TCN3132 Separation Processes

Lecture 3: Binary Distillation –

Equilibrium Design Basics

Dr Suraj Vasudevan
Email: [email protected]

Department of Chemical &

Biomolecular Engineering

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 Overview

• From flash to distillation

 Development of the cascades
 Improved purity and recovery

• Binary multistage distillation

 Nomenclature and design problem
 External and internal column balances
 Operating line equations
Reference:
Wankat 2nd, 3rd
and 4th editions
Chapters 3 and 4

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From Flash to Distillation: Development of the Cascade
• Flash does not give high purity products
• Can be addressed by adding more flash
units

𝑇𝑇5  Unit 3 is the first flash unit

𝑇𝑇4
 V3 and L3 are sent to flash units 2
and 4 respectively
𝑇𝑇3
𝑇𝑇2  Similarly, V2 and L4 are sent to flash
𝑇𝑇1 units 1 and 5 respectively
 Purity of V1 and L5 will be high
 But what about the intermediate
products (L1, L2, V4 and V5)?
=> Recovery of more volatile
component in V1 and of less volatile
𝑇𝑇1 < 𝑇𝑇2 < 𝑇𝑇3 < 𝑇𝑇4 < 𝑇𝑇5
component in L5 will be low

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From Flash to Distillation: Development of the Cascade
• Take L1 and L2 and send to flash units 2
and 3
• Take V4 and V5 and send to flash units 3
and 4
𝑇𝑇5
 A countercurrent cascade as liquid
𝑇𝑇4
and vapor move in opposite
𝑇𝑇3 directions
𝑇𝑇2
𝑇𝑇1  Both end products V1 and L5 can be
pure and obtained in high amounts
⇒ V1 will be almost 100% pure in the
more volatile component, and also
achieve close to 100% recovery of the
more volatile component in the feed
⇒ Likewise for L5 with respect to less
volatile component
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From Flash to Distillation: Development of the Cascade

𝑇𝑇5
• Stage 1 is at the lowest temperature
𝑇𝑇4
• Stage 5 is at the highest temperature
𝑇𝑇3  Temperature change/gradient
𝑇𝑇2
𝑇𝑇1 achieved by adding heaters/coolers
(reboilers/condensers) in between
the stages

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From Flash to Distillation: Development of the Cascade
• Vapor flow rate decreases as we go up to
stage 1
• Liquid flow rate decreases as we go
𝑇𝑇5 down to stage 5
𝑇𝑇4  Take part of the vapor product V1,
condense it and return to stage 1 =>
𝑇𝑇3
𝑇𝑇2 this is called reflux
𝑇𝑇1  Take part of the liquid product L5,
vaporize it and return to stage 5 =>
this is called boilup
• Allows us to control the internal liquid
and vapor flow rates in the cascade
 Stream D is distillate, B is bottoms
 L0 is reflux, V6 is boilup

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From Flash to Distillation: Development of the Cascade
• All heat can now be supplied at the bottom
(reboiler) and all cooling can be done at the
top (condenser)
• Partial condensation and vaporization of the
vapor and liquid can be done in intermediate
• L1 and V2 are called passing streams heat exchangers
• Likewise, L2 and V3; L3 and V4, etc.  For example, L1 will be partially vaporized
by V2 and V2 will be simultaneously
partially condensed
 As the heat of vaporization per mole is
usually constant, condensation of 1 mole
of vapour will vaporize 1 mole of liquid
=> Vapor and liquid flow rates tend to
remain constant

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From Flash to Distillation: Final Cascade

• Simplify further by building the entire system in a

column instead of a series of individual stages
• Heat exchangers replaced by bringing liquid and
vapor into direct contact with each other on each
stage
 Distillation column with stages
 Condenser at the top
 Reboiler at the bottom
 Top product highly concentrated in the more
volatile component
 Bottom product highly concentrated in the less
volatile component

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 Production of
Production of Benzene from Petroleum/Petrochemical Products
Toluene and Hydrogen from Crude Oil in a Refinery

Recycle
Compressor
Fresh Gas Recycle
Hydrogen

Furnace PFR
Fresh Outlet
Toluene
Total PFR
HX PFR Purge
Feed Toluene Inlet
Pump Purge Valve

Separator
Cooler
Recycle Toluene

Recycle Pump

Benzene Product Fuel Gas

Toluene Benzene
Column Stabilizer
Column

Diphenyl

VasudevanS/TCN3132/Binary Distillation - Equilibrium Design Basics 9

 Multistage Distillation

• The most widely used separation technique in the chemical

industry

• Separation based on difference in boiling points (relative

volatility)

• Mass transfer takes place between the liquid and vapor

phases

• Steady-state continuous operation is common

• Contacting on the stages is achieved by using different types

of equipment: trays or packing

This is one type of tray – sieve trays

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 Flash vs Distillation

• All stages act as equilibrium stages in the ideal scenario (deviations are
handled later)

 Vapor and liquid leaving each stage are in equilibrium with each
other

 Reliable equilibrium data is very important for proper design of

distillation

• Flash is just an empty vessel to separate the feed into liquid and vapor

• Distillation has elaborate internal arrangements to promote the mixing

of the vapor and liquid phases and promote mass transfer

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Distillation Column Internals

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Distillation: Nomenclature and Design Problem

• The vapor and liquid leaving stage k are in equilibrium

with each other

 Lk and Vk are in equilibrium

 xk and yk lie on the equilibrium curve

• Section above feed is called enriching section

• Section below feed is called stripping section

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Distillation: Nomenclature and Design Problem

• Circled variables are typically specified in design

problems

 Designer calculates distillate and liquid flow rates,

number of stages, feed stage location (at optimum
location), condenser and reboiler duties, and finally
column diameter

• Assumptions

 Column is well insulated and is adiabatic

 Column pressure is assumed to be constant

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Distillation: External Column Balances

• Overall mass balance:

𝐹𝐹 = 𝐷𝐷 + 𝐵𝐵

• More volatile component mass balance:

𝐹𝐹𝑧𝑧 = 𝐷𝐷𝑥𝑥𝐷𝐷 + 𝐵𝐵𝑥𝑥𝐵𝐵

• Energy balance:

𝐹𝐹ℎ𝐹𝐹 + 𝑄𝑄𝐶𝐶 + 𝑄𝑄𝑅𝑅 = 𝐷𝐷ℎ𝐷𝐷 + 𝐵𝐵ℎ𝐵𝐵

Note: Heat supply is positive and heat removal is

negative (i.e., 𝑄𝑄𝑅𝑅 is positive and 𝑄𝑄𝐶𝐶 is negative)

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Distillation: External Column Balances
• The condenser in the figure is a total condenser, that
is, all vapor is condensed to liquid

 Only phase change occurs

 Splitter after condenser only splits flow rates

𝒚𝒚𝟏𝟏 = 𝒙𝒙𝑫𝑫 = 𝒙𝒙𝟎𝟎 (compositions are unchanged)

• Condenser mass balance:

𝑉𝑉1 = 𝐿𝐿0 + 𝐷𝐷

𝐿𝐿0
• Since is known:
𝐷𝐷

𝐿𝐿0 𝐿𝐿0
𝑉𝑉1 = 𝐷𝐷 + 𝐷𝐷 = 1 + 𝐷𝐷 => 𝑉𝑉1 can be calculated
𝐷𝐷 𝐷𝐷

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Distillation: External Column Balances

• Condenser energy balance:

𝑉𝑉1 𝐻𝐻1 + 𝑄𝑄𝐶𝐶 = 𝐷𝐷ℎ𝐷𝐷 + 𝐿𝐿0 ℎ0

• 𝑽𝑽𝟏𝟏 is a saturated vapor as it is leaving an equilibrium stage

and ℎ𝐷𝐷 = ℎ0 as distillate and reflux have the same
composition, temperature and pressure

 Solving condenser energy balance for 𝑄𝑄𝐶𝐶 :

𝑄𝑄𝐶𝐶 = 𝐷𝐷 + 𝐿𝐿0 ℎ𝐷𝐷 − 𝑉𝑉1 𝐻𝐻1 = 𝑉𝑉1 ℎ𝐷𝐷 − 𝑉𝑉1 𝐻𝐻1 = 𝑉𝑉1 ℎ𝐷𝐷 − 𝐻𝐻1

 For total condenser, reflux is a saturated liquid:

𝐻𝐻1 − ℎ𝐷𝐷 = λ , the latent heat of vaporization

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 Test Your Understanding
Example 1: Basics of Distillation
1. Which of the following streams are saturated liquid and saturated vapor? Put a tick in the
corresponding boxes.
Stream Saturated Liquid Saturated Vapor
𝐹𝐹
𝐷𝐷
𝐵𝐵
𝑉𝑉1

2. Give the nomenclature for flow rate and compositions of stream entering and leaving stage 3 in a
distillation column.

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 Internal Mass Balances for the Enriching Section
First stage envelope
• Overall mass balance:
𝑉𝑉2 = 𝐿𝐿1 + 𝐷𝐷
• Component mass balance:
𝑉𝑉2 𝑦𝑦2 = 𝐿𝐿1 𝑥𝑥1 + 𝐷𝐷𝑥𝑥𝐷𝐷
Second stage envelope
• Overall mass balance:
𝑉𝑉3 = 𝐿𝐿2 + 𝐷𝐷
A. Stage 1, B. Stage 2, C. Stage j
• Component mass balance:
Stage j envelope
𝑉𝑉3 𝑦𝑦3 = 𝐿𝐿2 𝑥𝑥2 + 𝐷𝐷𝑥𝑥𝐷𝐷
• Overall mass balance:
𝑉𝑉𝑗𝑗+1 = 𝐿𝐿𝑗𝑗 + 𝐷𝐷
• Component mass balance:
𝑉𝑉𝑗𝑗+1 𝑦𝑦𝑗𝑗+1 = 𝐿𝐿𝑗𝑗 𝑥𝑥𝑗𝑗 + 𝐷𝐷𝑥𝑥𝐷𝐷
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 Internal Mass Balances for the Stripping Section

Below feed stage (f+1) envelope

• Overall mass balance:
𝑉𝑉�𝑓𝑓+1 = 𝐿𝐿�𝑓𝑓 − 𝐵𝐵
• Component mass balance:
𝑉𝑉�𝑓𝑓+1 𝑦𝑦𝑓𝑓+1 = 𝐿𝐿�𝑓𝑓 𝑥𝑥𝑓𝑓 − 𝐵𝐵𝑥𝑥𝐵𝐵
Stage k envelope
• Overall mass balance:
𝑉𝑉�𝑘𝑘 = 𝐿𝐿� 𝑘𝑘−1 − 𝐵𝐵 A. Below feed stage (f+1), B. Stage k, C. Partial reboiler
• Component mass balance:
𝑉𝑉�𝑘𝑘 𝑦𝑦𝑘𝑘 = 𝐿𝐿� 𝑘𝑘−1 𝑥𝑥𝑘𝑘−1 − 𝐵𝐵𝑥𝑥𝐵𝐵 • The reboiler is a partial reboiler
 Only part of the liquid is vaporized
 Serves as an additional equilibrium
stage, N+1

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 Constant Molal Overflow

• Lewis noted that the liquid and vapor molar flow rates in each
section were constant (that is, regions between any input and
output ports):
𝐿𝐿1 = 𝐿𝐿2 = ⋯ = 𝐿𝐿𝑗𝑗 = ⋯ = 𝐿𝐿𝑓𝑓−1 = 𝐿𝐿 Enriching
𝑉𝑉1 = 𝑉𝑉2 = ⋯ = 𝑉𝑉𝑗𝑗+1 = ⋯ = 𝑉𝑉𝑓𝑓 = 𝑉𝑉 section

𝐿𝐿�𝑓𝑓 = 𝐿𝐿�𝑓𝑓+1 = ⋯ = 𝐿𝐿� 𝑘𝑘−1 = ⋯ = 𝐿𝐿� 𝑁𝑁 = 𝐿𝐿� Stripping

𝑉𝑉�𝑓𝑓+1 = 𝑉𝑉�𝑓𝑓+2 = ⋯ = 𝑉𝑉�𝑘𝑘 = ⋯ = 𝑉𝑉�𝑁𝑁+1 = 𝑉𝑉� section

 For each additional column section, there will be another set

of equalities
 𝐿𝐿 ≠ 𝐿𝐿� and 𝑉𝑉 ≠ 𝑉𝑉� in general

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 Constant Molal Overflow

• These equations are valid when one mole of vapor condenses for
every one mole of liquid vaporized (that is, equimolar counter-
diffusion)

• This is called constant molal overflow and is valid when:

 Column is adiabatic

 Specific heat changes are small compared to latent heat changes

 The heat of vaporization per mole, λ, is constant. That is, λ does

not depend on concentration => most important assumption

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 Test Your Understanding
Example 2: Equilibrium in Distillation
Which of the following combinations of streams are in equilibrium with each other?

Streams Yes or No?

𝐹𝐹 𝑎𝑎𝑎𝑎𝑎𝑎 𝐷𝐷

𝐷𝐷 𝑎𝑎𝑎𝑎𝑎𝑎 𝐵𝐵

𝐿𝐿𝑗𝑗 𝑎𝑎𝑎𝑎𝑎𝑎 𝑉𝑉𝑗𝑗

𝐿𝐿𝑗𝑗 𝑎𝑎𝑎𝑎𝑎𝑎 𝑉𝑉𝑗𝑗+1

𝐿𝐿� 𝑘𝑘−1 𝑎𝑎𝑎𝑎𝑎𝑎 𝑉𝑉�𝑘𝑘

𝐵𝐵 𝑎𝑎𝑎𝑎𝑎𝑎 𝑉𝑉�𝑁𝑁+1

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Operating Line Equation for Enriching Section

Stage j envelope

• Overall mass balance becomes:

𝑉𝑉 = 𝐿𝐿 + 𝐷𝐷

• Component mass balance becomes:

𝑉𝑉𝑦𝑦𝑗𝑗+1 = 𝐿𝐿𝑥𝑥𝑗𝑗 + 𝐷𝐷𝑥𝑥𝐷𝐷

𝑳𝑳 𝑫𝑫
⇒ 𝒚𝒚𝒋𝒋+𝟏𝟏 = 𝒙𝒙𝒋𝒋 + 𝒙𝒙𝑫𝑫
𝑽𝑽 𝑽𝑽

This is the top operating line (TOL)

equation (that is, above feed stage)

𝐷𝐷 𝑉𝑉−𝐿𝐿 𝐿𝐿
How to draw TOL? = =1−
𝑉𝑉 𝑉𝑉 𝑉𝑉

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 Operating Line Equation for Stripping Section

Stage k envelope

• Overall mass balance becomes:

𝑉𝑉� = 𝐿𝐿� − 𝐵𝐵

• Component mass balance becomes:

� 𝑘𝑘 = 𝐿𝐿� 𝑥𝑥𝑘𝑘−1 − 𝐵𝐵𝑥𝑥𝐵𝐵
𝑉𝑉𝑦𝑦

𝑳𝑳� 𝑩𝑩
⇒ 𝒚𝒚𝒌𝒌 = 𝒙𝒙
� 𝒌𝒌−𝟏𝟏
− � 𝒙𝒙𝑩𝑩
𝑽𝑽 𝑽𝑽

This is the bottom operating line (BOL)

equation (that is, below feed stage)

𝐵𝐵 � −𝐿𝐿�
𝑉𝑉 𝐿𝐿�
How to draw BOL? −�= =1−�
𝑉𝑉 �
𝑉𝑉 𝑉𝑉

VasudevanS/TCN3132/Binary Distillation - Equilibrium Design Basics 25

 Example 3: Distillation Column Basic Calculations
A distillation column is separating ethylene dichloride from trichloroethane. The column has a total
condenser and a partial reboiler. Reflux is returned as a saturated liquid. The feed is 60 mole% ethylene
dichloride, the more volatile component. Feed rate is 100 kg moles/hr. Distillate mole fraction is 0.92
ethylene dichloride and bottoms mole fraction is 0.08 ethylene dichloride. Assume CMO. Pressure is 1
atm.

a) Find B and D.
𝐿𝐿 �
𝑉𝑉 𝐿𝐿 𝐿𝐿�
b) If the external reflux ratio = 2.0 and the boil-up ratio = 1.2, find and �
.
𝐷𝐷 𝐵𝐵 𝑉𝑉 𝑉𝑉

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