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Studies in Distillation

Design of Rectifying Columns for Natural and Refinery Gasolirw

by. K.


G. L.


Department of Chemical Engineering, Massachusetts Institute of Technology. Cambridge, Mas>.

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

HE design of rectifying equipment for natural and

that the molal heat of vaporization of the componeiits is

reasonably constant under ordinary conditions of rectification by assuming average constant values for Vn and On+
above the feed plate and for the corresponding values of
V , and 0, - I below it, thus making it possible to use the
graphical stepwise methods of design which have so generally
replaced the former algebraic technic.
I n using the above equation, Hausbrand calculated the
vapor composition, y., from the liquid composition on the
plate above, and then determined the liquid composition,
xn,by the use of the equilibrium diagram, thus proceeding
down the column. I n the case of natural gasoline the process can be simplified because of the fact that the components
of the mixture follow Raoult's law, a t least within the accuracy of design. Thus, assuming 100 per cent plate efficiency, the partial pressure of any particular component
above the nth plate is equal to XZ,,
and this in turn is identical with its partial pressure in the vapor above tJhe plate,
yn7r. Hence,

refinery gases is complicated by the presence in the

mixtures of a large number of components. The
problem can be solved by applying the ordinary Hausbrand
equations for binary mixtures successively to all of the components whose propelties influence the separation. However, the multiplicity of the operations of computation is
sufficient to confuse one unfamiliar with the technic of handling the equations. Because of the growing importance
of rectification in the industry, it seems worth while to outline and illustrate the steps to be taken in solving a problem of this sort.
The following nomenclature will be employed :
V = moles of vapor rising from any plate per unit time
0 = moles of overflow descending from any plate per unit time
z = mole fraction in liquid phase of any particular component
under consideration
y = mole fraction in vapor phaPe of any such component
F = moles of feed to the column per unit time
D = moles of final product (distillate), whether vapor or liquid,
leaving apparatus per unit time
W = moles of reqidue leaving bottom of apparatus per unit
P = vapor pressure of component under consideration in pure
state at temperature in question
= total pressure on apparatus
p = partial pressure of component under consideration

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:

= Tn+iOn+i


The left-hand side of the equation is the total amount of

component entering the top of the column from the nth
plate per unit time, while the first term of the right-hand
side is the amount of this component flowing in the overflow
from the top of the column down on the nth plate, and the
second term is the amount in the distillate. Hausbrand
employed weight units, but for reasons which will appear
presently it is more convenient in this particular case to use
moles. The expression X d D is determined by the conditions of the problem, and the amount of vapor and overflow can be calculated a t any temperature level from a heat
balance. I n recent years it has become common practice
in the case of binary mixtures to take advantage of the fact

Y" = znP,/n,

and consequently one may rewrite the Hausbrand equation as

Similarly, below the feed plate,

It should he clear that by means of these equations one can

compute the change in concentration from plate to plate in
any part of the column, once the conditions on any given
plate are known.
It will be worth while t o consider a characteristic problem in design. One will know the Composition and amount
of the feed to the column; the temperature and pressure
under which it exists; the temperature which it is practicable
to maintain in the reflux condenser a t the top of the column
with the cooling means available; the point a t which it is
desired to effect the separation; and the allowable o v e r l a p
i. e., the amount of high-boiling material which may be
tolerated in the overhead distillate and of low-boiling material in the residue from the still a t the bottom of the column.
With these data a t hand, the following steps of computation are necessary:
(1) Calculate the amount and exact composition of the dietillate and residue.
(2) Determine the pressure which must be maintained on the
condenser in order to produce the reflux which is necessary for
the functioning of the column. This is the operating pressure.
8, of the apparatus.


May, 1932


(3) Assuming for the moment a suitable value of the reflux,

the top of the column from the reflux condenser, calculate

0 , to

the composition of the reflux. This will, of course, depend on

the type and method of operation of the condenser employed.
(4) Calculate the composition of the vapor from the top
plate, and, from this, that of the liquid on the top plate and its
( 5 ) Calculate the temperature of the still and the composition
of the vapors rising from it.
(6). From a heat balance on the column, determine the variation in the reflux through the column. One can immediately
determine by such a balance the reflux from the bottom of the
column to the still, and it is usually sufficiently accurate to
wsume the change in reflux per degree of temperature rise up
the column constant, except at the feed plate where the reflux is
increased by the amount of liquid in the feed.
(7) By use of the Hausbrand equation applied from plate to
plate calculate the concentrations and temperatures on the
plates, working down from the top and up from the bottom.
(8) Tnspection of the results of the preceding operations as
the temperatures of the plates approach each other towards the
middle of the column will enable one to judge with reasonable
precision whether the amount of reflux assumed for the operation
of the column is satisfactory. If not, readjust it to a satisfactory
value and repeat steps 3 to 6, inclusive.
(9) By study of the compositions determined by working up
from the bottom, pick a suitable feed plate. Estimate the
concentration on t h s plate of that component of highest boiling
point which does not appear in the residue in appreciable amount.
If necessary, recalculate the composition on the plate below and
correct for the concentration of t,his component on it. Then
proceed with the computation of the concentrations up the
column until the concentration of the lowest-boiling constituent
of the residue which does not appear in appreciable amount in
the distillate has become negligible. If the concentrations thus
determined correspond substantially with those calculated by
starting down the column from the top, the problem is solved.
If not, the concentration on the feed plate must be reeatimated,
and this last operation repeated. The number of plates thus
determined, corrected for the plate efficiency, gives the number
of plates required in the column when operated under these conditions.
(IO) To determine t,he influence of reflux ratio in column size
and heat consumption, these operations must be repeated for a
number of different values of reflux. The plotted results will
make it easy to determine the best operating conditions.




The detail of these steps will be best understood from a

specific illustration. Assume as a feed stock a material
containing 26 mole per cent of methane and permanent
gases, 9 per cent ethane, 25 per cent propane, 17 per cent
butane, 11 per cent pentane, and 12 per cent of hexane and
higher. Assume that the amount of isomers of the normal
hydrocarbons may be neglected and that the hexane and
higher hydrocarbons average heptane. Assume that conditions are such that one can maintain a n effective top
e., a temperature of the gas and reflux,
within the condenser itself, of 70" F. (294" K.). The feed
is pumped in at 100" F. (311" K.). It is desired to take all
propane and lighter overhead, and all butane and heavier
as residue, but it is allowable to have 1 per cent of butane
in the overhead distillate and 0.1 per cent propane in the
residue. The reflux condenser is of a type in which the
vapors~travel with the liquid through the condenser and are
separated after having been brought to the final condenser
temperature of 70" F. Consequently, the final gas is in
equilibrium with the reflux liquid.
STEP1. Were the separation complete, there would be
60 moles of distillate and 40 of residue for each 100 moles
of feed. Consequently, in the actual column the butane
In the distillate will be approximately 0.6 mole and the
propane in the residue 0.04. On the basis of this, the following table, showing the distribution of the components of 100
moles of feed between distillate and residue, should be selfexplanatory:

CEHl4 +


M o l e yo



.Vole %







0: 1








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

14.2 =
++ 169.4
16.4 =




Since this vapor must be in equilibrium with the liquid

on the top plate, one can write the following equations:
1 = 320'
P z = 0 . 0 9 7 ( 1 8 . 1 ) = 1 . 7 5 5 = zzPz
P3 = 0 . 7 0 2 ( 1 8 . 1 ) = 1 2 . 7
= Zap3
PI = 0 . 0 5 8 ( 1 8 . 1 ) = 1 . 0 5 = zip,




1 ,000

These equations cannot be solved directly because they

contain six unknowns for three equations, although there
is the fourth relationship, Zx = 1. However, the values of
Pz,Pa, and P4 are determined by the unknown temperature
of the top plate. This temperature must be such that i t
will satisfy the above relation. It can easily be determined
by successive approximation. As a matter of fact, in this
case the top-plate temperature is 320" K., a t which temperature the pressure of each pure component and the corresponding mole fraction in the liquid phase on the top plate
are shown in the two columns following the equation. It
will be found that at no other temperature will the equations be satisfied. While solution by successive approximation is always in a certain sense unsatisfactory, in the

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'


case of equations of this type a little experience soon makes

it easy.
STEP5. The composition of the boiling liquid in the still
is known. Furthermore, it is boiling under a pressure of
18.1 atmospheres. Consequently, the temperature of the




When one endeavors to make a heat balance on this column

to determine the reflux a t the bottom, one finds that the data
available on heat of vaporization a t these high pressures (1)
are unsatisfactory, particularly in the case of the high-boiling
constituents (i. e., the liquid boiling in the still). Csing
the highest values which the available data would indicate
as possible, the overflow decreases somewhat as one goes
down the column. Using lower values gives a n opposite
result. I n order to eliminate confusing complications, it
will therefore be assumed that, in the case of this column,
the change in the overflow and consequently in the vapor
rising up the column is negligible from plate to plate except
a t the feed plate. Hence, on the basis of 100 parts of feed,
the overflow in the upper part of the column is 2 (60.57) =
121.1, and the vapor, 3 (60.57) = 181.7. The corresponding values below the feed plate are 176.3 and 136.9.
STEP 7. The Hausbrand equation of the operating line
above the feed plate is

However, in this equation the term P , is unknown because

one does not know the temperature of the plate below.
This must be assumed, the value of P read off for each component, the corresponding values of z computed, and the
process repeated until a value of t is found which makes
22 = 1.
1 =


Pax3 =
Pmr =




t =

413.5' K.






Y (as % )

The composition of the vapor from the still is given in the

fifth column.
STEP6. It is first necessary to determine the condition
in which the feed enters the column. This calculation is
most easily made by reference to the following equation,
derived from Raoult's law and a material balance. Call
N the total moles of feed which enter in the liquid state per
100 moles of total feed,
the total moles of a given component per 100 moles of feed, and n the moles of the component entering in the liquid in the feed. Equality of input and output gives
n o = ' + ; ( + P) 100 n

The composition of the liquid on the second plate down is

given in the last column. By repetition of this process,
using the same equations but with the proper values of P
and xn + 1, one can go down the column from plate to plate
The Hausbrand equation below the feed plate is



= zm -


+ 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 =






395' K.



0.00365 62
0,6680 23.5

The equation is applied successively to each component and

the condition imposed that Z n = N . At the feed temperature, 311" K., the pressure of ethane is 53 atmospheres,'
of propane 13.7, butane 3.7, pentane 1.05, and heptane 0.11.
Solving these equations, N equals 55.2. I n other words,
the feed enters this column as 55.2 per cent liquid and the
rest gas.



still must be determined by successive approximation as in

the preceding case, and Zy must. equal unity. The technic
is shown in the following table:

331' K.

++ 0.899
= 1.23
= 11.52
+ 2.485
0.0603 = 2.79






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


May, 1932

of 1: 1 is too small. Exactly what ratio to use must be

decided by the engineer on the basis of this type of computation, interpreted in the light of the operating conditions
in question.
STEP9. The conditions of the various plates in the column
thus computed are given in Figure 1. It will be noted that
four plates below the top plate the propane has fallen to
13.9 mole per cent, n-hile five plates above the still it has
risen t o substantially the same value. In other words,
this fifth plate above the still may well be chosen as the feed
plate. If, however, it is desired to introduce the feed on
plates above or below this point, this may be tried out by
the methods now to be discussed.


The difficulty with the computations so far conducted
lies in the fact that they take no cognizance of pentane or
heavier above the feed plate, or ethane below the feed plate.
There is a certain amount of high-boiling constituents in
the overhead product. Had this been exactly known, it
could have been allowed for in the computations, and the
amount of these constituents in the upper part of the column
computed. Similarly, had the exact data on the trace of
ethane in the residue from the still been known, its amount
up the column could have been calculated. Furthermore,
the composition of the liquid on the feed plate as determined
by these two computation operations-i. e., from the top
down and from the bottom up-would be the same. However, the analytical methods are incapable of determiiiing
with precision these traces of the lowest-boiling, materials
in the still product and the highest-boiling in the overhead
even in the case of an operating unit. Still less is the designer in a position to predict these in advance. However.
to design the unit with assurance, allowance must be made
for these factors.
Theoretically, one could make this allowance by assuming
the amount of these contaminating traces and checking
up by trial and error on the column calculations until the
compositions on the feed plate come together. The following is a practical method of making suitable allowance for
these corrections. The percentage of ethane on the feed
plate must necessarily be less than the percentage of thiq
component on the plate immediately above the feed. However, assume, for the moment, that these concentrations
differ by a negligible amount and apply the Hausbrand equation for ethane over the feed,

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
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


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.



z 36





This process may sound involved, but aboye the feed

plate the pentane and heavier usually fade out of the picture
so quickly that the estimation is reasonably rapid. At any
rate, it is far shorter and more satisfactory than the more
obvious method of estimating overhead and bottom concentrations of the materials present in traces only and checking them by refiguring the whole column.
I n computing the ethane, it is desirable to express the
amount on the feed plate to a precision far beyond that
with which it can possibly be known, a precision unjustified, for example, by the uncertainty in the extrapolated
value of Pz which is us3d in determining it. The reason
for this is the extreme sensitiveness of the larger and important concentrations on the plates above to very minor changes
in this value of the Concentration on the feed plate.

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.



It is worthy of note that the temperature gradient of

Figure 2 is nearly uniform above and below the feed plate.
This is quite different from the corresponding plot of a
binary mixture, where the temperature gradient is large
near the feed plate and small toward both ends of the column.
This difference is due to the fact that, in complex hydrocarbon mixtures of several components, the components
of intermediate boiling point accumulate in the middle of
the column in a way that effectively flattens out the temperature curve.
It should be clear that the low-temperature portion of
the curves is calculated down from the top of the column,
and the high-temperature part up from the bottom. These
two portions blend in tangentially where they meet. However, if the upper portions are continued down, they give
a too low value of temperature and a too high value of the
low-boiling constituents, because in calculating downward
from the top it is impossible to allow for the high-boiling
constituents. This portion of the curve is shown dotted
in Figure 1.
The only point regarding the concentration curve which
merits special attention is the accumulation of butane in
the middle part of the column. This is the component of
boiling point intermediate between the bottom and top temperatures of the column, and, as already indicated, this accumulation in the middle of the column is characteristic.
The slight rise in butane concentration on the first plate above
the feed is more striking. While the general trend of butane
concentration above the feed plate is downward, a rise of
this sort may occur where the temperature is sufficiently
high to give a value of P, sufficient to reverse the slope of
the Hausbrand line.
Dependable data as to plate efficiency in natural gasoline columns are exceedingly meager, but all the indications
are that the efficiencies are high. Thus, a sample of the
liquid on the plate in the upper part of a column gave upon
analysis 15.7 mole per cent propane and 70 mole per cent

Vol. 24, NO.,^

butane. Using Raoults law, the vapor in equilibrium with

this liquid should contain 47 per cent propane and 49.3 per
cent butane. A sample of the vapor rising from this plate
showed upon analysis 49.3 per cent propane and 53.8 per
cent butane. I n other words, the vapor rising from the
plate was richer in butane and poorer in propane than it
would have been had it left the plate in equilibrium with
the liquid on it. This is another way of saying that the
liquid on the plate had not completely dissolved the butane
out of the vapor rising into the plate, down to the equilibrium value. However, the difference in composition is
small. The vapor approached closely to equilibrium with
the liquid, which means that the plate efficiency was reasonably high. It is very desirable that accurate determinations
of actual plate efficiency and of the height of the equivalent
theoretical plate for the different types of tower-filling used
in the industry be made in order to serve as a suitable guide
for designing and operating engineers.

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.

(1) McAdams, W.

H., and Morrell. J. C. I N D ENO

(HEX..16. .<7.i


March 18, 1932.


Studies in Distillation
Graphical Method of Computation for Rectifying Complex
Hydrocarbon Mixtures
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

HE preceding article has shown how the classical

methods of design of rectifying columns for binary

mixtures may be applied to the rectification of complex mixtures of hydrocarbons. During the last decade the
algebraic technic of design has, in the case of binary mixtures,
been replaced by graphical methods. It is the purpose of
this article to develop suitable graphical procedure for the case
of the complex mixtures in question.

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

plate on to the plate below is given by a simple equation

representing a material balance, and that, assuming perfect
contact between liquid and vapor on a plate, the composition
of the vapor rising from a plate is a unique, known function of
the composition of the liquid on it.* Both of these relations
can be represented graphically on a vapor-liquid composition
diagram, the former, through proper choice of basis, at least
approximately by a straight line, and the latter by the equilibrium curve. The change in concentration from plate to
plate is obtained by staircasing between the two. The line
representing the materia1 balance is called the operating
line of the column.
1 A minor modification of t h e method takes care of t h e effect of plate
e5ciency, provided this is known.