Chemical Engineering Journal 215–216 (2013) 168–173

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Chemical Engineering Journal

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Catalytic wet air oxidation of a non-azo dye with Ni/MgAlO catalyst

Gabriel Ovejero, Araceli Rodríguez, Ana Vallet, Juan García ⇑
Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid,
Avda. Complutense s/n, 28040 Madrid, Spain

h i g h l i g h t s

" Ni supported over hydrotalcite calcined precursors as catalyst.

" Catalytic wet air oxidation in batch reactor for Basic Yellow 11 removal.
" Effects of reaction conditions and catalyst stability were tested.
" The catalyst proved to be stable and efficient for the dye degradation.

a r t i c l e i n f o a b s t r a c t

Article history: The catalytic activity of Ni supported over hydrotalcite by impregnation (Ni/MgAlO) as catalyst for Basic
Received 18 July 2012 Yellow 11 (BY11) degradation under moderate conditions was investigated. BET, XRD and XRF were
Received in revised form 15 October 2012 employed to characterize the catalyst. To evaluate the catalytic system, wet air oxidation of dye was car-
Accepted 6 November 2012
ried out at temperatures between 100 and 200 °C, and oxygen pressures ranging from 30 to 60 bar. The
Available online 12 November 2012
effect of initial concentration from 100 to 400 ppm on the degradation of Basic Yellow 11 was also inves-
tigated. The degradation process was monitored by UV–VIS spectroscopy, TOC and toxicity analyses. At
Keywords:
150 °C, 50 bar oxygen pressure and 200 ppm initial concentration, 64.5% selectivity towards CO2 was
Catalyst
CWAO
obtained after 3 h of treatment, while only 20.2% selectivity was achieved without catalyst at the same
Dye experimental conditions. The structure and morphology of the catalyst under different cycling runs show
Hydrotalcite that the catalyst is stable under such operating conditions and the leaching tests show low leaching
Nickel effect.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction
Effluents from the dying and textile industry are considered one
of the most problematic wastewaters and its disposal has become a
major environmental problem. Those wastewaters are character-
ized by the presence of color, high total organic carbon (TOC) levels
as well as an important chemical oxygen demand; mainly due to
the presence of dyes and other organic by-products. Dye contain-
ing wastewaters are usually recalcitrant to degradation by the con-
ventional biological treatments due to its high toxicity, as these
compounds are often hardly biodegradable or even biocides. As a
consequence, those effluents should be remediated by means of
physicochemical technologies before its discharge or a biological
treatment.
Abbreviations: WAO, wet air oxidation; CWAO, catalytic wet air oxidation;
BY11, Basic Yellow 11; TOC, total organic carbon; TN, total nitrogen; TU, Toxicity
Units; SNOC, selectivity towards nonorganic compounds; XTOC, TOC conversion; Xdye,
dye conversion.
⇑ Corresponding author. Tel.: +34 91 394 5207; fax: +34 91 394 4114.
E-mail address: juangcia@quim.ucm.es (J. García).
Nowadays, some physical operations [1] are available for the re-
moval of organic pollutants from contaminated water, especially
adsorption methods [2,3]. However, these techniques only allow
the removal of pollutants, not its destruction, and additionally,
generate large amounts of sludge [4,5].
Advanced Oxidation Processes (AOPs) are a promising alterna-
tive for wastewater treatment as they can provide complete
mineralization of organic pollutants [6]. Among AOPs, wet air oxida-
tion (WAO) is an attractive technique for industrial wastewater
treatment. WAO involves the combustion of pressurized organic
matter at relatively high temperatures. The main drawback of this
technique is its high energetic requirements [6]. In order to be able
to employ milder operating conditions and reduce the operating
costs, catalytic wet air oxidation processes (CWAO) have been
developed [7,8]. The presence of a catalyst may improve the overall
reaction rate and enhances the removal of reaction intermediates
compounds, which are refractory to the WAO process [9], improving
the formation of hydroxyl radicals, well-known promoters of the
oxidation [10].
Hydrotalcites (HTs) are anionic clays with a layered structure
with high similarity to the Brucite, where cations Mg2+ have been

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.11.028
 G. Ovejero et al. / Chemical Engineering Journal 215–216 (2013) 168–173
partially substituted by Al3+ generating a positive charge in each
layer which needs to be compensated by the introduction of
anionic compounds in the interlayer space. These materials have
received an increasing interest in recent years due to the number
of potential applications in various fields such as catalysis, adsorp-
tion, medicine, and electro applications [11]. A large number of
HT-like compounds have been extensively studied as catalyst
precursors, since they show good dispersion values for the metal
catalyst. Ni–Al–Mg mixed oxides, obtained from the calcination
of nickel containing HT-like compounds, have shown remarkable
properties as catalysts precursors such as high metal dispersion
and stability against sintering, even under extreme conditions
[11–14].
Non-azo dyes have been much less studied in the literature
than azo dyes. Recently, the CWAO of the triaryl methane dye,
Crystal Violet, has been studied in the presence of a Ni–hydrotal-
cite like catalyst in batch experiments [12]. In the present work,
the degradation of the Basic Yellow 11 (BY11) was studied using
the same catalyst. This particular non-azo dye has been selected
as it is hardly biodegradable by the conventional biological treat-
ments, but has also a wide use in a high number of industries, such
as textile, paint, ink, paper and plastic ones.
The main objective of this work was to investigate the wet air
oxidation of Basic Yellow 11 on aqueous solution employing Ni/
MgAlO as catalyst. The influence of the temperature, initial concen-
tration of dye, catalyst and pressure on dye removal was analyzed
in detail. The catalyst efficiency was determined by the color
degradation, TOC removal and toxicity reduction. Additionally,
the reuse of the catalyst was also examined.
2. Materials and methods
2.1. Materials and catalyst synthesis
The dye was purchased from Sigma–Aldrich (Steinheim, Ger-
many) and employed without further purification (dye purity
40%). The principal characteristics of BY11 can be seen in Table 1.
The hydrotalcite precursor was prepared by coprecipitation as
described by Ovejero et al. [12]. Mg(NO3)26H2O (0.05 mol) and
Al(NO3)29H2O (0.01 mol) were mixed in 100 ml of deionized water
to obtain solution A. Besides, Na2CO3 (0.03 mol) and NaOH
(0.07 mol) were dissolved in 60 mL of deionized water to form
solution B. All the reactants were provided by Sigma–Aldrich.
Solution B was stirred for 1 h at constant temperature of 65 °C
and once this solution has reached the desired temperature
(65 °C), solution A is slowly dropped, forming a white precipitate.
The resulting precipitates were aged at 60 °C during 18 h in order
to allow the formation of the HT structure. Then, the precipitates
were filtered and washed with distilled water at 40 °C for 2 h
and dried at 100 °C for 12 h. Nickel was added by incipient wetness
impregnation of an aqueous solution of Ni(NO3)26H2O (Panreac,
Barcelona, Spain). The Ni(NO3)26H2O amount was calculated in
order to obtain a 7 wt% of nickel in the final material. Finally, the
Table 1
Main characteristics and structure of BY11.
Dye Structure Chemical
class
Basic Cationic
Yellow dye
11
169
impregnated catalyst was dried in an oven at 110 °C during 12 h
and afterwards the solids were calcined at 550 °C during 5 h to
form the Ni/MgAlO catalyst.
2.2. Catalyst characterization
The support and the nickel catalyst were characterized by phys-
ical adsorption of nitrogen at 196 °C in a Micromeritics ASAP
2010 apparatus. XRD analyses were performed using a SIEMENS
D-501 diffractometer. Metallic content was established by means
of X-ray Fluorescence (XRF) (Broker S4 Explorer). More detailed
characterization procedures can be found in previous works
[12,13].
2.3. Procedures and analysis
Dye concentration was determined at the wavelength corre-
sponding to the BY11 maximum UV–VIS absorption (Table 1)
which was monitored by a Shimadzu UV–VIS spectrophotometer.
TOC analyses were performed in a Shimadzu TOC-VCSH appartus,
after filtration of the samples (pore diameter 10 mm). The effi-
ciency of catalytic activity, color and TOC removal was evaluated
by calculating the ratio between the color and TOC measured at
each instant and the values for this parameter for the initial solu-
tion. Since TOC analysis only provides information about the global
removal of total organic carbon from the liquid-phase, selectivity
towards non-organic compounds (SNOC) was defined as 100 (XTOC/
Xdye) where XTOC and Xdye are TOC and dye conversion respectively.
The toxicity of the samples collected at the end of the reaction
was measured with a Microtox 500 Analyzer on samples before
and after decoloration according to the test protocols defined by
the manufacturer (Azur Environmental, Newark, Del.) with a
Microtox data analysis program (Microtox Omni Software). This
assay is based on the decrease of light emission by Vibrio fischeri
as the result of its exposure to a toxicant according to ISO
11348-2. The pH of the samples was adjusted to 7.0 ± 0.5. Percent-
age inhibition of the bioluminescence was obtained mixing 0.5 mL
of the final effluent of each experiment and 0.5 mL of the lumines-
cent bacterial suspension. The toxicity of each sample was
expressed as the percent of the inhibition of the luminescence
relative to a non-contaminated blank (Milli-Q water). Results are
given in Toxicity Units (TUs) after 15 min of exposure [12].
2.4. Wet air oxidation and catalytic wet air oxidation experiments
Batch tests were performed in a Hastelloy C22 high-pressure
microreactor. The reactor was equipped with an electrically heated
jacket and an adjustable speed magnetic stirrer. The temperature
and the stirring speed were controlled by means of a PID controller.
The gas inlet, gas release valve, pressure gauge, rupture disk, and
cooling water feed line were situated on the top of the reaction
vessel. The liquid sampling line and the thermocouple well were
immersed in the reaction mixture. The batch reactor was charged
with 100 mL of an aqueous solution of BY11, in the presence of
C.I. name C.I. Molecular weight Dye Molecular kmax
number (g mol1) content (%) formulae (nm)
Cationic Yellow 48055 372.89 20 C21H25ClN2O2 413
11 GI
170 G. Ovejero et al. / Chemical Engineering Journal 215–216 (2013) 168–173

(a) 1.0 BY11 (b)1.0

0.9
Normalized concentration

0.8 CWAO - 100ºC

Normalized concentration
CWAO - 120ºC 0.8
0.7 CWAO - 150ºC
CWAO - 180ºC
0.6 WAO - 100ºC 0.6
WAO - 120ºC
0.5
WAO - 150ºC
0.4 WAO - 180ºC
0.4
0.3
TOC
0.2 0.2 CWAO-100ºC WAO-100ºC
0.1 CWAO- 120ºC WAO-120ºC
CWAO-150ºC WAO-150ºC
0.0 0.0 CWAO-180ºC WAO-180ºC
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120
Time / min Time/min

Fig. 1. (a) BY11 and (b) TOC conversion at different temperatures at 50 bar, 200 ppm, 800 rpm.

0.4 g of the catalyst for the CWAO tests. Before starting the heating
process, the reactor is purged with nitrogen, in order to ensure an
inert atmosphere during the heating process. Once the desired
temperature is reached, a sample is withdrawn and the reaction
starts. This can be considered as zero time for the experiment.
Then, the reactor is pressurized with air and samples are collected
at regular intervals after sufficient flushing of the sampling line.
Pressure drop was monitored and additional air was charged into
the reactor in order to keep the total pressure constant during each
test [11]. To check the BY11 adsorption onto the catalyst a control
experiment was run following the previous procedure, but this
time N2 was employed instead of air during the test to ensure that
no oxidation reaction were produced.
3. Results and discussion
3.1. Catalyst characterization
Detailed results for the solid characterization can be consulted in
previous publications [12,15]. It was proved that in the presence of
nickel, the BET area of the solid decreased from 182 to 169 m2 g1. It
was also shown that the metallic particles exhibited a high metallic
dispersion (27%). No remarkable differences in the XRD patterns
were found for the uncalcined catalyst and the support, showing
that the presence of nickel did not modify the layered structure of
the hydrotalcite. After calcination at 550 °C the formation of mixed
oxides structures (Ni/MgAlO) was observed [12].
3.2. Influence of the reaction variables
3.2.1. Effect of the temperature
Temperature is one of the most influent variables in WAO and
CWAO reaction [10,12]. To study its effect, it was varied from
100 to 180 °C, keeping constant the pressure and initial dye con-
centration. The obtained results indicate that BY11 removal was
very sensitive to the variation of the temperature, being this sensi-
tivity more intense in the case of the non-catalytic process (Fig. 1a).
At 100 °C, the dye conversion attained 83% at the end of the test
(3 h), whereas this value reached 98% within the 15 first minutes,
in the test carried out at 180 °C. No differences between the cata-
lytic processes for the BY11 removal were observed. The apparent
activation energy for WAO and CWAO process were calculated
from the Arrhenius plot for the evolution of the initial BY11
conversion rate as a function of the reaction temperature. They
were found to be 57.1 and 32.0 kJ mol1 respectively, showing
the effectiveness of the catalyst. Additionally, initial reaction rates
were calculated and presented in Table 2. A difference of two mag-
nitude orders between the values obtained for the WAO and CWAO
processes can be observed. It can be added that up to 150 °C, the
higher the temperature, the higher the initial reaction rate. Above
this point, there is also a slight improvement, but less important
than for the previous temperatures. The efficiency of the studied
catalyst for BY11 removal is then proved by these results.
The same conclusions can be made for the TOC removal, having
the temperature a notorious effect both in WAO and CWAO pro-
cesses. An improvement of 7.5% was made in the range of 100–
180 °C for the WAO reaction and of 49.1% for the CWAO process.
It is also interesting to point out that the TOC conversion obtained
at the lowest temperature (100 °C) in the CWAO reaction was sim-
ilar to the one reached for the WAO reaction at the highest temper-
ature (180 °C). This proves that the employed catalyst can reduce
the energetic requirements to reach a certain conversion degree,
reducing the economic cost of the process. Higher temperatures
led to a higher production of free radicals [10,16], which are
responsible of the initiation of the oxidation reaction. This explains
why the performances obtained for reactions carried out at higher
temperatures are better.
Table 2 also shows that selectivity towards nonorganic
compounds is enhanced both by the catalyst presence and by high
reaction temperatures. This may suggest that the reaction
pathway is different for the WAO and CWAO reactions, being the

Table 2
Reaction rates, selectivity and toxicity in WAO and CWAO processes with a Ni/MgAlO catalyst at 50 bar, 200 ppm and 800 rpm.

WAO CWAO
100 °C 120 °C 150 °C 200 °C 100 °C 120 °C 150 °C 200 °C

Reaction rate ðmmol dye min 1

g1 5.6  105 1.9  104 3.6  104 3.61  104 0.0378 0.0697 0.1157 0.160
Ni Þ
SNOC/% 19.5 19.9 20.2 26.1 54.0 56.9 64.5 73.5
Toxicity/TU 2.83 2.36 1.92 1.72 1.46 1.23 1.04 0.97
 G. Ovejero et al. / Chemical Engineering Journal 215–216 (2013) 168–173 171

(a)1.0 BY11
(b)1.0
0.8 CWAO-30 bar
Normalized concentration
0.8

Normalized concentration
CWAO-40 bar
CWAO-50 bar
CWAO-60 bar
0.6 WAO-30 bar 0.6
WAO-40 bar
WAO-50 bar
0.4 WAO-60 bar 0.4
TOC
0.2 0.2 CWAO-30 bar WAO-30 bar
CWAO-40 bar WAO-40 bar
CWAO-50 bar WAO-50 bar
CWAO-60 bar WAO-60 bar
0.0 0.0
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120
Time/min Time/min

Fig. 2. (a) BY11 and (b) TOC conversion at different pressures at 150 °C, 200 ppm, 800 rpm.

intermediates formed during the catalytic tests less refractory to
oxidation than those obtained via WAO.
Toxicity of the 200 ppm BY11 solution was found to be 3.2 TU.
The obtained values for the different experiments are presented in
Table 2. After the treatment, the toxicity decreased drastically, par-
ticularly for the catalytic experiments. Furthermore, toxicity values
were lower when the temperature increased.
Analyses of the pH of the collected samples showed lower pH in
the CWAO effluents, as the catalyst is of a basic nature. However, in
both cases it was noticed a slight acidification of the media, mostly
at higher temperatures and at the end of the reaction. HPLC analy-
ses were performed in a C18 column and revealed the presence of
traces of acids, such as acetic and hexanoic. More details of the
formed reaction intermediates will be revealed in further
publications.
3.2.2. Effect of the reaction pressure
It has been reported that the formation of free radicals is depen-
dent upon the concentration of dissolved oxygen [10,17]. There-
fore, WAO and CWAO of BY11 might be affected by the partial
pressure on the reactor. The effect of pressure on the reaction rate
(between 30 and 60 bar) was assessed using the optimized tem-
perature reaction at 150 °C.
Fig. 2a shows that the difference in final BY11 conversion be-
tween catalytic and non-catalytic experiments is minimal. Only a
difference of 4.4% was observed between the lowest and the high-
est conversion, being all these conversions above 93.3%. Reactions
rates were found to be very similar for every pressure but showed
notable differences when considering the presence or no of the cat-
alyst. Reaction rates ranged from 3.3  104 mmol min1 to
11.5  102 mmol min1 g1 Ni (Table 3).
Fig. 2b shows the TOC conversion for WAO and CWAO reactions
at the mentioned range of pressures. An increase, for both catalytic
and non-catalytic reaction, in TOC conversion with pressure was
observed. This tendency can be explained as follows: based on a
previously described free-radical involved reaction mechanism
[10], the concentration of free radicals increases with oxygen pres-
sure and then enhances the organic compounds degradation
[10,18]. It can also be observed that above 50 bar, an increase in
the reaction pressure has no effect in TOC conversion. Above this
point, recalcitrant intermediates (as mentioned in Section 3.2.1)
are formed and the mineralization of organic compounds cannot
go any further.
Selectivity is also influenced by total pressure. For example, the
calculated values for SNOC in the reaction varied from 19.2% to
36.4% (WAO reaction) and from 54.8% to 63.8% (CWAO reaction)
for 30 and 60 bar, respectively (Table 3).
Pressure seems not to have a clear influence in toxicity removal,
and initial reaction rate, as it can be seen in Table 3.
3.2.3. Effect of the initial dye concentration
The influence of the ratio initial dye conversion/catalyst mass
was studied varying the initial BY11 concentration introduced into
the reactor and keeping constant the rest of the operational vari-
ables. Fig. 3a shows only a slight difference, up to 2.4% in dye con-
version between the experiments carried out with or without
catalyst. Nevertheless, no appreciable differences are observed
for the final conversion of each kind of reactions. This indicates
that the reaction is not controlled by the adsorption of BY11 mol-
ecules onto the catalyst surface [19].
Initial reaction rates did not vary significantly for the WAO
experiments, with values in the range of 3.5  104 mmol min1.
On the other hand, initial reaction rates for CWAO reactions were
improved for the highest BY11 initial concentration. Values ranged
from 6.9  102 to 11.5  102 mmol min1g1 Ni (Table 4). The dif-
ference observed could be attributed to an enhancement of the ini-
tial adsorption of the dye molecules onto the catalyst surface.
On the other hand, TOC removal showed substantial differences
between WAO and CWAO experiments. For example, for the
400 ppm initial dye reaction carried out without the presence of
the catalyst TOC conversion was up to 18.2% whereas for the cata-
lytic experiment this value attained the 71.3% (Fig. 3a). Differences
are also appreciable between the TOC conversion (Fig. 3b) at differ-
ent initial concentrations for each set of experiments (11.9 and

Table 3
Reaction rates, selectivity and toxicity in WAO and CWAO processes with a Ni/MgAlO catalyst at 150 °C, 200 ppm and 800 rpm.

WAO CWAO
30 bar 40 bar 50 bar 60 bar 30 bar 40 bar 50 bar 60 bar
4 4 4 4
Reaction rate ðmmol dye min
1
g1 3.3  10 3.4  10 3.6  10 3.6  10 0.0645 0.0813 0.1157 0.113
Ni Þ
SNOC/% 19.2 25.6 20.2 36.4 54.8 58.8 64.1 63.8
Toxicity/TU 1.85 1.96 1.92 1.82 1.16 1.03 1.04 1.11
172 G. Ovejero et al. / Chemical Engineering Journal 215–216 (2013) 168–173

(a) 1.0 BY11 (b) 1.0

CWAO-100 ppm
0.8 0.8
Normalized concentration

CWAO-200 ppm

Normalized concentration
CWAO-400 ppm
WAO-100 ppm
0.6 WAO- 200 ppm 0.6
WAO- 400 ppm

0.4 0.4

0.2 TOC
0.2
CWAO-100 ppm WAO-100 ppm
CWAO-200 ppm WAO-200 ppm
0.0 CWAO-400 ppm WAO-400 ppm
0.0
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120
Time/min Time/min

Fig. 3. (a) BY11 and (b) TOC conversion at different dye concentrations at 150 °C, 50 bar, 800 rpm.

Table 4
Reaction rates, selectivity and toxicity in WAO and CWAO processes with a Ni/MgAlO catalyst at 150 °C, 200 ppm and 800 rpm.

WAO CWAO
100 ppm 200 ppm 400 ppm 100 ppm 200 ppm 400 ppm

Reaction rate ðmmol dye min1 g1 3.58  103 3.6  104 3.58  103 0.04117 0.1157 0.0692
Ni Þ
SNOC/% 32.1 25.6 18.7 57.7 64.1 72.1
Toxicity/TU 1.86 1.96 2.26 1.01 1.04 1.12

(a) 1.0 BY11 (b) 1.0

Ni/MgAlO 0.9
0.8 Ni/MgAlO first re-use
0.8
Normalized concentration

Normalized concentration

Ni/MgAlO second re-use

0.7
0.6 0.6
0.5
0.4 0.4
0.3 TOC
0.2 Ni/MgAlO
0.2 Ni/MgAlO first re-use
0.1 Ni/MgAlO second re-use
0.0 0.0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time/min
Time/min

Fig. 4. (a) BY11 and (b) TOC conversion for the catalyst recycle at 150 °C, 50 bar, 200 ppm, 800 rpm.

24.2 for WAO and CWAO respectively between 100 and 400 ppm of
initial BY11 concentration). It can be observed that even if the car-
bon mineralization increases with the initial dye concentration, the
difference observed between 200 and 400 ppm is lower than be-
tween 100 and 200 ppm for both set of experiments. This could
be due to the formation of higher reactions intermediates as the
initial dye concentration is higher which has to compete for the
oxygen present in the media that has been kept constant. Selectiv-
ity decreased as the initial concentration augmented (from 32.1%
to 18.7%) for the WAO reaction whereas for CWAO tests, selectivity
increased with this variable.
3.2.4. Catalyst stability
In order to check the catalyst stability, the solid was tested in
three consecutive assays. After the first run; carried out at
150 °C, 50 bar and an initial concentration of 200 ppm, the catalyst
was washed with water and dried overnight in an oven at 60 °C.
After this treatment, the catalyst was tested again employing the
same reaction conditions. A second run, with fresh catalyst solu-
tion was performed after washing and drying the re-used catalyst.
Fig. 4a and b shows the catalytic results obtained with the re-used
catalysts compared with fresh ones for the BY11 and TOC removal
respectively. The reutilization of the catalyst gave satisfactory re-
sults, as only a difference of 7% compared with the fresh catalyst
for BY11 removal, was found.
As far as the TOC removal is concerned, differences observed in
the different cycles were higher between the second and third cy-
cle than between the first and the second. Only a difference of 4%
between the fresh catalyst and the first cycle was observed while
this difference reached the 6% between the second and the third.
The recovered and re-used catalysts were analyzed after each
reaction. A loss in the surface area occurs after reaction as shown
in Table 5. It can be noticed that the loss of surface area was pro-
duced only during the first reaction, as no considerable differences
 G. Ovejero et al. / Chemical Engineering Journal 215–216 (2013) 168–173
Table 5
BET area and metallic dispersion for the Ni/MgAlO catalyst after the successive reuses.
Fresh First re-use Second re-use
2 1
BET area (m g ) 172.9 163.2 161.3
Metallic dispersion (%) 26.6 26.5 26.1
could be observed during the first and the second recycle. How-
ever, the final reduction of the surface area was of 11.6 m2 g1.
The reduction of the solid surface is not too high and might not
be the main cause of the catalyst deactivation.
On the other hand, TOC analysis of the catalyst after reaction re-
vealed the presence of adsorbed products on the catalyst surface
(0.6 wt% C, measured by means of a SSM-5000A module coupled
to a TOC-VCHS analyser), possibly polymeric compounds, which
could make more difficult the access of the dissolved compounds
to the active sites [20]. Analyses of the liquid effluents collected
at the end of the reaction, revealed the presence of traces of Ni
(0.6%, measured by ICP-AES). The catalyst deactivation is then
probably due to the formation of the carbon deposit, as the Ni
leachate is negligible.
4. Conclusion
The results of our study showed that the CWAO of BY11 in
aqueous media was successfully carried out using Ni/MgAlO as
the catalyst at moderate conditions (T = 100–200 °C; oxygen pres-
sure = 30–60 bar). An improvement of 7.5% was made in the range
of 100–180 °C for the WAO reaction and of 49.1% for the CWAO
process. An increase, for both catalytic and non-catalytic reaction,
in TOC conversion with pressure was observed. Initial reaction
rates for CWAO reactions were higher when the initial BY11 con-
centration augmented. On the other hand, the amount of Ni leach-
ing was 0.6% and the catalyst was stable in three reuses. This study
provides an efficient approach for the treatment of non-azo dye
containing wastewater.
Acknowledgements
The authors gratefully acknowledge the financial support from
Ministerio de Economía y Competitividad CTQ2011-27169 and
Comunidad de Madrid through REMTAVARES Network S2009/
AMB-1588.
173
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