502 PETROLEUM REFINERY ENGINEERING

0.546 mole fraction of pentane is evolved. This vapor is condensed by cooling

it with a liquid that has the same composition as the vapor ; and as the liquid is
heated , it evolves a vapor having a composition of y = 0.782. By repeating
this operation several times, a vapor that is almost pure pentane is produced at
still Z). The heating coils in the stills are really unnecessary because the vapor
within the coils is of the same composition as the liquid on the outside of the coils,
and hence the liquid and vapor can be mixed . The same change in composition
will reflult, and the exchange of heat will be much more effective. The bubble
tower shown in Fig. 16-176 is essentially the same as the series of stills except
that the liquid from each plate is allowed to flow continuously to the still or the
.
plate beneath The compositions indicated in Fig. 16-17 are not practical ones
because only a small quantity of purified vapor can be produced , but exactly the
same principle is utilized in actual fractionating towers. In actual towers a finite
amount of vapor or product must be produced, and hence the vapor is not so rich
in pentane as indicated in Figs. 16-15 to 16-17. Thus more plates are required
-
in actual towers because of the less rich vapor that is produced at each plate and
because several bubble plates may be required to produce an equilibrium . The
top plate must be continuously fed with a cooling liquid (reflux), or it would soon
become dry. The vapor from the top plate is the final product; and hence the
reflux must be rich in pentane, or the vapor will be contaminated. Accordingly,
the overhead product (0.975) is used as the reflux medium. The reflux flows
down the column, but it changes composition from plate to plate so that all the
material that is originally put into the top of the column as reflux is vaporized
and returns to the product storage tank.
.
Theory of Fractionating Columns The derivation of formulas describing two -
component fractionation involves the following assumptions; (1) the molal latent
heats of all materials are equal; (2) no reflux for cooling the overhead product
from the feed-plate temperature is provided.
The assumption of equal molal latent heats greatly simplifies the calculations.
If 1 mole of vapor (any composition) is condensed , the heat that is removed is
just sufficient to vaporise a mole of liquid (at its boiling point ) . Thus the num¬
ber of mole3 of vapor that travel up the column is the same at any plate, provided
that the feed is introduced as a liquid at its boiling point. Likewise, the reflux
or overflow from plate to plate is a constant amount in each section of the tower
'

-
(see envelope II, Fig. 16 18) because the reflux is equal to the moles of vapor
minus the moles of product for the rectifying section and to moles of vapor plus
moles of waste for the exhausting section .
Material Balances. A number of envelopes enclosing parts of a fractionating
-
tower are shown in Fig. 16 18. The following symbols are used:
F = moles of liquid feed at its boiling point
P = moles of liquid product at its boiling point
B •= moles of liquid residue product
B = moles of reflux , at its boiling point, at any plate above the feed plate ( R1
below feed )
V moles of vapor at any plate above the feed plate ( V‘ below feed )
~
x “ mole fraction of lower boiling component in liquid
y = mole fraction of lower boiling component in vapor
 FRACTIONATION AND TOWERS 503
Subscripts :
p = product from top
b = residue product
/ feed
n
n +1
—
=
any plate in rectifying section
plate above the nth plate Product
n — ==
1
t
plate below the nth plate
top plate
t
t-
i — =—
1
m
plate below the top plate
any plate in the exhausting sec¬
tion n+ l
; HI I
a = still
Envelope I encloses the entire tower n-l
ri T
system and shows the relation between
the feed and thd products. Feed f+ l
F M
F = B+P f
m* l
And for the low-boiling component:
m-
Fxj = Bxb 4" Pxv s+1
Envelopes II and II' show the relation
among the vapor, reflux , and moles of
overhead product: Bottom
product
V =P+R
and Vyt — Pxv + Rxp (16-11 )
eat
Similar equations for the plates below the FIG. 16-18. Continuous fractionation
feed are system.
V' ~ S’ - B and .-
V’ y - Bxb
The change in composition from plate to plate is shown by envelope III :
Vyn + Rxn = V / «-i 4“ Rx*+\
-
ft { x » \
+ xn) = * -
V { yn y^ j )
ft yn - Vn-1
V
=
Xn+1 ' Xn
- (16 12)

also y* — i ~ ~R i%n ~~ 4 “
Y
Minimum Vaporization and Reflux. With minimum vaporization or reflux, an
infinite number of plates are required for the separation . Although this amount
of vaporization cannot be used commercially, it is the limiting condition upon
which practical vaporizations are based . The other extreme condition is the use
of an infinite amount of vaporization, Eor infinite vaporization a minimum num¬
ber of plates is required to effect a separation. The minimum vaporization may
be computed aa follows (envelope IV) :
Vyj = Rx/ +1 4- Pxp
 504 PETROLEUM REFINERY ENGINEERING

But at minimum vaporization an infinite number of plates are used and the
change in composition from plate to plate is very small . Hence z/+ i is equal to xt .

But
Vm« y } Ra^Zj + Pxp
Rwn — V .IT. — P 'irt
- TT

Vmluyj = ( Kola - P )t / -f Pxp

- P 9 - Xf )
- x, ^
Vi
(16-13)

or R„u - P(i/ * - I
/ ^
( 16-14)

In practice, more reflux than the minimum is used . The relative values of
i/ nnd }// can be found by the equilibrium relation for the compounds that are
being separated . The use of a basis of 1 lb-mole of product P simplifies the
computations!
Example 15-8. Number of Perfect Plates by Mathematical Method. A mixture of
pentane and hexane containing 0.6 molo fraction of pentane is to be fractionated at
atmospheric pressure to produce a product containing 0.95 mole fraction of pentane.
The feed is at its boiling point . Use twice the minimum reflux .
How many theoretically perfect plates arc required to get the separation ?
Basis: 1 mole of product (see Eq . (16-14) ) .
yi = 0.82 (Fig. 16-16 )
n _ ~ Vi 0- 96 0.82 “
0.69
0.82 - 0.60
Actual reflux :
R = 2 X 0.59 1.18 moles
V = 1.18 + l 2.18 moles [see Eq . ( 16-11) 1
R 1.18
0.541
V “ 2.18
Considering the top plate [see Eq. ( 16-12)]:
R _ yt - Vi-, i
V xp -x
For this plate,
VI = Xp

Also xt in equilibrium with t/ i (0.95) is 0- 86 (Fig. 16-16) .

For the t — 1 plate,

R __ vi — ~> - yi 1
= 0.901
V Xt — * _ i |
t

0.901 — y,-2
z, _ t - 0.745 ( Fig. 16-16 )

0.641 Vis « 0.839

0.86 - 0.745
The h quid flowing from this plate has a composition of 0.625. Obviously only a
'

part of another perfect plate is required to complete the rectifying section, because
the feed composition is 0.6.
Graphical Method. If infinite reflux is used , the composition of the vapor leav¬
ing the plate and the liquid arriving at the plate is the same, that is, y« = Zn+ i ,
i
 FRACTIONATION AND TOWERS 505
yn+1 = «n+ j, etc. At each plate the composition of the vapor and that of the
liquid are related to each other by the equilibrium relation shown in Fig. 16-16.
The equilibrium relation is plotted in Fig. 16-19 and also a 45-deg line whose equa¬
tion is x =* y . The 45-deg line is the operating line for the condition of infinite
reflux . The operating line relates the composition of the vapor leaving the plate
and the composition of the liquid entering the plate. For conditions other than
infinite reflux, the liquid composition x does not equal y and the operating line is
less steep than a 45-deg line . The equation of the operating line may be formu¬
lated as follows ; At the top plate when producing 1 mole of product ,
R y t-1 y t
V = zt - zP
-
But y , = xv
R _ V t- i x p —
V ~ xt -. Z p
Vt --i Xp = - Xp )
y( xt
R, V
-
Vt i = y ( Xt - t p) + y X p
.

But V = R+ P
,
R( z - xp ) + ( R + P ) xv \R
'
, P
-
Vt i = y = y + y xt <16-15a)
R , P
or Vn- l = y X n + y X p ( 16-155)

This is an equation of a straight line having a slope of R / V and having an inter¬

cept on the y axis of (P / V ) xp . Since the operating line extends from (xpt yp ) to
the intercept, the line can also be drawn without using the slope.
Example 18 -9. dumber of Plates by Graphical Method . Example 16-8 will be
repeated using the graphical method .
The y intercept of the operating line is

V X p ** 2l8 X 95 = 0 435 Isee Eq ‘

°‘

The operating line is drawn through the intercept y = 0.435, 2 = 0, and through
the point x?t yt (0.95) (Fig. 16-19) . The number of plates can then be ascertained by-
drawing horizontal and vertical lines as shown in Fig. 16-19. Each point on the equi¬
librium curve indicates one theoretical plate . Thus about 3 }£ perfect plates are
-
required (see Example 16 8) for the rectifying section .
The dotted lines indicate the number of plates required at infinite reflux . The oper¬
ating line for infinite reflux is the 45-deg line. Only a little more than two plates are
required if infinite reflux is used.
Exhausting Section. The number of plates required in the exhausting section
in order to separate a particular bottoms product can be formulated in exactly the
Bame manner as for the rectifying Section . However , the computation by graph¬
ical methods can be simplified by noting that the exhausting operating line passes
through the point A (Fig. 16-19) and through point B . Hence the easiest way to
handle the exhausting section is to determine and draw the rectifying operating
line and then draw the exhausting line . The equation of the exhausting operating
506 PETROLEUM REFINERY ENGINEERING

line ( A B on Fig. 16-19) ia

y«
R'»+\Xm+\ Bxb _ R'n+ ix^ i Bxi (16-16)
Rm+\ — B RmA
m+-1
l “ B vL
Example 16-10. Graphical Method for Number of Plates if Feed Is at Center of
-
Column. Examples 16 8 and 16-9 will be continued for a column that is to produce
a bottoms product xi = 0.05 as well as a top product xp = 0.95.
1.0 ‘
I | 1 W t K L ^7
(xt-i.yt -o J?
iz
Eh —
.
0.9 -
(*t -a
0.8
/ 1/
a7 Zi
*
£
E
0.6
6 /
''
Y * /
7
/
/1

/
§ 0-5
o 0435
"

/
/
/
/
/
z
js_ 0.4 V 77 / y
u
|03 /7
/y
0.2
3y /

0.1
2? a
0 00501 2 0.3 0.4 CL5 0.6 07 08 0.9 0951.0
* b
Mol Fraction in Liquid
* f *p
FIG . 16 19. MeCabe-Thiele diagram for pentane-bexane ( Example 16-9)
- .
The exhausting operating line is drawn as indicated above. The stepwise procedure
is continued past the feed composition until the liquid has a composition of 0.05 or less
(see Fig. 16-19). About nine perfect plates are required.
If the plate efficiency is 60 per . cent,

Actual plates = 14.7

Ponchon Method. A weakness of the MeCabe-Thiele method, as out¬

lined heretofore, is the fact that the transfer of heat is not directly intro¬
duced . Heat must be transferred on each plate , reboiler heat must be
supplied at the base of the fractionator , and cooling by reflux must be
accomplished at the top . The method devised by Ponchon56 does not
ignore these relationships, and although space is not available for an
explanation of the Ponchon method, Example 16-11 will indicate its gen¬
eral usefulness.
ss Ponchon, M., Tech, mod ., 13, 20 (1921).

i
 FRACTIONATION AND TOWERS 507
-. .
Example 16 11 Solution by Graphical Ponchon Method The same problem as
that explored in Examples 16-8 to 16-10 will be solved by the Ponchon method .
The total beat contents of liquid and vaporized pentane, and the same for hexane,
are plotted at zero and 100 mole fraction of pentane (Fig. 16-20) . The enthalpies
( Btu per lb) are:

Boiling point Vapor Liquid

Hexane 155 , 7 °F 325 180

Pentane 96.7flF 305 150

The enthalpies of hydrocarbon mixtures are usually straight lines as shown in Fig .
16-20, but for nonideal systems the lines may be curved .
Dashed lines connecting vapor and liquid are the equilibrium compositions of
Fig. 16 16 or 16 16. For the condition of minimum reflux, the composition of the
- -
vapor leaving the feed plate is in equilibrium with the feed liquid which contains
0.6 mole fraction pentane, i.e., 0.817. This is shown as a dotted line leading to an
overhead ( x p or y9 ) composition of 0.05, and this indicates that 406 to 306 Btu per lb
of product must be withdrawn as (minimum ) reflux heat. Twice the minimum is
actually employed, and hence heat is present in the reflux in the amount of 505 Btu
per lb ( point marked y9 a ) - A total of 200 Btu per lb of product must be removed
at the top of the tower, and the condenser must also handle the product making a
total of 355 Btu per lb. A line leading from this point (600 Btu per lb) through the
saturated Liquid feed composition of 0.6 and on to XTA (located at the bottoms composi¬
tion ) indicates the lack of heat at the reboiler or base of the fractionator . This is
negative to the extent of 380 Btu per lb of bottom product and accordingly , 380 plus
178 or 558 Btu per lb must be introduced into the bottom product to heat and reboil
the bottom of the colunm .
The number of plates required , or the heat exchanged on each plate, is obtained by
a step-wise operation . The liquid composition (0.86 from Fig . 16-16) in equilibrium
with the composition of the top product (0.95) ia connected with a dashed line. This
point ia then connected with the yv\ point obtaining the vapor composition yr-i at
the ( T — 1) plate. Such operations are continued until the feed composition is
passed , whereupon the other or XIA turning point is used . Continuing as before, it
appears thnt 8.9 theoretical trays are adequate.

FRACTIONATION OF COMPLEX MIXTURES

Although the process of fractionating complex mixtures can be outlined

mathematically for certain simplified situations, the practical application
of such computations is not satisfactory because vapor-liquid equilibrium
data are inadequate, because human patience is tried to the point of fre¬
quent errors by the laboriousness of the computations, and because the
assumption of equal roolal latent heats should not be made for wide-boil ¬
ing-range mixtures . The first data that must be had are the compositions
of the products that are to be produced, and ordinarily these compositions
cannot be wisely selected by the designer because they are fixed by the
608 PETROLEUM REFINERY ENGINEERING

500

Hr i
|
!
439
\S
-
T5 -
it t
/ /
300 7
/ / 3
//
9 Sil
/
/
-rl/ /
/
«5
/
/

; /j
/ /
/

200 / /
f
%
xr-
i

/ XA

I too
%
is

1
«2
0

-too i
£

'L
300

- 400
0.2 0.4 a6 o.e
Mot froclton pentone
FIG . lfr-20. Fractionation by the Ponchon method (see Examples 16-11 and 16-9).
fractionation attained in a system that has yet to be designed. Only
when the fractionation is to be so complete that only two of the many
components are found in both the overhead and bottoms product , or when
the number of components is limited to about three, can the designer
adopt reasonable terminal compositions. If at the end of the laborious
 FRACTIONATION AND TOWERS 509
computations it is found that the split of each component between the top
and bottoms products is incorrect, a new assumption as to terminal com¬
positions must be made and the entire computation must be repeated
almost ad infinitum..
Each component in the mixture behaves independently of the others
except as the equilibrium constants may be altered by the presence of
other components, and for a known reflux ratio an operating equation
-
[Eqs. (16-15a) and (16 16)] can be computed for each component. A
-
plate-by plate computation can then be undertaken starting at the bot¬
tom by assuming a plate temperature and checking by new avssumptions
-
until the summation of Kx*& [Eq. (15 5)] equals 1.0. The value of x for
each component on the next tray can then be computed by use of the
-
operating-line equations [Eqs. (16-15a) and (16 16)]. Similarly, a plate -
-
by plate computation starting at the top and summing y s/ K’ a is con¬ ’
ducted until at some plate the composition found is the same as one
found when starting from the bottom. If the assumed terminal compo¬
sitions are not perfect, a perfect matching of composition at some inter¬
mediate plate is never found and new terminal compositions must be
assumed .
-
Example 16 12. Three-component Fractionation. A feedstock contains 60, 30,
and 20 mole per cent of pentane ( A ) , hexane (B ) , and heptane ( C ) . It is desired to
produce an overhead product that contains only 0.5 mole per cent hexane and a bot¬
toms product that contains only 1 per cent pentane . The reflux ratio is to be 4 and
the pressure 1 atm. The feed is preheated to its bubble point, and it is introduced at
a plate which is at the same temperature.
By a pentane material balance based on 100 moles feed , P moles of overhead and B
moles of bottoms are produced .
- P.^ + BIVA -
At x f i
50 —
0 995
= 99.6 - 0.98B
50

B 50.25
P = 100 - 50.25 => 49.75
-
(100 - B )TPA + 0.01 B

The terminal compositions are

Overhead Bottoms
Feed ,
moles Moles Moles
Fraction Fraction

Pentane ( A ) 50 49.50 0.995 0.50 0.010

Hexano ( B ) 30 0.25 0.005 29.75 0.592
Heptane (C ) 20 0.0 20.0 0.398
100 49.75 1.000 50.25 1.000

The computations must be started at the bottom because only the bottoms product
shows heptane, whereas it was assumed that heptane in the overhead was negUgible .

The overhead actually contains about 0.000000? mole fraction heptahe, and no one