MAY 1986
ISSN 00188190
Hydrocarbon
Processing
REFLUX AND SURFACE TENSION EFFECTS ON DISTILLATION
Reflux and surface tension effects on distillation
Theoretical and experimental data suggest how to set reflux ratio for the most efficient distillation separation in packed towers. Surface tension effects also are considered
T. D. Koshy and F. Rukovena, Norton Co., Akron, Ohio
EASY SEPARATION SYSTEMS (those with relative volatili ties of approximately 2.0 or greater) are influenced signifi cantly by reflux ratio. Theoretical relations suggest the best separation efficiency occurs when X, the ratio of the slopes of the equilibrium and operating lines (mG\{/L\), is approxi mately 1.0. Then, experimental data are obtained to relate X to its equivalent reflux ratio.
2.0
1.5
1.0
o
0
o
a
o
° 0
More difficult separation systems (relative volatility close to 1.0) have more uniform separation efficiencies over the entire concentration range (i.e., X has a lesser influence).
A difference in surface tension can explain some differ
ences in efficiencies. Comparing two easy separation sys tems, one with a negative surface tension gives a lower sepa ration efficiency than another with a positive surface tension.
Operating efficiency. The operating efficiency of packed towers is generally expressed as Height Equivalent to a The oretical Plate (HETP) or Height of a Transfer Unit (HTU). But note, a minimum HETP or HTU represents a maxi mum separation efficiency. The effect of reflux ratio is shown in Fig. 1, a plot of HETP versus a vapor capacity factor CY These data are for
a methanolwater binary distillation at atmospheric pres
sure. The upper plot is for total reflux. The lower plot is for an internal reflux ratio, L\i/G\, of 0.5. The HETP is signif icantly larger for total reflux than for partial reflux.
These data were obtained at Norton Company's Cham berlain Laboratories in Stow, Ohio. The distillation tower
had a diameter of 381 mm and was filled with a 3,048mm
deep bed of No. 25 IMTP stainless steel packing. Additiona runs were made to examine the relation between HETP ana*" reflux ratio. Further, HETP measurements were conducted
at a fixed boilup rate to eliminate the effect of Cy on HETP.
Theoretical analysis. A generalized (HTU)(X; correlation assuming a tworesistance theory12 is given as follows:
0.5
Total reflux Partial reflux, L/D = 1.0
0.2
\1
0.3
Cs at midpoint,ft/s Packed tower rectification of methanolwater.
2
3
45 6
810 1
2
3
45 6
810°
2
3
4 56
Slope ratio X Fig. 2—Relationship among variables.
(HTU)0(; = (HTU)C; + X(HTU),.
If the equilibrium curve and the operating line are as
sumed to be straight lines over a single stage, the following relation is obtained:
HETP = (HTU)oo(ln X)/(X  1) _{(}_{2}_{)}
_{(}_{1}_{)}
0.4 Then define
(3 = (HTU) L /(HTU) G
and
£ = HETP/(HTU)C;
Combining the foregoing equations gives:
(5)
£ = (l+X/3)(lnX)/(X  1)
Fig. 2 shows a plot of £ as a function of In X for various values of /3. For a fixed (8, the minimum £ is determined by setting the first differential of Eq. 5 to zero (i.e., d£/dX = 0). This gives:
(4)
810
/3 =
(X 
1 
X In X)/(X In X 
X2
+ X)
(6)
Substituting Eq. 6 into Eq. 5 gives:
L,,, = (lnX)2/(X 
1 
InX)
Table 1 shows the variation of £,„,„ with j3 and X.
Finding minimum HETP. If (HTU)(, is assumed to be a con
Reprinted from HYDROCARBON PROCESSING, May 1986
Copyright* 1986 by Gull Publishing Co., Houston, Texas. All rights reserved. Used with permission.
stant, it follows from Eq. 4 that having a minimum £ also means there is a minimum value for HETP. And since X, and to some extent /?, varies over the range of concentration for which HETP is measured, values of/? and X must be ob tained experimentally. The righthand term of Eq. 2, (In X)/(X 1), approaches '.0 as X approaches 1.0. Therefore, Eq. 2 suggests HETP ^approaches (HTU)OG; and it is feasible to correlate HETP as
a function of the physical properties. It is customary to use published correlations5"' to evaluate (HTU)oo using Eq. 1. Relative volatility, a, relates the vapor and liquid phase compositions of the more volatile component in a binary separation, i.e.,
y
= ax/[I
+ (a

l)x]
_{(}_{8}_{)}
Here, a is not necessarily a constant.
is assumed to be constant over a
small range of composition, the slope of the equilibrium curve can be given as follows:
(9)
On the other hand, if a
dy/dx
= m = a/[l
+ (a

\)x]2
The n whe n x 
—> 
1 , 
m —*• 
I/a 
(10 
) 

an 
d whe n x —> 0 , 
m 
—> 
a 
(11 
) 
and
x = 1.0, m lies betwee n
Difficult separations (those binary systems whose a. val ues are not significantly larger than 1.0), have values of m that do not greatly differ from 1.0. This also implies the in ternal reflux ratio, L\i/G\i, which is the slope of the operat ing line either in the rectifying or stripping sections, for these difficult separations will not vary significantly from 1.0. This is the case because the operating line is enclosed within boundaries created by the equilibrium curve and the diago
,nal.
Thus,
for liquid phase
compositions between
ex and
I/a .
x
= 0
As a result, X = mG\IL\, or
the ratio of the two slopes,
^emains close to 1.0 for such systems. One should not expect
X to be an important variable in the performance efficiency
of distillation towers making difficult separations. Under
such conditions HETP = (HTU)oo, and HETP is an ap propriate design tool. Easy separations, on the other hand, where a > > 1.0,
X can have values much less than 1.0 to much greater than
1.0. Therefore, X becomes an important variable in the per formance of a distillation tower making easy separations, es
pecially when making very pure products.
Surface tension effects can be considered using a defini tion given by Zuiderweg and Harmens.8 They termed distil lation systems positive or negative on the basis of whether the surface tension of the reflux liquid increases or decreases as it flows down the column.
Experimental data. Two binary systems that can be charac terized as easy separations were chosen in order to compare the performance of two high a systems and, at the same time, contrast the performance of a system with a positive surface tension with one having a negative surface tension. The first system was the methanolwater binary men tioned earlier in connection with Fig. 1. The a of this system ranged from 2.6 to 8.1 and the m ranged from 0.38 to 8.1, at atmospheric pressure. This is a strongly surfacetensionpos itive system. The second binary system was a waterdi methylformamide (DMF) system whose a varied from 3.6 to 6.8 and m varied from 0.28 to 6.8, at atmospheric pressure. This latter is a strongly surfacetensionnegative system.
log X for both systems are illus
•,—crated in Fig. 3. The HETP values were calculated using a modified McCabeThiele method taking into account the enthalpy difference between the components.'' Tower opera tions were held within a narrow range of boilup rates in or
The data for HETP versus
2.500
2,000
.
1.500
Methanolwater •* WaterDM F
'*«,, _{.}_{,}
I
I
0%
I III
10' 
2 
3 
456 
7 8910° Slope ratio X 
2 
3456 
7 
8910 

Fig. 3—Two binary systems compared. 

E 

E 

Q.200 

10' 
2 
3 
4 
56 
810° 
2 
3 
4 
5 6 
8 
10' 
2 
3 
4 
56 
810 2 
Slope ratio X
Fig. 4—Literature data for isopropanolwater.10
TABLE 1—Variation of £mm with 0 and X
(3
0
X
00
0.1 28
5.963
0.5
0.7 1.706
0.3
2.817
1.0 1.0
3.0 0.01954
5.0 0.0936
7.0 0.0583
9.0 0.0412
oo
0
£min
0
0.469
1.003
1.373
1.660
2.0
3.219
3.836
4.250
4.560
00
der to eliminate the effect of tower loading on efficiency. For both systems, HETP goes through a minimum at a X value of approximately 1, although boilup limitations prevented getting data for the waterDMF system at X values greater than 1.0.
Other data for an isopropanolwater system reported by
Deed, et al., are shown in Fig. 4.'° They performed atmo spheric rectification of the binary below azeotropic condition in a 152mmdiameter brass column with 1,194 mrn of 13
mm ceramic Raschig Rings. These data also indicate HETP goes through a minimum.
Based on the observation that (HTU)oo increased rapidly as X was raised, Deed, et al., concluded that the principal resistance to mass transfer was in the liquid phase. This ex planation implies that, at large values of X, /? defined by Eq. 3 increases. On the other hand, Norman, et al.,11 conclude that large variations in HETP are probably the result of poor liquid distribution over the packing and variations in the wetted area. This conclusion was based on wetted wall column data determined by other researchers in the field who found large variations in HETP in experiments with packed columns. However, based on recent experience with liquid distributors providing a widely varying number of distribution points
and liquid flowrates, there are no indications that liquid dis
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Fig. 5—Vaporliquid equilibrium diagram.
tribution was a limiting factor for our test data. Surface tension effects. According to Zuiderweg and Har mens,8 a binary system is positive if the less volatile compo nent has the higher surface tension. They demonstrated that, in apparatus where the interfacial area is mainly of the film type, mass transfer rates for positive systems(with stabi lized film) may be much higher than for negative systems. This generalization, however, may fail when applied to negative systems, where the reduction in contact angles may result in spray formation. The interfacial surface area in such formations is not significantly affected by surface ten sion changes. Fig. 3 illustrated that for the range of X values for which comparison can be made, the HETP for the methanolwater (positive) system is consistently lower than that for the water DMF (negative) system. Meier, et al.,12 who performed dis tillation at total reflux on both systems in a structured stain less steel tower packing, found that the HETP for the waterDMF system is approximately twice that of the metha nolwater system. For these tests, the concentration range of the methanol water mixture was 10% methanol at the bottom and 98% methanol at the top. The range of the waterDMF system was 30% water at the bottom and 99.5% water at the top. The authors attribute the lower HETP for the methanolwa ter system to its good wettability. The present study, how ever, demonstrates that wettability per se does not explain the widely differing values of HETP obtained for essentially the same range of separation at different reflux ratios. The data indicate that at X values much larger or smaller than 1.0, HETP increases dramatically. Application. The practical importance of our findings can be illustrated in Fig. 5 and the following:
X is much less than 1. The circumstances when
this happens are:
• high purity of the more volatile component, i.e., m —* I/
Case I:
a.
• reflu x ratio , i.e. , L_\ /G_\i ~*• 1.0 .
hig h
• both foregoing conditions mean X —* I/a.
Case
II.
X =
1.
The
this condition:
following situations will produce
• very low reflux ratio for high purity rectification, i.e., x
* i.o
• very high reflux ratio for high purity stripping, i.e., x " 0
• total reflux for a symmetric separation. Note, the term
"symmetric separation" is used here to mean that on a McCabeThiele diagram, the liquid phase compositions of the overhead product and bottom product are roughly equidistant from 0.5.
circumstances
Case III. X is much greater than 1. The
when this occurs are:
• high purity of bottoms products, i.e., x » 0 and m 
• lo w L/ V approachin g tota l reflux , i.e. , LIV —* • 1. 0
• both foregoin g conditions mean that X *• a.
NOMENCLATURE
Cs 
 capacity factor V svpc/(pL ~ PG)> m/s 

GM 
 ga s flowrate , 
kgmoles/ h 
HETP  height equivalent to a theoretical plate, m
HTU 
 height of a transfer unit, m 
LM 
 liquid rate, kgmoles/h 
m 
 slope of the equilibrium line 
Vs 
 superficial gas flow velocity based on tower area, m/s 
x 
 mole fraction of the more volatile component in the liquid phase 
y 
 mole fraction of the more volatile component in the vapor phase 
Greek symbols
a
/3
X
 relative volatility between components 1 and 2

 m GM/LM, ratio of the slopes of equilibrium and operating lines
  density, kg/m3
as defined in Eq. 3
as defined
4
  liquid phase
 moles of gas or liquid
gas phase
in Eq.
p
Subscripts
G
L
M
OG  overall gas phase
£
LITERATURE CITED
1 
Lewis, W. K., and Whitman, W. G., Industrial and Engineering Chemistry, Vol. 16, p., 

1215, 1924. 

: 
Whitman. W. G., Chemical and Metallurgical Engineering, Vol. 29, p. 247, 1923. 

:i 
Shulman, 
H. L., Ullrich, 
C. 
F, and Wells, N., AlChE Journal, Vol. 1, p 
" 
1955. 

4 
Shulman, H. L., Ullrich, C. F, Proulx, A. Z., and Zimmerman, J. O., AlChE 

Journal, Vol. 1, p. 259, 1955. 
~~'
Shulman,
259, 1955.
H.
L., Ullrich. C.
F., Wells, N., Proulx, A. Z., AlChE Journal, Vol.
1, p.
6 
Onda, K., Takeuchi, H., and Okumoto, Y.J., Chemical EngineeringJapan, Vol. 1, p. 

56, 1968. 

7 
Onda, K., Mem. 
Fac. 
Eng., Nagoya Univ., 24 (2), p. 64, 1972. 

R 
Zuiderweg, F. J., and Harmens, A., Chemical Engineering Science, Vol. 9, 
Nos. 
2/3, 

p. 89, 
1958. 

y 
Neretnieks, I., Ericson, I., Eriksson, S., British Chemical Engineering, Vol. 14. No. 

12, p. 653, 
1969. 
1(1 Deed, D. W., Schutz, P. W., Drew, T. B., Industrial and Engineering Chemistry, Vol.
39, No. 6, p. 766, 1947.
11 Norman, W. S., Cakaioz, T., Fresco, A. Z., Sutcliffe, D. H., Transaction of the Insti
tution of Chemical Engineers, Vol. 41, p. 61,
1963.
1 2 Meier , W., Hunkeler , R., Stocker, D., Institution of Chemical Engineers Symposium Se
ries No. 56, 3.3,
p.
1,
1979.
The authors
T. Dan Koshy is manager, mass transfer devel opment, Norton Chemical Process Products, Akron, Oft/o, where he manages pilot plant re search and data correlation. Earlier he was a design and development engineer (distillation) with Union Carbide Corp., Linde Division. He holds a BS degree from Nagpur University, In dia, an MS degree from Wayne State University, Mich., both in chemical engineering, and an AlChE membership.
Frank Rukovena, Jr., is manager, mass transfer engineering and development, Norton Chemical Process Products, Akron, Ohio, where he man ages mass transfer development, packed tower application and mechanical engineering. Earlier he was a research development engineer wit
Koppers Co.
with General Tire. Holder of a BS in chemical en gineering from \bungstown University, he is a member of AlChE.
and a design and project engine*, .„.
Printed in United States
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