Mass Transfer I (CH21202)

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Module IV

Distillation
 Outline of the Course

➢ Distillation:
o Introduction; Vapour liquid equilibrium, x-y, T-x-y, P-x-y and H-x-y diagrams
o Henry’s, Routh’s and Dalton’s laws
o Ideal and non ideal solutions; Azeotropes, relative volatility, flash vaporization
o Differential distillation, steam distillation, continuous rectification; stage calculation
using and McCabe-Thiele methods
o Minimum/maximum reflux ratio, Feed position, Fenske’s equation for minimum number
of trays
o Azeotropic distillation, extractive distillation
 Text Books

1. Mass Transfer Operations- Robert E. Treybal

2. Transport processes and Unit Operations – C. J. Geankoplis

3. Chemical Engineering, Volume 2 – J. M. Coulson, J. F. Richardson, J. R. Backhurst and

J. H. Harker

4. Unit Operations of Chemical Engineering – W. L. McCabe, J. C. Smith and P. Harriott

5. Principle of Mass Transfer and Separation Processes – B . K. Dutta

 Distillation: Introduction
Distillation is the technique of preferential separation of more
volatile component(s) from the less volatile once in a feed (liquid
mixture) solution by partial vaporization of the feed followed
by condensation.

Difference between Distillation and Evaporation:

o In evaporation one or more components should be non volatile
(ex. Separation of a solution of common salt and water)
o In distillation all components are appreciably volatile.
Separation of methanol (64.70C) and water (1000C)
o Light key component (more volatile component)
Example of Distillation in Process Industries: – methanol
o Heavy key component (less volatile component)
✓ Separation of aniline and nitrobenzene in the process manufacture
- water
of aniline
✓ Recovery of ethanol from its solution in water in alcohol industry
✓ Increase the benzene purity by removal of trace water o Direct separation
✓ Petroleum refinery industry into pure product
✓ Distillation is called workhouse of chemical industries
 Distillation Column:

Tray Tower

Preheat
Preheat
 Vapour Liquid Equilibrium (VLE)

➢ Vapour-liquid equilibria constitute the physical basis of separation of mixture by distillation

➢ Vapour pressure depends on the temperature and quantity of liquid and vapour

Vapour pressure can be calculated from Clausius-Clapeyron equation or Antoine equation

Clausius-Clapeyron equation: Antoine equation:

𝑩
𝒑 𝒗
𝝀 𝟏 𝟏 ln 𝒑𝒗 =A-
ln( 𝒗) = ( − ) 𝑻+𝑪
𝒑𝟏 𝑹 𝑻𝟏 𝑻

𝜆 = molar latent heat

𝑝𝑣, 𝑝1v = vapour pressure in pascal
T-x-y diagram at Constant Pressure:

Superheated vapour

Dew Point Curve (DPC)

(y vs. T)

Bubble Point Curve (BPC)

(x vs. T)
Subcooled Liquid

Fig. Constant pressure vapor liquid equilibria

Constant pressure Binary T-x-y
and x-y diagram
➢ Vapor-liquid equilibria at increased pressures

Fig. Vapor liquid equilibria at increased pressures

Relative volatility (α)
▪ This is the ratio of the concentration ratio of A and B in one phase to that in the other and is a measure of the
separability. *
y
(1 − y* ) y* (1 − x )
= = (1)
x x (1 − y* )
(1 − x )
x
y* =
1 + ( − 1) x

x − mole fraction of the more volatile substance in the liquid

y − mole fraction of the more volatile substance in the vapor
*

• The value of  will ordinarily change as x varies from 0 to 1.

• If y* = x (except at x = 0 or 1),  =1 and no separation is posssible.
• The larger the value of  above unity, the greater the degree of separability.
➢ P-x-y diagram for methanol-water

Subcooled Liquid

Bubble Point Curve (BPC)

(x vs. P)

Superheated vapour

Dew Point Curve (DPC)

(y vs. P)

Fig. Constant temperature vapor liquid equilibria

 Raoult's Law: (Ideal gas-liquid system)

p*A = xAPA
PA = vapour pressure of A at the given temperature
xA = mole fraction of the solute A in the liquid
p*A = equilibrium partial pressure exerted by the solute

yA = p*A/Pt yA = mole fraction of A in vapour phase

Pt = total pressure

Pt =p*A + p*B
 PB
Raoult's Law: (Ideal gas-liquid system)

*
distance FG P P x
y* = = A = A (5)
PA distance EG Pt Pt
PB* PB (1 − x )
1− y =
*
= (6)
Pt Pt
The relative volatility  is, by substitution in equation (1)
PA
= (7)
PB

Fig. Ideal solutions

Problem:
Prepare a the bubble point, dew point and equilibrium curve for an ideal binary
mixture of benzene and diethyl ether at 1 atm total pressure.

Component BP (oC) A B C
Benzene 80 15.9037 2789.01 220.79
Diethyl ether 34.5 16.5414 2847.72 253
➢ Positive deviations from ideality

▪ A mixture whose total pressure is greater than that

computed for ideality (eq. 4) is said to show positive
deviations from Raoult’s law.
➢ Minimum boiling mixtures - azeotropes

(b) (c)

(a)

Fig. Minimum boiling azeotropism in system carbon disulfide - acetone: (a) at constant temperature; (b) and (c) at constant
pressure.
➢ Partial liquid miscibility

Fig. Isobutanol-water at 1 std atm.

Insoluble liquids; steam distillation: The mutual solubility of some liquids is so small that they can be considered
substantially insoluble: points K and M (above fig.) are then for all practical purposes on the vertical axes of these diagrams.
This is the case for a mixture such as a hydrocarbon and water, for example.
➢ When the sum of the separate vapor pressures equals the total pressure, the mixture boils, and the vapor composition
is readily computed, assuming the applicability of the simple gas law,

PA + PB = Pt (8)
PA
y =
*
(9)
Pt
PB
1 − y* = (10)
Pt

So long as two liquid phases are present, the mixture will boil at the same temperature and produce a vapor of constant
composition.
 ➢ Negative deviations from Ideality

▪ When the total pressure of a system at equilibrium is less than the ideal value, the system is said to deviate negatively from
Raoult’s law.
➢ Maximum boiling mixtures - azeotropes

(b) (c)

(a)

Fig. Maximum-boiling azeotropism in the system acetone-chloroform: (a) at constant temperature; (b) and (c) at constant
pressure.
 Enthalpy
Dew –line (y – Hv)
Concentration
Diagram
o 40 wt% ethanol water
mixture at 84 oC

✓ xethanol = 0.28
✓ yethanol = 0.28
✓ HF = 165 Kcal/kg
✓ Hv = 380 Kcal/kg Boiling –line (x– HL)
✓ HL = 70 Kcal/kg 0.28 0.69
Enthalpy Concentration Diagram to Equilibrium Diagram
➢ Multicomponent Systems
DePriester Chart (K or m value)

Kixi = yi
 Distillation:

➢ Flash distillation

➢ Batch distillation

➢ Steam distillation

➢ Fractional distillation

➢ Azeotropic distillation

➢ Vacuum distillation
 Flash Distillation

Over all balance: F = D + W

Component balance: FzF = DxD +WxW
(D + W)zF = DxD +WxW
Enthalpy balance: FHF + Q = DHD +WHW
Problem:
Fifty kmol of 35 mole% aqueous solution of acetone at 25°C is heated and flashed
in a drum at 1 atm pressure when 35% of the liquid is vaporized. Using the
enthalpy-concentration data, calculate (a) the amounts and the concentrations of
the vapour and liquid products, and (b) the heat supplied to the feed.
Solution:
Problem 2:
A liquid mixture containing 50 mol % n-heptane (A) and 50 mol % n-octane (B), at 30 OC, is to be
continuously flash-vaporized at 1 std atm pressure to vaporise 60 mol % of the feed. What will
be the composition of vapour and liquid if the vaporizer is an ideal one. The vapour pressure of
A and B at 30 OC is 780 mmHg and 325 mmHg respectively.

Solution:
Batch Distillation or Differential Distillation
Total material Balance: -dL = dD
Component A balance: -d(Lx) = y*dD
D, xD
-Ldx = y*dD + xdL = y*dD –xdD = (Y* - x)dD
𝒅𝑳 𝒅𝒙 yD
=
𝑳 𝒚 ∗ −𝒙
𝑭 𝒙𝑭
𝒅𝑳 𝒅𝒙
න =න (Rayleigh equation) F, zF
𝑾 𝑳 𝒙 𝒚 ∗ −𝒙
𝑾
W, xW
𝑭 𝒙𝑭 𝒅𝒙
ln = ‫𝒙׬‬ 𝜶𝒙
𝑾 𝑾 −𝒙
𝟏+ 𝜶 −𝟏 𝒙
𝟏 𝒙𝑭(𝟏 − 𝒙𝑾) 𝟏 − 𝒙𝑾 𝑭𝒙𝑭 𝑭(𝟏−𝒙𝑾)
= 𝒍𝒏 + 𝒍𝒏 𝒍𝒐𝒈 = α𝒍𝒐𝒈
(α − 𝟏) 𝒙𝑾(𝟏 − 𝒙𝑭) (𝟏 − 𝒙𝑭) 𝑾𝒙𝑾 𝑾(𝟏−𝒙𝑭)
Problem 3:
A liquid mixture containing 50 mol % n-heptane (A) and 50 mol % n-octane (B), at 30 OC, is to be
were subject to differential distillation at 1 std atm pressure to vaporise 60 mol % of the feed.
What will be the composition of vapour and liquid if the vaporizer is an ideal one. The vapour
pressure of A and B at 30 OC is 780 mmHg and 325 mmHg respectively.

Solution:
 Steam Distillation:
❖Component are not miscible to each other

➢ Separation of a high boiling material from a solution.

Examples: decolourization/ deodorization of vegetable
oils, recovery and purification of essential oils
➢ Separation and purification of hazardous and
inflammable substances like turpentine
➢ Separation of a thermally unstable substance from a
mixture
➢ Separation of volatile impurities from waste water.
Examples: removal of ammonia, volatile organic
compounds (VOCs) like halogenated hydrocarbons from
waste water
 Steam Distillation:
Case 1: The substance A is immiscible with water. The feed contains A and traces of nonvolatile
impurities.

Pt = PA + PB Here partial pressure of a substant is same as vapour pressure

❖ If mA moles of substance volatilized out by putting in mB moles of steam and if the system is operate at
equilibrium then

mA P PA PA
= A = mA= mB
m𝑩 P𝑩 1 − P𝑨 1 − P𝑨
❖ if the system does not operate at equilibrium, the partial pressure of A will be less than its vapour
pressure. To take into account such a deviation, we define a factor called vaporizing efficiency E of the
product such that the partial pressure of A in the steam phase is pA = EPA

EPA
mA= mB E ~ 0.6 – 0.9
1 − P𝑨
 Steam Distillation:
Case 2: The feed is a mixture of A and C; C is an essentially non-volatile substance. A and
C form an ideal solution and are immiscible with water

If the moles of A in the still at any time t is mA , its xA=

mA
mole fraction in C is mA−mC

Partial pressure of A in the vapour: pA= ExAPA

Moles of A per mole of steam: pA = ExAPA

P𝑩 Pt −ExAPA

If m*B is the rate of supply of steam, the dmA p

= m*B A = m*B
ExAPA
rate of volatilization of A; then dt P𝑩 Pt −ExAPA

Integrating from t = 0, mA = mAi; to t

= t, mA = mAf
Problem: Geraniol (C10H18O) is an essential oil of commercial value. It is conventionally purified by steam
distillation. A pilot scale unit is charged with 0.5 kg of crude geraniol containing a small amount of non-
volatile impurities. Live saturated steam at 105°C is passed through the still at a rate of 20 kg/h. Calculate
the distillation time assuming that geraniol is immiscible with water. Neglect condensation of steam. The
vaporization efficiency is 0.8. Vapour pressure of water at 105°C is 1.211 bar and that of geraniol(A) is
given by
lnPA = 21.1 - 7217/T; PA is in mmHg and T in K
Fractional distillation
Distillation of Petroleum crude
Determination of the Number of Trays—the McCabe-Thiele Method
Assumptions:
➢ the molar rate of overflow of the liquid from one tray to another is constant
over any section of the column.
L0 = L1 = L2 =……… = Ln = L
Similarly, V0 = V1 = V2 =……… = Vn = V

Rectifying Section/Enriching section:

Overall balance: V = L + V

Component balance: V*yn+1 = L*xn + D*xD

L D
yn+1 = xn + xD
V V
L/D 𝟏
yn+1 = xn + x
V/D V/D D
R xD
yn+1 = x + ➢ Equation of operating line of the rectifying section
R+1 n R+𝟏
Slope Intercept
 Reflux Ratio (R):
It is the ratio of the reflux fed back to the top tray and the top product withdrawn is
called the reflux ratio (R).
𝑳𝟎 𝒓𝒆𝒕𝒖𝒓𝒏
R= ( )
𝑫 𝒘𝒊𝒕𝒉𝒅𝒓𝒂𝒘

Total Reflux: (no withdraw; D= 0) then R→ α

Minimum Reflux: ( no return; L → 0) R→ 0

Determination of the Number of Trays—the McCabe-Thiele Method
R xD This equation also satisfied by the point xn = xD and yn+1 = xD
yn+1 = x +
R+1 n R+𝟏

Stripping Section:

➢ Operating line equation

Boil-up ratio (Rv):

Problem:
A mixture of benzene and toluene containing 40 mole% benzene is to be separated continuously in a
tray tower at a rate of 200 kmol/h. The top product should have 95 mole% of benzene and the
bottom must not contain more than 4 mole% of it. The reflux is a saturated liquid and a reflux ratio
of 2.0 is maintained. The feed is a saturated liquid (i.e. it is at its bubble point). Obtain and plot the
operating lines for the rectifying and the stripping sections on the x-y plane. What is the boil-up
ratio? The vapour-liquid equilibrium data at the operating pressure of 101.3 kPa are given below.
 Feed Line:
As the feed enters the column, the liquid and vapour flow rates undergo step changes
depending upon the state of the feed (i.e. upon how much liquid and vapour it has). We shall
now write the material and energy balance equations over the plate to which the feed is
introduced.

F+L+𝑽=𝑳+V
FHF + LHL,f-1 + 𝑽HV,f+1 = 𝑳HL,f+ VHV,f
HL,f-1 ≈ HL,f ≈ HL, HV,F+1 ≈ HV,f ≈ HV
FHF + LHL + 𝑽HV = 𝑳HL+ VHV
(𝑳 – L)HL = (𝑽 – V)HV + FHF = (𝑳 – L)HV + (HF – HV)F
(𝑳 – L)(HL – HV) = (HF – HV)F
𝑳–𝑳 𝑯𝑭 −𝑯𝑽 𝑯𝑽 −𝑯𝑭
= = =q
𝑭 𝑯𝑳 −𝑯𝑽 𝑯𝑽 −𝑯𝑳
 Feed Line:
𝑳 - L = increase in the liquid flow rate across the feed tray as a result of
introduction of the feed = rate of input of liquid with the feed. So q is the
fraction of liquid in the feed
heat required to convert 1 mole feed to saturated vapour
q=
molar heat of vaporization of the saturated liquid

1. feed is a liquid at its bubble point (saturated liquid): q = 1;

2. if it is a vapour at dew point (saturated vapour), q = 0.
3. feed is a two-phase mixture of liquid and vapour, q represents the fraction
of liquid in it.
❖ So (1 - q) gives a measure of the ‘quality’ of the feed.
 Feed Line:
Vy = Lx + DxD
-(q – 1)y = -qx + xF
𝑽y = 𝑳x – WxD
𝒒 𝒙𝑭
(V - 𝑽)y = (L - 𝑳)x + (DxD + Wxw) = (L - 𝑳)x + FxF y= 𝒙 -
𝒒−𝟏 𝑸−𝟏
𝑽–𝑽 𝑳–𝑳
+1= =q
𝑭 𝑭

➢ feed is a saturated liquid, q = 1; and the slope of the feed line is infinite. So
the feed line is a vertical line through ( zF, zF).
➢ feed is a saturated vapour, q = 0; and the slope of the feed line is zero. So the
feed line is a horizontal line through (zF, zF).
➢ feed is a mixture of liquid and vapour or a superheated vapour or a subcooled
liquid, the slope of the feed line can be calculated from the enthalpy data
Feed Line:
Graphical Representation of
McCabe –Thiele Method:
Number of ideal tray calculation
 Minimum Number of trays
Total Reflux
➢ Reflux ratio becomes
R = Lo/D = Lo/0 = infinity
➢ No product is drawn from the reboiler either
➢ All the liquid following to the reboiler is vaporized and
feed back to the column
➢ So in a column operating at total reflux under steady
state conditions, there should not be flow of feed into it.
➢ Recycling all exiting vapour as reflux and all exiting liquid
as boil up. Operating line has slope of one.
➢ No product is produced: feed must then go to zero.
Fenske’s Equation (Minimum number of trays by Analytical Method)
𝒚𝑾 𝒙𝑾
= αW
𝟏−𝒚𝑾 𝟏−𝒙𝑾
The vapour leaving the reboiler and entering the lowest tray (tray number Nm in this case) has a mole fraction yw of the component A.
The liquid leaving this tray has a composition xNm. So the point (xNm, yw) lies on the operating line. Because the operating line coincides
with the diagonal at total reflux, xNm = yw

𝒙𝑵𝒎 𝒙𝑾 Now for Nm trays

= αW 𝒚𝑵𝒎 𝒙𝑵𝒎 𝒙𝑾
𝟏−𝒙𝑵𝒎 𝟏−𝒙𝑾
= αNm = αNmαW
Similarly, for (Nm – 1) trays 𝟏−𝒚𝑵𝒎 𝟏−𝒙𝑵𝒎 𝟏−𝒙𝑾

𝒚(𝑵𝒎−𝟏) 𝒙(𝑵𝒎−𝟏) 𝒙𝑾
= α(Nm – 1) = α(Nm – 1)αNmαW
𝟏−𝒚(𝑵𝒎−𝟏) 𝟏−𝒙(𝑵𝒎−𝟏) 𝟏−𝒙𝑾
[Note that the point (x(Nm-1), yNm) lies on the operating line which coincides with the diagonal; therefore, xNm-1 = yNm]
Continuing the procedure up to the top tray (where y1 = xD)

𝒙𝑫 𝒚𝟏 𝒙𝑾
= = α1α2……αNmαW F 𝒙 (𝟏−𝒙 )
𝟏−𝒙𝑫 𝟏−𝒚𝟏 𝟏−𝒙𝑾 𝒍𝒐𝒈 𝒙𝑫 (𝟏−𝒙𝑾)
Nm +1 = 𝒘 𝑫 Fenske’s Equation
𝒙𝑫 𝒚𝟏 𝒙𝑾 𝒍𝒐𝒈𝜶𝒂𝒗
= = (αav )Nm + 1.
𝟏−𝒙𝑫 𝟏−𝒚𝟏 𝟏−𝒙𝑾
 Azeotropic Distillation
Component Boiling Point (oC)
Water (A) 100.0
Acetic Acid (B) 118.1
N-butyl acetate (E) 125.0
Min. Azeotrope (A-E) 90.2

Component Boiling Point (oC)

Ethanol (A) 78.3
Water (B) 100.0
Original azeotrope (A-B) 78.2
Benzene (E) 80.2
Min. Azeotrope (A-B-E) 64.86

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distillation-part-1
 Extractive Distillation:
Extractive distillation is an effective separation technique for azeotrope mixtures or close boiling
point mixture.
➢ A polar solvent, entrainer or separating agent with high boiling point is added to interact with
the components in the azeotropic or close-boiling mixtures.

➢ Solvent will not forms no

azeotropes with the other
components in the mixture
 Extractive Distillation:
▪ Butadiene separation from C4-stream of naphtha cracker

❑ Butadiene is a byproduct of the steam

cracking process used to produce ethylene and
other alkenes.
❑ Aliphatic hydrocarbons mixed with steam at high
temperatures (900 °C), produce a complex mixture
of unsaturated hydrocarbons, including butadiene.
❑ Heavier feeds favor the formation of heavier olefins,
butadiene, and aromatic hydrocarbons
Feed (C4):
➢ Butanes, butene, butadiene (40-50%), C3 acetylene
and C4 acetylenes

Entrainer (Solvent):
➢ N –methyl–2–pyrrolidone (NMP), acetonitrile, dimethylacetamide, dimethyl-formamide
End Semester Syllabus (50 marks)

➢ Gas-liquid Contactors

➢ Absorption 40
➢ Distillation

➢ Crystallization 10
Thank You