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LEITIS .4KD
G. L.
hfATHESON
T h e Hausbrand equations f o r binary mixtures are applied to the solution of problems irc continuous rectification of natural gasoline. Steps of the computation are outlined, the
details of which are illustrated by a specijic problem
Count the plates up from the feed plate toward the top
and down toward the bottom. Call any particular plate
above the feed plate the nth plate and below, mth. Call
the top plate the pth and the bottom plate-i. e., the stillthe wth plate. Designate the conditions referred to by
means of a subscript indicating the location of the material
in question or the point from which the material came.
Thus, y,, is the composition (mole/fraction of the component in question) of the vapor rising from the nth plate,
xf is the composition of the feed to the column, etc.
Assuming continuous operation of such a rectifying column,
Hausbrand equated input to output of a given component
in a section of the apparatus above the nth plate, as follows:
y,V,
= Tn+iOn+i
XdD
Y" = znP,/n,
494
May, 1932
I N D U S T R I A L A S D E N G I NE E R I NG C H E A I I S T R Y
0 , to
OF
DETAILSOF
PROBLEM
HYDROCARBOS
CHI+
CzHe
C3H8
CIHK
CSHIP
CEHl4 +
Total
DISTILL~TE
Moles
M o l e yo
26.0
42.9
9.0
14.9
24.96
41.2
0.61
1.0
~
...
Moles
RESIDCE
.Vole %
...
...
...
0.04
16.39
11.0
100.0
39,43
0: 1
41.6
27.9
30.4
100.0
...
60.57
195
...
12.0
...
__
STEP 2. At the temperature of the condenser the pressure must Le such that the overhead ga.j or distillate is a t
its dew point, since it was separated from a liquid condensed
from it by cooling at constant pressure. Therefore, the partial pressure of each component in the gas must of necessity
equal the partial pressure of that same component in the
liquid from which the gas was last separated, and with which
it was in equilibrium. Kow a t the effective condenser
temperature, 294" K., the pressure of pure ethane is 38
atmospheres, of propane 8.8, and of butane 2.2. Consequently, one can write the following equations:
pz = 3822 = 0 . 1 4 9 ~
p , = 8 . 8 ~ 3= 0 . 4 1 2 ~
pa = 2.224 = 0.01 T
Furthermore, neglecting the solubility of methane and permanent gases in the liquid, the sum of the mole fractions
must obviously be unity-i. e., x~ x3
z4 = 1. Solving
these equations, one obtains s = 18.1 atmospheres, which
is the necessary operating pressure on the condenser, and
which, neglecting pressure drop through the colunin, is the
pressure throughout the apparatus. From the above calculations, 100 x2 = 7.1 mole per cent ethane in the liquid condensate, 100 z3 = 84.7 per cent propane, and 100 x4 = 8.2
per cent butane.
STEP3. Since, from the condenser on this equipment,
the final overhead gas leaves in equilibrium with the total
condensate, the figures just given also represent the composition of the reflux to the column.
STEP 4. Assume a reflux equal to double the amount of
overhead vapor. On the basis of 100 moles of distillate,
there will therefore be 200 moles of reflux. Consequently,
the vapor rising into the partial condenser from the top
plate will have the composition shown by the following table :
+ +
CHI = 4 2 . 9
C?.Ho = 1 4 . 9
CSHO = 4 1 . 2
CiHio = 1 . 0
Total moles
42.9
29.1
210.6
17.4
300.0
+
14.2 =
++ 169.4
=
16.4 =
?&
14.3
9.7
70.2
5.8
-
100.0
P
64
17
4.65
0.027
0.747
0.226
1 ,000
I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R I'
496
VOI.
24,
NO.
Pmz
=
Pax3 =
Pmr =
FIGURE1. CONCENTRATION
GRADIENT
THROUGH
CaHs
C4HlO
CaHiz
CBHl4'
0.1
41.6
27.9
30.4
t =
413.5' K.
80
32.2
13.3
0.08
13,39
3.71
0.90
18.08
2.95
90
21.5
6.2
0.014
0.536
0.450
Y (as % )
0.44
74.06
20,52
4.98
100.00
x,-,
P,T'
= zm -
TO
+ zul
= 0.0429xmP,
However, for
1 This temperature IS above the crltical point of ethane.
the purpose of romputing t h e small amount of ethane which wlll dlssolve
i n the liquid under theae conditions, in the absence of exact d a t a as t o the
solubility, it is allowable to extrapolate the vapor pressure curve to the
temperature i n question. The figure is rough but undoubtedly sufficiently
accurate for the purpose In hand
+ 0.2237~,
Since the temperature of the still is known, the corresponding values of P are determined, and one can calculate the
composition of the overflow from the plate above directly
as shown by the equations in the following table. The
arithmetical accuracy of the operation is checked by the
summation of the concentrations to unity. However, before one can proceed further up the column, it is necessary
to know the temperature of the plate above. This must
be such that the pressure will be 18.1 atmospheres. It is
determined by successive approximation as before, as shown
in the last two columns of the table:
f =
23
24
25
27
0.0429zmPm
0.0429zmPm
0.0429zmPm
0.0429zmPm
+
+
+
395' K.
0,000224
0,093
0,0624
0,068
=
=
Z
p
0.00365 62
0,6680 23.5
9.25
0.2214
0.1066
1.9
~
~
1,000
CoLu>rN
331' K.
++ 0.899
= 1.23
= 11.52
+ 2.485
0.0603 = 2.79
12.OGzn+i
12.06xn+i
12,06xn+i
0.99965
Pa
0.23
15.63
2.04
0.20
18.1
One can proceed from plate to plate up the column by repeating this step.
STEP 8. Working down the column from the top and
up the column from the bottom in this way, one finds that
the propane and butane concentrations come together quite
rapidly. I n other words, the reflux assumed is adequate.
If a reflux ratio of one be assumed in this case, it is found
that the concentration and temperature changes from plate
to plate through the column are far less and are too small
for satisfactory operation. I n other words, a reflux ratio
I N D U S T R I A L A N D E N G I N E E R I N G C H E RI I S T R Y
May, 1932
0.083~J'~ - 0.0745
The temperature of the feed is 363" IC., a t which 1' (extrapolated) is 125 atmospheres. Using this value and the assumption that z,,+~ = xn, it is seen that the concentration of
ethane on the feed plate must be a t least 0.00795. As will
appear later, it must actually be higher than this by a small
amount.
Below the feed plate the operating equation for ethane
isz,-, = 0 . 0 4 2 9 ~ 2 , . B y means of this, one can readily
determine the ethane concentration. Thus, on the plate
below the feed, the concentration is about 0.0015. On the
next plate below it would be 0.0003. It is obvious that
quantities as small as this may be neglected. Now using
any desired assumed value for the ethane concentration on
the feed plate, remembering that this value must be somewhat but not much above 0.008, one can calculate concentrations up the column from the feed plate by using the
Hausbrand operating equation for conditions above the feed
already employed above. Doing this, one finds that the
concentration of pentane and heavier above the feed fades
497
away rapidly and conditions then approximate those coniputed by figuring down from the top.
If one assumes a wrong value of ethane on the feed plate,
difficulties are encountered. Thus, if the value is too small,
the equations will indicate a negative incrpment in ethane
concentrations going up the column a t some plate, usually
the feed plate or the one above it. Larger assumed values
will avoid this difficulty, but, unless they are. correct, will
indicate on the upper plates where the concentrations of
pentane and higher have fallen to a negligible point-ratios
of ethane:propane:butane which are out of line with those
computed by working down the column and which, therefore, are incompatible with the column set-up. Thus, by
successive approuimation, one can determine the proper
ethane concentration on the feed plate.
P L A T E NUMBER FROM TOP OF COLUMN
42
40
z 36
34
32
PLATE
FIGIJRE2 . TEVPER
9TURE G R ~ D I E UTHROUGH
T
COLUMU
DISCLSSIOS
OF REsuLw
The concentrations and temperatures thus computed are
plotted in Figures 1 and 2. The abscissas are plate numbers indicated by subscripts 1, 2, etc. Where the point
was computed from the bottom of the column, the abscissas
are given a t the bottom of the figures; where computed
from the top the plate numbers are s h o m a t the top of the
diagram. It will be noted that these abscissas do not correspond exactly. The concentrations working up meet the
curve working down in between plates. This means that
the column balance is not such that an integral number of
theoretically perfect plates will function in this way. However, as in the case of design of columns for binary mixtures,
using the next largest number of integral plates will give
a column which will give a somewhat hetter separation.
I n this case, as in the ordinary one, it is unnecessary to try
to readjust top and bottom conditions so that the plate
numbers come out exactly integral.
498
The Hausbrand equation for the calculation of plate-toplate concentration gradients in the rectification of binary
mixtures can be applied directly to the calculation of gradients
in the isopiestic rectification of mixtures however compIex, provided the composition of the feed and the point and
sharpness of cut be known, and the components of the mixture follow Raoults law. These equations are, therefore,
directly applicable in the design of rectification equipment
for natural or refinery gasolines and, in general, for any
mixture of hydrocarbons in which the concentrations of
the individual components are known.
LITERATURECITED
(1) McAdams, W.
(HEX..16. .<7.i
(1924).
RECEIVED
March 18, 1932.
--
Studies in Distillation
Graphical Method of Computation for Rectifying Complex
Hydrocarbon Mixtures
J. Q. COPE,JR., AND W. K. LEWIS
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Mass.
The graphical method used in treating problems in the rectification of binary mixtures is developed to be applicable to hydrocarbon mixtures, however complicated, and is illustrated
by a typical problem in the fractionation of natural gasoline
REPRESENTATION
OF MATERIAL
BALANCE
The graphical technic for computation of the continuous
rectification of binary mixtures is based upon the facts that
the relation between the composition of the vapor rising into
any plate in a column and the liquid flowing down from that