VSRD International Journal of Technical & Non-Technical Research, Vol. 4 No.

3 March 2013 / 33
e-ISSN : 0976-7967, p-ISSN : 2319-2216 VSRD International Journals : www.vsrdjournals.com
REVIEW ARTICLE
TREATMENT OF WASTE WATER
WITH LOW COST ADSORBENT A REVIEW
1
Uttam Singh* and
2
Rajesh Kumar Kaushal
1
Research Scholar,
2
Head of Department,
1,2
Department of Chemical Engineering,
Institute of Engineering Science IPS Academy, Indore, Madhya Pradesh, INDI A.
*Corresponding Author : uttam.singh444@gmail.com
ABSTRACT
Electroplating Industry Wastewater containing heavy metal causes serious environmental problem. For the removal of heavy metals from
effluent waste streams the adsorption process with various commercial adsorbent is being widely used. Such adsorbent remains an
expensive material; the use of alternative and perhaps cheaper adsorbents is attractive. This review describes a brief description of
adsorption process and then the comparative analysis of conventional and non-conventional adsorbents for the removal of emerging
compounds.
Keywords : Adsorption, Heavy Metals, Electroplating Waste Water, Low Cost Adsorbent.

1. INTRODUCTION
Industrial waste constitutes the major source of various
kinds of metal pollution in natural water. Wastewaters
generated from industrial treatment plant contain
considerable metal contaminants. Their concentrations must
be reduced to safe levels before being released into the
environment. Rapid industrialization has led to increase
disposal of heavy metal into the environment. The metals
are of special concern because of their persistency.
Removal of heavy metals from wastewater has become a
major concern nowadays because of its ability to
contaminate water bodies. There are at least twenty metals
which cannot be degraded or destroyed. These heavy toxic
metals entered into the water bodies through waste water
from metal plating industries and industries of Cd- Ni
batteries, mining, pigments, and stabilizers alloys etc. The
important toxic metals are Cd, Zn, Pb Ni, Cr, Cu and Hg.
Disposal of industrial wastewater has always been a major
environmental issue. Heavy metals are present in low
concentration in wastewater and are difficult to remove
from water. Pollutants in industrial wastewater are almost
invariably so toxic that wastewater has to be treated before
its reuse or disposal in water bodies.
Therefore, effective recovery of heavy metals is as
important as their removal from waste streams. Major
importance has been attached to the treatment of industrial
wastewater effluent since local and international authorities
require that wastewaters from industries be treated and
made to meet a set standard before it is discharged into the
water bodies. The need of safe and economical methods for
the elimination of heavy metals from contaminated waters
has developed interest towards the production of low cost
alternatives to commercially available adsorbent. So there is
an urgent need that all possible sources of agro-based
inexpensive adsorbents should be explored and their
feasibility for the removal of heavy metals should be
studied in detail. For the treatment of industrial waste water
consisting heavy metals; there are several advanced
techniques to decrease their impact on the environment
such as physicochemical, biological and thermal processes.
A physicochemical technique includes adsorption,
coagulation, chemical precipitation, ultra filtration, etc.
Among of these methods, adsorption is the most effective
and economical because of their relative low cost. The
adsorption process is being widely used by various
researchers for the removal of heavy metals from waste
streams. Adsorption is one of the easiest, safest and most
cost-effective methods for the removal of these metals from
industrial effluent (Balkose and Baltacioglu, 1992; Shah et
al., 2009; Rahmani et al., 2009).Adsorption is suitable even
when the metal ions are present in concentration as low as
1mg/l. The adsorbents may be of minerals, organics, or
biological origin, zeolites, industrial bi products, agriculture
wastes, biomass and polymeric materials (Kurniawan et al.,
2005).The major advantage of an adsorption system for
water pollution control are less investment in terms of both
initial cost and operational cost, simple design, easy
operation and no effect of toxic substances compared to
conventional biological treatment processes.
The objective of this review is to contribute in the search
for less expensive adsorbents and their utilization
possibilities in adsorption process for the elimination of
heavy metals from wastewater.
Electroplating Industries Waste And Heavy Metal
Pollution : Electroplating industry has been generating a
huge amount of waste in the forms of wastewater, spent
solvent, spent process solutions and sludge (Freeman,
1988). The industry of Electroplating generates wastes in
Uttam Singh and Rajesh K. Kaushal VSRDIJEECE, Vol. IV (III), March 2013 / 34


different forms which are solid, liquid and gaseous and has
been declared under 17 major polluting industries in India
by central pollution control board. Hazardous waste is
generated during different steps of the process.
Electroplating wastewater may contain several types of
organic and inorganic matter in dissolved suspended and
colloidal states; may contain hazardous material and toxic
compound like phenols, cyanides and compound that are
potentially 'carcinogenic'. It may contain acids and alkalis,
heavy metals, flammable and even radioactive materials.
The industry of metal finishing and electroplating units are
one of the major sources of pollutants which contribute
greatly to the pollution load of the receiving water bodies
and therefore increase the environmental risks. The industry
of metal finishing and electroplating are one of the major
source of heavy metals (Zn, Cu, Cr,) and cyanide (Monser
& Adnoun, 2002, Low & Lee, 1991.).Heavy metal
pollution around plating factories has been associated with
the expansion of the plating industry in developing
countries (Morgan & Lee, 1997 and Brower et al., 1997).
Wastewater from the plating factories is divided into two
types, one from plating manufacturing process and from
rinsing process.
Table 1.1 : Effluents from the Electroplating Industry
(milligrams per liter, except for pH)
[39]
Parameter Maximum Value
PH 710
TSS 25
Oil and grease 10
Arsenic 0.1
Cadmium 0.1
Chromium (hexavalent) 0.1
Chromium (total) 0.5
Copper 0.5
Lead 0.2
Mercury 0.01
Nickel 0.5
Silver 0.5
Zinc 2
Total metals 10
Cyanides (free) 0.2
Fluorides 20
Trichloroethane 0.05
Trichloroethylene 0.05
Phosphorus 5
The overall wastewater stream is typically extremely
variable usually high in heavy metals, including Cadmium,
Chrome, Lead, Copper, Zinc, and Nickel, and in Cyanides,
Fluorides, and oil and grease, all of which are process
dependent. The metals are of special concern because of
their persistency. Industrial waste constitutes the major
source of various kinds of metal pollution in natural water.
There are at least 20 metals which cannot be degraded or
destroyed. The important toxic metals are Cd, Zn, Pb and
Ni. DebabrataMazumder et al (2011).
Table 1.2 : Tolerance limit of heavy metals in Effluent
waste water
[16]
S.
No
Heavy
Metal
Maximum Tolerance Limit in
(Mgpl)
1. Chromium 0.05 mg/l
2. Mercury 0.1 mg/l
3. Copper .25 mg/l
4. Iron 0.1 mg/l
5. Cadmium 0.01 mg/l
6. Zinc 0.8 mg/l
7. cobalt 0.5 mg/l
8. Arsenic .05 mg/l
2. ADSORPTION
Adsorption is a fundamental process in the physiochemical
treatment of wastewaters, a treatment which can
economically meet today's higher effluent standards and
water reuse requirements. Adsorption is a mass transfer
process which involves the accumulation of substances at
the interface of two phases, such as, liquidliquid, gas
liquid, gassolid, or liquid solid interface. The substance
being adsorbed is the adsorbate and the adsorbing material
is termed the adsorbent. The driving force for adsorption
process is Surface affinity. Chemical reactivity, pH, surface
area for adsorption per unit volume and reduction in surface
tension is key parameter for adsorption.
Adsorption is a sorption operations, in which certain
components of a fluid phase, called solutes, are selectively
transferred to insoluble, rigid particles suspended in a
vessel or packed in a column. Adsorption is a separation
process in which certain components of the fluid phase are
transferred to the surface of the solid adsorbents.
The phenomenon of the enrichment of chemical substances
at the surface of a solid is called adsorption. All adsorption
performance processes are depends on solid-liquid
equilibria and on mass transfer rates. The adsorption
operation can be batch, semi-batch and continuous.
Types of Adsorption : At molecular level, adsorption is
due to attractive interactions between a surface and the
species being adsorbed.
Physical adsorption: It is a result of intermolecular
forces of attraction between molecules of the adsorbent
and adsorbate. Physical adsorption occurs when the
intermolecular attractive forces between molecules of a
solid and the gas are greater than those between
molecules of the gas itself. Furthermore, it occurs
lower or close to the critical temperature of the
adsorbed substance.
Chemisorptions: it is a result of chemical interaction
between the solid and the adsorbed substance. It is also
called activated adsorption. Commercial adsorbents
rely on physical adsorption; catalysis relies on
chemisorptions.
Chemisorptions occur only as a monolayer and
Uttam Singh and Rajesh K. Kaushal VSRDIJEECE, Vol. IV (III), March 2013 / 35


substances chemisorbed on solid surface are hardly
removed because of stronger forces. Yadla et al.
(2012)
Adsorption Dynamics : It is generally accepted that
adsorption dynamics consists of the following consecutive
steps:
Transportation of adsorbate from the bulk solution to
external surface of the adsorbent by diffusion through
the liquid boundary layer.
Internal (interphase) mass transfer the by pore diffusion
from the outer surface of the adsorbent to the inner
surface the porous structure
Surface diffusion along the porous surface.
Adsorption of the adsorbate on the active sites on the
internal surface of the pores.
The last step, adsorption, is usually very rapid in
comparison to the remaining steps. Therefore, the overall
rate of adsorption is controlled by either film or intra
particle diffusion, or a combination of both. Adsorbent
Properties: To be suitable for commercial applications, a
sorbent should have high selectivity to enable sharp
separations, high capacity to minimize the amount of
sorbent needed, favorable kinetic and transport properties
for rapid sorption, chemical and thermal stability, including
extremely low solubility in the contacting fluid, to preserve
the amount of sorbent and its properties, hardness and
mechanical strength to prevent crushing and erosion, high
resistance to fouling for long life, no tendency to promote
undesirable chemical reactions, the capability of being
regenerated when used with commercial feed stocks.
Equilibrium consideration: Adsorption Isotherm : To be
suitable for commercial applications, a sorbent should have
a high selectivity to enable sharp separations, high capacity
to minimize the amount of sorbent needed, and the
capability of being regenerated for reuse. These properties
depend upon the dynamic equilibrium distribution of the
solute between the fluid and the solid surface; since no
acceptable theory has been developed to predict solid-
sorbent equilibria. Thus, it is required to evaluate the
Equilibrium consideration for a particular solute-sorbent
combination.
In adsorption, dynamic phase equilibrium has established
for the distribution of the solute between the fluid and the
solid surface. This equilibrium is usually expressed in terms
of:
Concentration if the fluid is a liquid or partial pressure
if the fluid is a gas of the adsorbate in the fluid.
(2)Solute loading on the adsorbent, expressed as mass,
moles, or volume of adsorbate per unit mass or per unit
BET surface area of the adsorbent.
Adsorption Isotherm : A systematic approach whereby the
data are taken over a range of fluid concentrations at a
constant temperature, a plot of solute loading on the
adsorbent versus concentration or partial pressure in the
fluid, called an adsorption isotherm.
This equilibrium isotherm places a limit on the extent to
which a solute is adsorbed from a given fluid mixture on an
adsorbent of given chemical composition and geometry for
a given set of conditions. The rate at which the solute is
adsorbed is also an important consideration.
Adsorption isotherms are important for the description of
how adsorbate will interact with adsorbent and are critical
in optimizing the use of adsorbent. Thus, the correlation of
experimental equilibrium data using either a theoretical or
empirical equation is essential for adsorption data
prediction.
Langmuir Model : Frequently used model for
monomolecular layer adsorption. Such model is derived
from simple mass-action kinetics. Such model is based on
assumption that the surface of the pores of the adsorbent is
homogeneous and that the forces of interaction between the
adsorbed molecules are negligible. It is a semi-empirical
isotherm derived from a proposed kinetic mechanism.
Let f be the fraction of the surface covered by adsorbed
molecules. Therefore 1- f is the fraction of the bare surface.
Then, the net rate of adsorption is the difference between
the rates of adsorption on the bare surface and desorption
from the covered surface:
dq /dt=k
a
p (l- f ) k
d
d f
At equilibrium, dq/dt = 0 and equation reduces to
f = K p/1+ K p.
Where K is the adsorption-equilibrium constant, K =k
a
/k
d

Also, f = qlq
m
; and q
m
is the maximum loading
corresponding to complete coverage of the adsorbent
surface by the solute.
Freundlich Empirical Model: The model attributed to
Freundlich, but which was actually devised earlier by
Boedecker and van Bemmelen, is empirical and nonlinear
in pressure:
logq = logk + (l/n) logp
Whenever the graphical method is employed, the data are
plotted as log q versus log p. The best straight line through
the data has a slope of (l/n) and an intercept of log k. In
general, k decreases with increasing temperature, while n
increases with Increasing temperature and approaches a
value of 1 at high temperatures.
3. PROCESSES FOR TREATMENT OF
EFFLUENT WASTE WATER
Over the last few decades, several methods have been
applied for the treatment of industrial waste water; there are
Uttam Singh and Rajesh K. Kaushal VSRDIJEECE, Vol. IV (III), March 2013 / 36


so many methods available for the removal of metal ions
from effluents; the commonly used procedures for
removing metal ions from aqueous streams include
Membrane separation, solvent extraction, Chemical
reduction, chemical precipitation, Evaporation, lime
coagulation, Cementation, ion exchange, reverse osmosis
and Electro deposition (Rich and Cherry, 1987).
Membrane separation processes have been applied to
inorganic wastewater treatment (EPA, 1980). These
processes involve ionic concentration by the use of
selective membrane with a specific driving force. The
application of the membrane process is limited due to
pretreatment requirements, primarily, for the removal of
suspended solids. The methods are expensive and requiring
a higher level of technical expertise to operate (Beszedits,
1988). Liquid-liquid extraction of metals or solvent
extraction from solutions on a large scale has experienced a
phenomenal growth in recent years due to the introduction
of selective complexing agents (Beszedits, 1988). In order
to recover the extracted metal, the organic solvent is
contacted with an aqueous solution whose composition is
such that the metal is stripped from the organic phase and is
reextracted into the stripping solution; such method become
inefficient whenever contaminants are present in trace
concentration Mahavi AH et al. (2005).Chemical reduction
has been used for recovery of chromium from metallurgical
effluent waste stream. Reduction of hexavalent chromium
can also be accomplished with electro-chemical units. The
electrochemical chromium reduction process uses
consumable iron electrodes and an electric current to
generate ferrous ions that react with hexavalent chromium
to give trivalent chromium (USEPA, 1979).main
disadvantage of Chemical reduction process is the high
operational cost relative to another process. Turner D.R, et
al (1998). Chemical precipitation of metals is achieved by
the addition of coagulants such as alum, lime, iron, salts
and other organic polymers. Chemical precipitation of
heavy metals as their hydroxides using lime or sodium
hydroxide is widely used; due to the low cost of precipitant,
ease of pH control in the range of( 8.0 10). Patterson et al,
1997 reported improved results using carbonate precipitate
for Cd (II) and Pb (II) from electroplating effluents. Since
most of the heavy metals form stable sulphides, excellent
metal removal can be obtained by sulphide precipitation.
The large amount of sludge containing toxic compounds
produced during the process is the main disadvantage.
Evaporation process have used for metal recovery in the
electroplating industry. Recovery is accomplished by
boiling sufficient water from the collected rinse stream to
allow the concentrate to be returned to the plating bath.
Both capital and operational costs for evaporative recovery
systems are high. Chemical and water reuse values must
offset these costs for evaporative recovery to become
economically feasible. Cementation is the displacement of a
metal from solution by a metal higher in the electromotive
series. It offers an attractive possibility for treating any
wastewater containing reducible metallic ions. In practice, a
considerable spread in the electromotive force between
metals is necessary to ensure adequate cementation
capability. Due to its low cost and ready availability, scrap
iron is the metal used often. The limitation of such process
is that it is suitable only for small wastewater flow because
a long contact time is required.
Ion exchange resins are available selectively for certain
metal ions. The cations are exchanged for H
+
or Na
+
. The
cation exchange resins are mostly synthetic polymers
containing an active ion group such as SO3H. The natural
materials such as zeolites can be used as ion exchange
media (Van der Heen, 1977). The modified zeolites like
zeocarb and chalcarb have greater affinity for metals like Ni
and Pb (Groffman et al., 1992). The limitations on the use
of ion exchange for inorganic effluent treatment are
primarily high cost and the requirements for appropriate
pretreatment systems. Ion exchange is capable of providing
metal ion concentrations to parts per million levels.
However, in the presence of large quantities of competing
mono-and divalent ions such as Na and Ca, ion exchange is
almost totally ineffective. Electrochemical deposition some
metals found in waste solution can be recovered by electro
deposition using insoluble anodes. For example, spent
solutions resulting from sulphuric acid cleaning of Cu may
be saturated with copper sulphate in the presence of
residual acid. These are ideal only for electro-plating where
the high quality cathode copper can be Electrolytic ally
deposited while free sulphuric acid is regenerated. Method
becomes ineffective when contaminants are present in trace
concentration. Kailas L. Wasewar et al. (2010).Since these
methods differ in their effectiveness and cost; and do not
seem to be economically feasible for such industries
because of their relative high costs Quek SY et al. (1998).
Therefore, there is a need to look into alternatives to
investigate a low-cost method which is effective and
economic. During the 1970s increasing environmental
awareness and concern led to a search for new techniques
capable of inexpensive treatment of polluted wastewaters
with metals. The search for new technologies involving the
removal of toxic metals from wastewaters has directed
attention to adsorption, based on binding capacities of
various biological materials. Watonabe and Ogawa (1929)
first presented the use of activated carbon for the adsorption
of heavy metals. The mechanism of removal of hexavalent
and trivalent chromium from synthetic solutions and
electroplating effluents has been extensively studied by a
number of researchers. For high strength and low volumes
of wastewater, heavy metal removal by adsorption
technique is good proposition. Adsorption is one of the
alternatives for such cases and is an effective purification
and separation technique used in industry especially in
water and wastewater treatments Kailas L. Wasewar et al.
(2010). Adsorption of Cr (III) and Cr (VI) on activated
carbon from aqueous solutions has been studied (Toledo,
1994). Granular activated carbon columns have been used
Uttam Singh and Rajesh K. Kaushal VSRDIJEECE, Vol. IV (III), March 2013 / 37


to treat wastewaters containing lead and cadmium (Reed
and Arunachalam, 1994, Reed et al., 1994). Granular
activated carbon was used for the removal of Pb (II) from
aqueous solutions (Cheng et al., 1993). The adsorption
process was inhibited by the presence of humic acid, iron
(III), aluminum (III) and calcium (II).
Adsorption has advantages compared with conventional
techniques (Volesky, 1999) some of these are listed below:
Cheap: the cost of the biosorbent is low since they
often are made from abundant or waste material.
Metal selective: the metal sorbing performance of
different types of biomass can be more or less selective
on different metals. This depends on various factors
such as type of biomass, mixture in the solution, type
of biomass preparation and physicochemical treatment.
Regenerative: biosorbents can be reused, after the
metal is recycled.
No sludge generation: no secondary problems with
sludge occur with biosorption, as is the case with many
other techniques, for example, precipitation.
Metal recovery possible: In case of metals, it can be
recovered after being sorbed from the solution.
Competitive performance: biosorption is capable of a
performance comparable tothe most similar technique,
ion exchange treatment.
Table 3.1: Performance characteristics of various heavy metal removal /recovery Technologies
[40]
Technology pH change Metal selectivity
Influence of
Suspended
Solids
Working level For
appropriate metal
(mg/I)
Adsorption,e.g
Granulated
Activated carbon
Limited
tolerance
Moderate Fouled <10
Electro
Chemical
Tolerant Moderate
Can be engineered
to tolerate
>10
Ion exchange
Limited
Tolerance
Chelate -resins can be selective Fouled >10
Membrane
Limited
Tolerance
Moderate Fouled >10
Precipitation
Hydroxide
(b) Sulphide
Tolerant
Limited
tolerance
Nonselective
Limited selective
pH dependent
Tolerant
Tolerant
>10
>10
Solvent extraction Some systems pH tolerant
Metal selective
Extractants available
Fouled >100

4. ADSORBENT
There are various types of Adsorbent is used in
electroplating industries for removal of heavy metal
according to requirement and availabilities.
Natural Adsorbent : There are many types of natural
adsorbents some of these have been explained as:
Zeolites: Basically zeolites are a naturally occurring
crystalline alumino silicates consisting of a framework of
tetrahedral molecules, linked with each other by shared
oxygen atoms. During 1970s, natural zeolites gained a
significant interest, due to their ion-exchange capability to
preferentially remove unwanted heavy metals such as
strontium and cesium [Grant et al., 1987]. Zeolites are
applied in drying of process air, CO
2
removal from natural
gas, CO removal from reforming gas, air separation,
catalytic cracking, and catalytic synthesis and reforming.
Adsorption in zeolites is actually a selective and reversible
filling of crystal cages, so surface area is not a pertinent
factor. Although naturally occurring zeolite minerals have
been known for more than 200 years, molecular-sieve
zeolites were first synthesized by Milton, who used very
reactive materials at temperatures of 25-100C.
Clay: It is widely known that there are three basic species
of clay: smectites (such as montmorillonite), kaolinite, and
micas; out of which montmorillonite has the highest cation
exchange capacity and its current market price is considered
to be 20 times cheaper than that of activated carbon [Virta,
2002]. Although the removal efficiency of clays for heavy
metals may not be as good as that of zeolites, their easy
availability and low cost may compensate for the associated
drawbacks.
Peat Moss: Peat moss, a complex soil material containing
lignin and cellulose as major constituents, is a natural
substance widely available and abundant, not only in
Europe (British and Ireland), but also in the US. Peat moss
has a large surface area (>200m
2
/g) and is highly porous so
that it can be used to bind heavy metals.
Chitosan: Among various biosorbents, chitin is the second
most abundant natural biopolymers after cellulose.
However, more important than chitin is chitosan, which has
a molecular structure similar to cellulose. Presently,
Uttam Singh and Rajesh K. Kaushal VSRDIJEECE, Vol. IV (III), March 2013 / 38


chitosan is attracting an increasing amount of research
interest, as it is an effective scavenger for heavy metals.
Chitosan is produced by alkaline N-deacetylation of chitin,
which is widely found in the exoskeleton of shellfish and
crustaceans. It was estimated that chitosan could be
produced from fish and crustaceans (Rorrer and Way 2002).
Commercial Adsorbent: Most industrial adsorbents fall
into one of three classes:
Oxygen-containing compounds Such adsorbent are
typical hydrophilic and polar, including materials such
as Silica gel, 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.
Table 4.1 : Representative Properties of Commercial Porous Adsorbents
[41]
Adsorbent Nature
Pore
Diameter
d
p
A
Particle
Porosity, E
p

Particle Density
p
P
, g/cm
3

Surface s,
m
2
/g
Capacity for
H
2
O
Vapor at
25C
and
4.6 mm Hg,
wt%
(Dry Basis)
Activated
alumina
Hydrophilic,
amorphous
10-75 0.50 1.25 320 7
Silica gel:
Small pore
Large pore
Hydrophilic
amorphous
hydrophobic,
amorphous
22-26
100-150
0.47
0.7 1
1.09
0.62
750-850
300-350

Activated
carbon:
Small pore
Large pore -
Hydrophobic,
Amorphous
Hydrophobic,
amorphous
10-25
>30
0.4-0.6
-
0.5-0.9
0.6-0.8
400-1200
200-600
1
-
Molecular-sieve
carbon
Hydrophobic 2-10 - 0.98 400 -
Molecdar-sieve
zeolites
Polar-hydrophilic,
crystalline
3-10 0.2-0.5 1,4 600-700 20-25
Polymeric
adsorbents
- 40-25 0.40-0.55 - 80-700 - -


Typical commercial adsorbents, which may be granules,
spheres, cylindrical pellets, flakes, and/or powders of size
ranging from O.5 mm to 1.2 cm, have specific surface areas
from 300 to 1,200( m
2
/g). Such a large area is made
possible by a particle porosity from 30 to 85 vol% with
average pore diameters from 10 to 200 A.
The adsorbents most commonly used on an commercial
scale are the activated carbon, silica gel, activated alumina
and molecular sieves (Lopez & Gutarra, 2000) (Yasemin &
Zaki, 2007). Charcoal has become the most widely used
solid, worldwide, as an adsorbent to remove pollutants in
wastewater.
Silica gel: This is a chemically inert, nontoxic, polar and
dimensionally stable (< 400 C or 750 F) amorphous form
of SiO
2
. It is prepared by the reaction between sodium
silicate and acetic acid, which is followed by a series of
after-treatment processes such as aging, pickling, etc. These
after treatment methods results in various pore size
distributions. Silica is used for drying of process air (e.g.
oxygen, natural gas) and adsorption of heavy (polar)
hydrocarbons from natural gas. Related silicate adsorbents
include magnesium silicate, calcium silicate, various clays,
Fuller's earth, and diatomaceous earth. Silica gel is also
highly desirable for water removal. Both small-pore and
large-pore types are available
Activated carbon: Activated carbon is a highly porous,
amorphous solid consisting of micro crystallites with a
graphite lattice, usually prepared in small pellets or a
powder. Activated carbon have high abrasion resistance,
high thermal stability and small pore diameters, which
results in higher exposed surface area and hence high
surface capacity for adsorption. It is non-polar in nature.
Activated carbon can be manufactured from carbonaceous
material, including coal (bituminous, sub bituminous, and
lignite), peat, wood, or nutshells (e.g., coconut). The
manufacturing process consists of two phases,
carbonization and activation. The carbonization process
Uttam Singh and Rajesh K. Kaushal VSRDIJEECE, Vol. IV (III), March 2013 / 39


includes drying and then heating to separate by-products,
including tars and other hydrocarbons from the raw
material, as well as to drive off any gases generated. The
most popular aqueous phase carbons are bituminous based
because of their hardness, abrasion resistance, pore size
distribution, and low cost, but their effectiveness needs to
be tested in each application to determine the optimal
product. One of main drawbacks of activated carbon
adsorbent is that it is reacts with oxygen at moderate
temperatures (over 300 C).
Activated alumina: This includes activated bauxite, is
made by removing water from hydrated colloidal alumina.
Activated alumina has a moderately high specific surface
area, with a capacity for adsorption of water sufficient to
dry gases to less than 1 ppm moisture content. Because of
its great affinity for water, activated alumina is widely used
for the removal of water from gases and liquids.
Activated charcoal: Charcoal has become the most widely
used solid to remove pollutants in wastewater due to its
own characteristic such as high porosity, chemical structure
and high surface area.
Polymeric adsorbents: Polymeric adsorbents are of lesser
commercial importance typically, they are spherical beads,
0.5 mm in diameter, made from microspheres about lop4
mm in diameter. They are produced by polymerizing
styrene and di vinyl benzene for adsorbing nonpolar
organics from aqueous solutions, and by polymerizing
acrylic esters for adsorbing polar solutes. They are
regenerated by leaching with organic solvents.
Low cost adsorbent: Activated carbon has been widely-
used adsorbent in wastewater treatment all over the world.
In spite of its prolific use, activated carbon remains an
expensive material, since higher the quality of activated
carbon, the greater its cost. Activated carbon also requires
complexing agents to improve its removal performance for
inorganic matters. Therefore, this situation makes it no
longer attractive to be widely used in small-scale industries
because of cost inefficiency. Due to the problems
mentioned previously, research has been interested into the
production of alternative adsorbents, especially those which
have metal-binding capacities and are able to remove
unwanted heavy metals from contaminated water at low
cost like natural zeolite, ash, rice husk, peat, volcanic
stones, bentonite and clinoptilolite for adsorption of heavy
metal ions . O.Kameswara rao et al. (2012). In particular,
some natural materials, such as polysaccharides, clays,
biomass, etc. that can remove pollutant from contaminated
water at low cost has been widely researched around the
world. Ronaldo Ferreira do et al. (2007). Agricultural
waste is one of the rich sources of low-cost adsorbents
besides industrial byproduct and natural material. Due to its
abundant availability agricultural waste such as peanut
husk, rice husk, coconut shell, wheat bran and sawdust offer
little economic value and, moreover, create serious disposal
problems (Igwe & Abia, 2007). Moreover the utilization of
these waste materials as such directly or after some minor
treatment as adsorbents is becoming vital concern because
they represent unused resources and cause serious disposal
problems. A growing number of studies have been carried
out in recent years to evaluate the behavior of emerging
adsorbents such as agricultural products and by-product for
emerging contaminants removal On the other hand
industrial wastes, such as, fly ash, blast furnace slag and
sludge, black liquor lignin, red mud, and waste slurry are
currently being investigated as potential adsorbents for the
removal of the emerging contaminants from wastewater
Mariangela Grassi et al. (2010). Carbonized Rice Husk
(CRH) and Activated Rice Husk (ARH) made out of rice
husks, available as agriculture waste, are investigated as
viable materials for treatment of Pb, Cd, Cu, and Zn
containing industrial wastewater at controlled pH. The
results obtained from the batch experiments revealed a
relative ability of the rice husk in removing some heavy
metals at pH 7. I Nhapi, et al (2012)
Industrial waste: Several industrial by-products have been
used for the adsorption of heavy metals. Certain waste
products, natural materials and biosorbents have been tested
and proposed for metal removal. It is evident from the
discussion so far that each low-cost adsorbent has its
specific physical and chemical characteristics such as
porosity, surface area and physical strength, as well as
inherent advantages and disadvantages in wastewater
treatment.
Table 4.2 : Performance index of various industrial waste adsorbent
[40]
Material Sources Pb2+ Hg2+ Cr6+ Zn2+ Cd2+ Cu2+
Waste slurry
Srivastava et al., 1985 1030 560 640
Lee and Davis, 2001 15.73 20.97
Iron (III) hydroxide
Namasivayam and Rangnathan,
1992
0.47
Lignin Aloki and Munemori, 1982 1865 95
Blast furnace slag Srivastava et al., 1997 40 7.5
Sawdust Ajmal et al., 1998 13.80
Activated red mud
Zouboulis and Kydros, 1993
Pradhan et al., 1999
1.6
Bagasse fly ash Gupta et al., 1999 260
Uttam Singh and Rajesh K. Kaushal VSRDIJEECE, Vol. IV (III), March 2013 / 40



Dates seed or modified date seed: modified natural seed
have also considered as adsorbent for treatment of waste
water due to its potential to overcome heavy metal pollutant
as well as these materials are cheaper, renewable and
abundantly available than other available natural resources.
The conditions of the preparation of the new activated
carbon derived from date stones (ACDS) was studied
Mohamed Abduelrahman et al. (2007) using hydrogen
peroxide as an activator. For the first time Mohamoud A.
Mohamoud et al. (2012) explore the efficiency of modified
date seeds on the removal of the carcinogenic bromate ion
from drinking water.
Characteristics of date seed is shown in table below:
Table 4.3 : Characteristics of date seed
[2]

Characteristic Value
Bulk density (g/ml) 0.393
Surface area (m2/g) 495.71
Ash content (%) 1.66
Moisture content (%) 7.80
Iodine number (mg/g) 475.88
The good adsorption possibilities of date seeds is based on
their dietary fiber content, which makes them suitable for
the preparation of adsorbent. It is a waste product of many
dates processing plants producing pitted dates, date syrup
and date confectionery. At present, seeds are used mainly
for animal feeds. Al- Farsi et al who researched the
functional properties of date seeds, their reported
composition has shown in table below.
Table 4.4 : Composition of Date Seed
[11]
Composition Value
Moisture 3.17.1%
Protein 2.36.4%
Fat 5.013.2
Ash 0.91.8%
Dietary fiber. 22.580.2%
Phenolics
(3102 4430 mg
Gallic acid equivalents/ 100 g),
5. CONCLUSION
A review of various agricultural adsorbents presented here
in shows a great potential for the elimination of heavy
metals from Industrial wastewater. The sorption capacity is
dependent on the type of the adsorbent investigated and the
nature of the waste water treated. More studies should be
carried out to better understand the process of low-cost
adsorption and to demonstrate the technology effectively.
This aspect need to be investigated further in order to
promote large scale use of non-conventional adsorbents. If
low cost adsorbents performance is well in removing heavy
metals they can be adopted not only to minimize cost but
also maximize the efficiency and profitability. The use of
low cost absorbent may contribute to the sustainability of
the surrounding.
6. LIST OF ABBREVIATIONS AND
NOTATION
BET = Brunauer-Emmett-Tellery component.
ACDS = activated carbon derived from date stones.
CRH =Carbonized Rice Husk and.
ARH =Activated Rice Husk
Gps = gallons per second
SG = silica gel
S.G = Specific gravity
B = Langmuir constant (energy of adsorption)
n = frendlich constant
q =amount of adsorbate adsorbed.
q
max
= Langmuir constant(adsorption capacity)
q
m =
maximum loading corresponding to complete
coverage of the adsorbent surface by the solute.
gmol =gram-mole
gpd = gallons per day
gph = gallons per hour
gpm = gallons per minute
kmol = kilogram-mole
avg = average
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