Jointly published by Akadmiai Kiad, Budapest and Kluwer Academic Publishers, Dordrecht

React.Kinet.Catal.Lett. 1 Vol. 76, No. 1, 61-68 (2002)

RKCL3972 AMMONIA OXIDATION OVER CONVENTIONAL COMBUSTION CATALYSTS Lara S. Escandn, Salvador Ordez*, Fernando V. Dez and Herminio Sastre
Department of Chemical and Environmental Engineering, University of Oviedo, Avda. Julin Clavera s/n; 33071-Oviedo, Spain Received September 18, 2001 In revised form December 20, 2001 Accepted January 14, 2002 Abstract The combustion of ammonia in air over different conventional oxidation catalysts has been studied in the present work. The final oxidation product is NO, although N2O is also formed at intermediate temperatures. The environmentally desirable product, N2, is only appreciably yielded over iron oxides catalysts. Keywords: Ammonia oxidation, supported noble metal catalysts, metal oxides

INTRODUCTION In addition to the fuel saving, one of the most important advantages of catalytic incineration, if it is compared with thermal incineration, is the no formation of nitrogen oxides from nitrogen and oxygen (so-called thermal NOx), because of the low reaction temperatures needed. This aspect has led to a wide use of catalytic incineration in the abatement of VOCs in industrial emissions (aromatics, alcohols, etc.). In the last years concern about methane emissions has increased because it is a powerful greenhouse gas. Catalytic incineration was shown to be an efficient technique even for the abatement of methane, although it is the less reactive hydrocarbon. However, in the main anthropogenic emissions of methane, such as emissions from coke ovens, wastewater treatment plants, sanitary landfills, farms or composting facilities, this compound is accompanied by variable amounts of ammonia. In these emissions, ammonia could be oxidized, producing nitrogen oxides.
0133-1736/2002/US$ 12.00. Akadmiai Kiad, Budapest. All rights reserved.

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The oxidation of ammonia focused on the minimization of nitrogen oxides was studied by Li and Armor and Ilchenko et al. [1, 2]. The main conclusion of Ilchenko, who studied the oxidation of ammonia over supported Pd, Pt, Fe and W catalysts, Co3O4, MnO2 and V2O5, is that V2O5 is the most selective catalyst for the ammonia oxidation to N2 [1]. However, this catalyst has two important drawbacks: it provides low NH3 conversions and it is not active for the abatement of VOCs. Li and Armor [2] compared the activity of ZSM-5- and Al2O-supported noble metal catalysts with V2O5/TiO2 and Co2O3/ZSM-5. They achieve much higher N2 selectivities (especially with Pd-ZSM-5), working with wet streams, low concentration of oxygen (5 %) and low temperatures, however these operation conditions are not applicable to VOCs abatement (especially methane containing emissions). Good selectivities to N2 at higher temperatures (325C) were found by Curtin et al. [3], using alumina-supported copper oxide catalysts, whereas Wllner et al. report that titania enhances the performance of copper and manganese oxides for these reactions [4]. The aim of this work is to study the oxidation of ammonia over conventional catalysts used for VOCs abatement, such as alumina-supported catalysts and metal oxide catalysts. EXPERIMENTAL The oxidation of ammonia was studied over two different kinds of catalysts. Five different noble metal catalysts supported on alumina (Pd, Pt, Ru, Rh and PdPt) and three metal oxide-based catalysts: a commercial Cr-Cu-Ti catalyst, a bulk perovskitic catalysts (La0.9Ce0.1CoO3, synthesized by the sol-gel method at the Catholic University of Louvaine, Belgium [5]) and a home-made catalyst based on red mud (that has shown high activity for oxidation reactions [6]) were tested. Composition and suppliers of all the catalysts are given in Table 1. Experiments were carried out at atmospheric pressure, in a U-shaped quartz reactor placed in electric furnace controlled by a PID. Feed gas consisted of a mixture of 0.02 % NH3 and 20 % oxygen balanced in argon. Catalyst (50 mg), was placed over a plug of quartz wool and a thermocouple was placed inside the catalyst bed. Before starting each run, catalysts were pretreated with 10 mL/min of pure He at 420C, in order to eliminate the possible compounds adsorbed over catalyst surface. After this pre-treatment, the reactor was cooled to 75C, the reactive mixture (10 mL/min) was introduced and the reaction was carried out. In all the experiments, the samples were heated from 75C to 950C with a ramping temperature rate of 10C/min. Previously a negligible influence of this parameter in the range 1-10C/min has been observed. This aspect, as well as the similar results obtained when catalyst loads were changed keeping

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constant the space time, lead to think that mass transfer or thermal effects are not important in these experiments. The effluent from the reactor was analyzed by a Gaslab 300 quadrupole mass spectrometer, which used a capillary inlet system for sampling and computer acquisition of multiple mass peaks. Calibration of the spectrometer was carried out using standard gaseous mixtures of the analysed compounds (NH3, N2, N2O, NO and NO2).

RESULTS AND DISCUSSION Two typical curves are shown in Figs 1 (supported palladium catalyst) and 2 (red mud-based catalyst).

1
470 313

0,8

Signal (a.u.)

0,6

NO N2O N2

0,4

0,2

0 0 200 400 600 800 1000

Temperature (oC )

Fig. 1. Products released in temperature-programmed ammonia oxidation over Pd/Al2O3 catalyst

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The parameter T50 (i.e. temperature needed to get 50% of ammonia conversion) was used to characterize the activity of the different catalysts. Its values for all the catalysts tested are listed in Table 1. In the case of noble metal catalysts, it is observed that rhodium (T50=125C) is the most active catalyst, followed by ruthenium (T50=213C), platinum and palladium (275 and 287C, respectively), and being the bimetallic Pd-Pt catalyst the less active catalyst (T50=390C). Concerning to the metal oxide catalysts, the differences in the reactivity are lower, T50 varying around 210C for the perovskites, 275C for the commercial catalyst and 287C for the red mud based catalyst.

1
470 313

0,8

Signal (a.u.)

0,6

NO N2O N2

0,4

0,2

0 0 200 400 600 800 1000

Temperature (oC )
Fig. 2. Products released in temperature-programmed ammonia oxidation over red mud based catalyst

However, the most important issue in the comparison of the catalysts is the selectivity for the different reaction products. The final product is NO in all the cases, being the only oxidation product at temperatures higher than 500C600C, depending on the catalyst. At lower temperatures, intermediate oxidation products, such as N2 or N2O, are formed. In the case of palladium catalyst NO2 is also released at intermediate temperatures. The temperature of the maximum

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of release of N2O, N2 and NO2 and the values of the selectivity and ammonia conversion at this temperature are summarized in Table 1. It is observed that in the case of noble metal catalysts, N2O is the main oxidation product at lower temperatures, only the formation of N2 being observed in the case of palladium catalyst and to a very low extent. It is also important to remark that the maxima for N2O formation are in a very narrow window (260 - 305C). These results indicate that N2O is probably formed by direct oxidation of NH3. At this point, Busca et al. [7] suggest four different mechanisms for N2O formation: direct oxidation of ammonia, reaction of ammonia and NO, decomposition of NO and disproportionation of NO. The reactions involved will be the following: 2 NH3 4 NH3 2 NO 3 NO + 2 O2 2 N2O + 3 H2O + 6 H2O + 1/2 O2 + NO2 (1) (2) (3) (4)

+ 4 NO + 3 O2 4 N2O N2O N2O

From these reactions, only the first one is likely to occur since at the temperatures, at which the release of N2O starts, the selectivity for NO is near zero over most of the catalysts. In the case of Pd containing catalysts and perovskite, NO2 formation was also observed, the maximum release of this compound being at 366C for Pd, 469C for Pd-Pt and 390C for perovskite. Although it is well known that this compound is a key intermediate in the SCR reactions in presence of oxygen, the formation of this compound is not well reported in the literature. Only Busca et al. [7] report the possibility of the formation of NO2 by disproportionation of NO (4). However, no N2O release is associated to the emission of NO2. Oxidation of NO is not likely to occur since this reaction is considered as equilibrium controlled. By these reasons a direct oxidation of NH3 to NO2 seems to be the most plausible possibility. Regarding the N2 formation, only the Pd catalyst and especially the iron oxide catalyst yield appreciable selectivities for this compound. In the case of Pd is observed that N2 is formed at low temperatures, (maximum at 240C), whereas in the case of iron oxide, the maximum occurs at higher temperatures (470C). These aspects suggest that the formation of N2 follows different reaction pathways in the two cases. In the case of Pd, N2 is formed by direct oxidation of ammonia, so it is observed that the maxima of N2 and N2O release occur at almost the same temperature. So, at low temperatures N2 and N2O are

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formed following a parallel mechanism and N2 is formed according to the reaction: (5) NH3 + 3/2 O2 N2 + 3 H2O However, in the case of red mud-based catalysts, two different pathways are possible, the catalytic decomposition of N2O and a typical SCR reaction between NO (its formation is important at these temperatures) and NH3. The reactions involved are the following: N2O 4 NH3 N2 + O2 + 6 NO 5 N2 + 6 H2O (6) (7)

Direct decomposition of NO is not likely to occur with the catalysts tested because only Cu-loaded strong acid catalysts (Cu-ZSM5) can catalyze this reaction to a significant extent [8]. It is also remarkable that bulk iron oxides have been reported to be slightly active for both N2O decomposition [9] and SCR reaction [10]. The results obtained with the red mud based catalyst are of great practical importance, since they indicate that ammonia is mainly transformed into inner nitrogen at the temperature needed for the oxidation of the most refractory organic compounds (e.g. methane). In the case of the other catalysts, ammonia will be transformed into nitrogen oxides. Concerning the presence of organic compounds, methane (which is commonly released with ammonia) is not a very effective reducing agent, except when the solid can catalyze the oxidative coupling of methane, such as several metal loaded zeolites or rare-earth oxides [11].

Acknowledgements. This research was financed by the Environmental Research Program of the European Union (ENV4-CT97-0599). Commercial catalysts tested were generous gifts from Sd-Chemie, BASF and Engelhard.

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G. Busca, L. Lietti, G. Ramis, F. Berti: Appl. Catal. B, 18, 1 (1998). Y. Li, W.K. Hall: J. Catal., 129, 202 (1991). W.M. Kalback, C.M. Sliepcevic: Ind. Eng. Chem. Fundam., 17, 165 (1978). A. Kato, S. Matsuda, F. Nakajima, Y. Watanabe: J. Phys. Chem., 85, 1710 (1981). C. Shi, A.B. Walkers, M.A. Vannice: Appl. Catal. B, 14, 175 (1997).