Journal of Environmental Management 90 (2009) 1336–1349

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Journal of Environmental Management

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Review

Adsorption of phenol and its derivatives from water using synthetic resins and
low-cost natural adsorbents: A review
Su-Hsia Lin a, Ruey-Shin Juang b, c, *
a
Department of Chemical and Materials Engineering, Nanya Institute of Technology, Chung-Li 320, Taiwan
b
Department of Chemical Engineering and Materials Science, Yuan Ze University, Chung-Li 32003, Taiwan
c
Fuel Cell Center, Yuan Ze University, Chung-Li 32003, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: In this article, the technical feasibility of the use of activated carbon, synthetic resins, and various low-
Received 19 June 2008 cost natural adsorbents for the removal of phenol and its derivatives from contaminated water has been
Received in revised form 26 August 2008 reviewed. Instead of using commercial activated carbon and synthetic resins, researchers have worked
Accepted 19 September 2008
on inexpensive materials such as coal fly ash, sludge, biomass, zeolites, and other adsorbents, which
Available online 7 November 2008
have high adsorption capacity and are locally available. The comparison of their removal performance
with that of activated carbon and synthetic resins is presented in this study. From our survey of about
Keywords:
100 papers, low-cost adsorbents have demonstrated outstanding removal capabilities for phenol and its
Synthetic resins
Low-cost natural adsorbents derivatives compared to activated carbons. Adsorbents that stand out for high adsorption capacities are
Adsorption coal-reject, residual coal treated with H3PO4, dried activated sludge, red mud, and cetyl-
Phenol and its derivatives trimethylammonium bromide-modified montmorillonite. Of these synthetic resins, HiSiv 1000 and
Wastewater treatment IRA-420 display high adsorption capacity of phenol and XAD-4 has good adsorption capability for
2-nitrophenol. These polymeric adsorbents are suitable for industrial effluents containing phenol and
its derivatives as mentioned previously. It should be noted that the adsorption capacities of the
adsorbents presented here vary significantly depending on the characteristics of the individual
adsorbent, the extent of chemical modifications, and the concentrations of solutes.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
Phenols are pollutants of high priority concerns because of
their toxicity and possible accumulation in the environment.
Phenols are introduced into surface water from industrial effluents
Abbreviation and notation: A, Redlich–Peterson constant (L/g); AC, activated
carbon; B, Redlich–Peterson constant (L/mg(1  1/A)); Ce, equilibrium concentration
of solute in liquid-phase (mg/L); BDNP, 2-sec-butyl-4,6-dinitrophenol; BFA, bagasse
fly ash; CDs, cyclodextrins; CEC, cation exchange capacity; CFA, coal fly ash; CNTs,
carbon nanotubes; CP, chlorophenol; CPB, n-cetylpyridinium bromide; CTAB,
cetyltrimethylammonium bromide; DCP, dichlorophenol; DMP, dimethylphenol;
DNBP, dinitrobutyl phenol; DNP, dinitrophenol; DVB, divinylbenzene; GAC, granular
activated carbon; HDTMAB, hexadecyltrimethyl ammonium bromide; Kd, distri-
bution coefficient (L/kg); KF, Freundlich constant (mg/g) (L/g)n; KL, Langmuir
constant (L/mg); MAAP, methacrylamidoantipyrine; MP, methylphenol; n, Freund-
lich exponent; NP, nitrophenol; OTMAC, octodecyl trimethylammonium chloride;
PAC, powdered activated carbon; PHEMA, poly(2-hydroxyethyl methacrylate); qe,
equilibrium amount of solute adsorbed (mg/g); SDS, sodium dodecyl sulfate; TCP,
trichlorophenol; b, exponent lying between 0 and 1.
* Corresponding author. Department of Chemical Engineering and Materials
Science, Yuan Ze University, 135 Yuan-Tung Road, Chung-Li 32003, Taiwan.
Tel.: þ886 3 4638800x2555; fax: þ886 3 4559373.
E-mail address: rsjuang@ce.yzu.edu.tw (R.-S. Juang).
such as those from the coal tar, gasoline, plastic, rubber proofing,
disinfectant, pharmaceutical and steel industries and domestic
wastewaters, agricultural run-off and chemical spills. Various
methods have been proposed for the treatment of wastewaters
containing organic and inorganic pollutants. These processes are
based on the principles of precipitation and coagulation, chemical
oxidation, sedimentation, filtration, adsorption, osmosis, ion
exchange, etc.
Adsorption technology is currently being used extensively for
the removal of organic and inorganic micropollutants from aqueous
solutions. There are many absorbents in use. Activated carbon is the
most widely used for the removal of a variety of organics from
waters, but the disadvantage associated with it is the high regen-
eration cost and the generation of carbons fines, due to the brittle
nature of carbons used for the removal of organic species. Thus this
has simulated research into specialty absorbents using synthetic
resins that may facilitate a cheap and effective chemical regener-
ation process. Davankvo et al. (1969) have first displayed their
hyper-crosslinked polymeric networks. The polymers were origi-
nally described as macroreticulated, offering characteristic
different from those of other polymer resins. Purolite International
Ltd., in collaboration with the Russian inventors, has developed an

0301-4797/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2008.09.003
 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349
optimal series of Hypersol-Macronet adsorption resins for indus-
trial applications. The wide variations in surface area, functionality,
and porosity of the polymeric absorbents reveal the possibility of
the resins for selective removal of specific organics (Abburi, 2003;
Ku and Lee, 2000).
Recently, some nature and cheap adsorbents have been
developed in the laboratory (Ahmaruzzaman and Sharma, 2005;
Ahsan et al., 1994; Batabyal et al., 1995; Gupta et al., 1998, 2004;
Haghseresht and Lu, 1998; Hobday et al., 1994; Jain et al., 2004;
Otero et al., 2003; Rio et al., 2005; Sarkar and Acharya, 2006;
Srivastava et al., 2006; Tarasevich, 2001; Tor et al., 2006; Wang and
Jiang, 2007). Research interests into the production of alternative
adsorbents to replace costly activated carbon and synthetic resins
have intensified in recent years. Attention has been focused on
various adsorbents, which have absorption capacities and are able
to remove unwanted phenols from contaminated water at low-cost.
Because of their low-cost and local availability, natural materials
such as bagasse, red mud, zeolites, clay, or certain waste products
from industrial operations such as fly ash, coal, and industry wastes
are classified as low-cost adsorbents.
Natural zeolites also gained a significant interest among scien-
tist, mainly due to their valuable properties such as ion exchange
ability and high surface areas. Large deposits of natural zeolites in
many countries such as Greece, UK, Italy, Mexico, Iran, and Jordan,
provide local industries some promising benefits such as cost effi-
ciency since they are able to treat wastewater contaminated with
organic solutes by modification at low-cost. Clay is one of the
potential alternatives to activated carbon as well. Similar to
zeolites, clay minerals are important inorganic components in soil.
Their sorption capabilities come from high surface area and
exchange capacities. The negative charge on the structure of clay
minerals gives clay the capability to be modified by surfactant. USA
and the former Republics of Soviet Union such as Lithuania, Geor-
gia, and Kazakhstan are well known for their large deposits of
natural clay minerals.
Industrial waste is also one of the potentially low-cost adsor-
bents for removal of phenol and its derivatives. It requires little
processing to increase its sorption capacity. Generally industrial
wastes are generated as by-products. Since these materials are
locally available in large quantities, they are inexpensive. There are
many types of industrial wastes such as waste slurry, fly ash, red
mud, rubber seed coat, and coal, which have been explored for their
technical feasibility to remove phenols and its derivatives from
contaminated water.
Coal is known to possess good microporosity and a large surface
area, and reported to be a good adsorbent for phenols. These
materials exist as large deposits in many countries, notably Aus-
tralia and India. Other low-cost adsorbents such as agricultural
wastes have been studied less extensively due to their local avail-
ability. Although many research studies have been done recently to
find the potential of using various alternative adsorbents, so far no
efforts have been made to obtain a comparative overview of all
adsorbents mentioned previously in terms of their removal
performance, adsorption capacity, and cost effectiveness. An over-
view of some low-cost adsorbents based on recent publications is
therefore presented in this paper and their removal performances
are compared.
2. Adsorption isotherms
Adsorption equilibrium measurements are used to determine
the maximum or ultimate capacity. Six types of adsorption
isotherms exist including types I–VI (Mohan and Singh, 2005; Sing
et al., 1985). Adsorption equilibrium data are formulated into an
isotherm model. The most commonly used models include
Freundlich, Langmuir, and Redlich–Peterson isotherms.
1337
2.1. Freundlich isotherm
This isotherm developed by Freundlich (1906) describes the
equilibrium on heterogeneous surfaces and does not assume
monolayer capacity. It is given by
1=n
qe ¼ KF Ce
where qe is the equilibrium amount of solute adsorbed per unit
mass of adsorbent (mg/g), Ce is the equilibrium concentration of
solute in bulk solution (mg/L), KF is a constant indicative of the
relative adsorption capacity of the adsorbent (mg/g) (mg/L)n, and
the constant 1/n indicates the intensity of the adsorption.
2.2. Langmuir isotherm
The Langmuir isotherm describes the surface as homogeneous
assuming that all the adsorption sites have equal solute affinity and
that adsorption at one site does not affect the adsorption at an
adjacent site (Langmuir, 1918). The Langmuir equation may be
written as
Qo KL Ce
qe ¼
1 þ KL Ce
where Q0 is the monolayer adsorption capacity (mg/g) and KL is the
constant related to free adsorption energy (L/mg) that is the
reciprocal of the concentration at which half saturation of the
adsorbent is reached.
2.3. Redlich–Peterson isotherm
The Redlich–Peterson isotherm (Redlich and Peterson, 1959) is
an empirical isotherm incorporating three parameters. It combines
elements from both the Langmuir and Freundlich equations, and
the mechanism of adsorption is a hybrid and does not follow ideal
monolayer adsorption:
ACe
qe ¼
1 þ BCeb
where A is the Redlich–Peterson constant (L/g), B is a constant having
unit of (L/mg)b, and b is an exponent that lies between 0 and 1.
3. Evaluation/comparison of adsorption properties
For simplicity, in this review adsorbents are divided into three
classes: (1) activated carbons, (2) synthetic and natural resins, and
(3) other low-cost adsorbents. The comparisons of adsorption
capacities of phenol and its derivatives using various adsorbents are
summarized in the following tables.
3.1. Activated carbons
Activated carbons can be further divided into commercially
available (Table 1) and synthetic activated carbons. The price of
activated carbon for industrial grade increased from US$ 2–4/kg
(Ferro-Garcia et al., 1988) to about US$ 20–22/kg depending on the
quality of activated carbon itself.
3.1.1. Commercial activated carbons
Sulaymon and Ahmed (2008) have studied the competitive
adsorption of furfural and phenolic compounds, in which a math-
ematical model was built to describe the mass transfer in a fixed-
bed with activated carbon. It was shown that the model involving
external mass transfer and pore diffusion using a nonlinear
isotherm well describes the adsorption process of furfural and
1338 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349

Table 1
Comparison of various commercial activated carbons for the adsorption of phenol and its derivatives.

Adsorbent Solute pH T ( C) Model used Capacity (mg/g) Reference

GAC Furfural 8.1 – Langmuir 374.4 Sulaymon and Ahmed (2008)
GAC Phenol 5.7 – Langmuir 350
GAC 4-CP 5.7 – Langmuir 319.9
APET Phenol 5 – Langmuir 262 Laszlo (2005)
APET Phenol 11 – Langmuir 184.2
APET Aniline 5 – Langmuir 243.6
APET Aniline 11 – Langmuir 283.6
CCM200 (carbon cryogel) Phenol – – Langmuir 140 Kim et al. (2006)
G-BAC Phenol – – Langmuir 235.4
PACT (power activated carbon treatment) Phenol – 25 Langmuir 135.7 Orshansky and Narkis (1997)
PACT Aniline – 25 Langmuir 126.6
PAC Phenol – – – 303 Ania et al. (2002)
Steam-PAC (from coal) Phenol – – – 226
Chemical-PAC (from coal) Phenol – – – 98
GAC (F400) F-DI Phenol – – Freundlich 75.2 Leng and Pinto (1997)
GAC(F400) F-HCl Phenol – – Freundlich 75.5
F400-N2 Phenol – – Freundlich 96
F400-Air Phenol – – Freundlich 54
CNTs Phenol – – – 15.9 Liao et al. (2008)
CNTs Catechol – – Langmuir 14.2
CNTs Pyrogallol – – Langmuir 33.6

phenolic compounds in a fixed-bed. Nevskaia et al. (2004) have
studied the removal of aromatic compounds (phenol, 2-chlor-
ophenol (2-CP), 4-initrophenol (4-NP), aniline, and their mixtures)
from water by the activated carbons with (high surface area
graphite with oxygen (HSAGox), activated carbon with oxygen
(ACox)) and without oxygen (HSAGT, ACT) surface groups. Micro-
porous carbons (called APET) of similar surface area (1200–
1500 m2/g) and porosity but different surface compositions were
prepared from poly(ethyleneterephthalate) (PET) based activated
carbon by chemical (HNO3) and thermal (700  C) post-treatment
(Laszlo, 2005). The waste removal capacity was studied by
adsorption from buffered aqueous phenol and aniline solutions.
Adsorption isotherms were satisfactorily fitted by both the Lang-
muir and Freundlich models. Moreover, TiO2-mounted activated
carbon was prepared through hydrolytic precipitation of TiO2 from
teraisopropyl orthotitanate and followed heat treatment at 650–
900  C for 1 h under a flow of N2 gas (Tryba et al., 2003). The
removal of phenol from aqueous solutions under UV irradiation
was measured on the prepared TiO2-mounted activated carbons.
Although the BET surface area of TiO2-mounted activated carbons
decreased drastically in comparison with the original activated
carbons, the efficiency of phenol removal under UV irradiation was
high. The sample was heated at 900  C, which consisted mainly of
rutile phase, showing the highest total removal of phenol. Effi-
ciency of phenol degradation was reduced because of phenol
adsorption on the catalyst. Orshansky and Narkis (1997) have used
PAC to remove organic toxic pollutants. From their adsorption
experiments, the Langmuir isotherm was suggested. Adsorption of
resorcinol and other phenolic derivatives on pristine multi-walled
et al., 2001), lignin (Gonzalez-Serranoa et al., 2004), apricot stone
shell (Daifullah and Girgis, 1998), activated sludge (Martin et al.,
2004), bagasse ash and charcoal (Mukherjee et al., 2007), coffee
grounds (Namane et al., 2005), paper mill sludge (Khalili et al.,
2002), and coconut shell (Radhika and Palanivelu, 2006). Table 2
lists various Industrial or agricultural by-products can be converted
into activated carbons or low-cost adsorbents. Schemes for the
production of activated carbons are either thermal procedures
(physical) or chemical routes. The former involves primary
carbonization of the raw materials (<700  C) followed by
controlled gasification at higher temperatures (850  C) in a stream
of an oxidizing gas (steam, CO2, N2, air, or a mixture). The chemical
route is done by impregnation of the precursor with H2SO4, H3PO4,
ZnCl2, or HNO3 (Daifullah and Girgis, 1998; El-Hendawy et al., 2001;
Gonzalez-Serranoa et al., 2004; Khalili et al., 2002; Martin et al.,
2004; Mukherjee et al., 2007; Namane et al., 2005; Radhika
and Palanivelu, 2006) and then by heat treatment at moderate
temperatures (400–600  C) in a one-step process (Derbyshire et al.,
1995). An additional one-step treatment route was developed and
reported where the raw agriculture residue was heated at moderate
temperatures (500–700  C) under a flow of pure steam (denoted as
steam-pyrolysis).
Table 2
Alternative feed stocks proposed for preparing activated carbon and low-cost
adsorbents used in wastewater treatment (Mohan and Singh, 2005; Pollard et al.,
1992).
Alternative feed stocks

carbon nanotubes (CNTs) and HNO3-treated multi-walled CNTs has Bones Fertilizer waste slurry Petroleum acid sludge
been also studied to explore the possibility to use multi-walled Bagasse Fish Pulp-mill waste
CNTs as efficient adsorbents for pollutants (Liao et al., 2008). The Bark Fruit pits Palm tree cobs
multi-walled CNTs showed higher adsorption ability in a rather Beat-sugar sludge Graphite Petroleum coke
Blood Jute stick Petroleum acid sludge
wide pH range of 4.0–8.0 for resorcinol, while decreased adsorption Blue dust Kelp and seaweed Potassium ferrocynide residue
capacity was found for acid-treated multi-walled CNTs. Carbohydrates Lignin Rubber waste
Cereals Lignite Rice hulls
3.1.2. Synthetic activated carbons Coal Lampblack Refinery waste
Coffee beans Leather waste Reffination earth
Precursors to the activated carbons are either of degraded and
Coconut shell Municipal waste Scrap tires
coalified plant matter (e.g., all ranks of coal, lignite and peat) or of Coconut coir Molasses Sunflower seeds
botanical origin (e.g., nut shells, wood, and coconut shells). Agri- Cottonseed hulls Nut shells Spent Fuller’s earth
cultural wastes are considered as very important feed stocks in Corncobs News paper Tea leaves
virtue of two facts: they are renewable and low-cost materials. The Distillery waste Oil shale Wheat straw
Fuller’s earth Olive stones Wood
most commonly used feed stocks include corncob (El-Hendawy
 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349
Radhika and Palanivelu (2006) have studied the adsorptive
removal of 4-CP and 2,4,6-TCP from aqueous solutions by activated
carbons prepared from coconut shell, and compared with
commercial-grade activated carbons (CAC). Various chemical
agents at different concentrations (KOH, NaOH, CaCO3, H3PO4, and
ZnCl2) were used for preparing coconut-shell activated carbon
(CSAC). The CSAC prepared using KOH as chemical agent showed
high surface area and best adsorption capacity and was chosen for
further studies. It was found that the Freundlich isotherms best
fitted the data for the adsorption of 4-CP and 2,4,6-TCP. Khalili et al.
(2002) have used the paper mill sludge with chemical activation
process (ZnCl2). The dried, chemically activated, and light and
humidity treated sludge was placed into a quartz reactor. The
pyrolysis was carried out under a flow of nitrogen gas (70 mL/min)
at 800  C for 2 h. Namane et al. (2005) have evaluated the
adsorption capacities of various phenols with granular activated
carbons (GAC) produced from coffee grounds by chemical activa-
tion. They used ZnCl2 and H3PO4 as chemical activator. Adsorption
of phenols on produced and commercial GAC were experimentally
determined in batch mode. Both the Freundlich and Langmuir
models were well suited to fit the isotherm data. Mukherjee et al.
(2007) have studied three carbonaceous materials, activated carbon
(AC), bagasse ash (BA), and wood charcoal (WC), as the adsorbents
for removing phenol from water. Approximately 98%, 90%, and 90%
removal efficiency was achieved for phenol-AC, phenol-WC, and
phenol-BA adsorption systems at given conditions. Experimental
studies indicated that phenol removal with the selected adsorbents
is a first-order adsorption and the Freundlich model well fitted the
data for the adsorption of phenol. Furthermore, Martin et al. (2004)
have converted waste biological sludge to an adsorbent by chemical
activation with H2SO4. Daifullah and Girgis (1998) have studied the
removal of phenol, 3-cresol, 4-cresol, 2-CP, 4-CP, 4-NP, 2,4-DCP, 2,4-
DNP by activated carbons prepared from apricot stone shell using
H3PO4 as activators. Adsorption of phenols increased in the order p-
cresol < 4-NP < 2,4-DNP < 2,4-DCP.
Gonzalez-Serranoa et al. (2004) have studied the adsorption of
phenols by activated carbons prepared from pyrolysis of H3PO4-
impregnated lignin precipitated from kraft black liquors. The appli-
cations of these carbons for removing pollutants were evaluated by
measuring the adsorption capacities for phenol, 2,4,5-TCP and Cr(VI)
as the representatives of toxic contaminants. An impregnation ratio
and an activation temperature of 2 g H3PO4/g lignin and 430  C,
respectively, are recommended as the best combination of operating
conditions to prepare carbons for aqueous-phase applications. Dried
and crushed corncobs were carbonized at 500  C and steam activated
(in one- or two-step scheme), or activated with H3PO4 (El-Hendawy
et al., 2001). Adsorption capacity was demonstrated by the iodine and
phenol numbers, and the isotherms of methylene blue and Pb2þ,
from aqueous solutions. Enhanced porosity was best associated with
chemical activation. Phenol uptake was found to depend on surface
chemical nature of the carbon rather than its porous properties.
Corncobs were postulated to be feasible as feed stock to produce good
adsorbing carbons, under one-step activation scheme outlined here.
3.2. Synthetic resins and zeolite
3.2.1. Zeolites
Zeolites are a naturally occurring crystalline aluminosilicates
consisting of a framework of tetrahedral molecules, linked with
each other by shared oxygen atoms (Mampton, 1997; Townsend,
1991). The price of zeolite itself is considered very cheap about US$
0.03–0.12/kg, depending on the quality of zeolite. Zeolites contain
a wide variety of species such as clinoptilolite and chabazite, in
which clinoptilolite is most abundant in nature and is readily
available from more than 40 natural zeolite species (Vaca-Mier
et al., 2001). Only seven types (mordenite, clinoptilolite, chabazite,
1339
erionite, ferrierite, phillipsite, and analcime) exist in a sufficient
quantity and purity to be considered exploitable. Zeolites have been
received increasing attention for pollution control. An important
property of zeolites is the capacity to be easily regenerated while
keeping their initial properties (Khalid et al., 2004).
Guisnet and Gilson (2002) have studied the application of
zeolite as catalyst and adsorbent. Khalid et al. (2004) have ever
examined the removal of phenol by various zeolites and compared
to that of activated carbons. Zeolites, modified by surfactant, can be
used for the adsorption of different organics. Li et al. (2000) have
studied the adsorption of ionizable organics on a natural zeolite
modified with hexadecyltrimethylammonium bromide (HDTMAB),
a cationic surfactant. The adsorption of phenols using the HDTMAB-
modified zeolite, prepared at different HDTMAB surface coverages,
was affected by solution pH. All of the adsorption isotherms were
linear and could be described by a distribution coefficient (Kd).
Razee and Masujima (2002) have also studied the adsorption of
environmentally important phenolic compounds including phenol,
4-aminophenol, 2-aminophenol, 4-NP, 2-NP, and 2-methyl-4-
nitrophenol. For the removal of tested pollutants, natural zeolites,
natrolite, and clinoptilolite were examined in which the latter
showed better adsorption ranging from 45 to 64% of pollutants
from aqueous solution in 4 h. Modification of zeolites with cyclo-
dextrins (CDs), especially a-CD, considerably improves the
adsorption efficiency to 65–74% for clinoptilolite. Kuleyin (2007)
has studied the adsorption characteristics of phenol and 4-CP by
surfactant-modified zeolite. The adsorption kinetics was tested by
intraparticle diffusion, Elovich equation, and the pseudo-second-
order reaction. The Freundlich isotherm was found to best repre-
sent the adsorption data for phenol and 4-CP. The adsorption of
phenol and three CP isomers from aqueous solution (in the
concentration range 6–600 mg/L) at 20  C has been studied in an
agitated batch vessel using activated carbon and Na–Y and Ni/Na–Y
zeolites as adsorbents (Okolo et al., 2000).
3.2.2. Synthetic resins
Roostaei and Tezel (2004) have examined the liquid-phase
adsorption of phenol from water by silica gel, HiSiv 3000, activated
alumina, activated carbon, Filtrasorb-400, and HiSiv 1000. The
Langmuir–Freundlich type of isotherm model was the best to
describe adsorption equilibrium data for phenol for all the adsor-
bents studied. Kinetic results indicated that HiSiv 1000 had the
highest adsorption rate among the adsorbents. The effects of
particle size, temperature, and thermal regeneration on the
adsorption of phenol by HiSiv 1000 were evaluated. It was found
that adsorption capacity decreased with increasing temperature.
Thermal regeneration of HiSiv 1000 was performed at 360  C. It was
observed that adsorption capacity of HiSiv 1000 did not change
after 14 regeneration cycles. Equilibrium experiments showed that
the adsorption capacities of activated carbon and Filtrasorb-400
were several times higher than that of HiSiv 1000. Removal of
phenolic compounds from industrial wastewater was studied by
adsorption in fixed-bed with polymeric resins (Pan et al., 2005). A
model developed based on constant-pattern wave approach theory
and the Freundlich model was adopted to describe the break-
through curves of phenol and 4-NP adsorption from aqueous
solution through a bed packed with macroreticular resins NDA-100.
Ghiaci et al. (2004) have studied the removal of nonionic organic
contaminants such as benzene, toluene, and phenol from
contaminated wastewater by organo-zeolites. Organo-zeolites
were prepared from synthetic ZSM-5 and natural zeolites, by
exchanging the quaternary amines, HDTMAB and CPB. The
maximum adsorption of CPB on these zeolites is in the order cli-
noptilolite > ZSM-5-88 (SiO2/Al2O3 ¼ 88%) > ZSM-5-31 (SiO2/
Al2O3 ¼ 31%) which is mainly dependent on the external cation
exchange capacity (CEC) of each zeolite. In addition, as-synthesized
1340 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349
MCM-41 molecular sieve was employed for the removal of organic
contaminants from aqueous solution. According to the evaluation
using the Langmuir equation, the maximum organics adsorption by
MCM-41 was much greater than that by natural clinoptilolite and
ZSM-5 zeolites. Carmona et al. (2006) have studied the adsorption
of phenol from water using a strong-base anion exchanger. It was
found that the removal capacity was higher than that of other well
known adsorbents. The pH-dependent equilibrium isotherms can
be explained assuming that the adsorption of phenol in the resin is
accomplished by two ways: ion exchange and molecular adsorp-
tion. Adsorption of phenol onto IRA-420 is predominant at acidic
pH, whereas both adsorption and ion exchange are important at
alkaline pH. Kujawski et al. (2004) reported that Amberlite XAD-4
had the better properties in decontamination of phenol from
solutions. It was shown that regeneration of the resin bed could be
effectively performed with NaOH solution.
Streat and Sweetland (1997) have studied the removal of 2-CP, 3-
CP, and 4-CP from potable water using Hypersol-Macronet resins
(MN-100, MN-150, MN-200). Vinylpyridine-DVB copolymer was
found to have an excellent capacity for removing phenol from water
(Kawabata and Ohira, 1979). The breakthrough capacity of the
copolymer was remarkably higher than that found with porous
styrene-DVB resins with no ionic functional group, and compared
well with that obtained with a weak-base anion exchange resin in
the free base form. The breakthrough capacity of the copolymer was
scarcely affected by the presence of NaCl and Na2SO4. Elution of the
adsorbed phenol from the copolymer was easily accomplished by
a simple treatment with organic solvents such as acetone and
methanol, which was notably easier than those from anion exchange
resins, and thus the copolymer was efficiently regenerated. Ersöz
et al. (2004) have also investigated the removal of phenols with a NP-
imprinted polymer from water by a newly functional monomer,
methacrylamidoantipyrine (MAAP). The adsorption capacity for NP
and other phenols on molecularly imprinted polymers (MIPs)
significantly depend on the use of functional monomers. The
maximum adsorption of NP on MIP beads was 24.1 mg/g for MAAP
and 13.5 mg/g for MAAP-based imprinted polymers. Furthermore,
the pH significantly affected the adsorption capacity of MIPs.
The hyper-crosslinked polystyrene beads with bimodal pore size
distribution were prepared through the Friedel-Crafts modification
using macroreticular poly(vinylbenzylchloride-DVB) copolymer
beads as base polymers (Oh et al., 2003). Their adsorption behav-
iors were examined with aqueous solutions of phenol, 4-CP, and
2,4-DCP. The biporous hyper-crosslinked beads gave not only faster
adsorption kinetics than commercial polystyrene adsorbents, but
also larger adsorption capacity. Abburi (2003) has studied the
removal of phenol and 4-CP from synthetic single and bisolute
aqueous solutions at 30  C through the adsorption on Amberlite
XAD-16 resin under batch equilibrium and dynamic column
conditions. The equilibrium data from single component solutions
were fitted to the Langmuir and Freundlich models to evaluate the
model parameters, and the parameters in turn were used to predict
the extent of adsorption from bisolute aqueous solutions using the
ideal solution adsorption model. The effects of pH on the removal of
phenol and 4-CP from single and bisolute systems were also
studied. The breakthrough capacity and total capacity of the resin
for the solutes at different concentrations were evaluated through
column studies. Attempts were made to regenerate the resin by
solvent washing using methanol. The limited number of adsorp-
tion–desorption cycles indicated that the adsorption capacity of the
resin remained unchanged.
The adsorption of phenols (2-CP, 2,4-DCP, 2,4,6-TCP, 2-NP, 2,4-
DNP, 2-methylphenol (2-MP), and 2,4-DMP) from aqueous solution
by Amberlite XAD-4 resin was studied under different conditions (Ku
and Lee, 2000). The adsorption of various phenols by XAD-4 could be
described by either the Langmuir or Freundlich model. The removal
of phenols by XAD-4 resin for aqueous solutions with different pH
varies significantly and can be explained by the species distribution
of phenols in solutions. Phenols were effectively removed by XAD-4
at acidic medium where the presence of molecular phenol species
dominates. The removal decreased sharply at alkaline medium
where the negatively-charged phenol species is dominant. Denizli
et al. (2001) have used cibacron blue F3GA-carrying poly(2-hydrox-
yethylmethacrylate) (PHEMA) microbeads as dye-affinity adsorbents
for the removal of phenol, 3-CP, 4-CP, and 2,4,6-TCP. Adsorption rates
of CPs were very high, and equilibrium was achieved in 20 min. The
maximum adsorption onto cibacron blue-carrying microbeads was
8.4 mg/g for phenol, 18.7 mg/g for 2,4,6-TCP, 12.5 mg/g for 4-CP, and
14.1 mg/g for 3-CP. The affinity decreases in the order 3-CP > 4-
CP > 2,4,6-TCP > phenol. The adsorption of chlorophenols (CPs)
decreased with increasing pH. Moreover, desorption of CPs was
achieved using methanol (30% v/v). The cibacron blue F3GA-carrying
microbeads are suitable for repeated use for more than five cycles
without any noticeable loss of adsorption capacity. Besides, they also
used PHEMA microbeads as the dye-affinity adsorbents for the
removal of phenol, 2-NP, 4-NP, and 2,4-DNP from aqueous solutions
(Denizli et al., 2002). The PHEMA microbeads were prepared by
radical-suspension polymerization of HEMA in the presence of azo-
bisisobutyronitrile as the initiator. The maximum adsorption of
phenols onto the microbeads carrying alkali blue 6B was 13.7 mg/g
for phenol, 16.2 mg/g for 2,4-DNP, 15.6 mg/g for 4-NP, and 14.5 mg/g
for 2-NP. The affinity decreases in the order phenol > 4-NP > 2-
NP > 2,4-DNP. The desorption of NPs was also achieved using 30% v/v
methanol solution.
3.3. Industrial waste/by-product
Recently, many studies focused on the removal of phenols from
water by industrial wastes or by-products. The most important
ones of such adsorbents are coal (Ahmaruzzaman and Sharma,
2005; Ahsan et al., 1994; Haghseresht and Lu, 1998; Hobday et al.,
1994; Tarasevich, 2001), fly ash (Acharya, 2005; Batabyal et al.,
1995; Gupta et al., 1998; Srivastava et al., 2006; Wang and Jiang,
2007), red mud (Gupta et al., 2004; Tor et al., 2006), and waste
sludge (Jain et al., 2004; Rio et al., 2005; Otero et al., 2003).
3.3.1. Coal
Coal has been reported to be a suitable adsorbent for 4-NP by
Hobday et al. (1994). In fact, the adsorption of phenolic compounds
on coal-reject-derived adsorbents was also investigated
(Haghseresht and Lu, 1998). Carbonaceous adsorbents were ever
prepared by heat treatment of coal-reject at 600  C, after chemical
treatment by HNO3, H2SO4, and NaOH at 25 and 75  C. Pore
structure characterization and phenol adsorption capacities of
the adsorbents showed that HNO3-pretreatment significantly
enhanced the surface properties, consequently the adsorption
capacity of the adsorbent. In their case, the Freundlich equation
was found to give the best fit. However, pretreated coal has been
found to be better than the original coal as an adsorbent for phenol
removal (Ahsan et al., 1994). Coal is known to possess good
microporosity and thus a large surface area, although the utiliza-
tion of the pores in the reaction/interaction of the surface is poor.
Attempts to improve the surface and porosity of the coal by
different coal conversion processes such as oxidation, pyrolysis,
and solvent extraction, separately or in combination, appear to be
a rewarding field of research on adsorption. Ahmaruzzaman and
Sharma (2005) have used coal, residual coal, and the residual coal
treated with H3PO4 as a medium for removal of phenol from
wastewater. Other low-cost adsorbents such as petroleum coke,
coke breeze, rice husk, and rice husk char have also been used. The
effects of system variables such as pH, contact time, and temper-
ature were examined. Tarasevich (2001) has shown that natural
 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349 1341

long-flame coal from the Donbas field has a well-developed micro-
and meso-porous structure and may adsorb a wide range of
organic compounds from water. This property, along with its low-
cost, makes this coal a promising material for the purification of
natural and wastewaters.
3.3.2. Red mud
Red mud residues as unconventional adsorbents for water and
wastewater treatment are motivated by the fact that red mud is
a fine-grained mixture of oxides and hydroxides, capable of
removing several contaminants, as well as being widely available.
The waste red mud from alumina refineries costs about US$ 25/ton,
which includes the cost of its purchase, transport, chemicals,
electrical energy used in the process, and labor required. Thus, the
developed red mud adsorbent may be considered as a good
replacement for commercially available carbon. Tor et al. (2006)
have studied the adsorption of phenol with red mud as functions of
contact time, pH, initial phenol concentration, red mud dosage, and
effect of salt addition. Experimental results demonstrated that the
maximum phenol removal was obtained in a wide pH range of 1.0–
9.0 and it took 10 h to attain equilibrium. The isotherm data were
analyzed using the Langmuir and Freundlich models, and it was
found that the latter represented the measured data better. The
influence of added salt on phenol removal depends on the relative
affinity of the anions for red mud surface and the relative
concentrations of the anions.
Efforts have been made to convert red mud into a low-cost
adsorbent, and the final material has been used for the removal of
phenol, 2-CP, 4-CP, and 2,4-DCP from wastewater (Gupta et al.,
2004). The adsorption was endothermic in nature and follows both
the Langmuir and Freundlich models. The adsorption decreases in
the order 2,4-DCP > 4-CP > 2-CP > phenol, which indicates that the
substitution of chlorine atom increases the adsorption capacity.
Higher adsorption of 2,4-DCP is due to free availability of para-
chlorine atom, while the ortho-chlorine atom of 2-CP remain
bound with phenolic group through intramolecular hydrogen
bonding. On the other hand, the chlorine atom of 4-CP remains
bounded with phenolic group through intermolecular hydrogen
bonding and, hence, not available for adsorption. Briefly, the
adsorption of phenols on red mud is due to the positive surface of
red mud, which attracts the negatively-charged phenolic species
(Gupta et al., 2004).
3.3.3. Bagasse fly ash (BFA)
Bagasse fly ash, obtained from the sugar industry, could be
utilized for phenol removal (Gupta et al., 1998; Srivastava et al.,
2006). The waste bagasse fly ash costs about US$ 20.0/ton including
the cost of purchase, transport, chemicals, electrical energy used in
the absorbent development and labor required. Srivastava et al.
(2006) have studied the adsorption of phenol on carbon rich
bagasse fly ash (BFA). Optimum conditions for phenol removal were
found to be pH 6.5, adsorbent dosage 10 g/L of solution, and equi-
librium time 5 h. Adsorption of phenol followed the pseudo-
second-order kinetics with the initial rate on laboratory-grade
activated carbon being the highest, followed by those on BFA and
commercial-grade activated carbon. The Redlich–Peterson
isotherm was found to best represent the data for phenol adsorp-
tion on all the adsorbents. The change in entropy and enthalpy for
phenol adsorption on BFA was 169 J/(mol K) and 47 kJ/mol,
respectively. The highly negative change in Gibbs free energy
indicated the spontaneous adsorption of phenol on BFA.
The removal of phenol and 4-NP using BFA was also studied by
Gupta et al. (1998), in which the effects of pH, BFA dosage, phenol
concentration, and added surfactants on the adsorption were
examined. The adsorption data follow both the Langmuir and
Freundlich models. The negative value of enthalpy change
(10.4 kJ/mol for phenol, 15.8 kJ/mol for 4-NP) suggested the
exothermic nature and the possibility of strong bonding between
solutes and the adsorbent. A positive entropy of adsorption (88.6 J/
(mol K) for phenol, 68.9 J/(mol K) for 4-NP) also reflected the
affinity of the adsorbent material toward phenol and 4-NP.
3.3.4. Coal fly ash (CFA)
Coal fly ash (CFA) is produced as a fine, non-combustible residue
carried off in the flue gas during burning of coal. The disposal
requires large quantities of land and water. Currently, CFA appli-
cations are limited to civil engineering use including cement and
brick production and use in roadbeds. Hobday et al. (1994) had
studied the removal of NP from aqueous solution using low rank
coal-based adsorbents. Sarkar and Acharya (2006) have studied the
removal of phenol and its analogs from water with CFA. The equi-
librium data was best fitted by the Langmuir model. The process
was endothermic and thermodynamically spontaneous in nature.
The positive value of entropy change suggested the increased
randomness. The use of CFA as an adsorbent for phenolic
compounds was found to be cost effective and thus can be
considered as an alternative to activated carbon. The leaching test
carried out with water indicated that the disposal of CFA did not
pose any extra load of phenolic compounds to the landfill, as no
release of phenols from CFA bed occurs. Moreover, phenolic
compounds can be recycled and utilized as industrial raw materials
as they can be recovered quantitatively from the CFA bed. Batabyal
et al. (1995) have studied the adsorption of 2,4-DMP from aqueous
solutions with CFA. The rate follows first-order kinetics, and is
affected by diffusion and kinetic resistance. Equilibrium adsorption
data satisfy both the Langmuir and Freundlich isotherms.
Wang and Jiang (2007) have also reported that CFA was effective
for the removal of 2-sec-butyl-4,6-dinitrophenol (BDNP) from
wastewater. The high adsorption capacity and removal efficiency of
BDNP from solutions can be achieved at pH 4.0 with an adsorbent

Table 3
Comparison of various synthetic-activated carbons for the adsorption of phenol and its derivatives.

Adsorbent Solute pH T ( C) Model used Capacity (mg/g) Reference

Coconut-shell AC 4-CP – – Langmuir 72.8 Radhika and Palanivelu (2006)
Coconut-shell AC 2,4,6-TCP – – Langmuir 122.3
IIT carbon Phenol – – Freundlich KF ¼ 0.44, 1/n ¼ 0.87 Khalili et al. (2002)
PAC Phenol – – Langmuir 3.22 Namane et al. (2005)
PAC Phenol – – Freundlich KF ¼ 1.07, 1/n ¼ 1/2.7
AC Phenol – 25 Freundlich KF ¼ 2.60, 1/n ¼ 1.14 Mukherjee et al. (2007)
BA Phenol – 25 Freundlich KF ¼ 0.233, 1/n ¼ 1.51
WC Phenol – 25 Freundlich KF ¼ 0.171, 1/n ¼ 0.93
AC (apricot stone shell) 2,4-DCP – – Langmuir 339 Daifullah and Girgis (1998)
AC (apricot stone shell) 2,4-DNP – – Langmuir 232
AC (from kraft black liquor) Phenol 6 25 Langmuir 227 Gonzalez-Serranoa et al. (2004)
AC (from kraft black liquor) 2,4,6-TCP 6 25 Langmuir 476
AC (from corncob) Phenol – – – 177.6 El-Hendawy et al. (2001)
1342 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349

dosage of 5 g/L of particles with a size of 160–200 mesh at 20  C and
a contacting time of 120 min. The adsorption of BDNP increases
when temperature is increased, thereby indicating that the removal
is endothermic in nature. The rate of BDNP adsorption on CFA
appeared to be controlled by film diffusion at lower concentrations,
but dominated by a particle diffusion mechanism at higher
concentrations. The pseudo-second-order kinetic model can be
applied to determine the rate constants in the temperature range
20–40  C at constant concentration. Their study revealed that CFA
can be fruitfully used as an adsorbent for BDNP removal.

Table 4
Comparison of various synthetic resins for the adsorption of phenol and its derivatives.

Adsorbent Solute T ( C) Model used Capacity (mg/g) Reference

Filtrasorb-400 Phenol 205.1 Roostaei and Tezel (2004)
HiSiv 1000 Phenol 319
NDA-100 Phenol 25 Langmuir 207.7 Pan et al. (2005)
NDA-100 Phenol 30 Langmuir 154.1
NDA-100 4-NP 25 Langmuir 140.9
ZSM-5-31 (HDTMA-zeolite) Phenol – Langmuir 7.4 Ghiaci et al. (2004)
HDTMA-Clinoptilolite zeolite Phenol – Langmuir 11.4
MCM-41 Phenol – Langmuir 59.4
IRA-420 Phenol – Langmuir 316.8 Carmona et al., 2006
XAD-7 Phenol – Freundlich KF ¼ 0.03, n ¼ 0.71 Deosarkar and Pangarkar (2004)
XAD-4 Phenol – Freundlich KF ¼ 0.02, n ¼ 0.57
XAD-2 Phenol – Freundlich KF ¼ 0.08, n ¼ 1.17
IMN-2 Phenol – Freundlich KF ¼ 0.34, 1/n ¼ 1.2
XAD-7 Phenol 25 Freundlich KF ¼ 16.1, 1/n ¼ 2.2 Kujawski et al. (2004)
XAD-16 Phenol 25 Freundlich KF ¼ 22.5, 1/n ¼ 2.2
XAD-4 Phenol 25 Freundlich KF ¼ 31.8, 1/n ¼ 2.3
MN-100 Phenol 25 Langmuir 72.5 Streat and Sweetland (1997)
MN-150 Phenol 25 Langmuir 85.4
MN-200 Phenol 25 Langmuir 86.6
MN-100 2-CP 25 Langmuir 125.7
MN-150 2-CP 25 Langmuir 125.7
MN-200 2-CP 25 Langmuir 136.2
MN-100 3-CP 25 Langmuir 143.9
MN-150 3-CP 25 Langmuir 151.6
MN-200 3-CP 25 Langmuir 174.1
MN-100 4-CP 25 Langmuir 140.6
MN-150 4-CP 25 Langmuir 144.4
MN-200 4-CP 25 Langmuir 163.2
Copolymer of 72 mol% 4-vinylpyridine (4-VP) with DVB Phenol – Breakthrough capacity 275 Kawabata and Ohira (1979)
Copolymer of 71 mol% 2-vinylpyridine with DVB Phenol – Breakthrough 240
Amberlite IRA-400 Phenol – Breakthrough 405
Amberlite IR-45 Phenol – Breakthrough 272
XAD-4 Phenol – Breakthrough 150
XAD-2 Phenol Breakthrough 89
MAAP 4-NP Kd 21.2 Ersöz et al. (2004)
MAAP Phenol Kd 6.2
MAAP 2-cresol Kd 8.4
MAAP 4-CP Kd 10.1
MAAP 2,6-DCP Kd 4.3
MAA 4-NP Kd 10.9
MAA Phenol Kd 5.2
MAA 2-cresol Kd 4.7
MAA 4-CP Kd 5.7
MAA 2,6-DCP Kd 2.6
20% PVBC Phenol 25 Freundlich KF ¼ 1.04, 1/n ¼ 2.56 Oh et al. (2003)
Amberlite XAD-4 Phenol 25 Freundlich KF ¼ 0.21, 1/n ¼ 0.98
Ambercorb XE340 Phenol 25 Freundlich KF ¼ 0.09, 1/n ¼ 0.57
Amerlite XAD-2 Phenol 25 Freundlich KF ¼ 0.01, 1/n ¼ 0.34
20% PVBC 4-CP 25 Freundlich KF ¼ 1.31, 1/n ¼ 2.22
Amberlite XAD-4 4-CP 25 Freundlich KF ¼ 0.56, 1/n ¼ 1.59
Ambercorb XE340 4-CP 25 Freundlich KF ¼ 0.35, 1/n ¼ 1.23
Amberlite XAD-2 4-CP 25 Freundlich KF ¼ 0.24, 1/n ¼ 1.33
20% PVBC 2,4-DCP 25 Freundlich KF ¼ 1.04, 1/n ¼ 2.56
Amberlite XAD-4 2,4-DCP 25 Freundlich KF ¼ 10.1, 1/n ¼ 1.78
Ambercorb XE340 2,4-DCP 25 Freundlich KF ¼ 0.85, 1/n ¼ 1.58
Amberlite XAD-2 2,4-DCP 25 Freundlich KF ¼ 0.83, 1/n ¼ 0.98
Amberlite XAD-16 Phenol – Langmuir 141 Abburi (2003)
Amberlite XAD-16 4-CP – Langmuir 291.6
XAD-4 2-NP – Langmuir 931.3 Ku and Lee (2000)
XAD-4 2-NP – Freundlich KF ¼ 0.21, 1/n ¼ 1.3
PHEMA microbead modified cibacron blue Phenol 20 – 8.3 Denizli et al. (2001)
PHEMA microbead modified cibacron blue 2,4,6-TCP 20 – 18.7
PHEMA microbead modified cibacron blue 4-CP 20 – 12.5
PHEMA microbead modified cibacron blue 3-CP 20 – 14.0
PHEMA microbead modified alkali blue 6B Phenol 20 – 13.6 Denizli et al. (2002)
PHEMA microbead modified alkali blue 6B 2,4-DCP 20 – 16.1
PHEMA microbead modified alkali blue 6B 4-NP 20 – 15.6
PHEMA microbead modified alkali blue 6B 2-NP 20 – 14.5
 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349 1343

Table 5 process for different industrial applications. Carbonization experi-

Comparison of various coal adsorbents for the adsorption of phenol and its ments were carried out on two kinds of sludge, namely viscous
derivatives.
liquid sludge and limed sludge by varying carbonization tempera-
Adsorbent Solute T ( C) Model used Capacity Reference ture between 400 and 1000  C. The basic character of the carbon-
(mg/g) ized residues increases with increasing carbonization temperature.
Samla coal Phenol 25 Langmuir 13.3 Ahmaruzzaman and Then, carbonization allowed specific surface area and pore volumes
Sharma (2005)
to be developed. Carbonized viscous liquid sludge and carbonized
Samla coal 4-NP 25 Freundlich 51.5
Samla coal 4-CP 25 Langmuir 50 limed sludge are mainly mesoporous in nature, with specific
Residual coal (RC) phenol 25 Redlich– 45.5 surface areas reaching 100 and 60 m2/g, respectively. Finally,
Peterson adsorption experiments showed that carbonized viscous liquid
Residual coal (RC) 4-NP 25 Langmuir 86.9 sludge and limed sludge can remove effectively Cu2þ, acid/basic
Residual coal (RC) 4-CP 25 Langmuir 82.6
RC treated with H3PO4 Phenol 25 Langmuir 142.8
dyes, and phenol. According to the properties of pyrolyzed sludge,
RC treated with H3PO4 4-NP 25 Freundlich 256.4 the preparation of activated carbons by physical activation process
RC treated with H3PO4 4-CP 25 Langmuir 243.9 seemed to be encouraged.
Petroleum coke Phenol 25 Langmuir 6.0 Otero et al. (2003) have used the adsorbents produced from
Petroleum coke 4-NP 25 Langmuir 11.1
sewage sludge in organic pollutant removal. After chemical acti-
Petroleum coke 4-CP 25 Freundlich 9.3
Rice husk Phenol 25 Langmuir 4.5 vation and pyrolysis treatment, sewage sludge provided materials
Rice husk 4-NP 25 Langmuir 15.3 of great porosity and high surface area. The properties of this type
Rice husk 4-CP 25 Langmuir 14.4 of material were studied by liquid-phase adsorption using crystal
Rice husk char Phenol 25 Langmuir 7.9 violet, indigo carmine, and phenol as the solutes. It is found that
Rice husk char 4-NP 25 Freundlich 39.2
Rice husk char 4-CP 25 Langmuir 36.2
activated carbons prepared from sewage sludge were promising for
Coal-reject Phenol 25 Langmuir 277.0 Haghseresht and this purpose.
Lu (1998)
Coal-reject 4-NP 25 Langmuir 56.2 3.3.7. Clay and modified clay
Coal-reject 4-CP 25 Langmuir 60.2
It is known that there are three basic species of clay: smectites
Natural coal Phenol 25 – 18.8 Tarasevich (2001)
(such as montmorillonite), kaolinite, and micas; out of which
montmorillonite has the highest CEC and that its current market
price (US$ 0.04–0.12/kg) is considered to be 20 times cheaper than
3.3.5. Carbonaceous adsorbents that of activated carbon. Clay minerals are widespread and abundant
Jain et al. (2004) have utilized blast furnace slag, dust, and in both aquatic and terrestrial areas. They can adsorb cationic,
sludge from steel plants, as well as carbon slurry from fertilizer anionic, and neutral species. They also take part in cationic and
plants after treatment as inexpensive adsorbents for the removal of anionic exchange processes. The adsorption capacities due to
phenols. The characterization of the adsorbents has shown that cationic and anionic exchange and the binding energy varied widely.
carbonaceous adsorbent prepared from carbon slurry possesses Bentonite typically has low organic carbon content; thus, nonionic
high porosity and maximum surface area (380 m2/g), compared to solute adsorption by partition into the bentonite organic matter is
those prepared from blast furnace slag, dust, and sludge adsorbents also relatively weak. Thus, bentonite is not a strong medium for
(4–28 m2/g). The adsorption of phenols on carbonaceous adsorbent adsorption of nonionic organics from water (Banat et al., 2000; Boyd
was substantial and found to be 17.2, 50.3, 57.4, and 132.5 mg/g for et al., 1988; Nayak and Singh, 2007; Smith and Jaffe, 1991).
phenol, 2-CP, 4-CP, and 2,4-DCP, respectively. The adsorption Many studies on adsorption removal of phenol and its deriva-
process follows the Langmuir model, first-order, and was pore tives from water by organoclay were reported (Banat et al., 2000;
diffusion controlled. As the adsorption of phenols on prepared Nayak and Singh, 2007). Organobentonites are produced by the
carbonaceous adsorbent (US$ 0.1/kg) is significant, its performance exchange of organic cations (typically having a quaternary ammo-
has been evaluated with respect to standard activated charcoal. The nium and aliphatic structure) for inorganic ions (e.g., Hþ, Naþ, Ca2þ)
removal efficiency of phenols using carbonaceous adsorbent was on the layer surfaces of bentonite (Zhu and Zhu, 2007). The surface
found to be about 45% of that using a standard activated charcoal properties of modified bentonite may be altered significantly by
sample. this exchange reaction. The modified surfaces of organobentonite
may become organophilic because that the organic functional
3.3.6. Sewage sludge groups of quaternary ammonium cations are not strongly hydrated
Sewage sludges are by-products derived from regular activities by water. As a result, organobentonites are powerful adsorbents for
of wastewater treatment plants. An average production of 40–60 g nonionic organics relative to natural bentonite and other clays
dry matter/inhabitant/day is typical for urban sewage plants, to (Huang et al., 2007; Juang et al., 2002). Some organobentonites
which must be added a corresponding amount produced by could effectively remove organic pollutants from water, and were
industrial sewage plants. Rio et al. (2005) have prepared the suggested for use in wastewater treatments (Holsen et al., 1991;
adsorbent from sewage sludge by pyrolysis (or carbonization) Park and Jaffe, 1993). Smith et al. (1990), Smith and Galan (1995)
have shown that adsorption of tetrachloromethane on the
bentonite modified with exchanged small organic cations was
Table 6
Comparison of various red mud adsorbents for the adsorption of phenol and its
characterized by nonlinear isotherms, strong solute adsorption, and
derivatives. competitive adsorption. Zhu and Zhu (2007) have studied

Adsorbent Solute T ( C) Model used Capacity Reference Table 7

(mg/g) Adsorption capacity of phenol and its derivatives on bagasse fly ash (BFA)
Red mud 2,4-DCP 30 Langmuir 130 Gupta et al. (2004) adsorbents.
Red mud 4-CP 30 Langmuir 127.1
Red mud 2-CP 30 Langmuir 117.3 Adsorbent Solute T ( C) Model used Capacity (mg/g) Reference
Red mud Phenol 30 Langmuir 59.2 BFA Phenol 30 Langmuir 23.83 Srivastava et al. (2006)
Neutralized Phenol – Langmuir 4.13 BFA Phenol 30 Langmuir 0.67 Gupta et al. (1998)
red mud BFA 4-NP 30 Langmuir 1.15
1344 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349

Table 8
Comparison of various ash adsorbents for adsorption of phenol and its derivatives.

Adsorbent Solute pH T ( C) Model used Capacity (mg/g) Reference

Fly ash BDNP 4 30 6.6 Wang and Jiang (2007)
Coal fly ash 2,4-DMP – 31 Langmuir 3.0 Batabyal et al. (1995)
Coal fly ash Phenol – 40 Langmuir 17.1 Sarkar and Acharya (2006)
Coal fly ash 2-hydroxyphenol – 40 Langmuir 8.2
Coal fly ash 3-hydroxyphenol – 40 Langmuir 9.1
Coal fly ash 4-NP – 40 Langmuir 10.8
Briquette char 4-NP – – – 95.0 Hobday et al. (1994)
Tower char 4-NP – – – 80.0
Yallourn coal 4-NP – – – 12.0

simultaneous adsorption of organic compounds and phosphate and it was represented by a second-order polynomial. Although the
from water by inorganic–organic bentonites (IOB), which would Freundlich equation fitted well, it failed to represent the plateau
contribute to the treatment of wastewater containing both of these and the second region that appeared in the isotherm. Hence, an
contaminants. The organoclay was synthesized by intercalating equation correlating the equilibrium concentration and initial and
bentonite with cetyltrimethylammonium bromide (CTAB). adsorbent concentrations was suggested. Borisover et al. (2001)
Adsorption experiments with phenol, 4-CP, or 2,4-DCP, together have used the dye–clay complexes for the removal of non-ionic
with phosphate, demonstrated that IOB could simultaneously organics from water. Danis et al. (1998) have also studied the
remove organics and phosphate from water, due mainly to the removal of chlorinated phenols from aqueous solutions by
partition and ligand exchange mechanism, respectively. adsorption on alumina pillared clays. In their study, the removal
Juang et al. (2002) have also studied the equilibrium and kinetic efficiency was 26.3%, 75.6%, and 95.2% for 2,4-DCP, 2,4,6-TCP, and 4-
of the adsorption of phenol, 3-NP, and o-cresol from water on CP, respectively, with an initial concentration of 25–200 mg/L and
montmorillonite modified with CTAB. The adsorption capacity a dosage of 10 g/L.
decreased in the order phenol > 2-cresol > 3-NP. The Langmuir,
dual-mode adsorption, and Redlich–Peterson models were tested 3.3.8. Metals
to fit the isotherms of single solute systems, whereas the Langmuir Adak et al. (2006) have indicated alumina to be a very efficient
competitive model was used to describe bisolute equilibria. Huang adsorbent for the removal of anionic surfactant from highly
et al. (2007) have studied the removal of phenol using octodecyl concentrated wastewater. After the removal of surfactant in several
trimethylammonium chloride (OTMAC)-modified attapulgite from cycles, the exhausted surfactant-coated alumina becomes useless.
aqueous solutions. The comparison of natural attapulgite and This exhausted alumina, however, possess the ability to remove
modified attapulgite showed that it is possible to utilize the organics from aquatic environment through the process called
sonication-modified OTMAC-attapulgite in the treatment of adsolubilization. In their study, the exhausted alumina, hereafter
phenol-polluted water. The adsorption kinetics was described by designated as surfactant (sodium dodecyl sulfate, SDS)-modified
a pseudo-second-order model. The Freundlich model was found to alumina (SMA), was used for adsorptive removal of phenol from
be applicable for describing the equilibrium data. water. It was found that the removal followed the second-order
Yapar et al. (2005) have studied the effect of adsorbent dosage kinetics. Studies were conducted to see the effect of SMA dosage on
on the adsorption of phenol by hexadecyltrimethylammonium the removal of phenol. The pH was maintained at 6.7. SMA was
bromide (HDTMAB)-modified bentonite. Experiments were con- found to be very efficient and 90% efficiency could be achieved
ducted in two stages. The adsorption of HDTMAB on bentonite was under optimized conditions for the removal of phenol from phenol-
studied in the first group of experiments. It was found that the all spiked distilled water. Desorption of both SDS and phenol from the
HDTMAB was adsorbed by bentonite, even when the amount used SMA surface was possible using 0.25 M NaOH solutions. Desorption
exceeded 100% of CEC. After the modification of bentonite by of phenol only is also possible by acetone or rectified spirit.
HDTMAB in an amount equivalent to 100% of CEC, adsorption
experiments were performed at different adsorbent dosages 3.3.9. Biosorbents
ranging from 2 to 10 g/L. A type V isotherm and a nonlinear Microorganisms such as bacteria, fungi, yeast, algae, and plant
increase in percent removal with adsorbent dosage were observed. can remove some pollutants from aqueous solutions, and such
The nonlinear relationship between the percent removal and biological phenomena are called biosorption. This term is adopted
adsorbent dosage was due to the effect of intraparticle interactions, to indicate a number of metabolism independent processes
(physical and chemical adsorption, ion exchange, complexation,
Table 9 chelation, and micro-precipitation) taking place essentially in the
Comparison of various waste sludge adsorbents for the adsorption of phenol and its cell wall. The main attraction of biosorption is cost effective and has
derivatives. good removal performance. Raw materials which are either abun-
Adsorbent Solute T ( C) Model used Capacity Reference dant (sea weeds) or wastes from other industrial operations
(mg/g) (fermentation wastes, activated sludge processing wastes) can be
Carbonaceous adsorbent Phenol 25 Langmuir 17.2 Jain et al. (2004) used as the biosorbents presenting performances often comparable
Carbonaceous adsorbent 2-CP 25 Langmuir 50.3
Carbonaceous adsorbent 4-CP 25 Langmuir 57.4 Table 10
Carbonaceous adsorbent 2,4-DCP 25 Langmuir 132.5 Comparison of various sewage sludge adsorbents for the adsorption of phenol.
Blast furnace sludge Phenol 25 Langmuir 7.5
Blast furnace sludge 2-CP 25 Langmuir 20.4 Adsorbent Solute T ( C) Model used Capacity Reference
Blast furnace sludge 4-CP 25 Langmuir 22.8 (mg/g)
Blast furnace sludge 2,4-DCP 25 Langmuir 29.1 Activated sewage sludge Phenol 25 Langmuir 42.0 Otero et al. (2003)
Blast furnace dust Phenol 25 Langmuir 5.3 (H2SO4)
Blast furnace dust 2-CP 25 Langmuir 14.0 Pyrolysis sewage sludge Phenol 25 Langmuir 5.56
Blast furnace dust 4-CP 25 Langmuir 16.2 Thermal (400–800 C) Phenol 20 Langmuir 152–185 Rio et al. (2005)
Blast furnace dust 2,4-DCP 25 Langmuir 29.1 sewage sludge
 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349 1345

Table 11
Comparison of various clay or metallic adsorbents for the adsorption of phenol and its derivatives.

Adsorbent Solute pH T ( C) Model used Capacity (mg/g) Reference

Bentonite Phenol 5 – Langmuir 1.7 Banat et al. (2000)
Clay (quartz, kalinite, etc.) 50 mm Phenol 6.5 30 Langmuir 30.3 Nayak and Singh (2007)
CTAB-bentonite Phenol – – Linear Kd ¼ 150 Zhu and Zhu (2007)
CTAB-Al1-bentonite Phenol – – Linear Kd ¼ 160
CTAB-Al4-bentonite Phenol – – Linear Kd ¼ 140
CTAB-Al10-bentonite Phenol – – Linear Kd ¼ 130
CTAB-montmorillonite Phenol – 25 Langmuir 94.9 Juang et al. (2002)
CTAB-montmorillonite 3-NP – 25 Langmuir 105.6
CTAB-montmorillonite 2-cresol – 25 Langmuir 97.3
OTMAC-attapulgite Phenol – 25 Freundlich KF ¼ 14.53, 1/n ¼ 0.843 Huang et al. (2007)
HDTMAB-bentonite Phenol – 25 Freundlich KF ¼ 0.017, 1/n ¼ 1.16 Yapar et al. (2005)
SDS-alumina Phenol 6.7 Langmuir 6.6 Adak et al. (2006)
Dye-montmorillonite (rhodamine B) Phenol – 22 Nonlinear Kd ¼ 81 Borisover et al. (2001)
Dye-montmorillonite (crystal violet) Phenol – 22 Nonlinear Kd ¼ 151

with those of ion exchange resins. The mechanism of binding by
inactivated biomass may depend on the chemical nature of
pollutant (species, size, ionic charge), type of biomass, its prepa-
ration and its specific surface properties, and the environmental
conditions (pH, temperature, ionic strength, existence of competing
organic or inorganic ligands in solution). As hydrophobic organic
pollutants show a high tendency to accumulate onto microbial cells
or sludge, the microbial biomass could be used as an adsorbent of
biological origin for the removal of very low level hazardous
organics from wastewater. For these reasons biosorption can be
considered a promising technology for phenol removal from
industrial streams and polluted natural waters. For simplicity bio-
sorbents are subdivided into the following categories: (1) activated
sludge, (2) fungi, and (3) plants.
Aksu and Gönen (2004) have used Mowital B30H resin immo-
bilized dried activated sludge as a biosorbent for the removal of
phenol from aqueous solutions. The effect of flow rate and inlet
phenol concentration on the adsorption characteristics was studied
at pH 1.0. The equilibrium data could be fitted by both Freundlich
and Langmuir models under the concentration ranges studied.
Aksu and Yener (1998) have studied the biosorption of phenol, 2-
CP, and 4-CP from aqueous solutions on the dried activated sludge.
The maximum loading capacity of biosorbent was found to be
86.1 mg/g for phenol, 102.4 mg/g for 2-CP, and 116.3 mg/g for 4-CP.
Tsezos and Bell (1989) have also compared the biosorption and
desorption of toxic organic pollutants by live and dead biomass. Rao
and Viraraghavan (2002) have investigated the removal of phenol
from water using non-viable pretreated cells of Aspergillus niger.
Five types of non-viable pretreated A. niger biomass powders were
used as biosorbents to remove phenol from water at a concentra-
tion of 1 mg/L. The H2SO4-treated non-viable biomass powder,
which was the most effective, was used in further studies. The
maximum removal of phenol was observed at an initial pH of 5.1 for
the H2SO4-treated biomass. Garcia et al. (2000) have studied the
adsorption capability and kinetic behavior of several fungi to deal
with olive mill wastewater to reduce phenol content. The removal
of total phenols relative to the total organic load consumed, which
might indicate a measure of the selectivity with which the micro-
organisms remove phenols among other organic compounds
present, indicates the order Phanerochaete chrysosporium >
Aspergillus niger > Aspergillus terreus.
Calace et al. (2002) have studied the adsorption of paper mill
sludge for phenol, 2-CP, 3-CP, 4-CP, 2-NP, 4-NP, 2,4-DCP, 3,4-DCP,
3,5-DCP, and 2,4,5-TCP. Kinetic experiments showed that adsorp-
tion of substituted phenol on paper mill sludge was rapid (equi-
librium was reached after 3 h); conversely, the time taken by
phenol to reach equilibrium conditions was 260 h. Experimental
data showed that particle diffusion was involved in the adsorption
process but was not the only rate-limiting mechanism. The
adsorption isotherms indicated the following order of retention
capacity of paper mill sludge 2-NP ¼ 4-NP << 2-CP < phenol <
4-CP < 3-CP < 2,4-DCP <3,4-DCP ¼ 2,4,5-TCP < 3,5-DCP. In all cases,
the experimental data showed a good fit with the Hill equation,
which is mathematically equivalent to the Langmuir–Freundlich
model obtained by assuming that the surface is homogeneous and
the adsorption is a cooperative process influenced by solute–solute
interactions. Sathishkumar et al. (2007) have also investigated the
removal of 2,4-DCP from aqueous solutions on palm pith carbon

Table 12
Comparison of various sludge adsorbents for the adsorption of phenol and its derivatives.

Adsorbent Solute pH T ( C) Model used Capacity (mg/g) Reference

Dried activated sludge Phenol 1 25 Langmuir 9.6 Aksu and Gönen (2004)
Dried activated sludge Phenol 1 25 Langmuir 86.1 Aksu and Yener (1998)
Dried activated sludge 2-CP 1 25 Langmuir 102.4
Dried activated sludge 4-CP 1 25 Langmuir 116.3
H2SO4-treated Aspergillus niger Phenol 5.1 21 Langmuir 0.33 Rao and Viraraghavan (2002)
Paper mill sludge 2-CP 7 20 Langmuir 0.34 Calace et al. (2002)
Paper mill sludge 3-CP 8 20 Langmuir 1.04
Paper mill sludge 4-CP 8 20 Langmuir 0.99
Paper mill sludge 2-NP 8 20 Langmuir 0.12
Paper mill sludge 4-NP 8 20 Langmuir 0.31
Paper mill sludge 2,4-DCP 8 20 Langmuir 2.72
Paper mill sludge 3,4-DCP 8 20 Langmuir 4.97
Paper mill sludge 3,5-DCP 8 20 Langmuir 2.97
Paper mill sludge 2,4,5-TCP 8 20 Langmuir 2.74
Dried activated sludge 2-CP 1 25 Langmuir 281.1 Aksu and Yener (2001)
Dried activated sludge 4-CP 1 25 Langmuir 287
Palm pith carbon 2,4-DCP – – Langmuir 19.6 Sathishkumar et al. (2007)
Coir pith carbon 2,4-DCP – – Langmuir 19.1 Namasivayam and Kavitha (2003)
1346 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349

under varying conditions such as agitation time, adsorbent dosage, Table 14

pH, and temperature. More 2,4-DCP was removed with decreasing Evaluation of the best adsorbents for CP removal.

initial concentration of 2,4-DCP and increasing adsorbent dosage. Solute Adsorbent Adsorption Reference
Kinetic studies showed that the adsorption of 2,4-DCP on palm pith capacity (mg/g)
carbon was a gradual process. Adsorption capacity of 2,4-DCP was 4-CP GAC 319.9 Sulaymon and Ahmed (2008)
19.2 mg/g for the particle size of 0.25–0.5 mm. Acidic pH was 4-CP Coconut-shell AC 72.7 Radhika and Palanivelu (2006)
2,4,6-TCP Coconut-shell AC 122.3
favorable for the adsorption of 2,4-DCP. Studies on pH effect and
2,4-DCP AC (apricot atone shell) 339 Daifullah and Girgis (1998)
desorption showed that chemical adsorption seemed to play a major 2,4,6-TCP AC (kraft black liquor) 476 Gonzalez-Serranoa et al.
role in the adsorption process. In the adsorption of 2,4-DCP on palm (2004)
pith carbon, the changes in entropy and enthalpy were estimated to 2-CP MN-100 125.7 Streat and Sweetland (1997)
be 30.7 J/(mol K) and 7.2 kJ/mol, respectively. The highly positive 2-CP MN-150 125.7
2-CP MN-200 136.2
change in Gibbs free energy indicated the feasible and spontaneous 3-CP MN-100 143.9
adsorption of 2,4-DCP on palm pith carbon. 3-CP MN-150 151.6 Streat and Sweetland (1997)
3-CP MN-200 174.1
4-CP MN-100 140.6
4. Comparative evaluation of adsorbents
4-CP MN-150 144.4
4-CP MN-200 163.2
As shown in Tables 3–12, it is very difficult to compare 4-CP Samla coal 50 Ahmaruzzaman and Sharma
adsorption performance of various adsorbents due to a lack of (2005)
consistency in the literature data. Adsorption capacities were 4-CP Residual coal 82.4
4-CP H3PO4-treated coal 243.9
evaluated at different pHs (and not necessarily at the optimum pH), 4-CP Rice husk 14.4
temperatures, aromatic organic concentration ranges, and adsor- 4-CP Petroleum coke 9.3
bents. Some adsorption capacities were reported in batch experi- 4-CP Rice husk char 36.2
ments and others in continuous column modes. These cannot be 4-CP Amberlite XAD-16 291.6 Abburi (2003)
4-CP Coal-reject 60.2 Haghseresht and Lu (1998)
readily compared with each other. In batch experiments, the
2,4-DCP Red mud 130 Gupta et al. (2004)
adsorption capacities were computed by the Langmuir or Freund- 4-CP Red mud 127.1
lich isotherm. This makes comparison more complicated. However, 2-CP Red mud 117.3
some adsorbents that stand out for high adsorption capabilities of 2-CP Blast furnace sludge 20.4 Jain et al. (2004)
phenol and its derivatives are the activated carbons, resins and 4-CP Blast furnace sludge 22.8
2,4-DCP Blast furnace sludge 29.1
industrial wastes. 2-CP Carbonaceous material 50.3
Tables 14–16 present a summary of some of the highest 4-CP Carbonaceous material 57.4
adsorption capacity reported. Obviously, some low-cost adsorbents 2,4-DCP Carbonaceous material 132.5
prepared from agricultural or industrial wastes reveal outstanding 2-CP Blast furnace dust 14
4-CP Blast furnace dust 16.2
performance. These include red mud, sewage sludge, treated
2,4-DCP Blast furnace dust 29.1
2-CP Dried activated sludge 102.4 Aksu and Yener (1998)
Table 13 4-CP Dried activated sludge 116.3
Evaluation of the best adsorbents for phenol removal. 2-CP Dried activated sludge 281.1 Aksu and Yener (2001)
4-CP Dried activated sludge 287
Adsorbent Adsorption Reference
2,4-DCP Paper mill sludge 2.7 Calace et al. (2002)
capacity (mg/g)
3,4-DCP Paper mill sludge 5
GAC 350 Sulaymon and Ahmed (2008) 3,5-DCP Paper mill sludge 3
PAC 303 Ania et al. (2002) 2,4-DCP Palm pith carbon 19.6 Sathishkumar et al. (2007)
Steam-PAC 226 2,4-DCP Coir pith carbon 19.1 Namasivayam and Kavitha
HCl-PAC 98 (2004)
CNTs 15.8 Liao et al. (2008)
Kraft black liquor 227 Gonzalez-Serranoa et al. (2004)
GAC (corncob) 117.6 El-Hendawy et al. (2001)
Filtrasorb-400 205 Roostaei and Tezel (2004)
HiSiv 1000 319
NDA-100 154.1 Pan et al. (2005)
ZSM 7.4 Ghiaci et al. (2004) Table 15
HDTMAB-clinoptilolite 11.4 Evaluation of the best adsorbents for NP removal.
MCM-41 59.4
IRA-420 316.8 Carmona et al., 2006 Solute Adsorbent Adsorption Reference
MN-100 72.4 Streat and Sweetland (1997) capacity (mg/g)
MN-150 85.4 2,4-DNP AC (apricot atone shell) 232 Daifullah and Girgis (1998)
MN-200 86.6 4-NP NDA-100 140.9 Pan et al. (2005)
Samla coal 13.3 Ahmaruzzaman and 4-NP Samla coal 51.5 Ahmaruzzaman and
Sharma (2005) Sharma (2005)
Residual coal 45.5 4-NP Residual coal 86.9
H3PO4-treated coal 142.8 4-NP H3PO4-treated coal 256.4
Coal-reject 227 Haghseresht and Lu (1998) 4-NP Rice husk 15.3
Red mud 59.2 Gupta et al. (2004) 4-NP Petroleum coke 11.1
Bagasse fly ash 23.8 Srivastava et al. (2006) 4-NP Rice husk 39.2
Activated sewage sludge (H2SO4) 42 Otero et al. (2003) 4-NP Coal-reject 56.2 Haghseresht and Lu (1998)
Thermal sewage sludge 185 Rio et al. (2005) 4-NP Bagasse fly ash 1.2 Gupta et al. (1998)
Pryolysis sewage sludge 5.6 DNBP Fly ash 6.6 Wang and Jiang (2007)
CTAB-montmorillonite 94.9 Juang et al. (2002) 4-NP Coal fly ash 10.8 Sarkar et al. (2006)
Coal fly ash 17.9 Batabyal et al. (1995) 4-NP Briquette char 95 Hobday et al. (1994)
Clay (quartz, kalinite, etc.) 30.3 Nayak and Singh (2007) 4-NP Yalloum coal 12
SDS-alumina 6.6 Adak et al. (2006) 4-NP Tower char 80
H2SO4-treated Aspergillus niger 0.33 Rao and Viraraghavan (2002) 3-NP CTAB-montmorillonite 105.4 Juang et al. (2002)
Dried activated sludge 86.1 Aksu and Gönen (2004) 4-NP XAD-4 931.3 Ku and Lee (2000)
 S.-H. Lin, R.-S. Juang / Journal of Environmental Management 90 (2009) 1336–1349
Table 16
Costs of several adsorbents.
Adsorbent Cost (US$/kg)
AC 20–22
Natural zeolite 0.03–0.12
Coal 0.19–0.15
Red mud 0.025
BFA 0.02
Carbonaceous adsorbent 0.1
Clay 0.04–0.12
residual coal, carbons developed from agricultural waste (apricot
stone shell and kraft black liquor), biosorbents (paper mill sludge,
dried activated sludge), etc. Of the many low-cost adsorbents
compared in this review, carbon from kraft black liquor and coal
treated with H3PO4 offered best performance for the removal of
phenols. In case of phenol removal, Amberlite IRA-420 and HiSiv
1000 resins were the best (Table 13). On the other hand, carbon
from the kraft black liquor was the best for the removal of CPs
(Table 14) while XAD-4 was best for the removal of 4-NP (Table 15).
5. Cost estimation
The costs of adsorbents are roughly shown in Table 16. Basically,
the cost of adsorbent for phenol and its derivatives developed from
waste materials was seldom reported in literature because it
strongly depends on local availability, processing required, treat-
ment conditions, and both recycle and lifetime issues. That is, cost
varies when these adsorbents are made in (and for) well-devel-
oped, developing or underdeveloped countries. Numerous
commercially available activated carbons or low-cost adsorbents
have been used for the adsorption of phenol and its derivatives,
both as-received and after chemical modifications.
Moreover, no consistency exists in the data presented. Most
articles describe only batch experiments and no consideration was
given to fixed-bed studies. Batch adsorption isotherms cannot
simulate or predict dynamic performance. Most research review
herein was limited to initial laboratory evaluation of adsorption
capacity and mechanism. Pilot-plant scale studies and cost evalu-
ation remain to be explored. In the growing literatures on natural
adsorbents for phenol and its derivatives, little information exists
containing full cost and application comparisons of various adsor-
bents. Also, different adsorbents are difficult to compare due to
inconsistencies in the data presentation. Much work is thus
necessary to demonstrate application costs at the sale of a single
home, a village, a municipal region or an industrial process.
6. Conclusions
Chemical contamination of water from a wide range of toxic
compounds, in particular aromatic molecules, is a serious envi-
ronmental problem owing to their potential human toxicity. Phenol
and its derivatives appear to be the major organic pollutants
globally in this century. They, derived from industrial effluent
discharge, present an ongoing and serious threat to human health
and to natural water. There are a large number of technologies
available for the treatment of phenol and its derivatives, but none of
them is applicable to all the situations. Adsorption is relatively new
practice for the removal of phenol and its derivatives. The role of
activated carbon for the removal of phenol and its derivatives from
water and wastewater was discussed. However, it is only able to
remove few milligrams of phenol and its derivatives per gram of
activated carbon and there are still some problems encountered in
the regeneration process. This makes activated carbon an expensive
adsorbent for this purpose. Therefore, low-cost materials are sorely
1347
needed that are comparable to activated carbon or synthetic resins
in terms of adsorption capacity and should be locally available. The
present review shows that some such materials have equivalent or
even more adsorption capacity to activated carbon and synthetic
resins. On the other hand, some solid waste such as sludge has
become one of the society’s most vexing problems. If the solid
waste can be converted into low-cost adsorbents for the treatment
of discharged wastewater, the cost of removal might decrease.
Although the organoclays revealed good adsorption capability, they
were still non-economic. Preliminary studies have also revealed the
applicability of the substances such as dried activated sludge, red
mud, fertilizer wastes, different types of coal, and so on, as scav-
engers of phenol and its derivatives.
Last but not the least, if the alternative adsorbents mentioned
previously are found to be highly efficient for the removal of phenol
and its derivatives, not only the industries but the living organisms
and the surrounding environment will be also benefited from the
potential toxicity due to phenol and its derivatives. Thus the use of
low-cost adsorbents may contribute to the sustainability of the
surrounding environment. Undoubtedly low-cost adsorbents offer
a lot of promising benefits for commercial purpose in the future.
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