Indian Journal of Chemical Technology

Vol. 13, May 2006, pp. 203-217

Conventional and non-conventional adsorbents for removal of pollutants from

water A review
Amit Bhatnagara,b* & A K Minochab
a
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, India
b
Environmental Science & Technology Division, Central Building Research Institute, Roorkee 247 667, India
Email: amit_b10@yahoo.co.in
Received 7 September 2005; revised received 28 February 2006; accepted 10 March 2006

In the present article, the suitability of activated carbon and other alternative adsorbents for wastewater treatment has
been reviewed. It is evident from literature survey of last 20-25 years that researchers have gained success to some extent in
developing inexpensive adsorbents for water pollution control utilizing naturally available and waste materials. However,
still there is a need to find out the practical utility of such developed adsorbents on large-scale and safe and eco-friendly
disposal of spent adsorbents.

Keywords: Water pollution, Wastewater treatment, Adsorption, Activated carbon, Low-cost adsorbents

Among the various known forms of pollution, water However, these methods have their own shortcomings
pollution is of great concern since water is the prime and limitations. For example, the methods based on
necessity of life and extremely essential for the chemical/biological oxidation, ion exchange and
survival of all living organisms. Indeed, it is a part of solvent extraction have shown low efficiency for the
life itself, since the protoplasm of most living cells removal of trace levels of pollutants3. Further,
contains about 80% of water. It is worthy noting that coagulation4 requires pH control and causes further
only 0.02% of the total available water on the earth is problems of sludge disposal, whereas, ozonation5
immediately available for use in the form of rivers, while removing colour effectively does not minimize
lakes and streams. chemical oxygen demand (COD).
However, years of increased industrial, agricultural Among various available technologies for water
and domestic activities have resulted in the generation pollution control listed above, adsorption process is
of large amount of wastewater containing a number of considered better as compared to other methods
toxic pollutants, which are polluting the available because of convenience, easy operation and simplicity
fresh water continuously. With the realization that of design. Further, this process can remove/minimize
pollutants present in water adversely affect human different type of pollutants6 and thus it has a wider
and animal life, domestic and industrial activities, applicability in water pollution control.
pollution control and management is now a high Although certain phenomenon associated with
priority area. The availability of clean water for adsorption were known in ancient times, the first
various activities is becoming the most challenging quantitative studies were reported by C.W. Scheele7
task for researchers and practitioners worldwide. in 1773 on the uptake of gases by charcoal and clays.
As a result of the serious efforts of researchers all This was followed by Lowitz observations who used
over the world in the field of pollution control and charcoal for decolorization of tartaric acid solutions.
management, a number of methodologies with Larvitz8 in 1792 and Kehl8 in 1793 observed similar
varying degrees of success have been developed to phenomenon with vegetable and animal charcoals,
manage water pollution. Some of them involve respectively. However, the term adsorption was
coagulation, foam flotation, filtration, ion exchange, proposed by Bois-Reymond but introduced into the
sedimentation, solvent extraction, adsorption, literature by Kayser9. Ever since then, the adsorption
electrolysis, chemical oxidation, disinfection, process has been widely used for the removal of
chemical precipitation and membrane process1,2. solutes from solutions and gases from air atmosphere.
204 INDIAN J CHEM. TECHNOL., MAY 2006

The extent of adsorption depends on the nature of mg/L were achieved from a raw water with 3 mg/L
adsorbent especially its porosity and surface area. As fluoride by using activated alumina as adsorbent.
such, various adsorbents showing higher and Activated alumina is receiving renewed attention as
sometimes selective adsorption have been developed. an adsorbent18-20.
A fundamentally important characteristic of good On the other hand, bauxite consists of mainly
adsorbents10,11 is their high porosity and consequent aluminum hydroxide minerals but also contains
larger surface area with more specific adsorption small and variable amounts of silica, iron oxides-
sites. Most adsorbents which have been used in hematite, Fe2O3, and magnetite, Fe3O4, rutile or
pollution control have porous structure. The porous titanium oxide and alumina silicate clays. It is
structure not only increases surface area and widely used in place of alumina. Its surface area
consequently adsorption but also the kinetics of the ranges7 from 25 to 250 m2/g.
adsorption. A better adsorbent is the one with large
surface area and which requires less time for Zeolites and ion exchange resins
adsorption equilibrium. Hence, one generally looks to Zeolites are aluminosilicates with Si/Al ratios
adsorbents with high surface area and faster kinetics between 1 and infinity. There are 40 natural and over
for the removal of pollutants. Some of the important 100 synthetic zeolites. They are also considered as
adsorbents used in pollution control and various selective adsorbents. Zeolites generally show a
industrial operations are discussed herein. surface area15 in the range of 1-20 m2/g. Zeolite-based
Silica gel is the most widely used desiccant materials are used in detergent manufacture, ion-
(adsorbent for moisture) because of its large exchange resins (i.e. water softeners), catalytic
adsorption capacity for water (~ 40% by weight). This applications in the petroleum industry, separation
quality is due to its relatively weak bonds with water process (i.e. molecular sieves) and as an adsorbent for
as well as larger pore volume and mesoporosity12. water, carbon dioxide and hydrogen sulphide. Various
Further, ease in regeneration (~ 150C) makes silica zeolites have been employed for the removal of water
gel most widely used desiccant. The gel is considered pollutants by various researchers e.g. Handreck et
a good adsorbent and is used in many industries for al.21 employed zeolites for the removal of methylene
drying of gases and liquids, purification of blue dye from water, whereas Okolo et al.22 utilized
hydrocarbons etc.13,14. zeolites for the removal of phenols and chlorophenols.
Besides this, Ellis and Korth23 investigated the use of
Activated alumina and bauxite zeolites for the removal of geosmin and
Activated alumina comprises partially methylisoborneol from drinking water.
hydroxylated alumina oxide, Al2O3. They are porous A number of ion-exchange resins have also been
solids made by thermal treatment of aluminum used for the removal of specific organic compounds.
hydroxide precursors and find applications mainly as Weak and strong acid-type resins used for removal of
adsorbents, catalyst and catalyst support. In general, cations are called cation exchangers whereas base-
as a hydrous alumina precursor is heated, hydroxyl type resins that remove anions are called anion
groups are driven off leaving a porous solid structure exchangers. The primary applications of ion-exchange
of activated alumina. One of the earliest uses of resins are the softening and deionization of water.
activated alumina was removal of water vapour from Other applications are waste treatment, catalysis,
gases and this still remains an important application. purification of chemicals and pharmaceutical.
Activated alumina having the surface area ranging Recently, anion-exchange resins have been used by
from 200-300 m2/g15, is a versatile adsorbent and has Karcher et al.24 for the removal of dyes.
been successfully utilized for the removal of As(V),
PO43-, Cl- and F- from water besides other Activated carbon
applications12. Alumina is particularly effective for Activated carbon has undoubtedly been the most
adsorption of As(V) which exists in water as H2AsO4-. popular and widely used adsorbent in wastewater
Studies16 have shown that use of fixed bed activated treatment throughout the world. Charcoal, the
alumina can reduce the concentrations of arsenic from forerunner of modern activated carbon has been
50-70 to 5 g/L in treated waters. Similarly, activated recognized as the oldest adsorbent known in
alumina has also been found a potential adsorbent in wastewater treatment. Its ability to purify water dates
defluoridation of water17, where fluoride contents < 1 back to 2000 B.C. Lowitz established the first use of
 BHATNAGAR & MINOCHA: ADSORBENTS FOR POLLUTANTS REMOVAL FROM WATERREVIEW 205

charcoal for the removal of bad tastes and odours forms viz. activated carbon fibrous (ACF) and
from water on an experimental basis in 1789-1790. activated carbon clothe (ACC) are also in use39,40.
The credit of developing commercial activated Activated carbon has become the standard
carbon25 however goes to Raphael von Ostrejko adsorbent for the reclamation of municipal and
whose inventions were patented in 1900 and 1901. industrial wastewaters to potable water quality.
Early applications of carbon in water treatment plant Numerous researchers have studied the applications
to remove chlorophenolics were reported by Baylis in of activated carbon in water and wastewater
U.S. and Sierp in Germany in 1929. treatment. It is not possible here to discuss each and
Activated carbon is produced by a process every finding, however, some of the important
consisting of raw material dehydration and findings are being discussed herein illustrating the
carbonization followed by activation. The starting role of activated carbon for the removal of different
material is dehydrated and carbonized by slowly types of pollutants from water.
heating in the absence of air. Carbonization converts
Removal of phenolic pollutants by activated carbon
this organic material to primary carbon, which is a
Activated carbon has been successfully employed
mixture of ash, tars, amorphous carbon and crystalline
for the removal of phenol and substituted phenols
carbon (elementary graphitic crystallites). During
from water by various researchers. The mechanism of
carbonization, some decomposition products or tars
phenol adsorption on carbon surface was explained by
are deposited in the pores, but are then removed in the
Mattson et al.41. They suggested that the role of
activation step.
donor-acceptor complex mechanism involving
Activation is essentially a two phase process
carbonyl oxygen groups of the carbon surface acting
requiring burn off of amorphous decomposition
as electron donor and aromatic ring of the adsorbate
products (tars), plus enlargement of pores in the
as acceptor is important in the adsorption of phenols
carbonized material. Burn off frees the pore openings,
on carbon surface. Zogorski et al.42 studied the
increasing the number of pores, and activation
removal of phenols using activated carbon and
enlarges these pore openings. The resulting product
suggested that the process is feasible, efficient and
obtained is known as activated carbon and it generally
economical to diminish the phenol concentration to
has a very porous structure with a large surface area
acceptable levels in drinking waters. Paprowicz43
ranging from 600-2000 m2/g.
proved that chemical methods based on oxidation of
Activated carbons can be prepared from a variety phenol by chlorine, ozone or chlorine dioxide and
of carbon containing materials25,26, such as coke27, biochemical methods of decompositions of phenols
olive stones28, pinewood29, rice hulls30, palm shell31, on biologic beds or activated sludge, do not remove
Pinus caribaea sawdust32, anthracite33, plum whole load of phenol from wastewater. It was
kernels34, Moringa oleifera seed husks35, peat, suggested that activated carbons are suitable for
bituminous coal, coconut shell36, palm fruit bunch phenol containing wastewater treatment and
particles37 etc. However, the activated carbon used in powdered form may be used in conjunction with
wastewater treatment is generally prepared from coagulation chemical process.
coconut shells, peat, sawdust, wood char, lignin, Adsorption of phenol, p-chlorophenol and p-
petroleum coke, bone char, anthracite coal etc.6 nitrophenol on activated carbons was studied by
The activated carbon generally exists in two forms Wang et al.44 who found that adsorption ability of
(i) powdered activated carbon (PAC) and (ii) granular granular carbon is better than powdered carbon for
activated carbon (GAC). Since granular form is more removal of phenols. Colella et al.45 investigated the
adaptable to continuous contacting and there is no adsorption of twelve mono-, di- and trichlorophenols
need to separate the carbon from the bulk fluid, most from aqueous solutions while Jung et al.46 studied the
of the work on the removal of pollutants from water adsorption of phenol and chlorophenols on four
has been on GAC. On the other hand, the use of PAC commercial granular activated carbons. The results of
offers some practical problems because of separation these investigations46 suggest that the adsorption of
requirement of the adsorbent from the fluid. However, phenol and chlorophenols is controlled by interaction
inspite of these problems, PAC is also used for of electrons of activated carbon and phenols.
wastewater treatment due to low capital cost and Recently, the influence of carbon-oxygen surface
lesser contact time requirements38. Two more specific groups on the adsorption of phenols by activated
206 INDIAN J CHEM. TECHNOL., MAY 2006

Table 1 Adsorption capacities of some conventional and non-conventional adsorbents for the removal of phenols from water
S. No. Adsorbent Phenols Adsorption capacity (mg/g) References
1 Activated carbon Phenol 213 50
p-Chlorophenol 434
2 Activated carbon Phenol 256.97 51
3 Activated carbon Phenol 140 52
2,3,4-Trichlorophenol 500
4 (ACF-307) Phenol 239.2 47
(ACF-310) 263.1
(GAC-S) 142.8
(GAC-E) 10.44
5 Activated carbon from bituminous coal Phenol 93-213 53
6 Activated carbon from apricot stone shells Phenol 27.5-120 54
m-Cresol 28-113
p-Cresol 48-120
2-Chlorophenol 54-125
4-Nitrophenol 48-248
2,4-Dichlorophenol 125-595
2,4-Dinitrophenol 162-333
7 Activated carbons from used tea leaves Phenol, 80-438 48
o-, m-Cresol,
4-Chlorophenol,
4-Nitrophenol,
2,4-Dichlorophenol,
2,4-Dinitrophenol
8 Biological activated carbon Phenol 25 55
2,4-Dichlorophenol 43.7
9 Burnt wood charcoal Phenol 1-7 56
10 Bentonite p-Chlorophenol 10.63 57
11 Bentonite Phenol 0.43-1.71 58
12 Perlite p-Chlorophenol 5.84 57
13 Lake sediments Phenols 28-67 59
14 Na and Phenol, m-Cresol, 29-109 60
K- montmorillonite m-Nitrophenol,
p-Bromophenol
15 Chemically treated saw dust Pyrogallol, Pyrocatechol 28-52 61
16 Sawdust Phenol 146.25 62
Polymerized sawdust 185.18
Sawdust carbon 138.88
17 Iron(III) hydroxide loaded marble Pyrogallol, Pyrocatechol 9-10 63
18 Palm seed coat o-Cresol 19.58 64
19 Bituminous shale 2-Chlorophenol 3.1 65
2,4-Dichlorophenol 4.2
20 Fly ash Phenol 67 66
3-Chlorophenol 20
2,4-Dichlorophenol 22
21 Fly ash Phenol 5.58-6.48 67
4-Chlorophenol 8.62-10.0
2,4-Dichlorophenol 8.16-8.72
22 Fly ash Phenol 0.23 68

23 Fly ash and impregnated fly ash Phenol, 3.8-6.3 69

o-Cresol, 3.1-4.7
m-Cresol, 3.5-5.5
p-Cresol, 4.6-6.7
o-Nitrophenol, 5.8-6.9
m-Nitrophenol, 6.5-8.3
p-Nitrophenol 7.8-9.6
24 Coal fly ash Phenol 549.99 51
 BHATNAGAR & MINOCHA: ADSORBENTS FOR POLLUTANTS REMOVAL FROM WATERREVIEW 207

Table 2 Adsorption capacities of some conventional and non-conventional adsorbents for the removal of dyes from water
S. No. Adsorbent Dyes Adsorption capacity (mg/g) References
1 Activated carbon Deorlene yellow 200 70
Filtrasorb 400 Talon blue 175
2 Activated carbon Indigo carmine dye 16.3 77.7 78
3 Carbon prepared from waste jack fruit peel Malachite green 166.37 79
4 Buffing dust based activated carbon Acid brown dye 6.24 80
5 Charfins Direct brown dye 6.4 81
Lignite coal 4.1
Bituminous coal 2.04
Activated carbon 7.66
6 Carbonaceous adsorbent prepared from pearl millet husk Methylene blue 82.37 82
7 Activated carbon Acid red 1495 83
Activated carbon from Hazelnut 111
Raw kaolinite 29
Montmorillonite 19
8 Rice husk carbon Safranine 236310 84
Methylene blue 182274
9 Rice husk ash Acid violet 49 99.4155 85
Acid blue 15
Acid violet 17
Acid violet 54
Acid red 119
10 Coal Chrome dye 0.620.74 86
11 Sagaun sawdust Crystal violet 2.13.5 87
Methylene blue 2.03.3
Malachite green 1.93.3
Rhodamine b 1.42.3
12 Activated clay Basic blue 69 394 88
Basic red 62 406.3
Acid blue 25 256.1
Disperse blue 183 49.64
Direct red 227 37.88
Reactive red 123 36.63
13 Neem leaf powder Brilliant green 133.69 89
14 Chitin R 222 100 90
15 Eucalyptus bark Remazol B.B 90 91
16 Dead fungus Aspergillus niger Congo red 14.72 92
17 Maize cob Atrazon blue 160.0 93
18 Orange peel Acid violet 17 19.88 94
19 Banana peel Methyl orange 17.2 95
Methylene blue 15.9
Rhodamine B 13.2
Congo red 11.2
Methyl violet 7.9
Amido black 10 B 7.9
20 Orange peel Methyl orange 15.8 95
Methylene blue 13.9
Rhodamine B 9.1
Congo red 7.9
Methyl violet 6.1
Amido black 10 B 3.8
21 Peat, bentonite, slag, fly ash Disperse red I 23-50 96
22 Metal hydroxide- Sludge Azo reactive dyes 48-62 97
23 Chrome sludge Acid blue 69 58.8 98
Acid blue 25 32.3
Reactive yellow 2 41.7
Basic blue 3 0.18
Methylene blue 0.51
Contd.
208 INDIAN J CHEM. TECHNOL., MAY 2006

Table 2 Adsorption capacities of some conventional and non-conventional adsorbents for the removal of dyes from water Contd
S. No. Adsorbent Dyes Adsorption capacity (mg/g) References
24 Refused derived fuel Methylene blue 83 99
25 Bagasse Methyl violet ~5 100
Wood charcoal ~ 1.6
26 Activated carbon Remazol brilliant- 13.6 101
Chitin Violet 5 R 38.2
Radish leaves 40.0
27 Calcium alunite Reactive blue 114 170.7 102
Reactive yellow 64 236
Reactive red 124 153

carbons was studied by Bansal et al.47. The results of et al.73 investigated the effect of carbon surface
these studies indicated that while the presence of chemistry using Filtrasorb 400 activated carbon on the
acidic carbon-oxygen surface groups which were adsorption of three anionic reactive dyes in water. The
evolved as CO2 suppressed the adsorption of phenol, adsorption followed the following order: Remazol
the presence of non-acidic surface groups which were yellow > Remazol black > Remazol red. Porter74
evolved as CO tends to enhance the adsorption of demonstrated that adsorption by activated carbon is an
phenol. effective and complete treatment for the textile
Singh and Srivastava48 reported that the adsorption wastewater. Granular activated carbon Filtrasorb 400
on activated carbon increases up to pH 6 and then was used by Walker and Weatherley75 to treat a
decreases with further increase in pH. Favourable ternary solution of acid dyes and the process plant
adsorption of phenol at low pH on activated carbon effluents containing the dyes in a fixed-bed column
was also observed by Mahesh et al.49. Several other system. The breakthrough data obtained by column
reports50-69 are also available dealing with the studies correlated with equilibrium adsorption
removal/adsorption of phenols with activated carbons capacities of 537, 535 and 852 mg/g for tectilon blue
and other low cost adsorbents. Table 1 shows some of 4R (TB 4R), tectilon red 2B (TR 2B) and tectilon
the conventional and non-conventional adsorbents orange 3G (TO 3G), respectively. The authors
used in removing phenols from water along with their suggested that a dye possessing a higher adsorption
respective adsorption capacities. capacity will show a long breakthrough time and
relatively efficient use of carbon in column systems.
Removal of dyes by activated carbon Meshko et al.76 studied the adsorption of two basic
dyes, Maxilon Schwarz FBL-01 (MS-300) and
Activated carbon has also been investigated Maxilon Goldgelb GL EC (MG 400) from water by
extensively for the removal of different classes of granular activated carbon alongwith zeolite in a batch
dyes and colouring materials from water. McKay70 system. The results showed that activated carbon
investigated the ability of one activated carbon showed stronger affinity compared to zeolite for dyes
Filtrasorb type (size 1.4-2.8 mm) to remove a range of removal. It was also obsereved that saturation
dyestuffs (acidic, basic, disperse and direct dyes) from capacities for both adsorbents for MG-400 were lower
water. For the basic, acidic and disperse dyes, carbon than the MS-300. It was argued that the molecules of
was found to be an excellent adsorbent, but direct dye MS-400 are probably unable to penetrate easily into
showed less affinity for adsorption. The author the pores of the adsorbents whereas the molecules of
reported high adsorption capacities for deorlene MS-300 have less hindrance. Competitive adsorption
yellow (200 mg/g) and telon blue of three basic dyes was studied by Allen et al.77 who
(175 mg/g). In another report the same author also found that the adsorption potential of an individual
provided an evidence71 of high adsorption capacities dye decreased in the presence of second or third dye.
(985 mg/g) for basic dyes on carbon (150-200 m). Several other reports78-102 are also available dealing
Al-Degs et al.72 used different types of activated with the removal/adsorption of dyes with activated
carbons for the removal of cationic dye, methylene carbons and other low cost adsorbents. Table 2 shows
blue and an anionic dye, reactive black and reported some of the conventional and non-conventional
that adsorption of dyes is higher on activated carbons adsorbents used with their respective adsorption
having higher surface area. In another study, Al-Degs capacities in removing dyes from water.
 BHATNAGAR & MINOCHA: ADSORBENTS FOR POLLUTANTS REMOVAL FROM WATERREVIEW 209

Table 3 Adsorption capacities of some conventional and non-conventional adsorbents for the removal of metal ions from water
S. No. Adsorbent Metal ions Adsorption-capacity (mg/g) References
1 Activated carbon Cr(III) 35 50
Hg(II) 138
2 Activated carbon Pb(II) 30 103
3 Activated carbon Cr(VI) 145 105
4 Activated carbon Cd(II) 8 106
5 Activated carbon prepared from coirpith Ni(II) 62.5 108
6 Activated carbon from solvent extracted olive-pulp Zn(II) 4.6-33.6 109
7 Parthenium carbon Hg(II) 10 110
8 Peat Cu(II) 19.56 111
9 Sphagnum peat moss Cr(VI) 132 112
10 Perlite Cd(II) 0.42 113
11 Wollastonite Ni(II) 6.52 114
12 Chitin Cd(II) 14 115
13 Chitosan Cd(II) 5.93 116
14 Chitosan Hg(II) 815 117
Cu(II) 222
Ni(II) 164
Zn(II) 75
15 Saw-dust Cu(II) 13.8 118
16 Treated sawdust Cr(VI) 111.6 119
Anion resin 17.1
Activated alumina 9.6
17 Rice husk carbon Cr(VI) 45.6 120
18 Orange peel Ni(II) 158 121
19 Red mud Cu(II) 19.72 122
Zn(II) 12.59
Cd(II) 10.57
Ni(II) 10.95
20 Waste Fe(III)/Cr(III)-hydroxide Cr(VI) 1.38-1.5 123
21 Blast furnace sludge Pb(II) 64.17-79.87 124
Cu(II) 16.07-23.66
Cr(III) 9.55-16.05
Cd(II) 6.74-10.15
Zn(II) 4.25-9.65
22 Blast furnace slag Pb(II) 40 125
Cr(VI) 7.5
23 Fly ash Cu(II) 1.39 126
24 Fly ash Hg(II) 2.82 127

Removal of metal ions by activated carbon adsorbents. Adsorption of Cr(VI) from water using
Activated carbon has also been employed for the activated carbon was also investigated105. Maximum
removal of many toxic metal ions from water. McKay adsorption capacity of activated carbon105 was found
et al.50 investigated the ability of Filtrasorb 400 for to be 145 mg/g for Cr(VI) within a pH range of
the removal of Hg(II) and Cr(III) ions besides other 2.53.0. Activated carbon was also used for the
pollutants. The saturation capacity of the activated removal of Cd(II) from water106. The maximum
carbon was found to be 35 and 138 mg/g for Cr(III) adsorption potential of activated carbon was reported
and Hg(II) ions, respectively. Lead removal studies to be 8 mg/g at pH 8 for Cd(II).
with activated carbon were performed by Reed and Different types of granular activated carbons were
Arunachalan103. The adsorption capacity of activated used by Leyva-Ramos et al.107 for removal of Zn(II)
carbon was found to be 30 mg/g for lead removal by and they reported the adsorption capacity of about 18
the authors. The adsorption of mercury, cadmium and mg/g at pH= 7.0. Adsorption of Ni(II) from water on
lead on heat treated and sulphurized activated carbon activated carbon (prepared from coirpith) has been
was investigated by Gomez-Serrano et al.104. They investigated by Kadirvelu et al.108. The adsorption
pointed out that adsorption was very much higher for capacity of activated carbon was found to be 62.5
mercury than for Cd(II) and Pb(II) for all the mg/g at initial pH of 5.0 at 30C for the particle size
210 INDIAN J CHEM. TECHNOL., MAY 2006

of 250-500 m. The authors further reported that columns are generally made with activated carbons.
adsorption of Ni(II) increased with pH from 2-7 and After use, the columns get exhausted and are no more
remained constant upto 10. The removal of Zn(II) by capable of further adsorption of pollutants. Once the
activated carbons (prepared from solvent extracted activated carbon has been exhausted, it has to be
olive pulp) was carried out by Galiatsatou et al.109 regenerated for further use. A number of methods are
who reported adsorption capacity in the range of used for this purpose. The most common technique
4.6-33.6 mg/g for the prepared activated carbon for practiced in the regeneration of used activated carbon
Zn(II). is thermal treatment142,143. Besides this, chemical
Several other reports110-127 are also available regeneration of spent activated carbon has also been
dealing with the removal/adsorption of metal ions tried. Martin and Ng144 used acetic and formic acids to
with activated carbons and other low cost adsorbents. regenerate carbon exhausted by adsorption of
Table 3 shows some of the conventional and non- commercial humic acid and reported high
conventional adsorbents used with their respective regeneration efficiencies. Regeneration of exhausted
adsorption capacities in removing metal ions from carbon has been reported using NaOH by Newcombe
water. and Drikas145, acetone by Kilduff and King146,
Besides the above pollutants viz. phenols, dyes and methanol by Rollar and co-workers147 and through
metal ions, activated carbon has also been oxidation by Notthakum148. Regeneration of
successfully utilized for the removal of exhausted activated carbon has also been investigated
detergents128,129, pesticides130,131, humic through electrochemical technique by Narbaitz and
substances132,133, chlorinated hydrocarbons134,135 and Cen149 and Zhang et al.150. They also reported good
many other chemicals and organisms136-138. regeneration efficiencies for activated carbons.
Modified activated carbon
Low cost alternative adsorbents
It has been observed by various workers that
Activated carbon has been found to be a versatile
chemical treatment, at the time of activation during
adsorbent, which can remove diverse types of
the manufacture of activated carbons, often enhances
pollutants such as metal ions, dyes, phenols and a
the adsorption properties. Swiatkowski et al.139
number of other organic and inorganic compounds
modified activated carbons for the adsorption of
and bio-organisms. However, its use is sometimes
selected heavy metal ions. They reported that carbon-
restricted due to higher cost. Due to the higher cost of
oxygen and carbon-nitrogen surface species were
activated carbon, attempts are being made to
formed on the activated carbons by treating it with
regenerate the spent activated carbon. Chemical as
concentrated HNO3 or NH3. Choma et al.140
well as thermal regeneration methods are used for this
investigated the changes in surface and structural
purpose. However, these procedures are not very
properties of porous carbons modified by different
cheap and also produce additional effluents and result
oxidizing agents such as H2O2, HClO4 and HNO3.
in considerable loss of the adsorbent. Therefore, in
They reported that the surface properties of oxidized
situations where cost factors play a major role,
carbons depend on the type of oxidizing agent as well
scientists are looking for low cost adsorbents for
as oxidation conditions. Activated carbons were also
control of water pollution. As such, for quite
chemically modified by Park and Jang141 by treating
sometime, efforts have been directed towards
them with hydrochloric acid and sodium hydroxide.
developing low cost alternative adsorbents. A wide
They observed that the adsorption of Cr(VI) ions was
variety of materials have been investigated151 for this
more in the case of acid treatment on activated
purpose and they can be classified into three
carbons resulting due to the increase of acid values (or
categories: (i) natural materials (ii) agricultural wastes
acidic functional groups) of activated carbon surfaces.
and (iii) industrial wastes. These materials are
However, activated carbons treated with a base was
generally available free of cost or cost little as
not significantly effective for the adsorption of Cr(VI)
compared to activated carbons.
ions, probably due to the effect of the decrease of
specific surface area and basic nature of Cr(VI). Naturally occurring materials as adsorbents
Regeneration of spent activated carbon Various naturally occurring materials having
The activated carbons are used to purify water and characteristics of an adsorbent, are available in large
this is mostly done with column operations. The quantities. The abundance of these materials in most
 BHATNAGAR & MINOCHA: ADSORBENTS FOR POLLUTANTS REMOVAL FROM WATERREVIEW 211

continents of the world and their low cost make them capacity for the dye varied from 6.95 to 11.56 mg/g
suitable as adsorbents for the removal of various for particle size ranging from 710-1000 and 150-250
pollutants from wastewaters. Among the naturally m, respectively. The drawback of this adsorbent was
occurring adsorbents, chitin is fairly abundant. It is the long equilibration time required for adsorption and
found in the exoskeleton of shellfish and crustaceans. the low adsorption capacity. However, the same
It has been used as an adsorbent for the removal of adsorbent when used for the removal of Astrozone
pollutants from effluents115. Benguella and blue161 exhibited a higher adsorption capacity of 100.1
Benaissa115 reported the adsorption capacity of 14 mg/g for the dye for particles of size 150-250 m and
mg/g of chitin for Cd(II) ions. However, as compared much lesser equilibration time (2 h).
to chitin, chitosan, which is produced by alkaline N-
The natural coal was used as an adsorbent for the
deacetylation of chitin, is considered more important
removal of dyes by Mittal et al.162. The coal was
than chitin for adsorption purposes and has been
sulphonated, heated in a water bath and was used as
investigated intensively. Jha et al.116 studied the
adsorbent. Sorption and desorption of two basic dyes,
utilization of chitosan for cadmium removal. They
rhodamine B and methylene blue and acidic dye
reported an adsorption capacity of 5.93 mg of Cd(II)/g
Sandola rhodine was studied. The desorption studies
of chitosan at a pH range of 4.0-8.3 and further
indicated that methylene blue and rhodomine B
observed that the presence of ethylene diamine tetra
sorption is not governed by physiosorption while the
acetic acid (EDTA) significantly decreased the
adsorption of sandola rhodine is physical in nature.
cadmium removal. The adsorption of some other
The coal was also used as adsorbent for the removal
metal ions on chitosan was also investigated by
of chrome dye from aqueous solutions by Gupta
McKay et al.117. It was found that the adsorption
et al.86 who reported very low adsorption capacity
capacity of chitosan for Hg(II), Cu(II), Ni(II) and
(0.620.74 mg/g). Besides natural coal, other coal-
Zn(II) were 815, 222, 164 and 75 mg/g, respectively.
based adsorbents viz. charfins, lignite coal and
Chitosan was also investigated for dyes removal by
bituminous coal were also examined by Mohan et
various researchers152-154.
al.81 for dye removal and adsorption capacities of
Peat is another naturally occurring material these adsorbents were found between 6.4 and 7.66
containing lignin and cellulose as major constituents mg/g. Bhattacharya and Venkobachar163 investigated
and has been studied as an adsorbent by various the use of Girdish coal (GC) for the removal of
workers. Poots et al.155 studied the utilization of peat cadmium and found that it had an adsorption capacity
without any treatment for the removal of Talon blue. of 0.91 mg/g.
The adsorbent was found to possess adsorption Bentonite, another naturally occurring material
capacity of 16.3 mg/g on particles of size 150-200 shows a wide range of industrial applications
m. These workers suggested that in spite of its low including clarification of edible and mineral oils,
adsorption capacity, peat could be used as a low cost paints, cosmetics and pharmaceuticals. The
adsorbent in place of activated carbon and the spent abundance of bentonite in most countries and its low
material can be disposed off. Sharma and Forster112 cost makes it a suitable adsorbent for the removal of
investigated the utility of sphagnum peat moss for the many pollutants from wastewaters. Studies have
removal of Cr(VI). A good adsorption potential (132 shown its ability to bind and remove pathogenic
mg/g) of sphagnum peat moss in removing Cr(VI) viruses, pesticides, herbicides and other toxins164,165.
was reported112 at pH 1.5-3.0. Viraraghavan and The potential of bentonite for phenol adsorption from
Maria156 investigated adsorption characteristics of aqueous solutions was studied by Banat et al.58. They
peat alongwith fly ash and bentonite for the removal reported that the adsorption of phenol increases with
of phenol from wastewater and found that the removal increasing phenol concentration and decreases with an
efficiency is in the order: peat > fly ash > bentonite. increase in the pH of solution. Bentonite showed
Peat has also been used by a number of other adsorption capacity in the range of 0.43-1.71 mg/g for
workers157-159, as an adsorbent for metals and dyes phenol removal in this study. Bentonite along with
removal from wastewaters. perlite was also investigated as adsorbent by
Wood is the most widely spread natural material Koumanova and Peeva-Antova57 for the removal of p-
and its use as adsorbent for the removal of Talon blue chlorophenol. In this case, a higher adsorption
was first investigated by Poots et al.160. Its adsorption capacity (10.63 mg/g) was observed as compared to
212 INDIAN J CHEM. TECHNOL., MAY 2006

that for perlite (5.84 mg/g). Perlite was also used by Rengaraj et al.168 developed activated carbon from
Mathialagan and Viraraghavan113 for cadmium rubber seed coat for removal of phenols using batch
removal from aqueous solutions. The adsorption and column operations. It was suggested that the
capacity of perlite113 for Cd in column operations adsorbed phenol can be desorbed by sodium
using Thomas model was found to be 0.42 mg/g. hydroxide. The adsorption process was found to
The adsorption potential of Sagaun sawdust follow first order kinetics and the isotherm fitted to
(Tectona grandis), a naturally occurring material in both Freundlich and Langmuir equations. Rengaraj et
removing four basic dyes from water was investigated al.64 also examined the suitability of palm seed coat
by Khattri and Singh87. Low adsorption capacities for the adsorption of o-cresol and found it to have an
(1.4-3.55 mg/g) of this adsorbent for dyes removal adsorption capacity of 19.58 mg/g with film diffusion
were observed by these workers. Eucalyptus bark was as the rate limiting step. Daifullah and Girgis54 used
also investigated91 as adsorbent for the removal of chemically treated and low activated apricot stone
Remazol BB dye. The dried bark showed a good shells for the removal of substituted phenols and
adsorption potential of 90 mg/g of dye at pH 2.5 and reported that di-substituted phenols are adsorbed in
at 18C. The ability of wollastonite (an abundantly larger amounts than mono-substituted ones. Almond
naturally occurring clay mineral), to remove Ni(II) husk was used as a potential adsorbent for the
ions from water was investigated by Sharma et al.114. removal of Ni(II) ions by Hasar169. The activated
They reported adsorption capacity of wollastonite as carbons were prepared from almond husk by
6.52 mg/g for Ni(II). activating without (MAC-I) and with (MAC-II)
H2SO4 at different temperatures. The studies proved
A comparative study of activated carbon with that MAC-II performed better. Hirata et al.170
natural adsorbents (chitin and radish leaves) for the investigated the feasibility of carbonaceous material
removal of a reactive dye, remazol brilliant violet 5R produced from coffee grounds for the removal of two
from aqueous solutions was carried out by Sanghi and basic dyes, methylene blue and gentian violet and
Bhattacharya101. They found adsorption capacities of found that the adsorption of dyes depended upon the
activated carbon, radish leaves and chitin to be 13.6, surface polar groups present on the carbonaceous
40.0 and 38.2 mg/g, respectively. The ability of a wild material. The potential of pearl millet husk (PMHC)
plant material viz. Parthenium for the removal of as an adsorbent was explored by Inbaraj et al.82 who
Hg(II) was tested by Kadirvelu et al.110. The reported an adsorption capacity of 82.37 mg/g of this
adsorption capacity of this material was found to be adsorbent for methylene blue at pH 6.0. They further
10 mg/g at initial pH of 5.0 at 30 2C for the reported that methylene blue adsorption on PMHC is
particle size of 125250 m. Varghese et al.166 a chemisorption process and formic acid could be
investigated the use of aquatic plant, water hyacinth to used to remove the adsorbed dye. Peanut hull was
prepare a novel activated carbon for the removal of converted into an adsorbent by Namasivayam and
phenol, p-chlorophenol and p-nitrophenol. The Periasamy171 by treating it with concentrated
maximum adsorption capacity of the prepared sulphuric acid, then carbonizing it in air and further
activated carbon was reported to be 1.20, 1.28 and treating with 1% sodium bicarbonate overnight. The
1.35 mmol/g for phenol, p-chlorophenol and p- treated material was used as an adsorbent for the
nitrophenol, respectively. removal of Hg(II) ions from aqueous solutions and
the adsorption was found to conform to both
Agricultural wastes as adsorbents
Freundlich and Langmuir isotherms. The same
The disposal of waste materials is increasingly adsorbent was also used172 for Cd(II) removal and it
becoming a cause for concern52,166,167 because these was observed that the adsorption conforms to
wastes represent unused resources. A large amount of Freundlich model better than Langmuir.
solid wastes are produced in the agricultural sector in
most countries of the world. A major part of this Chamarthy et al.173 also prepared an adsorbent
waste is normally used as a domestic fuel. However, from peanut shell by heat treatment in presence of
for better utilization of this cheap and abundant phosphoric acid or citric acid and used it for the
agricultural waste, it can be explored as a low cost adsorption of Cd(II), Cu(II), Ni(II), Pb(II), and Zn(II).
alternative adsorbent owing to relatively high fixed Their investigations showed that phosphoric acid
carbon content and presence of porous structure. modified shells adsorbed metal ions in larger amounts
 BHATNAGAR & MINOCHA: ADSORBENTS FOR POLLUTANTS REMOVAL FROM WATERREVIEW 213

compared to citric acid modified shells. Farro-Gracia adsorbent for bulk use. Some studies on this aspect
et al.174 examined the use of processed almond shell, have been carried out. Haribabu et al.67 investigated
olive stones and peach stones, for the removal of the use of fly ash for the removal of phenol and
Zn(II), Cd(II) and Cu(II) from aqueous solutions. The chlorophenols and found the process to be
prepared adsorbents were found to have appreciable endothermic with first order kinetics. In a similar
surface areas, 876, 1103 and 1316 m2/g, respectively. study Akgerman and Zardkoohi66 investigated the use
Bagasse pith, a waste product from sugarcane of fly ash as an adsorbent for the removal of phenolic
industry has been studied by McKay et al.175 without compounds and found that it had the adsorption
any pretreatment for the removal of two basic dyes capacity of 67, 20 and 22 mg/g for phenol,
and two acidic dyes from aqueous solutions. High 3-chlorophenol and 2,4-dichlorophenol, respectively.
adsorptive capacity was observed for the adsorption Fly ash was also studied by Viraraghavan and
of basic dyes, 158 mg/g for basic blue 69 and 177 Ramakrishna179 for the removal of cationic and
mg/g for basic red 22 while lower capacity of 23 mg/g anionic dyes. The process was found to follow first
and 22 mg/g was observed for acid red 114 and acid order kinetics and the isotherms conformed to both
blue 25, respectively. Freundlich and Langmuir models. Panday et al.126
Besides these, several other agricultural wastes viz. used fly ash without any pretreatment for the removal
rice husk84,85,120, corncob waste176, coir pith108,177, of Cu(II) and found that the adsorption data conforms
plum kernels178 have also been investigated. However to Langmuir model. The results of all these studies
besides few reports, the adsorption potential of these have revealed that fly ash is not a very good adsorbent
adsorbents was found low as compared to activated due to its low adsorption efficiency as compared to
carbon. activated carbon. Fly ash has also been used in
conjunction with other materials180, but the adsorptive
Industrial wastes as adsorbents
capacities were found to be on the lower side for these
Widespread industrial activities are producing large
mixtures also.
amount of solid waste materials. Some of these
materials are being put to use while others find no The steel industry produces a number of wastes in
proper utilization and are dumped elsewhere. The large quantities such as blast furnace slag, dust and
industrial waste material is available almost free of sludge etc. and these have also been investigated as
cost and causes major disposal problem. If the solid adsorbents. Yamada et al.181 studied phosphate removal
wastes could be used as low cost adsorbents, it will using soft and hard granulated slag and observed that
provide a two-fold advantage in reducing the phosphate adsorbed well on soft granulated slag than the
pollution. Firstly, the volume of waste materials could hard granulated slag and explained this observation on
be partly reduced and secondly the developed low the basis of porosity of the adsorbent. On the other hand,
cost adsorbent can reduce the pollution of Dimitrova182 investigated ungranulated blast furnace
wastewaters at a reasonably cost. In view of the low slag for the removal of Cu(II), Ni(II),
cost of such adsorbents, it would not be necessary to and Zn(II) ions from water in the concentration range of
regenerate the spent materials. With this view, a 1 10-41 10-3 M and reported that slag alkalizing
number of industrial wastes have been investigated activity creates conditions for adsorption through
with or without treatment as adsorbents for the hydroxo complex formation and colloidal particles of
removal of pollutants from wastewaters. The major silicic acid. Recently, slag columns were utilized by the
solid waste byproduct of thermal power plants based same workers183 for lead removal. Other waste materials
on coal burning is fly ash. Fly ash is produced as a generated in steel industry are blast furnace sludge and
fine, non-combustible residue carried off in the flue blast furnace flue dust, which have also been tried as
gas with relatively uniform particle size distribution in possible adsorbents. Jallan and Panday184 reported the
the 1-10 m range. The annual production of fly ash use of untreated blast furnace sludge as adsorbent for the
from coal burning power plants has continued to removal of some toxic ions viz. Pb(II), Ni(II), Cd(II),
increase, yet its overall utilization is marginal. Cu(II), Zn(II) and CN-. It was found that sludge has a
Currently, the main uses of fly ash include good adsorptive capacity for metal ions as well as
construction of roads, bricks, cement etc. The high cyanide but the adsorption (9 mg/g) was poor in the case
percentage of silica and alumina in fly ash make it a of Zn(II). Sludge was also tested as adsorbent for the
good material for utilization as an inexpensive removal of some heavy metal ions by Lpez-Delgado
214 INDIAN J CHEM. TECHNOL., MAY 2006

et al.124 who reported that metal ions are adsorbed in the first reports described how abundant biological
order, Pb> Cu > Cr > Cd > Zn. Patnaik and Das185 materials could be used to remove, at very low cost,
investigated the use of blast furnace flue dust as even small amounts of toxic heavy metals from
adsorbent for the removal of Cr(VI) and found the first industrial effluents189. Various biosorbents190-195 have
order kinetics for the adsorption process. been tested for the removal of pollutant especially
Red mud, a solid waste product of aluminium metal ions with very encouraging results.
industry produced during bauxite processing, was
tested as adsorbent by Lpez et al.122 for wastewater Conclusions
treatment. The maximum adsorption capacities for In spite of prolific use of activated carbon in
Cu(II), Zn(II), Ni(II) and Cd(II) were found to be wastewater treatment, its use is sometimes restricted
19.72, 12.59, 10.95 and 10.57 mg/g, respectively for a because of its higher cost. To replace the expensive
contact time of 48 h. Red mud was also studied by activated carbon, a wide range of inexpensive
engelolu et al.186 for the removal of fluoride from adsorbents have been investigated utilizing naturally
aqueous solutions. They used both the original and occurring materials and waste products of different
activated red mud forms in batch equilibration industries. Some of them were found to be quite
technique and found that the adsorption capacity of satisfactory. However, still, there is a strong need to
activated form, for fluoride removal, was higher than conduct extensive research on the following points:
that of original form. The maximum removal of (i) To improve the removal
fluoride occurred at pH 5.5. Chrome sludge, a solid efficiencies/adsorption capacities of such
waste material from electroplating industry, was prepared adsorbents after chemical
used98 as an adsorbent for removal of colour. The modifications or appropriate treatment.
results indicated that the sludge had a better affinity (ii) Cost factor is also an important point that
for acid dyes than basic dyes. Fe(III)/Cr(III) should be considered before selecting
hydroxide, a waste material from the fertilizer such developed adsorbents in water
industry has been used by Namasivayam et al.123 for pollution control.
the adsorption of Cr(VI) from aqueous solutions. The (iii) Last but not the least, it is very important
adsorption data fitted with both Freundlich and to dispose of the spent adsorbents in an
Langmuir models. The use of another fertilizer environmental friendly way. Only limited
industry waste viz. carbon slurry was also explored by information is available in literature about
Srivastava et al.187. Sekaran et al.80 used buffing dust, safe disposal of spent adsorbents. More
waste generated from leather industry, for the removal efforts should be made in this direction.
of dyes. The adsorption capacity of buffing dust was
If it is possible to develop such adsorbents having
found to be 6.24 mg/g at pH 3.5 and at temperature
all the above-mentioned characteristics, then these
30C for acid brown dye. The adsorption of phenols
adsorbents may offer significant advantages over
on papermill sludges was studied by Calce et al.188
currently available commercially expensive activated
who observed its retention capacity in the order: 2-
carbons and, in addition contribute to an overall waste
nitrophenol = 4-nitrophenol << 2-chlorophenol <
minimization strategy.
phenol <4-chlorophenol 3-chlorophenol < 2,4-
dichlorophenol < 3,4-dichlorophenol = 2,4,5- Acknowledgements
trichlorophenol < 3, 5-dichlorophenol. Amit Bhatnagar is grateful to Prof A K Jain,
The adsorbents developed by utilizing industrial Department of Chemistry, IIT, Roorkee for guidaance
wastes have shown a tendency to remove inorganic and encouragement. The authors wish to thank the
contaminants (metal ions) more effectively as reviewers for their valuable comments and useful
compared to organic constituents (dyes, phenols etc.) suggestions, which significantly improved the quality
Biosorbents of this paper.
The removal of pollutants from effluents utilizing
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