Chemical Engineering Operations

Distillation

Dr. Anand V. Patwardhan

Professor of Chemical Engineering
Institute of Chemical Technology
Nathalal M. Parekh Road
Matunga (East), Mumbai−400019

Email: anand@udct.org; avpuict@gmail.com, avpiitkgp@gmail.com

1
REVIEW of the following BASICS of BINARY distillation:
1. Vapour liquid equilibrium
2. Relative volatility
3. Enthalpy − Concentration Diagram
4. Application of enthalpy − concentration diagram to FLASH
distillation of a BINARY mixture
5. Steam distillation
6. Differential distillation / Rayleigh distillation
7. Continuous multistage fractionation of binary mixtures
(McCabe−Thiele method)
a) Material and energy balances
b) Determination of number of stages
c) Total reflux – Fenske’s equation – Minimum number of stages
d) minimum reflux ratio
8. Continuous multistage fractionation of binary mixtures (Ponchon
Savarit Method)
a) Determination of number of stages
b) Minimum reflux ratio
c) Total reflux
2
Distillation: Technique of preferential separation of
MORE VOLATILE COMPONENT(S) from
LESS VOLATILE COMPONENT(S) by partial
vaporisation, followed by condensation.
Distribution of components in two phases = f
(vapour−liquid equilibrium).
Distillation column consists of:
(1) Column having trays or packing and
suitable internals
(2) Reboiler
(3) Condenser

3
Functioning of distillation column:
(1) Feed enters at a suitable point.
(2) Reboiler partially vaporises the liquid received from
the column bottom.
(3) Vapour flows UP through the trays (or packing),
leaves at the column top and enters into overhead
condenser.
(4) A part of the condensate is withdrawn as TOP
PRODUCT, and the rest is fed back to the column as
REFLUX that flows down the trays (or packing).
(5) Intimate contact between UPFLOWING vapour and
DOWNFLOWING liquid occurs on the trays (or
packing).
(6) EXCHANGE of mass takes place between the liquid
and vapour phases: M.V.C. from liquid → vapour;
4
L.V.C. from vapour → liquid.
 Vapour
Schematic of a 3
typical
distillation
column 4

2 D
Reflux
F
Feed 1 F: Feed (L, V, or a mixture of
L and V)
D: Distillate or top product
W: Bottom product

1: Distillation column
2: Feed preheater
3: Condenser
Steam 4: Reflux drum
5
5: Reboiler
W 5
Condensate
 Vapour−Liquid Equilibrium
Under a given set of conditions, the equilibrium
vapour composition is related to the liquid
composition.
Gibb's Phase Rule
F = C - P + 2
where C = number of components
P = number of phases
F = degrees of freedom

6
 Example
ƒ Aqueous solution of C2H5OH in a closed vessel fitted with a
valve
ƒ Boiled for some time to expel the air ⇒ contains only H2O +
C2H5OH
ƒ Vessel put in a constant temperature bath for sufficient time
ƒ System reaches equilibrium ⇒ L and V compositions, and PT in
the vapour space attain unique constant values
⇒ Number of Components = 2 (C2H5OH and H2O)
⇒ Number of Phases = 2 (L and V)
⇒ Degrees of Freedom = 2
¾ Total number of parameters = 4 (T, PT, L composition,
V composition)
¾ 2 of these 4 parameters can be fixed to define system
COMPLETELY
7
ƒ Accurate Vapour−Liquid Equilibrium (VLE)
data are essential for reliable design of a
distillation column.

ƒ If the experimental data are not available

(multicomponent systems), a suitable predictive
method can be adopted, for example, UNIFAC
method.

ƒ If data for prediction is also not available,

conduct experiments to determine the VLE.

8
 Constant T & Constant P Binary V−L Equilibria
TB H VAPOUR
N1
M1 T−y
(dew point)

N H1
M
F V
G L
a
T−x
(bubble point) L1 V1
LIQUID G1 TA
x zF y
1

↑
y Diagonal
y=x
b
Equilibrium
(x−y) diagram

9
(0, 0) x→ 1
ƒ At constant P: Boiling Temperature versus liquid
composition ⇒ T−x (bubble point) curve
ƒ At constant P: Boiling Temperature versus vapour
composition ⇒ T−y (dew point) curve
ƒ Liquid at Point G → heated gradually → Point M
ƒ → heating continued → Liquid becomes progressively
POORER in A
ƒ → Liquid Boiling Point (bubble point) increases
ƒ → Last liquid droplet at M1
ƒ → Final VAPOUR at N1
ƒ → further heating gives SUPERHEATED vapour
ƒ Same description can be given for LV, L1V1, G1H1

10
ƒ F = amount of two-phase mixture, kmol (zF = mole
fraction)
ƒ L = amount of liquid, kmol (x = mole fraction)
ƒ V = amount of vapour, kmol (y = mole fraction)
ƒ Overall mole balance: F = L + V
ƒ Component A balance: F zF = L x + V y
L y* - z length of section VF
Elimating F: = F
V z -x length of section FL
F
( Lever Arm Rule )

11
ƒ Raoult’s Law: vapour-liquid equilibria for Ideal
Solutions:
p
A
= x P v and p
A A B B B (
= x Pv = 1 - x ) Pv
A B

A B A A (
Total pressure = p + p = x P v + 1 - x ) Pv
A B
Mole fraction of A in vapour phase = y
A
= p P
A T ( )
= x Pv P
A A T
The above equation can is used to compute V−L
equilibrium data for IDEAL BINARY mixtures.

12
 Deviation from Ideality and Formation of
Azeotropes

POSITIVE deviation: a liquid mixture exerting an

equilibrium total vapour pressure more than that
computed by ideal equation.

NEGATIVE deviation: a liquid mixture exerting an

equilibrium total vapour pressure less than that
computed by ideal equation.

13
 AZEOTROPES
¾If there is LARGE POSITIVE deviation from ideality,
and the vapour pressures of A and B are not much
different, the TOTAL PRESSURE CURVE may have a
MAXIMUM at a certain liquid composition ⇒ constant
boiling mixture ⇒ minimum boiling AZEOTROPE.
¾The x−PT and y−PT curves touch at Azeotropic
Composition.
¾The x−T and y−T curves pass through a common
minimum.
¾The equilibrium curve crosses the diagonal line at the
azeotropic composition.

14
V−L Equilibria of a Minimum−Boiling Azeotrope (ethanol − benzene)
x − PT curve

Equilibrium pressure →
x − PB curve

x − PA curve
a
Ideal
behaviour

↑
y b
Azeotropic
point, x = y

15
(0, 0) x→ 1
¾If there is LARGE NEGATIVE deviation from ideality,
the partial pressures of individual components are <
ideal values, the TOTAL PRESSURE CURVE may
have a MINIMUM at a certain liquid composition ⇒
constant boiling mixture ⇒ MAXIMUM boiling
AZEOTROPE.
¾The x−PT and y−PT curves touch at Azeotropic
Composition.
¾The x−T and y−T curves pass through a common
minimum.
¾The equilibrium curve crosses the diagonal line at the
azeotropic composition.

16
 RELATIVE VOLATILITY
Relative volatility of a component A in a mixture
indicates the EASE of its SEPARATION from
another component B.
Relative volatility of A =
( concentration of A concentration of B ) vapour phase
( concentration of A concentration of B )liquid phase
y (1 - y ) y (1 - x )
α = =
AB x (1 - x ) x (1 - y )
αx
⇒ y =
1 + ( α - 1) x

17
For IDEAL binary solutions, α can be expressed in
terms of vapour pressures of the components:

α =
y (1 - y )
=
( pA PT ) ( pB PT )
x (1 - x )
( p Pv
A A )( p Pv
B B )
Pv vapour pressure of A
= A =
Pv vapour pressure of B
B

18
 Equilibrium in a Multicomponent System
¾ Hydrocarbons of a homologous series are nearly ideal
solutions.
¾ For an IDEAL solution, we can write: v
i=n p x P
v i = j j
y P = p = x P and P = ∑ p ⇒ y =
j T j j j T i j P i=n
i=1 T v
∑ x P
i i
i=1
where P v = vapour pressure of pure component j at the given temperature
j
Noting that αij = Piv Pjv , the above equation can be rewritten as:
x x
j j
y = =
j ⎛ ⎞ i=n
⎜ 1 ⎟ i=n v ∑ x α
i ij
⎜ v ⎟ ∑ xi Pi i=1
⎜ Pj ⎟ i = 1
⎝ ⎠
For hydrocarbon mixtures, a quantity called “equilibrium
vaporisation ratio” is extensively used: y Pv
K = i = i
i x P
i T 19
 Equilibrium in a nonideal system
At equilibrium, the FUGACILITIES of the component i in the
vapour phase and in the liquid phase are EQUAL.
fV = fL
i i
f V = Φ V y P and f L = ΦL x P = x γ f 0
i i i T i i i T i i i
where Φ V = fugacity coefficient of component i in vapour phase
i
γ = activity coefficient of component i in liquid phase
i
f 0 = fugacity of component i at standard state
i
For low−to−moderate pressures, the “fugacity at standard state”
can be approximated to the “vapour pressure” at the given
temperature, that is: f L = x γ Pv
i i i i
Thus, at equilibrium: Φ V y P = x γ P v
i i T i i i

20
 ENTHALPY − CONCENTRATION DIAGRAM
Change in “composition” is accompanied by a change in
“enthalpy”. For a given T and concentration x of a liquid, the
molar enthalpy HL can be calculated using the equation:
HL = cPS Mav (T − T0) + ΔHS
HL = molar enthalpy of the solution at temperature T,
kJ/kmol
CPS = specific heat of the solution, kJ/(kg K)
Mav = average molecular weight of the solution
T0 = reference temperature, K
ΔHS = heat of solution at the reference temperature T0,
kJ/kmol
21
 ENTHALPY − CONCENTRATION DIAGRAM

Since the heat of mixing of the vapour is negligible, we can

use the following equation to compute the molar enthalpy of
the saturated vapour HV at a given T and y:

HV = y MA {cPA (T − T0) + λA} + (1 − y) MB {cPB (T − T0) + λB}

cPA, cPB = specific heats of pure LIQUIDS A and B, kJ/(kg K)

λA, λB = heats of vaporisation of A and B at temperature T,

kJ/kg

22
 ENTHALPY − CONCENTRATION DATA (Example)
Aceone (A) − Water (B) system at 1 atm total P. Integral heat of solution (15 0C)
at different concentrations, specific heat of solutions and x−y data are given:

T, 0C X y ΔHS cPS ƒ Average specific heat of liquid

56.5 1 1 0 0.54 acetone = 0.57 kcal/(kg K)
57 0.95 0.963 0 0.56 ƒ Specific heat of water = 1
57.5 0.9 0.935 −10.55 0.56
kcal/(kg K)

58.2 0.8 0.898 −23.88 0.61 ƒ Heat of vaporisation of acetone

= λA = 128.8 − (T 0C − 50),
58.9 0.7 0.874 −41.11 0.66
kcal/kg
59.5 0.6 0.859 −60.3 0.7
ƒ Average heat of vaporisation of
60 0.5 0.849 −83.56 0.75
water = λB = 550 kcal/kg
60.4 0.4 0.839 −121.5 0.8
61 0.3 0.83 −171.7 0.85
62.2 0.2 0.815 −187.7 0.9
66.6 0.1 0.755 −159.7 0.96
75.7 0.05 0.624 −106.8 0.98
91.7 0.01 0.253 −22.2 1
100 0 0 0 1 23
 x−y−H (Enthalpy−Concentration Diagram)
15000 kcal/mol

D y − HV curve N
P
M J

Δ(HV)2 Tie Lines

F

x − HL curve
Δ(HV)1
(a)
W I

0
x, y →
1
Q

↑
y (b)
R

24
(0, 0) x→ 1
 ENTHALPY − CONCENTRATION DIAGRAM
ƒ The amount of vapour and liquid phases SEPARATED can be
determined by “Lever Arm Rule”.
ƒ Point R on the x−y diagram corresponds to Tie Line WD.
ƒ Point Q on the x−y diagram corresponds to Tie Line IJ.
Consider 2 solutions whose states (H and x or y) and amounts are
given by M and N. After MIXING, the resultant solution is P. Hence:
Total material balance: M + N = P
Component A balance: M zM + N zN = PzP
Enthalpy balance: M HM + N HN = PHP

Eliminating P: M/N = (zN − zP)/(zP − zM)

Eliminating P: M/N = (HN − HP)/(HP − HM)

⇒ (HN − HP)/(zN − zP) = (HP − HM)/(zP − zM)

⇒ Slope of section NP = Slope of section MP
⇒ Points M, N, and P are collinear.

25
 Vapour
Schematic of a
FLASH
distillation unit
Top product
baffles D, xD = yD , HD
Feed
F, zF , HF
Flash drum
+Q

Bottom product
W, xW , HW
26
 Flash vaporisation of a BINARY MIXTURE
ƒ If a sufficiently hot liquid is THROTTLED into a vessel, a part of it
vaporises ⇒ vapour will be richer in MVC ⇒ partial separation.
ƒ The liquid is heated under Pressure, and throttled into a vessel
under Reduced pressure.
ƒ Let the Flow Rate, Composition, Enthalpy of FEED,
DISTILLALATE (TOP), and BOTTOM products be (F, zF, HF), (D,
xD, HD), (W, xW, HW), and Q be the rate of supply of heat exchanger:
Total material balance: F = D + W
Component A balance: F zF = D xD + W xW
⇒ (D + W) zF = D xD + W xW
Enthalpy balance : F HF + Q = D HD + W HW
⎛ Q⎞
x − z H − ⎜H + ⎟
W D ⎝ F F ⎠
E lim inating F: − = D F =
D x − z ⎛ Q⎞
W F H − ⎜H + ⎟
W ⎝ F F ⎠
27
 Flash Vaporisation of a Binary Mixture
15000 kcal/mol

y − HV

Enthalpy (HL, HV),

D

kcal/kmol
F (zF, HF + Q/F)

x − HL (a)
W
F1
0
x, y →
1

↑
y F′ (zF, zF) (b)
W x −z
Slope = − = D F
D x −z
W F

28
(0, 0) x→ 1
 Flash vaporisation of a BINARY MIXTURE
ƒ Cold feed at F1 ⇒ passes through preheater ⇒ receives Q heat
energy ⇒ hot feed F ⇒ FLASHES into vapour (D) and liquid (W)
upon throttling into the flash drum.
ƒ The enthalpy and composition of vapour (D) and liquid (W) streams
are obtained by drawing TIE LINE through F.
ƒ The point F′ (zF, zF) is located on the diagonal of x−y plot.
ƒ Point P is located on the equilibrium curve such that the slope of the
line F′P = −W/D. The line F′P is the ‘operating line’ for flash
vaporisation process.
ƒ By using the H−x−y and x−y curves, the amounts and compositions
of D and W can be calculated for a given feed for given Q.
ƒ Alternatively, if the fraction of feed to be vaporised is specified, the
required Q can be computed.
ƒ The analysis can be extended to the case of a real stage with a given
value of stage efficiency (How ?).

29
Schematic of a STEAM
DISTILLATION unit Vapour

Receiver A

Feed
B
Steam (water)
coil
Open
steam
Steam
sparger
Residue
30
 Steam Distillation
ƒ For an ideal binary solution, yA = pA/PT = (xA PAV)/PT
ƒ However, if A and B are IMMISCIBLE, their mixture
exerts a vapour pressure = Σ (vapour pressures of
individual components).
ƒ Hence the BUBBLE POINT of such a mixture < boiling
point of either A and B.
ƒ Process: Live steam is passed through a liquid ⇒ A
vaporises ⇒ leaves WITH steam ⇒ condenser ⇒ 2 layers
(A and B) ⇒ separated by decantation.

31
Applications of steam distillation:

¾ Separation of high boiling materials (decolourisation,

deodourisaion of vegetable oils, purification of essential
oils).

¾ Separation and purification of hazardous materials like

turpentine

¾ Separation of thermally unstable materials

¾ Separation of volatile impurities from waste water

(removal of ammonia, VOCs)

32
 Separation of A immiscible with water
ƒ PT = PAV + PBV ⇒ PBV = PT − PAV
ƒ If mA moles of A are volatilised by putting in mB moles of
steam, and if the system operates at equilibrium,
mA/mB = PAV/PBV = PAV/(PT − PAV)
⇒ mA = mB PAV/(PT − PAV)
ƒ However, if the system does not operate at equilibrium, pA
< PAV
⇒ A factor called “vaporisation efficiency E” is defined =
pA/PAV
⇒mA = mB E PAV/(PT − PAV)
ƒ The above equation can be used to compute the steam
requirement.
ƒ The vaporisation efficiency usually ranges from 60% to
90%. 33
 BATCH DISTILLATION of a Binary Mixture
(Differential Distillation / Rayleigh Distillation)
ƒ Equilibrium is assumed in the still.
ƒ Feed is charged to a still pot.
ƒ heat is continuously supplied.
ƒ As boiling continues, MVC in liquid decreases with time
ƒ Vapour is led to condenser
ƒ The condensate (top product) is collected in a receiver.
ƒ At the beginning, the condensate is very rich in MVC.
ƒ MVC in the condensate decreases with time.
ƒ Applicable when the components greatly differ in volatility
and when ultra−pure products are NOT required.

34
BATCH DISTILLATION of a Binary Mixture
ƒ Theoretical analysis is based on “differential mass balance”.
ƒ Let, at instance of time,
L = moles of liquid, having mole fraction x
D = moles of accumulated condensate
y = mole fraction of equilibrium vapour
dL = change in amount of liquid over differential time
dD = change in amount of vapour withdrawn over
differential time

35
ƒ Differential mass balance:
Total material balance: − dL = dD
Component A balance: − d(L x) = y dD
⇒ − L dx = y dD + x dL = y dD − x dD = (y − x) dD
Putting dD = − dL, and rearranging: dL = dx
L y − x
ƒ If distillation starts with F moles of feed (xF), and continues
till the liquid reduces to W moles (xW), above equation is
integrated as:
W dL x x
W dx F W dx
∫ = ∫ ⇒ ln = ∫
F L x y − x W x y − x
F F
(Rayleigh equation)
36
 x
F W dx
ln = ∫ (Rayleigh equation)
W x y − x
F

ƒ If x−y data is available, the RHS can be solved graphically.

ƒ If y = f(x) is available, RHS can be solved analytically /
numerically.
ƒ If α = αAVERAGE, then RHS can be solved analytically, as
follows:

ln
F
x
= ∫
W dx
=
1
ln
x
F (
1 − x
W ) + ln (1 − xW )
W x
F 1 +
αx
( α − 1) x
- x α − 1 x
W (
1 − x
F ) ( 1 − xF )
Fx F (1 − x )
In a more convenient form : ln F = α ln W
Wx
W W (1 − x )
F

37
ƒ The above equation involves 4 quantities: F, W, xF, xW.

ƒ The AVERAGE composition of the ACCUMULATED

distillate is given be TOTAL and COMPONENT material
balances:

Total material balance: F = D + W

Component material balance: F xF = D yD,Average + W xW

38
Continuous Multistage
Fractional Distillation of
Binary Mixtures

39
 Vapour

Rectifying
Envelope 1

section
−QC
Envelope 2
1
n
Feed Ln Vn+1 Top product
F, zF , HF xn yn+1 D, xD, HD
HL,n HV,n+1
f
m L’m V’m+1
Envelope 3
xm ym+1
HL,m HV,m+1 Envelope 4
Stripping
section

N Vapour

+QB
Bottom product
W, xW , HW
40
 MATERIAL AND ENERGY BALANCE EQUATIONS
ƒ The determination of number of stages is based on steady
state M & E B equations over the ENVELOPES as shown
in the Figure.
ƒ L & V: liquid and vapour flows ABOVE the feed location.
ƒ L’ & V’: liquid and vapour flows BELOW the feed
location.
ƒ Ln & Vn = molar liquid and vapour flow rate LEAVING nth
stage.
ƒ HL,n & HV,n = molar liquid and vapour enthalpy LEAVING
nth stage.
ƒ L0 = flow rate of reflux to the top stage (suffix ‘0’ signifies
that the stream is ‘as if’ coming from a hypothetical 0th
stage above top stage.

41
ƒ QC = heat removal rate from overhead condenser.
ƒ QB = heat supply rate to reboiler (to vaporise a part of the
liquid leaving the bottom stage).
ƒ F = feed rate to the column.
ƒ zF = mole fraction of MVC in feed.
ƒ D = rate of distillate removal from reflux drum.
ƒ xD = mole fraction of MVC in distillate.
ƒ W = rate of bottom product removal from reboiler.
ƒ xW = mole fraction of MVC in bottom product.
ƒ L0/D = R = reflux ratio.

42
 Vapour: V1, y1, HV1

Envelope 1
−QC
Stage 1

Reflux: L0, x0, HL0 Top product:

D, xD, HD

43
 ENVELOPE 1
(condenser + reflux drum)

Overall balance:
V1 = L0 + D = R D + D = D (R + 1)

Component “A” balance:

V1 y1 = L0 x0 + D xD

Enthalpy balance:
V1 HV1 = L0 HL0 + D HD + QC
⇒ QC = D { (R + 1) HV1 − R HL0 − HD }

Please note: y1 = xD = x0 (for total condenser)

44
 Vapour

−QC Envelope 2
Rectifying
section
Stage n
Top product
D, xD, HD
Ln Vn+1
xn yn+1
HL,n HV,n+1

45
 ENVELOPE 2
(part of rectifying section + condenser)

Overall balance:
Vn+1 = Ln + D

Component “A” balance:

Vn+1 yn+1 = Ln xn + D xD

Enthalpy balance:
Vn+1 HV,n+1 = Ln HL,n + D HD + QC
If you put n = 0, equations for Envelope 1 are obtained !

46
 Stage m
Stripping
section

L’m V’m+1 Envelope 3

xm ym+1
HL,m HV,m+1
Vapour

+QB
Bottom product
W, xW, HW
47
 ENVELOPE 3
(part of stripping section + reboiler)

Overall balance:
L’m = V’m+1 + W

Component “A” balance:

L’m xm = V’m+1 ym+1 + W xW

Enthalpy balance:
L’m HL,m + QB = V’m+1 HV,m+1 + W HW

48
 Vapour
−QC

Rectifying
section
Top product:
D, xD, HD
Feed: Feed stage
F, zF, HF
Stripping
section
Envelope 4

Vapour

+QB
Bottom product
W, xW, HW 49
 ENVELOPE 4
(entire column + condenser + reboiler)

Overall balance:
F=D+W

Component “A” balance:

F z F = D x D + W xW

Enthalpy balance:
F HF + QB = D HD + W HW + QC

50
ƒ Above the FEED POINT: Vapour is enriched OR
purified by discarding the LVC into the downflowing
liquid ⇒ MVC concentration in vapour is more than
that in the feed ⇒ Rectifying OR enriching section.

ƒ Below the FEED POINT: MVC is removed or

stripped out of the downflowing liquid ⇒ MVC
concentration in vapour is less than that in the feed
⇒ stripping section.

51
ƒ Flow rate, composition, state of FEED: T, P, phase, etc.
Feed may be L, V, or V+L (two-phase).
ƒ Required degree of separation: requirement of QUALITY
or PURITY.
ƒ Reflux ratio and the condition of the reflux: The ratio of
reflux FED BACK to the top and the top product
WITHDRAWN. Reflux may be SATURATED liquid or
SUB−COOLED liquid.
ƒ Operating pressure and allowable pressure drop across the
column: operating pressure also determines the
TEMPERATURE of column. The ΔP = f (type, number of
hydraulic design of trays OR type and size of packings). ΔP
is very important if the column is run at LOWER
PRESSURES.
ƒ Tray / packings type: determine the efficiency of
separation. 52
 Determination of Number of Trays: McCabe−Thiele Method
ƒ Developed in 1925: graphical solution of material balance
equations together with the equilibrium relation x−y (or
equilibrium data).
ƒ Assumptions:
1. CONSTANT MOLAR OVERFLOW of liquid (and vapour) from
one tray to another over any section of the distillation column, that
is:
L0 = L1 = L2 = ... = Ln = L (RECTIFYING section);
L’m = L’m+1 = ... = L’N = L’ (STRIPPING section), AND
V1 = V2 = V3 = ... = Vn+1 = V (RECTIFYING section);
V’m+1 = V’m+2 = ... = V’N+1 = V’ (STRIPPING section);
2. Heat loss from distillation column is negligible. (If there are heat
losses, there will be NET condensation within the column, leading
to a corresponding variation in the flow rates along the column.

53
Steps:

ƒ (1) Draw equilibrium curve using available x−y data

ƒ (2) Draw operating lines for the rectifying and the

stripping sections

ƒ (3) Draw the STEPS between the equilibrium curve

and the operating lines to find out the number of
IDEAL stages.

54
 The RECTIFYING Section
ENVELOPE 2 (part of rectifying section + condenser)
Component “A” balance: Vn+1 yn+1 = Ln xn + D xD
since R = L
0
D=L D ( CMO: constant molar overflow )
L D LD x
⇒ y = x + x = x + D
n+1 V n V D V D n V D

R x
⇒ y = x + D
n+1 R + 1 n R + 1
ƒ The above equation is a STRAIGHT line, having
slope = R/(R+1), and Y−intercept = xD/(R+1). It is
satisfied by xn = xD; yn+1 = xD. This equation is called
the “operating line for RECTIFYING section”.
55
 The STRIPPING Section
ENVELOPE 3 (part of stripping section + reboiler)
Component “A” balance: L’ xm = V’ ym+1 + W xW
since V' = L' - W
L' W
⇒ y = x - x
m+1 V' m V' W
L' W
⇒ y = x - x
m+1 L' - W m L' - W W
ƒ The above equation is a STRAIGHT line, having
slope = L’/(L’ − W), It is satisfied by the point (xW,
xW). This equation is called the “operating line for
STRIPPING section”.
56
 The FEED line

Consider the plate ON WHICH the feed is introduced (feed plate).

L, HL, f−1 V, HV, f Total material balance:

F + L + V’ = L’ + V
Enthalpy balance:
F, zF, HF
f F HF + L HL, f−1 + V’ HV, f+1 =
L’ HL, f + V HV, f
Assuming Uniform Enthalpy:
HL, f−1 ≈ HL, f ≈ HL
L’, HL, f V’, HV, f+1 and HV, f+1 ≈ HV, f ≈ HV

⇒ F HF + L HL + V’ HV = L’ HL + V HV
⇒ (L’ − L) HL = (V’ − V) HV + F HF
Eliminating V and V':
L' - L = HV - HF = q (say)
F H -H
V L
57
L’ − L = increase in the liquid flow rate across the feed stage as a
result of introduction of the feed

= Rate of LIQUID INPUT with the feed

⇒ LIQUID FRACTION in the feed

Also, q = heat required to convert 1 mole feed to saturated vapour

molar heat of vaporisation of the saturated liquid

ƒ If the feed is at its bubble point (saturated liquid), q = 1

ƒ If the feed is at its dew point (saturated vapour), q = 0

ƒ If the feed is a two-phase mixture, q = fraction of liquid in the feed

⇒ (1 − q) = quality of the feed

58
ƒ If the point of intersection of RECTIFICATION operating
line and STRIPPING operating line is (x, y), then
V y = L x + D xD and V’ y = L’ x − W xW
ƒ Subtracting the above equations, and using the equation for
component balance for the complete column (F zF = D xD +
W xW), we get:
(V − V’) y = (L − L’) x + (D xD + W xW) = (L − L’) x + F zF
ƒ Total material balance on feed plate:
F + L + V’ = L’ + V
ƒ Using the above two equations, and the definition of q, we
get the equation of FEED LINE:
z
y =
q
q − 1
x −
q − 1
(
F , passing through z , z
F F )and

the intersection of two operating lines

59
ƒ The number of IDEAL TRAYS are determined by step
(staircase) construction between the equilibrium curve and
operating lines.
ƒ (xn, yn): on equilibrium curve.
ƒ (xn, yn+1): on operating line.
ƒ Construction may start from either D (xD) or W (xW).
ƒ When the FEED LINE is crossed, a CHANGEOVER from
one operating line to the other is done (that is, a transition
from RECTIFICATION to STRIPPING section, or vice
versa).

60
1. If feed is Superheated Vapour: feed line has +VE slope
(q < 0): Explain.
2. If feed is Saturated Vapour: feed line is horizontal
(q = 0): Explain.
3. If feed is Liquid + Vapour: feed line has −VE slope
(0 < q < 1): Explain.
4. If feed is Saturated Liquid: feed line is vertical
(q = 1): Explain.
5. If feed is Subcooled Liquid: feed line has +VE slope
(q > 1): Explain.

61
 Various Types of Feed Lines

4 5

3
Subcooled Liquid
Vapour + Liquid (+, −)
(−, +)
Saturated Liquid
2 F
Saturated vapour

L' − L H V − HF
1 q=
F
=
H −H
V L
Superheated vapour q z
Feed line: y = x − F
(+, +) q−1 q-1

62
 Feed Tray Location and Number of Ideal Trays

D
N
S’’

S’ F Feed =
Saturated Liquid
E

W
63
 TOTAL REFLUX
If the liquid from the overhead condenser is TOTALLY
recycled to the column (D = 0), the column is said to run at
“total reflux”. Also no product is drawn from the reboiler
either ⇒ there should not be any Feed.
R = L0/D = L0/0 = ∞ x
R D
Operating line for Rectifying section: y = x +
n+1 R+1 n R+1
When R → ∞ , Slope = 1, Y-intercept = 0
⇒ Operating line coincides with DIAGONAL
ƒ Naturally, the number of stages corresponding to infinite R
are minimum.
ƒ Total reflux is very often used during the startup of a
distillation column till the steady state is attained. After
this, continuous flow of feed, top product, and bottom
product withdrawal are SIMULTANEOUSLY started.
64
 Fenske’s equation

ƒ Used to compute theoretically the minimum number of

trays if the relative volatility remains reasonably (more or
less) constant. It also assumes a total reboiler (analogous to
total condenser).

ƒ If αw is relative volatility of A at the reboiler temperature,

and xW, yW are Liquid and Vapour concentrations in the
reboiler, then:
y x
W = α W
1-y W 1-x
W W

65
ƒ The Vapour leaving the reboiler and entering the lowest
tray (Nm) has a mole fraction yW of component A. The
Liquid leaving this tray has a composition xNm ⇒ (xNm, yW)
lies on the Operating Line ⇒ xNm = yW. Therefore, the
above equation can be rewritten as:
x x
Nm = α W
1-x W 1-x
Nm W
ƒ Applying the same procedure to the case of tray number
Nm, we get:
y x x
Nm = α Nm = α α W
1-y Nm 1-x Nm W 1-x
Nm Nm W

66
 Fenske’s equation (continued … )
ƒ Continuing the procedure up to the top tray (where y1 =
xD), we get:
x y x
D = 1 = α α ...α α α W
1-x 1-y 1 2 Nm-1 Nm W 1-x
D 1 W
x N +1 x
D ⎛ ⎞ m W
⇒ = ⎜α ⎟
1-x ⎝ average ⎠ 1-x
D W
⎧x
⎪ D
log ⎨
(1-x
W ) ⎫
⎪
⎬

⇒ N +1 =
⎪x
⎩ W (
1-x ⎪ )
D ⎭
m ⎛ ⎞
log ⎜ α ⎟
⎝ average ⎠
ƒ The above equation is called the “Fenske’s equation”, which
is useful for the calculation of MINIMUM number of trays.
67
 Minimum Reflux Ratio
ƒ This is exactly analogous to the (L/G)min for gas absorption. This is
based on the identification of “pinch point”.
The following procedure is followed to determine Rm:
ƒ Locate the points D (xD, xD) and W (xW, xW) on the DIAGONAL of
the x−y diagram. These are the terminal points of operating lines.
ƒ Draw the feed line through F from the known feed composition zF,
and feed quality (given by q); locate the point of intersection of the
feed line and the equilibrium curve (x−y diagram). Call this point
M.
ƒ Join DM (operating line for rectifying section), and extend this line
till the Y-axis.
ƒ Y−intercept = E = xD/(Rm + 1). Get Rm from the intercept.
ƒ At Reflux Ratio = Rm, the number of stages for the given separation
are infinity (driving force becomes ZERO at the PINCH POINT).
68
 Minimum Reflux Ratio

E F Slope = Rm/(Rm + 1)

Y−intercept = xD/(Rm + 1)

W
69
Sieve Tray

70
Tray Columns

71
Tray Deck

72
Reboilers

73
 Reboilers
Bottom Bottom
Tray Tray

Heating Heating
Medium Medium

Bottoms Bottoms
Product Product
Circulating Pump

Forced Circulation Vertical Thermosiphon

74
 Reboilers

Bottom Bottom
Tray Tray
Heating
Heating Medium
Medium

Bottoms
Bottoms Product
Product

Kettle Horizontal Thermosiphon

75
Feed Distributors

76
 The “Real” World

Fouled Structured Packing Damaged Valve Tray

77
 The “Real” World

Plugged Distributor
Tray “Blanking” Strips

78
Valve Tray Deck

79
Major Tray Damage

80
Fouled Bubble Cap Tray

81
 Structured Packings

Fair, J.R., Seibert, A.F., Behrens, M., Saraber, P.P., and Olujic, Z. “Structured Packing
Performance − Experimental Evaluation of Two Predictive Models”, Industrial and
Engineering Chemistry Research 2000, 39, 1788−1796.
82
Structured Packing Wetted Area

83
 Ponchon Savarit Method (Calculation of Number of Stages)
ƒ Calculations on an Enthalpy−Concentration (H−x−y) diagram.
ƒ If the dew point and bubble point lines are more or less straight
and roughly parallel ⇒ Latent heat of vaporisation is basically
constant with respect to composition ⇒ Prerequisite for constant
molar overflow, energy balances may be neglected.
ƒ If the saturation curves show significant changes in curvature ⇒
constant molar overflow cannot be assumed.
ƒ H−x−y diagram is more general than a McCabe−Thiele
construction, because it takes direct account of the thermal
effects and does not require an assumption of constant equimolar
overflow.
ƒ Feed and product points (F, D, W) can be located on H−x−y
diagram. The coordinates are their composition and enthalpy.

84
 Vapour

Rectifying
Envelope 1

section
−QC
Envelope 2
1
n
Feed Ln Vn+1 Top product
F, zF , HF xn yn+1 D, xD, HD
HL,n HV,n+1
f
m L’m V’m+1
Envelope 3
xm ym+1
HL,m HV,m+1 Envelope 4
Stripping
section

N Vapour

+QB
Bottom product
W, xW , HW
85
 MATERIAL AND ENERGY BALANCE EQUATIONS
ƒ The determination of number of stages is based on steady
state M & E B equations over the ENVELOPES as shown
in the Figure.
ƒ L & V: liquid and vapour flows ABOVE the feed location.
ƒ L’ & V’: liquid and vapour flows BELOW the feed
location.
ƒ Ln & Vn = molar liquid and vapour flow rate LEAVING nth
stage.
ƒ HL,n & HV,n = molar liquid and vapour enthalpy LEAVING
nth stage.
ƒ L0 = flow rate of reflux to the top stage (suffix ‘0’ signifies
that the stream is ‘as if’ coming from a hypothetical 0th
stage above top stage.

86
ƒ QC = heat removal rate from overhead condenser.
ƒ QB = heat supply rate to reboiler (to vaporise a part of the
liquid leaving the bottom stage).
ƒ F = feed rate to the column.
ƒ zF = mole fraction of MVC in feed.
ƒ D = rate of distillate removal from reflux drum.
ƒ xD = mole fraction of MVC in distillate.
ƒ W = rate of bottom product removal from reboiler.
ƒ xW = mole fraction of MVC in bottom product.
ƒ L0/D = R = reflux ratio.

87
 Vapour: V1, y1, HV1

Envelope 1
−QC
Stage 1

Reflux: L0, x0, HL0 Top product:

D, xD, HD

88
 ENVELOPE 1
(condenser + reflux drum)

Overall balance:
V1 = L0 + D = R D + D = D (R + 1)

Component “A” balance:

V1 y1 = L0 x0 + D xD

Enthalpy balance:
V1 HV1 = L0 HL0 + D HD + QC
⇒ QC = D { (R + 1) HV1 − R HL0 − HD }

Please note: y1 = xD = x0 (for total condenser)

89
 Vapour

−QC Envelope 2
Rectifying
section
Stage n
Top product
D, xD, HD
Ln Vn+1
xn yn+1
HL,n HV,n+1

90
 ENVELOPE 2
(part of rectifying section + condenser)

Overall balance:
Vn+1 = Ln + D

Component “A” balance:

Vn+1 yn+1 = Ln xn + D xD

Enthalpy balance:
Vn+1 HV,n+1 = Ln HL,n + D HD + QC
If you put n = 0, equations for Envelope 1 are obtained !

91
 Stage m
Stripping
section

L’m V’m+1 Envelope 3

xm ym+1
HL,m HV,m+1
Vapour

+QB
Bottom product
W, xW, HW
92
 ENVELOPE 3
(part of stripping section + reboiler)

Overall balance:
L’m = V’m+1 + W

Component “A” balance:

L’m xm = V’m+1 ym+1 + W xW

Enthalpy balance:
L’m HL,m + QB = V’m+1 HV,m+1 + W HW

93
 Vapour
−QC

Rectifying
section
Top product:
D, xD, HD
Feed: Feed stage
F, zF, HF
Stripping
section
Envelope 4

Vapour

+QB
Bottom product
W, xW, HW 94
 ENVELOPE 4
(entire column + condenser + reboiler)

Overall balance:
F=D+W

Component “A” balance:

F z F = D x D + W xW

Enthalpy balance:
F HF + QB = D HD + W HW + QC

95
 Rectifying Section
ENVELOPE 2 (part of rectifying section + condenser)
Total material balance: Vn+1 = Ln + D
Component A balance: Vn+1 yn+1 = Ln xn + (Vn+1 − Ln) zD
⇒ Ln / Vn+1 = (zD − yn+1) / (zD − xn)
Note: Reflux may be a sub−cooled liquid and hence the
composition is denoted by zD.
Energy balance:
Vn+1 HV, n+1 = Ln HL,n + D (HD + QC/D) = Ln HL, n + D Q’D
where Q’D = Enthalpy removed from the TOP section of the
column per mole of distillate. Substituting D = Vn+1 − Ln :
Vn+1 HV, n+1 = Ln HL, n + (Vn+1 − Ln) Q’D
⇒ Ln / Vn+1 = (Q’D − HV, n+1) / (Q’D − HL, n)
The quantity Ln/Vn+1 is called “internal reflux ratio”.
96
 From the above two equations:

z −y Q' − H Q' − H Q' − H

D n+1 = D V, n + 1 D L, n D V, n + 1
⇒ =
z −x Q ' −H z −x z −y
D n D L, n D n D n+1

⇒ The 3 points z( D )
, Q' , ⎛⎜ x , H
D ⎝ n
⎞,
L, n ⎟⎠

and ⎛⎜ y ,H ⎞ , are COLLINEAR.

⎟
⎝ n + 1 V, n + 1 ⎠

that is, the points L , V , and Q' are COLLINEAR.

n n+1 D

97
⇒ The point D’ (zD, Q’D) can be considered as a “phase
obtained by subtracting Ln from Vn+1”.
ƒ The flow rate of phase D’ is also denoted by D’ = Vn+1 − Ln.
ƒ However, NONE of the phases can have the composition
zD, and enthalpy Q’D = HD + QC/D.
ƒ The stream D’ is a “fictitious stream” defined for the
purpose of graphical construction.
ƒ D’ lies vertically above D, because they have same abscissa
= zD.
ƒ If D lies below H−x curve, D is sub−cooled liquid.
ƒ Put n = 0 ⇒ D’, D, V1 are collinear.
ƒ Point L1 (x1, HL1) is located by drawing a tie line from V1.
ƒ L1D’ is joined to get point V2, and so on …

98
 L Q' - H V Q' - H
Consider: n = D V, n+1
⇒ n+1 = D L, n
V Q' -H L Q' -H
n+1 D L, n n D V, n+1

V Q' - H L + D Q' - H
Putting n = 0 ⇒ 1 = D L, 0
⇒ 0 =
D L, 0
L
0 Q' - H L
0 Q' - H
D V, 1 D V, 1

Q ' -H L Q' - H vertical distance D'V

D D V, 1
⇒ 1+ = D D ⇒ R= 0 = = 1
L Q ' -H D H -H vertical distance V D
0 D V, 1 V, 1 D 1

ƒ If the “reflux ratio” is given, the above relation is used to

locate D’.
ƒ First, D (zD, HD) is located from the given “state” of the
distillate.
ƒ A vertical line through zD intersects the y−HV curve at V1.
ƒ Then, obtain D’ so that the above relation for R is satisfied.
99
 Rectifying Section D’

y−HV curve
HL , HV

Vn+1 Vn V3 V2 V1

x−HL curve

Ln Ln−1
L2 L1
Tie lines
D
Operating line SEGMENTS

0.0 x, y zD 1.0
100
 Stripping Section
ENVELOPE 3 (part of stripping section + reboiler)
Total material balance: L’m = V’m+1 + W
Component A balance: L’m xm = V’m+1 ym+1 + (L’m −
V’m+1) xW
⇒ L’n / V’m+1 = (ym+1 − xW) / (xm − xW)
Energy balance:
L’m HL, m − V’m+1 HV, m+1 = W HW − QB = W (HW − QB/W)
⇒ L’m HL, m − V’m+1 HV, m+1 = W Q’W
where Q’W = Enthalpy supplied to the BOTTOM section of
the column per mole of bottom product. Substituting D = L’m
− V’m+1 :
L’m HL, m − V’m+1 HV, m+1 = (L’m − V’m+1) Q’W
⇒ L’m / V’m+1 = (HV, m+1 − Q’W) / (HL, m − Q’W)
101
 From the above two equations:

y −x H − Q' H − Q' H − Q'

m+1 W = V, m + 1 W V, m + 1 W L, m W
⇒ =
x −x
m W H − Q' y
m+1
−x
W
x −x
m W
L, m W

⇒ The 3 points x( W )
, Q' , ⎛⎜ x , H
W ⎝ m
⎞,
L, m ⎟⎠

and ⎛⎜ y ,H ⎞ , are COLLINEAR.

⎟
⎝ m + 1 V, m + 1 ⎠
that is, the points L , V , and Q' are COLLINEAR.
m m+1 W

102
ƒ The flow rate of phase W’ is also denoted by W’ = L’m −
V’m+1.
ƒ The stream W’ is a “fictitious stream” defined for the
purpose of graphical construction.
ƒ W’ lies vertically below W, because they have same
abscissa = xW.
ƒ V’N+1 (reboiler vapour) should lie on the y−HV curve on the
tie line drawn from W.
ƒ The line connecting V’N+1 and W’ intersects x−HL curve at
L’N (collinearity condition).
ƒ The tie line through L’N intersects the y−HV curve at V’N,
and so on…

103
 Stripping Section D’

VN+1
VN
HL , HV

VN−1 y−HV curve

V1
F

W
LN
x−HL curve
D
xW
0.0 x, y zD 1.0

Tie lines
Operating line SEGMENTS
W’ 104
 Feed Plate
ƒ A changeover from one section to the other is necessary at the feed
plate, and hence feed line is required.
ƒ Consider the material and enthalpy balances over “envelope 4”,
that is, entire column + condenser + reboiler.
Component A balance:
(D + W) zF = D zD + W xW ⇒ (D/W) = (zF − xW) / (zD − zF)
Enthalpy balance:
(D + W) HF + QB = D HD + W HW + QC
⇒ D HF + W HF = D (HD + QC/D) + W (HW − QB/W)
⎛ Q ⎞
H −⎜H + C ⎟
D F ⎜ D D ⎟ H − Q' z −x H − Q' H − Q' Q' − H
= ⎝ ⎠ = F W ⇒ F W = F W ⇒ F W = D F
W ⎛ Q ⎞
B Q' − H z −z
D F Q' − H z −x
F W
z −z
D F
⎜H − ⎟−H D F D F
⎜ W W ⎟ F
⎝ ⎠

⇒ The 3 points W’(xW, Q’W), F(zF, HF), and D’(zD, Q’D) are collinear.

105
ƒ The intermediate point F(zF, HF) denotes the state of
feed in terms of composition and enthalpy.
ƒ F(zF, HF) lies on the line joining D’ and W’.
ƒ W’ represents a fictitious stream of flow rate W’ =
L’m − V’m+1.
ƒ D’ represents a fictitious stream of flow rate D’ =
V’n+1 − L’n.
⇒ F = D + W = D’ + W’
ƒ Therefore, F, a real stream can be viewed as a
stream obtained by mixing the 2 fictitious streams
D’ and W’.
ƒ The line D’W’ is called “feed line”.
106
The steps (graphical) for obtaining the number of ideal stages
on H−x−y diagram:
1. Data supplied (directly or indirectly): Concentrations,
Enthalpies, Flow Rates of Distillate, Bottom Product, as
well as Reflux Ratio.
2. Points D, D’, and F are located.
3. D’F is joined, and extended to meet the vertical line
{drawn through W(xW, HW)} at point W’.
4. Stages can be constructed either from D’ or from W’.
5. A changeover has to be made after the feed line is crossed.
6. The stage at which the changeover is made is “feed stage”.
7. Construction continues till the other end point is reached.
107
The steps (graphical) for obtaining the number of ideal stages on x−y
diagram:
1. Draw the equilibrium curve (x−y diagram) using separate axes
below the H−x−y diagram using matching scale.
2. Locate (zD, zD) and (xW, xW) on the diagonal line.
3. Since any line starting from D’ and W’ intersects the H−x and H−y
curves at xn and yn+1 respectively, the point (xn, yn+1) is point on the
operating line in the x−y diagram.
4. Several lines can be drawn from D’ and W’, and for each of these
lines, the point (xn, yn+1) is located on the x−y diagram.
5. All these points are joined, giving rise to two curves; these are the 2
operating curves, namely, rectifying section operating curve and
stripping section operating curve.
6. Since the flow rates in both these sections are not constant
(constant molar overflow is not applicable), the operating lines are
not straight.
7. Staircase construction gives the number of ideal stages.
108
 Minimum Reflux Ratio
ƒ If a line through D’ or W’ coincides with tie line, the corresponding
(x,y) values give a pinch point. ' '
L Q -H vertical distance D V
ƒ Reflux ratio is given by: R = 0 = D V, 1 1
=
D H -H vertical distance V D
V, 1 D 1
ƒ The above relation indicates that the smaller the distance D’V1 (or
the nearer the point D’ to the H−x curve), the smaller is the reflux
ratio.
ƒ Most commonly, when the line D’W’ coincides with the tie line
through the feed point, minimum reflux ratio occurs.
ƒ However, for some highly nonideal mixtures, it may happen that a
tie line through a point other than F intersects the vertical line
(drawn through zD) at the smallest distance. In that case, the same
should be taken as the true pinch point.
ƒ Once (D’)min has been located on the H−x−y diagram, then the
minimum reflux ratio is computed using the above relation.

109
 Total Reflux
ƒ In this case, the reflux ratio is infinite.
ƒ Naturally, the points D’ and W’ are located at infinity.
ƒ Therefore, all the lines through D’ and W’ are vertical
lines.
The graphical construction involves:
ƒ Locate V1 vertically above zD, on the H−y curve.
ƒ Draw a tie line from V1, which will intersect H−x curve at
L1.
ƒ Draw a vertical line from L1, which will intersect H−y
curve at V2.
ƒ Continue the above construction till xW is reached.
ƒ This (obviously) gives the minimum number of ideal
stages.
110