Chemical Engineering Science 59 (2004) 4113 – 4123

www.elsevier.com/locate/ces

A transient response study of the selective catalytic oxidation of

ammonia to nitrogen on Pt/CuO/Al2 O3
Göran Olofssona,∗ , Andreas Hinzb , Arne Anderssona
a Department of Chemical Engineering, Lund University, Chemical Center, P.O. Box 124, SE-221 00 Lund, Sweden
b Volvo Technological Development AB, SE-405 08 Gothenburg, Sweden

Received 1 December 2003; received in revised form 4 March 2004; accepted 30 March 2004
Available online 11 August 2004

Abstract
The reaction mechanism for the selective catalytic oxidation of ammonia to give nitrogen on CuO/Al2 O3 , Pt/Al2 O3 and Pt/CuO/Al2 O3
was investigated using transient experiments. Temperature-programmed desorption and reaction of adsorbed ammonia indicated the
formation of NHx species at the surface, and that this species is the precursor for the formation of nitrogen and nitrogen oxides.
Pt/CuO/Al2 O3 is the most active sample for nitrogen formation. In experiments pulsing alternately ammonia and oxygen it is observed
that nitrogen is predominantly formed at the oxygen pulse on Pt/CuO/Al2 O3 and at the ammonia pulse on Pt/Al2 O3 and CuO/Al2 O3 .
Results obtained in the alternate pulsing of ammonia and NO over preoxidised samples exclude NO from being a reaction intermediate
for nitrogen formation. The performance of Pt/Al2 O3 and CuO/Al2 O3 in NH3 –NO2 alternate pulsing reveals that nitrogen formation on
these two samples occurs by formed NO2 reacts with an NHx species. Over Pt/CuO/Al2 O3 , on the other hand, most nitrogen is formed
by the direct oxidation and combination of two NHx species using adsorbed oxygen. The data obtained suggests that the reaction takes
place at the Pt/CuO phase boundary between NHx species being adsorbed on CuO and oxygen on Pt sites.
䉷 2004 Elsevier Ltd. All rights reserved.

Keywords: Ammonia oxidation; Pt/CuO/Al2 O3 ; Selectivity; Environment; Packed bed; Transient response

1. Introduction by-product. Another application for SCO of ammonia con-

The abatement of ammonia from industrial waste streams
and agricultural sources is becoming increasingly important
due to environmental concerns. Depending on the specific
conditions various techniques can be used for the removal of
ammonia, e.g. absorption, adsorption, thermal incineration,
chemical treatment and catalytic conversion. For the clean-
ing of large gas flows containing oxygen and low concentra-
tion of ammonia, the selective catalytic oxidation (SCO) of
ammonia to form nitrogen and water is especially attractive
(Sazonova et al., 1996; Li and Armor, 1997). The applica-
tion area includes the treatment of waste gases from chem-
ical production processes where ammonia is a reactant or a
∗ Corresponding author.
E-mail address: goran.olofsson@chemeng.lth.se (G. Olofsson).
0009-2509/$ - see front matter 䉷 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2004.03.047
cerns selective catalytic reduction (SCR) facilities, where
ammonia is fed to react with NOx to give nitrogen. In this
case, however, the degree of NOx conversion is limited
due the fact that a slip of ammonia has to be avoided.
Therefore, a NH3 /NOx molar ratio of about 0.9 is usually
not exceeded. Combining the SCR and SCO techniques
would increase the NOx removal efficiency and eliminate
the risk of ammonia slip (Li and Armor, 1997; Long and
Yang, 2001; Gang et al., 2002). Moreover, the SCO tech-
nique can be attractive for the production of nitrogen in
a small scale. In the energy sector, the use of renewable
energy sources such as biomass is of interest since it gives
no net emission of CO2 . However, a problem with the use
of biomass for the combined heat and power production
is the content of fuel-bound nitrogen, which in combus-
tion/gasification forms ammonia. The use of a catalyst for
conversion of the ammonia to nitrogen would thus prevent
the ammonia from being converted to NOx in the subsequent
4114 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123
combustion of the biogas in the gas turbine (Amblard et al.,
1999; Burch and Southward, 2000).
In the first step in nitric acid production, Pt is used
as a catalyst to oxidise ammonia at high temperature to
give NO (Satterfield, 1991). At temperatures below 600 ◦ C
nitrogen is the main product; however, the simultaneous
formation of N2 O is a problem. Compared with Pt, alumina
and ZSM-5 supported Pd gives better performance with
selectivity to nitrogen of about 90% at 100% ammonia con-
version (Li and Armor, 1997). Many other catalyst systems
have been reported to be active for the SCO reaction of
ammonia, e.g. MoO3 /SiO2 promoted with Pb (Biermann
et al., 1990; Lietti et al., 2000), V2 O5 /TiO2 (Sazonova et al.,
1996; Li and Armor, 1997), CuO/TiO2 (Sazonova et al.,
1996; Gang et al., 1999; Curtin et al., 1998), NiO/Al2 O3
(Amblard et al., 1999), Fe2O3 /TiO2 (Long and Yang,
2002), Pd–V2 O5 –WO3 /TiO2 –SiO2 (Ueshima et al., 1998),
Cu/ZSM-5 (Sazonova et al., 1996; Long and Yang, 2000),
Cu/Y-zeolite (Gang et al., 1999) and Fe/ZSM-5 (Long and
Yang, 2000, 2001). A problem encountered with these sys-
tems is that a temperature above 375–400 ◦ C is required
for obtaining complete conversion of ammonia and the se-
lectivity to nitrogen usually decreases with increase of the
temperature. Recently, it has been shown that the combina-
tion of supported CuO with a high activity component gives
a synergy effect. The Pt/CuO/Al2 O3 (Burch and Southward,
2000) andAg/CuO/Al2 O3 (Gang et al., 2002) systems were
reported to be active for ammonia oxidation to nitrogen at
temperatures below 300 ◦ C. About the reaction mechanism
it was proposed that the nitrogen is formed via internal SCR
(iSCR) between NHx species adsorbed on CuO and NO
formed on Pt and Ag. However, details about the reaction
mechanism are still missing and the investigation reported
here concerns transient reaction studies of the SCO of am-
monia on Pt/CuO/Al2 O3 using a TAP-2 multifunctional
reactor system (Gleaves et al., 1997).
2. Experimental
2.1. Catalyst preparation
Three different catalysts were prepared, namely CuO/
Al2 O3 , Pt/Al2 O3 and Pt/CuO/Al2 O3 with the contents of
CuO and Pt being 20 and 1 wt%, respectively. The first two
samples were synthesised by incipient wetness impregna-
tion of Al2 O3 (Condea, 120 m2 /g) with a water solution of
Cu(NO3 )2 · 3H2 O (Merck, p.a.) and Pt(II) nitrate solution
(Heraeus, 15.46 wt% Pt), respectively, containing the appro-
priate amount of the metal. After impregnation, the samples
were dried first at ambient conditions for 5 h and then at
120 ◦ C for 24 h. A subsequent calcination of the samples was
performed step-wise in air. First, the temperature was in-
creased by 10 ◦ C/min up to 300 ◦ C, where it was held for 1 h.
In this step most of the nitrate decomposed to form nitrogen
oxides. Then, the temperature was increased by 10 ◦ C/min
up to 450 ◦ C and 500 ◦ C, respectively, for Pt/Al2 O3 and
CuO/Al2 O3 . For preparation of the Pt/CuO/Al2 O3 sample,
the as prepared CuO/Al2 O3 sample was impregnated with
the appropriate amount of Pt(NO3 )2 solution in water. The
drying and calcinations steps were then repeated following
the procedure being used for the Pt/Al2 O3 sample.
All three catalyst products were ground and sieved. The
fraction of particles with diameters in the 250–425
m
ranges was collected and used in the experiments. A Mi-
cromeritics ASAP 2400 instrument was used to determine
the specific surface areas of the catalysts, which were 96
m2 /g for CuO/Al2 O3 , 120 m2 /g for Pt/Al2 O3 and 94 m2 /g
for Pt/CuO/Al2 O3 to be compared with 119 m2 /g for the
Al2 O3 support.
2.2. Transient response experiments
The transient experiments were performed using a TAP-2
reactor system, consisting of a manifold with a microreac-
tor connected to four high-speed pulse valves, a heated slide
valve assembly, a vacuum system, a mass spectrometer (UTI
100C), a gas blending station and computer based data ac-
quisition and control (Gleaves et al., 1997). All experiments
were performed loading about 50 mg of catalyst in between
inert layers of quartz sand of the same particle size. Before
starting an experiment the catalyst was always subjected to
a standard pre-treatment, which comprised heating the sam-
ple for 10 min at 350 ◦ C with pure O2 flowing through the
reactor (40 Nml/min). This treatment was followed by cool-
ing to the desired temperature and evacuation of the reactor.
For temperature-programmed desorption (TPD) experi-
ments, after the standard pre-treatment in oxygen, the sam-
ple was cooled down to 50 ◦ C and evacuated. Then, a flow
with either 20 vol% NH3 in Ar (58 Nml/min), or 1.5 vol%
NO in He (47 Nml/min) was passed through the sample for
30 and 60 min, respectively. After evacuation of the reactor,
the temperature was increased linearly by 10 ◦ C/min from
50 ◦ C up to 350 ◦ C. Simultaneously, desorption of the unre-
acted species and the products were registered.
A pump-probe experiment comprises the alternate puls-
ing at high repetition rate of two pulse valves, each being
connected to a gas tank. In the present study pump-probe ex-
periments were performed pulsing alternately (i) 33% NH3
in Ar and 93% O2 in Ar, (ii) 1.5% NH3 in He and 1.5%
NO in He, and (iii) 1.5% NH3 in He and a mixture of
1.5% NO and 1.5% O2 in He. In the experiments the pump-
probe interval was 0.25 s and the time between two identical
pulses (total cycle time) was 1.0 s. The pressure in the gas
tanks was 2.0 bars, and due to the small pulse size (∼ 1013
molecules/pulse) it remained almost unchanged during a set
of experiments. Before running an experiment the valves
were pulsed for sufficient time to ensure that the pulse size
did not vary more than ± 5%. The responses from reac-
tants and products were followed on the mass spectrometer,
and 50 pulses were averaged for each selected amu (m/e).
Additionally, an experiment was performed using one valve
 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123 4115

only to pulse repeatedly a mixture of 10% NH3 and 20%
O2 in Ar.
For the analysis of reactants and products with the mass
spectrometer, the following mass to charge (m/e) ratios were
followed: 2 (H2 ), 4 (He), 17 (NH3 , H2 O), 18 (H2 O), 28 (N2 ,
N2 O), 30 (NO, NO2 , N2 O), 32 (O2 ), 33 (NH2 OH), 40 (Ar),
44 (N2 O) and 46 (NO2 ).
3. Results and discussion
3.1. TPD of adsorbed ammonia
Fig. 1 displays the TPD profiles of ammonia and products
as obtained after the adsorption of ammonia at 50 ◦ C. Fig. 1a
shows that desorption of ammonia occurs over all catalysts

Fig. 1. Desorption profiles of ammonia and products formed during TPD after adsorption of ammonia at 50 ◦ C on preoxidised CuO/Al2 O3 , Pt/Al2 O3
and Pt/CuO/Al2 O3 catalysts.
4116 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123

up to 250–350 ◦ C with a maximum around 80–90 ◦ C. This

feature shows that ammonia is comparatively strongly ad-
sorbed at 50 ◦ C. The desorption profiles of hydrogen in
Fig. 1b present likewise ammonia a maximum around
80–90 ◦ C, indicating that in parallel to desorption of the am-
monia some of it is further activated forming NHx species at
the surface. Moreover, some hydrogen reacts with adsorbed
oxygen to form water as was evidenced by the resemblance
of the hydrogen and water profiles.
Figs. 1c–f show that the chemisorbed NHx species reacts
with oxygen on the catalyst surfaces to produce nitrogen and
nitrogen oxides. The nitrogen profiles in Fig. 1c reveal clear
differences between the three catalysts. On Pt/CuO/Al2 O3
the nitrogen profile has a maximum at 225 ◦ C while
CuO/Al2 O3 gives a maximum at 260 ◦ C. On the other hand,
Pt/Al2 O3 gives a maximum at 290 ◦ C with a well-developed
shoulder at 225 ◦ C. Concerning NO, Fig. 1d shows that on
CuO/Al2 O3 it desorbs in the form of two peaks at 260 ◦ C
and 310 ◦ C, respectively. On the contrary, there is almost no
desorption of NO from Pt/CuO/Al2 O3 , and from Pt/Al2 O3
NO desorbs above 300 ◦ C. The formation and desorption
of NO2 takes place below 200 ◦ C on Pt/CuO/Al2 O3 and
Pt/Al2 O3 (Fig. 1e) while from CuO/Al2 O3 there is almost
no desorption of NO2 . The almost concurrent desorption of
ammonia, hydrogen and NO2 on the two Pt-catalysts infers
that some of the formed NHx species quickly react with
oxygen species being held to Pt. On the CuO surface there
is predominantly O2− lattice species (Larsson et al., 1996),
which obviously requires a temperature above 200 ◦ C for
being active (Figs. 1c–f). The desorption profiles in Fig. 1f
show at low temperature that desorption of N2 O only occurs
from Pt/CuO/Al2 O3 , which besides a predominant peak at
80–90 ◦ C shows a smaller peak at 260 ◦ C. Remarkably, N2 O
is not formed on CuO/Al2 O3 and on Pt/Al2 O3 it appears
only above 280 ◦ C. For Pt/CuO/Al2 O3 the low temperature
peak at 80–90 ◦ C can be explained by the presence of reac-
tive oxygen species, not present on the other two catalysts,
and an appropriate distance between the NHx species, being
caused by either a high concentration or structural features.
Considering the above results and comparing the three
catalysts, it can be concluded that Pt/CuO/Al2 O3 is the most
active catalyst at 200–250 ◦ C for nitrogen formation and
also gives the least amount of NOx . Moreover, CuO/Al2 O3
and Pt/Al2 O3 , compared with Pt/CuO/Al2 O3 , present higher
activation energy for nitrogen formation.
Fig. 2. Oxidation of NH3 over Pt/CuO/Al2 O3 at 200 ◦ C.
Height-normalised response curves recorded in a pump-probe experiment
3.2. Pump-probe experiments with alternate pulses of pulsing alternately 93% O2 in Ar and 33% NH3 in Ar, respectively. The
oxygen and ammonia pump-probe interval is 0.25 s and each response curve is the average of
50 pulses.

Pump-probe experiments pulsing alternately oxygen and

ammonia were performed and the results are presented in
Figs. 2–4 for Pt/CuO/Al2 O3 , CuO/Al2 O3 and Pt/Al2 O3 ,
respectively. In all cases it is notable that water is formed
at the ammonia pulse and so is predominantly hydrogen.
This result is in agreement with the TPD data and confirms
that the ammonia adsorbs as an NHx species at the cata-
lyst surface. Both after oxygen and ammonia pulsing, the
ammonia response peak does go to zero but rather seems
to increase again. This observation might be caused by
 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123 4117

Fig. 3. Oxidation of NH3 over CuO/Al2 O3 at 200 ◦ C. Height-normalised Fig. 4. Oxidation of NH3 over Pt/Al2 O3 at 200 ◦ C. Height-normalised
response curves recorded in a pump-probe experiment pulsing alternately response curves recorded in a pump-probe experiment pulsing alternately
93% O2 in Ar and 33% NH3 in Ar, respectively. The pump-probe interval 93% O2 in Ar and 33% NH3 in Ar, respectively. The pump-probe interval
is 0.25 s and each response curve is the average of 50 pulses. is 0.25 s and each response curve is the average of 50 pulses.

interaction of the desorbing ammonia with the Al2 O3 sup- and broad nitrogen peak appears at the oxygen pulse and
port (Sobczyk et al., 2003). Of the reaction products, the there is a relatively smaller and narrower peak at the ammo-
nitrogen formation shows remarkable differences between nia pulse. Over CuO/Al2 O3 (see Fig. 3) nitrogen is mainly
the catalysts. Fig. 2 shows that for Pt/CuO/Al2 O3 a large formed at the ammonia pulse and the response is sharp. The
4118 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123

nitrogen response for Pt/Al2 O3 (Fig. 4) shows a large and Table 1

extended peak at the ammonia pulse, and almost no nitrogen The surface residence time (
surf ) and the reaction time (
react ) for
reactants and the major products, respectively
is formed and at the oxygen pulse. For both Pt/CuO/Al2 O3
and CuO/Al2 O3 the N2 O response is similar to that of nitro- Catalyst Response Oxygen pulse Ammonia pulse
gen although somewhat broader. Pt/Al2 O3 , however, shows
surf ,
react (s)
surf ,
react (s)
larger differences between the nitrogen and N2 O responses. Pt/CuO/Al2 O3 Ar 0.00 0.00
Here N2 O is formed at both pulses. At the oxygen pulse the O2 −0.12a
N2 O response is very broad and at the ammonia pulse it NH3 5.64
shows up as a distinct peak. Concerning the formations of H2 14.04
H2 O 7.56
NO and NO2 , the responses in Figs. 2–4 shows for all cata-
N2 3.18 9.18
lysts that NO exclusively appears at the oxygen pulse while NO 0.54
NO2 is mainly formed at the ammonia pulse. It is notewor- NO2 7.32
thy that besides these products a response was observed at N2 O 3.72 7.26
33 amu (Figs. 2–4), which possibly is from hydroxylamine NH2 OH 0.54 8.94
NH2 OH (Hinz and Andersson, 1999). This signal shows
CuO/Al2 O3 Ar 0.00 0.00
up at both the oxygen and the ammonia pulses and is the O2 −0.18a
largest at the latter pulse. The formation of hydroxylamine NH3 5.82
is reasonably due to the reaction between an -NH2 and an H2 14.28
-OH surface species. H2 O 7.32
N2 9.06
From the pump-probe responses the average surface res-
NO 0.54
idence time (
surf ) and the average reaction time (
react ) for NO2 7.26
reactants and products, respectively, can be calculated from N2 O 7.98
the relationship
surf,react =
−
diff , where
is the measured NH2 OH 8.64
residence time in the reactor and
diff is the diffusion time
Pt/Al2 O3 Ar 0.00 0.00
through the reactor (Hinz et al., 2001). The measured resi-
O2 −0.12a
dence time
can be calculated from the zero m0 and first NH3 5.46
m1 moments of the response curve according to
= m1 /m0 H2 14.52
(Gleaves et al., 1988). Concerning the diffusion time
diff , H2 O 8.22
it can be calculated from the residence time measured for N2 9.24
NO 0.54
the inert argon (
Ar ) in the pulse. Considering that the TAP
NO2 7.80
experiments are performed in the Knudsen diffusion region N2 O 3.66 7.56
the relationship
diff =
Ar (M/MAr )1/2 is valid for reactants, NH2 OH 0.72 9.00
where M and MAr are the molecular weight for the species a The negative value for O is a consequence of its lower mass compared
2
in question and argon, respectively. In the case of a prod- to Ar, which peak time is set to zero (see Section 3.2).
uct, it can be assumed that it is formed in the middle of
the catalyst bed and therefore
diff = 1/2
Ar (M/MAr )1/2 .
The
react and
surf values calculated for the responses in responses in Fig. 5a are very similar for all three cata-
Figs. 2–4 are given in Table 1. lysts. In Fig. 5b the oxygen response for Pt/CuO/Al2 O3 is
Burch and Southward (2000) have proposed that on compared with the response being simulated for an inert
Pt/CuO/Al2 O3 nitrogen is formed in a reaction between component with the mass of oxygen diffusing through the
NHx species and NOx . In this regard it is of interest to note bed. It is seen that the experimental curve does not intersect
that the pump-probe results in Table 1 and Fig. 2 reveal the curve for diffusion only. Gleaves and coworkers (1997)
that on Pt/CuO/Al2 O3 both nitrogen and NO are released have demonstrated that such behaviour is indicative of ir-
at the oxygen pulse and in time the NO peak appears be- reversible adsorption and reaction, in this case of oxygen.
fore that of nitrogen. This fact might be an indication of Fig. 5c shows a similar ammonia response for all three
NO together with NHx being the intermediate species for catalysts. However, the responses for Pt/Al2 O3 and
nitrogen formation on this catalyst. On the other hand, the Pt/CuO/Al2 O3 are wider than that for CuO/Al2 O3 , indicat-
data in Table 1 and the responses in Figs. 3 and 4 show that ing less amount of ammonia being adsorbed on the latter
over CuO/Al2 O3 and Pt/Al2 O3 nitrogen is produced at the sample. According to Fig. 5d the nitrogen response for
ammonia pulse and so is NO2 . Moreover, in both cases the Pt/CuO/Al2 O3 is very similar to that for CuO/Al2 O3 while
residence time is shorter for NO2 than for nitrogen, which the nitrogen response for Pt/Al2 O3 is broader and delayed
could imply that on these catalysts NO2 is the intermediate in time, indicating a longer reaction time at the surface.
NOx species being involved in the formation of nitrogen. The same tendency is shown by the hydrogen profiles in
Fig. 5 shows the height-normalised response curves ob- Fig. 5e, suggesting that the formation of NHx species on
tained as a result of pulsing a mixture of ammonia and Pt/CuO/Al2 O3 involves Cu-sites rather than Pt-sites. How-
oxygen in argon using one pulse valve only. The oxygen ever, both sites work in symbiosis as evidenced by the TPD
 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123 4119

Fig. 5. Oxidation of NH3 at 200 ◦ C over CuO/Al2 O3 , Pt/Al2 O3 and Pt/CuO/Al2 O3 catalysts. Height-normalised response curves recorded in multipulse
mode pulsing a mixture of 10% NH3 and 20% O2 in Ar. Each response curve is the average of 50 pulses.

profiles of nitrogen formation in Fig. 1. Concerning the NO2
responses in Fig. 5f there is an almost perfect overlap of the
profiles of the three catalysts, showing that the reaction time
for NO2 formation is small compared to the diffusion time.
The nitrogen responses, which are compared in Fig. 5d
after height-normalisation, are shown in Fig. 6 after normal-
isation with respect to the argon peak. Comparing the sizes
of the nitrogen profiles of the three samples, it is clearly
seen that Pt/CuO/Al2 O3 is the most active sample for nitro-
gen formation. This result is in perfect agreement with the
tendency shown by the TPD curves for nitrogen formation
in Fig. 1.
4120 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123

Fig. 6. Nitrogen response curves recorded in multipulse experiments at Fig. 7. TPD of NO after adsorption of NO at 50 ◦ C on preoxidised
200 ◦ C pulsing of a mixture of 10% NH3 and 20% O2 in Ar over CuO/Al2 O3 , Pt/Al2 O3 and Pt/CuO/Al2 O3 catalysts.
CuO/Al2 O3 , Pt/Al2 O3 and Pt/CuO/Al2 O3 . The response curves are the
average of 50 pulses and have been normalised with respect to the Ar
peak area.

3.3. TPD and pump-probe experiments with NO

To study the adsorption of NO on the catalysts, these were

treated with flowing NO (1.5% NO in He) for 1 h at 50 ◦ C.
After evacuation, the temperature was increased linearly up
to 350 ◦ C while recording a selection of mass signals. The
TPD profiles of NO (m/e = 30) are displayed in Fig. 7.
In all cases the intensity of the signal is low, showing that
only a small amount of NO is adsorbed since no product
formation was observed. The Pt/Al2 O3 and Pt/CuO/Al2 O3
samples both show desorption of NO above 250 ◦ C with a
maximum around 325 ◦ C. CuO/Al2 O3 , on the other hand,
besides desorption above 250 ◦ C shows a distinct desorption
peak at 125 ◦ C, which also is noticeable in the profile for
Pt/CuO/Al2 O3 .
According to the pump-probe experiments with oxygen
and ammonia (Fig. 2 and Table 1) there is the possibility that
on Pt/CuO/Al2 O3 nitrogen is formed in a reaction between
an NHx species and NO. This possibility is not in conflict
with the TPD profile of NO in Fig. 7, although the amount
of NO adsorption being small. To gain more insight into this
matter pump-probe experiments were performed at 200 ◦ C Fig. 8. Height-normalised response curves recorded in a pump-probe
pulsing alternate pulses with NO and ammonia, respec- experiment at 200 ◦ C pulsing alternately 1.5% NO in He and 1.5% NH3
in He, respectively, over preoxidised Pt/CuO/Al2 O3 . The pump-probe
tively. The response profiles recorded, which are presented in
interval is 0.25 s and each response curve is the average of 50 pulses.
Fig. 8, show complex behaviour. Peaks from both NO and
ammonia appear at both pulses, indicating competitive ad-
sorption of NO and ammonia probably via the nitrogen atom. and a surface oxygen species. Some of the formed NO2 is re-
Moreover, identical products are formed at both pulses. NO2 tained at the surface and desorbs at the ammonia pulse. Con-
is possibly formed due to a reaction between adsorbed NO cerning hydroxylamine it seems that this product can form
 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123 4121

from both ammonia and NO, while N2 O possibly is formed

in a reaction between an NHx species and NO or NO2 . The
fact that hydrogen and water are formed at both pulses is
consistent with the latter reaction. However, it is obvious
that other types of experiments are needed to explain the
product pattern in more detail. Focusing on the SCO mech-
anism, the 28 amu responses in Fig. 8 is at the noise level
and thus reveals that there is no nitrogen formation puls-
ing NO and ammonia. This observation thus excludes that
nitrogen is formed on Pt/CuO/Al2 O3 in a reaction between
adsorbed NO and NHx species. Thus, for this catalyst, it
seems most probable that nitrogen is formed in direct am-
monia oxidation involving two NHx species. This possibil-
ity is not in conflict with the results in Fig. 2, showing ex-
tensive nitrogen formation at the oxygen pulse. Concerning
nitrogen formation on CuO/Al2 O3 and Pt/Al2 O3 , the results
in Figs. 3 and 4,respectively, show for these samples a dif-
ferent mechanism, most likely involving reaction between
an NHx species and NO2 (Table 1). Nitrogen formation by
NHx reacting with NO is unlikely since also in this case no
nitrogen was observed to form pulsing alternately ammonia
and NO. Fig. 9. The composition of a mixture of 1.5% NO and 1.5% O2 in He as
a function of the temperature under the condition that no N2 is formed.

3.4. Pump-probe experiments with alternate pulses of

ammonia and NO2

The importance of the reaction between NHx species and

NO2 for nitrogen formation was investigated in pump-probe
experiments at 200 ◦ C. In this case alternate pulsing was
performed from tanks with 1.5% ammonia in He and a mix-
ture of 1.5% NO and 1.5% O2 in He, respectively. The
composition at 50 ◦ C in the latter tank corresponds to 1.5%
NO2 (NO2 + N2 O4) and 0.7% O2 as shown by the plot in
Fig. 9 of the composition calculated using HSC Chemistry
software. Formation of nitrogen was not included in the cal-
culation as it is well known from nitric acid production that
O2 and NO react at atmospheric pressure and low temper-
ature to give NO2 and N2 O4 without N2 being formed. In
order to achieve the calculated composition, the gas mix-
ture was stored in the tank for at least an hour before being
pulsed. Any possible shift of the pulse composition due to
the temperature and the pressure in the reactor will not dis-
turb the results since no nitrogen was produced in NO–NH3
pulsing. The nitrogen responses obtained for the three cata-
lysts are shown in Fig. 10. In all cases NHx surface species
are formed at the ammonia pulse as was concluded from the
TPD results in Fig. 1.
Concerning the CuO/Al2 O3 and Pt/Al2 O3 samples, the
responses in Fig. 10 show that most nitrogen is formed at
the NO2 –O2 pulse. In the pump-probe experiments with al- Fig. 10. Height-normalised response curves recorded in pump-probe ex-
periments at 200 ◦ C pulsing alternately 1.5% NH3 in He and an equi-
ternate ammonia and oxygen pulsing (Figs. 3 and 4), the
librated mixture of 1.5% NO and 1.5% O2 in He, respectively, over
formation of nitrogen predominantly does not occur at the preoxidised CuO/Al2 O3 , Pt/Al2 O3 and Pt/CuO/Al2 O3 . The pump-probe
oxygen pulse but at the ammonia pulse where also NO2 interval is 0.25 s and each response curve is the average of 50 pulses.
is being formed. Consequently, the results in Fig. 10 for The composition of the equilibrated mixture (see Fig. 9) corresponds to
these two samples agree with most nitrogen is formed by approximately 1.5% NO2 and 0.75% O2 .
4122 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123
NO2 reacting with adsorbed NHx species. The appearance
of a minor nitrogen peak at the ammonia pulse suggests that
there may be a secondary route for nitrogen formation, in-
volving the preadsorbed oxygen species (see Experimental)
and NHx species. Some support for the secondary route on
CuO/Al2 O3 and Pt/Al2 O3 is found in Figs. 3 and 4, respec-
tively, showing especially for CuO/Al2 O3 that some nitrogen
is formed at the oxygen pulse in alternate oxygen/ammonia
pulsing.
For Pt/CuO/Al2 O3 the nitrogen profile in Fig. 10 shows
that nitrogen is formed at both the ammonia pulse and the
NO2 –O2 pulse. This result is consistent with the inference
(see Section 3.3) that on this catalyst the direct oxidation of
ammonia via adsorbed oxygen and NHx species is a major
route for nitrogen formation. However, in agreement with
the nitrogen and NO2 responses to the ammonia pulse in
Fig. 2, some nitrogen may form in a secondary route with
NHx and NO2 reacting.
3.5. The reaction mechanism
For the SCO of ammonia over oxide and metal catalysts
three types of mechanisms for nitrogen formation have been
proposed in the literature, namely (i) reaction between ad-
sorbed NHx species and formed NO or NO2 (Gang et al.,
2001, 2002; Burch and Southward, 2000; Curtin et al., 1998;
Long and Yang, 2002; Fogel et al., 1964); (ii) dissociation
of formed NO (Bradley et al., 1995); and (iii) direct oxida-
tion of ammonia via intermediate NHx species (Biermann
et al., 1990; Lietti et al., 2000; Bradley et al., 1995; Mieher
and Ho, 1995). Mechanism (i) was proposed (Fogel et al.,
1964) for ammonia oxidation at low temperature on poly-
crystalline Pt wire. However, in a study of ammonia oxida-
tion on Pt(1 1 1) using TPD, TPRS and EELS (Mieher and
Ho, 1995) it was concluded that nitrogen is formed by the
combination of two adsorbed nitrogen atoms, which were
formed from NHx species reacting with adsorbed oxygen.
The same type of mechanism was concluded to take place
below 350 K on Pt(1 0 0) considering molecular beam re-
sults (Bradley et al., 1995). Above 350 K, on the other hand,
the results indicated the formation of nitrogen via dissoci-
ation of NO. Our results for Pt/Al2 O3 under the reaction
conditions being used, Figs. 4 and 10, are in agreement with
the type (i) mechanism being predominant for nitrogen for-
mation from ammonia, involving the reaction between NHx
species and formed NO2 . Moreover, the responses indicate
that there may be a contribution to nitrogen formation from
a secondary pathway of type (iii). No indication was ob-
tained for NO being involved in the formation of nitrogen,
e.g. nitrogen was not a product in pump-probe experiments
with alternate ammonia and NO pulsing over pre-oxidised
Pt/Al2 O3 .
Concerning CuO/Al2 O3 the results in Figs. 3 and 10 show
that the oxidation of ammonia to nitrogen obeys mechanism
(i). This finding is consistent with the report (Curtin et al.,
1998) that on CuO/Al2 O3 the overoxidation of ammonia
produces NO2 , which reacts with NHx to form nitrogen.
The results in Figs. 1 and 6 show that Pt/CuO/Al2 O3 is
the most active sample for the SCO of ammonia to nitro-
gen. This sample, compared with Pt/Al2 O3 and CuO/Al2 O3 ,
presents a different major mechanism for nitrogen forma-
tion, namely a mechanism of type (iii). In this case a suc-
cessive stripping of hydrogen from adsorbed NHx species
takes place through reaction with adsorbed oxygen species
followed by the combination of two nitrogen species. Pos-
sibly a hydrazine-like intermediate can form on the surface
(Amores et al., 1997), although no evidence was obtained
for the formation of gaseous hydrazine. Besides this mech-
anism, there can be a secondary pathway of type (i) to ni-
trogen formation comprising adsorbed NHx species react-
ing with NO2 (Figs. 2 and 10). Mechanisms similar to the
latter pathway have been concluded in previous investiga-
tions of the low-temperature oxidation of ammonia to ni-
trogen on Pt/CuO/Al2 O3 (Burch and Southward, 2000) and
Ag/CuO/Al2 O3 (Gang et al., 2002) catalysts. In the former
investigation (Burch and Southward, 2000), however, no dif-
ferentiation was made between NO and NO2 , and in the lat-
ter investigation (Gang et al., 2002) the reacting NOx species
was indicated to be NO. Our results, however, reveal that
the reacting NOx species is NO2 and not NO.
The pulsing of a mixture of ammonia and oxygen, see
Fig. 5, shows for Pt/Al2 O3 delay of the hydrogen response
compared to the same response for Pt/CuO/Al2 O3 and
CuO/Al2 O3 , suggesting that the formation of NHx species
on Pt/CuO/Al2 O3 involves Cu-sites rather than Pt-sites. The
observation that nitrogen is formed on Pt/CuO/Al2 O3 at
the oxygen pulse (Fig. 2) and on CuO/Al2 O3 (Fig. 3) and
Pt/Al2 O3 (Fig. 4) at the ammonia pulse points to a synergy
effect between Pt and CuO on Al2 O3 . Support for this ef-
fect is also found comparing for the three catalysts the TPD
profiles of nitrogen in Fig. 1 and the data in Fig. 6. These
features suggest that on Pt/CuO/Al2 O3 the main route to
nitrogen involves reaction at the phase boundary between
NHx species adsorbed on CuO and oxygen adsorbed on Pt.
An option is that there is spill over of oxygen from Pt to
CuO.
4. Conclusions
The study of the reaction mechanisms operating in
the SCO of ammonia over CuO/Al2 O3 , Pt/Al2 O3 and
Pt/CuO/Al2 O3 show that the latter composition is the most
active and selective for nitrogen formation. Moreover, the
transient experiments demonstrate that the main route over
this catalyst to form nitrogen proceeds via direct oxidation
involving two NHx species. Comparison of the results ob-
tained for the three catalysts suggest that the NHx species
is adsorbed on a Cu site. The observed synergy between the
copper oxide and Pt can be explained by the reaction takes
place at the phase boundary, or, by spill over of oxygen
 G. Olofsson et al. / Chemical Engineering Science 59 (2004) 4113 – 4123
from Pt. No indication is obtained from the results that NO
is involved in the route to nitrogen, however, the results in-
dicate that reaction between formed NO2 and a NHx species
constitutes a secondary pathway to nitrogen formation on
Pt/CuO/Al2 O3 . On the other hand, over CuO/Al2 O3 and
Pt/Al2 O3 the situation is reversed in that the latter reaction
pathway being predominant.
References
Amblard, M., Burch, R., Southward, B.W.L., 1999. The selective
conversion of ammonia to nitrogen on metal oxide catalysts under
strongly oxidising conditions. Applied Catalysis B: Environmental 22,
L159–L166.
Amores, J.M.G., Escribano, V.S., Ramis, G., Busca, G., 1997. An FT-
IR study of ammonia adsorption and oxidation over anatase-supported
metal oxides. Applied Catalysis B: Environmental 13, 45–58.
Biermann, J.J.P., Janssen, F.J.J.G., de Boer, M., van Dillen, A.J., Geus,
J.W., Vogt, E.T.C., 1990. Molybdena on silica catalysts: selective
catalytic oxidation of ammonia to nitrogen over MoO3 on SiO2
catalysts. Journal of Molecular Catalysis 60, 229–238.
Bradley, J.M., Hopkinson, A., King, D.A., 1995. Control of a biphasic
surface reaction by oxygen coverage: the catalytic oxidation of
ammonia over Pt{1 0 0}. Journal of Physical Chemistry 99 (46),
6073–17042.
Burch, R., Southward, B.W.L., 2000. A novel application of trapping
catalysts for the selective low-temperature oxidation of NH3 to N2 in
simulated biogas. Journal of Catalysis 195, 217–226.
Curtin, T., O’Regan, F., Deconinck, C., Knüttle, N., Hodnett, B.K., 1998.
The catalytic oxidation of ammonia: influence of water and sulfur on
selectivity to nitrogen over promoted copper oxide/alumina catalysts.
Catalysis Today 55, 189–195.
Fogel, Ya.M., Nadykto, B.T., Rybalko, V.F., Shvachko, V.I.,
Korobchanskaya, I.E., 1964. Catalytic oxidation of ammonia over
platinum by using the second ion emission method. Kinetika i kataliz
5 (3), 496–504.
Gang, L., van Grondelle, J., Anderson, B.G., van Santen, R.A., 1999.
Selective low temperature on NH3 oxidation to N2 copper-based
catalysts. Journal of Catalysis 186, 100–109.
Gang, L., Anderson, B.G., van Grondelle, J., van Santen, R.A., 2001.
Intermediate species and reaction pathways for the oxidation of
ammonia on powdered catalysts. Journals of Catalysis 199, 107–114.
Gang, L., Anderson, B.G., van Grondelle, J., van Santen, R.A., van
Gennip, W.J.H., Niemantsverdriet, J.W., Kooyman, P.J., Knoester,
A., Brongersma, H.H., 2002. Alumina-supported Cu–Ag catalysts for
4123
ammonia oxidation to nitrogen at low temperature. Journal of Catalysis
206, 60–70.
Gleaves, J.T., Ebner, J.R., Kuechler, T.C., 1988. Temporal analysis
of products (TAP)-a unique catalyst evaluation system with
submillisecond time resolution. Catalysis Reviews—Science and
Engineering 30 (1), 49–116.
Gleaves, J.T., Yablonskii, G.S., Phanawadee, P., Schuurman, Y., 1997.
TAP-2: an interrogative kinetics approach. Applied Catalysis A: General
160, 55–88.
Hinz, A., Andersson, A., 1999. Propane ammoxidation on an Al–Sb–V–W
oxide catalyst, a mechanistic study using the TAP-2 reactor system.
Chemical Engineering Science 54 (20), 4407–4421.
Hinz, A., Skoglundh, M., Fridell, E., Andersson, A., 2001. An investigation
of the reaction mechanism for the promotion of propane oxidation
over Pt/Al2 O3 by SO2 . Journal of Catalysis 201 (2), 247–257.
Larsson, P.O., Andersson, A., Wallenberg, L.R., Svensson, B., 1996.
Combustion of CO and toluene; characterisation of copper oxide
supported on titania and activity comparisons with supported cobalt,
iron, and manganese oxide. Journal of Catalysis 163, 279–293.
Li, Y., Armor, J.N., 1997. Selective NH3 oxidation N2 to in a wet stream.
Applied Catalysis B: Environmental 13, 131–139.
Lietti, L., Ramis, G., Busca, G., Bregani, F., Forzatti, P., 2000.
Characterization and reactivity of MoO3 /SiO2 catalysts in the selective
catalytic oxidation of ammonia to N2 . Catalysis Today 61, 187–195.
Long, R.Q., Yang, R.T., 2000. Superior ion-exchange ZSM-5 catalysts
for selective catalytic oxidation of ammonia to nitrogen. Chemical
Communication 1651–1652.
Long, R.Q., Yang, R.T.J., 2001. Selective catalytic oxidation (SCO) of
ammonia to nitrogen over FE-exchanged zeolites. Journal of Catalysis
201, 145–152.
Long, R.Q., Yang, R.T., 2002. Selective catalytic oxidation of ammonia
to nitrogen over Fe2 O3 –TiO2 prepared with a sol–gel method. Journal
of Catalysis 207, 158–165.
Mieher, W.D., Ho, W., 1995. Thermally activated oxidation of NH3
on Pt(111): intermediate species and reaction mechanisms. Surface
Science 322 (1–3), 151–167.
Satterfield, C.N., 1991. Heterogeneous Catalysis in Industrial Practice.
2nd Edition. McGrawHill, New York.
Sazonova, N.N., Simakov, A.V., Nikoro, T.A., Barannik, G.B., Lyakhova,
V.F., Zheivot, V.I., Ismagilov, Z.R., Veringa, H., 1996. Selective catalytic
oxidation of ammonia to nitrogen. Reaction Kinetic Catalysis Letter
57 (1), 71–79.
Sobczyk, D.P., Hensen, E.J.M., de Jong, A.M., van Santen, R.A., 2003.
Low temperature ammonia oxidation over Pt/-alumina: the influence
of the alumina support. Topics in Catalysis 23 (1–4), 109–117.
Ueshima, M., Sano, K., Ikeda, M., Yoshino, K., Okamura, J., 1998. New
technology for selective catalytic oxidation of ammonia to nitrogen.
Research in Chemical Intermediate 24 (2), 133–141.