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Fredenslund1975 (UNIFAC) PDF
Fredenslund1975 (UNIFAC) PDF
v, = - VS V,
1-x Greek Letters
is more nearly constant than V,. Examination of the present Ap = difference in densities of dispersed and continuous
holdup data, data of Gayler, Roberts, and Pratt (1953), phases, g/cm3
and data from an earlier study of Gayler and Pratt (1951) E = void fraction of the packing, dimensionless
reveals that neither V, nor V, is a satisfactory parameter p = viscosity, poise
for correlating holdup over a wide range of fluid proper- AVc,01/2= defined by Equation (5)
ties and flow rates. Both our data and that of Gayler and AV,,01/2 = defined by Equation ( 5 )
Pratt (1951) contained primarily high values of holdup (> Subscripts
l o % ) , and in such cases V, appears to be the preferred c, d = continuous and dispersed phases, respectively
correlating parameter. This is illustrated in Figure 2 of
o = intercept value; flow rate of other phase ap-
Watson and McNeese (1973). The data of Gayler, Roberts,
proaching zero
and Pratt (1933) contained lower values of holdup (most
values were < 10% ) , and V, was shown to be more nearly
LITERATURE CITED
constant. At low values of holdup, there is little difference
between V, and V,. Generally, V, is believed to be a more Ballard, J. H., and E. L. Piret, “Limiting Flow Phenomena in
useful correlating parameter over a wide range of holdup Packed Liquid-Liquid Extraction Columns,” Ind. Eng.
values. However, neither of the parameters is as accurate Clrem., 42, 1088 (1950).
as one may desire, and improved correlations, especially Breckenfeld, R. R., and C. R. Wilke, “Limited Flows in Packed
those with a theoretical basis, are needed. Extraction Columns,” Chem. Eng. Progr., 46, 187 ( 1950 ).
Crawford, J. W., and C. R. Wilke, “Limited Flows in Packed
Extraction Column; Correlations for Larger Packing,” ibid.,
ACKNOWLEDGMENT 47,423 ( 1951).
This work was sponsored by the U.S. Atomic Energy Com- Dell, F. R., and H. R. C. Pratt, “Liquid-Liquid Extraction,
mission under contract with Union Carbide Corporation. The Part I. Flooding Rates for Packed Columns,” Trans. Inst.
authors would like to express their appreciation to John S. Chenz. Engrs., 29, 39 ( 1951).
Taylor, R. 0. Payne, and several students and Directors of the Gayler, R., and H. R. C. Pratt, “Liquid-Liquid Extraction,
Massachusetts Institute of Technology Chemical Engineering Part 11. Holdup and Pressure Drop in Packed Columns,’’
Practice School who made most of the measurements and ibid., p. 110.
otherwise assisted in the study. Gayler, R., N. W. Roberts, and H. R. C. Pratt, “Liquid-Liquid
Extraction, Part IV: A Further Study of Hold-up in Packed
Columns,” ibid.,31,57 ( 1953).
NOTATION Hannaford, B. A., J. S. Watson, C. W. Kee, and H. D. Cochran,
Jr., “Hydrodynamics and Mass Transfer in Packed Columns,”
a = cm2 of packing surface/cm3 of packing volume paper presented at the National Meeting of AIChE, St.
d p = diameter of packing, cm Louis, Mo. ( 1972).
vc = superficial velocity of the continuous phase, cm/s Johnson, T. R., R. D. Pierce, F. C . Tents, and E. F. Johnson,
vd = superficial velocity of the dispersed phase, cm/s “Behavior of Countercurrent Liquid-Liquid Columns with
- superficial continuous phase velocity at flooding, a Liquid Metal,” AlChE J., 17, 14 ( 1971).
Vc.f - Watson, J. S., and L. E. McNeese, “Holdup, Flooding, and
cm/s
- Pressure Drop in Packed Columns During Countercurrent
Vd,f - superficial dispersed phase velocity at flooding, Flow of Mercury and Water,” ibid., 19,230 ( 1973).
cm/s
v, = characteristic velocity defined by Equation ( 6 ) , Manuscript received February 11, 1975; reoision received May 11, ‘
cm/s and accepted June 9, 1975.
CONCLUSIONS A N D SIGNIFICANCE
The UNIFAC method for predicting liquid-phase activ- liquids. Predicted activity coefficients agree well with
ity coefficients provides the process design engineer with those obtained from experimental vapor-liquid equilib-
a useful tool for calculating vapor-liquid equilibrium rium data not included in the determination of group-
compositions in the frequently encountered situation interaction parameters. In most typical cases, predicted
where no binary (or higher) experimental information is activity coefficients at infinite dilution deviate less than
available. The UNIFAC method is applicable to a wide 2001, from measured results. These measured results, how-
range of mixtures exhibiting either positive or negative ever, are often subject to appreciable experimental un-
deviations from Raoult's law. Parameters are given for
certainties.
eighty-three different group interactions in the temperature
region 275' to 40O0K. While the present range of applicability is already
Prediction of liquid-phase activity coefficients is demon- much larger than that of any other correlation, this range
strated for a variety of binary and ternary mixtures in- can readily be expanded as new experimental results be-
cluding those containing alcohols, water, or other polar come available for data reduction.
Since chemical process design is often concerned with For example, we would not expect the contribution of a
separation of fluid mixtures, design engineers must fre- carbonyl group in a ketone (say, acetone) to be the same
quently estimate liquid-phase activity coefficients. In as that of a carbonyl group in an organic acid (say, acetic
those fortunate cases where phase equilibrium data are acid). On the other hand, experience suggests that the
at hand, such estimates can usually be made with ease. contribution of a carbonyl group in, for example, acetone,
In many other cases, however, where the required experi- is close to (although not identical with) the contribution
mental data are not available, it is difficult to make even of a carbonyl group in another ketone, say, 2-butanone.
rough estimates on a rational basis. This work is a con- Accuracy of correlation improves with increasing dis-
tribution toward alleviating this common problem in tinction of groups; in considering, for example, aliphatic
chemical process design. alcohols, in a first approximation no distinction is made
The method presented here is based on the well-known between the position (primary or secondary) of a hy-
group-contrillution concept which has been successful for droxyl group, but in a second approximation such distinc-
estimating a variety of pure-component properties such as tion is desirable. In the limit, as more and more distinc-
liquid densities, heat capacities, and critical constants. The tions are made, we recover the ultimate group, namely,
basic idea is tliat whereas there are thousands of chemical the molecule itself. In that event, the advantage of the
compounds of interest in chemical teclinology, the num- group-contribution method is lost. For practical utility, a
ber of fiinclional groups which constitute these compounds compromise must be attained. The number of distinct
is much smaller. Therefore, if we assume tliat a physical groups must remain small but not so small as to neglect
propertv of 11 fluid is the sum of contributions made by significant effects of molecular structure on physical prop-
the molecule's functional groups, we obtain a possible erties.
teclinique for correlating the properties of a very large Extension of the group-contribution idea to mixtures is
number of fluids i n terms of a much smaller number of extremely attractive because, while the number of pure
parameters which characterize the contributions of indi- fluids in chemical technology is already very large, the
\idual groups. number of different mixtures is still larger, by many
Any group-con tribulion method is necessarily approxi- orders of magnitude. Thousands, perhaps millions, of
mate because the contribution of a given group in one multicomponent liquid mixtures of interest in the chemi-
molecule is not necessarily the same as that in another cal industry can be constituted from perhaps twenty, fifty,
molecule. The fundamental assumption of a group-con- or at most one hundred functional groups.
tribution method is additivity; the Contribution made by Estimation of thermodynamic properties of liquid mix-
one group is assumed to be independent of that made by tures from group contributions was first suggested by
another group. This assumption is valid only when the Langniuir ( 1925). This suggestion, however, received
influence of anv one group in a molecule is not affected little attention until Derr and co-workers (Redlich, Derr
by the nature of other groups within that molecule. and Pierotti, 1959; Derr and Papadopoulos, 1959) used
@i
@i
qi In - + Zi - -pjxjZj
Xi
(2)
is the area fraction of group m, and the sums are over all
different groups. O , is calculated in a manner similar to
and that for ei:
where X , is the mole fraction of group m in the mixture. where Urn, is a measure of the energy of interaction be-
The group interaction parameter Ymn is given by tween groups m a n d n. The group-interaction parameters
TABLE
3. GROUPIKTERACTION
PARAMETERS,
a,,, O K
CH2 687.5 472.6 422.1 800.0 1,330 601.6 523.2 60.45 194.2 1
C==c X X 349.9 515.2 X 691.3 253.8 259.5 X 2
ACH 159.1 37.24 179.7 487.2 680.0 290.1 124.0 X -99.9 3
ACCH2 110.0 680.0 X X 640.0 3,000 33.84 X X 4
COH 174.3 -204.6 -166.8 3,000 X 79.85 194.6 X 69.97 5
H20 X X 385.3 743.8 -314.6 118.5 158.4 247.2 190.6 6
ACOH -470.2 X X X X X X X X 7
co -180.1 475.5 X X X -307.4 628.0 874.5 X 8
CHO X X X X X X X X X 9
coo 0 -26.15 X X X X X X X 10
0 -290.0 0 X X X X X X X 11
CNH2 X X 0 X X X X X - 10.0 12
NH X X X 0 X X X X -60.0 13
ACNHz X X X X 0 X X X 3,000 14
CCN X X X X X 0 - 100.0 X 25.0 15
c1 X X X X X 100.0 0 -308.5 X 16
CHClz X X X X X X 790.0 0 X 17
ACCl X X 3,000 3,000 110.0 3,000 X X 0 18
10 11 12 13 14 15 16 17 18
TABLE4. OBSERVED
AND CALCULATED
ACTIVITYCOEFFICIENTS
AT INFINITE
DILUTION
Diethylamine( 1) -chlorobenzene( 2 ) 313 1.17 1.17 Included in data base. For ref-
Chlorobenzene( 1)-diethylamine( 2 ) 313 1.41 1.43 erences see supplement.
Ethanol( 1)-diethyl ether( 2 ) 273 2.82 3.21
Diethyl ether( l)-ethanol(2) 273 3.84 3.50
Benzene( 1)-water(2 ) 298 488 458
Water( 1)-benzene(2 ) 298 430 359
Phenol( l)-hutyl acetate( 2 ) 318 0.12 0.13
Butyl acetate( 1)-phenol(2 ) 318 0.18 0.19
n-propanol( 1)-n-propylamine( 2 ) 320 0.37 0.35
n-butylamine ( 1 ) -n-butanol( 2 ) 392 0.50 0.48
The discussion of predictions is divided into three parts: ACTIVITY COEFFICIENTS AT INFINITE DILUTION
activity coefficients at infinite dilution, binary systems, and Table 4 shows activity coefficients at infinite dilution.
ternary systems. The infinitely dilute region provides an especially severe
test of the UNIFAC method, since the corresponding cal-
culated activity coefficients are very sensitive to the inter-
action parameters. By taking into account that the activity
coefficients in this region are subject to relatively large
I .4
I
I experimental error, the predicted and experimental activity
coefficients at infinite dilution' agree satisfactorily. The
activity coefficients listed in Table 4 span five orders of
I .2 magnitude. The pentane-acetonitrile, butane-ethylamine,
and 1,2-dichloroethane-propanol systems were not in-
cluded in the data base at all, and neither were systems
I .o containing dienes or methylamine.
0 Figure 1 shows infinite-dilution activity coefficients for
alkane-water, olefin-water, and diene-water systems as
AN 0.8 functions of the number of carbon atoms. These results
-
C are typical for systems with very large activity coefficients
L
[exp( 14) = lo6]. The UNIFAC method gives correct
0 trends wihh respect to number of carbon atoms and num-
0.6
h- ber of double bonds. The prediction of the activity coeffi-
cients for dienes is encouraging.
-
C
Among the mixtures covered in this work, negative
0.4 deviations from Raoult's law are observed for the systems
phenol-ester, benzene-ether, amine-alcohol, and ketone-
chloroalkane. The last four entries of Table 4 indicate that
0.2 the UNIFAC method also represents well systems with
negative deviations. Predictions for systems of this type
outside the data base could not be tested owing to scarcity
0 of experimental data.
L 0.2 0.4 0.6 0.8 1.0
BINARY SYSTEMS
x"
-
C
L
0
x-
c
-
0
UN I FAC
Observed, 1- Hexene
- Observed,
0
FAC UNI
Cyclohexone
A Observed, l , l , 2-Trichloro- A Observed, lt2-Dichloroethane
ethane
Fig. 5. Activity coefficients for the 1-hexene (1)-1.1,2-trichloroethane Fig. 6. Activity coefficients for the cyclohexane (1)-1.2-dichloroethane
(2) system a t 333°K. (Hanson and Van Winkle, 1967). (2) system a t 1 atm. (Mesnage and Marson, 1971).
I
I I I I
-
A
c
-
,
similar calculations for alcohol-heptane systems. Predic-
tions for the system 1-octanol-heptane are encouraging.
No alcohol larger than propanol entered into the data base
for the determinetion of the (COH, CH2) group interac-
tion parameters. Table 5 shows that whereas activity CQ-
efficients for secondary alcohol-heptane systems are lower
than those for primary alcohol-heptane systems, the magni- I .6
tude of the decrease is exaggerated in the calculated ac-
tivity coefficients. Although the predictions for the sec-
ondary alcohols are not highly erroneous, we believe that
systems containing alcohols should be reexamined to
ensure the successful inclusion of methanol and secondary
alcohols in the UNIFAC method and to improve predic-
tions for systems containing primary alcohols in the very
dilute region.
Experimental data are scarce for systems containing
many different functional groups. One of the main ad-
vantages of the UNIFAC method is its ability to predict
activitv coefficients for systems of this type from experi-
mental information on normal systems, that is, those with
only a few different functional groups. Results for the XI
system ethylbenzene ( 1CH3, 1ACCH2, SACH) cellosolve
(ICHn, 2CH2, ICOH, 10) shown in Figure 10 illustrate
-UNI FAC
Observed,
0 E t h y l benzene
this ability. Twenty group-interaction parameters were
used in the calculation of these activitv coefficients. Sys- A Observed, Cel IoSOlVe
tems containing cellosolve ( CH&H20CH2CH20H) were Fig. 10. Activity coefficients for the ethylbenzene (l)-Cellosolve (2)
not included in the data base. system a t 1 atm. (Murti and Van Winkle, 1957).
Observed Calculated
Alcohol T,"K y1 at x1 = 0.1 72 at r 2 = 0.1 y1 at XI = 0.1 y2 at xz = 0.1 Reference
I-propanol 303 6.02 4.98 6.01 4.74 Van Ness et al. 1967)
I-propanol 333 5.38 4.58 5.29 4.42
2-propanol 303 5.75 4.98 3.10 2.68
2-propnnol 333 5.06 4.43 2.80 2.53
1- oct anol 313 3.90 2.45 3.06 2.08 Geiseler et al. ( 971 )
2-octanol 313 3.59 2.27 2.03 1.61
3-octanol 313 3.31 2.23 2.03 1.61
TABLE
6. OBSERVED
AND CALCULATED
ACTIVITY COEFFICIENTS
FOR THREE-COMPONENT
SYSTEMS
r p r(o,o, 1, 0 ) =1
-
0.274 0.00611
} ]= 0.2664
+ 0.726 - 0.00611 + 0.274
In pure n-propanol ( 2 )
0.726 * 0.000057
- { +
0.726 0.274 * 0.000057
Example 2
It is desired to obtain the activity coefficients for the acetone
(1)-n-pentane ( 2 ) system at 307°K and zl = 0.047:
0*274
-
0.726 0.00611 + 0.274 } ]= 0.8284
0.0321 0.0336
(0.5187 + 0.4721 )0.00611 + 0.0092 J
In yIC = In - 5 * 2.336
0.047
+ In -- 0.3860
0.0321 In r8
+-0.0321 (0.047 0.3860 + 0.953 * 0.2784) = -0.403 1 - In ((0.5187 + 0.4721) * 0.00611 + 0.0092)
0.047
CH3 = 1A; CH2 = 1B; 60 = 8 (0.5187 + 0.4721) 0.000057