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327335
a, )
, D.M.T. Newsham
Abstract
In this work molecular solvent design for liquidliquid extraction using a chemical graphics system is
presented. Solvent structures are generated according to specified combinatorial rules and the screening of the
solvent is performed using the UNIQUAC model where the required molecular interaction parameters are
directly obtained from a molecular graphics system. The method is tested with two different industrial examples:
toluenern-heptane and phenolrwater system. q 1999 Elsevier Science B.V. All rights reserved.
Keywords: Molecular graphics; Extraction; Solvent design; Activity coefficients
1. Introduction
The great majority of the molecular solvent design methods for liquidliquid extraction processes
described in the literature, are carried out in the following three main steps: a. selection of a number
of groups, according to the nature of the compounds to be separated; b. assembling these groups
according to well-established rules which would prevent any unusual combination to occur, avoiding
violation of the rules of chemistry and ensuring the intramolecular stability of the resulting compound;
c. assessment of the resulting compounds, using thermodynamic and group contribution models,
according to specified criteria like selectivity, capacity, solvent loss, etc. For this step, as an
approximation, these properties can be related to activity coefficients at infinite dilution of the
different compounds present in the extract and raffinate phases and. The UNIFAC model is the most
widely used predictive group contribution method.
0378-3812r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 9 9 . 0 0 0 7 9 - 5
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A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335
Generally these group contribution methods present certain advantages like simplicity, low cost in
terms of computer time, etc., but they are limited for two main reasons:
a. They are just an approximation because the contribution of a given group for a particular
property is not necessarily the same in two different molecules. Additivity is also the fundamental
assumption of this theory which considers the contribution made by one group as independent of that
made by another one, ignoring how and where the groups are connected to each other. As an
illustrative example, it is clear that with different combinations of a same set of groups, the resulting
molecular structures would have completely different values and orientations of the dipolar moment,
which is, in most but not all the cases, an important parameter for quantitative andror qualitative
interpretations of many physical properties such as solubility, and therefore, misleading conclusions
may be drawn since a group contribution method would predict a same and unique value for all the
resulting isomers.
b. The second problem is the lack of the necessary group interaction parameters for the property
calculations. For instance, for the UNIFAC model, interaction parameters between certain groups may
not be available, a fact which restricts the number of the groups that can be chosen. As an example,
for the design of solvents for the separation of aromatic and nonaromatic hydrocarbons, the sulphone
SO 2 ., sulphoxide SO. and sultone SO 3 . groups cannot be considered because they are not included
in any existing UNIFAC interaction parameters table although it is known that the organo-sulphur
solvents are among the most selective solvents for this type of separation, as reported by Rawat and
Gulati w1x. Therefore, this is a serious limitation.
Also for the separation of acetic acidwater mixtures considered by Gani et al. w2x, 29 out of 238
solvent candidates had to be discarded because of a nonavailability of certain interaction parameters.
Thus, potentially good solvents may be missed.
To overcome this problem, a molecular solvent design method is presented in this work. It still uses
certain molecular design strategies already elaborated by former workers such as Gani and Brignole
w3x and Brignole et al. w4x, but with the particularity of introducing a molecular graphics system
MGS. as a means of overcoming some of the limitations of group contribution models. The MGS is
operating with a package known as CHEM-X developed and distributed by Chemical Design,
Oxford, England. which is capable of simulating molecular structures, molecular interactions and
hence interaction parameters as reported in a previous work of Meniai and Newsham w5x.
1.
where m and n denote molecules or groups, amn is the corresponding interaction parameter in units of
Kelvin, Umn is the interaction energy between molecules or groups and R is the universal gas
constant.
The calculation of the interaction energy has been thoroughly discussed by Meniai and Newsham
in Ref. w5x. It consists of positioning the two molecules or groups by constructing a simple cube
whose dimensions are calculated according to the experimental density of the system as has been
A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335
329
Fig. 1. Simulation box for the phenolrwater system a. before minimisation, b. after minimisation.
done for the simulation of dilute solutions by Meniai and Newsham w7x., one at the centre of the cube
and the other at one of its corners as shown, as an example, in Fig. 1 for the case of the phenolrwater
system.
One molecule or group is kept fixed i.e., having no translational or rotational degrees of freedom.
while the other one is shifted and rotated, until the minimum energy configuration is reached which
corresponds to the most favourable orientation of the two molecules or groups when they are facing
one another. Since only relative motion is important, the fact of moving just one molecule and
keeping the other fixed does not limit the validity of the calculated thermodynamic properties as
stated by Owicki and Scheraga w8x. The determination of the necessary interaction parameters is
straightforward from Eq. 1.. The energy calculation and its minimisation with respect to various
variables like translations or intermolecular orientations and positions, are performed directly by
CHEM-X which incorporates appropriate potential energy functions as already described by Meniai
and Newsham w7x.
330
A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335
Fig. 2. Building of a molecular structure from three groups. FA: free attachment.
the required solvent properties. Alternatively, it is proposed to calculate group interaction parameters
by using the MGS, whenever their values are not available from the current UNIFAC table of
Magnussen et al. w6x. The method is best described by the flow diagram shown in Fig. 3.
4. The solvent properties
The selectivity at infinite dilution of a solvent to extract i from an i and j mixture, is generally
calculated as follows:
`
rg i`,s
Sij` s g j,s
2.
`
`
where g i,s
and g j,s
are the activity coefficients at infinite dilution of components i and j, respectively,
in the solvent-rich phase.
Usually the distribution coefficient of the solute between the extract and raffinate phases is a
measure of the solvent capacity as reported by Mukhopadhyay w10x and an estimate of the maximum
value of this property is also calculated at infinite dilution according to the following:
K `ij f 1rg i`,s
3.
`
with g i,s
as defined above.
It should be noted that the solvent capacity has an even greater influence than selectivity when
selecting an optimum extraction process because it determines the flow rate of the circulating solvent
and consequently the design of the extractor. However in most cases Eq. 1. is only a rough estimate
of capacity and the distribution or partition coefficient should be calculated as follows:
m s g i`,rrg i`,s
4.
`
`
with g i,r
and g i,s
the activity coefficients at infinite dilution of components j and i in the raffinate and
extract phases, respectively.
Another important solvent property usually considered in the selection of solvents for separation
processes is the solvent loss or the solvent solubility in the raffinate phase and which can be estimated
from the following expression:
Sl s 1rgs`,r
5.
where gs,r` is the activity coefficient at infinite dilution of the solvent in the raffinate phase.
A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335
331
Clearly, for a liquidliquid extraction, it is desired to have a solvent with a high selectivity and
capacity and a low solvent loss.
332
A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335
Table 1
A sample set of optimal solvents for the toluener n-heptane separation
Constituting groups of the
solvent candidate
aST r K
aTS r K
aHS r K
aSH r K
Sij`
K `ij
Solvent
loss %.
1. CH 2 COO. CH 3 . CH 3 O.
2. SO 3 . CH 3 . CH 3 .
3. SO. CH 3 . CH 2 CN.
4. CH 2 COO. CH 3 O. CH 2 CN.
5. CHNO 2 . CH 3 . CH 3 .
6. CH 2 O. CH 3 . CH 2 CN.
1800.00
y305.00
y3.50
370.00
625.00
y55.00
y373.50
386.50
506.50
y123.50
y423.50
136.50
y455.00
y480.00
y160.00
y400.00
y210.00
y365.00
889.00
854.00
129.00
949.00
279.00
804.00
58.50
41.66
36.16
34.68
32.71
28.84
1.55
1.19
1.20
0.79
2.17
0.87
2.32
5.54
6.01
1.53
5.46
2.62
6.191
5.965
1.812
3.921
1.370
2.361
A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335
333
Table 2
A sample set of optimal solvents for the waterrphenol separation
Constituting groups of the
solvent candidate
a PS r K
aSP r K
a WS r K
aSW r K
Sij`
K `ij
Solvent
loss %.
1. CH 2 COO. CH 3 . CHO.
2. CH 2 . OH. CHCl 2 .
3. CHCl. CH 3 . OH.
4. CH 2 COO. CH 3 . CH 3 .
5. CH 2 . HCOO. CH 2 CN.
CH 2 CO. CH 3 O. CH 2 CN.
y575.00
y510.00
y575.00
y475.00
y510.00
y563.00
1150.00
740.00
1260.00
580.00
855.00
1030.00
305.00
490.00
280.00
705.00
355.00
15.00
255.00
y35.00
340.00
y15.00
55.00
y165.00
477.96
333.91
263.45
227.78
108.67
105.56
194.25
288.98
79.39
155.16
76.31
277.98
555.57
679.03
177.96
640.42
273.60
889.17
0.213
0.244
0.422
0.028
0.431
2.769
From this table it can be seen that each group combination from 4 through 7 can lead to two
compounds isomers. depending on whether the two methyl groups present are positioned as adjacent
or separated by a different group such as CH 2 NO 2 , CH 2 CN, etc. and this without violating the rules
described by Gani et al. w2x. Therefore, this offers an opportunity to explore the differences in solvent
properties of the two isomers by the simulation and optimisation of their molecular structures with all
Table 3
Use of calculated group interactions parameters for solvent properties calculation for the acetic acidrwater separation
Constituting groups of the
Solvent candidate
1. C. CH3. 3CH 2 NH 2 .
2. C. CH3. 3CH 3 NH.
3. C. CH3. 3CH 2 CN.
4. C. CH3. 2 CH 2 NH 2 .
CH 2 NO 2 .
5. C. CH3. 2 CH 2 NH 2 .
CH 2 CN.
6. C. CH3. 2 CH 2 CN.
CH 2 NO 2 .
7. C. CH3. 2 CH 3 O.
CH 2 CN.
aCOOH CH2NH2
aCH2NH2 COOH
aCOOH CH3NH
aCH3NH COOH
aCOOH CH2CN
aCH2CN COOH
aCOOH CH2NH2
aCH2NH2 COOH
aCH2NH2 CH2NO2
aCH2NO2 CH2NH2
aCOOH CH2NH2
aCH2NH2 COOH
aCH2NH2 CH2CN
aCH2CN CH2NH2
aCOOH CH2CN
aCH2CN COOH
aCOOH CH2CN
aCH2CN COOH
aCH2CN CH2NO2
aCH2NO2 CH2CN
aCOOH CH2CN
aCH2CN COOH
aCH3O CH2CN
aCH2CN CH3O
Calculated
value from
MGSrK
Sij`
K `ij
y85.00
y581.55
y202.25
y711.80
y315.50
y848.55
y85.00
y581.55
y326.75
97.75
y85.00
y581.55
y59.50
y96.00
y315.50
y848.55
y315.50
y848.55
y614.50
246.50
y315.50
y848.55
y265.75
414.25
415.51
6.85
17.63
0.046
1.37
0.38
0.97
0.004
160.43
47.62
122.57
0.005
31.09
3.82
9.82
0.001
525.44
62.50
160.88
0.092
94.40
20.00
51.48
0.001
131.37
28.57
73.54
0.179
Solvent
loss %.
A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335
334
Table 4
Use of calculated molecular interaction parameters for comparison of isomer properties for the acetic acidrwater separation
aSAc r K
a ws r K
asw r K
Sij`
K `ij
aAcS r K
Solvent
loss %.
y340.00
95.00
410.00 y750.00 55.26 34.84 65.50 0.001
y220.00 y105.00 y505.00 1055.00 107.44 17.64 33.16 1.264
y495.00
655.00
360.00 y265.00
2.92 3.51 6.60 0.020
y380.00
350.00
825.00 y220.00
1.53 1.07 2.01 0.231
y540.00 1055.00
95.00
275.00 14.80 2.32 4.36 0.026
y470.00
755.00
505.00 y45.00
4.80 1.51 2.84 0.590
y540.00 1020.00
200.00 y15.00
3.43 1.85 3.48 0.010
y520.00 1115.00
555.00
415.00
9.94 0.46 0.86 0.001
the groups properly interconnected and the calculation of the necessary molecular interactions and
hence the required molecular interaction parameters. Table 4 presents the results for isomers only
where different values have been obtained for each component pair, showing again the need for a
method which relies not only on the type of the groups involved in the system but more on the way
they are interconnected.
6. Conclusion
The obvious solution to the fact that any group contribution method does not distinguish between
the many isomers that may be generated from different combinations of a same set of groups, would
be to consider the molecule as it is structured as a whole. However the original the idea behind a
group contribution method is that with a limited number of groups, a huge number of different
molecules of various compounds can be handled. But with the advent of powerful computing systems
like CHEM-X, which are able to simulate molecular structures as well as interaction energies, an
answer to this problem can be found if reliable molecular interaction parameters can be readily
determined for property calculations, whenever they are required.
From another point of view, the approach proposed in this work can be seen as an attempt to
establish a link between chemical graphics systems and molecular design of solvents. This may be
considered as an important step forward, in the computer-aided molecular-design strategies, which are
based on group contribution methods.
7. List of symbols
a ij
K ij
m
R
A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335
Sij
Sl
Greek letters
gi, gj
Subscripts
i,j
m
r
s
Superscripts
`
infinite dilution
References
w1x
w2x
w3x
w4x
w5x
w6x
w7x
w8x
w9x
w10x
w11x
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