6:ENVIRONMENTAL

ELSEVIER Applied Catalysis B: Environmental 15 (1998) 269-274

Catalytic wet peroxide oxidation (CWPO) of phenol over

mixed (Al-Cu)-pillared clays
J. Barraulta,*, C. Bouchoulea, K. Echachoui”, N. Frini-Srasrab, M. Trabelsi”, F. Bergayab
a Laboratoire de Catalyse en Chink Organique, URA CNRS 350, ESIF: 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex, France
b Centre de Recherche sur la Mati&e Divise’e, CNRS, 1 bis rue de la Ferollerie. 45071 Orleans Cedex 2, France
’ UANE, INRST, B.I? 95, 2050 Hamman-Lij Tunisia

Received 23 March 1997; received in revised form 15 June 1997; accepted 17 June 1997

Abstract

New mixed (Al-Cu)-pillared clays are prepared from a crude bentonite sample (H) (Tunisia deposit) by two discrete
procedures: (a) a classical ‘D’ method by which Al or (Al, Cu) nitrate solutions, hydrolyzed with NaOH, are added to a 2%
clay suspension and (b) a ‘P’ method where the clay powder is directly dispersed in the pillaring solution. Intercalation
reactions are performed at 40°C with an OH/(Al, Cu) molar ratio equal to 1.5 or 2 and an initial atomic percentage of copper
(100 Cu/Al + Cu) of 0, 5 or 10%. Chemical analyses, XRD spectra and surface properties show that clays are intercalated
after calcination at 300°C from both preparation procedures. There is increase of the Al content, dcai and of the BET surface
area, the copper content remains quite low whatever the conditions of preparation. Nevertheless, it seems that the copper
content resulting from the ‘P’ method is higher. During phenol oxidation with hydrogen peroxide (CWPO reaction), the
copper content and the procedure of preparation significantly influence the catalytic activity. Moreover, the very low copper
solubilization proves that copper is certainly associated with alumina at the surface of the catalyst in mixed species
intercalated or/and dispersed on the clay surface. 0 1998 Elsevier Science B.V.

Keywords: Clay; Pillared clay; Mixed (Al-Cu)-pillared clay; Hydrogen peroxide; Phenol oxidation; CWPO reaction

1. Introduction tory products. Some improvements have been recently

In the past decades, potential alternatives to incin-
eration and biological treatments such as WA0 (wet
air oxidation) or WPO (wet peroxide oxidation) have
been the subject of numerous investigations to reduce
the amount of organic effluents in waste waters. The
usual WO processes, especially the WA0 treatment,
generally require high temperatures and pressures to
obtain a high conversion of the more toxic or refrac-
*Corresponding author. Fax: +33 49453349
obtained in the use of homogeneous or heterogeneous
catalysts. Catalytic wet oxidation (CWO) has been
recently reviewed by Luck [I] and Levee [2]. Mn/Ce
[31,Cu/Zn/Al [41and noble metals (Pt. Rh, Ru)
supported on carbon, titania, ceria [5,6] have been
proposed for the catalytic wet air oxidation (CWAO)
of different compounds like phenol and light car-
boxylic acids. If, in some cases, no metal leaching
in solutions was detected for the most severe condi-
tions [5,7], there were problems of stability and of
safety with Ru/C catalysts [6]. It must be noticed that

0926-860X/98/$19.00 0 1998 Elsevier Science B.V. All rights reserved.

PII SO926-3373(97)00054-4
270 J. Barrault et al. /Applied Catalysis B: Environmental
the CWAO is generally performed between 100” and
300°C and at a pressure in the l-10 MPa range, and
also that differences in the experimental conditions
could influence the catalyst lifetime.
The WPO process, first adapted from the classical
Fenton’s reagent allows to obtain efficient oxidation in
rather mild conditions (0.1-0.5 Mpa, T < 100°C) with
a homogeneous Fe’+ catalyst and hydrogen peroxide
[7]. More recently, the WPO reactions were studied in
different places. Various materials have been proposed
as catalysts for the oxidation of substituted phenols at
atmospheric pressure and T 5 50°C (copper/iron sup-
ported over alumina or silica [8], iron + ZSM5 zeolite
[9], supported metallo-porphyrins or metal phtalocya-
nins [lo]), but few of them could be used due to a lack
of stability or a low activity. . . Nevertheless, should
these problems be resolved, the CWPO would find
numerous applications.
The aim of the present work was to study a hetero-
geneous catalytic WPO of organic compounds using
clay-based catalysts [ll]. To improve the catalytic
efficiency of the process, the idea was to combine a
porous support and active sites for the adsorption of
organic compounds for the activation of H202 and to
obtain complete oxidation. Natural clays were then
intercalated or pillared with aluminum or mixed (alu-
minum-copper) polyoxocations. In the latter case, an
increase in both, the specific surface area and the
number of active sites was expected. Previous works
carried out in this domain were mainly concerned with
the preparation of thermally stable materials which
can be used in numerous areas and replace other acid
materials like zeolites [12-141. Besides their textural
role, the intercalating species can also act as active
sites for different reactions (oxidation, (CO, Hz),
functionalization. . .), especially if mixed pillared enti-
ties can be prepared and intercalated [ 151. We report in
this paper the first results obtained in the oxidation of
an aqueous solution of phenol over mixed (Al-Cu)-
pillared bentonites.
2. Experimental
2.1. Oxidation procedure
Oxidation of the phenol solution was performed in a
thermostated glass reactor of 250 ml equipped with a
15 (1998) 269-274
stirrer and a pH electrode. A 100 ml phenol solution
containing 5 x 10e5 M of phenol was placed over a
0.5 g solid catalyst in the presence of an excess of
hydrogen peroxide (5 ml/O.5 N or 0.1 N) at atmos-
pheric pressure and at 293 K. All the experiments were
carried out at the same pH in the 4-5 range.
Samples of the reaction medium were analyzed in
order to obtain the phenol and the hydrogen peroxide
conversions. Total organic carbon (TOC) was mea-
sured with a DC 80 Dohrmann equipment. Phenol and
products of phenol conversion were analyzed with a
Waters HPLC equipped with a Cis column. The main
detected products were: catechol, hydroquinone, qui-
nones, muconic acid, maleic acid, oxalic acid and
acetic acid. The H202 concentration was obtained
by a calorimetric method [ 181 with a UV/Visible
DMS 90 Varian spectrophotometer. The content of
metal ions in the solution was determined from atomic
absorption analysis (Perkin-Elmer 2380).
2.2. Methods of preparation of Al-and (Al-G)-
pillared clays, XRD characterization and N2
adsorption
(a) A crude Tunisian clay (H) from the Hdidoudi
deposit was used without any purification. This clay is
an interstratified illite/smectite bentonite, well char-
acterized and described in a previous work [ 161. The
illitic fraction represents ca. 13% of the interstratified
material. The smectic fraction, in sodium-form, has a
pronounced beidellitic character, quartz being the
main impurity. The average elemental formula deter-
mined from the Na-exchanged purified fraction is:
Nac.78 K0.15 Lsi7.27 A40.731’” FA12.78 Feo.79 Mgo.5#’
Ozo (OH)+ The CEC of the calcined solid is ca.
75 meq/lOO g and its nitrogen BET surface area is
59 m’/g.
The pillaring solutions were prepared by dissolving
0.1 M-Al and Cu nitrates in 0.2 M-NaOH solutions.
The hydrolysis molar ratio, R = OH/(Al + Cu), was
1.2 or 2. Solution volumes were adjusted to have an
atomic ratio Cu/(Al+ Cu) of 0, 5 or 10%. The
solutions always remain clear and the pH is around
3.8. Above this pH, the Cut+ ions hydrolyze and
precipitate as hydroxides [ 171.
Two methods were used for pillaring:
?? the usual ‘ex-situ’ method, called ‘D’, where the
pillaring solution is slowly added to the clay
 .I. Barrault et al./Applied Catalysis B: Environmental 15 (1998) 269-274 271

Table 1
Main characteristics of (Al-Cu)H clays

Preparation method: D P

R: 1.5 2.0 1.5 2.0

Al (%) 10.74 13.58 13.4 12.87 13.42 13.75 12.95 13.43

cu (%) 43 ppm 0.16 0.26 60 ppm 0.15 0.39 28 PP~ 0.25
0
&ml A 17.9 17.8 17.8 17.2 17.5 17.0 18.0
s aETm 2g -I - 143 109 139 159

suspension (2% w/w). This method requires the
handling of large volumes of liquid; and
. a discrete method, called ‘P’, where the dry clay
powder (2 g) is directly dispersed in the same
amount of a pillaring solution. This method pre-
sents some advantages: (i) it decreases the amount
of liquid used for the preparation; and (ii) it is
easier to reduce the final pillared air-dried catalyst
to powder.
The pillaring reaction was performed with continu-
ously stirring at 40°C. The mixture was left to settle
for 48 h to reduce the liquid volume, the suspension
was then washed by five dialysis with distilled water
until a Cl-free supernatant was obtained, and then
dried at 80°C. The dry materials were crushed and
calcined for 2 h at 300°C.
(b) Samples are labeled as a function of the initial
conditions and methods of preparation (Table 1). Only
the daai pillared sample interlamellar distances which
give a significant information on the efficiency of the
pillaring method appear in Table 1. XRD spectra were
obtained by reflexion (Xc,) with a Siemens D500
diffractometer.
(c) Nitrogen adsorption experiments were per-
formed at liquid nitrogen temperature using a Carlo
Erba Sorptomatic 1900 instrument. The samples were
degassed overnight at 140°C before analysis.
3. Results and discussion
3.1. Characterization of clay catalysts
Whatever the preparation method (‘D’ or ‘P’) and
the ratio R (1.5 or 2), all the crude pillared (inter-
calated samples heated at 300°C) samples with 0,5 or
10% Cu in the initial pillaring solution, exhibit X-ray
dool diffraction peaks ca. 1.7-1.8 nm. These results
confirm that Keggin ‘Alis’ species formed in
the solution migrated into the interlamellar space
or/and that these species were formed inside the
clay.
Chemical analyses of the aluminum and copper in
the pillared clays show that the copper content of the
mixed pillared clays is generally very low (< 1%) and
that the alumina content is the same (Table 1). The
final copper content which does not correspond to the
value expected could indicate a partial incorporation
of copper in agreement with previous observations on
(Al-Fe)-laponites.
In our previous works, based on H2 TPR, XRD and
27A1 NMR, we suggested that a fraction of iron was
associated with pillaring species which could mean
that a limited isomorphic substitution of aluminum for
iron was obtained [15,19]. A similar result could be
obtained with mixed copper systems. However, recent
ESR studies of Cu centers supported on Al-, Ti- and
Zr-pillared montmorillonite clays show that cupric
ions could form links with the pillars rather than with
the silicate sheet and that these materials show superior
catalytic performance in the hydroxylation of phenol
POI.
The influence of the preparation method and the
copper concentration in the initial pillaring solution on
the nitrogen BET surface area, microporous volume
and total porous volume values are also listed in
Table 1. Al-pillaring leads to the expected increase
of textural parameters. The same increase can be
observed with the mixed (Al-Cu)-pillared clays.
The BET surface area increases from 59 m2/g to
ca. 170 m2/g for the mixed (Al-Cu) clays.
These materials, like the (A1a5Cug)HP2 sample,
have a very good ageing and thermal stability. The
&,i spacing, the surface area and the microporous
volume remain practically unchanged after one-year
ageing and heating at 500°C (10 h).
212 J. Barrault et al./Applied
Fig. 1. Effect of copper on the catalytic properties of pillared clays
(‘D’ preparation, R = 1.5). Copper content: (A) 0%; (m) 0.16%;
and (+) 0.26%.
3.2. Phenol oxidation
3.2.1. ‘Blank experiments’
In the absence of a catalyst, no significant phenol
conversion was observed from ‘blank experiments’ of
phenol oxidation with hydrogen peroxide.
When the clay was pillared with pure aluminum
oxyhydroxides species and used in phenol oxidation,
the activity was very low which, owing to the absence
of active sites, is quite normal.
3.2.2. Effect of copper
Since the solids are prepared via the ‘D’ process,
after the addition of copper to the pillaring solution
there is a strong increase of the phenol conversion
(Fig. 1) even if the copper content is low. The plateau
observed for a phenol conversion around 50% is due to
the complete hydrogen peroxide conversion. The
H202 content was checked periodically during the
oxidation experiment. Moreover, an increase of phe-
nol conversion was obtained when fresh hydrogen
peroxide was added to the reaction medium. The
analysis of the reaction medium after a 24 h reaction
indicates that, in both cases, the copper concentration
in the solution is under 2 ppm. This result clearly
shows the increase of the stability of copper when it is
introduced via a pillaring solution and mixed hydro-
xides. Indeed, when an ‘Alis’-pillared clay was simply
impregnated or exchanged with a copper salt, then
dried and calcined according to the usual procedure
for the preparation of heterogeneous catalysts, copper
was more easily solubilized, its content in the solution
after phenol oxidation being ca. 30-40 ppm. These
species, therefore, are more active in the phenol
Catalysis B: Environmental 15 (1998) 269-274
Time (h)
Fig. 2. Phenol oxidation over (AlLCu)-pillared clays. Effect of
preparation procedure: (+) ‘P’ (Cu = 0.39%); (I) ‘D’
(CLI = 0.16%), (R = 1.5).
oxidation (Fenton-type reaction) than the solid dis-
persed in the solution [ 111.
3.2.3. Effect of the preparation process
From Fig. 2, we can see how the procedure of the
preparation (over mixed (Al-Cu)-pillared clays) influ-
ences the phenol conversion. As mentioned in the
experimental part, the main difference between the
two procedures is that the clay powder is introduced in
the ‘AlCuOH’ solution (‘P’), whereas the ‘AlCuOH’
solution is added to the clay suspension (‘D’). When
the preparation is changed, there is a strong modifica-
tion of the phenol conversion: the ‘P’ solid being much
more active than the ‘D’ solid. In fact, the higher
activity could be due to the higher copper content
(0.39% instead of 0.16%) resulting from the change in
the preparation procedure.
During the first period of the reaction (8 h) over the
‘D’ sample, there are primary transformations of
phenol into intermediate products, especially light
acids. This is in agreement with the reactional scheme
proposed by Devlin and Harris [21]. The conversion of
these light acids is generally the rate-limiting step and
could be favored by the increase of the copper content.
A surface characterization of these materials, now in
progress, will fetch more information on the nature of
the copper species.
3.2.4. Effect of the hydrolysis
In our work, we found that the change of the
(OH/Al + Cu) ratio from 1.5 to 2, when the solids
were prepared via the ‘D’ process, significantly mod-
ified the phenol conversion (Fig. 3) even if the copper
content was the same. When the materials were
 .I. Barrault et al/Applied Catalysis B: Environmental
Fig. 3. Phenol oxidation over (Al-Cu)-pillared clays. Effect of the
R: (OH/Al + Cu) ratio during: (a) the ‘D’ preparation; (A) R = 2
(Cu=O.15%) and (+) R=lS (Cu=O, 16%); (b) the ‘P’ prepara-
tion; (A) R = 2 (Cu = 0.25%) and (4) R = 1.5(Cu = 0.39%).
obtained from the ‘P’ procedure (Fig. 3b), it could be
observed that the increase of the R ratio increased the
initial efficiency of the catalyst. The significant effect
of the pH could be due to the modification of the
mechanism of hydroxide formation, because of
changes of (i) the nature of ligands surrounding the
cation, (ii) the formal charge of the complex, and (iii)
the initiation of the different condensation steps. . .
[22]. Previous results showed clearly such modifica-
tions of the final composition and of the properties of
the solids [ 171. Here, it seems that when using the ‘P’
preparation the number of active sites or the dispersion
increases, and that the nature and the composition of
the (Cu-Al) sites are different.
3.2.5. Role of the homogeneous reaction
In all these experiments with H (Al, Cu) pillared
clays, the copper ‘solubilization’ was low, showing
that copper species were not simply dispersed over the
clay surface. Indeed, the copper content of the solution
was below 2 ppm after each run of phenol oxidation.
In order to discriminate between homogeneous and
15 (1998) 269-274 273
0: i----i
0 1 2 3 4 5 6 7
Time (h)
Fig. 4. Homogeneous phenol oxidation in the presence of soluble
copper species (2.5 ppm)
heterogeneous oxidation, several experiments were
done in similar experimental conditions with soluble
copper species (2.5 ppm). The results presented in the
Fig. 4, compared to those of Figs. 1-3, showed that
the rate of the homogeneous phenol oxidation to CO2
was much lower (3% conversion) than the rate of the
heterogeneous reaction, especially over (Al, Cu) mate-
rials issued from the ‘P’ preparation method.
3.2.6. Reproducibility of the results, stability of the
catalyst
Two sets of experiments were carried out in order to
check the reproducibility of the catalytic properties of
a H-(Al, Cu)-P-pillared clay.
Similar rates of phenol oxidation to CO2 were
obtained over different (fresh) samples of this
catalyst used in similar experimental conditions.
Five successive batch reactions were carried out
with the same catalyst sample without any change
of the reaction rate.
The solution obtained after the catalyst filtration
was inactive for the phenol oxidation.
Conclusion
These preliminary results show that H clays are
easily intercalated with aluminum species and that
copper is either incorporated (partial substitution of
Cu for Al) into the Al polyoxocations or associated to
other aluminum by forming different species. The low
copper content obtained, whatever the initial copper
concentration in the solution could be an indication of
the formation of ‘insoluble’ mixed ‘Al-Cu’ entities.
274 J. Barr-auk et al. /Applied Catalysis B: Environmental 15 (1998) 269-274
Moreover the change of copper content, even if
slight, with the modification of the preparation pro-
cedure is a good way for increasing the copper sub-
stitution and the catalytic properties. Indeed, most
important is the large increase in the rate of phenol
oxidation into carbon dioxide after the addition of
copper mainly due to a heterogeneous oxidation (in
the presence of the pillared clay) rather than to a
homogeneous Fenton-like oxidation. Work now in
progress is focused on the surface characterization
of these materials, especially on the characterization
of aluminum-copper interactions.
Acknowledgements
This work has been done within the framework of
the AVICENNE EEC program. The funding thereof is
gratefully acknowledged.
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