ARTICLE IN PRESS

Water Research 38 (2004) 2155–2165

Comparison between thermal and ozone regenerations of spent

activated carbon exhausted with phenol
!
P.M. Alvarez a,
*, F.J. Beltra! na, V. Gomez-Serrano
! b
, J. Jaramilloa, E.M. Rodr!ıgueza
a
Departamento de Ingenier!ıa Qu!ımica y Energ!etica, Facultad de Ciencias, Universidad de Extremadura, Avda Elvas S/N, Badajoz 06071,
Spain
b
!
Departamento de Qu!ımica Inorganica, Facultad de Ciencias, Universidad de Extremadura, Avda Elvas S/N, Badajoz 06071, Spain
Received 16 December 2002; received in revised form 27 October 2003; accepted 28 January 2004

Abstract

Thermal and ozone regenerations of granular activated carbons (GAC) used in the removal of phenol from aqueous
solution have been studied. The phenol isotherms for virgin GAC could be well represented by the Langmuir equation.
Direct ozonation of GAC introduced large amounts of acidic surface oxygen groups, which caused a decrease in the
phenol uptake. Thermogravimetric methods were used to investigate the mechanism of phenol adsorption onto virgin
and ozonated carbons. Thermal regeneration was carried out at 1123 K using nitrogen (pyrolysis alone) or nitrogen and
carbon dioxide (pyrolysis plus oxidation). Results showed that spent carbons do not recover their adsorption
characteristics when heated under inert conditions whereas carbon dioxide regeneration was effective at about 15% wt
burn-off. Regeneration of GAC was also carried out with ozone as oxidizing gas at room temperature. Ozone dose and
the nature of GAC have much influence on the regeneration performance. For an individual GAC there exits an
optimum ozone dose for which phenol is eliminated together with most of its oxidation by-products without incurring
in carbon surface chemical alterations. However, if excessive ozone is applied some acidic surface groups are formed on
the GAC, thereby decreasing the adsorption capacity for phenol. Results showed that spent carbons can recover most
of their adsorption characteristics and specific surface areas when regenerated through a number of adsorption-ozone
regeneration cycles.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: Activated carbon; Adsorption; Ozone; Regeneration

1. Introduction regeneration [1]. In spite of being the most widely

The water purification industry is currently one of the
largest market for activated carbon (AC). In fact AC
filters are used today in many drinking water and
wastewater treatment plants to remove organic micro-
pollutants and some metals by adsorption. The econom-
ics of the adsorption process greatly depends on the
reuse of AC. There are several well-established methods
for the regeneration of spent AC that can be classified in
three broad groups: thermal, chemical and biological
*Corresponding author. Tel./fax: +34-924-289-385.
!
E-mail address: pmalvare@unex.es (P.M. Alvarez).
regeneration technology, thermal regeneration has an
important energy demand since temperature must be
kept above 1100 K. Also, considerable amount of
carbon (5–15%) is usually lost by attrition, burn-off
and washout [2]. Chemical regeneration can be carried
out by desorption of adsorbates using specific solvents
or by decomposition of adsorbed species using oxidizing
chemical agents. Extraction with solvents requires
further purification of the solvent and it is only
recommended when a valuable product is recovered
[3]. Oxidative chemical regeneration is usually accom-
plished by wet oxidation (WO) under either subcritical
or supercritical conditions. Although these techniques

0043-1354/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2004.01.030
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P.M. Alvarez et al. / Water Research 38 (2004) 2155–2165
have been successfully applied to a number of adsor-
bates, regeneration efficiency depends on the solubility
of the sorbed substances and the effect of pressure on the
chemical structure of carbon. Also, such a large
investment in high-pressure equipment makes the
method rather expensive [4]. Biological regeneration is
usually slow and requires adsorbed species totally
biodegradable, which is not an occurrence in many
water pollutants [5]. Because of these drawbacks, a
number of other alternative AC regeneration methods
are subject of current investigation. Among them, steam
regeneration [6], catalytic oxidation [7], microwave
regeneration [8], electrochemical methods [9] or extrac-
tion with supercritical fluids [10] can be highlighted.
In most of the cases special treatment facilities are
required for the implementation of the above-mentioned
methods of AC regeneration. Hence, regeneration
cannot be conducted in situ but spent AC must be
shipped to regeneration units outside the water treat-
ment plant, which produces additional cost. The
coupling of adsorption and regeneration to be con-
ducted in situ are, therefore, encouraged. In this sense,
AC regeneration methods by both liquid- or gas-phase
oxidation of adsorbed species at atmospheric pressure
have been shown as feasible techniques to be integrated
in a water treatment scheme [11]. Liquid-phase oxida-
tion requires desorption by temperature swing method
and subsequent oxidation. This latter step has been
carried out by a number of methods including catalytic
WO, supercritial WO, and homogeneous advanced
oxidation processes (AOP). However, results have been
found not to be completely successful because of high
capital cost of WO methods and high oxidizing reagents
consumption of AOP [4,12]. On the other hand, direct
oxidation with air on exhausted AC can be improved by
impregnating AC with metal oxides that can catalyze the
oxidation, which allows for the lowering of the
oxidation temperature up to 513–573 K [1,7,13]. Main
limitation of this oxidative catalytic regeneration arises
from the properly selection and impregnation of the
catalyst that can effectively improve both adsorption
and regeneration.
The use of ozone in drinking water and wastewater
treatment plant is of growing interest. Owing to its high
oxidant power, this can react with species adsorbed onto
AC, thus removing them from the surface. Reaction
may take place directly or through free radicals that
arise from ozone decomposition over the carbon surface
[14]. Based on this, a novel approach for the regenera-
tion of AC by direct ozonation of spent AC is proposed.
The method would have the suggested advantages: (1)
oxidation can be carried out at ambient temperature and
pressure conditions, which benefits the economy of the
process; (2) it can be easily combined with adsorption
and carried out in situ; (3) many water treatment plants
have ozonation facilities. However, interactions between
ozone and AC itself can occur. According to some
recent works [15–18] ozone can modify surface proper-
ties of AC such as specific surface area, pore volume and
chemical functional groups. In particular, Vald!es et al.
[18] have demonstrated that after high ozone uptake it
may decrease the AC adsorptive properties because of
the fixation of oxygen groups on the surface (SOG)
which obstruct the entrance of micropores.
In this work, a study of the adsorption onto a
granular activated carbon (GAC) and regeneration of
spent GAC with ozone is addressed. Also, thermal
regeneration is studied and the efficiency compared to
that of ozone regeneration. Phenol was chosen as target
compound for adsorption since it is a pollutant of many
wastewaters usually selected for adsorption and acti-
vated carbon regeneration studies.
2. Materials and methods
2.1. Activated carbons
A variety of GAC were prepared in the laboratory
using cherry stones (CS) as precursor. Literature reports
the benefits of this material for the manufacture of
activated carbon [19]. Prior to their use, CS were dried,
crushed and sieved into a uniform size of 1–1.6 mm. The
preparation of activated carbons was accomplished by
pyrolysis of CS particles at 1173 K for 2 h in nitrogen
followed by gasification of the obtained char with CO2
at 1123 K until achieving a given char burn-off. In this
way three different activated carbons were prepared,
referred to as CS-10, CS-20 and CS-30 with about 10%,
20%, and 30% char burn-off, respectively.
2.2. Adsorption equilibrium isotherms
Isotherms of phenol were performed at 298 K using
the bottle-point technique. A carbon sample weighing
from 50 to 500 mg was placed into each bottle and
20 mL of 1.5 g L
1 phenol (reagent grade, Sigma-
Aldrich) aqueous solution were then added. Bottles
were shaken for a week before sampling. Preliminary
kinetic experiments indicated that adsorption equili-
brium was reached within 3–4 days for all GAC used.
Samples were filtered with 0.45 mm nylon membrane and
analyzed by UV spectroscopy (Hitachi 2000,
lmax ¼ 270 nm) for phenol concentration. The amount
of adsorbed phenol was deduced from the mass balance
as follows:
ðC0
Ce ÞV
qe ¼ ; ð1Þ
M
where C0 is the initial liquid phase phenol concentration
(typically 1.5 g L
1), Ce is the equilibrium liquid phase
phenol concentration, V is the volume of solution in the
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P.M. Alvarez et al. / Water Research 38 (2004) 2155–2165 2157

equilibrium bottle and M stands for the mass of GAC
used in each of the batch test.
2.3. Spent activated carbons
GAC were saturated with phenol by contacting 1 g
sample with 0.5 L of the 1.5 g L
1 aqueous phenol
solution in an isothermal (298 K) stirred tank for a
period of 5 days at least. After that time, the amount of
phenol adsorbed was calculated from the mass balance
(see Eq. (1)). According to the experimental adsorption
isotherms, after phenol adsorption tests all the GAC
resulted in high surface covered by phenol.
gas stream entering and leaving the reactor was
measured by means of an Anseros Ozomat GM19
analyzer. Thermoregulated water was circulated through
the reactor jacket to keep constant reaction temperature.
By means of a thermocouple connected to the carbon
bed, temperature was measured throughout the regen-
eration process. In all cases temperature was controlled
at 29872 K. Reaction times between 20 and 90 min were
employed to produce different degrees of regeneration.
Additionally, blank ozonation runs were conducted with
virgin activated carbons (without phenol adsorbed) at
conditions similar to those used in ozone regeneration
runs.

2.4. Carbon samples characterization 2.7. Evaluation of regeneration

A Quantachrome Autosorb 1 automated gas adsorp- Efficiency of regeneration was evaluated by means of
tion system was used for the measurement of the the following analytical techniques: thermogravimetric
nitrogen adsorption isotherms at 77 K. Surface areas analysis (TGA), BET surface areas and isotherms of
were then calculated by applying the BET method [20]. phenol adsorption on regenerated GAC. The percentage
Apparent and true densities were determined by mercury of GAC regeneration was evaluated following recom-
and helium displacement (Quantachrome analyzers), mendations of Narbaitz and Cen [22].
respectively. Thermal analysis was carried out by
heating about 100 mg of sample from room temperature
up to 1123 K at a rate of 10 K min
1 under flowing 3. Results and discussion
nitrogen (150 ml min
1) using a thermobalance system
(Mettler MTA 3000). The content of surface oxygen 3.1. Characterization of original CS-activated carbons
groups (SOG) both acidic (i.e., carboxylic, phenolic,
lactone and carbonyl) and basic was determined by Table 1 summarizes densities, porosity, BET surface
Boehm’s titrations [21]. areas and total SOG of the three virgin GAC prepared
from CS and used throughout this investigation. From
2.5. Thermal regeneration of spent GAC Table 1 it is clear that the increase of burn-off led to a
development of total pore volume and surface areas.
Experiments of thermal regeneration were conducted The increase in microporosity with burn-off is also
in a lab-scale experimental device consisting of a vertical noticeable, which means that at moderate burn-off
furnace (i.d., 4 cm; height, 20 cm) provided with a (o30%) CO2 opens micropores rather than widens
temperature controller. About 2 g of the spent carbon them. Although values of surface areas are not high if
sample were loaded into the furnace and the system was compared with best commercial GAC, they are
heated from room temperature to 1123 K (heating rate, similar to those obtained for other agricultural by-
20 K min
1) and then held at this temperature for 10 min products [23]. With regard to chemical surface, basic
under 200 mL min
1 nitrogen flow. In some cases, this
was followed by oxidation in CO2 (200 mL min
1 flow Table 1
rate) at 1123 K up to achieve a selected burn-off between Properties of virgin CS-activated carbons
5% and 20%.
Property CS10 CS20 CS30
2.6. Ozone regeneration of spent GAC Char burn-off 10.7% 21.4% 33.6%
Apparent density (rHg ), g cm
3 0.81 0.77 0.75
Regeneration of the spent GAC was conducted in a True density (rHe ), g cm
3 1.99 1.93 1.89
hastelloy C lab–scale tubular jacketed fixed-bed reactor Total pore volume (VT ), cm3 g
1a 0.73 0.78 0.80
(i.d., 2 cm; length, 30 cm) operating at atmospheric BET specific surface area, m2 g
1 367.9 574.3 658.1
pressure. Typically, 1 g of spent GAC samples were Micropore volume (W0 ), cm3 g
1b 0.17 0.29 0.34
packed into the reactor and a 250 mL min
1 continuous Total basic SOG (meq g
1) 347 385 420
flow of an oxygen-ozone mixture from a Sander ozone Total acidic SOG (meq g
1) 124 138 156
generator was supplied (2.5% ozone by volume) through a
VT ¼ 1=rHg
1=rHe :
the gas inlet port to generate oxidizing conditions b
Calculated using Dubinin–Raduskevich equation applied to
required for regeneration. Ozone concentration in the N2 adsorption isotherms.

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P.M. Alvarez et al. / Water Research 38 (2004) 2155–2165
0.20
0.15
q (gPh·gGAC-1)
0.10
0.05
0.00
0.0 0.2 0.4 0.6 0.8
-1
C (g·L )
e
Fig. 1. Batch adsorption isotherms of CS-activated carbons.
Symbols: (’) CS-10; () CS-20; (m) CS-30. Dotted lines
represent simulation using Langmuir model.
Table 2
Parameters of the Langmuir adsorption model determined at
25 C for virgin CS-activated carbons
Activated carbon - CS-10 CS-20
q0 (gPh g
1
GAC) 0.12670.005 0.21170.009 0.20970.010

1
b (L g ) 3.30270.404 3.21170.373 3.73870.485
SOG concentration prevailed over acidic SOG for the
three GAC prepared.
The ability of virgin samples of CS-10, CS-20 and CS-
30 to adsorb aqueous phenol was checked by measuring
adsorption isotherms at 298 K, as shown in Fig. 1. Data
were well fitted into the Langmuir equation in agree-
ment with other studies reported in the literature
[7,13,24]. Accordingly, Eq. (2) was fulfilled:
bCe
qe ¼ q0 ; ð2Þ
1 þ bCe
where q0 and b are parameters related to the maximum
phenol adsorption monolayer capacity and the affinity
constant, respectively. Table 2 shows the values of both
parameters as estimated from the experimental results of
Fig. 1 after applying a non-linear regression method.
From these results, it can be concluded that the
maximum adsorption capacity for phenol (q0 ) was
practically the same for CS-20 and CS-30, and lower
for CS10. Accordingly, it seems that the adsorption of
phenol onto CS-activated carbons is controlled, at least
in part, by physical parameters such as surface area and
micropore volume, which are lower for CS-10 than for
the other CS-activated carbons (see Table 1). If one
takes into account the cross-sectional area of a phenol
molecule as 30.2  10
20 m2 [25], and the maximum
adsorption capacity from the Langmuir equation, q0 (see
ARTICLE IN PRESS
0.20
0.15
q (gPh·gGAC-1)
0.10
0.05
0.00
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
1.0 1.2 1.4
Ce (g·L-1)
Fig. 2. Batch adsorption isotherms of virgin CS-20 and various
ozonated CS-20 activated carbons. Symbols: (&) virgin CS-20;
() 20 min ozonated CS-20; (m) 40 min ozonated CS-20; (.)
60 min ozonated CS-20.
CS-30 Table 2), the fraction of BET surface of GAC covered
with phenol can be up to 66.3%, 71.1% and 61.4% for
CS-10, CS-20, and CS-30, respectively.
3.2. Effect of direct ozonation of virgin CS-activated
carbons on the adsorption of phenol
Direct ozonation of virgin CS-activated carbons was
carried out to gain insights into changes in GAC
adsorption capacity induced by ozonation. As an
example, Fig. 2 shows phenol adsorption isotherms on
CS-20 samples after ozonation for 20, 40 and 60 min. As
observed, the longer the ozonation time the larger the
decrease in the phenol uptake. CS-10 and CS-30
behaved in a similar way. An attempt was then made
to correlate adsorption equilibrium data on ozonated-
activated carbons using the Langmuir model. However,
as inferred from the double stepped shape of isotherms
of Fig. 2 this model failed to describe adsorption data.
Similar changes in the phenol adsorption isotherm shape
were found by Nevskaia and Guerrero-Ruiz [26] after
oxidizing a microporous-activated carbon with HNO3.
More recently, Rivera-Utrilla and S!anchez-Polo [27]
have observed that ozonation of a commercial-activated
carbon (i.e., Filtrasob 400) also can produce a sharp
reduction in the adsorption capacity for naftalensul-
phonic acids.
The loss in the adsorption capacity of activated
carbons after ozonation was evaluated following the
second method reviewed in the work of Narbaitz and
Cen that uses identical conditions for n batch adsorption
tests with virgin and treated carbons [22]. Accordingly,
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P.M. Alvarez et al. / Water Research 38 (2004) 2155–2165 2159

Table 3
Concentration in meq g
1 of surface oxygen complexes (SOG) in ozonated and regenerated CS-20 carbons

Sample Carboxylic groups Lactones Phenolic groups Carbonyl groups Basic groups

CS-20 15.7 5.9 74.1 42.2 385.1

CS-20/O3/20 31.9 12.9 89.2 57.9 330.3
CS-20/O3/60 48.7 14.1 97.9 63.4 301.6
SCS-20/RO3/20 21.4 8.8 71.3 45.9 364.9
SCS-20/RO3/40 26.2 9.4 75.8 51.6 349.3
SCS-20/RO3/60 36.9 14.1 88.9 57.1 331.0
SCS-20/RO3/90 54.2 16.8 96.3 61.0 306.4

Nomenclature: CS-20=virgin; SCS-20=spent CS20; CS-20/O3/20=ozonation of virgin CS-20 for 20 min; SCS-20/RO3/20=regen-
eration of spent CS-20 for 20 min.

the percentage of adsorption capacity lost (PL) due to

ozone reactions may be expressed as 0

Xn  
ðC02
Ce2 ÞV =M
PL ¼ 1
 100; ð3Þ
nqe1
i¼1
where subscript 1 and 2 refer to the adsorption batch
tests conducted with virgin and ozonated-activated
carbon, respectively. Thus, calculated PL were found
to be 22.4%, 40.5% and 43.4% for CS-20 ozonated for
20, 40 and 60 min, respectively.
Adsorption of phenol on activated carbon is known to
develop through physical adsorption and surface poly-
merization. The presence or absence of SOG on the
GAC can play an important role in both types of
adsorption [28]. Therefore, to explain the observed
change in adsorption behavior of GAC after ozonation,
the SOG of CS-20 ozonated samples were measured. As
shown in Table 3, acidic groups were drastically
increased by means of ozonation. Particularly, a
threefold increase in the carboxylic groups concentra-
tion were observed after 1 h of CS-20 ozonation.
Accordingly to some literature reports the introduction
of acidic SOG may affect adsorption of phenol in
different ways: (1) removal of p-electrons from the
carbon surface leading to weaker the dispersive interac-
tions with phenol [29]; (2) formation of water clusters, so
that some porosity become blocked and the access of
phenol is not fully allowed [30]; (3) inhibition of
irreversible adsorption of phenol onto activated carbon
under oxic conditions via oxidative coupling reactions
[31]; (4) chemisorption of phenol on carbonyl groups
through donor–acceptor complex mechanism [32]; (5)
chemisorption on carboxylic groups via ester formation
[33]. In connection with experimental findings of this
work, it is concluded that for CS-activated carbons
negative effects (1)–(3) prevail over (4) and (5).
3.3. Thermal analyses of spent GAC
Thermal analysis was used to provide insights into
phenol adsorption mechanism. First, blank analysis was
-dW/dT x 10 2 (mg/K)
2
T=500 K
T=900 K
4
6
8
200 400 600 800 1000 1200
T (K)
Fig. 3. DTG of virgin (solid line) and 1 h ozonated (dotted line)
CS-20.
carried out with virgin and ozonated GAC. As an
example, Fig. 3 shows the DTG thermograms for virgin
and 1 h ozonated CS-20 activated carbons. While that
corresponding to virgin CS-20 does not show appreci-
able effect apart from some water loss below 400 K, the
thermogram of ozonated CS-20 exhibits two thermal
effects with maxima at about 500 and 900 K. According
to thermal decomposition of SOG on carbon surface
[34], the weight loss during the first effect can be
attributed to the decomposition of carboxylic groups
that evolve as CO2 while the second is likely due to
release of CO2 from decomposition of lactones and CO
from decomposition of various oxygen surface groups
such as carbonyl, phenolic and ether-type structures.
Spent virgin and ozonated CS-activated carbons were
also subjected to TGA in nitrogen to determine the
temperature range in which phenol underwent thermal
desorption from the surface of GAC. As an example,
Fig. 4 shows the DTG curves for the virgin CS-20-
phenol and 1 h ozonated CS-20-phenol systems. Notice-
able changes can be observed when comparing Figs. 3
and 4. In Fig. 4 three different thermal effects can be
observed for the spent virgin CS-20. The weight loss
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P.M. Alvarez et al. / Water Research 38 (2004) 2155–2165

0 0.20

10
-dW/dT x 103 (mg/K)

0.15

q (gPh·gGAC-1)
20

T3 0.10
30
T2

40 0.05
T1

200 400 600 800 1000 1200 0.00

T (K) 0.0 0.2 0.4 0.6 0.8 1.0 1.2

Fig. 4. DTG of virgin (solid line) and 1 h ozonated (dotted line) Ce (g·L-1)
CS-20 exhausted with phenol.
Fig. 5. Batch adsorption isotherms of thermally regenerated
CS-20. Symbols: (&) virgin CS-20; () pyrolysis alone: 0%
burn-off; (J) 4.1% burn-off; (.) 9.2% burn-off. (~) 14.7%
Table 4 burn-off; (’) 19.4% burn-off.
Temperature and weight loss (as percentage of overall phenol
adsorbed) of effects attributed to phenol desorption from spent
CS-activated carbons during the thermal treatment
olysis of chemisorbed phenol [36]. On the other hand, an
Sample T1 Removal T2 and T3 (K) Removal important fraction of phenol adsorbed onto ozonated
(K) (%) (%) CS-20 could be released by heating at about 400 K (i.e.,
physisorbed). This means that, in the case study, the
Spent CS-10 375 17.2 575 640 28.6
Spent CS-20 410 21.4 560 670 38.2 formation of SOG by ozonation influences adsorption
Spent CS-30 415 27.8 595 675 24.3 behavior by inhibiting chemisorption of phenol rather
Spent CS-20/O3/20 410 37.9 than physisorption.
Spent CS-20/O3/60 415 51.0

Nomenclature as in Table 3. 3.4. Thermal regeneration

According to the results discussed above, for the

between 300 and 500 K (maximum T1 ) can be assigned
to physisorbed phenol while the other two (in the 500–
750 K temperature range) with maxima at T2 and T3
likely correspond to chemisorbed phenol that is evolved
as light gases and heavy products. Literature reports
similar results when regenerating other GAC exhausted
with substituted phenols [35,36]. The DTG correspond-
ing to ozonated CS-20 is unclear. Although a first effect
at about 400 K, most likely due to physisorbed phenol,
can be distinguished, the peaks between 500 and 1100 K
may be a result of the overlapping of different effects as
desoprtion of chemisorbed phenol and various SOG.
Results from the thermogravimetric analyses of spent
GAC allowed one to evaluate desorption temperatures
and to quantify the overall mass released by thermal
treatment as shown in Table 4. Form this table, it can be
deduced that less than 30% of phenol was physically
sorbed onto saturated virgin GAC and that at least 50%
of the overall mass of phenol was not removed upon
heating up to 1100 K. Such a fraction that remained
onto activated carbon after the heat treatment is likely
associated with polymeric products formed from pyr-
successful thermal regeneration of CS-activated carbons
exhausted with phenol, an oxidative step following the
pyrolitic stage would be necessary for the removal of the
charred residue. With this aim, a series of thermal
regenerations were carried out using CO2 as oxidizing
agent. The adsorption isotherms for various ozone-
regenerated CS-activated carbons are shown in Fig. 5
together with isotherms for virgin GAC. As expected,
when pyrolysis was applied alone (i.e., 0% burn-off), the
phenol uptake of the resulted GAC was lower than that
of virgin CS-20. This was also true for pyrolysis plus
oxidation with burn-off different than about 15%. From
experimental isotherms, the efficiency of regeneration
was then calculated by method 3 recommended by
Narbaitz and Cen [22]. Accordingly, the percentage of
regeneration is as given by Eq. (4):
Xn  
ðC02
Ce2 ÞV =M
PR ¼  100; ð4Þ
nððq0 bCe2 Þ=ð1 þ bCe2 ÞÞ
i¼1
where subscript 2 refers to conditions of batch adsorp-
tion test conducted with regenerated carbon and the
Langmuir parameters, q0 and b; are those calculated for
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P.M. Alvarez et al. / Water Research 38 (2004) 2155–2165 2161

Table 5
Efficiency of thermal and ozone regenerations of spent CS-activated carbons

Sample PR Ozone consumed Ozone consumed/ phenol adsorbed

(%) (mg O3/g C) (g O3/g Ph)

SCS-20/TR/0%BO 49.9 — —
SCS-20/TR/4.1%BO 65.2 — —
SCS-20/TR/9.2%BO 81.5 — —
SCS-20/TR/14.7%BO 99.3 — —
SCS-20/TR/19.4%BO 80.8 — —
SCS-10/RO3/40 87.8 262.0 2.08
SCS-10/RO3/60 58.1 343.1 2.72
SCS-20/RO3/40 64.8 276.8 1.31
SCS-20/RO3/60 74.8 360.4 1.71
SCS-30/RO3/40 67.0 327.0 1.56
SCS-30/RO3/60 79.2 424.8 2.03

Nomenclature: Examples: SCS-20/TR/4.1%BO=thermal regeneration (4.1% burn-off) of CS-20; CS-20/RO3/40=ozone regeneration

of spent CS-20 for 20 min.

0 dW/dT x 103 (mg/K) 0

dW/dT x 103 (mg/K)

-10 -10

-20 -20
T=670 K
T= 375 K T=640 K T=570 K
-30 -30
T=570 K
-40 -40

200 400 600 800 1000 1200 200 400 600 800 1000 1200
T (K) T (K)
(A) (B)

0 0
dW/dT x 103 (mg/K)

dW/dT x 103 (mg/K)

-10 -10
T=870 K

-20 -20 T=490 K T=970 K

-30 -30

-40 -40

200 400 600 800 1000 1200 200 400 600 800 1000 1200
T (K) T (K)
(C) (D)
Fig. 6. DTG of spent CS-10 exhausted with phenol and various ozone-regenerated activated carbons: (A): spent CS-10; (B): 20 min
ozone-regenerated CS-10; (C): 40 min ozone-regenerated CS-10; (D): 60 min ozone-regenerated CS-10.

virgin GAC (see Table 2). Percentages of CS-20 3.5. Ozone regeneration
regeneration obtained after applying Eq. (4) are sum-
marized in Table 5 for the conditions used in this work. Ozone regenerated GAC were saturated with phenol
It can be observed that proper regeneration (i.e., >90%) and analyzed by TGA. As an example, Fig. 6 shows the
was only achieved when gasification was extended up to DTG thermograms for the spent CS-10 before (A) and
burn-off of about 15%. It is believed that pyrolysis and after ozonation for 20, 40 and 60 min (B, C and D,
gasification to levels below 15% has limited effect on the respectively). As observed in Fig. 6, important changes
development of surface areas and porosity. On the other are noticed in the DTG curves. First, the thermal effect
hand, when gasification progresses above this optimum corresponding to physisorbed phenol (T ¼ 375 K in
burn-off value an important decrease in microporosity thermogram A) is practically absent from the thermo-
can occur [2]. grams of regenerated samples, which means that
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physically adsorbed phenol was removed by ozonation
even at the lowest ozonation time of 20 min. The small
peak below 400 K observed for all regenerated samples
may be due to the volatilization of some by-products of
phenol ozonation pathway (e.g., organic acids.) that
remains adsorbed onto carbon rather than phenol itself.
The peaks of chemisorbed phenol (T ¼ 570 K and 640 K
in thermogram A) are still present in thermogram B,
though they are somewhat weaker in this curve.
However, for 20 and 40 min ozonation time, chemi-
sorbed phenol was also removed to a large extent from
activated carbons since no peak is detected in the
thermograms C and D in the 500–750 K temperature
range. The presence of a weak peak at 870 K in
thermogram C and peaks at 490 and 970 K in
thermogram D is remarkable. Such features may not
be attributed to phenol residue removal but to oxygen
surface groups that are formed onto activated carbon by
means of ozonation and that decompose by heating
effect. In fact, these thermal effects coincide with those
shown in Fig. 3. The existence of SOG on ozone
regenerated carbons was also confirmed by quantitative
determinations as shown in Table 3.
The ability of ozone to restore specific surface areas of
CS- activated carbons after the removal of adsorbed
phenol was studied by measuring N2 adsorption
isotherms of regenerated samples. Fig. 7 shows the
evolution of BET surface areas of CS-activated carbons
through phenol adsorption and subsequent ozone
regeneration. For all GAC, an important decrease in
the surface area was observed after phenol adsorption.
As seen in Fig. 7, such a decrease was in good agreement
with the calculated surface area covered with phenol.
After regeneration with ozone, the surface area was
600
SBET (m2/g)
400
200
0 completely removed from the surface while at much
0 20 40 60 80
Adsorption
Ozone regeneration time (min)
Fig. 7. Changes of BET surface areas of CS-activated carbons
during phenol adsorption and ozone regeneration. Symbols:
(’) CS-10; ()CS-20; (m)CS-30. Open symbols correspond to
data of calculated SBET of spent GAC from the amount of
phenol adsorbed.
restored to some extent depending on the ozonation
time and the GAC itself. For a given CS-activated
carbon there is an optimum ozonation time (about
40 min for CS-10 and 60 min for CS-20 and CS-30) for
which the surface area of regenerated sample reaches a
maximum, which is at least 80% of that of the virgin
GAC. Further ozonation beyond the optimum time
gives rise to a slightly decrease of surface area. This final
surface area decrease could arise from the oxidation of
activated carbon when the ozone dose is higher than that
necessary to achieve just removal of phenol. In connec-
tion with this, it should be stated that, as a rule, SOG
formed by carbon oxidation decrease BET surface area
[37].
The phenol adsorption isotherms for ozone-regener-
ated CS activated carbons are shown in Fig. 8. It can be
observed that the phenol uptake was always higher for
virgin GAC than for regenerated samples. From the
isotherms the efficiency of regeneration was calculated
by Eq. (4) to take values shown in Table 5. As seen, in
general the percentages of regeneration obtained by
ozonation were somewhat lower than those achieved by
thermal regeneration at appropriate conditions. How-
ever, carbon weight loss after ozonation were negligible
if compared with thermal process. Both GAC char-
acteristics and ozonation time influences regeneration.
For CS-10 the highest regeneration percentage was
achieved after 40 min ozonation while for CS-20 and CS-
30 the regeneration was more efficient for 60 min
ozonation time. This behavior is in agreement with the
evolution of surface areas through ozone regeneration
(see Fig. 7). The influence of the GAC sample seems to
be related to the concentration of phenol adsorbed onto
spent activated carbons and the amount of ozone
transferred to carbon. Following an ozone mass balance
in the reactor, the ozone consumed in the overall process
could be estimated (see results in Table 5). Since the
concentration of phenol adsorbed on the spent activated
carbon could be estimated by q0, the ratio of ozone
consumed to phenol adsorbed was calculated as shown
in Table 5. The highest regeneration percentage was
obtained for CS-10 with a ratio of 2.08 g O3/g phenol,
which is in the range reported for phenol removal by
ozonation in aqueous systems [38]. For 1 h ozone
regeneration of spent CS-20 and CS-30 ratios were also
close to the former (i.e., about 2 g O3/g phenol) and the
percentages of regeneration were satisfactory as well
(about 75–80%). As a rule, at lower ratios phenol is not
higher ratio ozone can react with the carbon itself, thus
leading to SOG formation which inhibits phenol
adsorption to some extent. In both cases, the percentage
of regeneration is lowered.
Finally, the performance of ozone regeneration of CS-
activated carbons was tested through three successive
adsorption–regeneration cycles. Fig. 9 shows the phenol
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P.M. Alvarez et al. / Water Research 38 (2004) 2155–2165 2163

0.20 0.20

0.15 0.15

q (gPh·gGAC-1)
q (gPh·gGAC-1)
0.10 0.10

0.05 0.05

0.00 0.00
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
(A) Ce (g·L-1) (B) Ce (g·L-1)

0.20

0.15
q (gPh·gGAC-1)

0.10

0.05

0.00
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
(C) Ce (g·L-1)

Fig. 8. Batch adsorption isotherms of phenol on virgin and on ozone-regenerated CS-activated carbons. (A) CS-10; (B) CS-20; (C) CS-
30. Symbols: (’) virgin-activated carbon; (J) 40 min ozone-regenerated activated carbon; (&) 1 h ozone-regenerated activated
carbon.

adsorption isotherms obtained after each 1 h ozone 20

regeneration step of CS-30. It can be seen that after the
successive regenerations with ozone the shape of the
isotherm progressively changed from L-shaped to a two 15
stepped isotherm. The existence of an intermediate
q x102 (gPh/gC)

plateau has been also observed for the adsorption of

phenol and substituted phenols on other oxidized 10
carbons [33]. It has been argued that such a plateau
may be explained by the adsorption in different type of
sites (i.e., chemisorption via SOG and p–p interaction
5
between graphene layers and the aromatic ring of
phenol).
In spite of the change in adsorption mechanism, the
0
adsorption capacity was practically maintained through 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
the repetitive use of GAC. In fact, the percentage of
Ce (g/L)
regeneration calculated by means of Eq. (4) were found
to be 79.2%, 79.4% and 68.0% after 1, 2 and 3 repeated Fig. 9. Batch adsorption isotherms of phenol on virgin CS-30
use of GAC, respectively. and on various 1 h ozone-regenerated CS-300activated carbons.
Symbols: (’) virgin CS-30; () regenerated CS-30 (cycle 1); (.)
regenerated CS-30 (cycle 2); (m regenerated CS-30 (cycle 3).
4. Conclusions

The results presented in this work show that the

regeneration of CS-activated carbons exhausted with above 50% and is difficult to remove by pyrolysis
phenol may promisingly be carried out by ozonation at treatment since charred products are retained on carbon
ambient conditions. Phenol is adsorbed onto GAC surface. The use of an oxidant is compulsory for thermal
prepared from CS by physical and chemical mechan- regeneration to be feasible. When CO2 is employed, the
isms. The percentage chemically adsorbed is usually capacity of regenerated GAC to uptake phenol is
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P.M. Alvarez et al. / Water Research 38 (2004) 2155–2165
completely recovered only when burn-off is about 15%.
Direct ozonation of CS-activated carbons affects their
chemical structure by forming acidic SOG (mainly
carboxylic) that prevent, in part at least, the adsorption
of phenol. When used as regenerating agent, ozone is
able to remove both physically adsorbed and chemi-
sorbed phenol from the carbon surface, restoring most
of its surface area. According to findings of this work, it
can be postulated that during the regeneration of spent
GAC with ozone, phenol is first removed by ozonation.
However, if too much ozone is used, in addition to the
removal of phenol ozone undergoes interactions with the
carbon surface to produce various SOG, which decrease
surface areas and play a negative role on the adsorption
of phenol. Then, the key factor in ozone regeneration of
CS-activated carbons is the estimation of the optimum
ozone dose to be applied. The task now is to carry out
more experimental work with different activated car-
bons and adsorbates to widen these conclusions to other
systems.
Acknowledgements
The authors thank the C.I.CY.T of Spain and
European Feder Funds for the economic support
through the project PPQ2000/0412.
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