Professional Documents
Culture Documents
J6. DISTILLATION
J6.1 INTRODUCTION
Distillation is defined as an equilibrium-staged separation process in which a liquid or vapor
mixture or both, containing two or more components, is separated into its component fractions
of desired purity by the application and removal of heat. This process is based on the
equilibrium stage concept, which means that vapor and liquid streams, after contacting each
other, leave a stage or unit saturated with the more volatile component (has lower boiling
point) and the less volatile component (has higher boiling point), respectively. The separating
agent for distillation is heat, and the mechanism of distillation is by the addition of heat.
The important variables that affect phase equilibrium (Figure J6-1) in distillation are
temperature, pressure, and concentration.
A B
vapor
liquid
A B
Raoult’s law, an ideal law, can be defined for vapor-liquid phases in equilibrium.
PA PA x A (J6-1)
F=C–P+2 (J6-2)
J6-1
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
PA PB
yA xA or yB xB (J6-3)
P P
Equation (J6-3) is obtained by combining Raoult’s law (J6-1) and the relation that states that
the partial pressure of a component in an ideal gas or vapor is proportional to its mole
fraction.
PA yA P or PB yBP (J6-4)
The relationship between xA and xB and between yA or yB is obtained from the sum of the
mole fractions of components A and B being equal to unity.
xA + xB = 1 and yA + yB = 1 (J6-5)
J6-2
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
ln P A
B
(J6-6)
CT
The vapor pressure ( P ) calculated from equation (J6-6) can be substituted in equation (J6-3)
to get yA or yB.
120
vapor region
110 saturated
vapor curve
Temperature, °C
100 vapor-liquid
T mixture region
90
saturated
liquid curve
80
liquid region
70
xA yA
0 0.2 0.4 0.6 0.8 1
Mole fraction A in liquid or vapor, x A or yA
From the above boiling-point diagram, the relationship between xA and yA at a given
temperature, T, can be read with the lower and upper curves, respectively, as indicated by
broken lines.
J6-3
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
1
Mole fraction A in vapor, yA
0.8
equilibrium
0.6 curve
diagonal
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1
By definition, the volatility of a component is the ratio of its partial pressure to its mole
fraction in the liquid.
P
volatility (J6-7)
x
The relative volatility of the more volatile component, A, with respect to the less volatile
component, B, is
J6-4
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
AB
P x A (J6-8)
P x B
For ideal systems, pressure fraction equals mole fraction, i.e.,
PA Ptotal y A
(J6-9)
PB Ptotal y B
AB
y x A
y A x B yA 1 x A
(J6-10)
y x B x A yB x A 1 yA
y1 x
(J6-11)
x 1 y
Separation by distillation is much easier if > 1; the separation becomes difficult if the value
of is close to 1.
If Raoult’s law (J6-1) is valid, the volatility is numerically equal to the vapor pressure of the
pure component (or volatility P x P ) for ideal systems. Thus, the relative volatility, AB,
takes the form
AB
P x A PA
(J6-12)
P x B PB
y
K (J6-13)
x
In general, K values depend on temperature, pressure, and composition. For many systems,
however, K values are approximately independent of composition.
J6-5
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
1. Batch distillation
In batch distillation, the process is carried out in separate runs; the more volatile
component is evaporated from the still pot, and distillation is continued as long as the
change in the concentration of the more volatile component in the distillate is still
significant. Batch distillation is advantageous if small quantities of mixtures or varying
product compositions are required, if smaller number of plates is used, and if high purity
of the product is not desired.
J6-6
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
2. Continuous distillation
In continuous distillation, there is a steady input of feed to the distilling column and a
continuous withdrawal of streams of constant composition from the top and bottom of the
column. In terms of lowest operating costs, continuous distillation is advantageous if a
large number of plates are used and the reflux ratio approaches the minimum value.
There are two types of distillation columnsstaged and packed columns. For staged
distillation columns, calculations are of the equilibrium-based method; for packed distillation
columns, calculations are of the rate-based method.
Distillation may be carried out in staged or plate columns in which each plate provides
intimate contact between vapor and liquid in continuous countercurrent flow. Each plate
constitutes a single stage where there is simultaneous partial condensation of vapor and
partial vaporization of liquid.
Packed columns are used for smaller diameter columns since it is expensive to build a
staged column that will operate properly in small diameters. Packed towers have the
advantage of a smaller pressure drop and are, therefore, useful in vacuum fractionation.
Another advantage of packed columns is that they can be used to process corrosive
materials.
J6-7
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
Consider a liquid charge L1 in the still pot, with a composition x1 of the more volatile
component, A, as in the following diagram:
condenser
Vapor Distillate
V, y D, xD
L2, x2
still pot
If an amount dL, with a composition y of the more volatile component, is vaporized, then a
material balance on the more volatile component gives
x
dL dx
L2 2
L1 L
(J6-15)
x 1 y x
x
L 2 2 dx
(Rayleigh equation) (J6-16)
L1 x1 y x
This resulting Rayleigh equation is integrated graphically using the equilibrium y vs x data.
J6-8
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
1 m 1 m 1
L2 y2 x 2 L2 y2 x 2
or (J6-17)
L1 y1 x1 L1 y1 x1
where m = slope
L 1 x
ln 2 ln 2 (J6-18)
L1 H 1 x1
y1 x x
3. If the relative volatility , from which y , may be assumed
x 1 y 1x 1
constant over the range concerned
In terms of concentration
1 x 2 L2
1
x L
2 2 Note: 1 2 (J6-19)
1 x1 L1 x1L1
L 1 x 1 x1 1 x1
or ln 2 ln 2 ln (J6-20)
1
L 1 1
x 1 x
2 1 x 2
In terms of components
A B
ln 1 ln 1 Note: AB1 AB2 (J6-21)
A2 B2
J6-9
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
vapor and liquid in equilibrium with each other are separated. The system is called “flash”
distillation because the feed, after entering the drum, vaporizes very rapidly.
Feed
F, xF
Liquid
L, x
Figure J6-5. Flash distillation
For a binary system subjected to flash distillation, an overall mass balance gives
FVL (J6-22)
where F = feed
V = vapor
L = liquid
x FF yV xL (J6-23)
Therefore,
V xF x
(J6-24)
F yx
1 f x
y x F (equation of a straight line) (J6-25)
f f
J6-10
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
coordinates are x and y (indicated by broken lines). Or we can have an analytical solution by
trial-and-error method, since there are four unknowns (V, L, y, and x), and only three
equations are availabletwo material balances, (J6-22) and (J6-23), and the equilibrium
relationship between y and x.
equilibrium
curve
Mole fraction A in vapor, yA
0.8
y 1 f
0.6 slope =
f
0.4
0.2
0 x
0 0.2 0.4 0.6 0.8 1
The general equation for simple batch open steam distillation is as follows:
nA
P PA
dn S A
n n C dn S P n P 1
or 1 C (J6-26)
dn A nA dn A PA PA n A
PA
nA nC
J6-11
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
C = nonvolatile impurity
n = moles
= correction factor if vapor deviates from ideal behavior
PA = vapor pressure of volatile component
P = total pressure
P n P nA
n S 1 n A1 n A 2 C ln 1
PA n A 2
(J6-27)
PA
nS P PA mS P PA MS
or (J6-28)
n A1 n A 2 PA mA PA M A
In analyzing the distilling column for calculation purposes, it may be divided into three
sections, as indicated in Figure J6-7.
J6-12
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
condenser
L0 Distillate
D, xD
n
Ln, xn Vn+1, yn+1
Feed
F, xF
m
Lm, xm Vm+1, ym+1
Bottoms
B, xB
reboiler
Material balances can be made about each of the above three sections of the distilling column,
resulting in operating-line equations that relate the concentrations of the vapor and liquid
streams passing each other in each stage. An overall material balances at the top section of the
column gives the rectifying operating line; balances at the bottom section gives the stripping
operating line; and balances at the feed stage gives the feed line equation.
With these operating lines, the calculation of the amounts of streams entering and leaving the
column can be made. Calculations can be graphical using the McCabe-Thiele method
(sections J6.5 and J6.6) or the Ponchon-Savarit method (section J6.7), or they can be
analytical using the stage-to-stage method.
Vn 1 Ln D (J6-29)
J6-13
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
yn 1Vn 1 x n Ln x DD (J6-30)
From these two material balances, the following rectifying operating line equation results:
Ln x D
y n 1 xn D (J6-31)
Ln D Ln D
R x
y n 1 xn D (J6-32)
R 1 R 1
Vm1 Lm B (J6-33)
y m1Vm1 x m Lm x B B (J6-34)
From these two material balances, the following stripping operating line equation results:
Lm x B
y m 1 xm B (J6-35)
Lm B Lm B
F Vm 1 Ln Vn 1 Lm (J6-36)
From these two material balances, the following feed line equation results:
J6-14
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
Another form of equation (J6-38), in terms of the liquid content of the feed, q, is given as
follows:
q x
y x F (feed line or q-line) (J6-39)
q 1 q 1
1. There are no heat losses in the distilling column or the column is adiabatic.
2. The specific heat changes are negligible compared to latent heat changes.
3. The heat of vaporization per mole is constant; that is, the effect of concentration on the
molal latent heat of vaporization is insignificant.
The last assumption is the statement of constant molal overflow (CMO) and is the most
important.
It follows from the assumption of CMO for the McCabe-Thiele method that the V’s above the
feed or in the upper section of the distilling column are equal to each other, which means that
the L’s are also equal to each other; the same is true for the V’s and the L’s below the feed or
in the lower section.
The McCabe-Thiele method makes use of an xy diagram on which the following are plotted:
diagonal, equilibrium data, and operating linesthree straight lines that represent the entire
distilling column.
These three operating lines for the McCabe-Thiele y-x diagram have the following forms:
R x
y n 1 xn D (J6-32)
R 1 R 1
2. Stripping operating line this equation given in (J6-6), with the assumption of CMO,
becomes
L x B
y m 1 xm B (J6-40)
LB LB
J6-15
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
3. Feed together with equations (J6-41) and (J6-42) from the definition of q (quality of
feed or its liquid content),
Lm Ln qF (J6-41)
Vn Vm (1 q)F (J6-42)
material balances made at the feed stage (final form is given in equation (J9-38)), noting
that the feed line will intersect the rectifying and stripping operating lines at common
values of y and x, will give the following form of the feed line equation:
q x
y x F (feed line or q-line) (J6-39)
q 1 q 1
The feed entering the distilling column may have different conditions, as follows:
The above description of the McCabe-Thiele method can be visualized in Figure J6-8.
J6-16
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
1
1
equilibrium 2
curve
3
4
q-line
0.6
5
rectifying
6 operating line
0.4
7
0.2 8
stripping
9 operating line
10
0 xB xF xD
0 0.2 0.4 0.6 0.8 1
L0 L0
R (J6-43)
D 0
xD x
D 0 (J6-44)
R 1 1
Therefore, the overall operating line is the 45º diagonal line. This results in the number of
stages N being minimum.
J6-17
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
1
1
2
0.6
4
0.4
45 line
5
0.2 6
7
8
0 x
B xF xD
0 0.2 0.4 0.6 0.8 1
As indicated in Figure J6-9, the minimum theoretical number of stages is 7.1. This number is
based on stepping off horizontal lines then vertical lines, with the diagonal and the
equilibrium curve as boundaries, from xD to xB.
For an ideal equilibrium curve, the graphical representation on the McCabe-Thiele diagram of
an infinite number of stages, as shown in Figure J6-10, is the intersection of the rectifying
operating line and the feed line at the equilibrium curve. This point of intersection is called
the pinch point.
J6-18
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
0.6
pinch
point
0.4
y-intercept
for Rmin
0.2
0
xB xF xD
0 0.2 0.4 0.6 0.8 1
Figure J6-10. Minimum reflux ratio for ideal system by McCabe-Thiele method
To have an infinite number of stages for a nonideal equilibrium curve, the rectifying operating
line must touch the equilibrium curve at the point of tangency, as illustrated in Fig. J6-11.
This point is called the pinch point at which the compositions of vapor and liquid do not vary
from stage to stage.
J6-19
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
0.8 pinch
Mole fraction A in vapor, yA point
0.6
y-intercept 0.4
for Rmin
0.2
0 xB xD
xF
0 0.2 0.4 0.6 0.8 1
J6-20
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
30000
20000
tie line
10000
h vs yA (saturated liquid)
0
0 0.2 0.4 0.6 0.8 1
J6-21
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
Figure J6-12 shows the enthalpy-concentration plot for a binary vapor-liquid mixture of A and
B at a given constant pressure. The plot is based on arbitrary reference states of liquid and
temperature, and it considers latent heats, heats of solution or mixing, and sensible heat of the
components of the mixture.
x 1 xB
log D
1 x D x B
Nm Note: top bottom (J6-47)
log
For ideal mixtures, or if the relative volatility, , of a binary mixture could be taken as
constant, Rm may be obtained analytically using the Underwood equation as follows:
1 x D 1 x D
Rm
1 x F 1 x F
(J6-48)
J6-22
Philippine Handbook Distillation
in Chemical Engineering by Manuel De Guzman
Although packed towers have continuous contact of vapor and liquid, they can be analyzed
like staged towers in which contact between vapor and liquid is discontinuous. The
assumption is that the packed column could be divided into segments of equal height. Each
segment is taken as an equilibrium stage where leaving streams of vapor and liquid are in
equilibrium with each other. This staged model is only fictitious, but the model can be useful
for the purpose of designing packed columns.
The height of each imaginary stage is referred to as the height equivalent to a theoretical plate
(HETP).
height of packing
HETP (J6-49)
number of theoretical stages
J6-23