Dr.
Ranjana Das
Chemical Engineering Dept.
Jadavpur University, Kolkata
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Content
I. Vapor-liquid equilibrium;
[Link] distillation;
III.
Single stage batch and flash distillation;
[Link] fractionating column (single feed,
multi-feed and side stream) using McCabe
Thiele & Ponchon-Savarit method;
V. Azeotropic, extractive; Molecular distillation.
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Distillation
• Both the phase are of the same origin, one phase is created from other by
addition/ extraction of heat – no new components are added as in absorption,
extraction, leaching, etc.
• Separation is based on the difference in volatility
• Distillation processes depends on the vapor pressure characteristics of liquid
mixtures. The vapor pressure is created by supplying heat as separating agent. In
the distillation, the new phases differ from the original by their heat content
• Difference between distillation and evaporation: all the components are present
in both the phases /(no distribution)
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Vapor Pressure
• Vapor Pressure: The vaporization process changes liquid to gaseous state. The
opposite process of this vaporization is called condensation.
• At equilibrium, the rates of these two processes are same.
• The pressure exerted by the vapor at this equilibrium state is termed as the
vapor pressure of the liquid. It depends on the temperature and the quantity of
the liquid and vapor.
• Clausius-Clapeyron Equation or by using Antoine Equation, the vapor pressure
can be calculated.
Clausius-Clapeyron Equation
A differential equation giving the
interdependence of the pressure and
temperature along the phase
equilibrium curve of a pure substance.
where pv and p1vand are the vapor pressures in Pascal at
absolute temperature T and T1 in K. λ is the molar latent heat
of vaporization which is independent of temperature.
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Antoine Equation
The Antoine equation is a class of semi-empirical correlations
describing the relation between vapor pressure and temperature
for pure substances.
pv : Absolute vapour pressure, T: temperature, A, B and C Antonie
coefficient specific to substance
The Antoine equation cannot be used for the entire vapor
pressure range from the triple point to the critical point because
it is not flexible enough. Therefore two sets of coefficients are
commonly used: one set for vapor pressures at temperatures
below the normal boiling point (NBP) and one set for vapor
pressures at temperatures above the normal boiling point.
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Typical representative values of the constants A, B and C are given in the
following Table
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Extension of the Antoine equations
The additional parameters increase the flexibility of the equation
and allow the description of the entire vapor pressure curve. The
extended equation forms can be reduced to the original form by
setting the additional parameters D, E and F to 0.
The extended equations use the e as base for the exponential
function and the natural logarithm. This doesn't affect the equation
form.
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Fig: vapour pressure of a pure liquid
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Phase Diagram For binary mixture phase diagram only two-component
mixture, (e.g. A (more volatile) and B (less volatile)) are considered. There
are two types of phase diagram: constant pressure and constant
temperature
Intersection of the double surface with constant pressure plane will produce a
looped curve without maxim or minima from [Link] of pure B to that of pure A
at particular pressure.
Constant Pressure Phase Diagram
The Figure 5.1 shows a constant pressure phase diagram for an ideal
solution (one that obeys Raoult's Law). At constant pressure, depending on
relative concentrations of each component in the liquid, many boiling point
temperatures are possible for mixture of liquids (solutions) as shown in phase
diagram diagram (Figure 5.1).
Mole fraction of the more volatile
component in liquid x and
corresponding equilibrium mole fraction
y* in vapour
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• Upper curve temp-vap composition (t-y*) and lower curve temp-liquid
composition(t-x). Tie lines equilibrium mixture of vap. and liq.
• The temperature is called bubble point temperature when the liquid starts to
boil and dew point when the vapor starts to condense.
• Boiling of a liquid mixture takes place over a range of boiling points.
Condensation of a vapor mixture takes place over a range of condensation
points.
• The upper curve in the boiling point diagram is called the dew-point curve
(DPC) while the lower one is called the bubble-point curve (BPC). At each
temperature, the vapor and the liquid are in equilibrium.
Mixture rule is applicable:
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Relative volatility/ Separation factor
• For binary mixture, R.V. of more volatile component (A)
w.r.t. less volatile component (B), expressed as αAB, or
simply as α.
• The greater is the distance between equilibrium curve and
diagonal the greater is the difference in liquid and vapour
composition and the easier is separation by distillation.
α =1.0 no separation, larger the value of αabove unity the greater the
degree of separability (explanation from graph)
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Effect of pressure
• As pressure
increases, the
distillation
temperature increases
• Pt3 is the critical
pressure of
component A, above
which the distinction
between vapor-liquid
phase disappear
• At higher pressure,
looped region
becomes narrower,
distillation become
less feasible, because
of reduced relative
volatility
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Constant temperature equilibrium
If the vapor phase is also ideal
P-x-y diagram
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Constant temperature equilibrium
The system obeys Raoult’s law, i.e
* p*A pA x
y
= =
*If pressure is too high then we pt pt
should use fugacity instead of
pressure * pB* pB (1 − x)
1− y = =
pt pt
pA
Also, α A =
pB 16
for a binary mixture the x-y plot is VLE plot
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The curved line in Figure is called the equilibrium line and it describes the
compositions of the liquid and vapor in equilibrium at some fixed pressure.
The equilibrium line can be obtained from the Equation 1 once the relative volatility is
known
…..Eqn 1
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T-x-y diagram
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An azeotrope is a liquid mixture which when vaporized, produces the
same composition as the liquid. Two types of azeotropes are known:
minimum-boiling and maximum-boiling (less common).
Ethanol-water system (at 1 atm, 89.4 mole %, 78.2 oC; Carbon-
disulfide - acetone (61.0 mole% CS2, 39.25 oC, 1 atm) and Benzene -
water (29.6 mole% H2O, 69.25 oC, 1 atm) are minimum-boiling
azeotropes.
Hydrochloric acid - water (11.1 mole% HCl, 110 oC, 1 atm); Acetone
- chloroform (65.5 mole% chloroform, 64.5 oC, 1 atm) Nitric acid-
Water (68% HNO3, 122°C, ambient pressure. )are the examples of
Maximum-boiling azeotropes.
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Positive deviation from ideality
• A mixture whose total pressure is
more than that computed from
ideality is said to show positive
deviation from ideality
• Usually, the partial pressure of each
component is greater than ideal
• Minimum boiling mixture/ azeotropes:
when the positive deviation from
ideality is sufficiently large & the Vap.
Pr. of the two components are not too
far, the total pressure curve may pass
through a maximum at some constant
temperature.
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Positive deviation from ideality
CS2 (A) – Acetone (B) system
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Negative deviation from ideality
• When the total pressure of the
system is less than the ideal
value, the system is said to
deviate negatively from
Raoult’s law
• Maximum boiling mixtures
(Azeotropes):
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Negative deviation from ideality
Acetone (A) – Chloroform (B) system
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Although most distillations are carried out at atmospheric or near atmospheric pressure, it is
not uncommon to distill at other pressures. High pressure distillation (typically 3 - 20 atm)
usually occurs in thermally integrated processes.
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Heteroazeotrope (Partial liquid miscibility)
Liquid mixture which exhibit large positive deviation from ideality but do not
dissolve completely in liquid state. Ex. Isobutanol- water
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Insoluble liquids , Steam distillation
If the liquids are completely insoluble, the vapour pressure of
either component cannot be influenced by the presence of the
other and each exerts its true vapour pressure equals the total
pressure. When the mixture boils the vapour composition is
readily computed-
PA+PB = Pt
y*= PA/Pt
Till two liquid phases are present the mixture will boil at the
same temperature and produce a vapour of constant
composition.
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Problem
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By this method of distillation with steam, so long as the liquid water is present, the
high boiling organic liquid (2040C) can be made to vaporise at a temperature much
lower (99.150C) than its normal b. pt. without the necessity of a vacuum pump
equipment.
*Concept of steam stripping
Steam distillation concept used for separating fatty acids, other commercially
valuable organic compounds like isolation of essential oils, for use in perfumes.
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Batch Distillation
Consider a binary mixture of components A (more volatile) and B (less volatile).
The condensed vapor is known as the distillate. The distillate is collected in a condensate
receiver. The liquid remaining in the still is known as the residual. The process is unsteady state.
The concentration changes can be analyzed using the phase diagram, and detailed mathematical
calculations carried out using the Rayleigh Equation.
As the process is unsteady state, the derivation is based on a differential approach to changes in
concentration with time.
Let L1 = initial moles of liquid originally in still, L2 = final moles of liquid remained in still,
x1 = initial liquid composition in still (mole fraction of A),
x2 = final liquid composition in still (mole fraction A).
At any time t, liquid in the still is L, (mole fraction of A in the liquid being x).
After a small differential time (t + dt), a small amount of
vapor dL is produced.
composition of A in the vapor is y (mole fraction).
The vapor is assumed to be in equilibrium with the residue liquid. The amount of
liquid in the still is thus reduced from L to (L - dL)
while the liquid composition
changed from x to (x - dx).
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Initial amount in still = Amount left in still + Amount vaporized
xL = (x-dx)(L-dL) + ydL
xL= xL- xdL- Ldx+ dxdL+ ydL
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From VLE
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Problem:
Batch distillation 100 kmol of a 60 mole% benzene–toluene mixture is subjected to batch
distillation until a 30 mole% residue is obtained. How many kg of distillate is obtained,
and what is its benzene content?
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= 35
Continuous distillation columns
Continuous columns process : A continuous feed stream.
• Types of Continuous Columns
Continuous columns can be further classified according to the nature of the feed that
they are processing:
• Binary distillation column: feed contains only two components
• Multi-component distillation column: feed contains more than two components
• Multi-product distillation column: column has more than two product streams
where the extra feed exits when it is used to help with the separation,
• Extractive distillation: where the extra feed appears in the bottom product stream
Azeotropic distillation: where the extra feed appears at the top product stream the
type of column internals.
• Tray distillation column: where trays of various designs are used to hold up the
liquid to provide better contact between vapor and liquid, for better separation.
• Packed distillation column: where instead of trays, 'packings' are used to enhance
contact between vapor and liquid.
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Extractive distillation
Azeotropic distillation 37
A single-stage continuous distillation (Flash distillation)
A single-stage continuous operation occurs where a liquid mixture is partially
vaporized. The vapor produced and the residual liquids are in equilibrium in the
process are separated and removed.
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• Flash distillation (sometimes called "equilibrium distillation") is a single stage
separation technique.
• A liquid mixture feed is pumped through a heater to raise the temperature and
enthalpy of the mixture. It then flows through a throttle valve and the pressure is
reduced, causing the liquid to partially vaporize.
• Once the mixture enters a big enough volume (the "flash drum"), the liquid and vapor
separate.
• Because the vapor and liquid are in such close contact up until the "flash" occurs, the
product liquid and vapor phases approach equilibrium.
• Simple flash separations are very common in industry, particularly petroleum refining.
Even when some other method of separation is to be used, it is used as "pre-flash" to
reduce the load on the separation itself.
• When designing a flash system it is important to provide enough disengaging space in
the drum. Drums can also be designed as cyclone separators.
Modeling assumptions:
• No heat losses to surroundings
• Ideal gas behavior for vapor
• Perfect mixing
F, V, and L are the volumetric flows of the feed, vapor product, and liquid product, VT the total
volume of the tank 39