Faculty of Engineering and the

Built Environment

Department of Chemical
Engineering

ADVANCED DIPLOMA

PMO470S

LECTURER: M. AZIZ

2020
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In chemical engineering and related fields, a unit operation is a basic step in a process.
Unit operations involve bringing a physical change such as separation, crystallization,
evaporation, filtration etc. A process may have many unit operations to obtain the
desired product.

Historically, the different chemical industries were regarded as different industrial

processes and with different principles. Similar processes were summed-up into unit
operations. Each unit operation follows the same physical laws and may be used in all
chemical industries. The unit operations form the fundamental principles of chemical
engineering.

Chemical engineering unit operations consist of five classes:

1. Fluid flow processes, including fluids transportation, filtration, solids fluidization
2. Heat transfer processes, including evaporation, condensation
3. Mass transfer processes, including gas absorption, distillation, extraction,
adsorption, drying
4. Thermodynamic processes, including gas liquefaction, refrigeration
5. Mechanical processes, including solids transportation, crushing and
pulverization, screening and sieving

Chemical engineering unit operations also fall in the following categories:

1. Combination (mixing)
2. Separation (distillation)
3. Reaction (chemical reaction)

Chemical engineering unit operations and chemical engineering unit processing form
the main principles of all kinds of chemical industries and are the foundation of designs
of chemical plants, factories, and equipment used.
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CRYSTALLISATION

Crystallization is the (natural or artificial) process of formation of solid crystals

precipitating from a solution, melt or more rarely deposited directly from a gas.

Crystallization is also a chemical solid–liquid separation technique, in which mass

transfer of a solute from the liquid solution to a pure solid crystalline phase occurs. In
chemical engineering crystallization occurs in a crystallizer. Crystallization is therefore an
aspect of precipitation, obtained through a variation of the solubility conditions of the
solute in the solvent, as compared to precipitation due to chemical reaction.

Process

The crystallization process consists of two major events, nucleation and crystal growth.
Nucleation is the step where the solute molecules dispersed in the solvent start to gather
into clusters, on the nano-meter scale (elevating solute concentration in a small region),
that become stable under the current operating conditions. These stable clusters
constitute the nuclei. However, when the clusters are not stable, they re-dissolve.
Therefore, the clusters need to reach a critical size in order to become stable nuclei. Such
critical size is dictated by the operating conditions (temperature, super saturation, etc.). It
is at the stage of nucleation that the atoms arrange in a defined and periodic manner that
defines the crystal structure — note that "crystal structure" is a special term that refers to
the relative arrangement of the atoms, not the macroscopic properties of the crystal (size
and shape), although those are a result of the internal crystal structure.
 4

The crystal growth is the subsequent growth of the nuclei that succeed in achieving the
critical cluster size. Nucleation and growth continue to occur simultaneously while the
super saturation exists. Super saturation is the driving force of the crystallization; hence
the rate of nucleation and growth is driven by the existing super saturation in the solution.
Depending upon the conditions, either nucleation or growth may be predominant over the
other, and as a result, crystals with different sizes and shapes are obtained (control of
crystal size and shape constitutes one of the main challenges in industrial manufacturing,
such as for pharmaceuticals). Once the super saturation is exhausted, the solid–liquid
system reaches equilibrium and the crystallization is complete, unless the operating
conditions are modified from equilibrium so as to supersaturate the solution again.

Many compounds have the ability to crystallize with different crystal structures, a
phenomenon called polymorphism. Each polymorph is in fact a different thermodynamic
solid state and crystal polymorphs of the same compound exhibit different physical
properties, such as dissolution rate, shape (angles between facets and facet growth
rates), melting point, etc. For this reason, polymorphism is of major importance in
industrial manufacture of crystalline products.

Reference:
Tavare, N.S. (1995). Industrial Crystallization Plenum Press, New York
McCabe & Smith (2000). Unit Operations of Chemical Engineering' McGraw-Hill, New
York

Yield of crystals:
 5

1. The yield of crystals produced by a given cooling may be estimated from the
concentration of the initial solution and the solubility at the final temperature.

2. For the solvent, usually water, the initial solvent present is equal to the sum of the
final solvent in the mother liquor, the
water of crystallization within the crystals and any water evaporated or:

y (R − 1)
w1 = w2 + + w1E …..1
R

where: w1 & w2 are the initial and final masses of solvent in the liquor,

y - is the yield of crystals

R - is the ratio (molecular weight of hydrate/molecular
Weight of anhydrous salt)
E - is the ratio (mass of solvent evaporated/mass of solvent
in the initial solution)

Hydrate - include water

Anhydrous salt - without water

For the Solute:

y
w1c1 = w2c2 + …..2
R

where: c1 - the initial concentration of the solution in terms of

mass of anhydrous salt/unit mass of solvent
 6

(liquid)

c2 - the final concentration of the solution in terms of

mass of anhydrous salt/unit mass of solvent
(liquid)

The amount of crystals:

Rw1c1 − c2 (1 − E )
y=
1 − c2 (R − 1) …..3

Do Example 1

Example 1:

A solution of 500kg of Sodium sulphate (Na2SO4) in 2500kg of water is cooled from

333K to 283K in an agitated mild steel vessel of mass 750kg. The specific heat of
steel being 0,5 kJ.kg-1K-1. At 283K the stable crystalline phase is Na2SO4.10H2O and
at 291K the heat solution is 78,5 MJ.kmol-1. The mean heat capacity of the solution
is 3,6 kJ.kg-1K-1. If, during cooling, 2% by mass of the water is lost by evaporation,
estimate the yield of crystals formed and heat to be removed.
The solubility of the anhydrous salt at 283K is 8,9 kg/100kg of H2O

Note: The amount of evaporation taking place during vacuum operation may
be estimated by making a heat balance as follows:

solvent evaporated x latent heat = sensible heat drop + heat of crystallization(HOC)

Ew1 = C p (T1 − T2 )w1 (1 + c1 ) + qc y …..4

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where:  - the latent heat of vaporization per unit mass

qc - heat of crystallization
Cp - the mean heat capacity of the solution
T1 - initial temperature of the solution
T2 - final temperature of the solution

Rearrange equation 4:

Ew1 C p (T1 − T2 )w1 (1 + c1 )

y= − …..5
qc qc

Substitute Equation 5 into Equation 3, and make E the subject of the formula:

qc R(c1 − c2 ) + C p (T1 − T2 )(1 + c1 )1 − c2 (R − 1)

E=
 1 − c2 (R − 1) − qc Rc2

Example 1:

A solution of 500kg of Sodium sulphate (Na2SO4) in 2500kg of water is cooled from

333K to 283K in an agitated mild steel vessel of mass 750kg. The specific heat of
steel being 0,5 kJ.kg-1K-1. At 283K the stable crystalline phase is Na2SO4.10H2O and
at 291K the heat solution is 78,5 MJ.kmol-1. The mean heat capacity of the solution
 8

is 3,6 kJ.kg-1K-1. If, during cooling, 2% by mass of the water is lost by evaporation,
estimate the yield of crystals formed and heat to be removed.

The solubility of the anhydrous salt at 283K is 8,9 kg/100kg of H2O

Example 1: Solution

Crystals yield (y) = ?

Heat removed =?

The amount of crystals:

Rw1 c1 − c2 (1 − E )
y =
1 − c2 (R − 1)

MM(Na2SO4) = 144

MM(Na2SO4.10H2O = 322

heat of crystallization (HOC) :

HOS 78500
qc = = = 244kJ.kg −1
MMofsoluti on 322
 9

Latent heat of vaporization of water (  ) = 2395 kJ.kg-1.

322
R= = 2,27
142

500
c1 = = 0,2kg / kg.H 2O
2500

c2 = 0,089kg / kgH2O at 283K

w1 = 2500kg H2O

E = 0,02 kg/kg H2O (given as 2%)

Rw1c1 − c2 (1 − E )
y=
1 − c2 (R − 1)

2,27  25000,2 − 0.0089(1 − 0,02)

y=
1 − 0,0089(2,27 − 1)
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y = 723 kg

heat of crystallization (HOC) : = mass x qc

= 723kg x 244kJ.kg-1
= 176,412 kJ

heat removed from the solution:

QS = mC p T
QS = 500 + (2500  0,98) 3,6  (333 − 283)

Qs = 531,000kJ

m = 500 + (2500x0,98) (2% water is removed = 98% crystals)

heat removed from the vessel:

Qv = mC p T
Qv = 750  0,5(333 − 283)
Qv = 18, 750kJ

Total heat removed from:

176,412 + 531,000 + 18,750 = 726,162kJ
 11

heat lost by evaporation:

QE = m

QE = w1E

QE = (2500  0.02)2395

QE = 119,750 kJ

Therefore the heat removed:

Q = 725,162 − 119,750

Q = 615,412kJ

Example 2: Continuous crystallizers

 12

A solution of 23% by mass of sodium phosphate (Na3PO4) is cooled from 313K to

298K in a continuous crystallizer to form crystals of Na3PO4.12H2O. The solubility
of Na3PO4 at 298K is 15,5kg/100kg H2O, and the required flow of crystals is
0,063kg.s-1. The mean heat capacity of the solution is 3,2 kJ.kg-1K-1, and the heat
of crystallization is 146,5kJ.kg-1. If cooling water enters and leaves at 288 and 293K,
respectively, and the overall coefficient of heat transfer is 0,14 kW.m -2K-1. What
length of the crystallizer is required?

Example 2: Solution

Lenght (L) = ?

Area (A) = ?
Q=? ( Q=UA  T)
y=?

E=0

The amount of crystals:

Rw1 c1 − c2 (1 − E )
y=
1 − c2 (R − 1)

MM(Na3PO4) = 164

MM(Na3SO4.12H2O = 380

It will be assumed that the evaporation is negligible and that E=0

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MM (hydrate) 380
R= = = 2,32
MM (anhydrate) 164

The initial concentration = 0.23 kg/kg solution:

0.23
c1 = = 0,30kg / kg.H 2O
1 − 0.23

The final concentration = 15,5kg/100kg H2O:

c2 = 0,155kg / kgH2O at 298K

If 1 kg of initial feed solution is considered, then there is 0,23kg salt and 0.77kg H 2O and
hence:
w1 =0,77kg

Rw1 c1 − c2 (1 − E )
y =
1 − c2 (R − 1)

2,32  0,770,3 − 0.155(1 − 0)

y=
1 − 0,155(2,32 − 1)

y = 0.33 kg

In order to produce 0.063kg.s-1of crystals, the feed rate required must be:
 14

 0.063 
= 1 
 0.33 


= 0.191kg.s-1

heat required to cool the solution:

QS = mC p T

QS = 0,191 3,2  (313 − 298)

Qs = 9,2 kW

heat of crystallization (HOC) : =

•
mc c
= 0.063kg.s-1 x 146, 5kJ.kg-1
= 9,2 kW

Total Heat (Q) = 9,2 + 9,2 = 18,4kW

Assuming counter-current flow:

T1 = 313 − 293 = 20K

T2 = 298 − 288 = 10K

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20 − 10
And Tlm = = 14.4 K
 20 
ln 
 10 


The heat transfer area required is then:

Q = UATlm
Q
A=
UTlm

18,4
A=
(0,14)(14,4)

A = 9,1 m2

Note: A typical continuous crystallizers will provide 1m2 surface per meter
length. (1m2 /m length)

The length of the crystallizer required = 9,1m

Example 3: Batch crystallization

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What is the yield of sodium acetate as CH3.COONa.3H2O from a vacuum crystallizer

operating at 1,33 kN.m-2 when it is fed with 0,63 kg.s-1 of a solution containing 40%
sodium acetate in water at 355K? The solution has boiling point elevation of 11K
and the heat of crystallization is 144 kJ.kg-1. The mean heat capacity of the solution
is 3,5 kJ.kg-1K-1 and a pressure 1,33 kN.m-2, water boils at 284,5K at which the latent
heat of vaporization is 2477 kJ.kg-1.

Solubility Data
Temperature (K) 273 283 293 303 313
Solubility (kg/100kg H2O) 36,3 40,8 46,5 54,5 65,5

Example 3: Solution

y=?

The amount of crystals:

Rw1 c1 − c2 (1 − E )
y =
1 − c2 (R − 1)

MM(CH3.COONa) = 82

MM(CH3.COONa.3H2O ) = 136

136
R= = 1,66
82

Temperature of the liquid at Equilibrium:

 17

284,5 + 11K = 295,5K

At which, by interpolation, the concentration, from table:

c2 = 48,5 kg/100kg H2O = 0,485 kg/kg H2O

The initial concentration = 0.40 kg/kg solution: (be in fractions)

0.4
c1 = = 0,667kg / kg.H 2O
1 − 0.4

If 0,63 kg.s-1 of initial feed solution containing 40% sodium acetate (solute) and 60% H2O
(solvent), hence:

The initial mass of solvent (w1):

w1 =0,63 x 0,6 = 0,378 kg.s-1

E=?

qc R(c1 − c2 ) + C p (T1 − T2 )(1 + c1 )1 − c2 (R − 1)

E =
 1 − c2 (R − 1) − qc Rc2

144  1,66(0,667 − 0,485) + 3,5(355 − 295,5)(1 + 0,667 )1 − 0,485(1,66 − 1)

E=
24471 − 0,485(1,66 − 1) − 144  1,66  0,485

E = 0,178 kg/kg H2O

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y=?

Rw1 c1 − c2 (1 − E )
y =
1 − c2 (R − 1)

1,66  0,3780,667 − 0.485(1 − 0,178)

y =
1 − 0,485(1,66 − 1)

y = 0.248 kg.s-1

MULTI COMPONENT DISTILLATION

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Distillation Column Construction

Distillation columns are made up of several components, each of which is used

either to transfer heat energy or enhance material transfer. A typical distillation
contains several major components:

1. A vertical shell where the separation of liquid components is carried out

2. Column internals such as trays/plates and/or packing’s which are used to
enhance component separations
3. A reboiler to provide the necessary vaporization for the distillation process
4. A condenser to cool and condense the vapor leaving the top of the column
5. A reflux drum to hold the condensed vapor from the top of the column so that
liquid (reflux) can be recycled back to the column

Distillation columns also referred to as a separating column serve as a separating

mechanism in the chemical and associated industries. Examples of industrial applications
are alcohol rectification and fractionating of crude oil. Coulson and Richardson (2005) list
factors are to be considered during column design such as; degree of separation required,
operating conditions, contact type, stage and reflux requirement, column sizing and
column internals. Methods from Fenske, Colburn and Underwood, Erbar and Maddox,
Kirkbride and Depriester are used in determining these desired parameters.
 20

Multi-component distillation

Feed may consist of binary mixtures or more complex multi-component mixtures. In the
latter case it is rather intricate to specify the complete composition of top and bottom
products. This results in the introduction of light and heavy key components which are set
limits on two key components (Coulson and Richardson, 2005). It should be noted the
components are ranked according to volatility. Therefore, the limits are based upon the
following; component not desired in the bottoms becomes the light component and
similarly, component not desired in the tops become the heavy component. Components
which are present in both tops and bottoms are referred to as distributed components by
Coulson and Richardson, 2005). Often, more than one column is required to obtain one
pure product from a multi-component mixture. Stage and reflux estimations can be via
numerous short-cut methods; which can either be found by stage-by-stage analysis or
empirical methods which are based on column performance.

Distribution of non-key components

For the purposes of this report, the mass fractions light and heavy components are known
in both tops and bottoms, however, the fractions of non-key components are unknown
but can be determined by as stated in Coulson and Richardson (2005). Equation 1,
derived from Fenske’s equation (equation ), also, note that equation 1 yields an equation
resembling that of a straight line which allows for the two points (distillate and bottoms
mass fractions of both light and heavy components) to be plotted.
𝑑𝑖
𝑙𝑜𝑔 (𝑏𝑖 ) = 𝐴 + 𝑐 log 𝛼𝑖 … Equation 1

𝑦 = 𝑐 + 𝑚𝑥 … Equation 2
 21

From the equation obtained from the straight line graph, the rest of the components flow
rates and thereby fractions can be found using equations 3 and 4.
𝑓𝑖
𝑑𝑖 = 𝑏𝑖
… Equation 3
(( )+1)
𝑑𝑖

𝑓𝑖
𝑏𝑖 = 𝑑𝑖
… Equation 4
(( )+1)
𝑏𝑖

Minimum number of stages

The minimum number of stages are defined as the number of plates required to make a
specific separation at total reflux, using the Fenske equation in equation 5 and is
rearranged to give equation 6 (Perry, 1997). Total reflux is described as the condition
whereby all the condensate is returned to the column as reflux (Coulson and

Richardson, 2005). It is also observed that the number of stages depend on the reflux
ratio.
𝑥 𝑥
(𝑥 𝑖 ) = 𝛼𝑖 𝑁𝑚 (𝑥 𝑖 ) … Equation 5
𝑟 𝑑 𝑟 𝑏
𝑥 𝑥
log ( 𝐿𝐾 ) ( 𝐻𝐾 )
𝑥𝐻𝐾 𝑑 𝑥𝐿𝐾 𝑏
𝑁𝑚 = … Equation 6
log 𝛼𝐿𝐾

Minimum reflux ratio

The reflux ratio, according to Coulson and Richardson (2005) is depicted as the flow
returned as reflux over the flow of top product removed for a given separation. At total
reflux, the stage requirement is at its minimum and although this is rarely the case, it
gives an indication of the minimum number of stages required. Colburn and Underwood
equations are used to determine the minimum reflux ratio.

𝛼𝑖 𝑥𝑖,𝑓
∑ =1−𝑞 … Equation 7
𝛼𝑖 −𝜃
𝛼𝑖 𝑥𝑖,𝑑
∑ = 𝑅𝑚 + 1 … Equation 8
𝛼𝑖 −𝜃
 22

The value of q used in equation 7 is dependent on the feed condition. If the feed is
assumed to enter the column at its boiling point, q =1. Also, the θ value is said to range
between the relative volatility of the HK and LK.

Reflux ratio

Erbar and Maddox present a correlation (figure 1) which illustrates the ratio of the
number of stages required to the number at total reflux as a function of the reflux ratio
using Rm ratio as a parameter (Coulson and Richardson, 2005).

Figure 1: Erbar and Maddox correlation (Coulson and Richardson: Pg 524, 2005)
 23

Feed point location

The feed point location in the column can be estimated using Kirkbride’s method given
as equation 9. The region above the feed location is known as the rectifying section as
the concentration of the more volatile component is increased, defined as enrichment.
The region below the feed point is labeled the stripping section since the more volatile
component (Coulson and Richardson, 2005). And equation 10 illustrates the relationship
between the number of plates and Nr and Ns.
2
𝑁𝑟 𝐵 𝑥𝑓,𝐻𝐾 𝑥𝑏,𝐿𝐾
𝑙𝑜𝑔 [𝑁𝑠 ] = 0.206 𝑙𝑜𝑔 [(𝐷) ( 𝑥 )( ) ] … Equation 9
𝑓,𝐿𝐾 𝑥𝑑,𝐻𝐿𝐾

𝑁 = 𝑁𝑟 + 𝑁𝑠 … Equation 10

Dew and bubble point determination

Coulson and Richardson (2005) state that a when a vapor is dropped below its dew point
temperature, it results in the formation of liquid drops. Correspondingly, when a liquid’s
temperature is raised above its bubble point temperature, a bubble of vapor is induced.
Bubble and dew point temperatures can be determined using equations 11 and 12
respectively where k-values are obtained from De Priester charts (figure 2).
∑ 𝑦𝑖 = ∑ 𝐾𝑖 𝑥𝑖 = 1.0 … Equation 11
𝑦
∑ 𝑥𝑖 = ∑ 𝑖 = 1.0 … Equation 12
𝐾 𝑖
24
 25

EXAMPLE 1:

A summary of the flow in and out of a distribution column is shown below:

Feed Distillate Bottoms

Species i
(kmol/hr) (kmol/hr) (kmol/hr)
Cx 10 6
Cy 15 3.2
Cz (LK) 20 18 2 2.1
Cu (HK) 30 2 28 1
Ct 25 0.78

1. Using the FENSKE method, estimate the number of stages.

2. Using the KIRKBRIDE’S method, estimate the location of the feed-point.

3. Estimate the minimum reflux ratio if the feed is at its boiling point.
(Hint: select Θ = 1.4)

4. Estimate the minimum reflux ratio is assumed to be 2, what reflux ratio

must be used if 10 stages are used in this operation?
(Hint: Erbar/Maddox method)

Feed Distillate Bottoms

Species i
(kmol/hr) (kmol/hr) (kmol/hr)
Cx 10 10 0 6
Cy 15 15 0 3.2
Cz (LK) 20 18 2 2.1
Cu (HK) 30 2 28 1
Ct 25 0 25 0.78
F = 100 D = 45 B = 55
 26

1. Using the FENSKE method, estimate the number of stages.

X  X 
log  LK   HK 
 X HK  d  X LK  b
Nm =
log  LK

18   28 
log    
 2  2 
Nm =
log 2.1

Nm = 6.5

 7

2. Using the KIRKBRIDE’S method, estimate the location of the feed-point.

See table:
2
xb, LK = = 0.036
2 + 28 + 25

2
xd , HK = = 0.044
2 + 18 + 15 + 10

 D = 45, B = 55, F = 100 kmol/hr

 Nr   B  x f , HK  xb , LK 
2

log   = 0.206 log     
 Ns   D  x f , LK  x 
 b. HK 
 27

 Nr   55  30  0.036  2 
log   = 0.206 log  45  20  0.044  
 Ns      

 Nr 
log  = 0.018
 Ns 

 Nr 
 Ns  = 1.0

Nr
 1.0
Ns

 Nr  Ns

From 1. Nr + Ns = 7

 Nr  Ns  3.5

 Feed point location at 3 or 4

3. Estimate the minimum reflux ratio if the feed is at its boiling point.
(Hint: select Θ = 1.4)

Θ = 1.4 q=1

 i xi , f
  −  =1 − q
i

− 0.07  0
 28

From table:
10
xcx , d = = 0.22
10 + 15 + 20

15
xcy ,d = = 0.33
10 + 15 + 20
18
xcz ,d = = 0.4
10 + 15 + 20

2
xcu ,d = = 0.04
10 + 15 + 20

 i xi , d
 =Rm + 1
i −

1.97 = Rm + 1

Rm = 1.97 − 1

Rm = 0.97
 29

4. Estimate the minimum reflux ratio is assumed to be 2, what

reflux atio must be used if 10 stages are used in this
operation?
(Hint: Erbar/Maddox method)

Nm 7
= = 0.7
N 10

Rm 2 2
= = = 0.67
Rm + 1 2 + 1 3

R
From the Graph:  0.8
R +1

R=4
 30

Problem 1:

A mixture with 33 percent n-hexane, 37 percent n-heptane, and 30 percent n-octane is

to be ditilled to give a distillled product with 0.01 mole fraction n-heptane and bottoms
product with 0.01 mole fraction n-hexane. The column will operate at 1.2atm with
60percent vaporized fed. Calculate the complete product composition and the minimum
number of ideal plates at infinite reflux.

Given.: n-hexane (LK) , α = 2.21

n-heptane (HK), α = 1.0
n-octane (HNK), α = 0.457

Assume a feed rate of 100 mol/h

Hint.: Make sure to draw a table

1. Using the FENSKE method, estimate the number of ideal stages.

2. Using the KIRKBRIDE’S method, estimate the location of the feed-point.

3. Estimate the minimum reflux ratio (RDm) if the feed is at its boiling point (q=1).
(from trial, Ø = 1.45)
Use the Underwood method

4. Estimate the number of ideal plates required for the separation if the reflux ratio
is 1.5RDm what reflux ratio using Gilliland and Erbar/Maddox method
 31

ADSORPTION & ION EXCHANGE

Adsorption:

Molecules distribute themselves between phases, one of which is a solid whilst the other
can be liquid or gas. Molecules diffuse from the bulk of the fluid to the surface of the solid
adsorbent, forming a distinct adsorbed phase.

Absorption:

Solute molecules diffuse from the bulk of a gas phase to the bulk of the liquid phase.

In adsorption processes one or more components are removed from a gas or liquid
stream by contact with a solid phase

The adsorbent is usually in the form of small particles with a high surface area. The
internal surface area of a particle is usually significantly larger than its external surface
area.

To obtain a very large surface area per unit volume of solid requires that the solid is very
porous. The pores must have small diameters and be interconnected.

The adsorbed solute is referred to as the adsorbate while the solid is referred to as the
adsorbent.
 32

In an adsorption process the molecules diffuse into the pores of the solid where they bond
with the solid surface by physical or chemical forces. The latter process is referred to as
chemisorption.

In commercial processes, the solid particles are charged to a fixed bed. The fluid, from
which a component must be removed, passes through the bed. When the bed is nearly
saturated the process is stopped and normally it is thermally regenerated. In the

regeneration step desorption of the adsorbate occurs. The adsorbate is recovered and
the adsorbent is then ready for another cycle.

Liquid phase adsorption is used for the removal of organic compounds from water and
organic solutions, the removal of sulphur compounds from organic solutions and the
decolourisation of solutions

Gas phase adsorption includes the removal of organics and sulphur compounds from
vent streams, solvents and odours from air, CO2 from natural gas and NOx from N2.

Nature of Adsorbents:

- have a large internal surface area

- the area should be accessible through pores big enough to admit the molecules to
be adsorbed
- pores are small enough to exclude molecules is desired not to adsorbed
- the adsorbent should be capable of being regenerated easily
- should not age rapidly, that is lose its adsorptive capacity through continual recycling
- should be mechanically strong enough to withstand the bulk handling and vibration
that are part of any industrial unit
-
 33

Example of well known Adsorbents:

- activated carbon
- silica gel
- activated alumina
- molecular sieve carbon
- polymeric absorbents

In physical adsorption the process begins as a monolayer that can become

multilayered, and if the pores are close to the size of the molecules, condensation may
follow. The pores then are filled with adsorbate. The maximum capacity of a porous
adsorbent can

thus be closely related to the pore volume rather than to its surface area. For gases above
their critical temperatures, only mono layers are formed.

Chemisorption involves the formation of chemical bonds between the adsorbate and
adsorbent in a monolayer. The heat release is frequently much greater than the heat of
vaporization. Gas phase chemisorption normally only occurs appreciably above 200°C

Adsorption equilibria:

Adsorption equilibrium is a dynamic concept achieved when the rate at which molecules
adsorbed on to a surface is equal to the rate at which they desorb.
 34

The capacity of an adsorbent for a particular adsorbate involves the interaction of 3

properties:
- the concentration (C) of the adsorbate in the fluid phase
- the concentration (Cs) of the adsorbate in the solid phase
- the temperature of the system.

T = constant (Plot C vs Cs) = adsorption isotherm

Equilibrium relations:

The equilibrium relationship between the concentration of an adsorbate in the fluid and
its concentration on the adsorbent resembles the equilibrium solubility of a gas in a liquid.
Some typical isothermal relationships are shown below.

The linear relationship is not common but it can be used in the dilute region to
approximate the data of many systems. This relationship is similar to Henry's law and can
be expressed by:

q = Kc …1

Where: K has dimension of m3.kg-1 adsorbent.

The Freundlich empirical equation apparently often approximates the data for many
systems and is very useful for liquids. This equation is given by:

q = Kc n …2
Where: K and n are constants that must be determined
experimentally.
 35

The Langmuir equation is given by:

q0 c
q = …3
K +c

Where: K is a constant, kg.m-3.

q0 is a constant with kg adsorbate/kg adsorbent

Equation 3 can be rearranged to:

1 K +c K 1
= = + …4
q q0 c q0 c q0

y = mx + c
1 1
This is a equation of a straight line and when is plotted vs the slope is given
q c
K 1
by : and the intercept by:
q0 q0
 36

Example 1:

In batch experiments solutions of phenol in water were contacted with granular activated
carbon. The following results were obtained at room temperature.

c, kg phenol/m3 solution q, kg phenol/kg carbon

0,322 0,15

0,117 0,122

0,039 0,094

0,0061 0,059

0,0011 0,045

Assume that the Freundlich isotherm can be used to model this system. Determine the
constants
 37

Example 1:

Answer

Plot log c vs log q , thus shows that the data are on a straight line

log c log q

-0.492144128 -0.823908741

-0.931814138 -0.913640169

-1.408935393 -1.026872146

-2.214670165 -1.229147988

-2.958607315 -1.346787486

q = Kc n

log q = log K + n log c

log K = log q − n log c

 38

log q vs log c
1.6

1.4

1.2

1
log q

0.8

0.6 y = 0.2184x + 0.7183

0.4 R2 = 0.9941
0.2

0
0 0.5 1 1.5 2 2.5 3 3.5
log c

log q vs log c
0
-3.5 -3 -2.5 -2 -1.5 -1 -0.5 0
-0.2

-0.4

y = 0.2184x - 0.7183 -0.6

R2 = 0.9941
log q

-0.8

-1

-1.2

-1.4

-1.6
log c
 39

log q1 − log q2
n=
log c1 − log c2

− 8,8239 − (− 1,3468)
n= = 0,212
(
− 0,4921 − − 2,9586 )

log K = log q − n log c

log K = log q1 − n log c1
log K = (− 0,8239) − (0,212) (− 0,4921)
log K = −0,7196
K = 0,191

q = 0,191c 0, 212