Technical Lecture

Adsorption
Environmental Engineering Principles and Practice

August 22, 2022

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Adsorption and Filtration
• Adsorption : a mass transfer • Filtration: a physical or
process that is a chemical separation process
phenomenon of sorption of that separates solid matter
gases or solutes by solids or and fluid from a mixture using
liquid surface a filter medium

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Overview
• Adsorption : a mass
transfer process that
is a phenomenon of
sorption of gases or
solutes by solids or
liquid surface

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 4

Adsorption
Adsorption
• A process by which a material is concentrated on a solid surface from its liquid or gaseous
surroundings.
• It involves trapping atoms and molecules that incident on the surface

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Why Adsorption
happens?
• These surface molecules (in
blue) are experiencing a
bonding deficiency
• It is energetically favorable for
them to adsorb molecules (in
yellow)
• Adhesion of atoms, ions,
boimolecules or molecules
of gas, liquid or dissolved
solids to a surface is
called adsorption.

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Type of adsorption
• Physical adsorption • Chemical adsorption
• van Der Walls forces • Chemical bond forces
• Reversible • Irreversible
• Not specific • Highly specific
• Multi-molecular layers • Monolayers
• Does not require any activation • Requires activation energy
energy

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Adsorption process and mechanism

Wang et al., 2020 Nanoscale

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Fundamentals of adsorption
onto Activated carbon

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1. Activated
Carbon
• Porous carbonaceous
adsorbents
• A high adsorptive surface
area: 500 – 1500 m2 / gram
• Pore volume ranges between
0.7 and 1.8 cm3 / gram
• PAC (powdered activated
carbon) and granular activated
carbon

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Classes organic compounds adsorbed
on AC
Organic chemical class Examples
Aromatics Benzene, Toluene, Ethylbenzene, Xylene
Polynuclear Aromatics Naphthalene, Anthracenes, Biphenyls
Chlorinated Aromatics Chlorobenzene, Polychlorinated biphenyls
Phenolics Phenol, Cresol, Chlorophenols, Nitrophenols
High-molecular-weight hydrocarbons Gasoline, Kerosene
Chlorinated aliphatics Trichloroethylene, Carbon tetrachloride
Aliphatic and aromatic acids Tar acids, Benzoic acids
Ketones, esters, ethers, and alcohols Hydroquinone, Polyethylene glycol
Surfactants Alkyl benzene sulfonates
Soluble organic dyes Methylene blue, Indigo carmine

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2. Activated carbon types

• Granular activated • Powdered activated carbon

carbon(GAC) (PAC)
• GAC particles have sizes • crushed or ground carbon
ranging from 0.2 to 5 mm particles such that 95–100% of
• Widely used in purification it will pass through a
processes for drinking water, designated sieve of 0.297 mm
groundwater and wastewater • PAC may also act as a
as an advanced treatment step, coagulant for colloidal fractions
particularly for the removal of in the liquid phase.
toxic organic compounds

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3.1 Adsorption of activated carbon

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3.2 Factor influencing adsorption
• Surface area of adsorbent
• Physical and chemical characteristics of the adsorbate
• pH
• Temperature
• Porosity of the adsorbent
• Chemical surface characteristics

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3.1.1 Surface area of adsorbent
• The extent of adsorption is generally considered to be
proportional to the specific surface area
• The more finely divided and more porous adsorbents would be
expected to yield more adsorption per unit weight of adsorbent

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3.2.2 Physical and chemical
characteristics of the absorbate
• The adsorbability of a compound increases with
increasing molecular weight and increasing number of
functional groups
• Large molecule > smaller molecule
• Activated carbon adsorbs nonpolar molecules better
than polar molecules
• The presence of substituent groups also affects the
adsorbability of organic chemicals
• Example: Hydroxyl group reduce adsorbability

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3.2.3 pH
• Organic molecules form negative ions at high pH values,
positive ions at low pH values, and neutral molecules at
intermediate pH values.
• Adsorption of most organic materials is higher at neutral
conditions.

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3.2.4 Temperature
• The extent of adsorption should increase with decreasing
temperature because the adsorption reactions are exothermic.
• However, increased temperature also increases the rate of
diffusion of the solute through the liquid to the adsorption sites,
which eventually leads to an increased adsorption

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3.2.5 Porosity of the absorbent
• The total number of pores and their shape and size determine the
adsorption capacity and even the rate of adsorption.

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3.2.6 Chemical surface characteristics
• The adsorption performance is dependent on chemical surface
characteristics of the adsorbent.
• Heterogeneity of the activated carbon surface significantly
contributes to adsorption capacity.
• Example: surface acidity, polarity or hydrophobicity, and surface
charge.

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4. Kinetics of Adsorption
• Transport mechanism: bulk
solution transport
(advection)
• External diffusion
• Intraparticle (internal
diffusion)
• Adsorption

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5. Adsorption Equilibrium and Isotherms

The partition ration (wp) indicates the amount

of adsorbate mass adsorbed per amount of
initial total mass

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5.1 Freundlich isotherm
• to determine the adsorption capacity of activated carbon over
a wide range of concentrations.

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5.2 theoretical Langmuir equation,
• very widely used for the adsorption isotherms
• a clear concept of the monomolecular adsorption on
energetically homogeneous surfaces

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6. Activated carbon reactors in water and
wastewater
• PAC adsorbers
• continuous-flow drinking water systems
• Mainly for the removal of nonbiodegradable substances after
biological wastewater treatment
• proves to be mostly impractical compared to GAC adsorbers
• GAC adsorbers
• Surface and groundwater treatment, mainly for the removal of Natural
Organic Matter (NOM) and Synthetic Organic Compounds (SOCs)
• tertiary treatment of municipal and industrial wastewaters

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7. Operation of GAC adsorbers
Empty-Bed Contact Time (EBCT): The theoretical
residence time in the filter in the absence of packing
media

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7. Operation of GAC adsorbers (Cont)
Independent process variables
Adsorbent variables Adsorbent Type, Shape, Size, Porosity, Particle
Density, Apparent Density, Surface area, Molasses
number, Iodine number, Abrasion number, Dispersion
coefficient, Intrinsic permeability
Design Variables Hydraulic Loading Rate (HLR), Bed Area, Length of
Reactor Bed, Contact Time
Operating Variables Influent concentration of adsorbate, S0
Flow Adsorbent capacity as a function of S0 (in terms
of isotherm coefficients)
Hydraulic gradient (head loss per unit length)
Backwash rate
Mode of operation (upflow or downflow)
Carbon Usage Rate (CUR)

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7. Operation of GAC adsorbers (Cont)
• Breakthrough characteristics in a fixed-bed GAC adsorber
• Adsorption of contaminants takes
place in Zone A, called the mass
transfer zone (MTZ)
• Another zone (Zone-Sat) is saturated
with contaminants and is in
equilibrium with the influent
concentration S0 .
• a predetermined concentration (SB)
appears is defined as the
‘breakthrough point.’

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8. Regeneration and Reactivation
• The regeneration of spent adsorbents is the most difficult and
expensive part of adsorption technology.
• It accounts for about 75% of total operating and maintenance
cost for a fixed-bed GAC operations.
• Regeneration involves removal of the contaminants from the
carbon without destroying the contaminants
• Reactivation means destroying the contaminants and
reactivating the carbon, which usually occurs at very high
temperatures.
• GAC regeneration is accomplished primarily by thermal means
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9. Applications of Activated Carbon
• Agricultural application
• Environmental application:
groundwater, spill
• Cosmetic application: shampoos,
face masks
• Water purification
• Air and gas purification
• Mercury removal
• others
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