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T h e Hausbrand equations f o r binary mixtures are applied to the solution of problems irc con-
tinuous rectification of natural gasoline. Steps of the computation are outlined, the
details of which are illustrated by a specijic problem
T
HE design of rectifying equipment for natural and that the molal heat of vaporization of the componeiits is
refinery gases is complicated by the presence in the reasonably constant under ordinary conditions of rectifica-
mixtures of a large number of components. The tion by assuming average constant values for Vn and On+
problem can be solved by applying the ordinary Hausbrand above the feed plate and for the corresponding values of
equations for binary mixtures successively to all of the com- V , and 0, - I below it, thus making it possible to use the
ponents whose propelties influence the separation. How- graphical stepwise methods of design which have so generally
ever, the multiplicity of the operations of computation is replaced the former algebraic technic.
sufficient to confuse one unfamiliar with the technic of han- I n using the above equation, Hausbrand calculated the
dling the equations. Because of the growing importance vapor composition, y., from the liquid composition on the
of rectification in the industry, it seems worth while to out- plate above, and then determined the liquid composition,
line and illustrate the steps to be taken in solving a prob- xn,by the use of the equilibrium diagram, thus proceeding
lem of this sort. down the column. I n the case of natural gasoline the proc-
The following nomenclature will be employed : ess can be simplified because of the fact that the components
of the mixture follow Raoult's law, a t least within the ac-
V = moles of vapor rising from any plate per unit time curacy of design. Thus, assuming 100 per cent plate ef-
0 = moles of overflow descending from any plate per unit time
z = mole fraction in liquid phase of any particular component ficiency, the partial pressure of any particular component
under consideration above the nth plate is equal to XZ,, and this in turn is identi-
y = mole fraction in vapor phaPe of any such component cal with its partial pressure in the vapor above tJhe plate,
F = moles of feed to the column per unit time yn7r. Hence,
D = moles of final product (distillate), whether vapor or liquid,
leaving apparatus per unit time Y" = znP,/n,
W = moles of reqidue leaving bottom of apparatus per unit
time and consequently one may rewrite the Hausbrand equation as
P = vapor pressure of component under consideration in pure
state at temperature in question
T = total pressure on apparatus
p = partial pressure of component under consideration
Count the plates up from the feed plate toward the top Similarly, below the feed plate,
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 still-
the wth plate. Designate the conditions referred to by It should he clear that by means of these equations one can
means of a subscript indicating the location of the material compute the change in concentration from plate to plate in
in question or the point from which the material came. any part of the column, once the conditions on any given
Thus, y,, is the composition (mole/fraction of the com- plate are known.
ponent in question) of the vapor rising from the nth plate,
xf is the composition of the feed to the column, etc. CHARACTEI~ISTIC PROBLEM IN DESIGN
Assuming continuous operation of such a rectifying column,
Hausbrand equated input to output of a given component It will be worth while t o consider a characteristic prob-
in a section of the apparatus above the nth plate, as follows: lem in design. One will know the Composition and amount
of the feed to the column; the temperature and pressure
y,V, = Tn+iOn+i f XdD under which it exists; the temperature which it is practicable
to maintain in the reflux condenser a t the top of the column
The left-hand side of the equation is the total amount of with the cooling means available; the point a t which it is
component entering the top of the column from the nth desired to effect the separation; and the allowable o v e r l a p
plate per unit time, while the first term of the right-hand i. e., the amount of high-boiling material which may be
side is the amount of this component flowing in the overflow tolerated in the overhead distillate and of low-boiling ma-
from the top of the column down on the nth plate, and the terial in the residue from the still a t the bottom of the column.
second term is the amount in the distillate. Hausbrand With these data a t hand, the following steps of computa-
employed weight units, but for reasons which will appear tion are necessary:
presently it is more convenient in this particular case to use
moles. The expression X d D is determined by the condi- (1) Calculate the amount and exact composition of the die-
tions of the problem, and the amount of vapor and over- tillate and residue.
flow can be calculated a t any temperature level from a heat (2) Determine the pressure which must be maintained on the
condenser in order to produce the reflux which is necessary for
balance. I n recent years it has become common practice the functioning of the column. This is the operating pressure.
in the case of binary mixtures to take advantage of the fact 8, of the apparatus.
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 195
(3) Assuming for the moment a suitable value of the reflux, HYDROCARBOS DISTILL~TE RESIDCE
0 , tothe top of the column from the reflux condenser, calculate Moles M o l e yo Moles .Vole %
the composition of the reflux. This will, of course, depend on CHI+ 26.0 42.9 ... ...
the type and method of operation of the condenser employed. CzHe 9.0 14.9 ...
C3H8 24.96 41.2 0.04 0: 1
(4) Calculate the composition of the vapor from the top CIHK 0.61 1.0 16.39 41.6
plate, and, from this, that of the liquid on the top plate and its CSHIP ... ... 11.0 27.9
temperature. CEHl4 + ~ ... ~
... 12.0 __
30.4
Total 60.57 100.0 39,43 100.0
( 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 varia- STEP 2. At the temperature of the condenser the pres-
tion in the reflux through the column. One can immediately sure must Le such that the overhead ga.j or distillate is a t
determine by such a balance the reflux from the bottom of the its dew point, since it was separated from a liquid condensed
column to the still, and it is usually sufficiently accurate to from it by cooling at constant pressure. Therefore, the par-
wsume the change in reflux per degree of temperature rise up
the column constant, except at the feed plate where the reflux is tial pressure of each component in the gas must of necessity
increased by the amount of liquid in the feed. equal the partial pressure of that same component in the
(7) By use of the Hausbrand equation applied from plate to liquid from which the gas was last separated, and with which
plate calculate the concentrations and temperatures on the it was in equilibrium. Kow a t the effective condenser
plates, working down from the top and up from the bottom. temperature, 294" K., the pressure of pure ethane is 38
(8) Tnspection of the results of the preceding operations as atmospheres, of propane 8.8, and of butane 2.2. Conse-
, the temperatures of the plates approach each other towards the
middle of the column will enable one to judge with reasonable quently, one can write the following equations:
precision whether the amount of reflux assumed for the operation
of the column is satisfactory. If not, readjust it to a satisfactory pz = 3822 = 0 . 1 4 9 ~
value and repeat steps 3 to 6, inclusive. p , = 8 . 8 ~ 3= 0 . 4 1 2 ~
(9) By study of the compositions determined by working up pa = 2.224 = 0.01 T
from the bottom, pick a suitable feed plate. Estimate the
concentration on t h s plate of that component of highest boiling Furthermore, neglecting the solubility of methane and per-
point which does not appear in the residue in appreciable amount. manent gases in the liquid, the sum of the mole fractions
If necessary, recalculate the composition on the plate below and
correct for the concentration of t,his component on it. Then must obviously be unity-i. e., x~ x3 + +
z4 = 1. Solving
proceed with the computation of the concentrations up the these equations, one obtains s = 18.1 atmospheres, which
column until the concentration of the lowest-boiling constituent is the necessary operating pressure on the condenser, and
of the residue which does not appear in appreciable amount in which, neglecting pressure drop through the colunin, is the
the distillate has become negligible. If the concentrations thus
determined correspond substantially with those calculated by pressure throughout the apparatus. From the above calcu-
starting down the column from the top, the problem is solved. lations, 100 x2 = 7.1 mole per cent ethane in the liquid con-
If not, the concentration on the feed plate must be reeatimated, densate, 100 z3 = 84.7 per cent propane, and 100 x4 = 8.2
and this last operation repeated. The number of plates thus per cent butane.
determined, corrected for the plate efficiency, gives the number
of plates required in the column when operated under these con- STEP3. Since, from the condenser on this equipment,
ditions. the final overhead gas leaves in equilibrium with the total
(IO) To determine t,he influence of reflux ratio in column size condensate, the figures just given also represent the compo-
and heat consumption, these operations must be repeated for a sition of the reflux to the column.
number of different values of reflux. The plotted results will STEP 4. Assume a reflux equal to double the amount of
make it easy to determine the best operating conditions.
overhead vapor. On the basis of 100 moles of distillate,
there will therefore be 200 moles of reflux. Consequently,
ILLUS'FRATIOX OF DETAILSOF PROBLEM the vapor rising into the partial condenser from the top
The detail of these steps will be best understood from a plate will have the composition shown by the following table :
specific illustration. Assume as a feed stock a material Total moles ?&
containing 26 mole per cent of methane and permanent CHI = 4 2 . 9 42.9 14.3
gases, 9 per cent ethane, 25 per cent propane, 17 per cent C?.Ho = 1 4 . 9 + 14.2 = 29.1 9.7
CSHO = 4 1 . 2 ++ 169.4 = 210.6 70.2
butane, 11 per cent pentane, and 12 per cent of hexane and CiHio = 1 . 0 16.4 = 17.4 -
5.8
higher. Assume that the amount of isomers of the normal 300.0 100.0
hydrocarbons may be neglected and that the hexane and Since this vapor must be in equilibrium with the liquid
higher hydrocarbons average heptane. Assume that con- on the top plate, one can write the following equations:
ditions are such that one can maintain a n effective top
temperature-i. e., a temperature of the gas and reflux, 1 = 320' K
within the condenser itself, of 70" F. (294" K.). The feed P -
7
P z = 0 . 0 9 7 ( 1 8 . 1 ) = 1 . 7 5 5 = zzPz 64 0.027
is pumped in at 100" F. (311" K.). It is desired to take all P3 = 0 . 7 0 2 ( 1 8 . 1 ) = 1 2 . 7 = Zap3 17 0.747
propane and lighter overhead, and all butane and heavier PI = 0 . 0 5 8 ( 1 8 . 1 ) = 1 . 0 5 = zip, 4.65 0.226
1 ,000
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 These equations cannot be solved directly because they
residue. The reflux condenser is of a type in which the contain six unknowns for three equations, although there
vapors~travel with the liquid through the condenser and are is the fourth relationship, Zx = 1. However, the values of
separated after having been brought to the final condenser Pz,Pa, and P4 are determined by the unknown temperature
temperature of 70" F. Consequently, the final gas is in of the top plate. This temperature must be such that i t
equilibrium with the reflux liquid. will satisfy the above relation. It can easily be determined
STEP1. Were the separation complete, there would be by successive approximation. As a matter of fact, in this
60 moles of distillate and 40 of residue for each 100 moles case the top-plate temperature is 320" K., a t which tem-
of feed. Consequently, in the actual column the butane perature the pressure of each pure component and the corre-
In the distillate will be approximately 0.6 mole and the sponding mole fraction in the liquid phase on the top plate
propane in the residue 0.04. On the basis of this, the follow- are shown in the two columns following the equation. It
ing table, showing the distribution of the components of 100 will be found that at no other temperature will the equa-
moles of feed between distillate and residue, should be self- tions be satisfied. While solution by successive approxi-
explanatory: mation is always in a certain sense unsatisfactory, in the
I
of 1: 1 is too small. Exactly what ratio to use must be away rapidly and conditions then approximate those coni-
decided by the engineer on the basis of this type of compu- puted by figuring down from the top.
tation, interpreted in the light of the operating conditions If one assumes a wrong value of ethane on the feed plate,
in question. difficulties are encountered. Thus, if the value is too small,
STEP9. The conditions of the various plates in the column the equations will indicate a negative incrpment in ethane
thus computed are given in Figure 1. It will be noted that concentrations going up the column a t some plate, usually
four plates below the top plate the propane has fallen to the feed plate or the one above it. Larger assumed values
13.9 mole per cent, n-hile five plates above the still it has will avoid this difficulty, but, unless they are. correct, will
risen t o substantially the same value. In other words, indicate on the upper plates where the concentrations of
this fifth plate above the still may well be chosen as the feed pentane and higher have fallen to a negligible point-ratios
plate. If, however, it is desired to introduce the feed on of ethane:propane:butane which are out of line with those
plates above or below this point, this may be tried out by computed by working down the column and which, there-
the methods now to be discussed. fore, are incompatible with the column set-up. Thus, by
successive approuimation, one can determine the proper
ALLOWAKCESFOR HIGH- AKD LOW-BOILING
RIATERTALS ethane concentration on the feed plate.
The difficulty with the computations so far conducted P L A T E NUMBER FROM TOP OF COLUMN
lies in the fact that they take no cognizance of pentane or 42
heavier above the feed plate, or ethane below the feed plate.
There is a certain amount of high-boiling constituents in
40
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 L
ethane in the residue from the still been known, its amount z 36
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 34
down and from the bottom up-would be the same. How-
ever, the analytical methods are incapable of determiiiing 32
with precision these traces of the lowest-boiling, materials PLATE NUMBER F R O M BOTTOM OF COLUMN
in the still product and the highest-boiling in the overhead
even in the case of an operating unit. Still less is the de- FIGIJRE2 . TEVPER
9TURE G R ~ D I E UTHROUGH
T COLUMU
It is worthy of note that the temperature gradient of butane. Using Raoult’s law, the vapor in equilibrium with
Figure 2 is nearly uniform above and below the feed plate. this liquid should contain 47 per cent propane and 49.3 per
This is quite different from the corresponding plot of a cent butane. A sample of the vapor rising from this plate
binary mixture, where the temperature gradient is large showed upon analysis 49.3 per cent propane and 53.8 per
near the feed plate and small toward both ends of the column. cent butane. I n other words, the vapor rising from the
This difference is due to the fact that, in complex hydro- plate was richer in butane and poorer in propane than it
carbon mixtures of several components, the components would have been had it left the plate in equilibrium with
of intermediate boiling point accumulate in the middle of the liquid on it. This is another way of saying that the
the column in a way that effectively flattens out the tempera- liquid on the plate had not completely dissolved the butane
ture curve. out of the vapor rising into the plate, down to the equilib-
It should be clear that the low-temperature portion of rium value. However, the difference in composition is
the curves is calculated down from the top of the column, small. The vapor approached closely to equilibrium with
and the high-temperature part up from the bottom. These the liquid, which means that the plate efficiency was reason-
two portions blend in tangentially where they meet. How- ably high. It is very desirable that accurate determinations
ever, if the upper portions are continued down, they give of actual plate efficiency and of the height of the equivalent
a too low value of temperature and a too high value of the theoretical plate for the different types of tower-filling used
low-boiling constituents, because in calculating downward in the industry be made in order to serve as a suitable guide
from the top it is impossible to allow for the high-boiling for designing and operating engineers.
constituents. This portion of the curve is shown dotted
in Figure 1. SUhlM.4RY
The only point regarding the concentration curve which
The Hausbrand equation for the calculation of plate-to-
merits special attention is the accumulation of butane in
plate concentration gradients in the rectification of binary
the middle part of the column. This is the component of
mixtures can be applied directly to the calculation of gradients
boiling point intermediate between the bottom and top tem-
in the isopiestic rectification of mixtures however com-
peratures of the column, and, as already indicated, this ac-
pIex, provided the composition of the feed and the point and
cumulation in the middle of the column is characteristic.
sharpness of cut be known, and the components of the mix-
The slight rise in butane concentration on the first plate above
ture follow Raoult’s law. These equations are, therefore,
the feed is more striking. While the general trend of butane
directly applicable in the design of rectification equipment
concentration above the feed plate is downward, a rise of
for natural or refinery gasolines and, in general, for any
this sort may occur where the temperature is sufficiently
mixture of hydrocarbons in which the concentrations of
high to give a value of P, sufficient to reverse the slope of
the individual components are known.
the Hausbrand line.
Dependable data as to plate efficiency in natural gaso- LITERATURECITED
line columns are exceedingly meager, but all the indications
(1) McAdams, W. H., and Morrell. J. C. I N D ENO (’HEX..16. .<7.i
are that the efficiencies are high. Thus, a sample of the (1924).
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 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 de-
veloped to be applicable to hydrocarbon mixtures, however complicated, and is illustrated
by a typical problem in the fractionation of natural gasoline
plate on to the plate below is given by a simple equation