AUGUST, 1940 INDUSTRIAL AND ENGINEERING CHEMISTRY
Literature Cited (12) Martinsen, H . , Z . p h y s i k . Chem., 50, 385 (1904): 59,605 (1907).
(1) Farmer, R . C . , J. SOC.C h e m . I n d . . 50,751‘ (1931).
(2) Gilman, H . , “Organic Chemistry. an Advanced Treatise”,
Val. 11, p. 111, New York, John Wiley & Sons, 1938.
(3) Grignard, V.,“Trait6 de chimie organique”, Vol. IV, p. 232,
Paris, hlasson et Cie., 1936.
(4) Groggins. P. H . , “Unit Processes in Organic Synthesis”, p . 23,
New E-ork, McGraw-Hill Book Co., 1935.
(5) Hantssch. A , , Ber., 50, 1422 (1917), 58, 612, 941 (1925). 60,
1933 (1927): Z.Elektrochem., 24,201 (1918). 29,221 (1923),30,
194 (1924), 31,167 (1925); 2 . p h y s i k . C h e m . , 134,406 (1928).
(6) Hetherington, J. A , , and Masson. I., J . Chem. Soc.. 1933, 105.
( 7 ) Holleman, -1.F . , “Die direkte Einfuhrung Ton Puhstituenten
in den Bensolkern”, pp. 71, 97, Leipeig, Verlag von Teit und
Camp., 1910.
( 8 , Hough, -1.,Sal-age. W., and Van Malle. D. J . , C h e m . 12 .\let.
Eng., 23,666 (1920).
(9) International Critical Tables, 1-01. 111, p. 307, S e i v York,
McGraw-Hill Book Co., 1928.
(10) Kullgren. C., Z . ges. Schiess- Sprengstoflw., 3 , 146 (1908).
(11) Lauer, K., and Oda, R.,J . prakt. Chem., 144, 176; 146,61 (1936).
MULTICOMPONENT RECTIFICATION
Minimum Reflux Ratio’
E. R. GILLILAND
Massachusetts Institute of Technology, Cambridge, Mass.
.4pprosimate equations are derived for the
estimation of the minimum reflux ratio for
multicomponent mixtures, and these equa-
tions can be used to calculate upper and
lower limits for the true minimum reflux
F OR a given separation by rectification, the minimum
number of theoretical plates a t total reflux and the
minimum reflux ratio corresponding to an infinite num-
ber of plates render valuable aid to the designer, by defining
the limits within which his calculations must be confined to
give an operabIe design. Satisfactory methods for the calcu-
lation of both of these factors have been developed for binary
mixtures. However, for the case of multicomponent mix-
tures, the problem is more complev than for binary mixtures,
and only for the case of the minimum number of theoretical
plates a t total reflux have suitable methods been developed
( I ) . Several methods for predicting the minimum reflux ratio
for multicomponent mixtures have been published; of these,
that of Underwood (6) has been the most widely used by
other investigators. Underwood’s equation is:
This equation was derived on the basis of assumptions which
were equivalent to assuming that for the condition of mini-
mum reflux the concentrations of the key components mere
the same on the feed plate as in the feed. Such an assumption
i, true for binary mixtures of normal volatility but is seldom
triie for multicomponent mixture<. For complex mixtures of
1 The first paper in thim series appeared i n July (2).
1101
(13) Othmer. D. F . , ISD. EEG.CHEM.,20,743 (1928).
(14) Parks, G . S., and Huffman, H. M.,“Free Energies of Some Or-
ganic Compounds”, A . C. S. Monograph 60, p. 221, Xew
York, Chemical Catalog Co., 1932.
(15) Pounder, F . E., and Masson, 1..J. C‘hem. SOC.,1934,1352.
(16) Saposchnikow. A . W., 2. p h y s i k . C h e m . , 49, 697 (1904), 51,
609 (19051, 53, 225 (1905); Z. ges. Schiess- Spreng&o$w., 4,
441, 462 (1909).
(17) Schaeffer, K . , Z. anorg. allgem. Chem., 97, 285; 98, 70, 77
(1916).
(15) Bpindler, P . . B e r . , 16, 1252 (1883); Ann., 224, 283 (1884).
(19) Suen. T . J . , M a s s . Inst. Tech., 9c.D. thesis, 1937.
(20) Taylor, H . S.,“Treatise on Physical Chemistry”, 2nd ed., Vol.
11, p. 1026, Kew York. D. Van Nostrand Co., 1930.
(21) Tronov, B. V. et al., J . Russ. Phys. Chem. SOC.,62, 2267 (1930);
Ckrabz. Khem. Zhirr.. 7 , No. 1, Sci. pt. 55 (1932).
(22) Walker, W.H . , Lewis, W. K., and McAdams. W. H., “Principles
of Chemical Engineering”, 2nd ed., p. 128, New Tork, Mr-
Graw-Hill Book Co.. 1927.
(23) Wibaut, J . P . . Rec. trav. chim., 34,241 (1915); 54,409 (1935).
(24) Wyler. O., Hela. C‘him. .4cta. 15, 23, 591, 956 (1932).
ratio. The use of the equations is illus-
trated by several examples, and it is shown
that previous methods of estimating the
true minimum reflux ratio can be greatly
in error.
normal volatility the minimum reflux ratio is limited by the
fact that the ratio of the concentrations of the key compo-
nents in the vapor from the section below the feed has to match
the ratio of the vapor compositions for the upper section, but
the key components do not hare the same composition on the
feed plate as in the feed. Thus, heavy, relatively nonvolatile
components may enter with the feed and be present in large
concentrations on the feed plate, but not be present to any
appreciable extent on the plate above the feed. As an ex-
ample, consider the rectification of a ternary mixture of 10
mole per cent A, 10 mole per cent B, and 80 mole per cent C.
in which C is essentially nonvolatile. This feed is analogous
to the feed to a gasoline stabilizer, in which case a large amount
of relatively high-boiling hydrocarbons enter in the feed
together with small amounts of light components such as C3
and Cqhydrocarbons, and the main separation is to be made
in the C3-Cr range. Considering the A-B-C mixture it is
obvious that, a t all reflux ratios the sum of x4 plus ZH on the
feed plate would be greater than in the feed, since the reflux
from the plate above the feed would contain no C ; and a t
total reflux the concentration of C on the feed plate would be
zero and thus make the sum of the x . ~and z8 on this plate
equal to five times their iiim in the feed.
THE condition of the minimum reflux ratio requires that to
perform the given separation an infinite number of plate?
1102 INDUSTRIAL AND ENGINEERING CHEMISTRY
must be needed, which means that there must be a “pinched-
in” region where there are a large number of plates having the
same composition, but for multicomponent mixtures of nor-
mal volatility this region usually does not occur a t the feed
plate as it does in the case of binary mixtures. Under this
condition a relatively few plates above the feed serve to re-
duce the concentrations of the components less volatile than
the heavy key component to negligible values, and then a true
pinched-in condition does occur with only the heavy key and
more volatile components present. Likewise, below the feed
plate a relatively few plates reduce the concentrations of the
components more volatile than the light key component to
negligible ralues and a true pinched-in condition occurs with
only the light key and less volatile components present.
Thus the tower operating a t the minimum reflux ratio might
be considered as being composed of five sections: (1) Starting
a t the still the only components present in significant amounts
are the light key and the less volatile components, and in pro-
ceeding up the tower in this bottom section, the concentration
of the light key component increases relative to the concen-
trations of the heavy key and heavier components. ( 2 )
Above section 1 is a pinched-in region where the concentra-
tions of the light key and the less volatile components are all
constant and an infinite number of plates is required to
produce a finite change in the plate composition. (3) Next
there is an intermediate region where the concentrations of the
components less volatile than the heavy key component de-
crease to negligible values and where the concentrations of the
components more volatile than the light key component in-
crease t o significant values. (4) Above section 3 is another
pinched-in region where the concentrations of the heavy key
and the more volatile components are all constant and an in-
finite number of plates is required to produce a finite change
in plate composition. ( 5 ) A section exists where the concen-
tration of the heavy key component decreases relative to the
concentration of the more volatile components until the over-
head composition is obtained. Actually there is no sharp
line of demarcation between these five sections, but this divi-
sion serves as a useful picture for considering the case of the
minimum reflux ratio. The feed to the fractionating column
would be introduced on some plate in intermediate section 3,
and the true criterion for the minimum reflux ratio should be
based on matching the ratio of the concentrations of the key
components above and below the feed plate under conditions
such that a pinched-in section occurs both above and below
the feed plate. For mixtures of normal volatility a pinched-in
region in only one section does not necessarily indicate that an
infinite number of plates would be required to perform the
desired separation a t the reflux ratio under consideration, since
by relocating the feed plate, such as to shift the ratio of the
concentrations of the key components a t this plate, the sec-
tions that were not limited could be made to do more separa-
tion and thereby relieve the load on the pinched-in section.
In other words, the condition of the minimum reflux ratio is
not determined by either the fractionation above or below
the feed plate alone, but is determined such that the separa-
tion is limited both above and below the feed. The condi-
tions in the intermediate feed section lead to calculational
difficulties due to the fact that the concentrations are not
constant in this region. Actually in this region the ratios of
the concentrations of the key components may change in the
opposite direction from that desired for the separation; thus,
proceeding up the column from the feed plate a t the minimum
reflux ratio, the ratio of the concentrations of the light key to
the heavy key component may decrease instead of increase.
However, it is relatively simple to calculate the plate composi-
tion for a region where the concentrations are the same on
successive plates, and such calculations can be made the
basis for estimating the minimum reflux ratio.
VOL. 32, NO. 8
CASEI. I t can be assumed that the concentrations of all com-
ponents are constant for a number of plates above and below the
feed plate. This requires that the pinched-in condition between
the key components must occur with all the components present
in significant amounts; actually, as pointed out before, onlv cer-
tain of the components are present at the pinched-in condition.
The presence of these extra components makes the separation
more difficult,and for that reason the minimum reflux ratio calcu-
lated on the basis of the assumptions of case I will be equal t o or
greater than the true minimum reflux ratio.
CASE11. Alternately it can be assumed that the ratio of the
concentrations of the key components for the pinched-in region
below the feed plate (section 2) can be matched with the same
ratio for the pinched-in region above the feed plate (section 4),
which amounts t o neglecting the intermediate region (section 3).
However, for the actual operation section 3 must be present and
in this section the ratio of the concentrations of the key compo-
nents change in the opposite direction to that desired for the
separation; for that reason the assumptions of case I1 correspond
to an easier separation than the actual case and the minimum re-
flux ratio calculated by these assumptions will be equal to or less
than the true minimum reflux ratio.
Calculation of the minimum reflux ratio for these two cases
will give limits for the true minimum reflux ratio. To evalu-
ate these cases i t is necessary t o calculate the concentrations
of the various components for the pinched-in or constant
composition regions. Such compositions are easily calculated
by the use of the relative volatility, CY, and the fact that the
ratio of the concentrations of any two components are the
same on successive plates; thus for the volatile components
above the feed plate,
and
and for the less volatile components below the feed plate,
I n these equations the last term of the denominator is
usually small relative to the rest of the denominator and can
be neglected for the first estimations, making only the flow
quantities, relative volatilities, and terminal concentrations
necessary for the calculation of the asymptotic values. Cor-
rections can then be made for the last term in the denomi-
nators, but usually this is not necessary.
These equations can be used to calculate the concentrations
of the key components for evaluating the minimum reflux
ratios for cases I and 11, which would involve matching the
ratio of the concentrations of the key components above the
feed plate with the same ratio below the feed plate; but such a
procedure leads to a quadratic solution, and it is generally
easier to evaluate the ratio of the concentrations of the key
components at the feed plate and equate this to the concen-
AUGUST, 1940 INDUSTRIAL AND EKGISEERING CHEMISTRY
tration ratio of the key components either above or below this
plate. For case I the constant compositions of all compo-
nents above and below the feed plate make the assumptions
used for deriving the optimum feed-plate composition appli-
cable (2). Letting 4 be the ratio of the concentrations of the
key components at the plate where the upper section of the
fractionating tower is matched with the lower section, the
derivation for the optimum feed-plate composition indicated
that
Combining this equation with the assumption of constant
composition above the feed plate gives
The problem of calculating (OID), for case I thus becomes a
problem of evaluating the constant limiting value of the heavy
key component in the vapor, since all the other terms are
easily evaluated. This concentration, y h k , can be calculated
in several manners, such as by Equation 5, or by
yhk = (1 - ylk - ZyZ - Z y h )
l h
or Yhk ah@hk/~ffX
where the various terms are evaluated by Equations 2, 3, 4,
and 5. The use of Equation 5 alone leads to a simple criterion
for the minimum reflux ratio but it is not to be recommended,
since Equation 8 was derived from conditions above the feed
plate while Equation 5 was based on conditions below the feed
plate. Either of the other two methods for calculating y h i .
gives satisfactory results, and it is a matter of convenience as
t o which one is chosen. Thus a value of ( O / D ) , can be
assumed and the summation terms evaluated by Equations 2 ,
3, 4, and 5, and y h h can be calculated by one of these two
methods. Then ( O / D ) , can be obtained from Equation 8,
and the assumed value can be adjusted if necessary. This
trial and error calculation can be simplified by introducing the
y h k calculation into Equation 8; for example, using y = minimum reflux ratio for calculations above the feed plate
f f hk x h k / x C Y x ,
(O/D), + 1 = M [ N + +C(A + B S ) ]
Equations of this type but slightly different in form were
published by Robinson and Gilliland ( 5 ) . An alternate form
of Equation 9 that is more convenient for some cases is
(O/% + 1 = M [ N + E ( A / S + B)1
The first portion of Equations 9 and 10-i. e., that part other
than the terms involving A and B-represents the minimum
reflux ratio for a binary mixture of the two key components;
the last two terms represent the increase in the reflux ratio
due to the presence of the components more or less volatile
than the key components. These two equations give essen-
tially the same result, but it is better to use Equation 9 when
the value of B is small and to use Equation 10 when the value
of A is small. In using these equations, the terms al(D/O) x
@Dhk/Xhk) and f f h ( w / o m ) ( & d k / x l k ) are neglected for the
first trial since they are usually small in comparison with the
differences of the relative volatilities with 11 hich they are
grouped. Corrections can then be made for these groups,
calculating m k and x h k by Equations 2 and 3; but generally
such corrections are not necessary. The last terms in both
1103
equations involve the ratio of the molal overflows above and
below the feed plate; they require trial and error unless this
ratio is unity, as is approximately the case for an all-vapor
feed, or unless the last terms are zero, owing to the fact that
either there are no components less volatile than the heavy
key component which makes B equal to zero, or there are no
components more volatile than the light key component
which makes A equal to zero. I n the calculation of 4, trial
and error are required unless V* = Vm. However, the trial-
and-error procedure involved is relatively simple and gives
the desired solution in a short time. Equation 10 can be
modified by certain approximations to give :
(g) m + 1 = M { - V + E [(g) (2)A + B ] [ (11)
(7) Equation 11 is easier to use when V,, = I-,,,, since no trial and
error is involved; but in general, Equations 9 and 10 are more
satisfactory. However, in most cases all three equations mill
give nearly the same result, but occasionally the values will
differ somewhat due to the assumptions that have been made;
in general it is better to use Equation 9 or 10, the choice be-
tween them being based on the value of their last terms.
A number of alternate forms can be obtained from the same
set of assumptions, such as using different methods of evaluat-
ing u h k and by using the ratios below the feed plate instead
of the ratios above the feed plate as in Equation 7 ; but the
forms given in Equations 9, 10, and 11 are about as satisfac-
tory as any of the other possible arrangements for most cases.
For case I1 the ratio of the concentrations of the key com-
ponents are matched for the two pinched-in sections, and the
intermediate regjons are neglected. The derivation of Equa-
tions 7 and 8 will apply for this case, but since all of the com-
ponents are not present a t both pinched-in regions, the evalua-
tion of 4 and y i i k will differ from those given for case I. The
value of 4 given by Equation 6 could be used for this case, but
it leads to erratic values since the matching ratio is generally
different from the value of Equation 6. For example, suppose
T', = TTm, then Equation 6 makes 4 equal to the ratio of the
concentrations of the key components in the feed, but the
ratio required to match the section above the feed plate with
that below the feed plate is usually quite different from the
ratio of concentrations in the feed. The use of 4 from Equa-
tion 6, together with case 11, leads to different values of the
from those for calculations below the feed plate; the calcu-
(9) lated reflux ratio may range from values less than t o values
greater than the true minimum reflux ratio and for that reason
leaves the calculator in question as to the value of his result.
However, Equation 6 can be modified so as to give a value of 4
that is suitable for the matching and which when used for case
I1 will give a reflux ratio less than the true minimum reflux
(10) ratio. An approximate derivation for this case similar to that
made to obtain the optimum feed plate composition from
which Equation 6 was abstracted, gives
Above the feed plate only the heavy key and more volatile
components are considered for this case, and Equation 8 gives:
(OID),+ 1 = M'(N' + O'CA) (13)
 1104 IlDUSTRIAL .4ND ENGINEERING CHEMISTRY VOL. 32, NO. 8
Below the feed plate a similar equation can be derived using For this example Equations 10, 11, 13, 14, and 15 all give
only the light key and less volatile components: (0,1D)3,,= 1.7. By Underwood's equation (Equation 1):

Both equations give essentially the same result, and the
choice between the two depends on the relative number of
components more or less volatile than the key components.
Equation 13 would be easier to use for systems containing few
components more volatile than the light key component;
Equation 14 would be easier to use on systems containing few
components less volatile than the heavy key component. In
evaluating the ratio 4' by Equation 12, the Zy and By terms
1 h
are calculated by Equations 3 and 5 .
Constant relative volatilitier were assumed in these deriva-
tions, and the most satisfactory results will be obtained by
using values taken a t a temperature approximating the tem-
perature of the feed plate; but in most cases of mixtures of
normal volatility the calculations are not very sensitive to the
temperature taken for determining the relative volatilities.
Instead of using the ratio of the key components a t the feed
(OID), = 8.5
Stepwise plate calculations by the method of Lewis and
Matheson ( 3 ) indicate that the true minimum reflux ratio is
greater than 1.69 and less than 1.T1. By a modified McCabe
and Thiele diagram (4),it can be shown that the true value of
(0,D),,, is 1.7. For this particular example Equations 13 and
14 give the same result as Equations 9, 10, and 11 owing to
the fact that for the special mixture chosen, the pinched-in
condition does occur a t the feed plate. Equation 1 gives a
value that is much too high for this separation.
EXAMPLE 2, phenol-cresol separation, example from Robin-
son and Gilliland (5, page 174): feed enters such that T',& =
vm:
7-

Feed
l l u l e Fractiun-
Distillate Residue
- Volatilities Relative
6 0 o-Cresol
plate, it is possible to match the ratio of the key component
Piirnol 0.35 0.95 0,0524 1.26
for the pinched-in section above the feed plate n i t h the same (I-Cresol 0.15 0.05 0 199 1.0
ratio for the pinched-in section below the feed plate. It has ni-Cresol 0.30 ... 0.449 n ,063
Xylene 0.15 ... 0.224 n . 394
already been pointed out that this leads to a quadratic solu- Hesidue 0.05 ... 0 .n i 5 0.087
tion for the minimum reflux ratio. Thus for case I,
D 33.2, IT7 = 66.8 per 100 moles of feed. By Equation B
=
1 - Xhh - xh - n 51

(3 =
h
xlih
1 =("> Xhh n
=
4 = 0.35,/0.15 = 2.33.
Equation 10 will be more satisfactory than Equation 9 since
x1A there are no components more volatile than the light key com-
1 - 511. - zx* - v 21 ponent.
h 1 rir a first trial, neglecting the a h terms, (g) (*) xhk
On substituting the \yalues of Equations 2 and 4 and re-
arranging, (0.663) (0.449) + (0.394)(0.224) (0.087) (0.076) = o.607
B=
____ 0.597 0.866 + 1.173
[(g)I + J] + d(gI + J)' - 7 (7, - G H )
2
(15)
I n case 11,below the feed plate only the light key and less (O/D)," = 5.5
volatile components are considered, whereas above the feed
plate only the heavy key and more rolatile components are Using this value of (O/D),*,the neglected terms can be calcu-
considered : lat,ed. By Equation 2, xfi;can be approximated as
1 - XhL - xh (0.95) ( l l 5 . 5 )
("") =
1 -
Xi k
- s xi
.rik = -
0.26 + 1.26(0.05/0.25)(1/5.5) = 0.57
zhk m 511;
=("> xhk n
=
5ik
1
The value of x h h in the last term of the denominator was a-
The solution of this equation is the same as Equation 1.5, but sumed to be 0.25, but this term makes little difference in 3: .
instead of I and J , I ' and J', respect'ively, are used. Then
The method of calculating the minimum reflux ratio by
t,liese equations will be illustrated by the following examples.

ESARIPLE 1, A-B-C mixture; feed enters such that I:n =

These corrections give a R value of 0.594 and
v,>l:
--
Feed
l l o l e Fraction-?-
Distillate Residue
Yulatilities Relative
t o Component B
.I 0.10 0.95 n ,00556 2.0
B 0.10 n.n5 0,10556 i n
c 0.80 .. n ,5589 n
(O/D)., = 5.57
D 10, Tt' = 90 per 100 moles of feed.
= By Equation 6,
@ = 1. By Equation 9, This value is essentially the same as before the recalculation
was macle, and in general the correction can be neglected un-
( 0 9 - 0.05) less the difference between alk and a h i r is quite small.
(); +1- (2 - 1) (2 + 1) = 2.7 Equation 9 gives a value of ( O / D ) mequal to 5.4, and Equa-
tion 11 gives ( O / D ) , equal to 5.55. Using the assumptions
( O / D ) , , = 1.7 of case 11, by Equation 5:
AUGUST, 1940 INDUSTRIAL A S D ESGINEERIKG CHEhlISTRY 1103

Zy =
h
-[
66.8 (0.663)(0.449)
J77n~
(0.597) +
( 0 . 3 9 4 )(0.224)
_ 0.866 _
+ ~
limits for the true value but the limits are much wider than
those obtained by the use of Equation 9 or 10 together with
Equation 13 or 14.
1.173
EXAMPLE 3, gasoline qtabilization; example from Robinson
Assuming (O/D),, = 5 , then T-,,, = 199.2 and
and Gilliland (5, page 176) :
zy = 0.201; Z y = 0
h 1 7- Alole Fractioii- \'olatilities Relative
Feed Di.tillate Redidue to n-C1Hu
From Equation 12, c Ha 0 02 0 0683 26
C1H6 0 10 0 1(16 G
C3Hb 0 06 0 190 2.6
1 C3Hs 0 125 0.390 0 .'do.? 2 .3

+' =
35 + ( r o m j- 1) (66.8)(0.0524) = 1.95 Iso-CdHm
n-CI
0 035
0 1.50
0 022
0 019
0.041
0.211
1.2:1
1.0
1 C6 0 152 ... 0 222 0.4,3
C b 0 113 ... 0 1H3 0.18
l 5 + (1 - 0.204 CT 0 090 ... 0 132 0.08
C8 0 08.3 ... 0 124 0.03
Residue 0 070 ,.. 0 10" 0.00.j
Using Equation 13,
[(0.95/1.95) - 0.05][(1.26)(1.95) + 11 = j.8 D = 31.6, TV = 68.4 per 100 mole; of feed; feed enters such
(); +1 = 0.26 that I??,,- i7,&= 0.42 F .
This case differs from the previous examples in t h a t both
(O/D)r,z= 4.8
light and heavy components are present, and in the fact that
Recalculating 4' for ( O / D ) , , = 4.8 gives a value of 1.94 but the component isobutane is between the two key components
does not change the value of 4.8 significantly. Equation 14 propane and n-butane. The distribution of the isobutane
gives a value of (O,lD), equal to 4.7. given is that used a t a value of ( O / D ) = 1.5 from Robinson
Equation 15 gives a value of (OID),, equal to 6.0 for case I and Gilliland, and this distribution will change as the reflux
and 4.7 for case 11. By Equation 1, ratio is varied; but since the amount of this component is
small, it mill not greatly influence the results and will be
+ 0.95
1'26 (2) 0.35(0/0),
0.15(O/D),
=
(OID), = 8.83
+ 0.05 allowed to remain a t the values given. In using the equations
there is the problem of whether isobutane should be a light or
heavy component; but since its relative volatility is nearer to
that of the heavy key component than that of the light key
Detailed stepwise plate calculations indicate that the true component, it will be considered as a heavy component.
minimum reflux ratio is approximately 5.2. Equations 9, 10, Assuming a value of (OID),, = 0.7, J',, = 53.7, V,,, = 9 5 . 7 ,
and 11 give values about 6 per cent too high, and Equations 13 O,, = 22.1, and O,,, = 164.1. By Equation 4,
and 14 give values about 8 per cent too low. These percent-
age deviations from the true value are a function of the con- z h
(2.3)(0.21 1) (68.4/164.1) = o. 156
centrations of the components other than the key components 1.3
for the middle portion of the tower; the deviations are higher
when these concentrations are high. The values given by (26)(0.0633) (6)(0.316) 2.6(0.19) , o.6,
A =
+ +
~

Equation 15 show higher percentage deviations fro? the true 25 +4.5 + 5 1.04 + 1.6 0.45
minimum reflux ratio than the other equations.
The value given by Equation 1 is again much higher than B =
(1.25)(0.041)
1.07 +
(0.43) (0.222)
1.87 +
(0.18)(0.165)
2.12
+
the true value. I n the derivation of Equations 13 and 14 it
was pointed out that they could be used with+ calculated from (0.08)(0.132) (0.03)(0.124) (0.005)(0.102) = o.l 19
Equation 6 instead of +'
for Equation 12, but that the values 2.22 + 2.27 + 2.295
ryere liable to be erratic. Using Equation 13 with equal to + By Equation 6,
2.33 gives a value for ( O I D ) , of 4.4, whereas Equation 14
gives ( O I D ) , = 6.3; and in general results of this type will be + [(53.7/95.7) - 1](68.4)(0.0025) = 1.43j
obtained. The equation based on conditions above the feed
will give values on one side of the true value while the equation
' 12.5
= 15.0 + [(53.7/95.7) - 1](68.4)(0.211)
based on conditions below the feed will give values on the Since R is less than -4,Equation 9 will be used in preference t l )
opposite side of the true value. Thus Equations 13 and 14 Equation 10. By Equation 9,
+
can be used with instead of +' to give upper and lower limits
for the minimum reflux ratio, but in general the region defined
is broader than the region defined by Equations 9 or 10 with +
and Equations 13 or 14 withqb'.
If the feed to the column had been a vapor such that O,, =
Q,,,,the calculations would require trial and error to obtain + (O/D),, = 0.68
a n d 4'.
Assuming ( O I D ) , for this case to be 7.0, then Vrt= 266 and Calculating the lower limit by Equation 13, and assuming
= 166. By Equation 6 , + = 1.61.
(O/D),, = 0.4
The value of ( O / D ) , by Equation 10 is calculated to be V,L = 44.2; 0,, = 12.6
7.03, and the assumed value of ( O I D ) , is satisfactory; but if V,, = 86.2; O,, = 154.6
the difference between the assumed and the calculated values
had been larger, a recalculation mould have been necessary. By Equation 5 ,
Equation 9 gives a value for (O/D),, of 6.8 and Equation 13
gives a value of (OID),, equal to 6.3, which indicates that the
true minimum reflux ratio is between 6.3 and 7.0. Equations
13 and 14, together with r$ instead of +',
give values for ( O / D ) ,
of 5.6 and 7.0: and as indicated before, this method gives
 1106 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 32, NO. 8

zy = 26(0.0633)(1/1.4) 6(0.316)(1/1.4) xwh

1 25 +
0.105 + +
5 0.105 +
2.6(0.19)(1/1.4) = o.52
1.6 + 0.105
zy = 0.119
h ai - ahk + al -

By Equation 12,

12.5 + [( g ) (s9) - 11(68.4)(0.0025)

Q/ =
15.0 + [(46) (w9) - 1 1 (68.4)(0.211)
= 2.75

From Equation 13,

( O / D ) , = 0.39

By a similar calculation, Equation 14 gave a value of 0.42

for (OID),. These calculations would indicate that the true
minimum reflux ratio would be between 0.39 and 0.68.
Equation 15 gives upper and lower limits for the minimum
reflux ratio of 0.79 and 0.39, respectively. Stepwise plate
calculations indicated that the actual value was approximately
N = [elkc + ahkl

0.53. 11” = [elkc’ + ahk]

The use of Equation 1 gives a ralue of ( O / D ) , equal to 1.5, 0 or 0, = moles of overflow from a plate above feed plate, per
which is much higher than the correct value. unit time
0, = moles of overflow from a plate below feed plate, per unit
Conclusions time
Equation 9 or 10 when used with Equation 6 gives values
for the minimum reflux ratio equal t o or greater than the true
minimum reflux ratio; this is a conservative method of calcu-
lating the ratio. The use of Equation 13 or 14 with Equation
T =
(xwhk - 7)
12 gives calculated values that are equal to or less than the b l k - Uhk)
true minimum reflux ratio and serves as a lower limit for this
quantity. Equation 15 can be used to calculate the upper V or V , = moles of vapor t o a plate above feed plate, per unit time
and lower limits for the minimum reflux ratio, but in general,
V, = moles of vapor to a plate below feed plate, per unit time
W = moles of residue, or bottoms, per unit time
Equations 9 to 14 are easier to use and give more sharply de- p = (OTh- O,)/F
fined limits, and for these reasons the latter equations are pre- z = mole fraction in liquid
ferred to Equation 15. Equation 1 gives values that are much y = mole fraction in vapor
z = average mole fraction
higher than the correct values in most cases. ( O / D ) , = minimum reflux ratio
a = relative volatility
Nomenclature Q = term defined by Equation 6
6’ = term defined by Equation 12
Z = summation
z = sum for all components less volatile than heavy key com-
h ponent
= sum for all components more volatile than light key com-
1 ponent
Subscripts
D = distillate
F = feed
i = intersection of operating line equations
1 = components more volatile than light key component
lk = light key component
D = moles of distillate per unit time h = components less volatile than heavy key component
hk = heavy key component

Literature Cited
F = moles of feed per unit time (1) Fenske, IND.ENQ.CHEM.,24,482 (1932).
(2) Gilliland, IND.ENQ.CHEM., 32, 918 (1940).
(3) Lewis and Matheson, Ibid., 24,494(1932).
(4) McCabe and Thiele, Ibid., 17,605 (1925).
(5) Robinson and Gilliland, “Elements of Fractional Distillation”,
New York, McGraw-Hill Book CO.,1939.
(6) Underwood, Trans. I n a t . Chem. Enurs. (London), 10, 112 (1932).