Applied Catalysis B: Environmental 47 (2004) 37–45

Catalytic combustion of methane over red mud-based catalysts

J.R. Paredes, S. Ordóñez∗ , A. Vega, F.V. Dı́ez
Department of Chemical and Environmental Engineering, University of Oviedo, C/Julián Claverı́a s/n, 33071 Oviedo, Spain
Received 17 March 2002; received in revised form 16 March 2003; accepted 22 July 2003

Abstract

Three iron-based catalysts were prepared from waste materials from the aluminium industry (red mud (RM)) by dissolution–
precipitation methods, followed by calcination in air at 500 ◦ C for 2 h. The activity and stability of those materials for the catalytic combus-
tion of methane was studied at atmospheric pressure, temperatures between 300 and 626 ◦ C and space time between 106 and 526 g h/mol
of methane (WHSV = 48 h−1 ), and compared to that of hematite and a Cu-Cr-Ti commercial catalyst. The kinetics of the reaction was
successfully modelled considering pseudo-first order dependence on methane partial pressure. Superficial characterisation of fresh and used
catalysts were carried out by BET, X-ray diffraction (XRD) and temperature programmed techniques. Results obtained indicate that red mud
activated by the method of Pratt and Christoverson exhibits higher catalytic activity and good thermal stability.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Methane oxidation; Hematite; Red mud; Iron oxide catalysts

1. Introduction Due to these reasons, the search for alternative catalysts

Catalytic incineration has shown to be a technically, eco-
nomically and environmentally interesting alternative for the
abatement of organic pollutants in gaseous emissions [1].
This technique is well developed for most volatile organic
compounds (VOC), such as alkanes, aromatics, and oxy-
genated compounds. The catalytic combustion of methane is
more difficult, since this molecule is very difficult to activate
[2]. However, in the last years the need to decrease methane
emissions has been widely accepted, mainly in relation to
the global climate change, due to both the high amount of
methane emitted and the high global warming potential of
this compound. On the other hand, the difficulty in destroy-
ing methane by catalytic combustion makes this compound
an attractive model compound to test the efficiency of cata-
lysts for VOC combustion.
Pd and Ir catalysts are considered to be the most active for
methane combustion [3,4]. However, their use can present
some problems, besides their high price: volatilisation of the
active phase (Ir), sintering (Pd), or poisoning in presence of
water or sulphur compounds (both) [5–8].
∗ Corresponding author. Tel.: +34-985-103-440;
fax: +34-985-103-434.
E-mail address: salorga@correo.uniovi.es (S. Ordóñez).
based on oxides of non-noble metals has increased in the
last years. Important advantages of these catalysts would
be their higher resistance to poisoning and lower price.
Most of this research has been devoted to complex oxides
systems, such as spinels, perovskites or hexaaluminates
[9–12]. Some authors discard single oxides as combustion
catalysts because of its low thermal stability. However,
iron oxide (Fe2 O3 ) has shown high sintering resistance
[13–15], being then potentially interesting for methane ox-
idation. In a recent work, Barbosa et al. [16] showed the
importance of the preparation method (precipitation with
ammonia or citrates method) and precursor calcination tem-
perature in the catalytic activity of bulk iron oxide catalysts,
concluding that precipitation methods produce catalysts
with higher thermal stability, therefore making them more
suitable for methane oxidation.
On the other hand, development of catalysts based on
waste materials is an issue of great interest, since two
environmental objectives can be attained simultaneously:
the valorisation of wastes and the saving of raw materi-
als, such as the metallic precursor [17]. Red mud (RM)
is a by-product of the caustic leaching of bauxite in the
manufacture of aluminium by the Bayer process, formed
mainly by oxides of Fe (as hematite), Ti and Al. Due to
the great amount produced (0.7 kg of red mud per kg of
bauxite processed), its safe disposal, treatment or re-use is

0926-3373/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0926-3373(03)00325-4
38 J.R. Paredes et al. / Applied Catalysis B: Environmental 47 (2004) 37–45

of great practical interest [18,19]. Because of its low cost, Table 1

composition (mainly Fe content) and surface area (i.e. its SEM–EDX surface composition of the red mud-derived catalysts (wt.%)
surface area is much higher than that of hematite), red mud Element RM ARM PARM
has been studied as catalyst for a variety of reactions, such Fe 21.7 28.9 27.5
as anthracene oil hydrogenation and tetrachloroethylene hy- Ti 11.9 12.8 11.6
drodechlorination [20–23]. The main problem of red mud Al 7.4 7.9 9.3
when used as catalyst is the presence of sodium and calcium Na 3.0 0.4 0.0
oxides, which can lead to sintering at high temperature [22]. Ca 4.9 4.1 3.9
Si 3.6 2.7 3.6
Several methods have been proposed to improve the cat- P 0.7 0.7 3.1
alytic performance of red mud, mainly for hydrogenations, V 0.3 0.3 0.2
i.e. by decreasing the tendency to sintering or increasing the Cl 0.3 0.0 0.0
surface area. The method of Pratt and Christoverson [20]
which consists of dissolving the red mud into hydrochloric
acid, followed by precipitation with ammonia, and calcina- economical evaluation is out of the scope of this work, a
tion, decreases the red mud Na and Ca content, as well as preliminary evaluation, taking into account the costs of ma-
increases the surface area. The material produced by treat- terials, energy and transport, showed that the cost of red mud
ing red mud by this method will be called here activated derived catalysts is much lower than that of conventional
red mud (ARM). Alvarez et al. [21] modified this method catalysts, i.e. the final cost of ARM would be around at least
by dissolving the red mud in a mixture of hydrochloric 30% lower than that of hematite, on a Fe weight basis, and
and ortho-phosphoric acid. The material produced by this much lower than more complex metal oxide systems.
method will be called here phosphorous-activated red mud
(PARM). So, it was found that, although activation by this
method produces a slight decrease in the Fe concentration 2. Experimental
(the catalytically active metal in hydrogenations) and sur-
face area, the stability of sulfided PARM in hydrogenations 2.1. Catalysts preparation
is appreciably enhanced [21,22], when compared to sulfided
ARM. However, higher amounts of P lead to a sharp decrease The red mud used in this work was supplied by the San
in the surface area and hence poorer catalytic performance Ciprián (Lugo, Spain) plant of the Company Inespal-Alcoa.
[21]. Its main constituents were analysed by atomic absorption
In this work, the performance (activity and ageing) of red spectrometry and volumetric methods after acid dissolution
mud, red mud activated by the method of Pratt and Chris- and alkaline fusion (details of the analytical method can be
toverson, and red mud activated by the method of Alvarez found in [23]). The superficial concentration of red mud
et al., for the total oxidation of methane in air, is studied (around 1 ␮m depth of a polished and carbon-coated sample)
and compared with massive hematite synthesised by a pre- was determined by the X-ray microanalyser of a JSM 6100
cipitation method (called here iron oxide) and a Cu-Cr-Ti scanning electron microscope. The compositions obtained
commercial catalyst (called here commercial catalysts). In by both methods are given in Tables 1 and 2.
addition, the kinetics of the reaction is modelled, and aged The method of Pratt and Christoverson for enhancing
catalysts characterised. Red mud-derived catalysts are ex- the catalytic activity of red mud consists of dissolving the
pected to be active for this reaction due to their high Fe red mud in aqueous HCl, boiling the resulting solution for
content, besides possible catalytic or promoting effects by 2 h, and producing a precipitate by the addition of aqueous
other red mud constituents. This work is original, since no- ammonia until pH = 8 is reached. The precipitate is then
body studied the application of red mud-based catalysts as filtered, washed with distilled water, dried at 100 ◦ C, and
oxidation catalysts. Another original aspect of great interest calcined in air at 500 ◦ C for 2 h [19]. This method decreases
is the study of the effect of P as promotor in VOC oxida- the red mud content in Ca and Na and increases the specific
tion. This aspect, as far as we know, has not been reported surface (Na is known to enhance sintering [24], Table 3).
in the literature.
The potential advantages of these catalysts are both envi- Table 2
ronmental and economical. From the environmental point of Bulk composition of red mud-derived catalysts (wt.%)
view, taking into account the huge amount of red mud pro- Element RM ARM PARM
duced world-wide, and the very modest potential consump-
Fe 19.7 25.1 23.6
tion as catalyst, the main advantage would be the saving of Ti 13.0 16.1 14.5
the raw materials needed for the synthesis of conventional Al 7.9 9.0 8.4
catalysts. From the economical point of view, the cost of the Na 3.7 0.1 0.0
studied materials would be very low, taking into account the Ca 5.1 0.9 2.0
almost null price of the metal precursor (red mud), and the Si 4.7 4.9 4.1
P 0.1 0.2 3.9
simplicity of the preparation procedures. Although a detailed
 J.R. Paredes et al. / Applied Catalysis B: Environmental 47 (2004) 37–45
Table 3
Textural parameters of the catalysts used in this work
RM
BET surface area (m2 /g) 28.3
Mesopore volume (cm3 /g) 0.112
Pore average diameter (nm) 12.6
The alternative activation method used in the present work
consists of adding a mixture of aqueous HCl and H3 PO4
to the solution obtained after dissolving the red mud ac-
cording to the method of Pratt and Christoverson. The ratio
between the two acids is adjusted in order to get a 4 wt.%. P
in the calcined catalyst. The resulting precipitate is filtered,
washed, dried and calcined following the method described
previously.
Iron oxide was synthesised by adding ammonium hydrox-
ide solution to an aqueous solution of Fe(NO3 )3 ·9H2 O. The
precipitate was filtered, dried at 100 ◦ C overnight and sub-
jected to the same calcination protocol as the other catalysts.
All chemicals used were of analytical grade, supplied by
Panreac.
The commercial catalyst used for comparison purposes
was BASF-R3-20, with composition 7% CuO, 14% Cr2 O3 ,
79% TiO2 , and textural properties given in Table 3.
2.2. Reaction studies
Combustion experiments were performed in a continu-
ous packed bed reactor. The reactor consisted of a stainless
steel cylinder of 400 mm length and 9 mm internal dia-
meter. Two milligrams of catalyst, crushed and sieved to
250–315 ␮m, were placed in the middle part of the reactor,
whilst the upper and lower parts were filled with glass balls
(1 mm diameter). The reactor was placed inside an electric
furnace, temperature being controlled by a PID controller
(Honeywell) connected to a thermocouple situated inside
the reactor, that monitored the reaction temperature. The
system was provided with five additional thermocouples
that measured the reactor wall temperature at different
positions.
The reactor was fed with 1.6 L/min (s.t.p.) of a mixture of
N-50 synthetic air and 2.5% (vol.) methane in N-50 synthetic
air (Air Liquid). Flow rates were controlled by mass flow
controllers (Brooks 5850 TR). Analysis were performed by
gas chromatography (Hewlett-Packard HP 5890 Series II).
Methane in the inlet and outlet streams was analysed using
a 30 m fused silica capillary column with apolar stationary
phase SE-30, and a FID detector. CO and CO2 were anal-
ysed using a HayeSep N 80/100 and a molecular sieve 45/60
columns connected in series, and a TCD detector. Neither
CO, nor partial oxidation or cracking by-products were de-
tected in any experiment, the carbon mass balance fitting
in all the cases within 2%. Methane conversions were cal-
culated both form outlet methane and CO2 concentrations,
being both values very close in all the cases.
39
ARM PARM Iron oxide Commercial
131.1 111.7 6.6 52.7
0.283 0.326 0.047 0.269
8.4 10.8 16.3 19.1
2.3. Catalyst characterisation
The catalyst pore size distribution and surface area were
measured by nitrogen adsorption at −196 ◦ C with a Micro-
meritics ASAP 2000 surface analyser, considering a value
of 0.164 nm2 for the cross-section of the nitrogen molecule.
Powder X-ray diffraction (XRD) patterns were obtained with
a D-5000 Siemens diffractometer, using nickel-filtered Cu
K␣ as monochromatic X-ray radiation. The patterns were
recorded over a range of 2θ angles from 20 to 70◦ and
crystalline phases were identified using JCPDS files.
Temperature-programmed desorption, reduction and ox-
idation were carried out in a Micromeritics TPD/TPR
2900 apparatus connected to a TCD or a MS detector
(Gaslab-300). Methane-TPD was carried out saturating
the catalyst samples according to the method proposed by
Cordi and Falconer [25]. According to this method, cata-
lyst samples (40 mg) were cleaned in air at 550 ◦ C, cooled
in He to room temperature and saturated with methane at
room temperature by injecting methane pulses (2 min−1
during 0.5 h). After this, the samples were purged with
helium for 30 min, and the TPD experiments were started,
monitoring the peaks of CO2 , CH4 , CH2 O and CH2 O2 .
Temperature-programmed reduction (TPR) was carried out
in a Micromeritics TPD/TPR 2900 apparatus using a TCD
detector. Each sample, equivalent to 40 mg of Fe2 O3 , was
heated from 50 to 950 ◦ C at 10 ◦ C/min in a stream of 10%
H2 /90% Ar with a flow rate of 25 cm3 /min. The same proce-
dure was used for the TPO experiments, but using a stream
of 5% O2 /95% He. Gases used in temperature programmed
experiments were supplied by Carburos Metálicos with a
purity of 99.999%.
3. Results and discussion
3.1. Fresh catalysts characterisation
The composition of the three red mud-based catalysts
(RM, ARM and PARM), are given in Tables 1 and 2. Both
ARM and PARM samples show a similar decrease in Na
content, while the Ca content is higher in PARM than in
ARM.
The results of textural characterisation by nitrogen ad-
sorption are given in Table 3. The specific surface and pore
volume of PARM, although much higher than that of RM,
are slightly lower than that of ARM. Further increase in P
content in PARM resulted in a sharp decrease in surface area.
40 J.R. Paredes et al. / Applied Catalysis B: Environmental 47 (2004) 37–45

100

80
Conversion (%)

60

40

20

0
300 350 400 450 500 550 600 650

(a) Temperature (ºC)

1.4
mol CH4 converted/ min·mol Fe2O3

1.2

0.8

0.6

0.4

0.2

0
300 350 400 450 500 550 600 650

(b) Temperature (ºC)

Fig. 1. XRD patterns for fresh catalysts: RM (A), ARM (B), PARM (C), 2
2

and iron oxide (D). Crystallographic phases: RU, rutile; HE, hematite;
mmol CH4 converted/ min·m

1.75
GO, goethite; LE, lepidocrocite; IH, iron hydroxide; HA, halloysite; BA,
bayerite. 1.5
1.25

The following mineralogical constituents were identified 1

by X-ray diffraction (Fig. 1): rutile, TiO2 ; hematite, Fe2 O3 ; 0.75
goethite and lepidocrocite, both FeO(OH); iron hydrox- 0.5
ide, Fe(OH)3 ; halloysite, Al2 Si2 O5 (OH)4 ; and bayerite, 0.25
Al(OH)3 . The effect of the activation methods on these
0
constituents can be observed in Fig. 1. The PARM (sam-
300 350 400 450 500 550 600 650
ple containing 4% P) and ARM patterns are very similar.
Both activation methods produce the elimination of all (c) Temperature (ºC)
the detected Al-containing (bayerite and halloysite), and Fig. 2. Light-off curves for the combustion of 2000 ppmV methane over
Fe-containing (lepidocrocite and iron hydroxide) crystalline RM (䊐), ARM (+), PARM (䊊), Fe2 O3 (△), and commercial catalyst
forms. goethite decreases in ARM, while it disappears com- (䉫) expressed as: (a) methane conversion vs. temperature; (b) moles
pletely in PARM. PARM also shows a new unidentified of methane converted/min and moles of Fe2 O3 ; (c) moles of methane
converted/min per m2 of surface area.
peak, which probably is associated to a complex phase of
Fe, P and Al. Ramselaar et al. [26] found similar phases
in P-promoted Fe2 O3 /␥-Al3 O3 catalysts, using Mossbauer homogeneous or catalysed by reactor wall reaction took
spectroscopy. Iron oxide synthesised by precipitation pre- place below 750 ◦ C, its contribution being negligible at the
sented a pure hematite structure. conditions of the present work.
Results are shown in Fig. 2 (methane conversion (a);
3.2. Catalysts activity moles of methane converted/min and moles of Fe2 O3 (b);
moles of methane converted/min per m2 of surface area (c)),
Catalysts activity was studied by obtaining light-off whereas values of T50 (temperature at which 50% conver-
curves for the combustion of 2000 ppmV methane in air, sion is attained) are shown in Table 4.
at temperatures from 300 to 650 ◦ C and a heating rate of Data in Fig. 2a indicate that iron oxide shows the best
2 ◦ C/min. Preliminary blank experiments showed that no performance and RM the poorest, on a catalyst weight basis.
 J.R. Paredes et al. / Applied Catalysis B: Environmental 47 (2004) 37–45
Table 4
Values of T50 and T50 (hysteresis experiments) for the combustion of 2000 ppmV methane, and kinetic parameters for the oxidation of methane over
different catalysts
Catalyst T50 (◦ C) T50 (◦ C)
RM >650 18 (T25 )
ARM 530 15
PARM 557 18
Fe2 O3 461 3 0.60
The performance of PARM and specially ARM is substan-
tially better than that of RM. When conversion per Fe content
in the catalyst is considered (Fig. 2b), the difference between
the four Fe-containing catalysts considered is much smaller,
specially for iron oxide, ARM and PARM, and at low con-
versions. This would indicate that the other constituents of
red mud have little or no effect on the catalyst activity, ex-
cept Na and Ca, which can hinder the catalyst activity. This
in a good agreement with the literature [27,28]. So, Ti is
in the form of rutile (highly crystalline form, considered as
catalytically inert) whereas most Al is present in amorphous
phases (peak intensity of Al-containing crystalline phases is
very low in XRD patterns, in spite of the high content of Al
in the red mud-based catalysts) and the Al crystalline phases
detected (gibbsite and goethite) are considered as catalyt-
ically inert. Crystallographic phases containing more than
one of these metals have not been identified. Concerning to
Na and Ca (present in untreated RM), are considered as per-
nicious for the catalyst, promoting sintering. So, the lower
activity of RM could be explained both by the presence of
these elements, related to its low specific area.
According to Fig. 2c, the activity per unit of surface area
is very similar for the three red mud-based catalysts. The
very high values for iron oxide are expected, taking into
account that for this material the entire surface is formed
by hematite, whilst the surface of red mud-derived materials
contains other metal oxides and hydroxides.
Paulis et al. [29] reported that the light-off curves for the
combustion of toluene and oxygenated organic compounds
over bulk and supported manganese oxide catalysts were dif-
ferent depending on the calculation procedure (from VOC
disappearance or from CO2 formation). In our case, conver-
sions attained using both procedures are very similar. This
behaviour of methane suggests a less important role of the
adsorption of the organic compound in the case of methane;
this is in good agreement with the Elay–Rideal mechanisms
proposed for methane combustion over metal oxide catalysts
[11].
In order to check this point, methane-TPD experiments
were carried out for ARM, PARM and iron oxide. RM was
not studied, as it produced unspecific CO2 releases, even
with no methane adsorbed, probably caused by the presence
of carbonates in the catalyst. Methane-TPD experiments for
ARM, PARM and iron oxide produced CO2 release, with a
maximum at 350–500 ◦ C (as observed in Fig. 3), while no
methane release was detected. This suggests that very lit-
41
n Ea (kJ/mol) k0 (mol/(g·h·bar−n )) R2
0.53 104.0 7.6 × 104 0.990
0.3 98.0 2.6 × 104 0.989
0.67 83.6 1.7 × 104 0.983
99.9 130 × 104 0.994
PARM
Signal (a.u.)
ARM
100 300 500 700 900
T (ºC)
Fig. 3. TPD profiles (CO2 release) of fresh ARM and PARM catalysts
previously saturated with methane.
tle methane is adsorbed, the reticular oxygen of the catalyst
being enough for its complete oxidation (intermediate oxi-
dation products were not observed in any case). The impor-
tant role of reticular oxygen was described by Asakara and
Iwasawa [30], who explained the high activity of iron oxide
catalyst for methane oxidation by the combination of coor-
dinatively unsaturated basic O2− sites and acidic Fe3+ sites.
In a second set of experiments, reaction studies were
extended to different methane inlet concentrations (1000,
2000 and 4000 ppmV), keeping constant the total flow rate
(1.6 nl/min) and catalyst weight (2.0 g). The heating rate
was the same than in the previous section. These exper-
iments allow also a preliminary analysis of the reaction
kinetics. Results corresponding to conversions below 15%,
i.e. when thermal and mass transfer effects are negligible,
are represented in Figs. 4–7. As general trend, it is observed
that higher inlet concentrations lead to lower conversions
at a given temperature, and that the order of activity of the
materials is the one found in previous experiments, i.e. on a
catalyst weight basis: iron oxide > ARM > PARM > RM.
The kinetics of the oxidation of hydrocarbons over metal
oxide catalysts has been widely studied in the literature
[9,31,32], and power-law models often have been found to
be adequate for preliminary studies. In our experiments,
the influence of oxygen can be neglected, as it is present
in great excess and its concentration remains practically
constant. Additional experiments showed that, at our ex-
perimental conditions, the influence of water can be also
neglected. Taking into account these considerations, the
42 J.R. Paredes et al. / Applied Catalysis B: Environmental 47 (2004) 37–45

15
Conversion (%)

Conversion (%)

10 10

0 0
300 350 400 450 500 550 600 300 350 400 450 500 550

Temperature (ºC) Temperature (ºC)

Fig. 4. Light-off curves for RM for different methane inlet concentrations: Fig. 6. Light-off curves for PARM for different methane inlet concentra-
2000 ppmV (䊊) and 4000 ppmV (△). Lines correspond to the power-law tions (for symbols, see Fig. 5).
model predictions.

in Figs. 4–7. The values of the parameters obtained are very

following kinetic equation will be used:
−rA = kpnA
where −rA is the rate of disappearance of methane, k the
kinetic constant, and pA is the methane partial pressure.
If the reactor is considered as an integral plug flow reactor,
the integrated kinetic equation is
kpn W(1 − n) 1/1−n


xA = 1 − 1 − A0 (2)
FA0
where xA is the methane conversion, pA0 the inlet methane
partial pressure, n the reaction order for methane, W the
weight of catalyst in the reactor, and FA0 is the methane
molar feed rate. The kinetic constant is assumed to follow
an Arrhenius dependence with temperature.
The parameters obtained by fitting Eq. (2) to the exper-
imental data, together with the correlation coefficients are
listed in Table 4, and the quality of the fitting can be observed
similar to that reported in the literature for the oxidation of
(1) methane over other metal oxide catalysts. So, for a bulk iron
oxide a reaction order for methane close to 0.6, and acti-
vation energies between 80 and 105 kJ/mol were found by
Golodets [31], while Popovskii [33] reported an activation
energy of 120 kJ/mol and a reaction order of 0.6 for methane
oxidation over bulk Fe2 O3 , both in good agreement with
our results (except for ARM, that presents a lower reaction
order).
The presented model, although simple, is accurate enough
in the experimental range considered, and can be useful for
preliminary process design and evaluation, or for compari-
son with other catalysts.
3.3. Catalyst stability
Two different types of experiments were carried out in
order to check the catalytic stability of the solids. In the first

15
Conversion (%)

10
Conversion (%)

10

0
300 350 400 450 500 0
Temperature (ºC) 300 350 400 450
Temperature (ºC)
Fig. 5. Light-off curves for ARM for different methane inlet concen-
trations: 1000 ppmV (䊐), 2000 ppmV (䊊), and 4000 ppmV (△). Lines Fig. 7. Light-off curves for Fe2 O3 for different methane inlet concentra-
correspond to the power-law model predictions. tions (for symbols, see Fig. 5).
 J.R. Paredes et al. / Applied Catalysis B: Environmental 47 (2004) 37–45 43

100 100

80 80
Conversion (%)

Conversion (%)

60 60

40 40

20 20

0 0
300 350 400 450 500 550 600 650 0 5 10 15 20 25

(a) Temperature (ºC) Time (h)

Fig. 9. Methane conversion vs. time on stream for the different iron
100 catalysts at 625 ◦ C (for symbols, see Fig. 2).

80
faster. Due to the promising results obtained for ARM, an
Conversion (%)

60 experiment with a duration of 110 h was carried out for this

catalyst. Results (Fig. 10) indicate that after 110 h on stream,
40 ARM retains 70% of its initial activity at the high tempera-
ture used in this experiment.
20 Concerning the PARM, results indicate that the presence
of P enhances neither the activity nor the stability of red
0
mud for the oxidation of methane, in opposition to the
300 350 400 450 500 550 600 650
well-established promoting effect in hydrogenation reactions
([21] and references cited therein). To the best of our knowl-
(b) Temperature (ºC) edge, there are not published studies on the effect of the
Fig. 8. (a and b) Hysteresis cycles for RM (䊐), ARM (䊊), PARM (䉫), addition of P to metal oxides in oxidation reactions.
and Fe2 O3 (△). Open symbols correspond to increasing temperatures and
filled symbols to decreasing temperatures. 3.4. Characterisation of ARM samples

In order to characterise the process of ARM ageing,

samples were collected after 10 and 110 h time on stream.
type of experiments, methane conversion was measured at
The samples were characterised by nitrogen physisorp-
successively increasing (from 300 to 626 ◦ C) and decreasing
tion (BET), X-ray diffraction and temperature-programmed
(from 626 to 300 ◦ C) temperatures with a slope of 2 ◦ C/min
reduction.
in both cases (hysteresis experiments). In the second type of
experiments methane was fed to the reactor maintained at
constant temperature (625 ◦ C). In both types of experiments,
methane concentration was 2000 ppmV and space velocity 100
(WHSV) was fixed at 48 h−1 (GHSV = 48,000 cm3 /(g h)).
The results of the hysteresis experiments are shown in 80
Fig. 8, and the differences between the temperatures needed
Conversion (%)

to attain 50% conversion in the heating and cooling curves 60

(T50 ) are shown in Table 4. It is observed that pure iron
oxide is slightly more resistant to deactivation than ARM 40
and PARM. T50 was not recorded for RM because of
the low conversion attained with this catalysts; for this ma- 20
terial, T25 is included in Table 4 instead. At the same
reaction conditions, T50 for the commercial catalyst is 0
52 ◦ C [34]. 0 20 40 60 80 100 120
The results obtained in the experiments at constant tem- Time (h)
perature are shown in Fig. 9. ARM and pure hematite present
a similar behaviour, whereas RM and PARM are deactivated Fig. 10. Methane conversion vs. time on stream for ARM at 625 ◦ C.
44 J.R. Paredes et al. / Applied Catalysis B: Environmental 47 (2004) 37–45
Table 5
Textural parameters for ARM catalysts after different times on stream
Time on BET surface Mesopore Pore average
stream (h) area (m2 /g) volume (cm3 /g) diameter (nm)
0 131.1 0.283 8.4
10 121.1 0.270 8.6
110 88.6 0.242 10.6
Nitrogen physisorption data (Table 5) reveal a progres-
sive decrease of pore volume and especially surface area,
while the average pore diameter increases. The catalyst
activity, defined as the ratio between the pseudo-first order
kinetic constant (determined considering integral reactor),
and the value of this constant at 0 h on stream, correlates
well with the catalyst surface area (Fig. 11).
While XRD profiles of fresh and used catalysts reveal that
in both cases the predominant crystalline phase is hematite,
goethite and lepidocrocite were detected in the catalyst after
110 h on stream (Fig. 12). Although there is no information
in the literature about the catalytic activity of these phases,
they can be assumed to be less active than hematite (as
general trend, metal hydroxides and oxy-hydroxides are not
active). Considering that the procedure for XRD analysis
prevents the reaction of the catalysts with ambient mois-
ture, these results lead to think that water produced during
the reaction could react with hematite, producing iron hy-
droxide or oxy-hydroxide. Anyway, this effect seems to be
less important than thermal sintering, as confirmed by fur-
ther ageing experiments carried out at 650 ◦ C with different
amounts of water in the feed (up to 8000 ppmV), which
showed no additional catalyst deactivation.
TPR profiles for ARM, fresh and after 110 h on stream,
are shown in Fig. 13. Two different phenomena were
Fig. 12. XRD profile of ARM after 110 h on stream (for identification of crystalline phases, see Fig. 1).
Fig. 11. Catalytic activity vs. relative surface area for aged ARM samples.
Parameters referred to 0 h on stream.
observed for the aged sample: the displacement of the peaks
to higher temperatures, and the overlapping of the three
characteristic peaks. The displacement of the peaks can be
caused by a decrease in the exposed surface of Fe, produced
by the decrease in surface area. The presence of Fe phases
other than hematite could also hinder the reduction and com-
plicate the profiles (each phase experiments the reduction
through different mechanisms, with different characteristic
peaks).
Some authors state that the partial reduction of the active
phase is an important deactivation cause in iron oxide-based
catalysts [35]. In order to check this possibility, TPO ex-
periments were carried out with fresh and aged ARM
samples, no oxygen uptake being recorded. This leads
to think that ARM is not appreciably reduced during the
reaction.
These results suggest that ARM deactivation is caused
mainly by sintering, and in minor extension, by the transfor-
mation of hematite into less active phases. The same conclu-
sions were drawn by Barbosa and co-workers working with
pure hematite synthesised by different procedures [35].
 J.R. Paredes et al. / Applied Catalysis B: Environmental 47 (2004) 37–45 45

[2] J.H. Lee, D.L. Trimm, Fuel Proc. Tehnol. 42 (1995) 339.
[3] R.A. Dalla Betta, Catal. Today 35 (1997) 129.
[4] K. Foger, H. Jaeger, J. Catal. 120 (1989) 465.
[5] J.K. Lampert, M.S. Kazi, R.J. Ferrauto, Appl. Catal. B 14 (1997)
211.
[6] L.J. Hoyos, H. Praliaud, M. Primet, Appl. Catal. A 98 (1993) 125.
[7] T.C. Yu, H. Shaw, Appl. Catal. B 18 (1998) 105.
[8] R. Burch, F.J. Urbano, Appl. Catal. B 18 (1998) 121.
[9] M.F.M. Zwinkels, S.G. Järas, P.G. Menon, Catal. Rev.-Sci. Eng. 35
(1993) 319.
[10] S. Ponce, M. A Peña, J.L.G. Fierro, Appl. Catal. B 24 (2000) 193.
[11] G. Saracco, G. Scilibia, A. Ianibello, G. Baldi, Appl. Catal. B 8
(1996) 229.
[12] G. Groppi, C. Cristiani, P. Forzatti, Appl. Catal. B 35 (2001) 137.
[13] J.G. McCarty, M. Gussman, D. Lowe, D.L. Hindelbrand, K.N. Lau,
Catal. Today 47 (1999) 5.
[14] T. Kobayashi, N. Guilleaume, J. Miki, N. Kitamura, M. Haruta,
Catal. Today 32 (1996) 171.
[15] V. Sazonov, Z.R. Ismagilov, N.A. Prokudina, Catal. Today 47 (1999)
Fig. 13. TPR profiles for ARM fresh (A) and after 110 h on stream (B). 149.
[16] A.L. Barbosa, J. Herguido, J. Santamarı́a, Catal. Today 64 (2001) 43.
[17] O.E. Lebedeva, A.G. Samurzina, Appl. Catal. B 26 (2000) L1.
4. Conclusions [18] S. Ordóñez, H. Sastre, F.V. Dı́ez, J. Hazard. Mater. 81 (2001) 103.
[19] U.S.E.P.A., EPA Office of Compliance Sector Notebook Project:
Red mud-derived materials are active as catalyst for the Profile of the Non-Ferrous Metals Industry, US Government Printing
total combustion of methane, due to their hematite content. Office, Washington, DC, 1995.
Among them, red mud activated by the method of Pratt and [20] K.C. Pratt, V. Christoverson, Fuel 61 (1982) 460.
[21] J. Alvarez, S. Ordóñez, R. Rosal, H. Sastre, F.V. Dı́ez, Appl. Catal.
Christoverson showed the best performance (activity and A 180 (1999) 399.
resistance to deactivation), similar to that of pure hematite [22] S. Ordóñez, H. Sastre, F.V. Dı́ez, Appl. Catal. B 29 (2001) 263.
on a Fe content basis, and superior to a Cu-Cr-Ti commercial [23] S. Ordóñez, Ph.D. Thesis, University of Oviedo, Oviedo, 1999.
catalyst. The main cause of ARM deactivation is the loss [24] C.N. Satterfield, Heterogeneous Catalysis in Industrial Practice,
of surface area. The addition of P to this material improved McGraw-Hill, New York, 1980.
[25] E.M. Cordi, J.L. Falconer, J. Catal. 162 (1996) 104.
neither its activity nor its resistance to deactivation. [26] W.L.T.M. Ramselaar, V.H.J. de Beer, A.M. van der Kraan, Appl.
ARM, is then a very promising material for the catalytic Catal. 42 (1988) 153.
combustion of VOC, taking into account the very low cost [27] A.B. Stiles, Catalysts Supports and Supported Catalysts: Theoretical
of the raw material and the simplicity of the preparation and Applied Concepts, University of Delaware, Newark, DE, 1987.
method, when compared, not only with bulk hematite, but [28] M. Boudart, in: G. Ertl, H. Knozinger, J. Weitkamp (Eds.), Handbook
of Heterogeneous Catalysis, VCH, Weinheim, 1997.
also with some mixed oxides commercial catalysts, or newly [29] M. Paulis, L.M. Gandı́a, A. Gil, J. Sambeth, J.A. Odriozola, M.
developed catalysts such as perovskites, that present similar Montes, Appl. Catal. B 26 (2000) 37.
or worse performance, besides requiring costly raw materials [30] K. Asakura, Y. Iwasawa, Mater. Chem. Phys. 18 (1988) 489.
and preparation procedures (i.e. see [36]). [31] G.I. Golodets, Heterogeneous Catalytic Reactions Involving Mole-
cular Oxygen, Elsevier, Amsterdam, 1983.
[32] J.J. Spivey, Ind. Eng. Chem. Res. 26 (1987) 2165.
[33] V.V. Popovskii, Kinetica i Kataliz 13 (1972) 1190.
Acknowledgements [34] J.R. Paredes, S. Ordóñez, F.V. Dı́ez, H. Sastre, in: Proceedings of
the 8th World Congress on Catalytic Oxidation, Berlin, 2001.
This work has been supported by a grant from the Euro- [35] A. Sanz, A.L. Barbosa, A. Monzón, J. Herguido, J. Santamarı́a,
pean Community (Contract ENV4-CT97-0599). in: Proceedings of the 9th International Symposium on Catalyst
Deactivation, Lexington, 2001.
[36] R. Auer, M. Alifanti, B. Delmon, F.C. Thyrion, Appl. Catal. B 39
(2002) 311.
References

[1] E.C. Moretti, N. Mukhopadhyay, Chem. Eng. Prog. 7 (1993) 20.