National University of

Science and Technology

Faculty of Industrial Technology

Department of Chemical Engineering

MASS TRANSFER PROCESSES 1a TCE 2103

Handout Six

BATCH DISTILLATION
BATCH DISTILLATION

OBJECTIVES
After completing this chapter, you should be able to:

1. Derive the Rayleigh equation for a simple batch distillation (differential

distillation), and state the necessary assumptions.
2. Calculate, by graphical and algebraic means, batch-still temperature,
residue composition, and instantaneous and average distillate
composition for a binary mixture as a function of time for binary batch
distillation.
3. Calculate, by modified McCabeThiele methods, residue and distillate
compositions for binary batch rectification under conditions of equilibrium
stages, no liquid holdup, and constant or variable reflux ratio to achieve
constant distillate composition.

Introduction
In the previous sections conditions have been considered in which there has
been a continuous feed to the still and a continuous withdrawal of products
from the top and bottom. In many instances processes are carried out in
batches, and it is more convenient to distil each batch separately. In these
cases the whole of a batch is run into the boiler of the still and, on heating,
the vapour is passed into a fractionation column. As with continuous
distillation, the composition of the top product depends on the still
composition, the number of plates in the column and on the reflux ratio
used. When the still is operating, since the top product will be relatively rich
in the more volatile component, the liquid remaining in the still will become
steadily weaker in this component. As a result, the purity of the top product
will steadily fall.

Although batch distillations are generally more costly than their continuous
counterparts, there are certain applications in which batch distillation is the
method of choice. Batch distillation is typically chosen when it is not possible
to run a continuous process due to limiting process constraints, the need to
distill other process streams, or because the low frequency use of distillation
does not warrant a unit devoted solely to a specific product. A relatively
efficient separation of two or more components may be accomplished
through batch distillation in a pot or tank. Although the purity of the distilled

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product varies throughout the course of batch distillation, it still has its use in
industry.

Batch operations can be used to advantage when:

1) The capacity of a facility is too small to permit continuous operation at

a practical rate.
2) Seasonal or customer demands require distillation in one unit of
different feedstocks to produce different products.
3) Several new products are to be produced with one distillation unit for
evaluation by potential buyers.
4) Upstream process operations are batchwise and the compositions of
feedstocks for distillation vary with time or from batch to batch.
5) The feed contains solids or materials that form solids, tars, or resin that
can plug or foul a continuous distillation column.

DIFFERENTIAL (SIMPLE) DISTILLATION

The simple, batch distillation apparatus in Figure 6.1, which functions in an
unsteady state manner, was first quantified by Lord Rayleigh and is often
referred to as differential distillation. As shown in Figure 6.1, a feed is initially
charged to a tank, and the vapor generated by boiling the liquid is withdrawn
and enters a condenser. The condensed product is collected as distillate, D,
with composition xD, and the liquid remaining in the pot, W, has composition
xW. There is no reflux; at any instant, vapor leaving the still pot with
composition yD is assumed to be in equilibrium with liquid (residue) in the
still, which is assumed to be perfectly mixed. For total condensation, yD = xD.
The still pot is assumed to be the only equilibrium stage because there are
no trays above the still pot. This apparatus is useful for separating wide-
boiling mixtures.

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Fig 6.1 Differential (Rayleigh) distillation.

Total and component material balances around a batch distillation unit are
shown below:

F W D

FxF WxW Dx D

A convenient method for mathematically representing a binary batch

distillation process is known as the Rayleigh equation. This equation relates
the composition and amount of material remaining in the batch to initial feed
charge, F, and composition, xF:

The following nomenclature is used for variables that are a function of time,
t, assuming that all compositions refer to a particular species in the
multicomponent feed:

D = instantaneous-distillate rate, mol/h;

y = yD = xD = mole fraction in instantaneous distillate leaving the still pot;

W = moles of liquid (residue) left in still;

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x = xW = mole fraction in liquid (residue); and

0 = subscript referring to t = 0.

For any component in the mixture: instantaneous rate of output = DyD.

Instantaneous rate of depletion in the still is

d dx
WxW W W xW dW
dt dt dt
....1

Distillate rate and, therefore, liquid-depletion rate in the still, depend on the
heat-input rate, Q, to the still. By component material balance at any instant:
d dx
WxW W W xW dW Dy D
dt dt dt
..
..2

Multiplying equation 2 by dt:

d WxW WdxW xW dW Dy D dt
....
..3

And since by total balance, -Ddt = Dw

F W
D
t

WdxW xW dW y D Ddt y D dW
.....
..4

Separating variables and integrating from the initial charge condition of F

and xF ,

xW W
dxW dW W

xF
y D xW
W
F
ln
F

....5

Equation 5 is the well-known Rayleigh equation, which was first applied to

batch distillation of wide-boiling mixtures such as HClH 2O, H2SO4H2O, and
NH3H2O, where one stage is sufficient to get the desired separation. Without
reflux, yD and xW are assumed to be in equilibrium, and equation 5 simplifies
to

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x W
dx dW W

xF
y * x
W
F
ln
F

....
..6

Equation 6 is easily integrated when pressure is constant, temperature

change in the still pot is relatively small (close-boiling mixture). For a binary
mixture, if the relative volatility , is assumed constant, substitution of the
x
y
1 x 1
relative volatility equation into 6, followed by integration and
simplification, gives

W 1 xF 1 x
ln ln ln
F 1 x 1 xF
.....7

If the equilibrium relationship y = f (x) is graphical or tabular, integration of

equation 6 can be performed graphically or numerically.

BINARY BATCH RECTIFICATION

For a sharp separation and/or to reduce the intermediate-cut fraction, a
trayed or packed column is added between the still and the condenser, and a
reflux drum is added after the condenser. In addition, one or more drums are
provided to collect distillate cuts. For a column of a given diameter, the
molar vapor-boilup rate is usually fixed at a value safely below the column
flooding point.

Two modes of operating a batch rectification are cited most frequently

because they are the most readily modeled. The first is operation at a
constant reflux rate or ratio (same as a constant distillate rate), while the
second is operation at a constant distillate composition. With the former, the
distillate composition varies with time; with the latter, the reflux ratio or
distillate rate varies with time. The first mode is easily implemented because

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of the availability of rapidly responding flow sensors. For the second mode, a
rapidly responding composition sensor is required. In a third mode, referred
to as the optimal-control mode, both reflux ratio (or distillate rate) and
distillate composition vary with time to maximize the amount of distillate,
minimize operation time, or maximize profit. Constant reflux is discussed
first, followed by constant composition.

Constant Reflux Operation

If R or D is fixed, instantaneous-distillate and still-bottoms compositions vary
with time. Assume a total condenser, negligible holdup of vapor and liquid in
the condenser and column, phase equilibrium at each stage, and constant
molar overflow. Then, the Rayleigh equation applies applies with y D = xD. The
analysis is facilitated by a McCabeThiele diagram using the method.
Initially, the composition of the more volatile component in the liquid in the
still is the charge composition, xF. If there are two theoretical stages (the still-
pot and one equilibrium plate), the initial distillate composition, x D0 , at time
0 can be found by constructing an operating line of slope L/G = R/R + 1, such
that exactly two stages are stepped off to the right from x F to the y = x line.
At an arbitrary later time, say, time 1, at still-pot composition x W < xF, the
instantaneous-distillate composition is xD. In this manner, a time-dependent
series of points for xD as a function of xW is established, with L/G and the
number of stages held constant. The Rayleigh equation cannot be integrated
analytically because the relationship between y D = xD and xW depends on L/G
the number of theoretical stages, and the phase-equilibrium relationship.

However, it can be integrated graphically with pairs of values for x W and yD =

xD obtained from the McCabeThiele diagram, for a series of operating lines
of the same slope. The time t required for this batch rectification can be
computed by a total material balance based on a constant boilup rate G, to
give an equation

F W R 1
t F W
L G
G 1
G

8

With a constant-reflux policy, instantaneous-distillate purity is above

specification at the beginning and below specification at the end of the run.
By an overall material balance, the average mole fraction of LK in the
accumulated distillate at time t is given by

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 FxF Wt xWt
xDavg
F Wt

.9

Constant Distillate Composition

The constant-reflux-ratio policy described in the previous section is easy to
implement. For small batch-rectification systems, it may be the least
expensive policy. A more optimal policy is to maintain a constant G but
continuously vary R to achieve a constant x D that meets the specified purity.
This requires a more complex control system, including a composition sensor
on the distillate, which may be justified only for large batch-rectification
systems. Calculations for the policy of constant x D can also be made with the
McCabeThiele diagram. The method assumes negligible liquid holdup and
constant molar overflow. An overall material balance for the more volatile
component, at any time t, is given by a rearrangement of equation 9 at
constant xD, for W as a function of xW.

xD xF
W F
xD xW
......10

Differentiating equation 10 with respect to t for varying W and xW gives

dW xD xF dxW
F 2
dt ( xD xW ) dt
......11

For constant molar overflow, the distillation rate is given by the rate of loss
of charge, W:

dW dD
G L
dt dt
.....
..12

where D is now the amount of distillate, not the distillate rate. Substituting
12 into 11 and integrating:

F x D xF
xF
dxW
t
G 1 L x xW
2
xWt
G D

.....13
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For fixed values of F, xF , xD, G, and the number of stages, the McCabeThiele
diagram is used to determine values of L/G for a series of values of still
composition between xF and the final value of xW. These values are then used
with equation 13 to determine, by graphical or numerical integration, the
time for rectification or the time to reach any still composition.

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