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Equilibrium stage

 Definition:
An abstraction concept in which two phases in contact are
brought to physical equilibrium, followed by phase
separation.
Example: a vapor-liquid equilibrium stage
Equilibrium stage
 Definition:
In practice, it is a useful concept with real application in
industry.
Example: Cooling water tower
Equilibrium stage
 Definition:
In practice, it is a useful concept with real application in
industry.
Example: tray plate column.
Equilibrium stage
 Definition:
Example: a binary vapor-liquid equilibrium stage
 Two input and two output streams
 The exit streams are at physical equilibrium, i.e. they
have the same temperature and pressure
 The exit streams are at chemical equilibrium
Equilibrium stage
 Example:
Simple binary vapor-liquid equilibrium stage – flash
Equilibrium stage
 Example:
Simple binary vapor-liquid equilibrium stage: a flash
Equilibrium stage
 Example:
Simple binary vapor-liquid equilibrium stage: a flash
Equilibrium stage
 Example:
Simple binary vapor-liquid equilibrium stage: a flash

Flash conditions: T, P
Global molar balance: F= V + L
Molar balance on A: F z A= V y A + L x A
Energy balance: F h F +Q= V hV + L h L
yA
Equilibrium relation: K A =
xA
Equilibrium stage
 Design of an equilibrium separation process is based on two
steps:
 The determination of the best equilibrium conditions
for the separation task
 The design of the equipment that best promotes the
separation of the phases
Equilibrium stage
 What can be achieved with one equilibrium stage?
For binary vapor-liquid equilibrium, the relative
volatility is defined by:
KA
α A , B=
KB
For ideal solutions and at given T and P:

αA,B does not change with composition, it is


constant.

Deduce: y A= f ( x A , α A ,B)
Equilibrium stage
 What can be achieved with one equilibrium stage?
For binary vapor-liquid equilibrium, the relative
volatility is defined by:
KA
α A , B=
KB
For this example, compute the value for the relative
volatility at 370K and 1 atm.
Make a plot of the corresponding x-y diagram.
Equilibrium stage
 What can be achieved with one equilibrium stage?
For binary vapor-liquid equilibrium, the relative
volatility is defined by:
KA
α A , B=
KB
For this example, compute the value for the relative
volatility at 370K and 1 atm.
Make a plot of the corresponding x-y diagram.
( ya / xa) 0.57/ 0.35
α A , B= = = 2.5
( y b / x b ) (1− 0.57)/(1− 0.35)

α A,B xA
y A=
1+(α A , B − 1) x A
Equilibrium stage
 What can be achieved with one equilibrium stage?
In general, the relative volatility measures how easy is a
separation can be.

Given these two diagrams what can be said about them?


Equilibrium stage
 What can be achieved with one equilibrium stage?
In general, the relative volatility measures how easy is a
separation can be.

A flash operation will give:


 A vapor phase with yA = 0.984 and a liquid phase with
xA = 0.5
So, with a single equilibrium stage it is possible to get a
vapor very rich in A (purity: 98.4%).
Equilibrium stage
 What can be achieved with one equilibrium stage?
In general, the relative volatility measures how easy is a
separation can be.

A flash operation will give:


 A vapor phase with yA = 0.6 and a liquid phase with xA
= 0.5
So, with one equilibrium stage it is not possible to get a
very pure A.
Equilibrium stage
 Exercise:
A liquid containing 60 mol% toluene and 40
mol% of benzene is continuously distilled in a
single equilibrium stage at 1 atm. What
percentage of benzene in the feed leaves as
vapor if 90% of the toluene entering in the
feed leaves as liquid? Assume a relative
volatility of 2.3.
Equilibrium stage
 Separation goals can be achieved by using multiple
equilibrium stages

Most equilibrium based separation technologies contain


multiple equilibrium stages:
 distillation, absorption, stripping, liquid-liquid
extraction, etc…
 the equilibrium stages can be arranged in cascades of
different flow modes: cross-current, counter-current,
co-current and hybrid systems
Multiple equilibrium stages
 Cascades: aggregates of stages
 accomplish separations that cannot be achieved in a
single stage
 reduce the amounts of MSA or ESA required
 make efficient use of raw materials

a. Can you identify which streams are in


equilibrium?
b. Is this arrangement efficient? Why?
(suggestion: mass transfer and
driving forces)
Multiple equilibrium stages
 Some cascades configurations:

Counter-current cascade:
very efficient and widely used

Cross-current cascade:
not as efficient as counter-
current cascade

Co-current: ??
What is the interest of co-current cascade?

Two-section, counter-current cascade:


Distillation, liquid-liquid extraction
Absorption and stripping
 Absorption: used to separate gas mixtures; remove
impurities, contaminants, pollutants or catalyst poisons from
a gas; and recover valuable chemicals.
The species are transferred to the liquid absorbent are
called solutes or absorbate.
species in gas phase→liquid phase

 Stripping (desorption): a liquid mixture is contacted with a


gas to selectively remove components from the liquid to the
gas phase
Strippers are frequently aggregated with absorbers to allow
the regeneration of the liquid absorbent agent.

species in liquid phase→gas phase


Absorption and stripping
 Main industrial applications:
 Flue gas cleaning: removal of H2S, NOx, SOx, CO2
 Removal of volatile organic compounds (VOC’s) such
as: acetone, acetic acid, aromatic and chlorinated
compounds
Absorption and stripping
 2 main types of absorption (stripping) processes:
 Physical absorption: no significant chemical reaction
occur between the absorbent and the solute – when
water or hydrocarbon oils are used as absorbents

 Chemical (reactive) absorption: there is a rapid


chemical reaction that can be irreversible or
reversible:
 aqueous NaOH is used as the absorbent for
acid gas absorption there an irreversible
chemical reaction in the liquid phase
 an aqueous amine is used for the absorption of
CO2 or H2S an reversible chemical reaction
occurs in the liquid
Absorption and stripping
 Absorption example:
Describe what happens in the column…
What is the purpose of this unit?
Compute the separation factors for the different species in
the unit.
Absorption and stripping
 Absorption/stripping process:
The absorption process is usually combined with a stripping
process to recover the mass separating agent (MSA)
Absorption and stripping
 Absorption/stripping equipment:
Usually, in absorption/stripping processes are used packed
columns...
Absorption and stripping
 Absorption/stripping equipment:
The packed columns can have different sections with
different types of packing...
Absorption and stripping
 Absorption/stripping equipment:
However, there are other types of columns…

What is the objective of all these designs?

Spray tower Bubble column Centrifugal contactor


Absorption and stripping
 Absorption (stripping) process design
Requires consideration about these factors:
Specifications (normally given):
 Entering gas (liquid) flow rate, composition, T and P
 Desired degree of recovery of one or more solutes
Design of the equilibrium conditions:
 Choice of the absorbent (stripping agent)
 Operating P and T and allowable gas pressure drop
 Minimum and the actual absorbent (stripping agent) flow rate
 Number of equilibrium stages and stage efficiency
Column design:
 Type of absorber (stripper) equipment (trays or packing)
 Height of absorber (stripper)
 Diameter of absorber (stripper)
Absorption and stripping process
design
 Methodology for single-component absorption/stripping
Absorption and stripping involves, at least, 3 components and 2
phases
For simplicity, it is assumed:
 Carrier gas is insoluble (into the solvent)
 Solvent is non-volatile (negligible loss due to
vaporization)
 System is isothermal and isobaric
species

Gibbs phase rule: F= C− P+2= 3⏞ − 2⏟ +2= 3


temperature phases

F= 3− 1⏞ − 1⏟ = 1 Remains 1 D.O.F.
Used for equilibrium data
pressure
Absorption and stripping process
design
 Methodology for single-component absorption/stripping
The equilibrium relation for the solute between the two phases is
given by:
y A= K A x A
In general, the amount of solute is relatively low (diluted solution),
Henry’s law can be used:

HA
y A= xA
P
Absorption and stripping process
design
 Mass-energy balances

Remember, assumptions:
 Heat of absorption is negligible
 Operation is isothermal
 Solvent is non-volatile
 Carrier-gas is insoluble
L ' 0 = L ' 1= ⋯= L ' N = L'
So:
V ' 0= V ' 1= ⋯= V ' N = V '
 Energy balance is automatically satisfied
 Both liquid and gas (or vapor) flow rates
are constant
Absorption and stripping process
design
 Mass-energy balances

In other words:
 L’: the liquid flow rate must be the
molar flow rate of a non-volatile solvent
 V’: the gas flow rate must be the molar
flow rate of an insoluble carrier gas
 The mole fractions of A in the gas and the
liquid are defined as:
moles of solute A (gas phase)
y A=
moles carrier gas + moles solute A
moles of solute A (liq. phase)
x A=
moles solvent + moles solute A
Absorption and stripping process
design
 Mass-energy balances

The mole fractions of A in the gas and the


liquid have to be used in a different way:

moles of solute A (gas phase) yA


Y A= =
moles of pure carrier gas 1− y A

moles of solute A (liq. phase) xA


X A= =
moles of pure liq. solvent 1− x A
Absorption and stripping process
design
 Mass-energy balances

Using these concepts, write the mass balance on


the envelope
Absorption and stripping process
design
 Mass-energy balances

Based on the mass balance, it is possible to


define an operating line for absorption
V ' n+1 Y n+1 + L ' 0 X 0= V ' 1 Y 1 + L ' n X n

V ' Y n+1 + L ' X 0= V ' Y 1 + L ' X n


L' L'
Y n+1 = X n +Y 1− X0

V' ⏟ V'
slope offset
Absorption and stripping process
design
 Mass-energy balances

The operating line:


L' L'
Y n+1 = X n +Y 1− X0

V' ⏟ V'
slope offset

The equilibrium line:


y A Y A /(1+Y A )
K A= =
x A X A /(1+ X A )
Absorption and stripping process
design
 For the stripping?

The operating line?:

The equilibrium line is:


y A Y A /(1+Y A )
K A= =
x A X A /(1+ X A )
Absorption and stripping process
design
 For the stripping process

The operating line:


L' L'
Y n= X n+1 +Y 0 − X1

V' ⏟ V'
slope offset

The equilibrium line is:


y A Y A /(1+Y A )
K A= =
x A X A /(1+ X A )
Absorption and stripping process
design
 Exercise:
A 710 kmol/hr air stream is contaminated with
acetone at 1.5 mol% is treated in an absorption
column where it is washed with pure water with a
flow-rate of 1900 kmol/hr.

Draw the X-Y diagram representing this absorption


process. What is the final mole fraction of acetone
in the air stream, if the liquid stream exits with 0.5
mol% of acetone?

Data:
KA = 2.0
Absorption and stripping process
design
 Determination of the minimum liquid
molar flow-rate - Absorption
L' L'
Y n+1 = X n +Y 1− X0

V' ⏟ V'
slope offset
Absorption and stripping process
design
 Determination of the minimum liquid molar flow-
rate - Absorption

The minimum absorbent flow rate corresponds to a


value of XN (liquid leaving the tower) in equilibrium
with YN+1, the concentration in the feed gas.

X 0 L ' +Y N +1 V '= X N L ' +Y 1 V '

V ' (Y N +1− Y 1) Y N +1 /(1+Y N +1 )


( L ' )min = K=
X N− XO X N /(1+ X N )
Absorption and stripping process
design
 Determination of the minimum liquid molar flow-
rate - Absorption

Usually, absorption columns are operating at 1.5


the minimum liquid flow-rate:
L' (L ' )min
= 1.5
V' V'

Can you interpret what


is happening on the graph?
Absorption and stripping process
design
 Determination of the minimum liquid molar flow-
rate - Absorption

Usually, absorption columns are operating at 1.5


the minimum liquid flow-rate:

L' (L ' )min


= 1.5
V' V'

What about the stripping case?


Find its expression...
Absorption and stripping process
design
 Graphical determination of the number of theoretical
stages after selecting the liquid flow-rate
Absorption:
Absorption and stripping process
design
 Graphical determination of the number of theoretical
stages after selecting the liquid flow-rate
Stripping:
Absorption and stripping process
design
 Exercise:
A CO2 stream contains a small amount of ethanol. It is
treated in an absorption tower with pure water in order
to recover the ethanol. The entering gas flow rate is 180
kmol/hr with 2 mol% of ethanol. The required recovery
of ethanol is 97%.

Find the flow rate of water required and the number of


theoretical stages needed for this absorption tower.
Draw the X-Y diagram representing the operation.

Data:
K = 0.57
Summary
 Concept of equilibrium stage
 Understand the need for multiple equilibrium
stages
 Absorption and stripping processes
 Understand which conditions are best for
both processes
 Graphical design of absorption and stripping
columns: determination of liquid (gas) flow-
rate and the number of theoretical stages

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