Applied Catalysis B: Environmental 39 (2002) 97–113

Route of the catalytic oxidation of phenol in aqueous phase

A. Santos∗ , P. Yustos, A. Quintanilla, S. Rodrı́guez, F. Garcı́a-Ochoa
Department Ingenierı́a Quı́mica, Facultad CC, Quı́micas, Universidad Complutense, 28040 Madrid, Spain
Received 9 December 2001; received in revised form 6 February 2002; accepted 31 March 2002

Abstract
Catalytic oxidation of phenol in aqueous phase over a copper catalyst supplied by Engelhard (Cu-0203T) has been studied. A
reaction pathway of phenol oxidation under intermediate temperature and pressure has been proposed. Temperatures employed
were 140 and 160 ◦ C and catalyst concentration ranged from 4 to 1550 g l−1 of liquid phase. To achieve this wide interval
of catalyst concentration values, two experimental set-ups were employed: a basket stirred tank reactor (BSTR), with the
liquid phase in batch, and an integral fixed-bed reactor (FBR) with co-current up-flow of gas and liquid phases. The main
intermediates detected in the phenol oxidation were ring compounds (hydroquinone, catechol, benzoquinone), which break
to yield CO2 and short chain acids, mainly maleic, formic, acetic and oxalic acids, and also traces of malonic, succinic and
fumaric acids. Oxalic acid was also found to form a complex with the copper which oxidizes to CO2 . The only non-oxidizable
intermediate under the conditions sets was acetic acid.
In order to propose a phenol oxidation pathway, several runs were carried out where the main intermediates detected in
the phenol oxidation were fed to the FBR under different temperatures and catalyst loadings. It was found that catechol
oxidation does not yield either benzoquinone or maleic acid but oxalic acid which finally mineralized to CO2 . However,
benzoquinone and maleic acid are products clearly detected in the hydroquinone oxidation. Oxidation reactions of phenol
and those intermediates studied take place not only on the solid surface but also in the liquid phase.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Phenol oxidation pathway; Copper catalyst; Wet air oxidation (catalytic)

1. Introduction pressures and temperatures, and consequently high

The problem of pollution reduction in aqueous
streams containing refractory compounds is of great
importance in wastewaters from many industries
(food, pharmaceutical, fine chemical, and petro-
chemical industries) [1–3]. These effluents cannot be
treated through conventional processes of biological
oxidation, because of their poor biodegradability. The
process currently used is the non-catalytic wet oxi-
dation or supercritical oxidation, which requires high
∗ Corresponding author. Tel.: +34-91-3944171;
fax: +34-91-3944171.
E-mail address: aursan@quim.ucm.es (A. Santos).
cost [4–6]. Although, both procedures have shown
high effectiveness, the severe operational conditions
cause high operative and installation costs, partic-
ularly power consumption (unless the COD is over
20,000 mg l−1 ) and maintenance (corrosion, deposits
and incrustations, among other problems). An in-
teresting alternative is the heterogeneous catalytic
oxidation, because the catalyst permits a significant
reduction of the temperature and pressure, increas-
ing the oxidation rate of refractory compounds and
improving the economy of the process [7–9].
As it is well established in literature, the organic
pollutants initially present in the wastewaters from dif-
ferent industrial processes are oxidized not directly

0926-3373/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 3 3 7 3 ( 0 2 ) 0 0 0 8 7 - 5
98 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113

Nomenclature CODHPLC sum of the chemical oxygen
ACE acetic acid demand
B non-identified intermediates τ space time (gCAT min−1 g
from catechol oxidation as carbon)
(condensation products or
oxalic acid precursor) Subscripts
BQ p-benzoquinone o relative to the initial conditions
CCAT catalyst concentration i relative to a compound
(g l−1 of liquid phase)
CC reactant concentration as
carbon concentration to CO2 but many organic intermediates are formed
(mg carbon l−1 ) [10–16]. In most cases, the final products of the oxida-
COD chemical oxygen demand tion are organic acids of short chain, as acetic, formic,
CTL catechol oxalic etc. [9], independently of what initial organic
FC reactant molar flow rate compounds were present in the wastewater. The total
(g reactant as carbon min−1 ) mineralization of the initial refractory compounds can
FOR formic acid be in many cases prohibitively expensive. The poten-
FUM fumaric acid tial for use of an integrated wet catalytic oxidation with
hL liquid hold-up a biological treatment process is of great interest. In
HQ hydroquinone this case, the initial non-biodegradable compounds are
MAL maleic acid partially oxidized to intermediates amenable to biolog-
MLO malonic acid ical oxidation. In the few studies carried out about the
OXA oxalic acid biodegradability of intermediates, it has been proved
p ratio of difference between that the use of the catalyst decreases the number of in-
ppm of COD and ppm of TOC termediates and improves the biodegradability of the
measured and expected from treated wastewater [17]. From the previous remarks,
HPLC, defined in Eq. (9) it is obvious that in order to know the oxidation route,
Ph phenol it can be very helpful to design an integrated process
PO2 oxygen pressure (bar) to treat an industrial wastewater. The influence of the
QL liquid flow rate catalyst and the operational conditions in this scheme
(ml h−1 ) is also an important question to be solved.
QO2 oxygen flow rate (ml min−1 STP) Among the harmful organic compounds in indus-
t reaction time (min) trial wastewaters, phenol and phenolic substances
T temperature (◦ C) have deserved more attention in the last two decades,
TOC total organic carbon because of their toxicity and the frequency of industrial
tR residence time of the liquid processes producing waters contaminated by phenol.
in the FBR (min) Moreover, phenol is considered to be an intermediate
VL reactor volume occupied by product in the oxidation pathway of higher molecular
the liquid phase (ml) weight aromatic hydrocarbons, thus it is usually taken
VR reactor volume (ml) as a model compound for advanced wastewater treat-
W catalyst weight in the ments [13]. The oxidation route of phenol has been
reactor (g) the subject of some works in the last two decades.
X conversion Most of the papers try to identify the intermediates
and propose reaction schemes of different complex-
Greek symbols ity. These studies have been carried out without [10]

and with catalyst [11,13,14,18–21]. A summary of
CHPLC sum of the organic carbon
these schemes can be found in Fig. 1. Very recently
 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113 99

Fig. 1. Reaction pathways for phenol oxidation in aqueous phase proposed in literature: (a) [11], (b) [21], (c) [18], (d) [14], (e) [19], (f) [13].

a remarkable paper has been published [22], propos-
ing a kinetic model from a reaction scheme based on
the proposed by Devlin and Harris [10] and further
simplified by Duprez et al. [14]. As can be seen, all
the oxidation routes consider the hydroxylation of
phenol to hydroquinone and catechol as a first step
with a further oxidation of the dihydroxylbenzenes to
benzoquinones. At this step, no differences between
hydroquinone and catechol are made and it is assumed
that both dihydroxylbenzenes follow the same oxida-
tion route. However, the confirmation of the scheme
by stoichiometry and the influence of the variables
such as temperature, oxygen pressure, and catalyst
concentration in the formation and disappearance of
100 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113
the different intermediates are still an open question.
In some cases [13,19], it has been proposed that
oligomerization or polimerization reactions occur in
the liquid phase yielding non-oxidizable compounds.
The aim of this work is the determination of the ox-
idation route of phenol in liquid phase when a copper
catalyst is employed. The experimentation has been
carried out using a commercial catalyst from Engel-
hard. This catalyst was selected among other four in a
previous work because of its mechanical and chemical
stability and its high activity in the phenol oxidation
and mineralization [23]. First, the intermediates from
phenol oxidation have been identified, under wide
intervals of temperature and catalyst concentration
values. In order to achieve a wide catalyst concentra-
tion interval, two experimental set-ups, a basket stirred
tank reactor (BSTR) and an integral fixed-bed reac-
tor (FBR), have been employed. Oxidation runs have
been carried out using the intermediates previously
detected as feeding, under different operational condi-
tions, in order to propose a route for the catalytic ox-
idation of phenol and to elucidate the influence of the
operational conditions on the oxidation rate for each
intermediate.
2. Experimental
The commercial catalyst used was supplied by
Engelhard (Cu-0203) with copper as the active com-
ponent. The chemical composition was: 67–77% cop-
per oxide, 20–30% copper chromite, 1–3% synthetic
graphite. The catalyst was used in an extruded form
(1/8 in diameter), with the following properties:
10 m2 g−1 of surface area, 0.10 ml g−1 of total pore
volume and 2 g ml−1 as packed average bed density.
Chemical and physical stability of the catalyst were
tested in a previous work [23], being found that the
phenol conversion remained almost constant at least
during 200 h, with losses by abrasion and leaching
during this time under 15% of the initial weight.
Phenol oxidation runs have been carried out at dif-
ferent catalyst loading in the reactor. At the lowest
catalyst concentration (4 g l−1 ), the reactor employed
was a 0.5 l BSTR with 250 ml aqueous solution of
phenol in batch and the oxygen gas flowing con-
tinuously through the reactor with a flow rate set
at 150 ml min−1 (STP). Rotating speed was kept
constant at 700 rpm and the initial concentration of
phenol used was 1200 ppm.
At the other catalyst concentrations (320 and 1550 g
of catalyst per liter of liquid phase), the runs were
carried out in a FBR (a stainless steel tube of i.d.
0.85 cm and length 25 cm) with concurrent up-flow of
gas and liquid phases. The catalyst was diluted with
glass beads. Input phenol concentration was 1000 ppm
and the oxygen flow rate was set at 150 ml min−1
(STP).
Temperature of the runs above was set at 140 ◦ C and
the oxygen pressure was maintained at 16 bar (pure
oxygen was used as gas phase). The initial pH of the
liquid phase was 3.5, value selected from a previous
study carried out with the same catalyst quoted above
[23]. Detailed schemes of both experimental set-ups
are available elsewhere [24].
In order to propose a phenol oxidation route, a group
of runs were carried out using some of the intermedi-
ates detected in the phenol oxidation as feeding of the
FBR, at different temperatures (140 and 160 ◦ C) and
catalyst loading (240, 320 and 1550 g of catalyst per
liter of liquid phase). In these runs, the oxygen flow
rate and the pressure were always set at 0.15 l min−1
(STP) and 16 bar, respectively. The operational condi-
tions of these runs are summarised in Table 1. As can
be seen, some runs without catalyst have been carried
out. Blank runs for phenol were already reported in a
previous work [24].
Liquid samples were periodically drawn from the
reactors and analyzed. Phenol and organic intermedi-
ates were identified and quantified by HPLC (Hewlett-
Packard Model 1100) using a diode array detector (HP
G1315A). A Nucleosil C18 5 ␮m column (AV-750,
25 cm long, 4.6 mm diameter) was used as stationary
phase and 4 mM sulfuric aqueous solution as mobile
phase. Flow rate of the mobile phase was a gradient
from 1 to 1.9 ml min−1 and the UV detector was used
at wavelengths of 192, 210, and 244 nm. Total organic
carbon (TOC) values in the liquid phase were obtained
by a SGE analyzer setting the pH value of the sam-
ples at 3.0 by adding HClO4 . The COD values were
measured by the standard method of Cr2 O7 −2 /Cr+3
reduction and the Cr+3 determination by photometer
(Aqualitic AL282).
Succinic acid was measured with a enzymatic test
(TC Succinic Acid Boehringer Mannheim) using a UV
detector at wavelength of 340 nm.
 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113 101

Table 1
Operational conditions for runs carried out in the FBR feeding different intermediates
Intermediates CCo T (◦ C) W (g) CCAT tR (min) QL (ml h−1 ) W/FCo (×10−3 ,
(ppm) (g l−1 ) gCAT min gCo −1 )
Acetic acid (ACE) 200 140 1 320 2.88, 4.16, 9.35 65, 45, 20 4.61, 6.65, 15.0
140 5 1550 3.78 50 33.3
160 1 320 2.88, 4.16, 9.35 65, 45, 20 4.61, 6.65, 15.0
160 5 1550 3.78 50 33.32
Oxalic acid (OXA) 135 140 1.22 240 4.16, 9.35 45, 20 7.39, 16.6
140 5 1550 2.08, 2.88, 4.16, 9.35 90, 65, 45, 20 27.2, 37.6, 54.3, 122
160 1.22 240 4.16, 9.35 45, 20 7.39, 16.6
160 5 1550 2.08, 2.88, 4.16, 9.35 90, 65, 45, 20 27.2, 37.6, 54.3, 122
160 0 0 4,16 45
Formic acid (FOR) 52 160 5 1550 4.56 40 155
160 0 0 4.56 40
Malonic acid (MLO) 173 160 5 1550 3.78 50 38.5
Maleic acid (MAL) 240 140 1.22 240 2.08, 2.88, 5.35, 90, 65, 35, 20, 10 2.08, 2.88, 5.35,
9.35, 18.7 9.35, 18.7
140 5 1550 2.08, 3.78, 9.35 90, 50, 20 15.3, 27.8, 68.7
160 1.22 240 2.88, 4.16, 9.35 65, 45, 20 2.88, 4.16, 9.35
160 5 1550 2.08, 3.78 90, 50 15.3, 27.8
160 0 0 4.16 45
p-Benzoquinone (BQ) 335 140 1 320 2.08, 2.88, 4.16, 9.35 90, 65, 45, 20 2, 2.75, 3.97, 8.93
140 5 1550 2.08, 3.78 90, 50 11, 20
140 0 0 2.88 65
Hydroquinone (HQ) 195 140 1 320 1.56, 2.08, 2.88 120, 90, 65 2.56, 3.41, 4.72
140 5 15500 3.78 50 34.18
140 0 1.56 120
Catechol (CTL) 325 140 1 320 2.08, 4.16, 9.35 90, 45, 20 2.05, 4.10, 9.21
130 140 1 320 1.33, 2.67, 4.68 140, 70, 40 3.30, 6.62, 11.5
130 140 0.1 30 1.33, 2.67, 4.68 140, 70, 40 0.33, 0.66, 1.15
130 140 0 0 1.86 100

Fixed operational conditions: pH0 = 3.5, PO2 = 16 bar, QO2 = 150 ml min−1 .

To determinate the presence of quinones, 2,4-dinitro- On the x-axis, time for BSTR or residence time, tR , for
phenylhydrazone was precipitated in the liquid effluent FBR is represented. This residence time is defined as:
(50 ml) by adding an acidific solution (10 ml, H2 SO4 VL hL VR
50 mM) of 2,4-dinitrophenylhydrazine (25 mM) in tR = = (1)
QL QL
ethanol [25,26].
Microanalysis was performed on a Leco CHNS-932 being related to the spatial time through the catalyst
with a pyrolytical oven Leco RO478 for oxygen ana- concentration as follows:
lysis. W tR CCAT
τ= = (2)
FCo CCo
2.1. Intermediates detected in the oxidation of phenol On the y-axis, the ratio of ppm of carbon correspond-
ing to the different reactant or intermediates (CCi ) to
The results obtained in the catalytic oxidation of the initial ppm of carbon of the run (CCo ) is plotted.
phenol at 140 ◦ C for a catalyst concentration of 4, 320, As can be seen from Fig. 2, phenol yields inter-
and 1550 g l−1 are shown in Fig. 2a–c, respectively. mediate ring compounds as hydroquinone, catechol,
102 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113

Fig. 2. Experimental results obtained in the phenol oxidation. Operational conditions: T = 140 ◦ C, QO2 = 150 ml min−1 (STP), PO2 = 16 bar:
(a) CCAT = 4 g l−1 , CPho = 1200 ppm (CCo = 912 ppm C); (b) CCAT = 320 g l−1 , CPho = 1000 ppm (CCo = 760 ppm); (c) CCAT = 1550 g l−1 ,
CPho = 1000 ppm (CCo = 760 ppm).

p-benzoquinone and acids as maleic, acetic, formic
and oxalic. Malonic and fumaric acids were also
identified but only in trace amounts. Succinic acid
could not be determined with the analytical procedure
employed because this acid has a similar retention
time to maleic acid and a small response (low peak
height/amount ratio). It must be noted that the aro-
matic compound concentrations achieve a maximum,
first appearing and then disappearing with time, yield-
ing acids of short chain as maleic, oxalic, formic and
acetic acids.
A decrease of the required time for the conversion
and mineralization of phenol when the catalyst con-
centration increases can be observed. The sum of the
 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113 103

organic carbon
of phenol and all the intermediates

quoted above ( CPh+int ) were calculated at each time
and compared with the TOC measured. These val-
ues should be the same when no significant amounts
of other organic intermediates, different from those
quoted above, are formed. At the lowest catalyst con-
centration (4 g l−1 ), as shown in Fig. 2a, it was found
that the sum of organic carbon from these identi-
fied intermediates was lower than the TOC measured.
Therefore, some non-identified intermediate/s appear
at this catalyst concentration. Note that this/these un-
known intermediate/s reach a maximum concentra-
tion at about 60 min coinciding with the rapid fall in
the ring intermediate concentrations, mainly catechol, Fig. 3. Experimental results obtained in the oxalic acid oxidation.
hydroquinone and p-benzoquinone. Operational conditions: T = 160 ◦ C, CCAT = 240 and 1550 g l−1 ,
Succinic acid was determined by enzymatic kit, PO2 = 16 bar, COXAo = 500 ppm (CCo = 135 ppm), QO2 = 150 l
finding only a concentration of this acid of about min−1 (STP).
18 ppm as carbon, only about 10% of the no balanced
carbon at 60 min. Therefore, it can be established
that the rest of the non-identified carbon can be the was observed at temperatures of 140 and 160 ◦ C. This
result of the condensation or polymerization of the behavior agrees with the trend observed in Fig. 2a–c
aromatic or quinone compounds. This assumption is where the concentration of acetic acid rose slowly, but
confirmed by the presence of a brown solid precipi- remained throughout the time.
tated in these samples. The color of the liquid phase The results of the runs carried out by feeding a
is strongly brown when the aromatic compound con- 500 ppm solution of oxalic acid (135 ppm of initial
centration increases and becomes light brown when organic carbon) are shown in Figs. 3 and 4. At 140 ◦ C,
these compounds disappear. no oxidation of oxalic acid was observed. At 160 ◦ C,
At higher catalyst loading (320 and 1550 g l−1 ), the partial oxidation to CO2 was achieved and no inter-
balance of carbon from the intermediates detected, fits mediates were detected by HPLC. However, TOC and
quite adequately the TOC measured, as can be seen oxalic acid conversion curves are not coincident at
in Fig. 2b and c, therefore non-identified compounds
must not be considered. Moreover, the final samples
are non-colored.

3. Oxidation route proposal

A group of runs was carried out in the FBR by

feeding the intermediates identified above in order to
accurately determine the oxidation route of phenol and
the influence of the variables such as temperature and
catalyst concentration on this route as summarized in
Table 1. Runs carried out without catalyst, yielded a
negligible conversion of the intermediates. This fact
was also observed for phenol oxidation in a previous
Fig. 4. Influence of the homogeneous contribution on conversion
work [24]. of oxalic acid oxidation. Operational conditions: T = 160 ◦ C,
When acetic acid was fed to the reactor at the condi- CCAT = 240 and 1550 g l−1 , PO2 = 16 bar, COXAo = 500 ppm
tions given in Table 1, no oxidation of this compound (CCo = 135 ppm), QO2 = 150 l min−1 (STP).
104 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113

this temperature (see Fig. 3). This fact indicates that a

compound, which cannot be detected by HPLC with
the method used, must be formed by the oxidation
reaction. We consider that this compound could be
a complex of copper oxalate formed with the copper
on the catalytic surface or with copper leached in
solution as it has already been described in literature
[21,27]. Characterization of the catalyst surface has
been performed for the catalyst used in the oxalic acid
oxidation runs under the following operational condi-
tions: T = 160 ◦ C, CCAT = 1550 g l−1 , PO2 = 16 bar,
COXAo = 500 ppm. The results are shown in Fig. 4.
A crystalline phase of copper oxalate moolooite
(C2 CuO4 ·nH2 O) was obtained, being confirmed by
X-ray diffraction (Philips X’Pert).The difference be-
tween the TOC and oxalic curves becomes slightly
more important at a higher catalyst concentration,
as can be seen in Fig. 3. An increase of the cata-
lyst concentration implies more copper available and, Fig. 5. Experimental results obtained in the formic acid oxidation.
therefore, a higher copper oxalate complex produc- Operational conditions: T = 160 ◦ C, CCAT = 1550 g l−1 , PO2
tion. Therefore, the scheme proposed for the oxalic = 16 bar, CFORo = 200 ppm (CCo = 52 ppm), QO2 = 150 l min−1
(STP).
acid is as follows:

scheme proposed for this acid is as follows:

(3)

The positive influence of the catalyst (heteroge- (4)

neous reaction) in the oxidation rate of the oxalic
acid can be deduced from Fig. 3. However, a homo-
geneous contribution (reaction in the liquid phase)
must be also taken into account, as can be seen in
Fig. 4. This figure shows data from experiments car-
ried out at different values of W/FCo . Each curve
correspond to a different weight of catalyst (different
catalyst concentration) in the reactor. Data obtained at
the same values of W/FCo but changing the catalyst
weight differ in the residence time, tR , as indicated
by Eq. (2). As can be seen in Fig. 4, the curves
obtained at different CCAT are quite different. This
means that the results obtained are affected not only
by the W/FCo change (heterogeneous contribution)
but also by the residence time (homogeneous contri-
bution).
When a 300 ppm solution of formic acid (52 ppm
of initial organic carbon) is fed to the FBR at 160 ◦ C,
it was observed that this acid oxidizes to oxalic acid
and CO2 , as shown in Fig. 5. Therefore, the reaction
Oxalic acid formation from formic acid can be
explained as a termination path in free-radical oxida-
tion of formic acid. In this process a hydroxyl radical
attacks the aliphatic compound to remove a hydrogen
atom bonded to carbon, and the free-radicals • COOH
thus form oxalic acid.
As can be deduced for the phenol oxidation results,
malonic acid appeared only in trace amount. The data
obtained in a run carried out with a 500 ppm solution
of this compound (173 ppm of initial organic carbon)
at 160 ◦ C are shown in Fig. 6. These data indicate that
malonic acid undergoes decarboxylation to produce
acetic acid and CO2 . This reaction route fits the carbon
balance properly:
MLO → ACE + CO2 (5)
Maleic acid was detected in all the phenol oxidation
runs. The runs carried out feeding this acid at dif-
ferent temperatures and catalyst concentrations are
 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113 105

Fig. 6. Experimental results obtained in the malonic acid oxidation.

Operational conditions: T = 160 ◦ C, CCAT = 1550 g l−1 , PO2 =
16 bar, CMLOo = 500 ppm (CCo = 173 ppm), QO2 = 150 l min−1
(STP).

summarized in Table 1 and the results are shown by

Figs. 7–9. At the lowest catalyst concentration and
temperature used, an induction period is observed as
can be seen in Fig. 7a. This indicates that this reaction
takes place according to a free-radical mechanism.
The positive influence of the catalyst concentration
(heterogeneous mechanism) can be noticed at temper-
atures of 140 and 160 ◦ C by comparing the Fig. 7a and
b with Fig. 8a and b, respectively. The contribution of
the oxidation in the liquid phase (homogeneous reac-
tion) can be deduced from the data shown in Fig. 9a
and b, at 140 and 160 ◦ C, respectively. It can be seen
that the conversion increases when longer residence
time (tR ) of the liquid phase is used at the same space
Fig. 7. Experimental results obtained in the maleic acid oxida-
time value (W/FCo ). Therefore, both homogeneous
tion. Operational conditions: T = 140 ◦ C, PO2 = 16 bar, CMALo
and heterogeneous contributions were also found for = 500 ppm (CCo = 240 ppm), QO2 = 150 l min−1 (STP): (a)
maleic conversion and mineralization, as previously CCAT = 240 g l−1 ; (b) CCAT = 1550 g l−1 .
observed with oxalic acid. The temperature has a pos-
itive effect on both contributions, homogeneous and
heterogeneous, as can be seen in Figs. 7–9. Formic acid appears from the beginning, while acetic
The oxidation of maleic acid at 140 ◦ C yields as acid concentration rising is related to the malonic acid
intermediates fumaric acid, oxalic acid and traces of concentration increases.
malonic acid, as can be seen in Fig. 7a and b. When The scheme proposed in Eq. (6) takes into account
the temperature is raised to 160 ◦ C also formic and all these considerations and the previous ones pointed
acetic acid were found, as shown in Fig. 8a and b. out by Eqs. (3)–(5). The carbon balance (comparing
106 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113

Fig. 9. Influence of the homogeneous contribution on conversion

of maleic acid oxidation. Operational conditions: PO2 = 16 bar,
CMALo = 500 ppm (CCo = 240 ppm), QO2 = 150 l min−1 (STP):
(a) T = 140 ◦ C; (b) T = 160 ◦ C.

could be explained by a different oxidation rate of the

intermediates. An increase in the catalyst concentra-
tion produces a faster oxidation rate of the reaction
intermediates, which was noted previously for the
Fig. 8. Experimental results obtained in the maleic acid oxida-
oxalic acid.
tion. Operational conditions: T = 160 ◦ C, PO2 = 16 bar, CMALo
= 500 ppm (CCo = 240 ppm), QO2 = 150 l min−1 (STP): (a)
CCAT = 240 g l−1 ; (b) CCAT = 1550 g l−1 .

the CO2 calculated from the components species mea-

sured with the TOC measured) allows to verify the re-
liability of the scheme proposed in Eq. (6). TOC and


CMAL+int values are represented in Figs. 7 and 8.
As can be seen, the correspondence is fairly good.
The curves of maleic and TOC conversions are
closer when the catalyst concentration increases. This (6)
 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113
Fig. 10. Experimental results obtained in the benzoquinone ox-
idation. Operational conditions: T = 140 ◦ C, PO2 = 16 bar,
CBQo = 500 ppm (CCo = 335 ppm), QO2 = 150 l min−1 (STP): (a)
CCAT = 320 g l−1 ; (b) CCAT = 1550 g l−1 .
The results obtained from the runs carried out by
feeding 500 ppm of p-benzoquinone (335 ppm of ini-
tial organic carbon) are shown in Figs. 10 and 11. The
o-benzoquinone was not used because it is not a com-
mercial product. At the lowest catalyst concentration
(320 g l−1 ), an induction period was observed, which
means a free-radical mechanism for this oxidation
107
Fig. 11. Influence of the homogeneous contribution on conversion
of benzoquinone oxidation. Operational conditions: T = 140 ◦ C,
PO2 = 16 bar, CBQo = 500 ppm (CCo = 335 ppm), QO2 = 150 l
min−1 (STP).
reaction. As was already pointed out for oxalic and
maleic acid oxidations, both heterogeneous and ho-
mogeneous reactions contribute to the benzoquinone
oxidation and mineralization, as can be deduced from
Fig. 11. Leached copper from the catalyst for this three
compounds mentioned (oxalic and maleic acids and
benzoquinone) ranged from 20 to 100 ppm depending
on the catalyst concentration and the residence time.
Because of the negligible conversion obtained in the
blank runs, the homogeneous contribution observed
in Figs. 4, 9 and 11 must be caused by copper in solu-
tion. An additional work, that lies beyond the scope of
this paper, is required to quantify the contribution of
both, solid catalyst and leached copper, to the reaction
rates. The intermediates now involved are maleic, mal-
onic, acetic, formic and oxalic acids. It is significant
that maleic acid was present only in small amounts
whereas the formic acid appeared from the beginning.
This could indicate that the formic acid is produced
due to a fast maleic acid oxidation. When maleic acid
is formed as an intermediate from the benzoquinone
oxidation, the oxidation rate of this acid can be faster
than when maleic acid is the compound fed to the re-
actor. This fact can be explained due to in the first case
when maleic acid appears there are already some rad-
icals in the reaction medium (from the benzoquinone
oxidation), which can reduce the induction period
observed in Fig. 9. Fumaric acid was also found, but
only in trace amounts, surely due to the low con-
108 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113

centration of maleic acid. On the other hand, CO2 is

obtained from the first breakage of the benzoquinone
to maleic acid. In fact the TOC curve begins to fall
when benzoquinone concentration diminishes but
obviously both curves are not coincident because of
the acid intermediates involved. Taking all this into ac-
count, the rupture reaction of benzoquinone to maleic
acid and CO2 can be added to the scheme of Eq. (6) as
follows:

(7)

The scheme in Eq. (7) fits quite well the carbon bal-
ance. Only slight differences
due to the experimental
error were found between ( CBQ+int ) and TOC as
shown by Fig. 10a and b.
When a 300 ppm solution of hydroquinone is used
as reactant (195 ppm of initial organic carbon), a very
high disappearance rate of this reactant was observed,
even at the lowest temperature and catalyst loading, as
can be deduced from Fig. 12a and b. Thus, at 140 ◦ C
and CCAT = 320 g l−1 the total conversion of hydro-
quinone is reached at residence times shorter than
1.5 min. This agrees with the observations of other
authors [28] for the reaction of dihydroxybencenes
with ferric ions as catalyst. These authors [28] pro-
pose that an oxidative complex of pyrocatechol or
hydroquinone with the metal (copper in this case) is
formed which readily oxidizes (Hamilton reaction).
At the lowest catalyst concentration used (320 g l−1 ),
benzoquinone is the unique product at short times, as
can be seen in Fig. 12a. The benzoquinone concen-
tration passes through a maximum and then begins to
decreases, according to the scheme in Eq. (8); at this
point the TOC curve follows the same tendency, it
begins to decrease as well. This maximum in the ben- Fig. 12. Experimental results obtained in the hidroquinone
zoquinone concentration appears at shorter times than oxidation. Operational conditions: T = 140 ◦ C, PO2 = 16 bar,
CHQo = 300 ppm (CCo = 195 ppm), QO2 = 150 l min−1 (STP): (a)
those observed when higher catalyst concentration is
CCAT = 320 g l−1 ; (b) CCAT = 1550 g l−1 .
used, as can be seen in Fig. 12b.
HQ
BQ → Eq. (7) (8)
quoted about the production of a readily reactive com-
The results obtained from the runs carried out with plex of dihydroxybencenes with copper. However,
500 ppm of catechol (325 ppm of initial organic car- whereas benzoquinone was the initial intermediate in
bon) as feeding are shown in Fig. 13a. As it was found the oxidation of hydroquinone, this compound was
for hydroquinone, a fast disappearance of catechol not detected in the catechol oxidation and only traces
was observed confirming the hypothesis previously of maleic acid were detected.
 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113 109

Fig. 13. Experimental results obtained in the catechol oxidation. Operational conditions: T = 140 ◦ C, PO2 = 16 bar, QO2 = 150 l min−1
(STP), p defined in Eq. (9): (a) CCTLo = 500 ppm (CCo = 325 ppm), CCAT = 320 g l−1 ; (b) CCTLo = 200 ppm (CCo = 130 ppm),
CCAT = 320 g l−1 ; (c) CCTLo = 200 ppm (CCo = 130 ppm), CCAT = 30 g l−1 .

To check up an absence of o-benzoquinone in the to 10 ml of a solution of 2,4-dinitrophenylhidrazine

catechol oxidation, a test for the determination of
aldehydes and ketones (using the reagent 2,4-dinitro-
phenylhidrazine [25,26]) was applied to the FBR run
samples. Thus, 50 ml of the liquid effluent of FBR,
obtained at the shorter residence time used, were added
(0.025 M). Under these conditions, precipitate of
hydrazone was not observed. From this fact, it
can be concluded that o-benzoquinone is not
present in the catalytic catechol oxidation accompli-
shed.
110 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113

Moreover, at a wavelength of 244 nm, where
the maximum for benzoquinones concentration was
found, no signal was detected in the analysis by HPLC
during the 30 min, confirming the absence of benzo-
quinones in the samples obtained from catechol oxi-
dation. This result has not been described in literature
so far. Furthermore, the unique intermediate detected
in the oxidation of catechol by HPLC was oxalic
acid, which appears already at short times (2 min).
This disagrees with the schemes assumed in literature
shown in Fig. 1. Nevertheless, the sum of carbon from
catechol and oxalic acid does not fit the TOC values
obtained at each time in Fig. 13a. Consequently, some
unidentified organic intermediate must be present.
To determine the oxidation grade of the unknown
intermediate/s from cathecol oxidation, here called B,
the ratio p of the differences between the COD and
TOC values measured and expected from interme-
diates detected (oxalic in this case) was calculated
as:

To confirm the results obtained in Fig. 13a, two ad-
(COD − CODHPLC )
p=
(9)
(TOC − CHPLC )
The value of p means the ratio between the differ-
ence in the COD measured and expected from inter-
mediates detected by HPLC and the difference in the
TOC measured and expected by HPLC. The values
of p corresponding for each intermediate have been
calculated being shown in Table 2. By comparison
of values of p in Table 2 and values of p obtained in
Fig. 13a, the unidentified intermediate/s must have an
oxidation grade between catechol and succinic acid.
As can be seen in Fig. 13a, this/these unidentified
compound/s are oxidized at longer time. Enzymatic
test for succinic acid determination were applied to
the samples obtained at 4.16 and 9.35 min in Fig 13a.
Succinic acid concentration measured was only 5% of
the difference between the carbon calculated from in-
termediates detected by HPLC and carbon measured
by TOC.
On the other hand, the solvent of 200 ml of liquid
phase obtained in the run by feeding 500 mg l−1 of
catechol at the shortest residence time was removed
‘in vacuo’. The remaining solid was analyzed by H
RMN and 13− C RMN. The proton NMR spectra in-
formation allows three compounds to be identified
and quantified, catechol and traces of succinic acid
and 4,6-dihydroxidibenzofuran. Because of traces of
furan are also found it can be assumed that catechol
yield condensation products which could explain
the non-balanced carbon at intermediate reaction
times.
ditional runs changing the initial catechol concentra-
tion to 200 ppm and catalyst loading to 30 g l−1 have
been carried out. Results are shown in Fig. 13b and
c. Under the conditions of the run shown in Fig. 13b,
the p value calculated is lower (p = 0.9) than that
obtained previously in Fig. 13a (p = 2), probably due
to the lowest initial catechol concentration employed
in the run of Fig. 13b. This value of p is closer to that
obtained for oxalic acid and could be due to a precur-
sor of the oxalic acid or oxalic–copper complex which
can not be properly analyzed by HPLC. To confirm

Table 2
COD and TOC values per ppm of the intermediates detected in the phenol oxidation
Compound Molecular ppm C/ppm ppm COD/ppm p = ppm COD/ppm C
formula compound compound
Oxalic acid C 2 H2 O4 0.270 0.178 0.66
Formic acid CH2 O2 0.260 0.350 1.35
Malonic acid C 3 H3 O4 0.346 0.615 1.78
Acetic acid C 2 H 4 O2 0.400 1.067 2.67
Succinic acid C 4 H 6 O4 0.407 0.950 2.33
Maleic acid C 4 H 4 O4 0.483 0.828 1.71
Fumaric acid C 3 H3 O4 0.483 0.828 1.71
p-Benzoquinone C 6 H4 O2 0.670 1.627 2.43
Hydroquinone C 6 H6 O2 0.650 1.891 2.91
Catechol C 6 H6 O2 0.650 1.891 2.91
Dibenzofuran C12 H8 O3 0.720 2.000 2.77
Phenol C 6 H6 O 0.760 2.383 3.14
 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113
this hypothesis the following procedure has been fol-
lowed:
• The run at tR = 1.33 min in Fig. 13b has been
carried out again long enough to get 900 ml of liq-
uid effluent from the reactor. The solvent from this
liquid volume has been removed ‘in vacuo’ and the
remaining solid has been washed several times with
ethanol, to solve the organic compounds. It was
expected that the organic compounds complexed
with metals would not dissolve, the remaining solid
being about 94 mg.
• The elemental analysis of a portion of this solid
yields the following composition: 18.9% C, 1.7%
H, 43.3% O and 2.7% of S. Therefore, another
element/s by this elemental analysis is/are present
in about 33.4%.
• Another portion of this 94 mg of solid was dis-
solved in NaOH 2 M and the copper in solution
Fig. 14. Reaction pathway for the phenol oxidation in aqueous phase proposed in this work.
111
was measured, yielding about 29.4 mg of copper
and 0.5 mg of chromium related to the 94 mg of
solid. Therefore, a 31.3% of the 94 mg was copper
and about 0.6% was chromium. Sum of Cu and
Cr yields about a 32% of the solid and shows an
acceptably fair elemental analysis described above.
• The S must come from the sulfuric acid added to
acidify the liquid fed to the reactor and it can be
assumed to be in the solid as copper sulfate. The
chromium comes from the catalyst as copper chro-
mite. By resting the corresponding copper sulfate
and copper chromite, and recalculating the com-
position of the 94 mg of the solid, the following
elemental analysis is found: 22.8% C, 2.0% H,
45.0% O and 30.2% Cu. This may correspond to
a compound/s with an average empirical formula
C4 H4 O6 Cu, which is/are compound/s more oxi-
dated than maleic or succinic but less than oxalic
acid.
112 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113
Copper oxalate in the liquid phase has been found
by analysis of the liquid phase obtained from the
catechol oxidation run carried out at T = 140 ◦ C,
CCAT = 320 g l−1 , pO2 = 16 bar, CCTLo = 200 ppm
and residence time 1.33 min. After removing the
solvent of the liquid phase ‘in vacuo’ and drying
the remaining solid at 200 ◦ C for 10 h. A crystalline
phase of copper oxalate moolooite (C2 CuO4 ·nH2 O)
was obtained, being confirmed by X-ray diffraction
of this solid (Philips X’Pert).
In Fig. 13c, the results obtained when 200 ppm of
catechol are feeding to the FBR at 140 ◦ C and low
catalyst concentration (30 g l−1 ) are plotted. Because
of this low catalyst load the differences obtained be-
tween catechol conversion and TOC conversion are
greater than those found in Fig. 13a and b, and the
p value (≈2) of the unidentified compound/s, B, are
close again to those obtained in Fig. 13a. This fact can
be explained by considering a positive influence of the
catalyst in the mineralization rates of intermediates.
The TOC curves in Fig. 13a and b are closer to
the catechol curve than those results deduced from the
hydroquinone curve, given in Fig. 12a. This means
that fewer or more quickly oxidable intermediates are
produced from catechol than from hydroquinone. The
induction period observed in the TOC curve for the
hydroquinone is missed in the TOC curve when cat-
echol is oxidized and this could be related to the
non-production of benzoquinones from catechol.
Taking all the above facts into account the scheme
proposed for the catechol oxidation is as follows:
(10)
Therefore, the proposed pathway for the phenol
oxidation based on the previous discussion is shown
in Fig. 14.
4. Conclusions
The main difference in the phenol oxidation
pathway between the scheme proposed in this study,
shown in Fig. 14, and the ones proposed in literature,
summarized in Fig. 1, is the route for the catechol
and hydroquinone oxidations. Moreover, a possible
oligomerization and polymerization products have
been only detected at low catalyst loading (4 g l−1 )
and these compounds are finally oxidized to acid
intermediates.
It has been found that the catalytic oxidation of
phenol in aqueous phase, when a copper catalyst is
employed, follows a free-radical mechanism with an
induction period, which decreases when the catalyst
concentration increases, at least in the interval here
employed from 4 to 1550 g l−1 of catalyst. However,
the induction period is not observed for the oxida-
tion of some intermediates, such as catechol and
hydroquinone, which oxidation rates are much faster
than that of phenol. On the other hand, the TOC
curve in the hydroquinone oxidation decreases slower
than in the case of catechol oxidation because both
dihydroxybenzenes are oxidized through different
pathways. Benzoquinone, maleic acid and other acid
intermediates (malonic, acetic and formic acids) have
been obtained from hydroquinone, whereas oxalic
acid (free or complexed with copper) is the only
intermediate detected in the catechol oxidation. Nev-
ertheless, at short reaction times also condensation
products from catechol can appear which are further
oxidized to oxalic acid or mineralized to CO2 .
The unique non-oxidable intermediate detected,
under the operational conditions here employed, was
acetic acid. Benzoquinone and maleic acid oxidations
show an induction period at low catalyst concentra-
tion (320 and 240 g l−1 , respectively) and tempera-
tures (140 ◦ C). Oxalic acid is not oxidized at 140 ◦ C,
whereas it mineralizes at 160 ◦ C, and no induction
period has been observed at this temperature.
Phenol oxidation takes place in homogeneous and
heterogeneous phase, and therefore, both contribu-
tions must be taken into account in the oxidation
rate and in the intermediate formation rate (such as
benzoquinone, maleic and oxalic acids), because an
important extent of the reaction takes place in the liq-
uid phase due to the copper leaches. The reaction is
initiated either on the catalyst surface or in the solu-
tion by the leached copper ions, through a radical or
ionic mechanism, and the propagation step can take
place either on the catalyst surface or in the liquid
phase, involving or not the copper in this step, as
proposed by Sadana and Katzer [29].
 A. Santos et al. / Applied Catalysis B: Environmental 39 (2002) 97–113
The radical environment can also be responsible of
the different rates observed in the oxidation of the
same compound, depending on whether the compound
is the initial reactant or it is produced from other
reactant. For example, the oxalic acid was found to be
a non-oxidable compound at 140 ◦ C when was fed to
the FBR, whereas a maximum in its concentration was
obtained when it comes from phenol, catechol, hydro-
quinone or maleic acid at the same temperature. There-
fore, the reaction rate obtained when an intermediate
is fed to the reactor cannot be extrapolated in order to
obtain a further kinetic model of the phenol oxidation.
Acknowledgements
This work has been supported by CAM under
contract 07M/0069/2000 and CICYT under contract
PPQ2000-1763-C03-02 and FEDER 2FD97-1767.
The authors wish to thank Engelhard for kind supply
of the catalyst employed.
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