Distillation

Mass Transfer Operations-II

Introduction
• Distillation is a method of separating the components of a solution which
depends upon the distribution of the substances between a gas and a
liquid phase applied to cases where all the components are present in both
phases.
• The new phase is created from the original solution by vaporisation or
condensation
• Salt/water: Evaporation
• Ammonia/water: Distillation
• Advantage: No foreign substance introduced (gas absorption, etraction)
• Disadvantage: Addition/removal of heat needs utility
VLE: Vapour-Liquid Equilibrium
• Binary VLE
• x: mol fraction of more volatile
component in liquid
• y*: corresponding equilibrium
mol fraction of A in vapour
• Curve pA: VP of A lying at x=1
• Curve pB: VP of B lying at x=0
• TACA, TBCB
Constant Pressure Equilibrium
Relative Volatility
• Greater the distance between the equilibrium curve and the diagonal,
greater is the difference between the liquid and the vapor
compositions and easier is the separation.
• Relative Volatility is the ratio of concentration of A and B in one phase
to that in the other and is thus a measure of the separability.
• Larger the value of a above unity, greater is the separability
Increased Pressures
Constant Temperature Equilibrium
Ideal solutions: Raoult’s law
• For an ideal solution, the equilibrium partial pressure p ͞* of a
constituent at a fixed temperature equals the product of its vapor
pressure p when pure at this temperature and its mole fraction in the
liquid.

• If the vapour phase is also ideal,

For ideal solutions, it is possible to calculate the entire VLE from the
vapour pressure of pure substances.
Non-ideal:: Fugacity instead of pressures.
Positive Deviations from Ideality
• A mixture whose total pressure is greater
than that computed for ideality

• Partial pressures of each component is

larger than ideal
• As the conc. of each component
approaches unit mol frn., the pp for that
substance approach ideality tangentially.
• Raoult’s law is applicable to substances
present in large conc.
Minimum boiling mixtures: Azeotrope
• When positive deviations from ideality are sufficiently large and the
vapour pressures of the two components are not too far apart, the
total pressure curves at constant temp may rise through a maximum
at some concentration.
• Azeotrope or constant boiling mixture
• Liquid- and vapour-composition curves are tangent at L: point of
azeotropism
• At azeotropic composition, y*=x, a=1
• Common
• Most imp: Ethanol-water at 1 atm, at 89.4 mol % ethanol and 78.2 C.
Insoluble liquids: Steam distillation
• Insoluble liquids: eg hydrocarbon/water
• VP of either component uninfluenced by the presence of the other
and each exerts its true vp at that temp.
• Mixture boils when sum of the separate vapour pressures equals total
pressure
Negative deviations from Ideality
• Total pressure of a system at equilibrium is
less than the ideal values, the system is said
to deviate negatively from Raoult’s law.
• As with positive deviations, as the conc. of
each component approaches unit mol frn.,
the pp for that substance approach ideality
tangentially.
Maximum boiling mixtures: Azeotrope
• When difference in vp of the components is not too great and the
negative deviations are large, the curve for total pressure against
composition may pass through a minimum.
• Gives rise to a maximum in boiling temperature: Azeotrope
• The equilibrium vapour is leaner in the more volatile substance for
liquids whose x is less than the azeotropic composition and greater if
x is larger.
Single stage operation- Flash vaporisation
• Flash vaporisation or equilibrium distillation is a single stage
operation wherein a liquid mixture is partially vaporised, the vapour
allowed to come to equilibrium with the residual liquid, and the
resulting vapour and liquid phases are separated and removed from
the apparatus.
• Batchwise or continuous.
Differential or Simple Distillation
• If during an infinite number of successive flash vaporisation of a liquid
only an infinitesimal amount of the liquid were flashed each time, the
net result would be equivalent to a differential of simple distillation.
• F= moles of charge of composition xF
• W= moles of residual liquid of composition xW
• Rayleigh Equation

• In terms of Relative Volatility,

Continuous Rectification
• Continuous rectification, or fractionation, is a multistage countercurrent
distillation operation.
• The feed is introduced more or less centrally into a vertical cascade of stages
• Vapor rising in the section above the feed called the enriching or rectifying
section is washed with liquid to remove or absorb the less volatile component.
• The liquid returned to the top of the tower is called reflux and the material
permanently removed is the distillate, rich in more volatile component.
• In the section below the feed, called stripping section, the liquid is stripped of
volatile component by vapour produced at the bottom by partial vapourisation of
the bottom liquid in the reboiler.
• The liquid removed, rich in less volatile component is the residue or bottoms.
Terminology
• Reflux ratio
• Condenser, envelop 1

• For substance A,
• Ponchon-Savarit, energy balance
• McCabe-Thiele, material balance
Enthalpy-Concentration diagram
• Liquid solution enthalpy = sensible heat + heat of mixing

• Saturated vapour enthalpy

Characteristics of H-xy diagram
• Binary mixture
• Upper part: Hvapour v/s y and Hliquid v/s x
• Heat required for complete vaporisation of c is HD-HC
• Equilibrium liquid-vapour joined by tie line (EF)
• Represented by G on x,y
• Consider M at (HM, ZM) and N at (HN, ZN)
• Adiabatically mix to get P at (HP, ZP)
• Total MB
• A balance
• Enthalpy balance
• Elimination of P

• This is the equation of a straight line passing through

• Consider a mixture C(HC,ZC)
• C can be considered the result of adiabatically
removing liquid D from vapour E (DE is not a
tie line) or F from G or J from K or any such
combination.
• Projected on to x,y plot
Multistage Tray Towers: Method of
PONCHON-SAVARIT
• Enriching section: Envelop III
• Total MB

• Component A

• LHS: flow of A, up-down or net flow

upward: a constant, independent of tray no.
• Enthalpy balance
• Let Q’

• LHS: flow of heat, up-down: a constant, independent of tray no.

• elimination of D

• On the Hxy diagram, this is the equation of astraight line through

(HGn+1,yn+1) at Gn+1, (HLn,xn)at Ln and (Q’,zD) at ΔD (the difference
point)
• On the Hxy diagram, this is the equation of
a straight line through (HGn+1,yn+1) at
Gn+1, (HLn,xn) at Ln and (Q’,zD) at ΔD (the
difference point
• on xy plot this is the equation of line of
slope Ln/Gn+1. through (yn+1,xn) and
y=x=zD
• Total condenser
• Point D= point L0 (below bbl point)
• G1 has same composition as D and L0
• L1 in equilibrium with G1, at end of tie line 1
• Locate G2 by joining L1 ΔD
• On xy plot: points Ln,Gn+1, like L2,G3 projected
downwards to get point P, loci being operating
curve.
• Tie lines projected downwards produce the
equilibrium curve.
• Stepwise construction between operating curve
and equilibrium curve provide number of
theoretical stages in the enriching section.
Stripping section: Ponchon-Savarit
• Total MB
• Component A balance

• Enthalpy Balance

• Q‘’ = net heat flow out at the bottom,

per mole of residue
• LHS: difference in heat flow, down-up
• Eliminate W
Stripping section
• On the xy diagram, this is a straight line of
slope through

• On Hxy plot, line from GNp+1 to ΔW

intersects at Lm. This projected down give
operating curve. GNp+1 in equilibrium with
LNp+1 (tie line) projected down provides
equilibrium curve.
• Stepwise construction provide no. of
theoretical stages needed in the stripping
section.
The complete fractionator
• Envelop 2

• Eliminating F

• This is the equation of a straight line on

Hxy diagram through (Q’,zD) at
The complete fractionator
• F here is liquid below bbl point, situation may vary. In
any case, the two Δs and F must lie on a single straight
line.
• Locate F, zD, xW
• Locate ΔD vertically on x=zD by computation of Q’ or
line-length ratio using R
• Line ΔDF extended to x=xW locates ΔW ,whose
ordinate can be used to calculate QB.
• Random lines are drawn from ΔD and ΔW to locate the
enriching and stripping section operating line on the xy
diagram.
• The operating lines intersect at M.
• Steps drawn on xy diagram between equilibrium line
and operating line give the number of theoretical
stages.
 Reflux ratio R=L0/D
• Increased reflux ratio: As R is increased, ΔD is
located at higher value of Q’. Since ΔD, F and ΔW
lie on a straight line, ΔW gets lowered. The
operating curve moves closer to 45 axis and fewer
trays are required. But Qc, QW, L, G and all
increase, condenser and reboiler surfaces and
tower cross section must increase to
accommodate larger loads.
• Total reflux: Ultimately, when R=∞, the operating
line coincides with 45 and Δ points are at infinity.
Number of trays needed are minimum. The
condition can be realised practically by returning
all distillate to the top tray by reflux and reboiling
all the residue.
Minimum reflux, Rm
• The minimum reflux ratio Rm is the maximum
ratio which will require an infinite number of
trays for the separation desired, and it
corresponds to the minimum reboiler heat load
and condenser cooling load for the separation.
• Tie line extended to intersect lines x = ZD and x =
xw. It is clear that if ΔD were located at point K,
alternate tie lines and construction lines to AD at
the tie line k would coincide, and an infinite
number of stages would be required to reach tie
line k from the top of the tower. The same is true
if Δ w is located at point J.
Optimum Reflux Ratio
• Any reflux ratio between minimum
and total will provide the desired
separation with corresponding
number of theoretical stages
required varying from infinity to
minimum.
• Increase RR less trays, more heat
duty
• Ropt = 1.2 Rm to 1.5 Rm
Multistage Tray Towers: Method of McCabe-Thiele
• Principle of equimolal overflow and vaporisation: The rate of liquid
flow from each tray is constant on a molal basis, but since the average
molecular weight changes with tray number, the weight rates of flow
are different.
• Total condenser
• Reboiler: 1 equilibrium stage
Enriching section
Stripping Section
Introduction of
Feed
𝐿−𝐿 𝐻𝐺 −𝐻𝐹
• 𝑞= =
𝐹 𝐻𝐺 −𝐻𝐿

Quantity q is the heat required to convert 1

mol of feed from its condition 𝐻𝐹 to a
saturated vapour, divided by the molal latent
heat 𝐻𝐺 − 𝐻𝐿

q line is a straight line with slope q/(q-1)

passing through the point x=y=zF on the 45
diagonal.
Reflux ratio

Total Reflux Minimum Reflux

Azeotropic Distillation
• Low relative volatility of binary mixture: high reflux ratio, large
column diameter, more no. of trays OR impossible to produce nearly
pure products
• Add Entrainer: form new low boiling Azeotrope with one of the
original constituents, whose volatility is such that it can be separated
from the original constituent.
• Ex: AA (118 C)/water (100)
• Butyl acetate: slightly soluble in water: forms heteroazeotrope at 92 C
• Sufficient BA added to the top of the DC which forms Azeotrope with
all water
• Top product: BA+water
• Bottom product: AA
• BA+water: condensation:
two layers:
• nearly pure water saturated
with BA: stripped of BA in
second column
• nearly pure BA saturated
with water: returned to the
top as reflux
Example 2: Ethanol/water/benzene
• Ethanol-water: Azeotrope at 89.4 mol% ethanol at 1 atm
• Introduce Bz to the top
• Ternary Azeotrope ethanol 22.8%/water 23.3%/benzene 53.9% by
mol is formed at 69.4 C
• Ethanol bp 78.4 C residue
• Azeotropic overhead products separates into two layers: one, rich in
benzene: returned as reflux, second, water/ethanol/benzene
Entrainer/New Azeotrope
• Preferably form a low-boiling Azeotrope
• Azeotrope with one constituent, preferably the one present in
minority to reduce heat loads
• New Azeotrope: sufficient relative volatility with remaining
constituent
• New Azeotrope: preferably lean in entrainer content to reduce
separation load
• New Azeotrope: preferably of heterogeneous liquid type so that the
entrainer is easily separated. Else use other operations like LLE
• Cheap, readily available, chemically stable, non-corrosive, non-toxic,
Extractive Distillation
• Binary mixture difficult to separate
• Add third component: solvent: low volatility, hence not appreciably
vaporized.
• Ex: Separation of toluene (110.8 C) from isooctane (99.33 C)
• Solvent: Phenol (181.4 C) from top
• Relative volatility of isooctane is positively modified with 83 mol%
phenol
• Isooctane readily distilled as top product
• Toluene+phenol bottom product: second DC, relatively easy to
separate
Choice of solvent
• High selectivity: ability to alter VLE of the original mixture sufficiently
to permit easy separation with small quantity of solvent
• High capacity: ability to dissolve the components
• Low volatility: prevent appearance in the top product
• Separability: readily separable, should not form Azeotrope
• Cost, toxicity, corrosive character, chemical stability, freezing point,
viscosity, etc.
Azeotropic/Extractive Distillation
• Limitations of Azeotropic/Extractive Distillation
• Additional component: Can never be 100% recovered
• Need of separation: fixed + running cost
• Reduces purity of the product
• Inventory to be maintained
• Choice of material
• Extractive distillation more desirable
• Greater choice of solvent
• Smaller amount needs to be volatalised