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J Therm Anal Calorim (2014) 115:537543

DOI 10.1007/s10973-013-3293-y

Fundamental study on the thermal regeneration stages


of exhausted activated carbons: kinetics
lvarez-Murillo
B. Ledesma S. Roman A. A
E. Sabio C. M. Gonzalez-Garca

Received: 3 March 2013 / Accepted: 10 June 2013 / Published online: 23 July 2013
Akademiai Kiado, Budapest, Hungary 2013

Abstract In this work the thermal regeneration of activated carbons saturated with p-nitrophenol has been analysed. By thermogravimetry, it was possible to elucidate
the different events taking place during the thermal treatment, and relate them to the type of adsorption in the
interfacial system. It was found that the mass loss during
thermal treatment comprises a complex process in which
different stages are involved, such as drying, desorption of
physisorbed adsorbate, breaking up of surface functional
groups, cracking of products from adsorbatesurface-specific interactions, etc. The analysis of the textural and
surface chemistry characteristics of the pristine and
regenerated adsorbent confirmed the thermal desorption
mechanisms. Moreover, a kinetic study based on temperature-programmed desorption and Suzuki models was
performed, using thermogravimetry data at different heating rates (520 K min-1). From this analysis, the values of
activation energy involved in each degradation step were
estimated.
Keywords Thermal regeneration  Kinetics  Adsorption 
Activated carbon  Environment  Materials processing

Electronic supplementary material The online version of this


article (doi:10.1007/s10973-013-3293-y) contains supplementary
material, which is available to authorized users.
B. Ledesma
Department of Mechanical, Energetics and Materials
Engineering, University of Extremadura, Avda. Elvas s/n,
06006 Badajoz, Spain
lvarez-Murillo  E. Sabio 
S. Roman (&)  A. A

C. M. Gonzalez-Garca
Departament of Applied Physics, University of Extremadura,
Avda. Elvas s/n, 06006 Badajoz, Spain
e-mail: sroman@unex.es

Introduction
Activated carbons (ACs) are successfully used to remove
pollutants from water; however, they become saturated
after time, and their adsorption capacity is decreased. Since
industrial adsorption operations are a cyclic process composed of adsorption and regeneration steps, efficiency and
cost of regeneration play important roles in the overall
feasibility of an adsorption process [1].
Various processes are available for the regeneration of
spent adsorbents such as desorption by inert stream,
desorption at high temperature, microwave regeneration,
desorption by changing affinity between adsorbent and
adsorbate by chemical reagents, and removal of adsorbates
by thermal or biochemical decomposition [2, 3]. Among
them, thermal regeneration is the most used one, due to its
simplicity, low cost and versatility [1, 4].
Several authors have investigated the recovery of the
adsorption capacity of ACs by means of thermal regeneration methods [1, 48]. These studies highlight the complex
nature of adsorption and desorption processes, related to the
heterogeneity of the AC, which does not present a regular
distribution of active sites. In this way, some adsorbate
molecules will be physisorbed by weak interactions, and will
be desorbed without modifying their original structure when
subjected to a modest temperature treatment [9]. For the
same process, certain compounds adsorb strongly on the ACs
via chemical adsorption, in such a way that the adsorbate can
readily be splitted on the carbon surface and its derivatives
will be released during desorption [10].
Although the results on thermal degradation found in the
bibliography show satisfactory values of adsorption capacity
recovery, the analyses made on the process itself are very scant.
As a consequence, the operating parameters are not optimized
and the processes could be often improved on. Within this

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538

context, the knowledge of the thermal degradation kinetics is


essential for the proper design of regeneration systems.
Thermogravimetry has proven to be an effective technique for studying AC regeneration processes [3, 68, 11].
This technique allows the isolation of the different stages
involved in thermal regeneration, and the determination of
kinetics parameters by means of appropriate models.
In a previous work, our research group has investigated
the adsorption of p-nitrophenol (PNP) in aqueous solution at
neutral pH, and concluded that basic adsorbents are more
interesting [10]. These results suggested that PNP adsorption
systems are influenced by a complex interplay of different
forces, where dispersive interactions between the solute
aromatic ring and the carbon basal planes were enhanced,
while the participation of specific reactions such as chemical
and electrostatic interactions were also considered.
With the aim of getting further knowledge on this particular adsorption system, this study was undertaken to
assess the thermal regeneration potential of ACs following
their saturation with PNP. The study was focussed on the
degradation process itself, studying the kinetics implied in
the different stages and relating it to the nature of
desorption process. Moreover, the permanence of either the
adsorbate and/or derivatives on the carbon porous network
was investigated by means of N2 adsorption at 77 K and
Hg porosimetry. Also, the changes in the surface functionalities of the adsorbents after thermal treatment were
analysed by FT-IR Spectroscopy.

B. Ledesma et al.

[12] to calculate: (a) the value of the BET-specific surface


(SBET), (b) the external surface (SEXT) by the as-method, using
the reference non-porous solid proposed by Carrott et al. [13],
(c) the percentage of internal surface (Sint), by the difference
between SBET and SEXT, (d) the volume of micropores through
the DubininRadushkevich equation (VmiDR), and (e) the
volume of mesopores (Vme), as the difference between the pore
volume at p/p0 = 0.95 and p/p0 = 0.10.
The regeneration efficiency (RE, %) was determined
according to Eq. 1, using two different adsorbates: with
PNP data in aqueous solution at 298 K (taking the
adsorption quantity as the difference between the solution
initial and final concentration), and from N2 adsorption
data a 77 K, taking the adsorption capacity as the one
corresponding to the relative pressure of 0.95.
RE %

Adsorption capacity of regenerated AC


 100
Adsorption capacity of fresh AC
1

The mercury intrusion curves were collected at room


temperature with a conventional porosimeter (Autopore
4900 IV, Micromeritics, USA) and were used to determine
the meso (VmeP) and macropore (VmaP) volumes.
The surface chemistry was studied by means of FT-IR
spectroscopy. FT-IR spectra were recorded with a Perkin
Elmer model Paragon 1000PC spectrophotometer, using
the KBr disc method, with a resolution of 4 cm-1 and 100
scans.
Thermogravimetric analysis and kinetics study

Experimental
Preparation of activated carbon
A granular commercial AC (CB, from Chemviron Carbon)
was used in this study. The saturation of the carbon was
made by adding 5 g of this adsorbent to 1 L of PNP
solution (Sigma, purity [99 %, 3 g L-1). The suspension
was thermostated at 298 K and mechanically shaken for
72 h. Both the solution concentration and contact time
were chosen based on previous experimentation, which
demonstrated that these conditions guarantee the saturation
and adsorption equilibrium, respectively [10].
After equilibrium, the spent carbon was weighted and kept
in a desiccator. The PNP concentrations in the supernatant
solutions after adsorption were determined using UVVis
Spectrophotometry at the maximum wavelength of 225 nm.
Characterization of activated carbons
Nitrogen adsorption isotherms at 77 K were made using a
semiautomatic adsorption unit (AUTOSORB-1, Quantachrome). Experimental data were analysed by suitable methods

123

Thermogravimetric analyses of the spent ACs were made


using a thermobalance (Setsys Evolution, SETARAM).
Spent carbons were heated to 1,173 K in dry Argon
(100 cm3 min-1) at different heating rates (5, 10, 15,
20 K min-1). From the TG/DTG experimental data, the
different stages of thermal desorption and the corresponding temperature and residual mass values were identified.
The kinetics study was made according to classical
temperature programmed desorption theory [13], as well as
Suzuki [14] approach, which is described in details in
Kinetics study section.

Discussion of results
Thermogravimetric analysis
The TG/DTG profiles of PNP-spent AC have been plotted
in Fig. 1. From this figure it can be inferred that regeneration proceeds in several stages, which occur at different
velocities [15]. The existence of these periods are related to
the various physicochemical phenomena such as drying,

Fundamental study on the thermal regeneration stages

539

TG/m/m0100

98

TG

0.4

DTG

0.35
0.3

96

0.25
0.2

94

0.15
0.1

92

DTG/m/m0/K1

0.45

100

0.05
90
200

400

600

800

1000

0
1200

T/K
Fig. 1 TG/DTG curves of PNP-exhausted AC

physical desorption, breaking up of chemisorbed intermediates, as well as charring processes [6, 14]. In our study,
four stages can be observed along the heating process (see
Fig. 1):

First, we can notice a very slight decrease on the carbon


mass for temperatures below 423 K, which can be
associated with the content of moisture of the AC [2, 6].
Moreover, at these conditions, a certain amount of PNP
might be released because of the drag of the adsorbate
molecules during water evaporation and the removal of
the weakly adsorbed molecules [6].
Subsequently, the thermogravimetric curve exhibits a
significant peak centred at 517 K. This second peak can
be associated with the desorption of volatile compounds weakly adsorbed or physisorbed [1]. The
temperature value associated with this peak is influenced by the strength of the physisorbed molecules
and/or the ease to be desorbed due to steric impediments. In this sense, Ferro-Garca et al. [6] have
reported that a wider pore size distribution allows a
lower temperature for this peak.
Then, we find a slight peak at 692 K, which could be
related to the desorption of chemisorbed compounds
[5], not only the adsorbate as a molecule but also the
products resulting from the combination of the molecule with the surface groups of the adsorbent.
Finally, we can find for the range of temperatures above
736 K a very slight mass loss, which is extended up to
the end of the process. Previous works [47, 14] have
related this final stage to thermal cracking processes, as
well as pyrolytic polymerization of heavy molecules.
Ferro-Garca et al. [6] refer this stage to the decomposition of organic phenolic compounds from the
carbon surface in the case of ACs exhausted with
chlorophenols (CP), as they infer from the corresponding gas analyses.

With the aim of comparing the thermal behaviour of the


fresh and spent carbon, TG/DTG analyses were made on

the original adsorbent. The corresponding plots have been


included as Supplementary material (S1). As expected, it
was found that the thermal treatment of the fresh carbon
results in a lower overall mass loss, as compared to the
exhausted adsorbent (a residual mass fraction of 0.91 and
0.78 was obtained for the fresh and exhausted ACs,
respectively).
In the case of the fresh sample, the slight mass loss can
be related to the removal of surface heteroatoms in the
form of surface functional groups, as it has been pointed
out in previous works [6]. The greater intensity of mass
loss in the case of spent adsorbent is consistent with the
fact that apart from the thermal elimination of surface
functional groups, in the exhausted sample some other
compounds are being desorbed.
It is also noticeable that both TG/DTG curves follow a
similar pattern, suggesting that in any case we can find a
bimodal degradation mechanism, in which the first one has
to be related to the removal of weakly adsorbed compounds
or functionalities (as oxygen ones), while the second one
corresponds to more energetic interactions.
Suzuki [14] studied the thermal decomposition of different organics and found that TG curves could be classified into three different groups with regard to their shapes:
type I, corresponds to TG curves exhibiting concavity
towards temperature, and was characteristic of volatile
species such as hexane, heptane, benzene, etc.; type II,
related to high molecular mass compounds (as polyethylene glycol or sodium dodecylbenzenesulfonate), are convex to x axis, and show a marked mass loss during a narrow
temperature interval. Finally, type III TG curves showed a
gradual decrease of the carbon mass with temperature rise,
with a relatively high fractional residue at 1,073 K; this
shape has been related to species such as phenol, b-naphtol,
lignin and humic acid.
From Fig. 1 it can be inferred that the TG curve could be
classified as a combination of the three types. Most of the
works on TG analyses of ACs spent with phenols [14] and
phenol-derived compounds [6] have also found this trend.
From the TG data shown in Fig. 1 it can be inferred that
the first stage of thermal regeneration corresponds to a
mass loss of 1.4 %, at temperatures lower than 423 K. For
this period, the maximum velocity of mass loss (DTGmax)
is equal to 0.411 K-1. Later on, the second stage is located
from 473 up to 628 K, and involves a mass loss of 2.49 %.
In this case, the DTGmax has a value of 0.354 K-1. Then,
the third stage (628782 K) involves a mass loss of 1.02 %
and presents a DTGmax of 0.154 K-1. Finally, the residual
mass loss on the fourth stage (T [ 782 K) up to the end of
the process is equal to 2.23 %.
In general, adsorbates with low heat of sublimation are
easier to desorb, while those molecules with high boiling
points are more prone to be thermally cracked on the

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540

B. Ledesma et al.

adsorbent surface; in the case of phenols, they may undergo


polymerization processes. Zhou et al. [16] have found that
although pure PNP sublimes at 404 K, its sublimation from
an adsorption system occurs at higher temperatures, near
453 K. This is consistent with the fact that PNP is being
physically desorbed in the second stage.
On the other hand, the cracking temperature depends on
the type of particular reaction taking place. In this sense,
type II TG curve assumes that the fragments of reaction
products remaining on the carbon surface are easily
removed. Dissimilarly, type III is related to the nature of
organic adsorbates, which form polymeric products after
sequential cracking reactions in the adsorbent surface. This
explains the high residual mass found in these systems.
The permanence of cracking products remaining in the
carbon surface can be verified by the textural and chemical
analysis of the adsorbent, which may have changed significantly as a consequence of regeneration process.
Kinetics study
In Fig. 2 the effect of heating rate on the DTG profiles of
spent CB carbon has been plotted for the runs made in this
series (experiments denoted as HR-5, HR-10, HR-15 and
HR-20, for heating rates of 5, 10, 15 and 20 K min-1,
respectively).
In this Figure, the different thermal degradation steps
described in Thermogravimetric analysis section can be
observed, for the various heating rates. In this study, we
isolate the peak associated with drying (temperature close
to 373 K), and analyse the other two peaks. These two
peaks are denoted as peak A (or the peak associated with
the desorption of physisorbed compounds) and peak B (the
one related to desorption or splitting up of chemisorbed
compounds). From the experimental data, the temperature
(TdA and TdB) and residual mass loss (m/m0) corresponding to each desorption peak (RmA and RmB), as well as that
2.5

HR 5

where b is the heating rate (K min-1), R (8.314 J mol-1


K-1) is the universal constant of ideal gases, Tm (K) denotes
the peak temperature and A (min-1) represents the Arrhenius pre-exponential factor.
Application of Eq. (2) to thermogravimetry experimental data allowed to obtain values of Ea equal to 9.72 and
82.57 kJ mol-1 for peaks A and B, respectively, obtaining
correlation coefficients (R2) above 0.95 in both cases. The
distinct nature of the heat involved in the desorption of
weakly physisorbed (peak A) and strongly chemisorbed
species (peak B) is consistent with the great difference
between these two values.
Although the previous model has been used by most of
the authors studying desorption kinetics, it has a limitation;
it assumes that the mass loss proceeds following a pseudofirst order kinetics along the whole process, which rigorously would be related to a thermal decomposition process.
In order to overcome this constraint, Suzuki accomplished
the kinetics study by means of two different models,
depending on the nature of the process that is presumably
taking place. In this way, while the first stage of the thermal
treatment (ignoring the drying step) is related to the
desorption of volatile organic compounds, the second one
should be treated as a thermal cracking process.
According to Suzuki approach, whose complete development and application methodology can be found at Ref.
[14], the desorption step can be described in the basis of

HR 10

DTG/m/m0/K1

of the final process (Rmf) have been determined, and are


collected in Table 1.
From Fig. 2 and Table 1 it can be inferred that
decreasing the heating rate brings out a shift of the DTG
curves towards lower temperatures. This is consistent with
a better energy transference, due to longer residence times
for slower heat treatments, and is in agreement with temperature programmed desorption theory [17]. According to
this model, the activation desorption energy (Ea, kJ mol-1)
can be determined from Eq. 2:


bEa
Ea
A exp
2
RTm2
RTm

HR 15
HR 20

1.5

Table 1 Characteristical values of residual mass (m/m0, %) and


corresponding temperature (K)

Temperature/K
TdA

TdB

RMA

RMB

RMf

HR-5

517

692

0.9738

0.9564

0.9286

HR-10

544

696

0.9442

0.8651

0.8023

HR-15
HR.20

566
574

704
712

0.9154
0.8816

0.8488
0.8208

0.7826
0.7608

0.5
0
200

400

600

800

1000

1200

T/K
Fig. 2 DTG curves of PNP-loaded AC under different heating rate
conditions (5, 10, 15 and 20 K min-1)

123

Residual mass/%

Td desorption temperature, RM residual mass

Fundamental study on the thermal regeneration stages

541

Langmuir isotherm [18], which can be related to the isosteric heat of adsorption (Qiso), by the expression:
m

m
 1 m0 Qiso 

m0 1 RT
exp RT

where m, m0 and m? denote, respectively, the adsorbate


quantity in the carbon at the beginning of the process
(neglecting the drying process), at any time and at the
infinite (taken as the maximum desorbed value). On the
other hand, since Suzuki model indicates that the second
degradation stage has to be regarded as a cracking process,
a pseudo-first order equation (such as 2) would be used.
The application of Langmuir Desorption model to the
first thermal stage experimental data allowed the obtention
of an average value of Qiso equal to 14.25 kJ mol-1.

value of 64 m2 g-1. Moreover, the relative proportion of


mesopores of CB-spent is higher than that of pristine carbon, thus indicating that the pore blockage due to PNP
molecules is greater in the case of the smallest pores. This
information was also revealed from the N2 adsorption
isotherm, which showed a sharper knee at low relative
pressures and a better defined plateau for CB-pristine, in
comparison with CB-spent.
Finally, the thermal treatment caused an important
increase on the AC adsorption capacity (CB-regenerated)
Table 2 Textural parameters determined from N2 adsorption at 77 K

CB-pristine

Characterization of activated carbons

CB-spent
CB-regenerated

(a)

VmiDR/
cm3 g-1

Vme/
cm3 g-1

SEXT/
m2 g-1

Sint/
%

930

0.490

0.060

78

97

64

0.038

0.015

13

80

615

0.319

0.031

51

92

0.5
CB Fresh
CB Regenerated

0.4

CB Spent

V/cm3 g1

The study of the textural and surface chemistry characteristics of the ACs, made by the techniques described in
Experimental section, revealed the information described
below.
First, N2 adsorption isotherms at 77 K (Fig. 3) allowed
to obtain the characteristical textural parameters (Table 2)
described in Characterization of activated carbons
section.
From both the N2 adsorption isotherms and the corresponding values of pore volumes it can be inferred that the
pristine AC is a microporous solid with a high value of
apparent surface (SBET of 930 m2 g-1), and a little contribution of external area. It presents a micropore volume
of 0.490 cm3 g-1, and negligible mesopore volume.
As a result of saturation, the porosity of the adsorbent
was significantly decreased; the apparent surface of the
spent carbon diminished more than ten times, reaching a

SBET/
m2 g-1

0.3

0.2

0.1

0.0
1

10

100

1000

10000

100000

D/nm
400

(b) 0.35
dLogV/dLogD/cm3 g1 nm1

CB Fresh

V/cm3 g1

300

200
CB Fresh
CB Regenerated

100

CB Spent

0
0

0.2

0.4

0.6

0.8

P/P0
Fig. 3 N2 adsorption isotherms at 77 K on fresh, spent and regenerated ACs

0.30

CB Regenerated
CB Spent

0.25
0.20
0.15
0.10
0.05
0.00
1

10

100

1000

10000

100000

D/nm
Fig. 4 Hg intrusion analyses on fresh, spent and regenerated ACs.
a Hg intrusion data and b pore size distribution

123

B. Ledesma et al.

CB Fresh

Transmitance/a.u.

830 cm1

2300 cm1

2900 cm1

3400 cm1

Fig. 5 FT-IR spectra on fresh,


spent and regenerated ACs

1375 cm1
1100 cm1

542

CB Spent

5000

4000

3000

2000

900 1300 cm1

1580 cm1

CB Regenerated

1000

Wavenumber/cm1

increasing more than nine-fold the apparent surface of the


spent carbon. Moreover, the regeneration process enhanced
specially the development of microporosity, while the
mesopore volume was slightly increased.
Mercury intrusion data (Fig. 4) were consistent with the
above-mentioned results. First, Hg intrusion volume was
reduced as a result of saturation, while the subsequent
thermal regeneration brought out an increase on the
accessible pore volume. Also, from pore size distribution
plots, it is depicted that before exhaustion, the intrusion of
Hg onto the adsorbent is more marked in the range of
smaller pores, as compared to the spent and regenerated
samples.
Regarding the PNP adsorption recovery (R.E., %), as
determined according to Eq. 1, we obtained a value of
68.3 %. Previous works [4] have studied the thermal
regeneration of ACs exhausted with CP under similar
conditions and have achieved CP adsorption recoveries
close to 50 %, and concluded that the rest left on the carbon surface is made up of decomposition products of the
adsorbent.
Finally, the surface functionalities on the fresh, spent
and regenerated ACs were studied by FT-IR analyses. In
Fig. 5, the spectra corresponding to these adsorbents have
been plotted; the assignation of the corresponding functional groups was made according to suitable bibliography
[19]. From this Figure, it is obvious that the thermal
regeneration of PNP-exhausted CB brings out the modification of the surface chemistry of the carbon, in comparison with the virgin sample.
The wide band 3,400 cm-1 is the only one which is
found in all cases, and could be attributed to OH
stretching vibrations in hydroxyl groups, due to the moisture content of the adsorbent. Apart from this band, each

123

carbon shows different surface functionalities which are


discussed individually below.
In the case of the fresh carbon, the band located at
2,900 cm-1 is compatible with the presence of C=O bonds
in aldehydes. Also, the signal around 2,300 cm-1 might be
related to C=O bonds in ketones. The band at 1,580 cm-1
can be assigned to aromatic stretching C=C vibration,
while the signal centred in 1,375 is characteristical of
methyl groups. Finally, the band at 1,100 cm-1 denotes the
presence of secondary hydroxyl groups and the signal near
830 cm-1 can be related to phenyl groups.
The adsorption of PNP on the carbon surface gave rise
to the shrinkage of some of the previous bands for CBspent. Besides, the appearance of the band at 1,580 cm-1 is
remarkable, which can be associated with C=O vibrations
in carbonyl groups and aromatic rings.
Finally, for CB-regenerated, a wide signal in the range
1,0001,300 cm-1 was found, which might be attributed to
CO single bond, such as those in ethers, and also to COH
groups.

Conclusions
The present study showed that the thermal degradation of
PNP-exhausted ACs occurs via different stages, which are
primarily related to the particular adsorption mechanism.
Apart from the initial drying step, two main desorption
events are found: the one corresponding to the desorption
of physisorbed PNP, and the stage related to the desorption
of chemisorbed compounds (not only PNP-derived compounds, but also those products from thermal cracking
reactions occurring in the carbon surface as a consequence
of high temperatures).

Fundamental study on the thermal regeneration stages

The porosity and surface chemistry characterization of


Pristine and Regenerated ACs allowed to conclude the
previous findings. First, after regeneration, N2 adsorption
capacity was increased up to 65 %, in relation to that of the
fresh AC, indicating the presence of cracking products
blocking the accessible microporosity. This fact was verified by the FT-IR study, which showed a modification of
the surface functionalities in the regenerated samples, in
comparison with the virgin ones.
Finally, the study was completed by a kinetic analysis,
by means of Thermal Desorption Theory. For this task, TG
analyses at different heating rates were performed, and the
values of activation desorption energy (Ea) were calculated
for each step. The results obtained showed a significantly
higher Ea value for the second stage of desorption, which
corroborated the greater energy involved in the interactions
associated with this event, in accordance with the previous
description.
Acknowledgements The authors are grateful to the University of
Extremadura and the Gobierno de Extremadura for financial support
through Project PCJ1106. B. Ledesma thanks the Junta de Extremadura for the predoctoral grant.

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