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Topics Covered
Adsorbents
Equilibrium isotherms
Adsorption Processes Kinetic and transport considerations
Sorption systems
Process Integration and Unit Temperature and pressure swing processes
Operations
Prof. Joe Wood

Recommended Reading What is an adsorbent?

These slides are based on
J.D. Seader and E.J. Henley, Separation Process
Principles, 1998, John Wiley. Chapter 15,
Adsorption, Ion Exchange and
Chromatography.
Also Coulson and Richardson, Chemical
Engineering, Fourth Edition, 1991, Pergamon,
Chapter 17, Adsorption.
Molecules, atoms or ions diffuse to the surface of a
solid, where they are held by weak intermolecular
forces
The adsorbed solutes are called the adsorbate
The solid is called the adsorbent
To achieve a large surface area, highly porous
particles with inter-connected pores are used
After the adsorbent becomes saturated, it must be
regenerated

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Pressure-swing adsorption for

What is an adsorbent?
dehydration of air
Also used to separate air into oxygen and
nitrogen gases
Two adsorbers are used, which operate on a 10
minute cycle
Step 1 : 5 min for adsorption of water vapour from air
(21 C, 6.45 atm)
Step 2: 5 min for regeneration (depressurization
purging repressurization)
Water vapour content is reduced from 1.27 10-3
kgH2O/kg air to 9.95 10-7 kgH2O/kg air
Adsorbent Ion exchanger

Pressure swing adsorption process for Desirable features of an adsorbent

the dehydration of air
One bed is adsorbing
For commercial applications, an adsorbent should have:
High selectivity to enable sharp separations
High capacity
The other is Favourable kinetic and transport properties
being Chemical and thermal stability
purged/regene
rated Hardness and mechanical strength
Free flowing tendency (for emptying vessels)
High resistance to fouling

Does not promote undesirable reactions

Can be regenerated, even with trace poisons in feed
Low cost

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Adsorbents Specific Surface Area

Need a large specific surface area, usually has Specific surface area per unit mass of adsorbent is
calculated from
a microporous structure 4 P
Sg =
Pd p
Micropores < 20
= pellet porosity
Mesopores 20 500 p = pellet density (kg m-3)
Macropores > 500 dp = pore diameter (m)
Typical adsorbents are spheres, cylindrical
If an adsorbent has p=0.5 p = 1 g cm-3 and dp is 20 , what
pellets, flakes, powders is the value of Sg?
Surface area 300 1200 m2g-1
Note: Surface area is measured by BET method see
Reactors and Catalysis notes for details.

Commercial Adsorbents
Types of Adsorption Adsorbent Nature Pore
diameter
Particle
porosity
Particle
Density
Surface
Area
Capacity
for H2O
p p kg m-3 m2g-1 Vap. wt %*
Activated Hydrophilic 10-75 0.5 1.25 320 7
Physisorption Chemisorption alumina amorphous
Van der Waals forces Chemical bond between Silica gel Hydrophilic/
May be more than one layer Small pore Hydrophobic 22-26 0.47 1.09 750 850 11
adsorbate and surface Large pore amorphous 100-150 0.71 0.62 300 350
thick
Monolayer thickness Activated Hydrophobic
Similar to condensation
Heat release can be much carbon amorphous
Heat is released upon Small pore 10-25 0.4-0.6 0.5 0.9 400 1200 1
condensation larger than heat of Large pore >30 0.6 0.8 200 600
Heat of adsorption can be vapourisation Molecular Hydrophobic 2 10 0.98 400
greater or less than heat of Chemisorption from a gas sieve
vapourisation carbon
occurs above 200 C
Important for commercial Zeolites Polar- 3 10 0.2 0.5 600-700 20 - 25
adsorbents Important in catalysis hydrophilic
crystalline
Polymeric 40 - 25 0.4 0.55 80-700
adsorbent

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Most Commonly Used Adsorbents Pore-size distribution of adsorbents

Activated carbon can be made from partial oxidation
of materials such as coconut shells, fruit nutes, wood,
coal, lignite, peat etc. Useful for removal of organic
compounds from gases
Molecular sieve zeolites crystalline inorganic
polymers with general formula
Mx/m[(AlO2)x(SiO2)y]H2O
Silica gel made from colloidal silica, has a high affinity
for water and polar compounds
Activated alumina water is removed fro m hydrated
colloidal alumina during manufacture. Activated
alumina is useful for drying gases

Equilibrium isotherms of gases

Equilibrium Considerations
Classified in to 5 types (Brunauer et al)
Dynamic phase equilibrium is established
between fluid and solid surface
The equilibrium is usually expressed in terms of
Concentration (if the fluid is a liquid)
Partial pressure (if the fluid is a gas)
Solute loading on the adsorbent (mass, moles or
volume of adsorbate per unit mass or surface area of
adsorbent)
Need to obtain equilibrium data from
experimental measurements for a particular fluid
and solid

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Different ways of expressing amount Different displays of adsorption

adsorbed equilibrium data for NH3 on charcoal
Isotherm const T, variable P
Isobars Const P, variable T
Isotere cross plot of amount adsorbed as
function of T and P
The heat of adsorption can be determined
from the Clausius-Clapeyron equation
d ln p H ads d log p H ads
= =
dT RT 2 d (1 / T ) 2.303RT
Adsorption Isotherms Adsorption Isobars

Different displays of adsorption Adsorption Isotherms for pure

equilibrium data for NH3 on charcoal propane vapour at 298 303 K
Vary quite a lot with the type of adsorbent

Adsorption Isoteres Isoteric heats of adsorption

Pressure kPa

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Linear Isotherm Freundlich Isotherm

A form of Henrys law Empirical and non-linear in pressure

q = kp q = kp1/ n
Where k and n are empirical constants
Converting to linear form
q = equilibrium loading of amount
adsorbed/unit mass of adsorbent log q = log k + (1 / n ) log p
intercept slope
k = empirical experimentally determined
constant (varies with T) Derivation assumes a heterogeneous surface with a non-uniform
distribution of heat of adsorption over the surface
P = partial pressure of gas

Langmuir Isotherm Langmuir Isotherm

Restricted to Type I isotherms At equilibrium dq/dt =0 and the above
Derived from simple mass-action kinetics, reduces to:
assuming chemisorption Kp
=
Assuming surface of pores to be homogeneous 1 + Kp
(Hads=const), interaction forces between adsorbed
molecules negligible K is the equilibrium adsorption constant
Let be fraction of surface covered with adsorbed =q/qm
molecules
1- is fraction of unoccupied surface qm=maximum loading corresponding to a
Net rate of adsorption given by: complete monolayer coverage of gas
dq Thus Kqm p
= k a p (1 ) k d q=
dt 1 + Kp

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Langmuir Linearised form Kinetic and Transport Considerations

The linearised form of the Langmuir equation is: For adsorption of a solute onto the porous
p 1 p surface of an adsorbent, the following steps
= +
q qm K q m are required:
Plot gives p/q vs p: External mass transfer of the solute from the bulk
Slope =1/qm fluid by convection through boundary layer
Intercept = 1/(qmK) Internal mass transfer in pellet
The isotherm can be extended for multicomponent Surface diffusion along pore surface
mixtures
Adsorption of solute onto the porous surface
More complex isotherms are available if required Toth Heat transfer occurs simultaneously
and UNILAN equations

Profiles of solute concentration and

Rates of mass and heat transfer
temperature
Desorption
Adsorption Rate of convective mass transfer Mass transfer
coefficient Particle
dN i diameter
ni = = kc A(Cbi CSi ) kc D p
dt Sh =
Di Diffusivity
of
Rate of heat transfer component
i in mixture

dQ Heat transfer
q= = hA(Ts Tb ) coefficient
dt
hD p
Nu =
k
Thermal
conductivity

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Prediction of Mass Transfer Coefficient External Transport in a Fixed Bed

When particles are packed in a bed, the fluid flow patterns are restricted
For single particles and the single-particle correlations cannot be used to estimate the
Nu = 2 + 0.6 Re1/ 2 Pr1/ 3 average external transport coefficients
Correlations relate packed bed behaviour to single particle
Sh = 2 + 0.6 Re1/ 2 Sc1/ 3 Chilton and Colburn j factors

j D = St M Sc 2 / 3 = f (Re )
C p uD p GD p
Pr = Sc = Re = = j H = St Pr 2 / 3 = f (Re )
k Di
Different functions of Reynolds number apply for different regions
Heat transfer coefficient Mass transfer coefficient

Stanton number
St =
h Stanton number kc
for heat transfer for mass transfer St M =
C pG G
Specific heat capacity Fluid mass velocity Fluid density

Wakao and Funazkri Correlation

Wakao and Funazkri Correlation
Comparison with experimental data
Analysis of 37 data sets, with axial disperson correction
For mass transfer:
0.6 1/ 3
kc d p d G
Sh = = 2 + 1.1 p
Di Di

Equivalent expression for heat transfer:

0 .6 1/ 3
hd p d G C p
Nu = = 2 + 1.1 p
k k

dp is equivalent diameter of a spherical particle

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Internal Transport Internal Transport

Material balance between shells at r and r + r gives:
Amount diffusing through Amount adsorbed in Amount diffusing through
Shell at r + r Shell of thickness r Shell at r

c q c
4 (r + r ) De
2
= 4r 2 r + 4r 2
r r + r t r r
Effective Amount adsorbed
diffusivity per unit vol of pellet
Dividing by 4rr, taking the limit as r0, and collecting terms gives:

2 c 2 c q
De 2 + +
r r r t

Flux due to diffusion Total flux

Flux due to molecular diffusion (bulk and Knudsen) Is given by:
dci K dc
N i = Di pore N i = Di pore + (Di )S P i i
dx P dx

Flux due to surface diffusion (adsorbed molecules)

In terms of the effective diffusivity
P dqi
(N i )S = ( Di )S
P dx P 1 P Ki
Assuming linear adsorption according to Henrys law De = + (Di )S
Tortuosity (1 / Di ) + (1 / DK ) P
qi = K i ci (may be
different Bulk Knudsen Surface
for surface diffusivity diffusivity diffusivity
diffusion)

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Adsorption Systems Fixed Beds

Stirred vessel
Powdered adsorbent (dp < 1 mm) added to
form a slurry
Small particle, low mass transfer
resistance Cyclic batch system
Rapid rate of adsorption Adsorbent particle size 0.05 1.2 cm
Useful to remove small quantities of Trade off bed P (low P large particles) versus solute transport
pollutant or colour (large molecules) from
water
rate (high transport rate, small particles)
Removal of adsorbent by sedimentation or Often used in downflow mode
filtration (usually discarded) Removal of pollutants from water
Reactivation of adsorbent at high temperature
For gases, regeneration is usually performed in-situ

Temperature Swing Adsorption Temperature Swing Adsorption

Adsorbent is regenerated by a temperature
higher than that used during the adsorption
step
Heating coils used to heat bed
Vacuum or purge gas used to remove
adsorbate
Bed cooled prior to next adsorption step
Can take hours-days for each cycle

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Alternative Cyclic Regeneration

Pressure Swing Adsorption Flowsheet
Methods
Inert purge swing bed is regenerated at
same temperature by an inert gas. Weak
adsorption
Pressure swing adsorption at high pressure,
desorption in a low pressure cycle. Rapid
cycles
Vacuum swing adsorption adsorption occurs
near to atmospheric pressure and
regeneration is performed under vacuum

Pressure Swing Adsorption Cycles Continuous Countercurrent Operation

Operates at steady state, uses moving beds
Practical difficulties, such as attrition of adsorbent

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Fluidised bed adsorption system Analysis of Batch Adsorption

Adsorption Extract
Chamber Column The rate of adsorption of solute, as controlled by external
mass transfer is given by:
Mass External Concentration of
Concentration of transfer area of solute in equilibrium
solute in bulk coefft particles with loading on
adsorbent
dc

dt
(
= k L a c c* )
Rotary Raffinate
valve column
Starting from feed concentration, cF the instantantaneous bulk
concentration, c, at time t is related to instantaneous
Sorbex simulated moving bed process adsorbent loading, q, by material balance:
For bulk separation
Q = Liquid volume S = mass of adsorbent

cF Q = cQ + qS
q = Instantaneous adsorbent loading

If the equilibrium is represented by a linear isotherm

Equilibrium conc.
c* = q / k
Continuous Adsorption in a CSTR
Analytical integration gives
When both liquid and solids flow through a vessel, the
cF residence time is found from:
c= [exp( k L at ) + ] c + k L at res c*
cout = F

1 + k L at res
Where
Q Q Or rearranging
= = 1+ cF cout
(
= k L a cout c* )
Sk Sk t res

As the contact time approaches infinity, adsorption Material balance gives

equilibrium is approached and for the linear isotherm the cF Q = cout Q + qout S
above equation reduces to
An isotherm is needed to relate c* to qout
cF
c(t = ) =

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Fixed Bed Adsorption Ideal Fixed Bed Adsorption

Flow downwards through fixed bed of adsorbent
1) Low external mass transfer resistance gives plug flow
2) Axial dispersion negligible
3) Adsorbent is initially free of adsorbate
4) Adsorption equilibrium is achieved instantaneously
between fluid and solid
5) Adsorption begins at origin
This results in a shock like wave moving through the
bed called a stoichiometric front
This type of adsorption is ideal fixed bed adsorption

tideal, the time for an ideal front to reach Lideal. LES is Length of
equilibrium section Real Fixed Bed Breakthrough Curve
Q c t
QF cF tideal = qF SLideal / LB Lideal = LES = F F ideal LB
qF S In the real fixed bed the above assumptions
Length of unused bed
are not valid
LUB = LB LES Internal and external transport, and axial
Weight of equilibrium section dispersion influence the process
LES
WES = S These factors contribute to the development
LB of a broader concentration front moving
Weight of unused bed
QF = volumetric flowrate of feed
through the bed
WUB = S WES cF = conc. Solute in feed
qF = loading per unit mass of This is called a breakthrough curve
adsorbent in equilibrium with
feed concentration
S = total mass of adsorbent

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Breakthrough Breakthrough and Saturation Capacity

Curve in a Fixed Bed
Mass Transfer
Zone LES
(where adsorption Length of
Takes place) Equilibrium
Section

Breakthrough
point

Summary
In this lecture we have covered
Adsorption isotherms
External mass transfer
Transport in porous pellets
Liquid and gas phase adsorption
Batch adsorption
Fixed bed adsorption
Temperature and pressure swing processes

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