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Desalination 277 (2011) 377382

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Activated carbons from sewage sludge


Application to aqueous-phase adsorption of 4-chlorophenol
Victor Manuel Monsalvo , Angel Fernandez Mohedano, Juan Jose Rodriguez
Seccion de Ingenieria Quimica, Facultad de Ciencias, Universidad Autonoma de Madrid. C/Francisco Tomas y Valiente 7, Madrid 28049, Spain

a r t i c l e

i n f o

Article history:
Received 12 November 2010
Received in revised form 29 March 2011
Accepted 25 April 2011
Available online 18 May 2011
Keywords:
Sewage sludge
Valorisation
Activated carbon
Adsorption
4-Chlorophenol

a b s t r a c t
Activated carbons of different characteristics have been prepared from dried sewage sludge using CO2, air and
KOH as activating agents. The adsorption capacity of the resulting materials has been checked using 4chlorophenol as a target compound in aqueous solution. CO2 and air-activation led to carbons of low BET area
which increased with the activation temperature but did not reach 100 m 2/g at the best. The high ash content
of the starting material (23%, d.b.) limits the development of porosity since the partial gasication does not
affect the inorganic matter. In the case of air-activation, the resulting surface remains fairly low even in ashfree basis, reaching no more than 250 m 2/g.
Activation with KOH allows a much higher development of porosity. Using a KOH to solids ratio of 3:1 and a
temperature of 750 C a BET area above 1800 m 2/g with a mesopore volume higher than 0.35 cm 3/g was
reached.
In spite of those dramatic differences on the textural properties, the air-activated carbons showed an
adsorption capacity for 4-chlorophenol of almost 85% that of the KOH-activated carbons. These results
warrant in principle air-activation at moderate temperature as a promising way of sewage sludge valorisation
to inexpensive adsorbents for the removal of water pollutants.
2011 Elsevier B.V. All rights reserved.

1. Introduction
The increasing generation of sewage sludge derived from wastewater treatment demands the development of new ways of valorisation.
Nowadays, management of sewage sludge includes composting
for farmland utilization, incineration and landlling [1]. However, this
last will be severely limited in a short-term due to the increasing competition for landll space, growing costs and more stringent environmental regulations. Incineration of sewage sludge requires strict control
of the pollutants generated [2, 3] and in many cases suffers of social and
political opposition. Different ways of valorisation are being investigated
in the last two decades including the use of sewage sludge as precursor
for adsorbent materials with environmental applications.
Some authors have investigated the direct application of dried
sewage sludge as adsorbent [4] although its low surface area, below
5 m 2/g [57], represents a severe limitation in this respect. However,
more acceptable adsorbents can be obtained from sewage sludge by
different ways. Pyrolysis can produce a carbonaceous solid with around
60 m2/g surface area [8], requiring temperatures above 700 C to increase such porosity [9]. Although this type of carbons has been applied
on the decontamination of several gaseous and aqueous off-streams,
many industrial applications demand more efcient adsorbents. Acti Corresponding author. Tel.: + 34 4978035; fax: + 34 4973516.
E-mail addresses: victor.monsalvo@uam.es (V.M. Monsalvo),
angelf.mohedano@uam.es (A.F. Mohedano), juanjo.rodriguez@uam.es (J.J. Rodriguez).
0011-9164/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.04.059

vated carbon has been witnessed as an adsorbent with large porous


surface area, controllable pore structure, high thermo-stability and low
acid/base reactivity [10]. Owning to its low initial cost, simplicity of
design, insensitivity to toxic substances, high adsorption capacity and
regenerability, activated carbons appeared to be the most versatile and
suitable candidate for micropollutants removal from wastewaters [11,
12]. This fact has motivated a noticeable interest for the development of
carbon-based adsorbents from many different precursors for industrial
applications.
Activated carbons can be obtained by both the so-called chemical
[1318] and physical [6, 19, 20] activation of sewage sludge. Recent
works have demonstrated the possibility of developing surface areas
over 1500 m 2/g through activation with KOH [21, 22]. The resulting
materials have been tested in some gas-phase applications like odor
control in wastewater treatment plants [23]. The removal of heavy
metals and dyes from wastewaters by means of KOH and CO2activated sewage sludge has been also studied [7, 21, 22, 24].
Air-activation of sewage sludge has been scarcely studied in spite of
the fact that this appears in principle the easiest way for the valorisation
of that type of waste to an inexpensive adsorbent material with potential applications for the removal of gas and water pollutants. Activated carbons of less than 100 m 2/g BET surface area have been obtained
upon air-activation of pre-pyrolysed sewage sludge and tested for Fe3+
removal from water [20].
In this work we investigate the direct activation of dry sewage
sludge with CO2, air and KOH at different temperatures and holding

378

V.M. Monsalvo et al. / Desalination 277 (2011) 377382

times, since these two variables have been reported to be important for the nal characteristics of the resulting materials [18, 25],
which are evaluated as adsorbents for the 4-chlorophenol removal
from aqueous solution. Chlorophenols are a representative group of
harmful compounds specically included in the lists of priority and
hazardous pollutants. They are released into water from a diversity of
sources such as oil exploration and production, wood and textile
preservation, accidental spills, chlorination of water and wastewaters
containing phenol, degradation of herbicides and pesticides and
leaching from waste disposal [2629].

2.3. Adsorption experiments


100 mg of activated carbon were mixed in stoppered bottles with
100 mL of aqueous solutions containing different concentrations of 4CP (0.12.0 g/L) at 15 C and pH 7.0 (buffered solution of phosphate)
and stirred at 200 rpm (equivalent) in a thermostatized shaker up to
equilibration. The concentration of 4-CP was analyzed by HPLC/UV
(Prostar, Varian) using a C18 column as stationary phase (Microsorb
MW-100-5) and a mixture of acetonitrile and H2O (40:60, vol.) as
mobile phase. The ow rate was maintained at 1 mL/min and a
wavelength of 280 nm was used. The experimental data were tted to
the Langmuir (1) and RedlichPeterson (2) equations:

2. Materials and methods


2.1. Adsorbents preparation
The aerobic granular sludge was collected from a sequencing batch
reactor treating industrial wastewaters from a cosmetics factory.
Primarily, samples were washed with distilled water until constant
conductivity, and then they were dried at 105 C up to constant weight.
The resulting solids were ground and sieved to a particle size in the
range of 0.10.25 mm.
Activation was performed in a vertical tube furnace electrically
heated. The working temperature was reached at a 10 C/min heating
rate and the gas (CO2, air or N2 in the case of KOH-activation) was
continuously passed at a 100 N-mL/min ow rate. Different holding
times (0.5, 2.0 and 4.0 h) and temperatures (700 and 800 C) were
tested for the activation with CO2. Air-activated materials were also
obtained at different holding times (0.5, 2.0 and 4.0 h) and temperatures
(200, 300 and 400 C). The resulting materials were washed with
distilled water before being used in adsorption experiments. Chemical
activation with KOH was carried out by physical mixing of the ground
hydroxide lentils and dried sewage sludge. KOH to solids ratios of 1:1
and 3:1 (w:w) were employed. Activation was performed at 450 and
750 C under N2 atmosphere for 30 min and the resulting samples were
washed with 5 M HCl, and then with distilled water until constant pH.

2.2. Characterization of the starting material and the activated carbons


The C, H, N, and S elemental composition of the solid samples
was determined by a CHNS analyzer (LECO CHNS-932). The standard
test method ASTM D2866-94 was used to determine the ash content
by means of a thermogravimetric analyzer (SDTA851e). The metals
content was examined by inductively coupled plasma atomic emission
spectroscopy (ICP-MS) using a model Elan 6000 Sciex Perkin Elmer
apparatus. The porous structure was characterized from the 77 K N2
adsorption/desorption isotherms (Autosorb-1, Quantachrome). The
samples were previously outgassed for 8 h at 10 3 Torr and 150 C.
The pH slurry value of the carbons was measured upon stirring in
distilled water until constant pH. SEM images were obtained using a
Hitachi S-3000N apparatus.
Table 1 summarizes the characterization of the starting dried
sludge.

Table 1
Characterization of the starting sewage sludge (composition in %, d.b.).
C
H
N
S
Oa
Ash content (%)
SBET (m2/g)
pHslurry
a

By difference.

48.7
7.5
9.4
0.6
10.8
23
b3 m2/g
6.9

Na (mg/g)
Mg (mg/g)
Al (mg/g)
P (mg/g)
K (mg/g)
Ca (mg/g)
Ti (g/g)
Fe (g/g)

10.90
3.16
10.00
3.37
1.84
4.61
64
283

qe =

QL KL Ce
1 + KL Ce

qe =

A Ce
1 + BCe

where qe is the equilibrium adsorbate loading onto the adsorbent


(mmol/g), Ce the equilibrium liquid-phase concentration of the adsorbate (mmol/L), QL the monolayer adsorption capacity (mmol/g), KL the
Langmuir constant (L/mmol), A the RedlichPeterson constant (L/g), B
a constant having units of (L/mmol), and an exponent that lies
between 0 and 1.
The parameters of these equations were calculated by using a nonlinear regression tting method. The results reported were the average
values from duplicate runs. In all the cases, the standard errors were
lower than 5%.
3. Results and discussions
SEM images of the dried granules of aerobic sewage sludge used as
precursor and the resulting activated carbons are shown in Fig. 1. The
dried sewage sludge is a non-porous material with a surface area
lower than 3 m 2/g. The materials resulting from physical activation
had irregular shapes. The chemical activation process with KOH gave
rise to a uffy material of low density and high porosity.
3.1. CO2 and air activation
Table 2 summarizes the values of the BET surface area and
micropore volume of the carbon materials activated with CO2 and
air. BET surface areas below 100 m 2/g were developed with both
activating agents. With CO2, increasing the holding time up to 2 h gave
rise to BET surface areas higher than those reported in the literature
[7] at similar temperatures. No signicant increase of the BET surface
area was observed at higher holding times except with air at the
lowest temperature tested. This last variable shows some signicant
effect on the development of surface area upon activation both with
air and CO2 within the ranges investigated. The high ash content of the
precursor (23%, d.b.) limits severely the development of porosity on a
total weight basis since partial gasication does not affect to the
inorganic matter. Nevertheless, the resulting materials from both CO2
and air-activation showed higher BET surface areas than the 65 m 2/g
reported in the literature from steam-activation of sewage sludge at
800 C [6].
The C/H molar ratio increased up to 3.0 and 1.6 in the CO2 and airactivated carbons, respectively, versus 0.5 of the dry sludge consistently
with the dehydrogenative polymerisation and dehydrative polycondensation reactions commonly occurring upon thermal treatment, with
signicant loss of aliphatic hydrogen through olygomerisation. CO2activation was accompanied by a substantial decrease of the S content
which reached values of 0.10.2% on a dry basis versus the 0.6% of the
starting sludge solids (Table 1). The temperature must be a determining

V.M. Monsalvo et al. / Desalination 277 (2011) 377382

379

Fig. 1. SEM images of dried sewage sludge (a), CO2-activated carbon at 700 C for 4 h (b), air-activated carbon at 400 C for 4 h (c) and KOH-activated carbon at 450 C with 3:1 KOH:
solids ratio (d).

factor in this case, since air-activation, carried out at much lower temperature did not allow that reduction of the S content.
3.2. KOH activation
Activation with KOH gave rise to carbons with a well developed
porous structure showing both the temperature and the KOH to solids
ratio a benecial effect on that respect (Table 3). Increasing the temperature from 450 to 750 C provokes a dramatic increase of the BET
surface area affecting more remarkably to the microporosity although
with an important contribution of mesoporosity also. At that temperature using a KOH to solids ratio of 3 allows obtaining frankly high
values of BET and external or non-microporous surface areas (up to
around 1800 and 380 m2/g, respectively). This development of porosity
was higher than the obtained under similar activation conditions, from
other substrates like coals, bers, pistachio shells, corncob, pitch and r

Table 2
Surface areas and micropore volumes of the carbons from CO2 and air-activation.
T (C)

Holding time (h)

CO2 activation
700
0.5
2.0
4.0
800
0.5
2.0
4.0
Air activation
200
0.5
2.0
4.0
300
0.5
2.0
4.0
400
0.5
2.0
4.0

SBET (m2/g)

Vmicropores (cm3/g)

11
75
79
20
94
97

0.01
0.05
0.06
0.02
0.04
0.09

7
34
47
13
51
53
15
92
91

b 0.01
0.03
0.05
0.01
0.05
0.05
0.03
0.06
0.07

wood [3038]. Also, this activation procedure is much more effective


than other based on commonly used chemical activating agents such
as ZnCl2 [18, 39, 40], H3PO4 [18] or H2SO4 [5, 18, 3941] with the dry
solids from sewage sludge.
Ros et al. [21] used an acid washing step previous to KOH-activation.
That increased the surface area of the starting precursor but, according
to our results does not produce any signicant benet regarding the
nal surface area achieved upon KOH activation.
With regard to the evolution of the elemental analysis upon
KOH-activation, a dramatic decrease of the N content at the highest
activation temperature (750 C) is noteworthy. This has been attributed
by previous authors to the conversion of carbon-nitrogen moieties
into cyanides caused by the alkali activation through the dehydrogenation of amino groups derived from proteins, nucleic acids and dead
microorganisms [24, 42]. An important advantage of the chemical
activation process is that it takes a shorter time than the required for
physical activation.
3.3. Adsorption of 4-CP
Adsorption isotherms of 4-CP by the different activated carbons
are shown in Figs. 2, 3 and 4.
In general, the experimental data tted the RedlichPeterson
equation better than the Langmuir one most commonly used for
liquid-phase-adsorption. That was particularly true in the case of
the CO2-activated carbons. Table 4 summarizes the results of tting

Table 3
Porous structure of the KOH-activated carbons.
T (C)

KOH:solids
ratio

SBET
(m2/g)

Vmesopores
(cm3/g)

Vmicropores
(cm3/g)

Sexternal
(m2/g)

450

1:1
3:1
1:1
3:1

131
262
950
1832

0.12
0.16
0.23
0.36

b0.01
0.01
0.40
0.75

110
184
268
379

750

380

V.M. Monsalvo et al. / Desalination 277 (2011) 377382

Fig. 2. Adsorption isotherms of 4-CP onto the CO2-activated carbons.

the experimental adsorption data to the aforementioned isotherm


equations.
As can be seen in Fig. 2, similar adsorption capacities were observed for all the CO2-activated carbons, since the slight increase of
the surface area when increasing the activation temperature from 700

Fig. 4. Adsorption isotherms of 4-CP onto the KOH-activated carbons.

to 800 C (Table 2) did not cause any signicant improvement. The


analysis of the maximum adsorption capacity (QL) of the air-activated
carbons indicates that is related with the BET surface area developed.
Table 4
Fitting of the adsorption data of 4-CP onto the activated carbons from sewage sludge.
T (C) Holding
time (h)

RedlichPeterson

KOH:solids A
ratio
(L/g)

Fig. 3. Adsorption isotherms of 4-CP onto the air-activated carbons.

CO2-activated materials
700 2.0
0.722
4.0
0.646
800 2.0
0.862
4.0
0.903
Air-activated materials
200 0.5
0.060
2.0
0.389
4.0
0.315
300 0.5
0.538
2.0
1.317
4.0
0.291
400 0.5
0.280
2.0
0.254
4.0
0.235
KOH-activated materials
450 1:1
2.095
3:1
10.734
750 1:1
2.912
3:1
3.794

Langmuir

(L/mmol)

R2

KL
QL
R2
(L/mmol) (mmol/g)

0.134
0.033
0.251
0.231

0.978
0.988
0.676
0.873

0.993
0.992
0.995
0.998

0.583
0.404
0.134
0.573

1.999
2.570
3.205
1.970

0.980
0.960
0.972
0.941

0.052
0.927
0.108
0.071
0.752
0.031
0.431
0.010
0.346

1.062
0.811
1.140
1.067
0.943
1.074
0.883
0.747
0.804

0.995
0.996
0.995
0.993
0.997
0.998
0.997
0.997
0.993

0.249
0.382
0.185
0.456
0.598
0.237
0.261
0.201
0.159

0.332
0.697
1.922
1.815
1.993
1.644
1.555
2.046
2.372

0.998
0.991
0.993
0.984
0.995
0.997
0.994
0.997
0.965

1.607
10.844
1.712
1.235

0.935
0.742
0.969
1.044

0.996
0.995
0.997
0.996

1.165
1.910
1.478
1.474

1.498
1.559
1.809
2.820

0.997
0.989
0.996
0.994

V.M. Monsalvo et al. / Desalination 277 (2011) 377382

Nevertheless, the disturbances observed in such relation can be associated with differences in the surface chemistry. Despite the numerous
studies published on the adsorption of phenolic compounds by activated carbons, the mechanism by which these compounds are adsorbed
is not still completely well understood [43]. That mechanism is not
only determined by interactions and donoracceptor complex
formation but also by the solvent effect balancing the inuence of
those two contributions [44].
Additionally, the effect of the surface properties of activated
carbons on adsorption has to be considered [45]. A relatively large
amount of information describes the behavior of activated carbons
with oxygen containing basic functional surface groups that in general
cause enhanced sorption of phenolic compounds [4648]. In addition,
elimination of acidic oxygen-containing groups from activated carbons
was suggested to be a way to increase adsorbability of phenols [4650],
through both an increased water cluster formation, thus obscuring the
basal carbons, and a reduction of the availability of the electrons [43].
However, Yin et al. [51] also noted that at high phenols concentrations, those phenols could be adsorbed by not only the mechanism of
physisorption, but also by surface polymerisation, in which the phenolic
compounds undergo oxidative coupling reactions on the carbon surface to produce polymeric compounds [52]. For this process the presence of oxygen is necessary and the high inorganic content of sewage
sludge-based adsorbents could be advantageous for its potential use as
adsorbent [24].
As mentioned, adsorption experiments were carried out at neutral
pH, in which 4-CP is in the nonionic form (pKa = 9.38) and thus
the adsorption must be governed by non-electrostatic interactions
between the solute molecule and sorbent surface, i.e., the dispersive
interactions between the -electrons of the solute aromatic ring and
the adsorbent. The surface oxygen, nitrogen and sulfur complexes
inuence these dispersive interactions to a large extent thus affecting
the adsorption mechanism [50]. Owing to the high thermal stability of
N and S hetero-atoms, they remain in the carbon upon air activation
due to the low temperatures used. N and S contents of 7.5 1.2% and
2.2 0.8% (d.b.), respectively, were detected in these materials. The
presence of N-substituents gives to activated carbons increased
ability to adsorb chlorophenols from water [45]. On the opposite,
the high temperatures employed when using CO2 or KOH as activating
agents gave rise to a signicant decrease of S content to less than 1%
(d.b.), and a great reduction of N content was observed as well when
activating with KOH at 750 C (0.8%, d.b.). This fact could provoke
some loss of adsorption capacity [45]. Nevertheless, this phenomenon
is clearly overcome by the profuse porosity development upon KOH
activation.
Consistently with their much higher surface area the KOHactivated carbons yielded the highest adsorption capacities (Fig. 4).
Nevertheless, the differences are signicantly lower than the expected
from a direct dependence of the porous structure. The maximum value
obtained from the Langmuir equation for the monolayer capacity of the
air-activated carbon was only 16% lower than that of the KOH-activated
one in spite of the fact that the BET surface area of this last was about
twenty times higher.
It has to be pointed out that the adsorption capacities reported for
the KOH-activated carbons were obtained after washing these carbons
with 5 M HCl and, after that, with distilled water until constant pH.
Values up to almost four times lower were obtained when using only
distilled water for washing after the activation process. The positive
effect of HCl washing can be due to the liberation of the partial blockage
of the pores caused by the remaining potassium by-products from the
activating agent, which may be not completely removed upon washing
simply with distilled water [18, 24, 50, 53].
Most of the works dealing with the preparation of activated carbons from sewage sludge use the pre-pyrolysed material as precursor.
However, in the present work, dried sewage sludge was directly used
as starting material and KOH showed to be more effective with this

381

precursor itself than with its pyrolytic char where some porosity
had been already developed [53]. As can be observed in Fig. 4b, holding
times can be reduced from 2 to 0.5 h by using KOH instead of physical
activation agents without compromising the maximum 4-CP adsorption capacities obtained.
4. Conclusions
Activated carbons of fairly different porous structure can be
obtained by physical (CO2, air) and chemical (KOH) activation of dried
sewage sludge. Physical activation did not yield activated carbons
with more than 100 m 2/g BET surface area whereas around twenty
times higher surface area was achieved by chemical activation. The
high ash content of the starting material severely limits the development of porosity upon physical activation since CO2 or air partial
gasication do not affect to the ash components. Nevertheless, in
spite of these dramatic differences fairly close capacities were found
for 4-CP liquid-phase adsorption. Thus, air-activation can be viewed
as a simple way of valorisation of dry sewage sludge to inexpensive
activated carbon.
Acknowledgments
The authors greatly appreciate nancial support from the Spanish
MCI through the projects CTM2010-15682 and CDS2006-0044. Victor
M. Monsalvo thanks the MCI and the ESF for a research grant.
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