y =0.9448
9
10 NRTL mNRTL2 mNRTL1
11
12 aYb abY cYb dYb cYb
13
14 1216.27 1168.84 1192.32 1.02 1203.54
15
16 8.1.1. Stability analysis
17 Table 2 shows the calculation for the 2nd derivative of gmixt for a feed composition (x1= 0.5051)
18 involving the experimental data described above. The derivative sign obtained from the original
19 NRTL and modified models are identical, which indicates the accuracy of the modified models in
20
reproducing the findings of the original NRTL.
21
22
Table 2: Stability check based on experimental for nitromethane + cyclohexane
23
LLE data for all models for feed composition of x1= 0.5051
24
25
Derivative NRTL mNRTL2 mNRTL1
26
27
5eb cfgRh ⁄eR Y 6PijYj.Yl,miYn.nY
b
28 + + +
29
30
5eb cfgRh ⁄eRbY 6PijYj.Yl,miYn.nY - - -
31
32
5eb cfgRh ⁄eR Y 6PijYj.Yl,miYn.nY
33 b
+ + +
34
35
36
37 Following the flowchart (Figure 3), the next step is to determine the miscibility for the system. By
38 solving the 1st derivative equation (supplementary material: Equation (A-4) for original NRTL
39
and Equation (B-4) for mNRTL1 and mNRTL2) for gmixt, the number of related roots as well as a
40
graphical trend can be identified. The sign of the 2nd derivative (supplementary material:
41
42 Equation (A-7) for original NRTL and Equation (B-7) for mNRTL1 and mNRTL2) for 1st
43 derivative roots facilitates discovery of the number of phases. The sign sequence for the 2nd
44 derivative: 1st positive, 2nd negative (feed composition of x1= 0.5051), and 3rd positive indicates a
45 two-phase, liquid-liquid mixture. The modified NRTL models provide comparable results to the
46 original NRTL; albeit, minor differences in the liquid compositions are observed for the mNRTL1
47 model.
48 Table 3: Nitromethane + cyclohexane 1st derivative roots for locating coexisting liquid
49
phases from different models
50
*ecfgRh ⁄eR-PijYj.Yl,miYn.nY = n
51
52
53
NRTL mNRTL2 mNRTL1
54
55 nd nd nd
Root 2 Max/Min Root 2 Max/Min Root 2 Max/Min
56
57
58
59 12
1
2
3 Derivative Derivative Derivative
4 Sign Sign Sign
5
6 0.0579 + Min 0.0579 + Min 0.0577 + Min
7
8 0.5051 - Max 0.5051 - Max 0.5119 - Max
9
10 0.9446 + Min 0.9446 + Min 0.9481 + Min
11
12
13 Figure 4 presents a graphical construction of 2E!F /< as a function of composition for the
14 original NRTL and modified models. In general, the trends determined for this system using the
15 modified models are comparable to those obtained from the original NRTL. Again, the mNRTL1
16 model deviated slightly from the original NRTL at the mole fraction of the two minima. Those
17 minor differences aside, the graph illustrates the efficacy of the two modified NRTL models in
18 determining the double-tangency points.
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43 Figure 4: 2E!F /< as a function of composition for the original NRTL, mNRTL2,
44 and mNRTL1 models at 313.15 K
45
46 8.1.2. Miscibility, double-tangency points
47
48 In the previous section, the number of coexisting liquids was determined. Next, the double-
49 tangency calculation is used to determine the distribution of component in each phase. Table 4
50 presents the calculation results for locating the double-tangency points based on all models.
51 The percentage absolute deviation (%AD) errors are reported for each model for and . In
52 general, these results show the capability of the new NRTL modifications in characterizing the
53 LLE systems compared to the original NRTL model. In detail, the NRTL2 model produces
54 accurate predictions in comparison to the original NRTL model results. However, the NRTL1
55 model is less accurate, which may indicate the need for the flexibility provided by two-parameter
56 modeling.
57
58
59 13
1
2
3 Table 4: LLE compositions obtained from the NRTL, mNRTL2, and mNRTL1 models
4 using the tangent-plane technique at T=313.15 K
5
6 NRTL at aYb =1216.27, abY =1168.84
7
8
pRq pRq
9 RQao
Y RY %AD RQao
Y RY %AD
10
11
0.0581 0.0581 0.00 0.9448 0.9448 0.00
12
13
14 mNRTL2 at dYb =1.02, cYb =1192.32
15
16 0.0581 0.0581 0.00 0.9448 0.9448 0.00
17
18 mNRTL1 at cYb =1203.54
19
20 0.0806 0.0581 2.25 0.8594 0.9448 8.54
21
22
23 8.1.3. Consolute point coordinates
24 As stated earlier, the critical temperature solution or consolute temperature occurs at a point on
25 the border line between the one-phase and two-phase regions. This temperature and
26 corresponding mole fraction can be calculated by solving Equations 13 and 14 simultaneously
27
for given model parameters. Table 5 presents the consolute coordinates values for the model
28
parameters listed. The results demonstrate the relative accuracy of the modified models’
29
predictions compared to the original NRTL model. Here again, NTRL2 produces more accurate
30
31
predictions than NTRL1; albeit, the predictions form the latter are quite reasonable.
32 Additional consolute coordinate results for 15 LLE systems are presented in Table 1-1 of
33 Appendix 1.
34
35 Table 5: Consolute coordinates using the original NRTL, mNRTL2, and mNRTL1 models
36
37 NRTL mNRTL2 mNRTL1
38
aYb =1216.27, abY =1168.84 dYb =1.02, cYb =1192.30 cYb =1203.54
39
40
41
42 PQ (K) RQ PQ (K) RQ PQ (K) RQ
43
44 524.9 0.5034 524.9 0.5034 530.2 0.5079
45
46
47 Table 6 shows the effect of parameter variation due to temperature on the calculated consolute
48 coordinates. The parameter sets for each model at different temperatures are presented. Both
49 modified models reproduce reasonably the original NRTL model results on Tc and xc. The
50 mNRTL1 model shows less than 2 %AD difference in temperature and mole fraction, compared
51 to the original NRTL model. Also, the changes on mole fraction versus temperature for mNRTL1
52 are negligible. Understandably, the mNRTL2 model provides closer predictions to the original
53 NRTL model than those of the mNRTL1 because of the added flexibility of two model
54 parameters. In fact, the effect of parameter variations due to difference in temperature for
55
56
57
58
59 14
1
2
3 mNRTL2 is more significant than that resulting from model choice. In contrast, mNRTL1
4 produces the same value of xc for all temperatures since only one parameter is employed.
5
6 Table 6: Effect of model parameter variation due to temperature on consolute coordinates using
7
the original NRTL, mNRTL2, and mNRTL1 models: nitromethane + cyclohexane system
8
9
NRTL mNRTL2 mNRTL1
10
11 PQ PQ PQ
12 T aYb abY RQ cYb dYb RQ cYb RQ
(K) (K) (K)
13
14 284.15 1305.88 1402.02 595.9 0.4940 1353.04 0.97 595.9 0.4939 1410.30 621.3 0.5079
15
16 288.15 1316.02 1354.14 587.6 0.4976 1334.92 0.99 587.6 0.4976 1374.50 605.5 0.5079
17
18 293.15 1289.45 1321.37 574.6 0.4979 1305.32 0.99 574.6 0.4979 1340.73 590.7 0.5079
19
20 298.15 1265.67 1285.60 561.5 0.4987 1271.47 0.99 559.7 0.4984 1295.80 570.9 0.5079
21
22 303.15 1243.58 1248.00 548.3 0.4997 1245.83 1.00 548.4 0.5000 1245.90 548.9 0.5079
23
24 313.15 1216.27 1168.84 524.9 0.5034 1192.30 1.02 524.9 0.5034 1203.54 530.2 0.5079
25
26
27 Figure 5 presents a graphical construction of 2E!F /< as a function of composition for the
28 original NRTL and modified models at different isotherms. In general, the observed trend using
29 the modified models is consistent with the original NRTL model at different isotherms.
30
31
32
33
34
35 NRTL
36
37
mNRTL2
38 mNRTL1
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59 15
1
2
3 Figure 5: Effect of composition and temperature on 2E!F /< for the
4 original NRTL, mNRTL2, and mNRTL1 models
5
6 9. Conclusions
7
In this work, the efficacy of two recent modifications of the NRTL model is evaluated in
8
9 characterizing selected liquid-liquid equilibrium systems. All models were tested successfully
10 using a dataset comprised of 15 LLE systems and more than 150 data points. Based on the
11 systems considered, the results indicate that the modified NRTL models (mNRTL2 and
12 mNRTL1) provided comparable LLE characterizations in comparison to the original NRTL
13
model. Specifically, analyses for phase stability, miscibility, and consulate point coordinates, in
14
15 general, gave comparable results for all three models; albeit, the results from the mNRTL2
16 model are more precise than those of the mNRTL1 model. Nevertheless, the simplicity of the
17 modified NRTL models and their accuracy in handling multiphase behavior is indicative of their
18 merit.
19
20
Acknowledgment
21
22 This material is based on work partially supported by the U.S. Department of Energy,
23 DOE/EPSCOR (Grant DE-SC0004600).
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59 16
1
2
3 References
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6 1. Gebreyohannes, S., B.J. Neely, and K.A.M. Gasem, One-Parameter Modified Nonrandom
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9 2. Gebreyohannes, S., B.J. Neely, and K.A.M. Gasem, Generalized Nonrandom Two-Liquid
10 (NRTL) Interaction Model Parameters for Predicting Liquid-Liquid Equilibrium Behavior.
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Industrial & Engineering Chemistry Research, 2014. 53(31): p. 12445-12454.
13 3. Quifiones-Cisneros, S.E., Phase and Critical Behavior in Type III Phase Diagrams. Fluid
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Phase Equilibria, 1997. 134: p. 103-112.
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16 4. Wasylkiewicz, S.K., L.N. Sridhar, M.F. Doherty, and M.F. Malone, Global Stability Analysis
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and Calculation of Liquid-Liquid Equilibrium in Multicomponent Mixtures. Industrial &
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19 Engineering Chemistry Research, 1996. 35: p. 1395-1408.
20 5. Fotouh, K. and K. Shukla, An Improved Perturbation Theory and van der Waals One-Fluid
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Theory of Binary Fluid Mixtures Part 2. Phase Equilibria. Fluid Phase Equilibria, 1997. 137: p. 1-
23 16.
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6. Domańska, U., P. Morawski, and R. Wierzbicki, Phase Diagrams of Binary Systems
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26 Containing N-Alkanes, or Cyclohexane, or 1-Alkanols and 2,3-Pentanedione at Atmospheric
27 and High Pressure. Fluid Phase Equilibria, 2006. 242(2): p. 154-163.
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29 7. Giovanoglou, A., Adjiman, C. S., Jackson, G., and Galindo, A., Fluid Phase Stability and
30 Equilibrium Calculations in Binary Mixtures: Part II: Application to Single-Point Calculations and
31 the Construction of Phase Diagrams. Fluid Phase Equilibria, 2009. 275(2): p. 95-104.
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33 8. Królikowska, M. and M. Karpińska, Phase Equilibria Study of the (N-Octylisoquinolinium
34 Thiocyanate Ionic Liquid+Aliphatic and Aromatic Hydrocarbon, or Thiophene) Binary Systems.
35 The Journal of Chemical Thermodynamics, 2013. 63: p. 128-134.
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37 9. Królikowska, M., M. Karpińska, and M. Zawadzki, Phase Equilibria Study of (Ionic
38 Liquid+Water) Binary Mixtures. Fluid Phase Equilibria, 2013. 354(0): p. 66-74.
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40 10. Boshkov, L.Z. and L.V. Yelash, Closed-Loops of Liquid-Liquid Immiscibility in Binary
41 Mixtures Predicted from the Redlich-Kwong Equation-of-State. Fluid Phase Equilibria, 1997.
42 141: p. 105-112.
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44 11. Yushan, Z.H.U. and X.U. Zhihong, A Reliable Method for Liquid-Liquid Phase Equilibrium
45 Calculation and Global Stability Analysis. Chemical Engineering Communications, 1999. 176(1):
46 p. 133-160.
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48 12. Sofyan, Y., A.J. Ghajar, and K.A.M. Gasem, A Systematic Method to Predict Cloud Point
49 Temperature and Solid Precipitation. Petroleum Science and Technology, 2003. 21(3-4): p. 409-
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52 13. Sorensen, J.M., T. Magnussen, P. Rasmussen, and A. Fredenslund, Liquid-Liquid
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55 Prediction. Fluid Phase Equilibria, 1979. 2: p. 297-309.
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3 14. Gebreyohannes, S., K. Yerramsetty, B.J. Neely, and K.A.M. Gasem, Improved QSPR
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Generalized Interaction Parameters for the Nonrandom Two-Liquid Activity Coefficient Model
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6 (Vol 339, p. 20, 2013). Fluid Phase Equilibria, 2013. 353: p. 135-135.
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9 Butterworth.
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Fluid-Phase Equilibria. Third Ed. 1999: Prentice Hall International Series.
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19 Hydrocarbons, or an Alcohol} Binary Systems. The Journal of Chemical Thermodynamics,
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19. Domańska, U., M. Zawadzki, and M. Zwolińska, Thermophysical Properties and Phase
23 Equilibria Study of the Binary Systems {N-Hexylquinolinium Bis (Trifluoromethylsulfonyl)
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27 20. Arlt, W., M.E.A. Macedo, P. Rasmussen, and J.M. Sorensen, Liquid-Liquid Equilibrium Data
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30 21. Dadmohammadi, Y., S. Gebreyohannes, A.M. Abudour, B.J. Neely, and K.A.M. Gasem,
31 Representation and Prediction of Vapor-Liquid Equilibrium using the Peng-Robinson Equation
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35 22. Gebreyohannes, S., Y. Dadmohammadi, B.J. Neely, and K.A.M. Gasem, A Comparative
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38 Mixtures. Industrial & Engineering Chemistry Research, 2016. 55(4): p. 1102-1116.
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Phase Behavior Predictions Using QSPR-Generalized NRTL and UNIQUAC Models. Fluid
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42 Phase Equilibria, 2016. 409: p. 318-326.
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24. Simoni, L.D., Y. Lin, J.F. Brennecke, and M.A. Stadtherr, Reliable Computation of Binary
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45 Parameters in Activity Coefficient Models for Liquid-Liquid Equilibrium. Fluid Phase Equilibria,
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58
59 18
Appendix 1: Case study 4: consolute coordinates calculation for 15 LLE systems

1
2
3 In this section, we present the consolute coordinates calculations for 15 LLE systems. Table 1-1 shows the results for all three models. In general,
4
5 the modified mNRTL2 model exhibit in average 0.9 and 0.3 percent absolute deviation (%AD) error for xc and Tc, respectively, compared to the
6
7 original NRTL model. The %AD error for xc and Tc, is 9 and 6, respectively, for the modified mNRTL1.
8
9
10 Table 1-1: Consolute coordinates using the original NRTL, mNRTL2, and mNRTL1 models based 15 LLE systems
11
NRTL mNRTL2 mNRTL1
12
R -
Q PQ - RQ - PQ -
No System
13 dYb rao.
aYb abY RQ PQ (K) cYb dYb RQ PQ (K) cYb RQ PQ (K)
14 %AD %AD %AD %AD
15
1 DEE+H2O 904.9 1988.2 0.4361 631 1341.3 0.67 0.4351 0.2 632 0.2 508.8 0.20 0.3409 21.8 550 12.8
16
17
18 2 MEO+NC7 1048.2 761.1 0.5270 398 893.1 1.17 0.5265 0.1 397 0.1 903.3 1.83 0.5923 12.4 464 16.6
19
20
3 ACTN+H2O 589.5 1785.7 0.4140 514 1026.0 0.57 0.4129 0.3 516 0.4 490.5 0.23 0.3451 16.6 468 8.9
21
22
NITROMET
23 4 +CYC6
1262.1 1320.5 0.4962 568 1291.0 0.98 0.4966 0.1 568 0.0 1331.9 1.05 0.5083 2.4 587 3.2
24
25 5 NITROBEN
414.4 1030.0 0.4273 314 653.3 0.63 0.4263 0.2 315 0.3 755.6 0.98 0.4966 16.2 333 5.9
26 +NC6
27
28 6 MEO+CYC6 600.7 1153.0 0.4463 384 832.2 0.72 0.4459 0.1 384 0.1 842.8 0.74 0.4502 0.9 386 0.6
29
30 7 MEO+NC6 814.9 790.1 0.5026 353 802.4 1.02 0.5034 0.2 353 0.0 824.7 1.43 0.5585 11.1 384 8.6
31
32 NITROMET
33 8 +CS2
646.9 1375.3 0.4386 441 943.2 0.69 0.4395 0.2 440 0.2 503.4 0.29 0.3547 19.1 395 10.5
34
35 9 2BUTANON
4.9 1875.2 0.3282 387 91.0 0.05 0.3281 0.0 387 0.0 361.6 0.20 0.3409 3.9 391 1.0
+H2O
36
37 NITROMET
10 1071.1 370.8 0.5830 313 630.2 1.70 0.5830 0.0 313 0.0 506.6 2.73 0.6311 8.3 332 6.3
38 +1BUT
39
40 11 1BUT+H2O 33.1 2450.5 0.3320 513 353.0 0.15 0.3349 0.9 505 1.6 284.0 0.12 0.3323 0.1 496 3.3
41
42
43
44 19
46
47
1 12 MEO+CS2 49.1 1817.5 0.3366 387 8587.3 4.58 0.3273 2.8 385 0.4 361.7 0.20 0.3409 1.3 391 1.1
2
3 13
CYCHEXAN
-21.5 2457.7 0.3242 500 397.7 0.17 0.3372 4.0 499 0.2 478.0 0.20 0.3409 5.2 517 3.3
4 +H2O
5 3PENTANO
6 14
+H2O
645.3 2334.9 0.4030 642 1227.2 0.53 0.4040 0.2 640 0.4 462.4 0.17 0.3372 16.3 580 9.6
7
8 15 FURF+H2O 50.8 2459.0 0.3345 519 569.7 0.24 0.3465 3.6 524 0.9 571.2 0.24 0.3465 3.6 525 1.2
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44 20
46
47
1
2 LLE Characterization
3
4
5
6 Model Modified (mNRTL2-
Original (NRTL)
7 selection mNRTL1)
8
9
10
11
12 a12, a21, T, P, 𝑥1 , α g12, T, P, R12, 𝑥1 , α
13
14
15
16
17 0< 𝜕 2 𝑔𝑚𝑖𝑥𝑡 <0
18 Stability 𝜕𝑥1 2 Instability
19 𝑇,𝑃
20
21
22 𝜕𝑔𝑚𝑖𝑥𝑡 =0
𝜕𝑔𝑚𝑖𝑥𝑡
23 =0 =0
𝜕𝑥1 𝜕𝑥1
24 𝑇,𝑃 𝑇,𝑃
25
𝜕 3 𝑔𝑚𝑖𝑥𝑡
26 𝜕𝑥1 3 𝑇,𝑃 =0
27 1 Root
More than 1 root
28
29 Find the consolute
30 Complete miscibility Some partial miscibility
coordinates
31
32
33 Check for at least 2 local
34 minima & one maximum
35
36
37
Find LLE miscibility
38
39 ACS Paragon Plus Environment coordinates
40
41

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Appendix 1: Case study 4: consolute coordinates calculation for 15 LLE systems

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