Ind. Eng. Chem. Res.

2001, 40, 3921-3928 3921

Wet Peroxide Oxidation of Phenolic Solutions over Different

Iron-Containing Zeolitic Materials
Gabriel Ovejero,* Jose L. Sotelo, Fernando Martı́nez, Juan A. Melero, and
Luis Gordo
Chemical Engineering Department, Faculty of Chemistry, Complutense University, Madrid 28040, Spain

A series of iron-containing zeolitic materials, prepared by different procedures, have been tested
as heterogeneous catalysts for the oxidation of phenolic solutions with hydrogen peroxide under
mild conditions. Fe-TS-1 catalysts were synthesized through hydrothermal crystallization of
wetness-impregnated Fe2O3-TiO2-SiO2 xerogels. The iron content within the raw xerogel was
optimized with the aim of minimizing the degree of iron leaching into the solution. For the
purpose of comparison, Fe-silicalite and Fe-ZSM-5 zeolites free of Ti species, synthesized through
hydrothermal crystallization of basic hydrogels and Fe-NaY, Fe-USY, and Fe-ZSM-5 materials
prepared by an ion-exchange procedure, were also tested. Heterogeneous catalytic systems
showed a better catalytic performance than homogeneous systems based on dissolved Fe3+ salts.
Moreover, Fe-TS-1 zeolite with a moderate Fe content (Si-Fe molar ratio of 76) showed the
best results in terms of catalytic activity and loss of active species into the aqueous solutions.
Finally, the stability of Fe species has been shown to be strongly dependent on the Fe
environment into the zeolitic framework, the synthetic route, and the temperature of the
treatment.

1. Introduction research during the past decade.1,10-14 Furthermore,

Many wastewater streams coming from industrial
processes contain a high concentration of organic pol-
lutants, which must be removed to comply with the
environmental regulations. Phenol is one of the most
important of these pollutants because of its high toxicity
and poor biodegradability.
During past decades, serious environmental concerns
have led to extensive research into the removal of
harmful organic compounds from industrial wastewater
streams.1,2 Conventional treatments based on thermal
destruction and chemical or biological methods have
limitations in applicability, effectiveness, and cost in the
treatment of wastewater streams. In this context,
particularly attractive are oxidizing treatments through
which the contaminant substance is converted into CO2
and water. These treatments involve ozonation,3 wet air
oxidation (WAO),4,5 wet peroxide oxidation (WPO),6-8
and supercritical water oxidation (SCWO).9 Although
each procedure has its own drawbacks, WPO processes
using hydrogen peroxide as the oxidant have emerged
as a viable alternative for the wastewater treatments
of medium-high total organic carbon (TOC) concentra-
tions.6 Hydrogen peroxide does not form any harmful
byproducts, and it is a nontoxic and ecological reactant.
Likewise, although hydrogen peroxide is a relatively
costly reactant, the operating costs of WPO processes
are overcome by the lower fixed costs as compared with
ozonation, WAO, and oxidation in supercritical media.
However, to enhance the decomposition of hydrogen
peroxide to produce hydroxyl radicals and minimize
their decomposition to water, the use of a catalytic
system is desirable. These processes of catalytic wet
oxidation (CWO) have been a significant subject of
* To whom correspondence should be addressed. Phone: 34-
91-3944111. Fax: 34-91-3944114. E-mail: govejero@eucmos.
sim.ucm.es.
10.1021/ie000896g CCC: $20.00 © 2001 American Chemical Society
Published on Web 08/03/2001
these kinds of processes are particularly attractive
because of their lower energy requirements and higher
selectivity toward biodegradable compounds as com-
pared with those in the absence of catalyst. First
attempts of these advanced oxidation processes were
carried out under homogeneous catalytic systems. In
this sense, Fenton-type reactions using metallic salts
as catalysts have received special interest.15,16 The major
weakness of these Fenton-type homogeneous catalytic
systems is the tight pH control as well as the production
of additional toxic wastes, which need to be treated. For
these reasons, there has been a considerable interest
in the development of heterogeneous catalysts for the
oxidation of wastewater streams. Unlike the homoge-
neous systems, these solid catalysts could be recuper-
ated by means of a simple separation operation and
reused in the next runs. In this sense, one of the
principal goals of these types of processes is the devel-
opment of stable heterogeneous catalysts with minimal
leaching of active species under the reaction conditions.
The pioneering heterogeneous catalysts used for the
abatement of water pollutants consisted of a variety of
solids, including metal oxides (pure or mixtures) of Cu,
Mn, Co, Cr, V, Ti, Bi, and Zn, as well as noble metals
such as Ru, Pt, and Pd.1 Recently, interesting works
have been published dealing with the use of zeolites
containing active species for the oxidative treatment of
phenolic aqueous solutions. For example, iron-contain-
ing zeolites have evidenced high catalytic activity in the
presence of H2O2 for the removal of phenol17,18 and other
refractory organic compounds.19,20 These studies have
shown a significant dependence of the synthetic route
on the activity and stability of the catalysts.
In most studies described in the literature dealing
with the use of zeolites containing active species for
CWO processes, the metal has been supported onto the
zeolite through current impregnation methods8 or by ion
exchange of the protonated zeolite with the correspond-
3922 Ind. Eng. Chem. Res., Vol. 40, No. 18, 2001

ing salt.20 However, few works describe the use of Table 1. Physicochemical Properties of Fe-Containing
zeolitic materials containing metal active species tet- Zeolitic Materials Synthesized through Direct Synthesis
rahedrally coordinated into the zeolitic framework for Ti/Fe Zeolites
catalytic abatement of water pollutants. A direct syn- initial mixture zeolite textural
thesis route would allow metal species to be more composition composition
iron
properties
strongly bonded to the zeolite framework and possibly type of content SBET Vmicrop
less readily subjected to extensive leaching during catalyst Si/Ti Si/Fe Si/Ti Si/Fe (wt %) (m2/g) (cm3/g)
catalytic treatment. In this sense, Valange et al.21 have Fe-TS-1 (1) 40 155 60 141 0.64 518 0.18
studied the preparation of MFI zeolitic materials con- (2) 40 80 62 76 1.18 497 0.17
taining copper by direct crystallization of silica gels (3) 40 20 43 19 4.43 443 0.15
TS-1 40 ∞ 49 ∞ 0.00 510 0.19
admixed with the corresponding metallic salts and
various mineralizing agents. These materials have Al/Fe Zeolites
shown a negligible leaching of active species into the initial mixture zeolite textural
aqueous phase for phenol removal at atmospheric pres- composition composition
iron
properties
sure and 20 °C, although a low activity was clearly type of content SBET Vmicrop
observed (78% phenol conversion). catalyst Si/Al Si/Fe Si/Al Si/Fe (wt %) (m2/g) (cm3/g)
Fe-ZSM-5 zeolite has evidenced a remarkable cata- Fe-silicalite ∞ 30 ∞ 23 3.64
lytic activity for phenol elimination by H2O2 in an Fe-ZSM-5 20 30 18 33 2.48
aqueous medium.17,18 Additionally, the incorporation of Table 2. Molar Composition of the Zeolitic Materials
Ti atoms in framework positions of zeolites has received Synthesized by an Ion-Exchange Procedure
much attention in the past decade because the obtained
exchanged zeolite
materials have shown to be efficient selective oxidation
catalysts.22 In this context, we have considered it type of unexchanged zeolite iron content efficiency of
interesting to study the performance of zeolites contain- catalyst Si/Al molar ratio (wt %) exchange (%)a
ing simultaneously Ti and Fe atoms tetrahedrally Fe-NaY 2.13 1.29 5.3
coordinated into the MFI zeolitic framework (denoted Fe-USY 2.92 1.08 4.5
as Fe-TS-1) for the treatment of phenolic aqueous Fe-ZSM-5 37.4 0.33 25.1
solutions. a (Fe/Al molar ratio) × 100.
On the other hand, because the stability of the active
sites in zeolites is extremely dependent on the synthesis hydrothermal crystallization of basic hydrogels contain-
procedure, the other objective of the present work was ing Si, Fe, and Al species at 170 °C for 24 h under
to study the catalytic WPO of phenolic solutions using autogenous pressure following a procedure developed
different iron-containing zeolites under mild conditions. by Van Grieken et al.25 The initial mixtures of synthesis
These materials were prepared through several syn- had the molar compositions of 1:60:20.9:685 Fe2O3-
thetical procedures: metal ion exchange over zeolitic SiO2-TPAOH-H2O and 1:40:1.5:31.4:1190 Fe2O3-
materials (Na-Y, USY, and ZSM-5 zeolites) and tetra- SiO2-Al2O3-TPAOH-H2O. The materials after syn-
hedral incorporation of the iron atoms into the zeolitic thesis were calcined for 5 h at 550 °C under an air
MFI framework through hydrothermal synthesis (Fe- atmosphere. Table 1 summarizes the chemical composi-
silicalite, Fe-TS-1, and Fe-ZSM-5). The catalytic per- tions of the initial hydrogel and final zeolite.
formance of the different materials has been evaluated 2.1.3. Samples Prepared by Ion Exchange with
on the basis of the leaching degree of iron species into Metallic Salts. Fe-ZSM-5, Fe-NaY, and Fe-USY
the aqueous solutions as well as their activity for phenol zeolites were prepared by ion exchange starting from
removal and TOC reduction. the acidic-sodium form of the corresponding zeolites
(Table 2). ZSM-5 and USY zeolites (3 g) were exchanged
2. Experimental Section in 0.2 L of 0.002 M iron(III) chloride solutions at 70 °C
2.1. Catalyst Preparation. 2.1.1. Fe-TS-1 and TS-1 during 24 and 2 h, respectively. However, NaY zeolite
Samples. Fe-TS-1 samples were synthesized by hy- was exchanged at 25 °C for 2 h. The corresponding Fe-
drothermal crystallization of wetness impregnated exchanged zeolites were washed with redistilled water
Fe2O3-TiO2-SiO2 amorphous xerogels with a 20 wt % three times and dried at 110 °C overnight. Table 2
aqueous solution of tetrapropylammonium hydroxide summarizes the molar composition of the parent zeolite
(TPAOH; Alfa) at 170 °C for 24 h under autogenous and the iron content incorporated after exchange treat-
pressure. Raw mixed oxides of Fe2O3-TiO2-SiO2 were ment.
prepared following a two-step sol-gel process described 2.2. Characterization Techniques. Characteriza-
elsewhere23 using tetraethyl orthosilicate (TEOS; Alfa), tion of the samples was performed by different conven-
titanium butoxide (TNBT; Alfa), and iron(III) sulfate tional techniques. Chemical analyses were performed
pentahydrate (Fe2(SO4)3‚5H2O; Aldrich) as source ma- by X-ray fluorescence (XRF) with a Philips PW 1480
terials. Amorphous xerogels were prepared with a SiO2- spectrometer. X-ray diffraction (XRD) patterns were
TiO2 molar ratio of 40 and different SiO2-Fe2O3 molar collected with a Philips X’PERT diffractometer with Cu
ratios. The TS-1 sample was synthesized in a manner KR radiation. Crystallinity was determined from the
similar to that of Fe-TS-1 samples described above, peak area at 2θ ) 22-25° using a highly crystalline
starting from wetness-impregnated TiO2-SiO2 amor- TS-1 sample as the reference. Diffuse reflectance UV-
phous xerogels with a SiO2-TiO2 molar ratio of 40.24 vis spectra (DR UV-vis) were obtained under ambient
As-synthesized materials were calcined for 5 h at 550 conditions on a Cary-1 spectrophotometer equipped with
°C under an air atmosphere. Table 1 shows the chemical a diffuse reflectance accessory. 27Al magic angle spin-
composition of the initial xerogels and Fe-TS-1 and ning nuclear magnetic resonance (MAS NMR) spectra
TS-1 zeolites as well as their textural properties. of powdered samples were recorded at 78.14 MHz in a
2.1.2. Fe-Silicalite and Fe-ZSM-5 Samples. Fe- Varian VXR-300, with a spinning frequency of 4000 kHz
silicalite and Fe-ZSM-5 samples were synthesized by and time intervals of 5 s between successive accumula-

tions. Measurements were made at room temperature
with [Al(H2O)6]3+ as the external standard reference
with accumulations amounting to 400. Nitrogen adsorp-
tion-desorption isotherms were measured at 77 K using
a Micromeritics ASAP 2000. The materials prior to the
adsorption measurement were outgassed at 300 °C for
12 h. The surface area was estimated according to the
BET method, and the micropore volume was calculated
using the t-plot method.
2.3. Catalytic Tests. CWO experiments in the pres-
ence of hydrogen peroxide were carried out in a 200 cm3
Teflon-lined stainless steel batch reactor under continu-
ous mechanical stirring (300 rpm) in contact with an
air atmosphere. Such equipment eliminates the possible
catalytic effect of the steel wall surfaces.
All of the reactants, except hydrogen peroxide, and
the catalysts were placed into the Teflon-lined reactor.
Thereafter, the system was pressurized to 1 MPa with
air and heated to the corresponding temperature with
a heating rate of 3 °C/min. Once the temperature
reached the set-point value, the oxidant was added
completely. The evolution of the reaction was monitored
along the time. Typically, 140 cm3 of a 1 g/L phenol
aqueous solution (TOC ) 765 ppm; pH ) 5.6) and 0.6
g/L of catalyst were used with the stoichiometric amount
of hydrogen peroxide (ca. 5 g/L) for complete mineraliza-
tion of phenol according to the reaction
C6H5OH + 14H2O2 f 6CO2 + 17H2O
Phenol removal was quantified by gas chromatogra-
phy in a Varian Star 3400 CX chromatograph using a
capillary column SPB-1 (60 m × 0.25 mm) and a flame
ionization detector. Quantitative analysis of products
coming from incomplete mineralization of phenol was
performed by means of a high-performance liquid chro-
matography (HPLC) technique. HPLC chromatograph
model Varian Prostar was equipped with a Spherisorb
ODS column (250 × 4.6 mm) and an UV detector at 210
nm. A mixture of methanol (20% by volume) and water
(80% by volume) buffered at a pH of 2.6 was used as
the mobile phase. The TOC contents of the solutions
before and after the reaction were analyzed using a
combustion/nondispersive infrared gas analyzer model
Rosemount Dohrmann DC-190. The peroxide concentra-
tion after reaction was evaluated by iodometric titration,
except those solutions showing a brown color, where
HPLC chromatography was used to estimate the oxi-
dant conversion.
2.4. Leaching Tests. The aqueous solution after the
reaction was cooled to 60 °C and filtered at this
temperature to prevent the possible readsorption of
active species. Thereafter, the content of the active
metal in the filtered solution was measured by atomic
emission spectroscopy with induced coupled plasma
(ICP-AES).
2.5. Stability Tests. The stability of the catalysts was
analyzed as follows: solid was recovered from the
solution by hot filtration after the reaction, calcined at
550 °C for 5 h in order to remove any organic species
remaining adsorbed, and finally tested again at the
same reaction conditions. This procedure was repeated
twice.
3. Results and Discussion
3.1. Preliminary Experiments. 3.1.1. Hydrogen
Peroxide Conversion in the Absence of Phenol.
Ind. Eng. Chem. Res., Vol. 40, No. 18, 2001 3923
Figure 1. Blank experiments. Reaction conditions: initial
TOC[Ph-OH] ) 765 ppm; temperature ) 100 °C; air pressure ) 1
MPa; stoichiometric amount of H2O2; catalyst concentration ) 0.6
g/L. (0) B-1, in the presence of air without catalyst and oxidant.
(O) B-2, in the presence of oxidant without catalyst. (4) B-3, in
the presence of catalyst without oxidant.
The oxidizing properties of hydrogen peroxide are well-
known for the catalytic or not wet oxidation of phenol.26
These oxidation processes in the liquid phase are
promoted by the generation of different radical species
such as organic hydroperoxyl (ROO•), hydroxyl (OH•),
and hydroperoxyl (HO2•), whose formation rate is sig-
nificantly enhanced in the presence of metallic spe-
cies.12,26 To investigate this issue, two experiments were
carried out to observe the H2O2 decomposition in the
presence or absence of catalyst. In the first experiment
30 mg of an Fe-TS-1 zeolite (Si-Fe molar ratio of 76)
and 50 mL of redistilled water free of phenol were
charged into the Teflon-lined reactor at 1 MPa of air
pressure. Once the temperature reached up to 100 °C,
the oxidant was fed into the reactor (H2O2-catalyst
mass ratio of 8.5). After just 20 min of reaction, an
oxidant conversion of ca. 90% was measured. The second
experiment performed under similar conditions but in
the absence of catalyst led to an oxidant conversion of
ca. 15% after 30 min. These preliminary experiments
indicate the effectiveness of Fe species to promote H2O2
conversion for the formation of free radicals in contrast
with the slower thermal decomposition favored in the
absence of a catalytic system.
3.1.2. Blank Reactions. A first kinetic run was
performed in the presence of an aqueous solution of
phenol (TOC ) 765 ppm, pH ) 5.6) and an air
atmosphere but in the absence of either catalyst or
H2O2. The results after 2 h of reaction showed a low
phenol conversion and a negligible TOC removal (B-1
in Figure 1). An additional kinetic experiment was
carried out under experimental conditions similar to
those used in run B-1 but in the presence of H2O2 (B-2
in Figure 1). The data demonstrate the high oxidizing
power of hydrogen peroxide even in the absence of a
catalytic system. Furthermore, these results also indi-
cate the higher oxidizing activity of H2O2 in comparison
3924 Ind. Eng. Chem. Res., Vol. 40, No. 18, 2001

Table 3. Relative Standard Deviation of Reaction

Parameters for WPO of Phenolic Solutions over
Fe-TS-1(2)
Fe leached
runa XTOC (%)b XPhOH (%)c (ppm)d pHe
A 66.0 100 1.30 2.76
B 66.4 100 1.42 2.64
C 63.8 100 1.27 2.81
average value 65.4 ( 1.1 100 ( 0.0 1.33 ( 0.06 2.73 ( 0.07
[Ph-OH] ) 765 ppm; stoichio-
a Reaction conditions: initial TOC

metric amount of H2O2 for phenol mineralization; catalyst con-

centration ) 0.6 g/L; temperature ) 100 °C; air pressure ) 1 MPa;
reaction time ) 120 min. b TOC conversion defined as (initial TOC
- final TOC)/initial TOC × 100. c Phenol conversion defined as
(initial phenol - final phenol)/initial phenol × 100. d ppm of Fe
leached into the aqueous solution after 2 h. e Final pH after
reaction.

to oxygen from the air. Finally, an oxidation experiment

was performed in the presence of a catalysts (Fe-TS-
1(2)) in an air atmosphere but in the absence of H2O2
(B-3 in Figure 1), with the rest of the experimental
conditions being analogous to previous experiments.
From the results displayed in Figure 1, it can be clearly
inferred that the presence of Fe does not promote the
formation of radical species in the presence of oxygen.
However, the low iron concentration into the aqueous
solution under this particular condition after 2 h of
reaction must be pointed out (0.1 ppm). The pH of the
aqueous solutions after the reaction was around 4 for
B-1 and B-3 experiments and 3 for B-2. These results
show a higher contribution of carboxylic acids into the
aqueous solution for the run carried out in the presence
of H2O2, which is in fairly good agreement with its
catalytic performance.
3.1.3. Repeatability of Experiments. To check the
repeatability of the results obtained with our reaction
system, a similar run has been carried out three times
over Fe-TS-1(2) zeolite. The reaction parameters ob-
tained (TOC, phenol conversion, and pH) for each run
are shown in Table 3. A low relative standard deviation
for the different reaction parameters can be seen,
evidencing the accuracy of the results shown in this
contribution.
3.2. Catalytic Properties of the Fe-TS-1 Zeolitic
Material for the WPO of Phenolic Solutions. Three
Ti-containing zeolitic materials with MFI structure and
different contents of Fe species have been synthesized
as described in the Experimental Section and tested on
the CWO of phenolic solutions in the presence of H2O2. Figure 2. XRD and DR UV-vis spectra of the zeolitic materials:
These zeolites were tested with the objective of finding (a) TS-1; (b) Fe-TS-1(1); (c) Fe-TS-1(2); (d) Fe-TS-1(3); (e) Fe-
high active materials in terms of phenol removal and silicalite; (f) Fe-ZSM-5.
TOC reduction accompanied with a minimum leaching
of iron species into the solution. Kinetic runs of different Fe-TS-1 samples for the
Figure 2 illustrates the XRD spectra of the calcined catalytic wet hydrogen peroxide oxidation of phenol in
Fe-TS-1 zeolitic materials. The three samples show the air at 100 °C are shown in Figure 3a. The results
typical pattern corresponding to a MFI structure. indicate that the activity of the different catalysts is
However, a slight loss of crystallinity is observed in the closely related to the Fe content incorporated in the
final materials with an increase of the iron content in material. However, after 2 h of reaction, the three
the initial xerogel, which might be attributed to the catalysts display similar TOC reduction with a complete
presence of amorphous phases. The chemical analyses absence of phenolic species and the presence of carboxy-
of these samples are depicted in Table 1. These data lic acids such as maleic, acetic, formic, and oxalic as the
show that the presence of Fe in the initial xerogel lowers main reaction byproducts. Furthermore, these results
the incorporation of Ti in the zeolitic framework, are achieved using just the stoichiometric amount of
whereas Fe species seems to be completely incorporated H2O2, in contrast with other works described in the
independent of the initial amount into the xerogel. This literature, which used an excess of oxidant.14,17 Figure
trend has also been observed in previous works dealing 3b illustrates the chemical composition of the reaction
with the synthesis of Al- and Ti-containing materials mixture after 12 min. It can be seen that the content of
through wetness-impregnated mixed oxides.27 aromatic compounds decreases rapidly with the Fe
 Ind. Eng. Chem. Res., Vol. 40, No. 18, 2001 3925

Table 4. Catalytic Properties of Different Fe-Containing

Materials for WPO of Phenolic Solutionsa

XTOC XH2O2 leaching test

catalyst (%)b (%)c pHd [Fe]Catalyste [Fe]Dissolvedf % Fe
Direct Synthesis
Fe-TS-1(1) 64.1 100 2.89 3.8 0.6 15.7
Fe-TS-1(2) 66.0 100 2.76 7.1 1.3 18.3
Fe-TS-1(3) 70.7 100 3.08 26.2 11.1 42.4
Fe-silicalite 79.1 100 3.21 21.8 9.4 43.1
Fe-ZSM-5 68.2 - 3.11 14.8 14.1 95.3
Ion Exchange
Fe-NaY 78.5 95.7 4.74 7.6 2.1 27.6
Fe-USY 67.3 - 4.67 6.4 3.7 57.8
Fe-ZSM-5 54.5 - - 2.3 1.7 73.9
[Ph-OH] ) 765 ppm; stoichio-
a Reaction conditions: initial TOC

metric amount of H2O2 for phenol mineralization; catalyst con-

centration ) 0.6 g/L; temperature ) 100 °C; air pressure ) 1 MPa;
reaction time ) 120 min. b TOC conversion defined as (initial TOC
- final TOC)/initial TOC × 100. c Hydrogen peroxide conversion
defined as (initial oxidant - final oxidant)/initial oxidant × 100.
d Final pH after reaction. e Milligrams of Fe in the catalyst per

liter of dissolution. f Milligrams of Fe leached after the reaction

per liter of dissolution.

For the purpose of comparison, a catalytic test per-

Figure 3. WPO of phenolic solutions over zeolitic materials.
Reaction conditions: initial TOC[Ph-OH] ) 765 ppm; temperature
) 100 °C; air pressure ) 1 MPa; stoichiometric amount of H2O2;
catalyst concentration ) 0.6 g/L. (a) TOC conversion versus
reaction time: (]) B-2; (0) TS-1; (O) Fe-TS-1(1); (4) Fe-TS-1(2);
(3) Fe-TS-1(3). (b) Chemical composition of the reaction mixture
and peroxide conversion after 12 min. Aromatics include phenol,
catechol, and hydroquinone. Carboxylic acids include acetic, formic,
and oxalic acids. Others include oxygenated products such as
alcohols and aldehydes.
content during the first minutes of the reaction, whereas
the proportion of carboxylic acids and oxygenated
products such as alcohols and aldehydes increases
significantly. Figure 3b also evidences the enhancement
of peroxide decomposition with the increase of Fe species
within the zeolitic materials. These aforementioned
results are in fairly good agreement with the influence
of the Fe content on the catalytic efficiency of the
different materials outlined in terms of TOC conversion
in Figure 3a.
formed in the presence of hydrogen peroxide but in the
absence of a catalytic system (B-2 in Figure 1) has also
been included in Figure 3. It is readily observed that
the presence of a catalytic system enhances significantly
the TOC conversion and peroxide decomposition, con-
firming the important role of the metallic species in the
catalytic abatement of aqueous solutions of phenol.
Additionally, an experiment using a TS-1 zeolite was
carried out in order to assess the effectiveness of Ti
species in the oxidation process. From the results,
depicted in Figure 3, it can be inferred that titanium
species show a TOC conversion similar to that shown
by the blank experiment (B-2) after 2 h of reaction.
However, the rate of TOC reduction and aromatics
removal during the first minutes of reaction is higher,
as compared with that of run B-2. Analogously, the TS-1
catalyst shows a lower activity in terms of TOC conver-
sion than Fe-TS-1 materials. The low rate of peroxide
decomposition and high percentage of aromatic com-
pounds during the first minutes of the reaction also
confirm this fact (Figure 3b).
The amount of Fe species leached into the aqueous
solution after 2 h of reaction have been measured for
the different Fe-TS-1 materials (Table 4). It is readily
observed that the stability of Fe species decreases as
their contents increase, which suggests the coexistence
of different Fe environments in the synthesized materi-
als. DR UV-vis spectroscopy has been applied to assess
the Fe atoms coordination in the zeolitic framework.
From the studies described in the literature,28 two bands
centered at 215 and 240 nm can be assigned to Fe
species in the [FeO4] tetrahedral groups. However, Fe
species in octahedral complexes or present in small
clusters show strong and broad adsorptions centered at
280 and 333 nm, respectively.28 Analogously, Ti atoms
occupying tetrahedral positions on the zeolitic frame-
work show a narrow band centered on 220 nm, whereas
the presence of extraframework TiO2 can be detected
by the observance of an adsorption band at 330 nm.29
Figure 2 illustrates DR UV-vis spectra of the differ-
ent Fe-TS-1 and TS-1 samples. TS-1 and Fe-TS-1 with
low and medium Fe contents (samples b and c) evidence
a narrow band centered at 210 nm, which is ac-
companied with a slight shoulder at 240 nm for the Fe-
3926 Ind. Eng. Chem. Res., Vol. 40, No. 18, 2001
Figure 4. Influence of the temperature of WPO of phenolic
solutions over Fe-TS-1 zeolitic materials. Reaction conditions:
initial TOC[Ph-OH] ) 765 ppm; air pressure ) 1 MPa; stoichiometric
amount of H2O2; catalyst concentration ) 0.6 g/L; catalyst ) Fe-
TS-1(2).
TS-1 samples. These spectroscopic results indicate the
presence of Ti atoms in tetrahedral positions into the
zeolitic framework, whereas the signal located at 240
nm suggests the presence of iron atoms also incorpo-
rated in a tetrahedral environment.29 The Fe-TS-1
sample with the highest Fe content (sample d) shows a
wide absorption band. This band could indicate the
presence of extraframework Ti and Fe species as
octahedral complexes or small clusters.28,29
These different Fe environments detected by DR UV-
vis are closely related with the leaching of active species.
Assuming that nontetrahedrally coordinated Fe species
are more labile than those tetrahedrally coordinated,
the high amount of Fe leached for the Fe-TS-1(3)
sample can be easily explained. However, when Fe
species are mostly tetrahedrally coordinated into the
zeolitic framework, the leaching is clearly reduced.
Furthermore, the evidence of extraframework oxides of
Ti and Fe detected by DR UV-vis for the Fe-TS-1
sample with higher Fe content correlates fairly well with
the textural properties determined by means of N2
adsorption tests (Table 1). Fe-TS-1 samples with low
and medium Fe contents show BET surface areas and
micropore volumes corresponding to a pure MFI zeolitic
structure. In contrast, the Fe-TS-1 sample with a high
Fe content evidences a significant decrease of the BET
surface area and micropore volume. These adsorptive
data confirm the existence of extraframework Ti and
Fe species for this sample that might be located within
the zeolite pores in agreement with the DR UV-vis and
XRD results.
The influence of operating temperature has been
studied for WPO of phenol in the presence of Fe-TS-1
zeolitic material (molar ratio: 76). In this way, two
additional experiments have been performed at 80 and
60 °C, respectively. Figure 4 illustrates TOC conversion
and leaching results after 2 h of reaction. The experi-
ment at 80 °C allows retention of the catalytic activity
with enhancement of Fe species stability as compared
Figure 5. Stability of Fe-TS-1 zeolitic materials. Reaction
conditions: initial TOC[Ph-OH] ) 765 ppm; temperature ) 100 °C;
air pressure ) 1 MPa; stoichiometric amount of H2O2; catalyst
concentration ) 0.6 g/L; catalyst ) Fe-TS-1(2).
with the reaction performed at 100 °C. Furthermore, if
the temperature is diminished to 60 °C, the leaching of
Fe species is significantly minimized without an ap-
preciable change in phenol removal. However, a re-
markable reduction of TOC conversion must be pointed
out.
A further research was focused on the stability of the
Fe-TS-1 zeolitic materials. Fe-TS-1(2) was reused twice
at 100 °C, with the results being depicted in Figure 5.
The catalytic activity in terms of TOC conversion is
slightly modified after 2 h of reaction for the fresh and
reused catalysts. However, a similar leaching of Fe
species for the fresh and reused catalysts is readily
evidenced. This fact could be related with the possible
readsorption of iron species onto the catalyst surface
even although the solution was recovered by hot filtra-
tion after reaction.
3.3. Comparison of Different Fe-Containing
Zeolitic Materials. Because the nature of active sites
in zeolites is extremely dependent on the synthesis
procedure, it was our particular interest to see how the
activity and stability of Fe species are affected by
different procedures of synthesis. Table 4 reports the
results for the catalytic wet hydrogen peroxide oxidation
of phenol over different Fe-containing zeolitic materials
after 2 h of reaction. The different catalysts were
prepared according to different procedures: hydrother-
mal crystallization of either xerogels (Fe-TS-1 samples)
or basic hydrogels (Fe-ZSM-5 and Fe-silicalite) and ion
exchange (Fe-NaY, Fe-USY, and Fe-ZSM-5).
Catalytic oxidation results over Fe-containing zeolitic
materials prepared by ion exchange evidences that Fe-
NaY zeolite displays a higher stability than exchanged
Fe-USY and Fe-ZSM-5 zeolites. It must be noteworthy
for these exchanged materials that Fe species incorpo-
ration as well as the strength of their interaction with
the zeolite framework are markedly dependent on the
nature of the zeolitic counterion, strength, and concen-
tration of acidic sites and the conditions of exchange
 Ind. Eng. Chem. Res., Vol. 40, No. 18, 2001 3927

treatment. Consequently, the nature of the Fe-zeolite

framework interaction set clearly the leaching of Fe
species into the aqueous solution. Likewise, when
exchanged zeolitic materials (Fe-NaY and Fe-USY)
are compared with Fe-containing materials prepared
through a direct synthesis procedure with similar Fe
content (Fe-TS-1(2)), the leaching of Fe species for the
latter is clearly reduced. These results confirm that the
direct synthesis procedure with a moderate Fe content
in the synthesis mixture allows active species to be
incorporated into the zeolitic framework more strongly
bonded than by ion exchange.
Finally, a zeolitic material with MFI structure syn-
thesized through direct synthesis of basic hydrogels
containing Si and Fe atoms but free of Ti species (Fe-
silicalite) has been tested on the oxidation process (Table
4). This material shows a poor stability with a high
leaching of Fe species (ca. 40%), which agrees with the
high presence of extraframework Fe species detected by
DR UV-vis (Figure 2, sample e). Moreover, when this
material is synthesized in the presence of Al atoms (Fe-
ZSM-5), almost a complete leaching of Fe species is
detected. 27Al MAS NMR of this sample (figure not
shown) displays clearly just a signal centered at 50 ppm
associated with Al atoms in a tetrahedral environment
into the framework with a complete absence of a peak
at 0 ppm corresponding to the presence of an Al
extraframework.30 In contrast, DR UV-vis of this
material (Figure 2, sample f) shows a wide signal from
280 to 330 nm, which is a strong indication of the
presence of extraframework Fe species.28 Both charac-
terization results suggest that the incorporation of Fe
species into the MFI zeolitic framework is dramatically
influenced by the presence of Al atoms when this
synthetic route is used. This high content of Fe species
not incorporated effectively into the zeolitic framework
explains the high percentage of leaching evidenced for
this material.
Figure 6 illustrates the TOC conversion along the
reaction time for Fe-TS-1(2) and exchanged Fe-NaY
zeolites. For the purpose of comparison, two homoge-
neous Fe catalysts based on iron(III) sulfate and iron-
(II) chloride with an iron content in the aqueous solution
equivalent to that present in the above-mentioned
catalysts have also been included. These homogeneous
experiments demonstrated a higher efficiency of Fe2+
ions as compared with that shown by Fe3+ species
(Figure 6a). From the catalytic results, it can be clearly
inferred that the presence of Fe3+ species effectively
incorporated into a zeolitic framework (Fe-TS-1(2))
exhibits a higher activity than those directly dissolved Figure 6. WPO of phenolic solutions over different Fe catalytic
systems. Reaction conditions: initial TOC[Ph-OH] ) 765 ppm;
in an aqueous medium. This fact confirms that the temperature ) 100 °C; air pressure ) 1 MPa; stoichiometric
activity of heterogeneous systems in not due to the amount of H2O2; catalyst concentration ) 0.6 g/L. (a) TOC
presence of Fe species leached off to the aqueous conversion versus reaction time: (]) B-2; (0) Fe-TS-1(2); (O) Fe-
solution during the oxidation process. The catalytic NaY; (4) homogeneous FeIII; (3) homogeneous FeII. (b) Chemical
behavior shown by the Fe-NaY zeolite is also remark- composition of the reaction mixture and peroxide conversion after
able, where an initial induction time with low activity 12 min. Aromatics include phenol, catechol, and hydroquinone.
Carboxylic acids include acetic, formic, and oxalic acids. Others
is observed before reaching the highest TOC reduction include oxygenated products such as alcohols and aldehydes.
of the tested catalytic systems.
The catalytic activity observed in terms of aromatics
removal and transformation into refractory compounds, Finally, it must also be pointed out that all of the
such as carboxylic acids, after 12 min, depicted in Figure heterogeneous catalytic systems seem to tend toward a
6b, is in fairly good agreement with the TOC conversion maximum value for TOC conversion after 2 h of reac-
values. Fe-TS-1(2) shows a better catalytic performance tion. This upper limit is probably set for the total
for the degradation of aromatic compounds than homo- oxidation of phenolic species and the appearance of
geneous catalysts based on Fe3+ species and exchanged refractory carboxylic acids, which are not suitable to be
Fe-NaY zeolite. mineralized under the reaction conditions.
3928 Ind. Eng. Chem. Res., Vol. 40, No. 18, 2001
4. Conclusions
WPO of phenolic solutions over iron-containing TS-1
(Fe-TS-1) with a moderate Fe content is shown as a
promising technology for the abatement of water pol-
lutants. This catalytic system, in the presence of a
stoichiometric amount of hydrogen peroxide, has evi-
denced an outstanding activity and stability for the
direct mineralization of phenol in comparison with
homogeneous catalysts and ion-exchanged zeolitic ma-
terials. Several factors have been shown to be crucial
for the leaching of active species into the aqueous
solution: the environment of Fe species into the zeolitic
framework, the synthetic route for the preparation of
the catalytic solids, and the temperature of the treat-
ment.
Acknowledgment
This work has been funded by the “Comisión Inter-
ministerial de Ciencia y Tecnologı́a” from Spain (Project
CICYT AMB-97-500/96).
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Received for review October 16, 2000
Revised manuscript received March 12, 2001
Accepted May 30, 2001
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