SMJC 4533

INDUSTRIAL AND HAZARDOUS WASTE

TREATMENT
CARBON ADSORPTION

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 Introduction
• Definition
Adhesion of atoms, ions, bimolecules or
molecules of gas, liquid or dissolved solids
to a surface. This process creates a film of
the adsorbate, in which, the molecules or
atoms being accumulated, on the surface of
the adsorbent.

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 Introduction

• Adsorbent:
– The substance on whose surface the
adsorption occurs is known as adsorbent.
• Adsorbate:
– The substance whose molecules get
adsorbed on the surface of the adsorbent (
i.e. solid or liquid ) is known as adsorbate.

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 Introduction
Organic Compounds
High/Good Adsorption Potential Low Adsorption Potential
• Aromatic Solvents - benzene, toluene, • Alcohols
• nitrobenzenes • Low molecular weight ketones
• Chlorinated Aromatics - PCBs, • Acids and aldehydes
chlorobenzenes, chloronaphthalene • Sugars and starches
• Phenol and Chlorophenols • Very high molecular weight or colloidal
• Polynuclear Aromatics - acenaphthene, organics
benzopyrenes • Low molecular weight aliphatics
• Pesticides and Herbicides - DDT, aldrin,
chlordane, BHCs, heptachlor
• Chlorinated Nonaromatics – carbon
tetrachloride, chloroalkyl ethers,
hexachlorobutadiene
• High-molecular weight Hydrocarbons -
dyes, gasoline, amines, humics
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 Introduction
Inorganic Compounds
High/Good Adsorption Potential Low Adsorption Potential
Chlorine Nitrate
Bromine Phosphate
Iodine Chloride
Fluoride Bromide
Iodide

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 Introduction
Metals
High/Good Adsorption Potential Low Adsorption Potential
Antimony Lead
Arsenic Nickel
Bismuth Titanium
Chromium Vanadium
Tin Iron
Silver Copper
Mercury Cadmium
Cobalt Zinc
Zirconium Barium
Selenium
Molybdenum
Manganese
Tungsten
Radium
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 Types of Adsorption
• Physical adsorption (physisorption):
– Force of attraction between adsorbate and adsorbent are
Van der Waal’s forces → WEAK.
– Also known as Van der Waal’s adsorption.
– Can be easily reversed by heating or by decreasing the
pressure.

• Chemical adsorption (chemisorption):

– Force of attraction existing between adsorbate and
adsorbent are almost same strength as chemical bonds →
STRONG
– Also known as Langmuir adsorption.
– Cannot be easily reversed.

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Types of Adsorption

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Types of Adsorption

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 Factors affecting adsorption

• Nature of adsorbate and adsorbent

• The surface area of adsorbent
• Activation energy of adsorbent
• Experimental conditions e.g. temperature,
pressure
• Molecular structure of adsorbate
• Polarity of adsorbate
• Solubility of adsorbate
• Hydrocarbon saturation of adsorbate
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 Adsorption Isotherm

• Used to study adsorption process

Quantity of
pollutant adsorb
vs weight of
adsorbent

(C0 − Ce )V
qe =
m
Can also be represented
by concentration of
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adsorbent
 Freundlich Adsorption Isotherm
• Adsorption of a quantity of gas adsorbed by unit mass
of solid adsorbent with pressure.
– At low pressure, extent of adsorption is directly
proportional to pressure
X
α P1
m
– At high pressure, extent of adsorption is independent of
pressure
X
α P0
m
Where X = mass of the adsorbate, m = mass of adsorbent; P
= Pressure

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 Freundlich Adsorption Isotherm

– At intermediate pressure,
1
X
α Pn
m
Where 1/n = strength of adsorption
– Therefore, Freundlich Isotherm becomes
1
X X 1
= kP n = q e = kCe n
m m
Where k = adsorption capacity; Ce = equilibrium
concentration of pollutant in water

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 Freundlich Adsorption Isotherm

• Taking log both sides of equation,

X 1
log  = log k + logCe
m n

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Log Ce
 Freundlich Adsorption Isotherm

• Limitation
– Freundlich Adsorption Isotherm failed at
higher pressure as adsorption capacity is
saturated

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 Langmuir Adsorption Isotherm
• Measures the relationship between the number of active sites of
the surface undergoing adsorption and pressure.
• Assumptions:-
– Adsorption is monolayer.
– Fixed number of vacant or adsorption sites are available on the surface
of solid.
– All the vacant sites are of equal size and shape on the surface of
adsorbent.
– Each site can hold maximum of one gaseous molecule and a constant
amount of heat energy is released during this process.
– Dynamic equilibrium exists between adsorbed gaseous molecules and
the free gaseous molecules which depends on:-
• The relative stabilities of the adsorbed and gas phase species involved
• The temperature of the system (both the gas and surface, although these
are normally the same)
• The pressure of the gas above the surface

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 Langmuir Adsorption Isotherm
• Langmuir equation is developed based on
the dynamic equilibrium assumption

Where A (g) is unadsorbed gaseous molecule, B(s) is unoccupied

metal surface and AB is Adsorbed gaseous molecule.
At equilibrium,
Rate of forward reaction = rate of reverse reaction

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 Langmuir Adsorption Isotherm

• Number of sites of the surface covered with

gaseous molecules = θ. Thus, surface
unoccupied by gaseous molecules = (1 – θ).

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 Langmuir Adsorption Isotherm
At equilibrium,
Rate of adsorption = rate of desorption
Ka P (1 – θ) = Kd θ

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 Langmuir Adsorption Isotherm

• Limitations
– Adsorbed gas has to behave ideally in the vapor
phase (low pressure conditions only)
– Assumption of adsorption only occur in monolayer
which is only possible under low pressure condition.
– Assumption of homogeneous solid surface is not
realistic (Heterogeneous in reality)
– Interaction between gas molecules cannot be avoided

Langmuir Equation only valid under low pressure

condition. Same goes to Freundlich Equation

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 Example 1
Para-xylene concentration of 500 mg/L is injected into each of six 200 mL
beakers containing activated carbon. The beakers are shaken for 24 hours
followed by filtering through a 0.45 µm membrane filter. The concentration of
para-xylene in the filtrate is measured yielding the following results:-
Beaker Activated Para-Xylene in Filtrate
carbon Samples
(grams) (mg/L)
1 24 10.
2 20 14.6
3 16 23
4 12 29
5 8 48
6 4 107

First, plot the Freundlich isotherm. Then, determine its constants, K and 1/n,
based on the graph plotted.

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 Example 2
A groundwater located in Kelantan is contaminated with chlorobenzene
(C6H5Cl) of 100 mg/L. Daily, 1.0 MGD of groundwater will be withdrawn to meet
the consumption of the residents around the area. Assuming that the
concentration of 0.1 mg/L is acceptable for consumption, estimated the daily
carbon utilization to remove chlorobenzene from the groundwater. Employ
Freundlich isotherm in your calculation

Additonal information:
Density of C6H5Cl: 1.107 at 20°C
K = 91
1/n = 0.99

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 Commonly used Adsorbents – Activated
Carbon
• For adsorption of organic substances and
non-polar adsorbates in soluble or gas form.
• Most widely used adsorbent because most of
its chemical (eg. surface groups) and
physical properties (eg. pore size distribution
and surface area) can be tuned
• High surface area owing to its large
micropore volume

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 Commonly used Adsorbents – Activated
Carbon
• In the form of spherical pellets, rods, moldings, or
monoliths with hydrodynamic diameters between 0.5
and 10 mm.

• Possess high abrasion resistance, high thermal

stability and small pore diameters
• Contain distinct pore structure which enables fast
transport of the gaseous vapors.

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 Commonly used Adsorbents – Activated
Carbon
• Most industrial adsorbents fall into one of
three classes:
– Oxygen-containing compounds - Are typically
hydrophilic and polar, including materials such as
silica gel and zeolites.
– Carbon-based compounds - Are typically
hydrophobic and non-polar, including materials
such as activated carbon and graphite.
– Polymer-based compounds - Are polar or non-
polar functional groups in a porous polymer
matrix.

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 APPLICATION

• Two commonly used activated carbon

include:
– Granular activated carbon (GAC)

– Powdered activated carbon (PAC)

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 APPLICATION
(Granular Activated Carbon)

Fixed Bed

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APPLICATION

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APPLICATION

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 Design of Granular Activated Carbon
Contactor
1. Mass Balance
Accumulation = Inflow - Outflow - Amount Absorbed
0 = QC0 t - QCe t - m GACqe

– Q = flowrate, L/h
– C0 = Initial concentration of adsorbate, mg/L
– t = time, h
– Ce = final equilibrium concentration of adsorbate, mg/L
– mGAC = mass of adsorbent, g
– qe = adsorbent phase concentration after equilibrium, mg
adsorbate/g adsorbent

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 Design of Granular Activated Carbon
Contactor
2. Adsorbent usage rate
m GAC (C0 − Ce )
=
Qt qe

3. Empty bed contact time (EBCT)

The time where water passes through the carbon bed
by assuming the velocity is the same throughout the
bed Volume of the Length of the
carbon bed carbon bed

Vb Ab D D
EBCT = = =
Q v f Ab v f
Cross section of
Flowrate velocity 31
the carbon bed
 Design of Granular Activated Carbon
Contactor
4. Density of GAC
m GAC
 GAC =
Vb

5. Specific throughput (each m3 of water

treated per gram of GAC)
Qt Vbt t
Specific throughput = = =
mGAC EBCT  mGAC EBCT  GAC

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 Design of Granular Activated Carbon
Contactor
6. Carbon usage rate (CUR) = gram per carbon per each
m3 water treated
mGAC 1
CUR = =
Qt Specific throughput
7. Volume of water treated for a given EBCT
mGAC for a given EBCT
Volume of water treated, L =
GAC usage rate
8. Bed life
Volume of water treated for a given EBCT
Bed life, Q =
Q

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 Design of Granular Activated Carbon
Contactor
A fixed bed carbon adsober has a fast mass transfer rate. Based on the
following data, determine the carbon requirement to treat a flow
containing trichloroethylene of 1000 L/min and the bed life

• C0 = 1.0 mg/L
• Ce = 0.005 mg/L
• GAC density = 450 g/L
• Kf = 28 mg/g (l/mg)1/n
• 1/n = 0.62
• EBCT = 10 minutes

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