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d xW
d
dW
W x W ) =W
x W
(
dt
dt
dt
Distillate rate and, therefore, liquid-depletion rate in the still, depend on the heatinput rate, Q, to the still. By component material balance at any instant:
d xW
d
dW
W x W )=W
+ xW
=D y D
(
dt
dt
dt
Multiplying (13-1) by dt:
Wd x W + x W dW = y D (Ddt )= y D dW
since by total balance,
Ddt =dW
x Wo
W
d xW
dW
W
=
=ln
y D x W W W
W0
0
W0
and
x Wo ,
This is the well-known Rayleigh equation, which was first applied to batch distillation
of wide-boiling mixtures.
If rectification is present, there are two modes of operation: (1) operation at
constant reflux ratio, and (2) operation at constant overhead composition.
At constant reflux ratio, the reflux is set at a predetermined value at which it is
maintained for the entire run. Since the pot liquid composition is changing, the
instantaneous composition of the distillate also changes. In the case of a binary
mixture, the overhead is then typically diverted to another receiver, and an
intermediate or slop cut is withdrawn until the remaining pot liquid meets the
required specification.
At constant overhead composition, if it is desired to maintain a constant overhead
composition in the case of a binary mixture, the amount of reflux returned to the
column must be constantly increased throughout the run. As time proceeds, the pot
is gradually depleted of the lighter component. The increase in reflux is typically
gradual at first and more rapid near the end of a cut. Finally, a point is reached at
which there is little of the lighter component remaining in the pot and the reflux
ratio has attained a very high value. The receivers are then changed, the reflux is
reduced, and an intermediate cut is taken as before.
FLASH DISTILLATION
One of the simplest separation processes commonly employed is flash distillation. In
this process, part of a liquid feed stream vaporizes in a flash chamber or part of a
vapor feed condenses, and the vapor and liquid in equilibrium with each other are
separated. The more volatile component will be more concentrated in the vapor.
Usually a large degree of separation is not achieved; however, in some cases, such
as the desalination of seawater, complete separation results. It may be batch or
continuous.
The fluid is pressurized and heated and is then passed through a throttling valve or
nozzle into the flash drum. Because of the large drop in pressure, part of the fluid
vaporizes. The vapor is taken off overhead, while the liquid drains to the bottom of
the drum, where it is withdrawn. A demister or entrainment eliminator is often
employed to prevent liquid droplets from being entrained in the vapor. The system
is called flash distillation because the vaporization is extremely rapid after the
feed enters the drum. Because of the intimate contact between liquid and vapor,
the system in the flash chamber is very close to an equilibrium stage.
In Figure 2 a binary mixture of components A and B flowing at the rate of F mol/h
into a heater is partially vaporized. Then the mixture reaches equilibrium and is
separated. The composition of F is xF mole fraction of A. A total material balance on
component A is as follows:
F x F =Vy + Lx
Since F = V + L (overall material balance), the equation becomes,
F x F =Vy + ( FV ) x
Thus:
x x
V
= F
F
yx
Or:
y=
F
F
x x 1
V F
V
Where
L
=
( FV
)
V
V
Represents a straight line of slope passing through the point ( x F , x F ). The values
of x and y required must satisfy, not only the equation, but also the appropriate
STEAM DISTILLATION
A steam distillation is simply a distillation in which steam is involved as a process
component. Steam (water) is inexpensive and immiscible with many chemical
compounds (e.g., hydrocarbons and many organic chemicals) and hence is a special
case of azeotropic distillation. In the usual application, very little of the steam
condenses in the liquid phase, and thus problems of handling two liquid phases in
the contacting equipment are avoided.
Where a material to be distilled has a high boiling point, and particularly where
decomposition might occur if direct distillation is employed, the process of steam
distillation may be used. Steam is passed directly into the liquid in the still and the
solubility of the steam in the liquid must be very low. Steam distillation is perhaps
the most common example of differential distillation.
If a layer of liquid water (A) and an immiscible high boiling point component (B)
such as a hydrocarbon are boiled at 101.3 kPa abs pressure, then, by the phase
rule, for three phases and two components,
P A + P B=P
Where
PA
PB
is vapour pressure of
y A=
PA
P
yB= B
P
P
As long as the two liquid phases are present, the mixture will boil at the same
temperature, giving a vapour of constant composition
yA
. The temperature is
nB PB
=
nA PA
Steam distillation is commonly used for purification of essential oils in the perfume
industry, for distillation of organics obtained from coal, for hydrocarbon distillations,
and for removing solvents from solids in waste disposal. It is also sometimes used in
the food industry for the removal of volatile taints and flavours from edible fats and
oils. In many cases vacuum distillation is used instead of steam distillation to purify
high boiling materials. The total pressure is quite low so that the vapour pressure of
the system reaches the total pressure at relatively low temperatures.
CONTINUOUS DISTILLATION WITH REFLUX
Rectification (fractionation) or continuous distillation with reflux, from a simplified
point of view, can be considered to be a process in which a series of flash
vaporization stages are arranged in a series in such a manner that the vapour and
liquid products from each stage flows countercurrently to each other. The liquid in a
stage is conducted or flows to the stage below and the vapour from a stage flows
upward to the stage above. Hence, in each stage a vapour stream V and a liquid
stream leave in equilibrium.
In order to understand how such an operation is carried out, consider a single plate
in a column or cascade of ideal plates. Assume that the plates are numbers serially
from the top down and that the plate under consideration is the nth plate from the
top. It is shown diagrammatically in Figure 2. Then the plate immediately above this
plate is plate n 1 and that immediately below it is plate n+1. Subscripts are used
on all quantities showing the point of origin of the quality.
Two fluid streams enter plate n, and two leave it. A stream of liquid,
from plate n 1, and a stream of vapour,
V n+1
Ln
Ln1 mol/h,
Vn
streams are the V phase, their concentrations are denoted by y. The liquid streams
are the L phase and their concentrations are denoted by x. Then the concentrations
of the streams entering and leaving the nth plate are as follows: Vapor leaving plate
y
x
y
( n) , Liquid leaving plate ( n) , Vapor entering plate ( n+1) , Liquid
x
entering plate, ( n1) .
Figure 3 shows the boiling point diagram for the mixture being treated. The four
concentrations given above are shown in this figure. By definition of an ideal plate,
x n and
yn
represent
yn
x n1 is greater than
x n and
is greater than y n+1 . Although the streams leaving the plate are in
equilibrium, those entering it are not. This can be seen from Figure 3. When the
vapour from plate n + 1 and the liquid from plate n 1 are brought into intimate
contact, their concentrations tend to move toward an equilibrium state, as shown by
the arrows in Figure 3. Some of the more volatile component A is vaporized from the
liquid, decreasing the liquid concentration from
x n1 to
less volatile component B is condensed from the vapour, increasing the vapour
concentration from
y n+1
to
points and the vapour streams at their dew points, the heat necessary to vaporize
component A must be supplied by the heat released in the condensation of
component B. Each plate in the cascade acts as an interchange apparatus in which
component A is transferred to the vapour stream and component B to the liquid
stream. Also, since the concentration of A in both liquid and vapour increases with
column height, the temperature decreases, and the temperature of plate n is
greater than that of plate n 1 and less than that of plate n + 1.
The purities obtained for the two withdrawn products will depend upon the
liquid/gas ratios used and the number of ideal stages provided in the two sections of
the tower, and the interrelation of these must now be established. The crosssectional area of the tower, however is governed entirely by the quantities of
material handled.
be fed directly into the column, where the actual separation occurs. The height of
the feed point along the column can vary on the situation and is designed so as to
provide optimal results.