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DOI 10.1007/s10973-013-3293-y
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
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
123
538
B. Ledesma et al.
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
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,
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):
123
540
B. Ledesma et al.
HR 5
HR 10
DTG/m/m0/K1
HR 15
HR 20
1.5
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/%
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
CB-pristine
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
1375 cm1
1100 cm1
542
CB Spent
5000
4000
3000
2000
1580 cm1
CB Regenerated
1000
Wavenumber/cm1
123
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).
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