lIJIII'

coordinates.
= E and YOe = 00, since both are pure solvent -, • f,'lID'_ 6.5 may be rewritten for solvent-free

Lo' Y1 - X,~:
D' = XD
- Y1
(6.5b)
Since Lo'/D' = 10, X A, can be located if Y1 can be evaluated. VI' = Va' + (Lo' + D') by a material balance `around the solvent
separator (C). Y1 is determined by the intersection of line X D Yo with the extract curve, since VI is flowing from an equilibrium
stage. The line X D Yo is wrtical through XD because YOc = 00. After Y1 is located Equation 6.5b can be applied. 10 = Y1 - XA,
XD - Y1 Then X A, - Y1 = 1O(YI - XD ) and XA, is located as shown on Figure 6.5. This delta point is valid for calculating stages from
1 to F - 1, but the feed changes the net flow for stages F to N. Since 3.' =,6.' + F' (6.40) the points X A', Z F' and X~, lie on a straight
line. In addition, 3.' = LN ' - VN+1 (6.20) But VN+1 = 0, and so X~a = XNa, and X~ is located at the intersection of the line XA,Z F and
a vertical line through X N' as shown. Stages are now stepped off using X A' from stage 1 to the feed and X~, from the feed to the
end of the cascade. Figure 6.5 shows eleven stages in the enriching section and about twelve stages in the stripping section.
The required solvent flow rate can be determined. masis: 1000 lb of fresh feed Since F' = LN" + D',
LN' XD,ZF' 0.9 - 0.4 -=--= =059
F' XD,XN 0.9 - 0.05
~ ~H"
Therefore, LN' = 590 lb
With Equation 6.20
3.' = LN'= 5~lb
.,..",
From Figure 6.5, . X~'c = -23.8
Therefore, the net flow of ~ (-23.&~~) = -14,030 lb.-The solvent in the rafflriate is (590/0.992)0;008 =~. 4.7 lb. Therefore the
solvent feed rate is..r . VN+1 = 4.7 - (-14,030) = 14,0351b per 1000 lb feed At the solvent separator: since 3.' = ,6.' + F
,6.' = -410 lb XA'c = 34.2

Net flow of solvent = (34.2)( -410) = -14,030 lb. Since there is no solvent in Lo or D, StJ\f~ p;
;k-
Condenser
Lo
Xo
D ho
Xn
hn
Figure 6.6. Enthalpy and material
balances around the condenser. Distillation. Calculations for distillation are made on the enthalpy-concentration diagram. The heat
terms -qc and qB replace solvent streams Vc and VB+1' respectively. q is defined as the heat added to a system, according to the
usual convention in thermodynamics. Therefore, the heat added at the reboiler, or still, is the reboiler duty (q B), and the heat
removed atthe condenseris the condenser duty (-qa). Since -qc and qB have no mass, the net flows of mass defined by
Equations 6.1, 6.2, and 6.3 become Enriching: ~ = Lo - VI = Ln - Vn+I = -y (6.6) Stripping: ~ = LN - VB = Lm - Vm+1 = B
(6.7) and F = D + B = ~ - ~ (6.8) The net flow of enthalpy may be defined for the enriching section.
(6.9) -/
where hA is equal to the net flow of enthalpy per unit
of total mass net flow. For use in graphical calculations
hA may be related to qc by an enthalpy balance around
the condenser (Figure 6.6). The enthalpies of the streams
entering must equal the enthalpies of the streams leaving.
The condenser is a special type of heat exchanger, where
the heat removed from the vapor. in con~ensation is
transferred t<.> a coolant .liquid through a. metal wall .
An enthalpy balance for the coolant gives
-qc = enthalpy of coolant leaving
, - enth~lpy. of coolant entering
An enthalpy balance around the condenser then gives
V1HI = Loho + DhD' + (-qa)
The quantity of heat added at the condenser per unit
mass of distillate, QOD' can be defined
(6.10)
The enthalpy balance becomes
V1H1 = Loho + D(hD - QOD)

Combining this equation with Equation 6.9 gives

!1h:::,. = LohO - V1H1 = -D(hn - Qcn)
Solving for the enthalpy coordinate of the delta point
gives·
h - -D(hJ) - QeD) - h Q
,l - !1 - J) - CJ) (6.11)

net flow of heat

total net flow of mass
The x-coordinate of the delta point is obtained from
!1x,l = Loxo - VI!h = - Dx J)
-D
x,l = T Xl) = XJ) (6.12)
The two coordinates (h,l, x.:l) of the delta point, as
defined by Equations 6.11 and 6.12 can be used to locate
the delta point when distillate quantity and composition
and condenser duty are known. If the reflux ratio is
known, h.;,. may be determined from it, analogous to
the derivation of Equation 6.5 for extraction. A material
balance around the condenser gives
and an enthalpy balance around the condenser gives
LeA, + D(hn - QCD) = V1H1
Therefore, 4/10 + DhA = V1H1
Lo h.:l - HI
D = H1 - ho
Equation 6.13 is useful in determining h.:l from the
reflux ratio. The values of Lo/ D, Hi> and ho may be
substituted into Equation 6.13 to evaluate h.:l' or h.:l
may be located graphically using the equation as a guide.
For a total condenser, ho = hn and xn = YI'
A similar analysis of the stripping section will yield
the following relationships:
~=LN- Vs=Lm- Vm+1=B (6.14)
h = hB _ QSB = net flow of heat
a total net flow of mass
(6.1~

where ...... QSB = qs

B
(6.16){
Xa =xB
Vs hN - ha
Ii 0:::: Hs-hN

(6.17)
(6.18)
The direction of the net flows in the distillation column
should be considered. Distillation columns are built
vertically with the condenser at the top and the reboiler
at the bottom. Therefore, net flow defined as positive ...
to the right in Figure 6.2 will be positive in a downward
direction in a vertical distillation column. Equation
6.6 shows that the total net flow of mass in the .enriching
section is upwards, but Equation.6. 7 shows that the total
net flow in the stripping section is downward. Since
heat is added at the reboiler and removed at the condenser,
the net flow of heat is upward through both the
stripping and enriching sections. Therefore, h.:l is
always positive and ha is always negative..
The use of the equations -derived previously for
graphical calculations is shown in Figure 6.7. For the
illustration, the composition and thermal condition of-'*
the feed.Jl~ttoms, and distillate are assumed to be known.
In addition,either the reboiler or condenser duty is
known. The feed is shown as a subcooled liquid
(zF' hF)' The distillate is a liquid at its bubble point
(xn, hn), and the bottoms is a liquid at its bubble poin~
(xB, hB)' The reflux is also a liquid at its bubble point
(xo, ho)' Since h.:l = hn - QeD and X.:l = Xo = xn '
the delta point for the enriching section can be determined
from the condenser duty. The delta point for
the stripping section is located by the line x.:lzFextended
and the vertical line XB = x;\. Stages may be stepped
off from either end with use of the appropriate delta
poirtt. In Figure 6.7 the stages are stepped off from

the top of the column downward, by alternate use of

the equilibrium data and the delta point. Since the
column has a total condenser Yl = Xo = XD and the
point (YI' HI) can be located. This point represents
the vapor leaving the first stage. The liquid leaving the
first stage is in equilibrium with this vapor. Therefore,
its composition (xJ is determined from the equilibrium
curve, and its enthalpy is determined from its composition
and the saturated liquid enthalpy curve. To
locate (Y2' HJ a line is drawn from (xl> hJ to (xa, ha>.
From (Y2' H2) the equilibrium relation is applied to find
{~, hJ. This stepping-off of stages is continued using
(xa, ha) until ZF is reached. Then the construction
switches to the delta point for the stripping section
(x~, h~). The calculation is completed when the liquid
composition equals or exceeds the bottoms composition
xB • The calculation of stages across the feed stage as
outlined is not rigorous, considering the enthalpy and
pha&e characteristics of the feed. However, it is a
.. sufficiently accurate approximation and is generally
~-> used. About 5.4 stages are required in the enriching
section and about 3.4 are required in the stripping section.
The steps in this calculation are identical to those out-

lined in Illustration 6.1 for extraction. The analogy

between the two operations should be carefully studied.
Figures 6.2 and 6.6 show a total condenser in which all
the vapor (VI) is condensed and then split into distillate
(D) and reflux (4). In a partial condenser, on the other
hand, only the reflux is condensed and the distillate is
drawn off as a vapor. Since the liquid reflux and vapor
distillate are in contact, they may approach equilibrium
and give as much as one additional equilibrium stage,
as shown in Figure 6.8. In actual practice, the liquid
and vapor may not have sufficient contact to equilibrate,
so that a partial condenser functions as less than one
equilibrium stage.
Figures 6.2 and 6.7 show the bottoms wi~hdrawn
before the reboiler, so that the stream entering the reboiler
is totally vaporized. In most distillation towers the
bottoms are withdrawn from the still, as shown in
Figure 6.9. This results in a reboiler that way be
equivalent to as much as one equilibrium stage. The
reboiler is frequently a steam-heated heat exchanger.
Many types of reboiler construction are used in industry.
The design of reboilers is based upon heat-tn.nsfer
considerations covered in later sections of this book

One hundred pound moles per hour of

OPERA~G VARIABLES
For a feed of given composition and flow r~te, the
separation at a given pressure into a distillate product
and a bottoms product is dependent upon the variables
hF' xB' XD , -qc, qs, LoID, and N. When any four of
these values are specified, the other three are thereby
fixed and may be evaluated. Of the many possible
combinations of four specified variables, a few represent
most of the common engineering problems.
In the design of new equipment, the most common case
involves knowledge of hF' XB' and xD • LolD is then
chosen to give the most economical combination of
equipment costs and energy costs. Equipment costs are
proportional to the number of stages N, and energy
costs are directly related to the reboiler duty (qs), since it
represents steam supplied to the reboiler. As the number
of stages increases the reboiler duty decreases, so that a
minimum total cost of equipment plus energy will exist.
In evaluating the operation of existing equipment or _
in planning a new use for it, N is usually fixed, and ,,'
LoID, qs, and -qc may not exceed certain values determined
by the size of the equipment. Usually the
enthalpy and composition of the feed are known, and
the possible compositions of the products are to be evaluated.
Some flexibility exists, since Lol D, q s, and -qc may
be adjusted over a range below their maximum values.
a 20 mole percent ammonia-water solution is to be distilled
at 100 psia in a countercurrent column with reflux. The
distillate is to have a composition of 80 mole percent ammonia,
and it is to contain 95 per cent of the ammonia charged.
There is a total condenser, and the reflux ratio (Lo/ D) is to be I. -
The bottom product is withdrawn through the reboiler. The
feed enters at a temperature of 250°F, and the reflux is at its
bubble point. How many equilibrium stages are required?
Where is the feed stage?
Reflux. As the ratiool!eflux (Lo) t?~p!tll:s~l?roduct
(D) ,is deg~.ased,., ~.e_.~~1! .. ~!JL~e required _ for a
specified separation. Examination or-Equation 6.5
shows that, as Lol D is reduced for fixed values of Xo'
XD , and YI' x/j. approaches YI' This results in a smaller
change in composition between stages and requires a
greater number of stages. Similarly, Equation 6.13
shows that, as Lol D is reduc;ed, h/j. approaches HI' and
a greater numb~agesIt--reqU1red. ..:::~~-
SOLUTION. F = 100 Ib moles/hr, zp = 0.2, x D = 0.8
Ammonia in distillate is 95 per cent of that charged:

(O.95)(0.~)(l00) = 19 moles. // ,-,~. / -,-' -C)

_~ _ _ I '_~:...
D - 0.8 - 23.8, B - iZ~' xB - 76.2 - 0.01~~ ..
x B, x D = xo, and Z Fare located''On-F.igure-6;i(l .. 'Since the
feed is at 250°F at zp = 0.2, it is a mixture of liquid and
vapor lying on the 250°F tie line. h/j. is located from Equation
6.13.
Lo
-=1
D
and soh/j. - HI = HI - ho
From Equatio~ 6.8, ~ = ~ + F, and hll. is located at the
intersection of xll. = xB and the line h/j.hF' The stages are
now stepped off beginning with the still. hll. is used fromxB
to zp and hI>. from zp to xD • About 2.7 equilibrium stages
plus the still as one stage are required. The feed is at the
2.3 stage from the bottom.
~ If Lol ~,is reduced to a pomt wl1ere an extended tie
line passes th rough-.e.it her delta point, a pinch occurs.
and an infinite number of stages is required to accomplish
the specified separation. This value of Lol D is
referred to as the minimum reflux ratio. An Lol D belo ....
the minimum value cannot give the specified separatior.~
even with J!n infinite number of stages., A reflux ratic
higher than the minimum requires a finite number 0:
stages for the specified separation.
As the reflux is increased, the number of stages required
for a given separation decreases. At total reflux
no products are withdrawn (D = 0, B = 0), no feed Isupplied
(F = 0), and a minimum number of stages Irequired
for a specified separation. In such a case
LolD = 00 and VsIB = 00. Under this condition bot~
delta points lie at infinity, and construction lines to th~
delta point are vertical; or, in other words, Yn+l = x.
and Ym+1 = xm•
The concepts of minimum reflux and minimum stage;

at total reflux are useful in estimating the difficulty of

separation, in setting the actual operating reflux ratio,
and in analyzing column performance.
A higher reflux requires fewer stages but greater re-
at sl:!EElied tot~~ reb~l~osts mo~n~,_ a..n~conomic
l boiler and condenser duties in -IDstillation. ~ Sincetheh~

b~<::~between opera!iIJ,g costs and initial equipment.

co~!:,_ ~l determine the be_~t preflux ratiQu. Si.~~arly,
in extraction:3 higher r~flJ!X.Lll~ gi,:€:s few~r . stages but.
necessitates a ~h~r solv~ntrate_ and a greater 10ad-eIL
the ~l~entsepar~tor, thereby increasing operating QQ£t~.
A.!!. economic evaluailoncan be made to determine~theoJ>
ti~bm~tI~~ of equ~ent a.nd ope;.;:tingcosts .
for. a speciff(!(l.~.~'p~ra!ion. A typical evaluation is
sh£..'Y1l in Figure 6.11. The optim.!l~~~t!sign OC.CUIS a..t
mininiumtotal cost. ..
(

Illustration 6.3. Determine the minimum reflux ratio

and the minimum number of stages for the separation of
Illustration 6.2.
SOLUTION. From Illt1stration 6.2, zF = 0.2, xD = 0.8, and
xB = 0.0131. These points may be plotted on Figure 6.12.
As the delta points are moved closer to HI and h B along the
vertical lines at xD and XB, respectively, more stages are
required. Finally, a point is reached whe~~nite
number ~ §~e:e8 i~ ~Ied. POIiits sun closer to the
enthalpy cl!rves will ruso result in infinite stages, but they will
not give the desired separation. The delta points shown on
Figure 6.12 give the minimum reflux ratio for the desired
separation. That these delta points give an infinite number
of stages can be verified by attempting to step off stages from
either end of the cascade. A pinch occurs because the line
x ~x 2l coincides with a tie line. By Equation 6.13 the minimum
reflux ratio is
Lo hA, - HI 1225 - 825
15 = HI - ho = 825 - 25 = 0.5

At total reflux, LolD = 00, and both delta points are at

infinity. Construction lines XnYn+IXA, are vertical, as shown
on Figure 6.12. The minimum number of stages at total
reflux is about 2.5. Reference to Illustration 6.2 shows that
at a reflux ratio of twice the minimum 3.7 stages are required.
The occurrence of the pinch at the feed point, as in
Illustration 6.3, is characteristic of ideal solutions. For
many real systl!ms the equilibrium relationships produce
a pinch at other compositions. This will be considered
again in Chapter 7.
Subcooled Reflux. A total condenser may not only
<!.oJld~I1~~~_ ~t also cool the liquid reflu~ below its bubble
EQiI}t,_.-Such.a.~refluxjE~fe!.r~d tQ_as a subcooled rJ!jJy~.
When a subcooled reflux is fed into the distillation column,
it causes some vapor to condense and thereby produces a
liquid downflow greater than the reflux supplied. The
ratio L/ V is often referred to as the internal reflux ratio.
For the same value of the external reflux ratio (Lo/ D) a
subcooled reflux will produce a larger internal reflux
ratio than will a reflux at its bubble point. All the
derived equations hold for subcooled reflux, providing
ho is properly plotted below the saturated-liquid enthalpy
curve. It should be noted that subcooled reflux does
not change the net flow. A subcooled reflux in distillation
is analogous to an extract reflux in extraction which
contains a quantity of solvent less than that which would
give an over-all composition lying on the phase envelope.

Entrainment results when the heavier

L-phase is not completely separated from the lighter
V-phase before each leaves the equilibrium stage. The
carry-over of L-phase results in an effective V-phase
composition different from the equilibrium value. If
the ratio of entrained L-phase to V-phase is known, a
new effective V-phase locus can be determined and used

to calculate the required number of equilibrium stages.

Examples of entrainment of the L-phase in the V-phase
include carry-over ofliquid with the vapor in a bubble-cap
column in distillation and the carry-over 'Of insoluble
solids with the extract in leaching. In liquid-liquid
extraction both the extract and the raffinate may be
entrained in the other phase.
lNTERMEDIATE STRE.AMS
In any mass-transfer operation it is possible to have
more than one feed or more than two product streams.
For example, in crude-petroleum distillation, light gas,
propane-butane, gasoline, naphtha, kerosene, gas oil,
lubricating-oil stock, fuel oil, and asphalt may all be
withdrawn from the column at different points. A
typical industrial crude-petroleum distillation unit is
shown in Figure 7.13. Calculation of the distillation
behavior of such multicomponent mixtures is extremely
complex. A simple case of an intermediate stream for
binary distillation or extraction may be handled by the
methods already covered. An example of this, with two
feeds, is shown in Figure 6.13. The introductim or
removal of an intermediate stream (l) changes the net
flow. Therefore, a new delta point must be established.
In Figure 6.13 there are three different net flows and,
therefore, three delta points: ~ for stages I through I-I,
Ll for stages I through F-l, and a from stages F through
N.
. The equations for the total net flows are
~=Lo- V1=Ln - Vn+l= -(D+ VO>
a = LN - Vs = Lm - V m+l = (B - VS+l)

3 =L· - v.+1
. ..
(6.1)
(6.2)
(6.19)
The subscript i refers to any stage in the intermediate
section of the column between stage I and stage F-I.
The net flow at the left end of the cascade is~. Mter
the intermediate stream (I) is added, the net flow becomes
When the feed (F) is added, the net flow is
a=~+F=~+I+F (6.21)
The stream I may have either a positive value (a feed)
or a negative value (a product). Additional intermediate
streams may be calculated by defining additional net
flows.

Since there are three different net flows, there will be

three delta points. The determination of the three
delta points is shown in Figure 6.14, for a typical case.
If the reflux ratio is known, x/l may be located on the
line XOYI by use of Equation 6.5a. Once x/l has been .(
located, x,5, may be determined by reference to Equations
6.2 and 6.21. Equation 6.2 implies that x/l will be on
the line xBYS+l' so this line is drawn on the diagram.
Equation 6.21 can be utilized to construct another line
which intersects x BY S+l at X,5,. _ Since there are three terms
on the right-hand side of Equation 6.21, the addition
must be carried out in two steps. First I andF are graphically
added to give the sum I:. The I: and I). may be

X.lZ~:-The intersection~f this line with XBYS+l is Xa'

The sum L may be con~dered as a "fictitious feed."
The sections of the cascade between I and I and between
F and N behave as if there were a single feed L = I + F
at some point between I and F. The net flows in these
two sections may be determined by combining I and F
into the fictitious feed (L) and treating the cascade as
the usual case of one feed. Since the stream I was a
;>roduct in the illustration of Figure 6.13, the numerical
value of I is negative and z~ lies beyond ZF on the line
zIZF' as in the usual case of subtraction. The concept
of the "fictitious feed" is abandoned in order to determine
xX, which is an expression of the net flow from I to F.
The third delta point is located by inference from Equations
6.20 and 6.21 at the intersection of the lines XaZI
and xazF:
The stages may now be stepped off using the appropriate
delta point in w.ach section of the cascade.
Intermediate streams in distillation and other operations
are calculated in a similar manner. An "intermediate
stream" in distillation may consist of only 'the
addition or removal of heat.