See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/277352002

Ozonation of Cyanide Catalyzed by Activated Carbon

Article  in  Ozone Science and Engineering · May 2014

DOI: 10.1080/01919512.2014.965804

CITATIONS READS
4 122

4 authors, including:

Marco Antonio Sanchez Castillo Francisco R Carrillo-Pedroza

Universidad Autónoma de San Luis Potosí Autonomous University of Coahuila
39 PUBLICATIONS   1,331 CITATIONS    47 PUBLICATIONS   438 CITATIONS   

SEE PROFILE SEE PROFILE

Ma. De Jesús Soria-Aguilar

Autonomous University of Coahuila
32 PUBLICATIONS   128 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Right now, I am working in hydrometallurgy of lead, copper and zinc (leaching of sulphides, solutions purifications and iron precipitation). View project

All content following this page was uploaded by Francisco R Carrillo-Pedroza on 17 March 2016.

The user has requested enhancement of the downloaded file.

This article was downloaded by: [Marco Sanchez-Castillo]
On: 13 May 2015, At: 18:15
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Ozone: Science & Engineering: The Journal of the

International Ozone Association
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/bose20

Ozonation of Cyanide Catalyzed by Activated Carbon

a b a
Marco A. Sánchez-Castillo , Francisco R. Carrillo-Pedroza , Flor Fraga-Tovar & Ma. de Jesús
b
Soria-Aguilar
a
Facultad de Ciencias Químicas, Universidad Autónoma de San Luis Potosí, San Luis Potosí
78290, Mexico
b
Facultad de Metalurgia, Universidad Autónoma de Coahuila, Monclova, Coahuila 25710,
Mexico
Accepted author version posted online: 25 Sep 2014.Published online: 25 Sep 2015.

Click for updates

To cite this article: Marco A. Sánchez-Castillo, Francisco R. Carrillo-Pedroza, Flor Fraga-Tovar & Ma. de Jesús Soria-Aguilar
(2015) Ozonation of Cyanide Catalyzed by Activated Carbon, Ozone: Science & Engineering: The Journal of the International
Ozone Association, 37:3, 240-251, DOI: 10.1080/01919512.2014.965804

To link to this article: http://dx.doi.org/10.1080/01919512.2014.965804

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.

This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
 Ozone: Science & Engineering, 37: 240–251
Copyright © 2015 International Ozone Association
ISSN: 0191-9512 print / 1547-6545 online
DOI: 10.1080/01919512.2014.965804
Ozonation of Cyanide Catalyzed by Activated Carbon
Marco A. Sánchez-Castillo,1 Francisco R. Carrillo-Pedroza,2 Flor Fraga-Tovar,1
and Ma. de Jesús Soria-Aguilar2
1
Facultad de Ciencias Químicas, Universidad Autónoma de San Luis Potosí, San Luis Potosí 78290, Mexico
2
Facultad de Metalurgia, Universidad Autónoma de Coahuila, Monclova, Coahuila 25710, Mexico
In this work, the removal of cyanide from aqueous solutions
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
was accomplished by using the synergetic effect of activated
carbon and an oxidizing agent. A basic-character coconut
shell activated carbon (CAC) was used; experiments were
conducted in a semi-batch reactor, at 25 ◦ C, initial pH of
11.5, and using cyanide solutions with initial concentration
up to 1200 mg/mL. In particular, the beneficial effect of an
oxidizing agent such as air, oxygen or ozone on the removal
of cyanide by CAC was evaluated. At the optimum operating
conditions found in this study, 1200 mg/mL of cyanide were
totally decomposed in about 3 h, by using 1 g of CAC and
about 2 mgO3 /min. The experimental results were rational-
ized based on different mechanisms reported in the literature.
The findings provide the basis to optimize the removal of
cyanide from aqueous solutions in mining or metallurgical
effluents by using the synergetic effect of CAC and ozone.
Keywords Ozone, Activated Carbon, Cyanide, Advanced
Oxidation Process, Mining Effluent
INTRODUCTION
Cyanide leaching (cyanidation) is currently the most pre-
vailing process to extract precious metals, mainly gold and
silver, from geological ores (Botz 2001). This hydrometallur-
gical technique is so efficient that the mining of low-grade
precious metal ores has become profitable; however, several
practical, economic and environmental concerns are still mat-
ter of debate to optimize this process. For instance, the process
requires high cyanide consumption to improve metal recov-
ery but, in turn, it produces exceptionally large quantities
of cyanide-bearing wastes (cyanidation wastes) in the form
Received 12/31/2013; Accepted 9/8/2014
Address correspondence to Francisco R. Carrillo-Pedroza,
Facultad de Metalurgia, Universidad Autónoma de Coahuila,
Carr. 57, Km. 54.5, Monclova, Coahuila 25710, Mexico. E-mail:
raul.carrillo@uadec.edu.mx
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/bose.
240 M.A. Sánchez-Castillo et al.
of heap leach residues, tailings, and spent process waters
with several cyanide containing species (Mudder and Botz
2004). Among these species, free cyanide, which includes
cyanide anion (CN− ) and hydrogen cyanide, is considered
the most toxic cyanide form as it causes harmful effects at
relatively low concentration (U.S. Environment Protection
Agency 1999). Other cyanide species must be present in
higher concentration to induce toxicity; for example, hydro-
gen cyanate and cyanate ions are less toxic than cyanide and
they are easily dissolved under acid conditions. Similarly,
thiocyanate is relatively non-toxic as compared to free cyanide
(Akcil 2003).
The problem arising from the disposal of CN− from spent
solutions is also characteristic in other mining/metallurgical
industries, as it is the case when CN− is added as a modifier
in the flotation process to separate base metal sulfides from
pyrite; to a lesser extent, the problem is also found in the tex-
tile, plastics, jewelry, paint and agriculture industries (Young
et al. 2001). Thus, the safe industrial use of CN- requires
the appropriate transport, storage, handling, and mixing of
cyanide chemicals, as well as monitoring of the environment
when cyanide losses or discharges take place. In this case,
the appropriate treatment of the various cyanidation wastes is
required to avoid or minimize environmental and health issues
(Gijzen 2000).
Several biological, physical and chemical techniques have
been developed for the treatment of CN− solutions (Kitis
et al. 2005; Kuyucak and Akcil 2013; Sarla et al. 2004).
Biological treatments are a feasible alternative and environ-
mental friendly; however, these techniques are mostly used
for polishing applications because they cannot treat a highly
concentrated CN− waste (Dash et al. 2009a). Similar practical
limitations apply for physical methods, where CN− com-
pounds are removed from waste solutions by adsorption on
various organic and inorganic adsorbents such as minerals,
agricultural by-products, resins, activated carbon, and bone
charcoal (Agarwal et al. 2013; Asgari et al. 2014; Behnamfard
and Salarirad 2009; Gupta et al. 2012; Yeddou et al. 2010).
May–June 2015
 The application of activated carbon (AC) for the treatment
of cyanidation effluents is notoriously restricted due to the
limited adsorption capacity of AC to remove CN− (Adhoum
and Monser 2002). However, several studies have shown that
CN− removal can be significantly improved when the AC
surface is impregnated with metals such as Ag, Cu, Ni or
Fe (Adhoum and Monser 2002; Agarwal et al. 2013b; Depci
2012; Deveci et al. 2006, Yeddou et al. 2011, Zhang et al.
2010), and also when the adsorption process takes place in an
oxygen-containing atmosphere (Ahumada et al. 2002; Yasici
et al. 2009).
On the other hand, chemical oxidation methods such as
chlorination, ozonation, copper-catalyzed hydrogen peroxide,
electrolytic oxidation, as well as the AVR process and ther-
mal hydrolysis (Young and Jordan 1995), are either expensive,
require hazardous chemicals as reagents or cannot completely
accomplish the degradation of CN− species. Thus, the appro-
priate removal of CN− is a complex process that must be
further optimized and that requires the conjunction of several
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
approaches to improve the efficiency of the treatment. Suitable
alternatives to this purpose are advance oxidation processes
(AOP), which have been successfully used for the treatment
of other highly-toxic industrial effluents (Suty et al. 2004).
Some AOP for CN− decomposition have used a com-
bination of ozone (O3 ) with H2 O2 and UV light, or have
suggested the application of TiO2 to generate • OH radicals,
which, being a highly oxidizing species, increase the oxida-
tion rates of CN- and strong acid dissociable (SAD) cyanide
complexes (Ford et al. 2006; Kepa et al., 2008; Kim et al.
2003; Mert et al. 2014). It should be noticed that other AOP
combining the effect of O3 and AC have been suggested
to decompose diverse pollutants. In several applications, a
beneficial effect of AC has been documented when using
O3 for a faster removal of a number of recalcitrant model
compounds such as carboxylic acids (Faria et al. 2008),
alcohols (Kastner et al., 2008), phenols (Beltran et al. 2008;
Gu et al. 2008; Merle et al. 2010), phathalates (Ferreira de
Oliveira et al. 2011), dyes (Parsa and Negahdar 2012), and
some others resembling pharmaceuticals (Goncalves et al.
2013; Pocostales et al. 2010) and pesticides (Guzmán-Pérez
et al. 2011; Sanchez-Polo et al. 2006).
In the indicated AOP, the mechanism to explain the ben-
eficial effect of AC during the ozonation process is complex
and it is not fully elucidated. It is generally accepted that both
textural and surface chemical properties of AC, as well as the
operating conditions such as pH, temperature and initial solute
concentration, determine the extent of the decomposition of
organic pollutants. In addition, it has been postulated that both
homogeneous (liquid phase) and heterogeneous (AC surface)
reaction steps are required to explain the pollutant´s decom-
position (Ferreira et al. 2011; Rivera-Utrilla et al. 2010),
and also that some steps may involve . OH radical species in
the solution (Merle et al. 2010; Parsa and Negahdar 2012).
In addition, it has been suggested that basic-character acti-
vated carbon is the best catalyst, because the delocalized π
electrons or other oxygenated basic surface groups, such as
Ozonation of Cyanide Catalyzed by Activated Carbon
chromene and pyrrone or pyrrolic groups, have been identified
as active centers for the decomposition of O3 into • OH radi-
cals, which increases the oxidation or decomposition rates of
the pollutants.
Importantly, to date, there are no detailed studies of CN−
removal from aqueous solutions by using the combined effect
of AC and O3 . Therefore, in this work, we report the ben-
eficial effect of combining O3 and AC in the removal of
CN- from aqueous solutions. We studied different processes
that might take place in this system, including the adsorption
of CN− on CAC under different oxidizing atmospheres, and
the ozonation of CN− with and without CAC, for a better
understanding of the synergetic effect of AC and O3 for CN−
removal from aqueous solution.
MATERIALS AND METHODS
A commercial coconut shell activated carbon (named
CAC) was used to study the removal of free cyanide (CN− )
in aqueous solution under inert and oxidizing atmospheres.
CAC was crushed to get carbon particles in the range of -150
+106 microns. Carbon particles were sequentially washed
with deionized water to remove fine carbon powder; then, car-
bon particles were dried at 110 ◦ C and kept in a desiccator.
CAC was morphologically characterized by N2 physisorption
at 77 K to evaluate its surface area and pore volume; to this
purpose, a Coulter SA 3100 Series Surface Area and Pore Size
Analyzer (Brea, CA, USA) was used. Additionally, the surface
chemical properties of CAC were analyzed by Boehm’s and
mass titration methods. Boehm’s method (Boehm 1994) was
used to evaluate the surface acid and basic sites distribution
with a Titrino Metrohm 794 Basic acid-base titrator (Hereau,
Switzerland). Mass titration was used to determine the point
of zero charge (PZC) following a straightforward procedure
(Noh and Schwarz 1989) and using an Orion 720 A pH meter
(Waltham, MA, USA).
Experiments of CN− decomposition from aqueous solu-
tions were conducted in a semi-batch reactor, at room tem-
perature (25 ◦ C), and an initial pH (pHo ) of 11.5, which
was adjusted by adding 0.1 M NaOH. For all experiments,
250 mL of a CN− solution were loaded to the reactor; the
CN− initial concentration ([CN− ]o ) was varied from 100 to
1200 mg/L. An inert atmosphere was set in the reactor by
flowing 300 mL/min of He through the reactor. Similarly,
oxidizing atmospheres were set by flowing 300 mL/min of
air, O2 , or an O2 /O3 mixture. O3 was generated from air or
pure O2 by using an ozone generator (Pacific Ozone L21,
Benicia, CA, USA); the O3 inlet concentration ([O3 ]o ) was
varied between 0 and 6.88 mg/L. Typically, a given atmo-
sphere was secured in the reactor after the gas had flown
through the reactor for 10 min.
At the beginning of the experiment, a given CAC mass
(0–1.5 g), was contacted with the CN− solution. During the
experiment, CN− decomposition was monitored by periodic
analysis of both CN− and a cyanate (CNO-) concentration,
until an equilibrium condition was reached, or a total CN−
May–June 2015 241
 decomposition was achieved. CN− was measured by titration
with silver nitrate, in agreement with APHA-AWWA 4500-
CN D method. On the other hand, CNO− was indirectly
determined by measuring ammonia, which is a product of
cyanate hydrolysis, by using an Orion 95-12 ammonia elec-
trode. When necessary, O3 concentration was measured at
the reactor’s inlet and outlet by using an iodimetric method
(Gordon et al. 1992).
RESULTS AND DISCUSSION
CA Characterization
Surface area of CAC was calculated from the correspond-
ing N2 physisorption isotherm using the BET model; the
surface area of CAC was 731.5 m2 /g. In addition, by using
the t-plot model a micropore volume of 0.26 cc/g, and a
total pore volume of 0.39 cc/g were calculated for the CAC
used in this study. Results from mass titration showed that the
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
PZC of CAC was 9.0, which indicated the basic nature of
the CAC surface. In addition, results from Boehm’s method
showed that the concentration of basic surface sites of CAC
(0.54 meq/g) was higher than the acid surface sites concen-
tration (0.22 meq/g), in qualitative agreement with the PZC
of the CAC. A more detailed analysis of the surface acid sites
showed the presence of small surface concentrations of car-
boxylic, phenolic and lactonic surface groups. However, no
experimental work was made to determine the nature of the
basic surface groups of CAC, but these are typically associ-
ated to delocalized π electrons of the graphite layers and/or
to oxygenated surface groups such as chromene and pyrone
(Menendez 1999).
Cyanide Removal in the Presence of CAC under
Helium, Air, or O2 Atmospheres
The extent of CN− removal by CAC under an inert (i.e.,
He) or an oxidizing (i.e., air and O2 ) atmosphere was deter-
mined from the corresponding CN− adsorption isotherms,
which were measured at room temperature (∼25 ◦ C), [CN-]o
of 1200 mg/L, and [pH]o of 11.5, and by using 1 g of
CAC. Figure 1 shows the experimental data of the adsorption
isotherms under He, air and O2 atmospheres. In the pres-
ence of He, the extent of CN− adsorption on CAC was
limited to around 4 mgCN− /gCAC. In contrast, in the
experiments conducted under an air atmosphere (21% O2 ),
about 7 mgCN− /gCAC were removed from the solution;
this uptake was 75% higher than the CN− removal obtained
under a He atmosphere. Additionally, in a 100% O2 atmo-
sphere, the CN− adsorption capacity further increased up to
10 mgCN− /gCAC, which was more than 150% higher than
the CN− uptake under an inert atmosphere.
The experimental data of CN− adsorption isotherms has
been described in the literature by using 2- or 3-parameters
adsorption isotherm models. Based on the experimental
data profile found in this study, it was proposed that the
adsorption process could be described by either the Langmuir
242 M.A. Sánchez-Castillo et al.
12
10
Cs, mgCN/g CA
8
6
4
2
0
0 250 500 750 1000 1250
Cm, mg/L
He Air O2
FIGURE 1. Cyanide adsorption isotherms in CAC under He, air,
and oxygen atmospheres. The lines correspond to the predictions
of the Langmuir adsorption model.
(Equation [1]) or the Freundlich (Equation [2]) adsorption
models.
aCm
Cs = [1]
(1 + bCm )
Cs = KCmn [2]
where Cm is the concentration of solute (CN− ) at equilib-
rium or after adsorption, Cs is the mass of CN− adsorbed per
unit weight of CAC, a and b are the constants for Langmuir´s
model, and K and n are the constants for the Freundlich model.
In any case, the constants must be evaluated at a constant
temperature.
The linear fitting of the experimental data showed that both
Langmuir and Freundlich adsorption models were in close
agreement with the experimental data. A closer look of the
constants and r2 values (Table 1), suggested that the Langmuir
model was slightly better to describe the CN− adsorption pro-
cess on CAC. As it is shown by the solid lines in Figure 1,
under the experimental conditions used in this study, CN−
adsorption on CAC was reasonably well described by the
Langmuir isotherm. Accordingly, it could be initially assumed
that a reversible adsorption process takes place on the CAC
surface until a CN− monolayer condition is reached. This
finding is consistent with some works in the literature, which
also found that Langmuir model was more appropriate to
describe CN− adsorption in AC (Dash et al. 2009b; Deveci
et al. 2006; Gupta et al. 2012). It should be noticed that more
detailed work in the literature, modeling the thermodynamics
and kinetics of CN- adsorption on AC (Gupta et al. 2012),
has suggested that despite the fact that Langmuir model ade-
quately describes the process, the nature of CN− adsorption
could be chemical or physical, depending on the acidic or
May–June 2015
 TABLE 1. Parameters of the Freundlich and Langumir Adsorption
Models as Determined from a Linear Fit, for Experiments Conducted
under He, Air, and Oxygen Atmosphere
Freundlich K n r2
He 0.207 0.427 0.994
Air 0.0955 0.606 0.991
O2 0.0440 0.768 0.999
Langmuir a b r2
He 0.0286 0.0073 0.957
Air 0.0179 0.0019 0.998
O2 0.0163 0.0009 0.998
basic character of the AC sites, which might be changing as
the process is taking place.
In addition, it should be pointed out that the kinetics of
CN− adsorption was not evaluated in this work. However, it
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
has been suggested in the literature that, under similar exper-
imental conditions, kinetic data closely follows a pseudo–
second-order kinetic model, which assumes that two reactions
take place, one of them being fast and reaching the equilib-
rium quickly, and the other one being significantly slower
(Behnamfard and Salarirad 2009; Gupta et al. 2012). In more
detail, it could be assumed that at the beginning of the process
CN− adsorption is very fast, prevailing the adsorption of CN−
on the sites externally exposed on the CAC surface; even-
tually, the CN− adsorption rate slows down as the external
adsorption sites are occupied, and CN− are forced to a meso
and micro pore diffusion process, in order to find available
adsorption sites.
Furthermore, the limited CN− adsorption on CAC
observed in this study under a He atmosphere was in agree-
ment with previous findings in the literature (Deveci et al.
2006). The limited CN− adsorption capacity of CAC may be
explained in terms of the surface functional groups of CAC
and the nature of the CN− adsorption process taking place.
As indicated before, the surface character of the CAC used
in this study was mostly basic (i.e., ZPC 9.0). In addition,
it is reported that the basic character of AC is associated to
delocalized π electrons of the graphite layers, or to chromene-
like surface functional groups, such as quinone and pyrone
(Merle 2010, Parsa and Negahdar 2012). It is well known that
when a particle is dispersed in a solution with a pH higher
than its ZPC, the particle develops a surface charge that is
mostly negative. Therefore, under the pH condition used in
these experiments, a (pH)o = 11.5 that is required to keep
CN− in solution, it could be expected that the CAC particles
developed a mostly negative surface charge. In such a con-
dition (pH > pHZPC ), under an inert atmosphere (i.e., He),
it could be postulated that the negative surface groups of the
CAC acted as ion-exchange sites for CN− adsorption:
CA − OH − + CN − ↔ CA − CN + OH − [3]
Ozonation of Cyanide Catalyzed by Activated Carbon
It should be noticed that the CAC characterization by
Boehm’s method indicated that some acid character surface
groups with a positive charge were also present. If some of
these groups remained under the experimental conditions used
in this study, then the adsorption processes could also take
place via an electrostatic attraction mechanism between the
CN- ions and the positively charged sites. However, it should
be emphasize that this adsorption mechanism is feasible in
an inert atmosphere such as He only if the CAC surface kept
some positive surface charges. The conditions just described
explain the limited extent of CN− adsorption on CAC under a
He atmosphere.
Similarly, the beneficial effect of oxygen on the extent of
CN− adsorption on CAC observed in this study was also in
agreement with previous work in the literature (Yasici et al.
2009). To get a better insight on the effect of an oxidizing
atmosphere in the adsorption of CN− on CAC, two transient
experiments were conducted under the same conditions. One
experiment was performed without CAC and the other one
with 1 g of CAC; both experiments were carried out with
250 mL of a cyanide solution with a [CN-]o of 400 mg/L,
and 300 mL/min of 100% oxygen were flowed to the reactor
during the experiment. Figure 2 shows that in the experiment
without CAC there was not significant decrease of CN− con-
centration; the slight scatter observed in the experimental data
was due to the detection limit of the method used for CN−
analysis. In addition, no CNO− formation was detected in the
solution. These observations clearly suggested that no CN−
oxidation was taking place in the absence of CAC. On the
other hand, in the experiment conducted with 1 g of CAC, a
noticeable decrease in CN− concentration was observed.
The CN− concentration profile in this experiment clearly
showed two different regions. In the first region, which took
place within the first 9 h, a decrease of CN− concentra-
tion was observed at the beginning of the experiment and,
400
390
380
[CN-], mg/L
370
360
350
0 g CA
340
1 g CA
330
0 20 40 60
Time, h
FIGURE 2. Transient experiment of CN− oxidation under an O2
atmosphere with (1 g) and without CAC.
May–June 2015 243
 then, the CN− concentration asymptotically reached a pseudo-
equilibrium condition after 9 h of operation. In the second
region, the CN− concentration linearly decreased. In this
experiment, CNO− concentration was also measured. During
the first 9 h, corresponding to the first region previously
described, the CNO− concentration was practically negligible.
However, in the second region (i.e., after 9 h), CNO− con-
centration linearly increased. Additionally, the experimental
stoichiometric ratio of CN− decomposed to CNO− produced
in the solution under these conditions, closely matched the
theoretical value (CNO− /CN− = 1.6). The described trend
was similar for the experiments conducted with air (21% O2 )
and pure (100%) oxygen atmospheres.
The previous results suggested that two main processes
were taking place. One process was the adsorption of CN−
on the CAC surface. This adsorption process was more sig-
nificant at short operation times (i.e., during the first 9 h).
At the beginning of this stage, it could be postulated that
CN− concentration rapidly decreased due to the adsorption of
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
CN− on the sites easily accessible on the surface and, then,
the adsorption process was progressively slowed down due
to either thermodynamic constraints or to diffusional limi-
tations to reach accessible sites for CN− adsorption. In the
second process, it could be postulated that CAC catalyzed
the oxidation of CN− to CNO− , which was experimentally
supported by the production of CNO− when CAC was used,
and by the fact that no CNO− was detected in the experiment
without CAC. Importantly, under the conditions of this study,
the catalyzed CN− oxidation process became more signifi-
cant at long process time (i.e., after 9 h), once that the CN−
adsorption process seemed to reach an equilibrium condition.
As it has been suggested in the literature (Ahumada et al.
2002; Yasici et al. 2009) the beneficial effect of an oxidizing
atmosphere during the adsorption of CN− on CAC may be
the result of at least two main processes. One of them is the
adsorption of CN− on CAC, which surface sites might change
along the process due to the presence of oxygen. The other
one is that CAC catalyzes the oxidation of CN− to CNO− .
Related to the first process, it is known that an oxidiz-
ing atmosphere (i.e., air or O2 ) may oxidize the basic surface
groups of CAC (i.e., chromene, quinone, and pyrone), to gen-
erate positively charged surface sites (Ahumada et al., 2002).
As it was previously suggested in this work, these positively
charged sites may promote the adsorption of CN− via an
electrostatic mechanism:
CA − OH + + CN − ↔ CA − OH − CN [4]
This alternative adsorption mechanism may contribute to
increase the adsorption capacity of CAC under an oxidizing
atmosphere, as it was observed in this study. However, the
increase in CN− adsorption capacity shown in Figure 1 when
air or O2 atmospheres were used, might have limited practi-
cal applications because the total amount of CN− removed
from the solution was still low. To improve this condition,
244 M.A. Sánchez-Castillo et al.
some issues such as the number of oxidized (i.e., positively
charged) surface sites of CAC, under the actual experimental
conditions, have to be significantly increased.
Related to the second process, the catalytic effect of CAC
for the oxidation of CN− to CNO− , two main pathways have
been postulated (Yasici et al. 2009). One of them is that CAC
directly catalyzes the oxidation of CN-:
AC
CN − + 0.5 O2 (aq) −→ CNO− [5]
The other pathway suggests that oxygen could be catalytically
reduced by a basic character AC (such as CAC) to produce
hydrogen peroxide:
AC
2H2 O + O2 + 2e− −→ H2 O2 + 2OH − [6]
In this case, both products (H2 O2 and OH− ) are highly reac-
tive and could directly oxidize CN− to CNO− in liquid
phase:
AC
CN − + H2 O2 −→ CNO− + H2 O [7]
AC
CN − + 2OH − −→ CNO− + H2 O [8]
Thus, the overall reduction in CN- concentration observed
in the liquid phase should be the sum of both suggested
pathways. Under the conditions used in this study, no H2 O2
formation was detected and, therefore, it was assumed that the
preferential pathway was that given by Equation [5]. It is not
ruled out that reaction [6] could take place and have an effect
on the surface-site distribution that, in turn, might be more
favorable to promote the oxidation process. However, further
characterization studies of the spent catalyst are required to
test this idea.
Oxidation Process in Solution
Kinetic data of CN− decomposition were collected for
experiments conducted in an oxidizing atmosphere (air or O2 )
at 25 ◦ C, [CN− ]o of 1200, 800, 400, and 100 mg/L, and with
1 g of CAC. The kinetic data collected in the so-called second
region, that is when CNO− was found in solution, was used
to estimate the rate of CN− oxidation to CNO. This rate, at
constant temperature, can be determined from the CN− mass
or mole balance in a batch reaction system:
dNCN
− (−rCN − ) V = [9]
dt
where (-rCN- ) is the CN− oxidation rate. In agreement with the
literature (Adhoum and Monser 2002) this rate is zero order,
that is, it is independent of CN− concentration. Thus,
−rCN − = k [10]
May–June 2015
 TABLE 2. Rate Constants of CN− Oxidation under Air or Oxygen
Atmosphere, Evaluated at 25 ◦ C and Experiments with Different
[CN− ]o
[CN− ]o (mg/L) 100 400 800 1200
k (mg/L h) air 0.110 0.193 0.217 0.358
k (mg/L h) oxygen 0.240 0.303 0.479 0.595
where k is the rate constant at a given temperature. Therefore,
the concentration of CN− in solution (CCN ) could be calcu-
lated at any time by the following equation:
CCN0 − CCN = kt [11]
Equation [11] was used to fit the experimental data and, in
general, each set of kinetic data was appropriately fitted by
Equation [11]. The corresponding rate constants are reported
in Table 2. Note that the rate constants for each series of exper-
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
iments, air or oxygen, varied as a function of [CN− ]o . As the
intrinsic rate constant should not change with CN− concen-
tration, these apparent rate constants suggested that either the
assumed kinetic law was not appropriate or that some other
heterogeneous processes should be taken in consideration to
get the intrinsic rate constant. This observation is in agreement
with the fact that the pathway indicated in [5] is preferential
under the conditions of this study, as compared to the pathway
given by [6–8].
In agreement with the literature, the results previously
discussed verified the beneficial (synergetic) effect of an oxi-
dizing atmosphere when using CAC to remove CN− from an
aqueous solution. Importantly, we clearly identified that in
this condition, two processes were taking place in the system.
Initially, CN− was only adsorbed on CAC, validated by the
fact that the CNO− concentration in solution was negligible;
this process reached an equilibrium condition after 6 to 9 h, as
a function of the [CN− ]o . In the second process, the removal of
CN− from the solution was further promoted by the presence
of CAC carbon that promoted the oxidation of CN− to CNO− ,
which was experimentally validated by the gradual increase of
CNO− concentration in the solution.
These results were in line with other studies conducted
with different adsorbates, which have also suggested that
the linear reduction of the adsorbate concentration in an
adsorption process could be associated with the decom-
position of the adsorbate by chemical reaction (oxidation)
(Adhoum and Monser 2002; Deveci et al. 2006). Moreover,
results of this work showed that the CN− oxidation process
became relevant only after the adsorption process saturated
the surface sites of AC; it could also be suggested that the
oxidizing atmosphere prevailing in the system modified the
CAC surface group distribution in such a way that either, the
resulting surface group distribution favors the surface oxida-
tion of CN, or has the sites required to promote the formation
of the precursors (oxidizing species) required for liquid phase
oxidation.
Ozonation of Cyanide Catalyzed by Activated Carbon
Cyanide Removal in the Presence of CAC under O3
Atmosphere
The removal of CN− by CAC in the presence of a stronger
oxidant such as O3 , was also studied. These experiments were
conducted at room temperature (25 ◦ C), using 250 mL of
an aqueous CN− solution, which pHo was adjusted to 11.5.
To evaluate the independent effect of CAC and O3 , two series
of experiments were conducted. In one series, experiments
were carried out with and without activated carbon, at a fixed
O3 feed concentration. In another series, experiments were
carried out at different O3 concentrations for a fixed catalyst
load.
Catalyst Effect at a Constant O3 Feed Concentration
These experiments were conducted without (0 g) and with
1 g of CAC; in both cases, experiments were conducted with
[CN− ]o of 100, 400, and 1200 mg/L. The oxidizing atmo-
sphere was kept in the reactor by flowing 300 mL/min of a
gas stream with an O3 inlet concentration between 2.1 and
2.6 mg/min. Importantly, O3 concentration was also measured
at the reactor outlet through all the experiment.
Figure 3 shows the concentration of CN− in the solution
as a function of treatment time for each experiment. Clearly,
for experiments without (0 g) CAC, CN− concentration lin-
early decreased with time for all experiments with different
[CN− ]o . This linear trend was in agreement with the litera-
ture for liquid phase ozonation of CN− (Barriga et al. 2006;
Parga et al. 2003). Also, in agreement with previous findings,
it can be postulated that without CAC, the oxidation of CN−
in solution by O3 occurred according to the following reaction
(Gurol and Bremen 1985; Somboonchai et al. 2008):
CN − + O3 → CNO− + O2 [12]
1400
[CN-]o (mg/L)
1200 Triangles 1200
Squares 400
1000 Circles 100
[CN-], mg/L
800
600
400
200
0
0 1 2 3 4 5 6
Time, h
FIGURE 3. Transient experiment of CN− oxidation under an O3
atmosphere, with 1 g of CAC (full symbols) and without CAC (open
symbols), at various [CN− ]o .
May–June 2015 245
 According to Equation [12], the expected molar ratio of
O3 /CN− is 1 (mass ratio = 1.85), and the molar ratio of
CNO− /CN− is 1 (mass ratio = 1.615). Both molar and
mass ratios were experimentally verified in this work. The
amount of O3 consumed in a given experiment was deter-
mined by quantifying the O3 concentration at the reactor’s
outlet and subtracting the O3 concentration at the reactor’s
inlet. The experimental O3 /CN− mass ratios were 1.89, 1.89,
and 1.65 gO3 /gCN− , for experiments with [CN− ]o of 100,
400, and 1200 mg/L, respectively. In this way, the O3 /CN−
ratio was fulfilled in each experiment given the fact that the
higher deviation with respect to the stoichiometric ratio was
10%, for the experiment of [CN− ]o of 1200 mg/L.
On the other hand, Figure 4 shows the CNO− concentra-
tion as a function of time for the experiments before indicated.
It was clear that there was a linear increase of CNO− concen-
tration as CN− was being decomposed. Notoriously, the same
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
CNO− production rate (as given by the slope of the experi-
mental data curves) was practically observed for experiments
with [CN− ]o of 100, 400, and 1200 mg/L. For these exper-
iments, the average experimental mass ratio of CNO− /CN−
was 1.592; this ratio was in close agreement with the value
predicted by Equation [12].
In further detail, once that all CN− had been decom-
posed, Figure 4 shows that further treatment of the solution
with O3 led to CNO− decomposition, as it was clearly
observed in experiments with [CN− ]o of 100 and 400 mg/L.
According to the literature, products of CNO− decomposi-
tion include ammonia and carbonates (Kumar and Bose 2005;
Somboonchai et al. 2008), which were not monitored in this
study.
These results confirmed that, under the conditions used
in this study, all CN− in solution was oxidized to CNO−
by O3 ; in addition, the results qualitatively suggested that
CN− oxidation was faster than CNO− oxidation. Furthermore,
in agreement with the literature, a zero-order reaction was

2500 postulated to describe the rate of CN− oxidation by O3 , fol-

[CN-]o (mg/L) lowing a kinetic analysis similar to that shown in the previous
Triangles 1200 section. The corresponding rate constants, determined by an
2000 Squares 400
Circles 100
adequate linear fitting of the experimental data, were reported
in Table 3. Importantly, the rate constants were practically the
same (194, 195.1, and 212.2 mg L−1 h−1 ) for the experiments
[CNO-], mg/L

1500
conducted with different [CN− ]o (100, 400, and 1200 mg/L,
respectively), confirming a zero order kinetic for ozonation of
1000 CN− in aqueous solution.
On the other hand, Figure 3 also displays that the removal
500 of CN− on CAC under an O3 atmosphere showed the trend
previously described for experiments carried out in the pres-
ence of air and pure oxygen, that is, two clearly different
0 regions were found as it was evidenced by the CN− con-
0 2 4 6
centration profile. First, at the beginning of the process,
Time, h
CN− concentration decreased up to an adsorption equilib-
FIGURE 4. CNO production as a function of time under an O3 rium condition was reached on the CAC surface. Then, a
atmosphere, with 1 g of CAC (full symbols) and without CAC (open linear decrease of CN− concentration in the solution was
symbols), at various [CN− ]o . observed; as indicated above, this stage is associated to the

TABLE 3. Experimental Conditions and Apparent Rate Constants (Zero-Order Reaction) for the Ozonation of CN−

[CN− ]0 (mg/L) CA mass (g) O3 mass flow rate (mg/min) k(mg L−1 h−1 ) R2
100 1 0 0.240 0.987
400 1 0 0.383 0.965
1200 1 0 0.595 0.974
100 0 2.40 194.017 0.976
400 0 2.63 195.109 0.995
1200 0 2.10 212.157 0.997
100 1 2.11 198.56 0.972
400 1 2.58 253.36 0.987
1200 1 2.06 333.48 0.991
1200 0 0.21 26.96 0.977
1200 1 0.29 56.36 0.999
1200 1.5 0.36 91.24 0.999

246 M.A. Sánchez-Castillo et al. May–June 2015

 oxidation of CN− to CNO− . For the experiment with a [CN− ]o
of 1200 mg/L, the adsorption equilibrium conditions was
reached around 1 h.
The time required to reach this equilibrium condition
decreased as a function of the [CN− ]o , and it was almost
negligible for the case of the experiment with a [CN− ]o of
100 mg/L. Figure 3 also indicated that a higher [CN− ]o pro-
moted a larger extent of CN− adsorption on CAC. Given the
fact that the size of the CN− species is very small as compared
to the CAC pore size (by order of magnitude), no diffusional
limitations should be expected for CN− . In addition, consid-
ering that the same load of catalyst was used (1 g) and that the
adsorption equilibrium condition was reached at longer times
for experiments with higher [CN− ]o , it could be suggested that
these experiments favored a higher “local” CN− concentration
in the catalyst pores that, in turn, promoted a larger extent of
the CN− adsorption process.
It is important to indicate that for experiments with [CN− ]o
larger than 100 mg/L there was a beneficial (synergetic) effect
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
when using CAC and O3 , as compared when only O3 was
used. This synergetic effect was evident because a shorter
treatment time was required to remove a given CN− amount.
For the experiment with [CN− ]o = 400 mg/L, the time
required for total CN− removal was reduced by 0.5 h (from
2 to 1.5); for the experiment with an [CN− ]o = 1200 mg/L, the
time for total CN− removal was reduced by 2 h (from 5.5 to
3.5 h). In addition, it should be pointed out for the second
stage of the process, the rate of CN− removal from the solu-
tion, estimated from the slopes of the corresponding kinetic
data curves, was different for the corresponding experiments
without CAC. This difference is important because it may sug-
gest that the rate and maybe the mechanism of CN− oxidation
process were different in each experiment.
Figure 4 also shows the CNO− concentration as a func-
tion of treatment time for the experiments with 1 g of CAC.
Similar to the experiments without CAC, there was a linear
increase of CNO− concentration as CN− was being decom-
posed. The average experimental mass ratio of CNO− /CN−
for experiments with CAC was 1.59, which was in close agree-
ment (10%) with respect to the stoichiometric value. These
results confirmed that all CN− was oxidized to CNO− by
O3 in the presence of CAC. In addition, after all CN− had
been decomposed, further treatment of the solution also led to
CNO− decomposition, as it was the case for the experiments
conducted without CAC. Additionally, for a given treatment
time, experiments with CAC showed a larger decomposition
of CNO− due to the fact the CN− is decomposed faster in
the presence of AC, having then more time to promote CNO−
decomposition. It is emphasized that Figure 4 shows that the
rate of CNO− formation (as given by the slope of the exper-
imental data) was different for experiments with [CN− ]o of
400 and 1200 mg/L; for the latter experiment the rate and
the amount of CNO− produced were larger, in qualitative
agreement with the trends observed for CN− decomposition.
Another important observation was that a given amount
of O3 was detected at the reactor’s outlet for this series of
Ozonation of Cyanide Catalyzed by Activated Carbon
experiments, even when CN− was still present. This could
suggest that the residence time of O3 in the reactor was very
short, not having enough contact time to promote the oxi-
dation reaction in liquid phase (Equation [12]). In addition,
the experimental O3 /CN− mass ratios were 1.94, 2.17, and
1.78 gO3 /gCN− , for experiments with [CN− ]o of 100, 400,
and 1200 mg/L, respectively. These ratios were calculated
with the data collected when CN− was totally consumed;
therefore no secondary reactions could be associated to the
slightly higher O3 consumption found for these experiments.
Previous studies (Barriga et al. 2006; Somboonchai et al.
2008) have suggested that O3 consumption scales with the
amount of O3 fed to the reactor. However, this might not be
case in our experiments because the concentration of O3 fed
to the reactor was practically constant in all experiments.
Effect of CAC Load and O3 Feed Concentration
The effect of the catalyst load or catalyst external area on
CN− ozonation was evaluated in a set of experiments con-
ducted with a [CN− ]o of 1200 mg/L, and an average O3 mass
flow rate in the feed of 0.29 mg/min. This O3 mass flow rate
was 10 times smaller than that used in the previous experi-
ments, to have a limited amount of O3 in the feed and, thus, to
facilitate the observation of the effect of CAC load. The exper-
iments were conducted with 0, 1.0 and 1.5 g of CAC. Figure 5
clearly shows that a higher amount of CAC promoted higher
rates of CN− removal. For instance, in the experiment with
1.5 g of CAC the total amount of CN− was oxidized in 12 h;
at this treatment or reaction time, only ∼60 and ∼30% of CN−
had been oxidized when using 1 and 0 g of CA, respectively.
As expected, Figure 5 displays that the experiment without
CAC (i.e., 0 g) did not show a CN− adsorption stage; the data
displayed correspond to the oxidation (ozonation) of CN− in
liquid phase.
In the experiment with 1 g of CAC, the CN− concen-
tration profile evidenced the occurrence of the two stages
1400
CA, g
1200
0
1000 1
[CN-], mg/L
1.5
800
600
400
200
0
0 5 10 15 20 25 30
Time, h
FIGURE 5. Effect of the CAC load in the removal of CN− under
an O3 atmosphere.
May–June 2015 247
 1200
1000
[CN-]-[CN-]0, mg/L
800
600
400 CA, g
200
0
0 5 10 15 20 25
Time, h
FIGURE 6. Zero-order fitting of the kinetic data for CN−
with O3 and different CAC loads.
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
previously described, a CN− adsorption process followed by
a CN− oxidation or ozonation process. Finally, in the exper-
iment with 1.5 g of CAC the CN− concentration profile did
not show evidence of a CN− adsorption stage, only the CN-
oxidation/ozonation stage; it was assumed that the adsorption
stage was not observed probably due to experimental issues,
but additional experiments with a higher carbon amount might
be useful to elucidate if a different process is taking place at
short process time. In addition, the evidence of CN− oxida-
tion was a linear increase of CNO− in solution, similar to
that shown in Figure 4; however, no evidence of secondary
reactions was found in these cases because experiments were
stopped before the total consumption of CN− in solution.
For each experiment, the kinetic data of the stage when
CN− is oxidized was fitted by a zero order kinetic law
(Equation [12]). Figure 6 shows the fittings for each kinetic
data set, and the corresponding apparent rate constants are
reported in Table 3. For the experiment without CAC, the
apparent rate constant was 26.96 mg L−1 h−1 , and it increased
to 56.36 and 91.24 mg L−1 h−1 for experiments with 1 and
1.5 g of CA, respectively. These results clearly showed the
catalytic effect of CAC in the oxidation of CN− with O3 .
In addition, the difference in the rates or in the apparent
rate constants for experiments with different amount of CAC,
could be qualitatively explained in terms of the total surface
area or the total number of active sites of CAC exposed in
the experiment. As the total exposed area increases, a higher
number of sites become available to catalyze the oxidation
process.
Noticeably, if the rate constants are normalized by the cat-
alyst load, they are within the experimental uncertainty (less
than 10%). The advantage to have a relatively small O3 mass
flow rate when evaluating the synergetic effect of CAC could
be observed in data reported in Table 3. The comparison in
terms of the apparent rate constants for experiments con-
ducted with a 10 times higher O3 mass flow rate and with
[CN− ]o of 1200 mg/L was not as remarkable; this difference
248 M.A. Sánchez-Castillo et al.
2.5
2
O3/CN-, mol
1.5
1 [CN-]0, mg/L
0
1 100
1.5 0.5 400
30 1200
0
0 2 4 6 8 10
oxidation CA, g/L
FIGURE 7. Experimental mass ratio O3 /CN− ratio as a function
of CAC concentration, during the removal of CN− from aqueous
solutions using CAC and O3 .
became smaller for experiments with [CN− ]o of 400 mg/L,
and it was almost negligible for experiments with [CN− ]o of
100 mg/L.
In addition, the experimental data of this set of experiments
showed that the mass ratio CNO− /CN− was practically equal
to the stoichiometric value (1.615). On the other hand, the
mass ratio O3 /CN− seemed to be a function of the CAC mass.
As a result of various sets of experiments, Figure 7 shows that
the experimental mass ratio O3 /CN− decreased from about
2.0 for the experiment with no CAC to about 1.3 for an exper-
iment with 8 g/L of CAC. Therefore, as the CAC load was
increased in the reaction system, a smaller amount of O3
was required to oxidize CN− , confirming the catalytic role of
CAC.
Finally, the effect of O3 feed concentration could be esti-
mated by comparing experiments with and without CAC.
For experiments conducted without CAC, a [CN− ]o of
1200 mg/L, and an O3 mass flow rate of 0.21 and 2.1 mg/min,
Table 3 shows that the apparent rate constants were 26.96 and
212.57 mg L−1 h−1 , respectively. Similarly, for experiments
conducted with 1 g of CAC, a [CN− ]o of 1200 mg/L, and
an O3 mass flow rate of 0.29 and 2.06 mg/min; Table 3 shows
that the apparent rate constants were 56.36 and 333.48 mg L−1
h−1 , respectively. These results suggest that in the absence of
CAC, the rate of CN oxidation scaled with the O3 mass flow
rate. However, when CAC is in the system the use of a rela-
tively large amount of O3 was not beneficial. This might have
some economic implications if the application is scaled, and a
detailed study of the effect of O3 residence time and the hydro-
dynamics involved in the reaction when CAC is used would be
convenient in the future.
Mechanism Considerations
The CN− adsorption process as well as the sequential CN−
oxidation process identified when CN− is removed from an
May–June 2015
 aqueous solution by using CAC in the presence of O3 , could
be mostly described by the basic ideas discussed in the pre-
vious sections, for the case when air or oxygen were used
as oxidation agents. Of course, the oxidizing potential of O3
is significantly higher as compared than that of oxygen and,
therefore, a notorious enhancement on the rate and extent
of the overall CN− removal process was observed when O3
was flowed to the system. Based on this scenario, it could
be expected that the basic character sites of CAC, such as
quinone and pyrone could be oxidized to a larger extent, gen-
erating positively charged sites on the CAC surface. In this
condition, the ion- exchange type of CN− adsorption could
be extended by an electrostatic type of CN− adsorption,
increasing the overall extent of this process.
With respect to the CN− oxidation process by O3 , pre-
vious studies conducted without CAC (Barriga et al. 2006;
Somboonchai et al. 2008), showed that O3 could be easily
decomposed in aqueous solutions, at alkaline pH, to form
radicals or active species such as • OH, and O2 − :
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
O3 + OH − → HO−
2 + O2 [13]
O3 + HO− −
2 → OH + O2 + O2
•
[14]
On the other hand, Beltran et al. (2002), Guiza et al. (2004),
Rivera-Utrilla and Sánchez-Polo (2002), Sánchez-Polo and
Rivera-Utrilla (2003), and Sánchez-Polo et al. (2006) demon-
strated that CAC promotes de decomposition of O3 into • OH
radicals. Based on these findings, and the experimental results
obtained in this work, it could be postulated that oxidation of
CN− by O3 could be described as follows. O3 reacts to oxidize
the surface of CAC and also to form • OH radicals in solution,
according to the following reaction:
2 1
CA − H + O3 + H2 O → • OH + CA − OH + H2 O2
3 2
[15]
The • OH radicals thus formed are responsible for the oxi-
dation of CN− to CNO− , in agreement with the following
reactions (Jans and Hoigné 1998):
CN − + • OH → Intermediates → • CN + OH − [16]
O2
•
CN + OH − −→ CNO− + • HO2 [17]
The oxidation of the basic surface sites of CAC by O3
indicated above leads to the formation of surface acid sites.
Therefore, if the proposed mechanism is feasible, the PZC of
the CAC at the end of the experiment should be lower than that
before the experiment. This has been preliminary confirmed
by measuring the ZPC of CAC after one of the experiments
of CN− oxidation with O3 , finding a ZPC of 7.6. However,
it should be indicated that a more detailed characterization
Ozonation of Cyanide Catalyzed by Activated Carbon
of the CAC surface sites is required to figure out the nature
of some other surface groups that might play a role in the
catalytic effect of CAC.
It is important to emphasize that the proposal of a feasible
mechanism for the catalytic oxidation of CN− in the presence
of oxidizing species (air, O2 , or O3 ) provides a fundamental
and helpful framework to explain the nature of advanced oxi-
dation process. In this way we could guide the optimization
of the operating conditions for the treatment of contaminated
effluents, the development of new or modified materials, or
the development of new process to improve the efficiency of
cyanide removal from mining and metallurgical wastewaters.
CONCLUSIONS
An advanced oxidation process, combining the effects of
activated carbon (CAC) and ozone was found to be a very
adequate alternative for the removal of cyanide in aqueous
solutions. Under the oxidizing conditions used in this work,
the overall cyanide removal process consisted of two main
stages. In the first stage, cyanide was adsorbed on the CAC
until an equilibrium condition was reached; then, cyanide was
oxidized to cyanate in solution. The extent of the overall
process increased as air, oxygen and ozone were used as oxi-
dizing agents. At the optimum operating conditions found in
this study, 1200 mg/mL of cyanide were totally decomposed
in about 3 h, by using 1 g of CAC and about 2 mgO3 /min.
The use of larger loads of activated carbon decreased the con-
sumption of ozone up to 1.3 mol O3 /CN− , for an experiment
with 8 g/L of CAC ([CN− ]o = 1200 mg/L, 0.2 mgO3 /min).
The experimental results were rationalized based on dif-
ferent mechanisms in the literature. It was suggested that
oxidizing agents, preferably ozone, modified the basic charac-
ter of CAC surface to generate surface acid sites that improve
cyanide adsorption; in addition, they also contribute to the
catalytic generation of highly-reactive oxidizing species in
solution (such as • OH radicals in the case of ozone), which are
responsible for the oxidation of cyanide to cyanate. The find-
ings provide the basis to optimize the removal of cyanide from
aqueous solution in mining effluents by using the synergetic
effect of CAC and ozone.
FUNDING
A scholarship from the Mexican Council of Science and
Technology (CONACYT) for one of the authors (FFT) is
appreciated. The experimental work was partially supported
by SEP-CONACYT grants (Ref. 25713 and 61930).
REFERENCES
Adhoum, N., and L. Monser. 2002. “Removal of Cyanide from Aqueous
Solution with Impregnated Activated Carbon.” Chem. Eng. Proc. 41:
17–24.
May–June 2015 249
 Agarwal, B., C. Balomajumder, and P.K. Thakur. 2013. “Simultaneous Co-
adsorptive Removal of Phenol and Cyanide from Binary Solution Using
Granular Activated Carbon.” Chem. Eng. J. 228: 655–664.
Agarwal, B., P.K. Thakur, and C. Balomajumder. 2013. “The Use of Iron-
Impregnated Granular Activated Carbon for Co-adsorptive Removal of
Phenol and Cyanide: Insight into Equilibrium and Kinetics.” Chem. Eng.
Commun. 200(9): 1278–1292.
Ahumada, E., H. Lizama, F. Orellana, C. Suarez, A. Huidobro, A. Sepulveda-
Escribano, and F. Rodrıguez-Reinoso. 2002. “Catalytic Oxidation of
Fe(II) by Activated Carbon in the Presence of Oxygen, Effect of
the Surface Oxidation Degree on the Catalytic Activity.” Carbon 40:
2827–2834.
Akcil, A. 2003. “Destruction of Cyanide in Gold Mill Effluents: Biological
versus Chemical Treatments.” Biotechnol. Adv. 21(6): 501–111.
Asgari, G., A. Mohammadi, A. Poormohammadi, and M. Ahmadian. 2014.
“Removal of Cyanide from Aqueous Solution by Adsorption onto Bone
Charcoal.” Fresen. Environ. Bull. 23(3): 720–727.
Barriga, F., F. Nava, and A. Uribe. 2006. “Cyanide Oxidation by Ozone in a
Steady-State Flow Bubble Column.” Miner. Eng. 19: 117–122.
Behnamfard, A. and M. Salarirad, M. 2009. “Equilibirum and Kinetic
Studies on Free Cyanide Adsorption from Aqueous Solution by Activated
Carbon.” J. Hazard. Mater. 170: 127–132.
Beltrán F.J., I. Giráldez, and J. García-Araya. 2008. “Kinetics of Activated
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
Carbon Promoted Ozonation of Polyphenol Mixtures in Water.” Ind. Eng.
Chem. Res., 47: 1058–1065.
Beltrán F.J., F.J. Rivas, L.A. Fernandez, P.M. Alvarez, and R. Montero. 2002.
“Kinetics of Catalytic Ozonation of Oxalic Acid in Water with Activated
Carbon.” Ind. Eng. Chem. Res. 41: 6510–6517.
Boehm, H.P. 1994. “Some Aspects of the Surface Chemistry of Carbon
Blacks and Other Carbons.” Carbon 32: 759–769.
Botz, M.M. 2001. “Cyanide Treatment Methods.” In Mining Environmental
Management, edited by J. Chadwick and T.I. Mudder; Special Issue 9;
London: Mining Journal Books, Ltd, 28.
Dash, R., C. Balomajumder, and A. Kumar. 2009b. “Treatment of Cyanide
Bearing Water/Wastewater by Plain and Biological Activated Carbon.”
Ind. Eng. Chem. Res. 48: 3619–3627.
Dash, R., A. Gaur, and C. Balomajumder. 2009a. “Cyanide in Industrial
Wastewaters and its Removal: A Review on Biotreatment.” J. Hazard.
Mater. 15(1): 1–11.
Depci, T. 2012. “Comparison of Activated Carbon and Iron Impregnated
Activated Carbon Derived from Golbasi Lignite to Remove Cyanide from
Water.” Chem. Eng. J. 181: 467–478.
Deveci, H., E.Y. Yazici, I. Alp, and T. Uslu. 2006. “Removal of Cyanide from
Aqueous Solutions by Plain and Metal- Impregnated Granular Activated
Carbons.” Int. J. Miner. Proc., 79: 198–208.
Faria, P.C., J.J. Orfao, and M.F. Pereira. 2008. “Activated Carbon Catalytic
Ozonation of Oxaminic and Oxalic Acids.” Appl. Catal. B: Environ. 79:
237–243.
Ferreira de Oliveira, T., O. Chedeville, H. Fauduet, and B. Cagnon. 2011.
“Use of Ozone/Activated Carbón Coupling to Remove Diethyl Phthalate
from Water: Influence of Activated Carbon Textural and Chemical
Properties.” Desalination 276: 359–365.
Ford, J., R. Hernandez, and M. Zappi. 2006. “Bench-scale Evaluation of
Advanced Oxidation Processes for Treatment of a Cyanide-Contaminated
Wastewater from an Engine Manufacturing Facility.” Environ. Prog.
25(1): 32–38.
Gijzen, H.J. 2000. “Cyanide Toxicity and Cyanide Degradation in Anaerobic
Wastewater Treatment.” Water Res., 34: 2447–2449.
Goncalves, A., J. Orfao, and M. Pereira. 2013. “Ozonation of Benzafibrate
Promoted by Carbon Materials.” Appl. Catal. Environ. 140–141:
82–91.
Gordon, G., W.J. Cooper, R.G. Rice, and G.E. Pacey. 1992. Disinfectant
Residual Measurement Methods, 2nd edition. Denver, CO: AWWARF and
AWWA.
Gu, L., X. Zhang, and L. Lei. 2008. “Degradation of Aqueous p-Nitrophenol
by Ozonation Integrated with Activated Carbon.” Ind. Eng. Chem. Res.
47(18): 6809–6815.
250 M.A. Sánchez-Castillo et al.
Guiza, M., A. Ouederni, and A. Ratel. 2004. “Decomposition of Dissolved
Ozone in the Presence of Activated Carbon: An Experimental Study.”
Ozone: Sci. Eng. 26: 299–307.
Gupta. N., C. Balomajumder, and B.K. Agarwal. 2012. “Adsorption of
Cyanide Ion on Pressmud Surface: A Modeling Approach.” Chem. Eng.
J. 191: 548–556.
Gurol, M.D. and W.M. Bremen. 1985. “Kinetics and Mechanism of
Ozonation of Free Cyanide Species in Water.” Environ. Sci. Technol. 19:
804–808.
Guzmán-Pérez, C.A., J. Soltan, and J. Robertson. 2011. “Kinetics of Catalytic
Ozonation of Atrazine in the Presence of Activated Carbon.” Separ. Purif.
Technol. 79: 8–14.
Jans, U., and J. Hoigné. 1998. “Activated Carbon and Carbon Black
Catalyzed Transformation of Aqueous Ozone into OH-Radicals.” Ozone
Sci. Eng. 20: 67–78.
Kastner, J., R. Ganagavaram, R.P. Kolar, A.Y. Teja, and Ch. Xu. 2008.
“Catalytic Ozonation of Propanol Using Wood Fly Ash and Metal Oxide
Nanoparticle Impregnated Carbon.” Environ. Sci. Technol. 42: 556–562.
Kepa, U., E. Stanczyk-Mazanek, and L. Stepaniak. 2008. “The Use of the
Advanced Oxidation Process in the Ozone + Hydrogen Peroxide System
for the Removal of Cyanide from Water.” Desalination 223: 187–193.
Kim, Y.-J., T.I. Qureshi, and K.-S. Min. 2003. “Application of Advanced
Oxidation Processes for the Treatment of Cyanide Containing Effluent.”
Environ. Tech., 24, (10): 1269–1276.
Kitis, M., A. Akcil, E. Karakaya, and N.O. Yigit. 2005. “Destruction of
Cyanide by Hydrogen Peroxide in Tailings Slurries from Low Bearing
Sulphidic Gold Ores.” Miner. Eng. 18: 353–361.
Kumar, R., and P. Bose. 2005. “Modeling Free and Copper-Complexed
Cyanide Degradation in a Continuous Flow Completely Mixed Ozone
Contactor.” Ind. Eng. Chem. Res. 44(4): 776–788.
Kuyucak, N., and A. Akcil. 2013. “Cyanide and Removal Options from
Effluents in Gold Mining and Metallurgical Process.” Mineral Eng.
50–51:13–29.
Menendez, A. 1999. “On the Modification and Characterization of Chemical
Surface Properties of Activated Carbon: In the Search of Carbons with
Stable Basic Properties.” Langmuir, 12(18): 4404–4410.
Merle T., J.S. Pic, M.H. Manero, S. Mathe, and H. Debellefontaine. 2010.
“Influence of Activated Carbon on the Kinetics and Mechanisms of
Aromatic Molecules Ozonation.” Catal. Today 151: 166–172.
Mert, B.K., O. Sivrioglu, T. Yonar, and S. Ozciftci. 2014. “Treatment of
Jewerly Manufacturing Effluent Containing Cyanide Using Ozone-Based
Photochemical Advanced Oxidation Processes.” Ozone Sci. Technol.
36(2): 196–205.
Mudder, T.I., and M.M. Botz. 2004. “Cyanide and Society: A Critical
Review.” Eur. J. Miner. Proc. Environ. Protect. (1): 62–70.
Noh, J., and J. Schwarz. 1989. “Estimation of the Point of Zero Charge of
Simple Oxides by Mass Titration.” J. Coll. Interf. Sci. 130(1),157–164.
Parga J.R., S.S. Shukla, and F.R. Carrillo-Pedroz. 2003. “Destruction of
Cyanide Waste Solutions Using Chlorine Dioxide, Ozone and Titania
Sol.” Waste Manag. 23(2): 183–191.
Parsa, J.B., and S.H. Negahdar. 2012. “Treatment of Wastewater Containing
Acid Blue 92 Dye by Advanced Ozone-Based Oxidation Methods.”
Separ. Purif. Technol. 98: 315–320.
Pocostales, J.P., P.M. Alvarez, and F.J. Beltrán. 2010. “Kinetic Modeling of
Powdered activacted carbon ozonation od sultamethoxazole.” Chem. Eng.
J., 164, 70–76, (2010)
Rivera-Utrilla, J., and M. Sánchez-Polo. 2002. “Ozonation of 1,3,6-
Naphthalenetrisulphonic Acid Catalyzed by Activated Carbon in Aqueous
Phase.” App. Catal. B: Environ. 39: 319–325.
Rivera-Utrilla, J., M. Sánchez-Polo, G. Prados-Joya, M.A. Ferro-García, and
I. Bautista-Toledo. 2010. “Removal of Tinidazole From Waters by Using
Ozone and Activated Carbon in Dynamic Regime.” J. Hazard. Mater.
174(1): 880–886.
Sánchez-Polo, M., and J. Rivera-Utrilla. 2003. “Effect of the Ozone-Carbon
Reaction on the Catalytic Activity of Activated Carbon During the
Degradation of 1,3,6-Naphthalenetrisulphonic Acid with Ozone.” Carbon
41: 303–307.
May–June 2015
 Sánchez-Polo, M., E. Salhi, J. Rivera-Utrilla, and U. Von Gunten. 2006.
“Combination of Ozone with Activated Carbon as an Alternative to
Conventional Advanced Oxidation Processes.” Ozone: Sci. Eng., 28:
237–245.
Sarla, M., M. Pandit, D. Tyagi, and J. Kapoor. 2004. “Oxidation of Cyanide in
Aqueous Solution by Chemical and Photochemical Process.” J. Hazard.
Mater. 116(1–2): 49–56.
Somboonchai, W., M. Nopharatana, and W. Songkasiri. 2008. “Kinetics of
Cyanide Oxidation by Ozone in Cassava Starch Production Process.” J.
Food Eng. 84(4): 563–568.
Suty, H., C. De Traversay, and M. Cost. 2004. “Applications of Advanced
Oxidation Processes: Present and Future.” Water Sci. Technol., 49(4):
227–233.
U.S. Environmental Protection Agency. 1999. Integrated Risk Information
System (IRIS) on Cyanide. Washington, DC: National Center for
Environmental Assessment, Office of Research and Development.
Yasici, E.Y., H. Deveci, and I. Alp. 2009. “Treatment of Cyanide Effluents
by Oxidation and Adsorption in Batch and Column Studies.” J. Hazard.
Mater., 168: 1362–1366.
Downloaded by [Marco Sanchez-Castillo] at 18:15 13 May 2015
Ozonation of Cyanide Catalyzed by Activated Carbon
View publication stats
Yeddou, A.R., B. Nadjemi, F. Halet, A. Ould-Dris, and R. Capart. 2010.
“Removal of Cyanide in Aqueous Solutions by Oxidation with Hydrogen
Peroxide in Presence of Activated Carbon Prepared from Olive Stones.”
Mineral Eng. 23: 32–39.
Young, C.A., and T.S. Jordan. 1995. “Cyanide Remediation: Current and
Past Technologies.” In Proceedings of the 10th Annual Conference on
Hazardous Waste Research, edited by L.E. Erickson, D.L. Tillison,
S.C. Grant, and J.P. McDonald, 104–129. Manhattan, Kansas, May
23–24.
Young, C.A., L.G. Twidwell, and C.G. Anderson. 2001. “Remediation
Technologies for the Management of Aqueous Cyanide Species.” In
Cyanide: Social, Industrial, and Economic Aspects, edited by C.A.
Young, L.G. Twidwell, and C.G. Anderson, 175–194. Warrendale, PA:
The Minerals, Metals & Materials Society.
Zhang, W., W. Liu, Y. Lv, B. Li, and W. Ying. 2010. “Enhanced
Carbon Adsorption Treatment for Removing Cyanide from Cooling Plant
Effluent.” J. Hazard. Mater. 184(1–3): 135–140.
May–June 2015 251