Water Supply Lesson 8 - Adsorption

Adsorption
Zhibin Zhang
Professor, Shandong Jianzhu University, Jinan
Lech Smoczynski
Professor, University of Warmia and Mazury, Olsztyn
Learning targets
 Knowledge about the theoretical background of the

adsorption process (interactions between adsorbent
and adsorbate, adsorption equilibrium and kinetics)
 Overview over different adsorbents and their
respective properties and applications
 Understanding of basic process configurations and the
development of mass transfer zones in fixed beds
Water Supply: Adsorption 2

Outline
− Theoretical introduction to adsorption

 Factors influencing adsorption
 Steps of the adsorption process (adsorption kinetics)
 Adsorption isotherms
− Adsorbents
 Activated carbon (PAC and GAC)
 Activated alumina
 Molecular sieves
− Applications
− Process configurations and carbon regeneration
Theoretical introduction to adsorption
Adsorption process
Dissolved substances (adsorbates) accumulate on the surface
of a solid material (adsorbent).
Example:
Color can be removed from water using activated carbon. Color is
the adsorbate, activated carbon is the adsorbent.

Types of Adsorption:
Properties Physisorption Chemisorption
Bonding Van der Waals Chemical bonding
interactions (e.g. involving orbital overlap
London dispersion, and charge transfer.
dipole-dipole).
Enthalpy 20-40 kJ mol-1 80-240 kJ mol-1
Saturation Multi-layer Mono-layer
Surface No Yes
Specificity
Nature Reversible Mostly Irreversible
Factors influencing adsorption:
 Surface area of adsorbent
The extent of adsorption is proportional to the specific surface
area of the adsorbent.
 Solubility of the adsorbate
The greater the solubility, and the stronger the solute-solvent
bond, the smaller is the extent of adsorption.
 Hydrogen ion concentration (pH) of the solution

Factors influencing adsorption:
 Temperature
Heavy metal removal is usually better at higher temperature.
 Nature of the adsorbate
The physiochemical nature (e.g. surface functional groups)
 Mixture of adsorbates
The compounds may mutually enhance adsorption, may act
relatively independently, or may interfere with each another.

Types of interactions between adsorbent and adsorbate
(adsorption forces):
 Coulomb-unlike charges
 Dipole-dipole interactions
 London or van der Waals forces
 Hydrogen bonding
 Point charge and a dipole
 Point charge neutral species
 Covalent bonding with reaction
London or van der Waals forces are often predominant.

Steps of the adsorption process (adsorption kinetics):
 Bulk solution transport
 Film diffusion transport
 Pore transport
 Adsorption

Adsorption equilibrium:
If the adsorbent and the adsorbate are in contact long enough, an
equilibrium will be established between the amount of adsorbate
adsorbed and the amount of adsorbate in solution.
This equilibrium relationship is described by an isotherm.
Adsorption isotherm:
The mass of adsorbate per unit mass of adsorbent at equilibrium
and at a given temperature

Determination of
isotherms:
Calculation of adsorbed
material from a mass
balance:
where
qe = mass of material adsorbed (at equilibrium) per mass of adsorbent, mg adsorbate/g adsorbent
C0 = initial concentration of adsorbate, mg/L
Ce = equilibrium concentration in solution when amount adsorbed equals qe, mg/L
V = volume of liquid in the reactor, L
m = mass of adsorbent, g

Adsorption isotherms (examples):
K ⋅ Q0a ⋅ Ce
qe =
1 + K ⋅ Ce
K B ⋅ C e ⋅ Q a0 1
qe = q e = K FCe n
(C S − C e ){1 + (K B − 1)(C e / C S )}

Adsorption isotherms: Langmuir model
This model assumes monolayer coverage and constant binding
energy between surface and adsorbate.
The model equation is:
K ⋅ Q0a ⋅ Ce Q0a represents the maximum adsorption capacity

qe = (monolayer coverage) (g solute/g adsorbent).
1 + K ⋅ Ce
Ce has units of mg/L
K has units of L/mg

Adsorption isotherms: Shape of the Langmuir isotherm
qe
K ⋅ Qa0 ⋅ Ce
qe =
qe 1 + K ⋅ Ce
Ce

Adsorption isotherms: BET isotherm*)
This is a more general, multi-layer model. It assumes that a
Langmuir isotherm applies to each layer and no transmigration
occurs between the layers. It also assumes that there is equal
energy of adsorption for each layer except for the first layer.
CS = saturation (solubility limit)
K B ⋅ C e ⋅ Q 0a concentration of the solute (mg/liter)
qe =
(C S − C e ){1 + (K B − 1)(C e / C S )} KB = a parameter related to the binding
intensity for all layers
Note: When Ce << CS , KB >> 1 and K = KB/CS then the BET isotherm approaches the Langmuir isotherm.
*) Brunauer, Emmett and Teller
Adsorption isotherms: Freundlich isotherm
For the special case that the surface energies are heterogeneous
(particularly good for mixed adsorbates) in which the energy term,
“KF”, varies as a function of surface coverage, the Freundlich
model is appropriate.
1
q e = K FCe n KF and n are system specific constants.

Adsorption isotherms: Shape of the Freundlich isotherm
1
q e = K FCe n
qe
Ce

Adsorption isotherms: Shape of the Freundlich isotherm
(log-scale)
log qe (qe in mg/g)
logCe (Ce in mg/L)

Example 1
Each jar receives activated carbon and 100 mL of a 600 mg/L
solution of xylene and is then shaken for 48 h.
The following equilibrium concentrations are found:
Jar 1 2 3 4 5
Carbon (mg) 60 40 30 20 5
Ce (mg/L) 25 99 212 310 510

Example 1
The solid phase concentrations are calculated from a mass
balance and plotted vs. the liquid concentrations. The Freundlich
equation is then fitted to the data:

Example 2
Adsorption of benzene onto activated carbon has been reported
to obey the following Freundlich isotherm equation, where c is in
mg/L and q is in mg/g:
0.533
qbenz = 50.1 cbenz
A solution at 25oC containing 0.50 mg/L benzene is to be treated

in a batch process to reduce the concentration to less than
0.01 mg/L. The adsorbent is activated carbon with a specific
surface area of 650 m2/g.
Compute the required activated carbon dose.

Example 2
Solution:
The solid-phase concentration of benzene in equilibrium with ceq
of 0.010 mg/L can be determined from the isotherm expression:
0.533
qbenz 50.1
= = cbenz 4.30 mg/g
A mass balance on the contaminant can then be rewritten and
solved for the activated carbon dose
ctot ,=
benz cbenz + qbenz c AC where cAC = m/V
0.50 0.010 + ( 4.30 mg/g ) c AC
=
=c AC 0.114
= g/L 114 mg/L

Example 3
If 114 mg/L adsorbent is used to treat a 0.500 mg/L solution of
toluene, what will the equilibrium concentration and solid-phase
concentration be? The isotherm equation for toluene is:
0.365
qtol = 76.6 ctol
Solution:
The mass balance on toluene is:
ctot ,=
tol ctol + qtol c AC = ctol + ( 76.6 ctol 0.365 ) ( 0.114 g/L )
0.50
ctol = 3.93x10−4 mg/L

Adsorbents: Basic types
 Activated Carbon (AC)
Removal of all of the adsorbates mentioned above (to varying
degrees) by the far most popular adsorbent
 Activated Alumina
 Molecular Sieves (zeolite)
Clays with adsorptive properties

Adsorbents: Properties
Properties of Activated Carbon

Bulk Density 22-34 lb/ft3
Heat Capacity 0.27-0.36
BTU/lboF
Pore Volume 0.56-1.20 cm3/g
Surface Area 600-1600 m2/g
Average Pore Diameter 15-25 Å
Regeneration Temperature 100-140 oC
(Steaming)
Maximum Allowable Temperature 150 oC

Properties of Activated Alumina

Bulk Density
Granules 38-42 lb/ft3
Pellets 54-58 lb/ft3
Specific Heat 0.21-0.25 BTU/lboF
Pore Volume 0.29-0.37 cm3/g
Surface Area 210-360 m2/g
Average Pore Diameter 18-48 Å
Regeneration Temperature (Steaming) 200-250 oC
Maximum Allowable Temperature 500 oC

Properties of Molecular Sieves

Anhydrous Anhydrous Anhydrous
Sodium Calcium Aluminosilic
Aluminosilicate Aluminosilicate ate
Type 4A 5A 13X
Density in bulk (lb/ft3) 44 44 38
Specific Heat (BTU/lboF) 0.19 0.19 -
Effective diameter of pores (Å) 4 5 13
Regeneration Temperature (oC) 200-300 200-300 200-300
Maximum Allowable 600 600 600
Temperature (oC)

Adsorbents: Preparation of activated carbon
AC can be prepared from any carbonaceous material
e.g.
• Wood
• Lignite
• Coal
• Nutshells
• Bones
[Kan-Carbon, 2018]

Adsorbents: Preparation of activated carbon
Production process: Two steps
 Pyrolysis:
The carboneous material has to be pyrolyzed (heated in a
low oxygen environment). This forms a “char”.
 Activation:
The char is then activated by heating to 800-1000 oC in the
presence of steam, oxygen or C02 to form gaseous
products.

Adsorbents: Properties of activated carbon
AC has oxygen-containing groups on its surface:
[Mattson and Mark, 1971]

AC has a heterogeneous pore structure:
Increasing magnification
Photos of Activated Carbon [Zhang, 2015]

Definition of AC pore sizes:
 Micropores: d < 2 nm
 Mesopores: d = 2-20 nm
 Macropores: d > 20 nm
Distribution:
Pore size % pore volume % surface area
Micro 30 - 60 > 95
Meso < 10 <5
Macro 25 - 30 negligible
Adsorbents: Types of activated carbon
PAC: Powdered activated carbon
 Fine powder, d < 0.05 mm
 Surface area as much as 100 acres/lb (≈ 1000 m2/g)
 Pore sizes (radii) down to 10-9 m
GAC: Granular activated carbon

 Diameter: 0.5 - 4 mm
 Surface area equal or a bit less than PAC

Comparison of GAC and PAC [Zhang, 2015]:

How to use PAC (typically for taste and odor removal):
Mixing with raw water + removal by sedimentation or filtration
Flocculated water Settled

PAC +
coagulants water
Characteristics:
Sludge + PAC
one time use, i.e. no regeneration
particles
How to use GAC (typically for treatment of groundwater
and riverbank filtrate in order to remove taste, odor, and
micropollutants):
 Use of a fixed-bed column
 Downward flow through the column
Carbon Bed
 After exhaustion of the carbon capacity
regeneration in a furnace by oxidizing
the adsorbed organic matter

Applications
 Removal of refractory organic compounds

 Removal of inorganic compounds such as nitrogen,
sulfides, and heavy metals
 Chemical reduction of oxidants
 Removal of taste and odor compounds

Process configurations
Column flow system: Fixed-bed
 Provides filtration as well as adsorption
 Has to be periodically backwashed or cleaned
Principle: Practical design:
[Gao, 2016]

Column flow system: Fluidized-bed
 Continuous supply of fresh + removal of spent carbon
 Not effective as a filter
Solids
Principle: in Practical design:
Solids
[Gao, 2016]
out
Fixed-bed system: Breakthrough development
C0 C0 C0 C0 C0
Saturated zone The time to breakthrough

Adsorption zone is decreased by:
 Increased particle
Clean zone size of carbon
 Higher concentration
C C Cb Ce C0 in the influent
C0  Increased pH of the
Exhaustion
water
Cout
Breakthrough curve  Increased flow rate

Breakthrough point (switch  Lower bed depth
Ce to clean bed occurs before)
Amount of water treated
Fluidized-bed system: Mass transfer zone
Fresh Carbon Treated Effluent
Effluent zone C approx. 0
“S” zone: C goes from C0

to approx. 0
0 1 Saturated zone: C = C0
C/C0
Exhausted Carbon Influent

Carbon Regeneration
• Spent carbon is usually
regenerated at 500 oC
under low oxygen
conditions in the presence
of steam.
• Activated carbon loss is
about 5-15% for each
regeneration.
• Adsorbed organics are
volatilized and oxidized
during the regeneration
process.
[ Zhang, 2015]

Questions
 Which raw materials are used for activated carbon production,
and what are the main production steps?
 Describe briefly how an adsorption isotherm is determined
experimentally. Which models are available for the description
of isotherm data?
 Which steps are distinguished when describing adsorption
kinetics?
 Explain the development of a breakthrough curve in a fixed-bed
column and some factors that have an effect on it.
 What are important aspects when applying GAC and PAC,
respectively?
References
Gao, T.Y.: Water and Wastewater Treatment, 4th ed., Higher Education Press, Beijing, 2016 (in
Chinese)
Kan Carbon 2018

http://www.activatedcarbonindia.com/activated_carbon.htm, accessed April 2018
Mattson, J.S. and Mark, H.B.: Activated Carbon. Surface Chemistry and Adsorption from Solution.
Dekker, New York 1971
Zhang, Z.J.: Water and Wastewater Treatment, 4th ed., China Construction Industry Press, Beijing,
2015 (in Chinese)

Water Supply Lesson 8 - Adsorption

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Adsorption

 Knowledge about the theoretical background of the

Water Supply: Adsorption 2

− Theoretical introduction to adsorption

Water Supply: Adsorption 4

Water Supply: Adsorption 6

Water Supply: Adsorption 7

London or van der Waals forces are often predominant.

Water Supply: Adsorption 9

Water Supply: Adsorption 10

Water Supply: Adsorption 11

Water Supply: Adsorption 12

K ⋅ Q0a ⋅ Ce Q0a represents the maximum adsorption capacity

Water Supply: Adsorption 13

Water Supply: Adsorption 14

Water Supply: Adsorption 16

Water Supply: Adsorption 17

logCe (Ce in mg/L)

Water Supply: Adsorption 19

Water Supply: Adsorption 20

A solution at 25oC containing 0.50 mg/L benzene is to be treated

Water Supply: Adsorption 21

Water Supply: Adsorption 22

ctol = 3.93x10−4 mg/L

Water Supply: Adsorption 23

Water Supply: Adsorption 24

Properties of Activated Carbon

Water Supply: Adsorption 25

Properties of Activated Alumina

Water Supply: Adsorption 26

Properties of Molecular Sieves

Water Supply: Adsorption 27

Water Supply: Adsorption 28

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[Mattson and Mark, 1971]

Water Supply: Adsorption 30

Photos of Activated Carbon [Zhang, 2015]

Water Supply: Adsorption 31

GAC: Granular activated carbon

Water Supply: Adsorption 33

Water Supply: Adsorption 34

Flocculated water Settled

Water Supply: Adsorption 36

 Removal of refractory organic compounds

Water Supply: Adsorption 37

Principle: Practical design:

Water Supply: Adsorption 38

Saturated zone The time to breakthrough

Breakthrough curve  Increased flow rate

Effluent zone C approx. 0

“S” zone: C goes from C0

Exhausted Carbon Influent

Water Supply: Adsorption 41

Water Supply: Adsorption 42

Kan Carbon 2018

Water Supply: Adsorption 44

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