INDUSTRIAL AND ENGINEERING CHEMISTRY

1480
h,

= heat transfer coefficient be&;veen gas and solid, B.t.u. per

h,

=
qQ =

qs

q.

=
=
=
=

fb

tg
t,
=
tw =
A&,> =
p
=
ni, n, r

hour per square foot per F.

heat transfer coefficient between bed and wall, B.t.u. per
hour per square foot per a F.
thermal conductivity of gas, B.t.u. per hour per square
foot per O F. per foot
height in bed, inches
rate of heat flow to gas, B.t.u. per hour
rate of heat flow t o solid, B.t.u. per hour
rate of heat flow t o wall, B.t.u. per hour
cross-sectional area of tube, square feet
temperature of bed, F.
temperature of gas, F.
temperature of solid, F.
temperature of wall, O F.
mean temperature difference, F.
viscosity of gas, pounds per hour per foot
= exponents dimensionless equation
LITERATURE CITED

(1) Baerg, A , , Klassen, Jr., and Gishler, P. E., Can.J . Research, 28,
287-307 (1950).
(2) Rrinn, M . S., Friedman, S. J . ,Gluokert, F'. A . , and Pigford, R. L.,
1x0. ENG.CHEM.,40, 1050-61 (1948).
(3) Dalla Valle, J. M . , "Micromeritics," 2nd ed., pp. 331, 555, riew
York, Pitman, 1948.

Vol. 44, No. 6

(4) Deitz, V. K., and Robinson, H. E., IND.

ENG.CH
(1948).
(5) Gamson, B. W.,
Chem. Eng. Progress, 5, 19 (1951).
(6) Gamson, B. W., Thodos, G., and Hougen, 0. A , , Tians. Am.
Inst. Chenz. Engrs., 39, 1 (1943).
(7) Hurt, D. hf., IND.
ENG.CHEM.,35, 522 (1943).
(8) IND.
EKG.CHEM.,41, 1098-1250 (1949).
(9) Kettenring, K. N., Manderfield, E. L., and Smith, J. bI.,
Chem. Eng. Progress, 4, 139 (1950).
(10) Leva, M . , and Grummer, M.,
I X D E N GCHEM.,
.
40,415-9 (1948).
(11) Leva, RI.,Weintraub, M.,
and Grummer, M., Chem. Eng. Progress, 3, 563-72 (1949).
(12) Leva, M . , Weintraub, M., Grummer, M., and Clark, E. L.,
IND.
ENG.CHEM.,40, 747-52 (1948).
(13) Levenspiel, O., and Walton, J. S., Am. Sac. Mech. Engrs., Bound
Proceedings of Heat Transfer and Fluid Mechanics Institute,
Berkeley, Calif., pp. 139-43, May 1949.
(14) Lof, G. 0. G., and Hawley, R.W., IND.
ENG.
CHEM.,40,1061-70
(1948).
(15) Luckenbach, F. A., U. S.Patent 210,793, Oficial Gaz. C . S.Pat.
Ofice, 14, 890 (1878).
(16) Mickley, H. S., and Trilling, C. A., IND.
EXG.CHEW,41, 113747 (1949).
(17) Simon, R. H., Ph.D. thesis, Oregon State College, 1949.
(IS) Singer and Wilhelm, Chem. Eng. Progress, 4 , 343 (1950).
(19) Toomey, R. D., and Johnstone, H. F., paper presented at the
annual meeting of the Am. Inst Chem. Engrs., Columbus,
Ohio, Dec. 6, 1950.

RECEIVED
for review July 30, 1951.

!lCCEPTED

January 3, 1962

Holdup-Charge Ratio in
istillation
I

ARTHUR ROSE AND VICTOR J. O'BRIEN, JR.'

T H E P E N N S Y L V A N I A S T A T E C O L L E G E , STATE C O L L E G E , P A .

T WAS t,he purpose of this investigation to obtain experimental

data indicating the effect of the more important variables in

ternary batch distillation as well as to review and study various
methods of calculating the course of such distillations. In addition, it was of interest to determine whether the generalizations
deduced from prior binary studies were applicable to multicomponent systems.
A theoretical analysis was made of possible methods of calculating multicomponent' batch distillations under conditions of
both appreciable and negligible holdup. It was concluded from
this that, the only practical means available is the numerical
procedure of Rose, Johnson, and Williams ( 5 ) , regardless of
15-hether holdup is appreciable or negligible.
The experimental studies were limited to t'he system n-heptane-methylcyclohexane-toluene. The normal boiling points of
these are 98.4", 100.9", and 110.6" C., respectively, and the relative volatility ranges in the ternary are 1.07 to 1.15 and 1.1to 1.6
for the first and last pair, respectively. Complete vapor-liquid
equilibria >\-ereavailable and a convenient method of analysis had
been perfected by Kirk (I).
The laboratory-sized column used for the distillations had an
internal diameter of '/z inch and was packed x+th '/IB-inch 36gage stainless steel helices to a height of 5 feet. The column
shoTyed about 80 theoretical plates under total reflux xyith nheptane-methylcyclohexane near the maximum throughput of
400 ml. of methylcyclohexane per hour. The packing holdup
1 Present address, Standard Oil Co. of Indiana, Research Laboratory,
Whiting, I n d .

was approximately 60 ml. and the charge capacity was 5 liters, so

t h a t the rat'io of holdup (usually expressed as a per cent and called
per cent holdup or simply holdup) could be varied from 1.5p/,
to any desired large value by varying the size of the charge.
Column holdup was determined under conditions closely approximating the ternary distillations of this n-ork. This vas
done by adding nonvolatile diocA3-1phthalate to a ternary charge
and determining holdup throughout the-course of a batch distillation, done for the special purpose of determining holdup during
actual distillation. Holdup values were calculated by inat'erial
balance based on the quantity of charge and the concentration of
nonvolatile dioctyl phthalate in the charge, and its concentration
in a sample removed from the still at some particular time during
the distillation. The results of four of these holdup dist'illations
sho\yed that the molal column holdup could be considered to be
substantially constant for the column and components of this
work.
Twent,y-five ternary batch dist,illat'ions and four binary batch
distillat,ions were conduct'ed. Details are tabulat'ed in Table I.
Five of the ternary runs LTwe duplicates of earlier runs. These
check runs sho\+-ed that small discrepancies in distillate mole
fraction and break point vr-ere present from run to run. Kone of
the discrepancies were large enough to seriously affect the interpretations or the conclusions report,ed herein. All runs were
conducted a t total reflux startup and intermittent take-off,
Material balances usually showed 1 to 2% loss, largely because of
handling and drainage for which corrections were not determined.
The two ternary charge compositions were selected for specific

INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY

June 1952

TABLE
I.

SUMMARY
ON BATCH
DISTILLATIONS
Reflux
Ratio
Mole:
Reflux/Mole
Distillate

Run
NO.

1481

Distillate
Throughput
G./Hr.

Holdup,

Material

Loss,
Wt. "/o

TERNARY
R U N S , SERIES I"

"

20
30
M O L PERCENT DISTILLED

lo

T-12
T-10
T-13
T-4
T-28
T-5
T-6
T-1

40

7.5/1
7.5/1
7.5/1
15/1
15/1
15/1
15/1
30/1
30/1
30/1
30/1

T-9

Figure 1. Comparison of Binary and Ternary Experimental Distillations

T-27
T-8

-.-- Binary
run B-5
-.-Holdup,
Binary r u n B-1
9 mole %

Ternary run T-10

4.5
9
18
4.5
4.5
9
18
4.5
9
9
18

0 54
0.78
1 36
0 75
0 47
0 84
1 91
0 89
1.05

0.80
1 72

TERNARY
R U N S , SERIES
T-18
T-24
T-34
T-23
T-21
T-25
T-17
T-26
T-22
T-20
T-19
T-36
T-33
T-35

Reflux ratio, 7.5 to 1

For charge compositions, see Table I

reasons. The one charge composition had a small proportion of

n-heptane so that the effect of total reflux startup upon the
sharpness of separation of this component was large. Then too,
most of the n-heptane was distilled before appreciable toluene
appeared in the distillate because of the small proportion of
n-heptane present. The second ternary charge composition was
selected to reverse the above effects. The effect of total reflux
startup was small, while a t the lower reflux ratios appreciable
concentrations of all three components were present a t some time
during a distillation. The experimental reflux ratios were
selected to yield both good and poor separations between components, and charge sizes were chosen to give values of holdup
likely to be encountered in the practice of laboratory distillation.
COMPARISON OF BINARY AND TERNARY DISTILLATION

One of the purposes of this investigation was to determine the

extent to which general conclusions on binary distillations might
be extrapolated to predict sharpness of separation between two
components in a ternary mixture. This was done by conducting
binary distillations and comparing the resulting component
curves with the component curves of the corresponding ternary
distillations.
Binary runs B-5 and B-1 have been plotted together with the
corresponding ternary run T-10 in Figure 1. (In the figure, the
abscissa for B-5 is the moles distilled over rather than the mole
per cent distilled; for B-7 the abscissa is moles distilled over plus
7 . This method of plotting places all the curves on the same
absolute basis and makes them directly comparable.) Binary
runs B-4 and B-2 have been plotted with their corresponding
ternary run,*T-24, in Figure 2. (Abscissa for
B-4 is moles distilled over; for B-2 it is moles
distilled over plus 30.) In these figures the
binary values -of mole per cent distilled have
W
2 BO
been scaled to a ternary basis; the number of
2
theoretical plates used was 82. The binary runs
g60
were conducted under the same reflux ratio and
z
#with the same absolute number of moles of
$40
each component in the charge as for the correD:
L
sponding ternary. Thus, the charge for binary
20
run B-5 (Figure 1) consisted of 7 parts of nB
heptane and 21.7 parts of methylcyclohexane,
0
while for the comparable ternary run, T-IO, the
charge contained these quantities of heptane and
methylcyclohexane plus 71.3 parts of toluene.
Figure 2.
It might be expected that the sharpness of separation between methylcyclohexane and toluene
would be similar for the binary runs provided
there was little n-heptane present in the distillate a t the break (Figure 1).

7.5/1

7.6/1
7.5/1
7.5/1
15/1
15/1
15/1
15/1
30/1
30/1
30/1
60/1

60/1

60/1

IIb

4.5
9
9
18
4.5
9
18
18
4.5
9
18
4.5
18
18

0.75
0.87
0.72
1.66
0.65
1.3
1.72
2.4
1.04
1.08
2.3
1.0

2.41
2.5

BINARY
RUNS, SERIES IIIc

B-5

7.5/1
7.5/1
7.5/1
7.5/1

B-1
B-4
B-2

30
10
18
13

212
310
295
278

2.96
0.71
1.78
0.56

a n-Heptane, 7 inole %; methycyolohexane, 21.7 mole % ; and toluene,

71.3 mole %.
b %-Heptane,30 mole % : methylcyolohexane, 20 mole % ; and toluene,
50 mole %.
0 B-5:
7 parts (moles) n-heptane, and 21.7 parts (moles) methylcyclohexane B-1: 21.7 arts methyloyolohexane and 71.3 parts toluene. B-4:
30 par& heptane a n a 2 0 parts methyloyolohexane. B-2: 20 parts methylcyclohexane and 50 parts toluene.

IYhen appreciable n-heptane is still present in the distillate at

the break between methylcyclohexane and toluene as in Figure 2,
the component curves cannot be expected to agree. But it is
found that the ratio of methylcyclohexane to toluene is close for
the two cases. The distillation of n-heptane and methylcyclohexane during the first portion of these ternary batch distillations
was conducted in the presence of appreciable toluene in the pot.
Evidently, the effect of this third component was not too great,
a t least in the absence of appreciable toluene in the distillate, for
the binary n-heptane-methylcyclohexane curves agree with t h e
ternary curves.

_1

ID

20

30

40

50

MOL PERCENT DISTILLED

Comparison of Binary and Ternary Experimental

Distillations

-. -.-- BinaryrunB-4
Binaryarun B-2
9 mole $40

Ternary r u n T-24

Holdup,
Reflux ratio, 7.5 to 1
For charge eompositione, see Table I

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

1482

M O L FERCENT DISTILLED

Figure 3.

---

Effect of Holdup on Sharpness of Separation

Ternary run T-12

T-10
,
-.Reflux
.- ratio,
Ternary run T-13
7.5 t o 1
Ternarv
run
_
__.
.
.

-.

For charge compositions and mole per cent holdup, see Table 1

Vol. 44, No. 6

section show that the n-heptane-methylcyclohexane component

curves are very different when the holdups were 4.5, 9, and 18%
on a ternary basis. Thus, the sharpness of separation between
two components was apparently governed by the effective
holdup-Le., the per cent of holdup based upon the absolute
amounts of the two Components under consideration in the initial
charge. The n-heptane-methylcyclohexane curves of Figure 1
also illustrate this point.
The per cent of holdup to charge capacity of several commercial fractionators was estimated by Pigford and coworkers
( 3 )to be about 1%. Such a value of holdup might appear to be
negligible, but on the basis of the above discussion this holdup
would be quite important in certain multicomponent fractionations. For instance, if two components were present in a multicomponent mixture t o the extent of lo%, the effective holdup
governing the sharpness of separation between these components
would be 10% even if the relation between column holdup and
total charge were only 1%. If the ratio of column holdup to still
capacity or total charge were 2% (still an apparently negligible
value), the effective holdup for the above two components would
be 20%. For this reason, high effective holdups can be expected
to be regularly present and t o have a pronounced influence upon
the sharpness of separation between components in a multicomponent distillation. Since it was indicated that sharpness of
separation between components of a multicomponent mixture
can often be predicted from binary data, it follows that such
binary data should be obtained under conditions of appreciable
as well as small holdup.

0
lo

Figure 4.

--

20
M O L PERCENT DISTILLED

SHARPNESS OF SEPARATIOR IY TERNARY EXPERIWEYTS

40

30

Effect of Holdup on Sharpness of Separation

Ternary run T-5

-.-Reflux
.- ratio,
Ternary run T-6
15 to 1

Ternary run T-4

For charge compositions and mole per cent holdup, see Table I

TOLUENE

10

20

30

40

M O L PERCENT DISTILLED

Figure 5.

---- -

Effect of Holdup on Sharpness of Separation

Ternary run T-1

Ternary run T-9
Ternary run T-8
Reflux ratio, 30 t o 1
For charge compositions and mole per cent holdup, see Table I

-. .-

ABSOLUTE AND EFFECTIVE IIOLDU-P

Apparently the sharpness of separation between any two components of the ternary mixture was influenced by the ratio of the
holdup t o the absolute quantities of these two components in the
mixture rather than the ratio of holdup to total multicomponent
charge.
For example, the moles of total holdup and the absolute quantities of n-heptane and methylcyclohexane were the same for the
binary and ternary runs of Figure 2. The amount of holdup to
total ternary charge was 9 % for T-24, while to the binary charge
for B-4 it was 18%. Yet the component curves are almost
identical. The ternary runs of Figure 6 discussed in the following

EFFECTOF HOLDUP.The ternary runs were conducted a t

holdups of approximately 4.5,9, and 18% based upon the initial
ternary charge. I n general, a t reflux ratios of 15 to 1 or less an
increase in holdup increased the sharpness of scpai ation between
components. ilbove a reflux ratio of 30 to 1 an iriciease in the
per cent of holdup decreased the sharpness of separation. However, the magnitude of the effect was different foi the two pairs of
components, and it was also influenced by the piesenc'r of total
reflux startup.
The effect of holdup can be studied by superimposing a number
of batch distillation curves on one graph. This has been done in
Figures 3 to 9. (In each of these figures, the number of thcoretical plates was 82 and the distillation v a s operated a t total reflux
startup.)
Considering the break between methylcyclohexane and toluene
for the distillations in which the initial charges mere 30y0 nheptane, 20% methylcyclohexane, and 50% toluene (Figures 6 to
9), it is seen t h a t there was a definite increase of sharpness of
separation with an increasing per cent of holdup a t a reflux ratio
of 7.5 to 1 (Figure 6). At a reflux ratio of 15 t o 1 (Figure 7)
increasing the per cent of holdup was beneficial, but the over-all
effect was small. When the reflux ratio was 30 to 1 there %as no
appreciable effect of holdup (Figure 8 ) , while a t a 60 to 1 reflux
ratio (Figure 9) the 18% holdup break appeared to be slightly less
sharp than that of 4.5%. Figures 3 through 5 show effects of
holdup and reflux ratio for 7% n-heptane-21.7% methylcyclohexane-71.3 % toluene mixtures similar t o those shown for 3020-50% mixtures in Figures 6 through 9.
The effect of holdup on the sharpness of separation between the
components n-heptane-methglcyclohexanecan be noted by again
referring to Figures 6 to 9. Increasing the per cent of holdup was
beneficial in these runs up t o a reflux ratio of 30 t o 1. At a reflux
ratio of 60 to 1 there seemed t o be a small but definite decrease in
the sharpness of separation a t the larger holdup.
The sharpness of separation between n-heptane and methylcyclohexane was complicated by the presence of an effect due to
total reflux startup. Such an effect occurs whenever the distillate composition of the most volatile component of a batch distil-

June 1952

INDUSTRIAL AND ENGINEERING CHEMISTRY

1483

lation initially at total reflux is much

greater than if the column were operating at the finite reflux ratio to be used
throughout the distillation. I n such a
case the distillate composition tends t o
drop more or less sharply as soon as product removal is begun in order to attain
a distillate composition consistent with
still composition and the reflux ratio employed. This occurred in the runs of
Figures 3 to 5 . Increasing the holdup
from4.5 to 9% (ternary basis) noticeably
MOL PERCENT DISTILLED
improved the sharpness of separation
between n-heptane and methylcycloFigure 6. Effect of Holdup on Sharpness of Separation
hexane, even a t a reflux ratio of 30 t o 1.
Ternary run T-18
Ternary run T-24
When the holdup was increased from 9 to
Ternary run T-23
1S%, there was little improvement at
For charge compositions, reflux ratios, and mole per cent holdup, see Table I
reflux ratios of 15 and 30 to 1. This
was probably the result of depletion of
the n-heptane still pot composition at
t h e highest per cent of holdup (actually
a n effective holdup of 60%) so t h a t the
initial distillate mole fraction of nheptane was lower than at lesser values
of holdup. I n the absence of such a n
effect-Le., at valuee of holdup of 9% or
less-the data indicate t h a t increasing
t h e per cent of holdup will be beneficial
t o sharpness of separation a t much
higher reflux ratios than 30 t o 1.
These data show t h a t the general
MOL PERCENT DISTILLED
conclusions regarding the effect of holdup
Figure 7. Effect of Holdup o n Sharpness of Separation
in binary mixtures are applicable to
ternary mixtures. Colburn a n d
Ternary run T-21
TernaryrunT-27
Stearns (I), Pigford, Tepe, and Garrahan
Ternary run T-26
For charge compositions, reflux ratios, and mole per cent holdup, see Table I
(S), and Rose et al. (5-7) have indicated
or shown experimentally that increasing
the per cent of holdup could have either
100
a beneficial, detrimental, or little effect
w
upon the sharpness of separation between
!jeo
components of a binary system. The
I
data of this investigation substantiate
55 6 0
this for a ternary system and again show
B
t h a t the effect of holdup may be large in
k
batch distillation.
EFFECTOF REFLUXRATIO. In the
absence of appreciable effect of total reJ 20
8
flux startup increasing the per cent of
holdup had little influence on the sharp0
10
20
30
' 40
60
ness of separation between components
MOL PERCENT DISTILLED
at a reflux ratio of 30 to 1. Above this
Figure 8. Effect of Holdup on Sharpness of Separation
value of reflux ratio, increasing holdup
Ternary run T-22
was detrimental, while below this reflux
TernaryrunT-20
ratio increasing holdup was beneficial.
Ternary run T-19
Reflux ratio, 30 t o 1
Prevost ( 4 ) first observed this effect of
For charge compositions and mole per cent holdup, see Table I
reflux ratio while studying the binary
batch distillation of methylcgclohexaneferent. I n addition, no effect of charge composition was obtoluene in columns of 20 and 40 theoretical plates. He defined the critical reflux ratio as the ratio where holdup had no
served. If further experimental data should substantiate t h a t
effect on, the sharpness of separation.
critical reflux ratio depends only on the number of theoretical
Prevost believed t h a t the critical reflux ratio would depend not
plates, then the concept of a critical reflux ratio would become a
only on the number of theoretical plates of the column, but also
powerful tool for predicting the effect of increasing t h e per cent of
on the charge composition and relative volatility of the mixture
holdup upon the course of a batch distillation. The critical
being distilled. The data reported herein indicate t h a t the critireflux ratios obtained by Prevost were roughly 24 to 1 and 9 t o 1
cal reflux ratio, R,, is independent of the relative volatility. I n
in 40- and 20-plate columns, respectively. The data of this paper
the absence of effects caused by total reflux startup, it was obshow a critical reflux ratio of approximately 30 t o 1 in an SO-plate
served that R, was the same for both pairs of components, ncolumn. This would indicate t h a t R, for a given column might
heptane-methylcyclohexane and methylcyclohexane-toluene, albe expected t o be about one half of the number of theoretical
plates at total reflux of the column.
though the relative volatilities of the pairs were considerably dif-

--.-.--

---. .-

8"

---. .-

INDUSTRIAL AND ENGINEERING CHEMISTRY

1484

VOl. 44, No. 6

TERNARY EXPERIMENTAL vs. BIKARY

CALCULATED CCRVES

100
W

4 s stated, the shapes of the coniponent' curves for each of two experimental
ternary distillations were closely equivag60
P
lent to the corresponding curves of two
texperimental binary distillations performed under identical experimental conditions. In these ternary distillations
.J eo
the holdup on a ternary basis \vas 9%.
I
It, n-as of interest, therefore, to compare
0
10
PO
30
40
W
some of the other experimental ternary
MOL PERCENT DISTILLED
distillations for which the per cent of
Figure 9. Effect of Holdup on Sharpness of Separation
holdup was the smallest with binary
Ternary ruu T-36
curves
calculated on the assumption of
.. Ternarj r u n T-35
Reflux ratio, 60 to 1
negligible holdup. Such binary calculaFor charge compositions and mole per cent holdup, see Table I
tions \\-ere made for both the n-heptanemet,hylcyclohexane and methylcyclo100
hexane-toluene systems. In these binary
calculations the relative volatility of the
w
system n-heptane-methyl c y cl o h e x a n e
580
-I
was taken as 1.075. The relative vola!bo
tility of the syst,em methylcyclohexaneE
toluene varied and the calculations were
Imade with the aid of an equilibrium dia2"
gram plotted from the binary data of
Kirk (2). Aictually, the relative volaeo
I
tility of the system n-heptane-methylcyclohexane was not constant in the pres0
10
20
30
40
50
of toluene, but varied from 1.075
ence
MOL PERCENT DISTILLED
t,o 1.15. The relative volatility of methylFigure 10. Effect of Reflux Ratio at High Percentage of Holdup
cyclohexane-toluene in the ternary mixT-23
ture v a s close to that of the binary and
T-26
varied from 1.1 to 1.6. The binary cal-. .- T-19
. . T-35
culation procedure was that described by
Holdup, 18 m o l e %
For reflux ratios and charge rompositions, see Table I
Smoker and Rose ( 8 )and the calculations
Tvere made using the same mole rat,ios
and reflux ratios a8 for the corresponding
IO0
t,ernary distillations.
w
n-Iep t , a n e - m e t hylcyclohexane no$80
holdup binaries were calculated for comi
F
parison x-ith the 4.5% holdup ternary
E60
runs at reflux ratios of 15, 30, and 60 to 1
P
Iand are plotted on a ternary basis in
540
Figures 12, 13, and 14, together with
a
the experimental ternary runs, using 82
If
-1 20
theoretical plates. (In order to make
8
the binary curves directly comparable
_~___
with t,he ternary curves, the abscissa for
0
10
30
40
50
the n-heptane-methylcyclohexane binary
MOL PERCENT DISTILLED
curve has been plot,t,ed as moles disFigure 11. Comparison of Calculated Binary and Experimental Ternary Batch
tilled orer, and that for the methylcyDistillation Curves
clohexane-toluene binary as moles disExperimental T-18
. Calculated
for toluene from methylcs clohexane-toluene binary, assuming n o holdup
tilled over plus 30.) Agreement is
Binary charge composition. 20.0 moles of methylcyclohevane and 50.0 moles of toluene
surprisingly good c o n s i d e r i n g t h a t
For ternary charge composition, reflux rntio, and mole per cent holdup, see Table I
t h e e x p e r i m e n t a l effective holdups
were 9%.
Both Prevost ( 4 ) and Pigford and coxorkers ( 5 ) noted for
The methylcyclohexane-toluene binary batch distillation
binary systems that when holdup %-aslarge the effect of reflux
curves m r e calculated for the reflux ratios of 7.5 and.15 to 1 .
These have been plotted with the corresponding 4.5% holdup
ratio on the sharpness of separation between components TTas
ternary runs in Figures 11 and 12. ( I n Figure 11, in order t o
much less pronounced than RThen holdup was small. This was
make the binary curve directly comparable with the ternary
also indicated by the ternary data of this thesis. However, it
curves, the abscissa for the binary is plotted as moles distilled
shouId not be inferred that reflux ratio can be neglected under
over plus 30, instead of mole per cent distilled.) I n these t'iT-0
conditions of holdup of perhaps 20 to 30%. Thus, the runs of
cases there is almost no resemblance between the calculated and
Figure 10, using 82 theoretical plates and operating a t total reflux
experimental curves. The effective holdups of the ternary runs
startup, show a marked effect of reflux ratio on the sharpness of
were 6.491;. Although it might appear that some error mas made
separation between n-heptane-methylcyclohexane when the
in the calculations, none could be found. These results, then,
holdup was 18% on a ternary basis (effective holdup 36%).

80

_I

5"
E

--

i
_I

--. ..

-. -

INDUSTRIAL AND ENGINEERING CHEMISTRY

June 1952

cast doubt on the advisability of attempting to predict sharpness of separation

from no-holdup calculations when the
effective holdup is anything but negligible. Further experiments a t successively lower valuea of holdup should be
made to confirm the large difference between calculated no-holdup curves and
experimental curves a t 6% holdup. Or
alternately, the procedure of Rose, Johnson, and Williams (6) should be used to
calculate batch distillation curves under
holdup conditions of less than 6y0.
CONCLUSIONS

1485

100
W

5 eo

di j m
E
IE40

!? 20
-I

I
0

lum 1-1-11
IO

YflmLCVCLOWfXAMf

PO

30

[Tl__ 1

1 I r";?'ry,/

40

60

MOL PERCENT DISTILLED

Figure 12. Comparison of Calculated Binary and Experimental Ternary Batch

Distillation Curves

--. -.--

Experimental T-21
Calculated n-heptane-methylcyclohexane
Calculated methylcyclohexane-toluene
Binary charge oompositions. 30.0 moles of n-heptane and 20.0 moles of methylcyclohexane:
20.0 moles of methylcyclohexane and 50.0 moles of toluene
For ternary charge compositions, reflux ratio, and mole per cent holdup, see Table I

The general effects of holdup in ternary

batch distillation were the same as observed for binary systems (3, 4,7). The
effect of increasing the per cent of holdup
was found to be beneficial, detrimental,
or of no effect upon the sharpness of
separation between components of a ternary batch distillation, depending on
the reflux ratio.
In the absence of total reflux startup
effects, it was found that holdup was
beneficial a t reflux ratios of 7.5 and 15 t o
1,detrimental at reflux ratio of 60 to 1,
and exerted no effect when the reflux ratio
was 30 to 1. This was true of the separation of both n-heptane-methylcycloMOL PERCENT DISTILLED
hexane (relative volatility, 01 = 1.08 t o
Comparison
of
Calculated
Binary and Experimental Ternary Batch
Figure
13.
1.15) and methylcyclohexane-toluene (a
Distillation Curves
= 1.10 to 1.60). The reflux ratio of 30
Experimental T-22
t o 1, then, was the critical reflux ratio
Calculated n-heptane-methylcyclohexane
Binary
charge composition. 30.0 moles of n-heptane and 20.0 moles of methylcyclohexane
as defined by Prevost (4) for this column
For ternary charge compositions, mole per cent holdup, and reflux ratio, see Table I
of 82 theoretical plates.
The effect of holdup was complicated
100
by total reflux startup. When total reflux startup effects are present, the disW
tillate composition is much higher in the
80
most volatile component a t the start of
d
L
t h e batch distillation than it would be if
ijw
the column were operating a t the reflux
z
Iratio t o be used throughout the distillaE40
tion. I n such a case the mole fraction
of the most volatile component tends to
J eo
drop sharply, and the per cent of holdup
I
has a pronounced effect upon the shape
of the batch distillation curve. In the
0
IO
20
30
40
so
MOL PERCENT DISTILLED
presence of this effect it was found that
increasing holdup was beneficial t o the
Figure 14. Comparison of Calculated Binary and Experimental Ternary Batch
Distillation Curves
sharpness of separation between nheptane and methylcyclohexane in the
Ex erimentalT-36
Cafculated n-heptanemethylcyclohexane
ternary mixture at reflux ratios of 7.5,
Binary charge composition. 30.0 moles of n-heptane and 20.0 moles of methylcyclohexane
15, and 30 to 1.
For ternary charge composition, mole per cent holdup, and reflux ratio, see Table I
A comparison of the batch distillation curves of the ternarv and binarv
compared with the corresponding experimental ternary cases in
runs conducted under identical conditions of reflux ratio and
which all variables were the same except the per cent of holdup.
absolute charge of each component showed that the separaWhen the effective holdup of n-heptane-methylcyclohexane in the
tion between the two components of the binary was similar t o
experimental ternary distillations was 9%, the experimental curves
the separation of these two components in the ternary, proagreed well with the binary curves calculated a t reflux ratios of 15,
vided that only these two components were present in the ternary
30, and 60 t o 1. However, the experimental curves of methyldistillate in appreciable quantity.
cyclohexane-toluene in which the effective holdup was 6% did not
A number of binary batch distillation curves were calculated
agree with the binary calculated curves a t reflux ratios of 7.5
for the systems n-heptane-methylcyclohexane and methylcycloand 15 to 1.
hexane-toluene assuming negligible holdup. These curves were

--5

----

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

1486

The binary-ternary comparisons also indicated that the sharpness of separation between two components must be governed by
the effective holdup-that is, the per cent of holdup based on the
absolute amount of the two components under consideration in
the init,ial ternary charge. Since tsvo components may constitute a small portion of a multicomponent charge, large effective
holdups and, consequently, large effects on separation can be
expected t o be regularly present in multicomponent batch distillation.
ACKNOWLEDGMENT

Grateful acknowledgment is made to the Shell Oil Co. and Research Corp. for financial support that made this work possible.

Engrnyring

Vol. 44, No. 6

LITERATLRE CITED

(1) Colburn, A. P., and Steams, R. F., T r a n s . Am. Inst. Chem. Engrs.,
37, 291 (1941).

Kirk, N., Ph.D. thesis, The Pennsylvania State College, 1946.

(3) Pigford, R. L., Tepe, J. B., and Garrahan, C. J., IND.ESG.
CHEM., 43, 2592 (1981).
(4) Prevost, C., M.S. thesis, The Pennsylvania State College, 1948.
(5) Rose, Arthur, Johnson, R. C., and Williams, T. J., IND.ENG.
CHEM.,42, 2494 (1950).
(2)

(6) Ibid., 43, 2459 (1951).

(7)Rose, Arthur, Williams, T. J., and Prevost, Charles, Ibid., 42,
1876 (1960)
(8) Smoker, E. H., and Rose, Arthur, Trans. Am. Inst. Chem. Engrs.,
36, 285 (1940).

A C C ~ P T EJanuary
D
22, 1952.
Presented before the X I I t h International Congress of P u r e and Applied
Chemistry, S e w York, September 1961.

RECEIVED
for revieiv August 9, 1951.

Extraction of Mercaptans from

Process
development

Distillate
R.

L. YAHNME, J. H.KRAUSE, AND G. H. WEISEMANN

RESEARCH DEPARTMENT, STANDARD OIL CO. (INDIANA), WHITING, IND.

IRGIN light distillate fuel obtained from high-sulfur crudes

has a high mercaptan content and consequently an unpleasa n t odor. This oil boils in the range of 330" to 580" F. and contains 0.08% mercaptan sulfur. T o make this oil satisfactory for
use as a domestic heating fuel, it is necessary to remove the mercaptans or convert them t o compounds having less offensive odor.
Extraction processes employing sodium hydroxide and methanol
have been reported by other investigators for removing mercaptans from gasoline ( I ) and for improving the color stability of
cracked distillate fuels ( 2 ) . Since the mercaptans present in
virgin light distillate fuels are higher in molecular weight and more
complex structurally than those found in gasoline, they behave
more Iike hydrocarbons and are much less susceptible to extraction with a basic solvent. Nevertheless, the effectiveness of
caustic and methanol as a solvent for mercaptans \Tarranted a
detailed investigation of the extraction of high boiling distillate
with solvents of this type. In order to overcome the odor problem, special emphasis had to be placed on removal of the maximum amount of difficultly extractable mercaptans. Extensive
bench-scale and pilot plant studies have led to the development
of a continuous process in which operating conditions and solvcnt
composition are markedly different from those used in previous
processes.
BENCH-SCALE STUDIES

Bench-scale experiments were conducted to explore such fundamental variables as temperature, solvent composition, and
solvent-oil ratio. In viay of the high cost of methanol recovery, a
major objective was to obtain efficient extraction mith the minimum amount of methanol in the solvent.
The bench-scale studies were performed batchwise in glassware.
Generally, 1 liter of the oil and the desired quantity of solvent
were mechanically agitated for 15 minutes in a 2-liter flask
equipped with a thermometer, a heating mantle, and a stopcock
a t the bottom to facilitate draining; a stream of nitrogen was
bubbled through the mixture to prevent oxidation. Except when
the solvent-oil ratio was being investigated, the oil was twice
extracted with 20y0 by volume of fresh solvent.

Properties of the virgin light distillate employed in the present

studies are shown in Table I. On the basis of mercaptan sulfur
content and an average mercaptan molecular weight of 170, this
stock contained about 0.4% mercaptans by volume and had a
mercaptan number of 67. The term "mercaptan number" denotes
mercaptan sulfur content in milligrams per 100 ml. of sample.

TABLE
I. FEEDSTOCK
INSPECTION
DATA
(Virgin light distillate fraction from high-sulfur crude, prewashed mith dilute
caustic)
mg./100 ml.
67
0.081

+3170.862
9.7
329
379

413
443
476

552
579

Mercaptan sulfur contents of the oil before and after treatment

were obtained by titration with copper sulfate. Total sulfur was
determined by the lamp method (ASTBI D90-41T). Color
intensities were measured u ith the Saybolt chromometer (ASTM
D156-49).

EFFECTOF TEMPERATURE.
The effect of temperature on
mercaptan removal is illustrated in Figure l a . Mercaptan
extraction efficiency decreases mith rising temperature, so that
Ion-er temperatures are preferred. However, 90" F. appears to
be a practical lower limit, because the solvent begins to solidify a t
slightly loxver temperatures. The optimum range of 90" t o
100" F. was employed in the subsequent studies.
SOLVEST COMPOSITION.To prevent solidification of the
solvent a t 90" F., 5970 aqueous potassium hydroxide requires the
addition of 19% by volume of methanol, whereas a 48% solution
of sodium hydroxide requires 28% by volume of methanol. Of
these two solvents, the potassium hydroxide not only requires less
methanol but also is much more effective for the extraction of