BEng Tech: UNIT OPERATIONS

2B
UNOCHB2

Unit 1: DISTILLATION

01 August 2018
VISUALS
SINGLE STAGE DISTILLATION
 SINGLE STAGE DISTILLATION
L: Liquid stream
V: Vapour stream
1 & 2: Stream number
A & B: Component
x & y: Vapour or liquid fraction

 Two component system (A & B) with A being the more volatile

component (mvc)
 V2 and L0 brought into contact and produce Total and component
Balances:

Total 𝑳𝟎 + 𝑽𝟐 = 𝑽𝟏 + 𝑳𝟏
Component 𝑳𝟎 𝒙𝑨𝟎 + 𝑽𝟐 𝒚𝑨𝟐 = 𝑽𝟏 𝒚𝑨𝟏 + 𝑳𝟏 𝒙𝑨𝟏
 SINGLE STAGE DISTILLATION

For Constant Molar Flow

𝑽𝟐 = 𝑽𝟏 = 𝑽 𝑳𝟎 = 𝑳𝟏 = 𝑳

 Sensible heat effect (heat that causes change in temperature)

 Heat of vaporization (Latent heat) of A & B are the similar
 SINGLE STAGE DISTILLATION

Problem 𝑳𝟎 𝒙𝑨𝟎 + 𝑽𝟐 𝒚𝑨𝟐 = 𝑽𝟏 𝒚𝑨𝟏 + 𝑳𝟏 𝒙𝑨𝟏

Inlet flow (L0 & V2) and composition (XA0 & YA2) are known, finding Outlet
composition (XA1 & YA1) would require use of Trail and Error method

Operating Line???
 SINGLE STAGE DISTILLATION

Solution 𝑳𝟎 𝒙𝑨𝟎 + 𝑽𝟐 𝒚𝑨𝟐 = 𝑽𝟏 𝒙𝑨𝟏 + 𝑳𝟏 𝒚𝑨𝟏

• Assume value of XA1 and calculate

YA1 at least 3 times
• Plot on XY diagram
• The 3 points should form a straight
line
• Where The Line Cuts The
Equilibrium line would be your XA1
and YA1.
 EQUILIBRIUM/FLASH DISTILLATION

One feed that’s partially vaporized and

separated in a flash drum. Vapour and
Liquid are allowed to come to
equilibrium before separation of phases

Balances

Total 𝑭=𝑳+𝑽 𝑳=𝑭−𝑽

Component 𝑭𝒙𝑭 = 𝒚𝑽 + 𝒙𝑳

𝑭 𝑭−𝑽
Operating Line 𝒚 = 𝒙𝑭 − 𝒙( )
𝑽 𝑽
EQUILIBRIUM/FLASH DISTILLATION

Operating line passes through X=XF and Y=XF with

slope –(F-V)/V or –L/V
 DIFFERENTIAL/SIMPLE BATCH DISTILLATION

 Liquid charged to a heated kettle,

then boiled slowly. Vapours are
withdrawn as rapidly as they are
formed.
 First portion of condensate richer in
the more volatile component but it
becomes leaner with time

Suppose we initially charge L1 moles and thus form vapour V (V=dL). The
liquid composition changes from x to x-dx and the amount of liquid from L to
L-dL
Balances Original amount = amount of liquid left + amount of
vapour formed

𝒙𝑳𝟏 = 𝒙 − 𝒅𝒙 𝑳 − 𝒅𝑳 + 𝒚𝒅𝑳
DIFFERENTIAL/SIMPLE BATCH DISTILLATION
𝒙𝑳𝟏 = 𝒙 − 𝒅𝒙 𝑳 − 𝒅𝑳 + 𝒚𝒅𝑳

Expand

𝒙𝑳𝟏 = 𝒙𝑳 − 𝒙𝒅𝑳 − 𝑳𝒅𝒙 + 𝒅𝒙𝒅𝑳 + 𝒚𝒅𝑳

Neglect dxdL and Re-arrang

𝒅𝑳 𝒅𝒙
=
𝑳 𝒚−𝒙

Equation may be intergrated

𝑳𝟏 𝒙𝟏 𝒙𝟏
𝒅𝑳 𝒅𝒙 𝑳𝟏 𝒅𝒙
= ln( ) =
𝑳𝟐 𝑳 𝒙𝟐 𝒚−𝒙 𝑳𝟐 𝒙𝟐 𝒚−𝒙
 DIFFERENTIAL/SIMPLE BATCH DISTILLATION
𝒙𝟏
𝑳𝟏 𝒅𝒙
ln( ) = Rayleigh Equation
𝑳𝟐 𝒙𝟐 𝒚−𝒙

Y, average composition of total distillate can be determined graphically from

equilibrium data

𝒙𝟏
𝑳𝟏 𝒅𝒙
Area = ln( ) =
𝑳𝟐 𝒙𝟐 𝒚−𝒙
 STEAM DISTILLATION

 High boiling point liquids (HBPL) cannot be

separated by distillation at atmospheric pressure
because components of the liquid may
discompose at high temperatures
 HBPL are insoluble in water, they’re separation
may be done with simple steam distillation
 The two components in vapour phase each exert
their own vapour pressure

𝑷𝑨 + 𝑷𝑩 = 𝑷  PA and PB are the vapour pressures of pure

𝑷𝑨 water and pure B respectively
𝑷𝑩
𝒀𝑨 = 𝒀𝑩 =  Vapour Compositions
𝑷 𝑷  Constant vapour composition YA if both
𝒏𝑨 𝑷𝑨 phases remain in liquid phase
=
𝒏𝑩 𝑷𝑩
 STEAM DISTILLATION
Determining Temperature of Steam Distillation using Hausbrand diagram

Drawback: Requires large amounts of heat to simultaneously evaporate

water and the high boiling point compound
Solution: Vacuum distillation can be used because the total pressure of the
system is low, so system vapour pressure reaches total pressure at low
temperature
STEAM DISTILLATION
 SUMMARY

𝑳𝟎 𝒙𝑨𝟎 + 𝑽𝟐 𝒚𝑨𝟐 = 𝑽𝟏 𝒚𝑨𝟏 + 𝑳𝟏 𝒙𝑨𝟏

𝑭 𝑭−𝑽
𝒚 = 𝒙𝑭 − 𝒙( )
𝑽 𝑽

𝒙𝟏
𝑳𝟏 𝒅𝒙
ln( ) =
𝑳𝟐 𝒙𝟐 𝒚−𝒙
 SUMMARY
Binary mixture based on physical properties. More Volatile Component (mvc) –
lower boiling point OR higher vapour pressure. Less Volatile Component (lvc) –
higher boiling point OR lower vapour pressure

Vapour Liquid Equilibrium (VLE) – Size and Height of distillation column

determined using VLE data
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝ℎ𝑎𝑠𝑒
𝑥𝐴 = mole fraction of A in liquid phase =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 + 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐵 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝ℎ𝑎𝑠𝑒
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟 𝑝ℎ𝑎𝑠𝑒
𝑦𝐴 = mole fraction of A in vapour phase =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 + 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐵 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟 𝑝ℎ𝑎𝑠𝑒

Main Components of a Distillation Column:

• Vertical Shell where separation of liquid component takes place
• Trays/plates and/or packings for enhancement of separation
• Reboiler which provides vaporization necessary for distillation process
• Condenser to condense/cool vapour leaving top of column
• Reflux Drum which holds back condensed vapour to be recycled back in
column
DISTILLATION WITH REFLUX
May be considered as a series of
Flash-Vaporization Stage
 Return of condensate to the system.
Reflux Ration (R) depends on how
much liquid is sent back to column

𝑳 𝑳 𝑹
𝑹= =
𝑫 𝑽 𝑹+𝟏
 Increases the purity of the product
 Reduces the number of theoretical
plates
 Have constant vapour-liquid
contact
McCabe-Thiele METHOD

Enriching Upper Section

Stripping Lower Section

 McCabe-Thiele METHOD
Enriching Upper Section
Total Balance
𝑽𝒏 = 𝑳𝒏+𝟏 + 𝑫
Component Balance
𝒚𝒏 𝑽𝒏 = 𝒙𝒏+𝟏 𝑳𝒏+𝟏 + 𝒙𝒅 𝑫
For Constant Molar Flow
𝑽𝒏 = 𝑽𝒏+𝟏 = 𝑽
𝑳𝒏 = 𝑳𝒏+𝟏 = 𝑳
Upper Operating Line
𝑳 𝑫 𝑹 𝒙𝒅
𝒚𝒏 = 𝒙𝒏+𝟏 + 𝒙𝒅 𝒚𝒏 = 𝒙𝒏+𝟏 +
𝑽 𝑽 𝑹+𝟏 𝑹+𝟏
Reflux Ratio (R)
Upper Operating Line
𝑳 𝑳 𝑹 intersects x=y line at x=xd
𝑹= =
𝑫 𝑽 𝑹+𝟏
 McCabe-Thiele METHOD
Stripping Lower Section
Total Balance
𝑳𝒎+𝟏 = 𝑽𝒎 + 𝐖
Component Balance
𝒚𝒎 𝑽𝒎 = 𝒙𝒎+𝟏 𝑳𝒎+𝟏 − 𝒙𝒘 𝑾

For Constant Molar Flow

Lower Operating Line

𝑳 𝑾
𝒚𝒎 = 𝒙𝒎+𝟏 − 𝒙𝒘
𝑽 𝑽
Lower Operating Line intersects x=y line at x=xw
 McCabe-Thiele METHOD
Effect of Feed Condition (q)
Condition of entering feed determines relationship:
• Vapour flowrates in stripping and enriching sections (Vn & Vm)
• Liquid flowrates in stripping and enriching sections (Ln & Lm)
𝑳𝒎 = 𝑳𝒏 + 𝒒𝑭 𝑽𝒎 = 𝑽𝒏 + (𝒒 − 𝟏)𝑭

Feed Line
𝒒 𝒛𝒇
𝒚= 𝒙+
𝒒−𝟏 𝒒−𝟏

State of feed
q = 0 (saturated vapour)
q = 1 (Saturated liquid)
0 < q < 1 (mix of liq and vap)
q > 1 (subcooled liquid)
q < 0 (superheated vapour)
 McCabe-Thiele METHOD
Constant Molar Flow
 Negligible Heat losses
 Negligible Heat of mixing
 Equal heat of vapourisation

Calculating Number of Equilibrium

Theoretical Stages
 Determine number of trays required for
separation
 Use Graphical McCabe-Thiele method
 Use VLE Equilibrium Data & x=y line

Determine:
 Feed Operating Line
 Enriching/Rectifying Operating Line
 Stripping Operating Line
 McCabe-Thiele METHOD
Problem
A continuous fractionating column is to be designed for separating 10,000 kg
per hour of a liquid mixture containing 40 mole percent methanol and 60 mole
percent water into an overhead product containing 97 mole percent methanol
and a bottom product having 98 mole percent water. A mole reflux ratio of 3 is
used VLE Equilibrium Data
x 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
y 0 0.417 0.579 0.669 0.729 0.78 0.825 0.871 0.915 0.959 1

Determine:
 Upper Operating Line
 Bottom Operating Line
 If the condition of the feed is mixed liquid and vapour with q=0.6,
Determine feed line
 Determine Number of theoretical stages
 MINIMUM REFLUX RATIO
Top operating line in terms of R
𝑹 𝒙𝒅
𝒚𝒏 = 𝒙𝒏+𝟏 +
𝑹+𝟏 𝑹+𝟏
 Changes in R will result in changes in
operating line slope.
 And therefore alter the number of stages
required for separation

Total Reflux when D = 0, no distillate withdrawn

• Maximum slope, operating line coincides with x=y line
• Minimum number of stages
• Reduction of R, more stages are required and reduced operating line
slope

Further reduction in R will bring operating line to AG

• Infinite number of stages needed for separation
• Minimum Reflux Ratio (Rm)
 MINIMUM REFLUX RATIO
Economic Rm
 PARTIAL CONDENSATION & VAPOURIZATION
Binary mixture heated/cooled in a closed container at constant pressure with no
material loss or gain.

 VLE in terms of Temperature vs.

mole fraction
 Lower Equilibrium line with
respective liquid compositions
 Upper Equilibrium line with
respective vapour compositions
 PARTIAL CONDENSATION & VAPOURIZATION
Binary mixture Heated in a closed container at constant pressure with no
material loss or gain.

 Liquid mixture heated from point

G to B (boiling point of mixture)
 At which liquid & vapour
fractions of mvc will be B & E
respectively
 Further heating until due point is
reached
 Where liquid & vapour fractions
of mvc will be K & D
 PARTIAL CONDENSATION & VAPOURIZATION
Binary mixture Cooled in a closed container at constant pressure with no
material loss or gain.

 Superheated mixture cooled from

point H to D (due point of
mixture)
 At which the mixture condenses
and the 1st droplets will have
composition K and vapour fraction
D
 Further condensation
(Temperature drop) until mixed
phase region (M) where liquid &
vapour fractions will be L & N
 When boiling point is reached mcv
is richer in the Vapour phase
 PARTIAL CONDENSATION & VAPOURIZATION
Binary mixture in partial vapourizer (Stripping/Bottom Section)

 Liquid enters partial vapourizer and

is heated
 Composition of mvc in liquid phase
decreases
 Thus mvc is richer in vapour phase
 PARTIAL CONDENSATION & VAPOURIZATION
Binary mixture in partial condenser (Enriching/Top Section)

 Vapour enters partial condenser and

cooling commences
 At dew point vapour composition D
at T1
 Further cooling to T’ and vapour
composition of mvc increases
 Thus mvc is richer in vapour phase
 CONDENSATION & VAPOURIZATION
Total Condenser Partial Condenser

 Single phase  Two phase

 Everything condense and no
question about equilibrium stage
 In equilibrium and therefore
condenser will count as an
Equilibrium stage
 When finding the number of
stages, stage one will be the
Partial condenser
 CONDENSATION & VAPOURIZATION
Total Vaporizer
Vapour
 Single phase
 Everything condense and no
question about equilibrium stage
Partial Vaporizer
 Two phase
 In equilibrium and therefore
vaporizer will count as an
Equilibrium stage
 When finding the number of
stages, the last stage will be the
Partial vaporizer
CONDENSATION & VAPOURIZATION
 PARTIAL PRESSURE
In a binary mixture, partial pressure PA of component A would be the pressure
exerted by component A in vapour mixture.

Dalton’s Law

Total pressure equals to the summation of partial pressures.

𝑷= 𝑷𝑨

In ideal gas/vapour, partial pressure is proportional to the vapour mole fraction

of the component
𝑷𝑨 = 𝒚𝑨 𝐏
Where P is the total pressure, yA is the vapour mole fraction of component A
and PA is the partial pressure of component A
 PARTIAL PRESSURE
Raoult’s Law

In an ideal mixture the partial pressure is related to the mole fraction of the
component in the liquid phase:

𝑷𝑨 = 𝑷𝟎𝑨 𝒙𝑨

Where P0A is the vapour pressure of the pure component, xA is the liquid mole
fraction of component A and PA is the partial pressure of component A

Conditions:
 Only for high xA (mvc) values and corresponding xB (lvc) values
 Law is consistent for organic isomers mixture and hydrocarbon mixtures
 PARTIAL PRESSURE
Raoult’s Law

Partial pressure of an ideal mixture may be obtained graphically

 OA: Partial pressure of component

A (PA)
 CB: Partial pressure of component B
(PB)
 BA: Total pressure
 DG: vapour pressure line for ideal
mixture entering at component mole
fraction

 Thus PA is give by DE, PB by DF

and the total pressure P of the ideal
mixture by DG
 PARTIAL PRESSURE
Raoult’s Law

Component A partial pressure of an ideal mixture plotted against partial

pressure of a non-ideal mixture

 BA: Mixture Follows Raoult’s law

 OC: Mixture Follows Henry’s law

 PARTIAL PRESSURE

For cases where xA is small

Henry’s Law

A proportionality constant H is used instead of vapour pressure of pure

component

𝑷𝑨 = 𝑯𝒙𝑨
 MULTIPLESTREAMS
Feedstream

 Normally have the same mixture but with different compositions

 Easier separation by saving energy of separation
 Mixture are already partially separated
 And can therefore be fed at different stages in the column

Additional Material Balance will be require

 New feed operation line
 MULTIPLESTREAMS
Feedstream

 Upper operating line is not affected (xd)

 Middle line has a greater slope because
of the liquid entering F1
 Bottom operating line has a greater
slope where the liquid is the most
 MULTIPLESTREAMS
Sidestream

 Sidestream drawn intermediately from top or bottom

 Sometime products of different compositions other then completely
separated or waste separation are required
 Sidestreams are almost always liquid

Composition of sidestream is not the same as the plate at which it is drawn

from
 MULTIPLESTREAMS
Sidestream

 Sidestream remove material, therefore

intermediate operating lines has a slope
less than that in the zone immediately
above
 Side streams increase number of plates
required, due to the decrease in liquid
rate below the side stream