Applied Catalysis A: General 206 (2001) 1318

Ozone decomposition, benzene and CO oxidation over NiMnO3-ilmenite and NiMn2 O4 -spinel catalysts
D. Mehandjiev , A. Naydenov, G. Ivanov
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Soa, Bulgaria Received 15 December 1999; received in revised form 20 March 2000; accepted 21 March 2000

Abstract The catalytic activities of NiMnO3 and NiMn2 O4 during heterogeneous catalytic decomposition of ozone and ozone-catalytic oxidation (OZCO) of benzene at low temperatures (2080 C) have been investigated. The sensitivity of the two oxides towards strong catalytic poisons, such as nitrogen oxides, during the decomposition of ozone has also been estimated. On the basis of the experimental results obtained it is concluded that the NiMnO3 and NiMn2 O4 obtained have a high activity with respect to the reactions of ozone decomposition and CO and CH oxidation in the presence of ozone at temperatures close to the room temperature. The sample with an ilmenite structure shows, in all cases, a higher catalytic activity. The surface oxygen of NiMnO3 is more reactive at room temperature than is the case of NiMn2 O4 . The hypothesis according to which when the two metal cations are in octahedral coordination the catalyst activity is higher and the stability towards catalytic poisons is enhanced has proved to be correct. It should be noted that a catalyst has been synthesized which is able to decompose ozone at room temperature and to activate the organic molecule to a degree permitting catalytic oxidation by ozone at room temperature. In addition, this catalyst shows a relatively high stability with respect to poisoning by nitrogen oxides. 2001 Published by Elsevier Science B.V.
Keywords: Ozone decomposition; Ozone-catalytic oxidation; Catalytic poisons; Nickel-manganese oxides

1. Introduction The interest in developing catalysts to be applied to processes of low-temperature neutralization of organic pollutants in waste gases has increased considerably during the past years. One of the promising methods in this respect is the ozone-catalytic oxidation (OZCO) where heterogeneous catalytic decomposition of ozone is used to obtain highly reactive atomic oxygen able to oxidize harmful organic compounds at low temperatures including room temperature [1]. In previous studies [25] it has been shown that the simple oxides of Ni, Co, Fe and Mn have a

Corresponding author.

high activity in the decomposition of ozone and in the OZCO process of organic compounds. It is known that mixed 3d-transition metal oxides are more active than are simple oxides [611]. In [12] it has been shown that in oxidation reactions NiMnO3 with an ilmenite structure has a high activity which is comparable to that of the spinel NiMn2 O4 . That activity may be associated with the position of the two cations in octahedral coordination. It was of interest to compare the catalytic activities of these oxides during heterogeneous catalytic decomposition of ozone and OZCO of benzene at low temperatures (2080 C) and also to estimate the sensitivity of the two oxides towards the nitrogen oxides, which are known [4] to be strong catalytic poisons during the decomposition of ozone.

0926-860X/01/$ see front matter 2001 Published by Elsevier Science B.V. PII: S 0 9 2 6 - 8 6 0 X ( 0 0 ) 0 0 5 7 0 - 6

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D. Mehandjiev et al. / Applied Catalysis A: General 206 (2001) 1318

Fig. 1. FTIR spectra of the samples investigated.

2. Experimental 2.1. Synthesis and characterization of the catalysts Nickelmanganese mixed oxides were prepared from carbonate precursors. They were synthesized by adding, with constant stirring, a 0.5 M solution of metal nitrates (in a ratio of 1:1 and 1:2) to a 1 M solution of sodium bicarbonate. The precipitate formed was ltered and dried at atmospheric pressure. Ilmenite was obtained using the precursor with Ni:Mn=1:1. The thermal treatment consisted of heating with a rate of 10 C/min up to 450 C, maintaining this temperature for 5 h and, nally, rapid cooling to room temperature. The spinel was prepared by thermal treatment with a heating rate of 10 C/min up to 750 C, keeping the sample at this temperature for 5 h, then cooling it quickly to room temperature. The precursor used in this case had a Ni:Mn ratio of 1:2. For more details see [12,1416]. The atomic ratio of the metals was controlled by atomic absorption analysis and the results showed that the compositions of the two samples corresponded to NiMnO3 and NiMn2 O4 .

The structure of the samples obtained was characterized by X-ray analysis with a DRON (Russia) diffractometer using Cu K radiation. The magnetic studies were carried out with a Faraday type magnetic balance. According to the chemical analysis and the magnetic measurements the ion distribution in the sublattices of the spinel was: Ni2+ 0.20Mn2+ 0.80[Ni2+ 0.80Mn3+ 0.40Mn4+ 0.80]O4 . According to modern concepts [13], both ions are in octahedral coordination in the ilmenite. The FTIR-spectra of the samples are different in the region connected with the MO bond (Fig. 1). The specic surface area of the samples was determined by low-temperature adsorption of N2 . The results are 44 m2 /g for NiMnO3 and 8 m2 /g for NiMn2 O4 . 2.2. Reaction parameters The pre-treatment of the samples consisted in a 20 min heating at 300 C in an oxygen ow. A 0.20.4 mm fraction was used. Ozone was synthesized from dried oxygen (gas ow rate 4 l/h), using an ozone generator with silent discharge (68 kV). The generator was equipped with glass coaxial electrodes.

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The initial concentration of ozone ranged from 22.0 to 24.5 g/m3 . The ozone analysis was performed by an on-line ozone analyser (Ozomat GM, Germany) with an accuracy of 0.1 g/m3 . The residual ozone was decomposed in a catalytic reactor lled with an OCA-1 (Bulgaria) catalyst [17]. The experiments were carried out with a circulation ratio of 1:70. The reaction temperature varied between 19 and 80 C and was maintained with an accuracy of 0.2 C. Carbon monoxide and benzene were dosed by an Ismatex MS2/6 (Switzerland) pump. The initial concentrations were varied within the limits of 0.51.5 vol.% for CO and 0.010.03 vol.% for benzene. The carrier gas was air and oxygen (99.8%). The rate of complete oxidation was estimated by measuring the quantity of CO2 (by Infralyt 2106, ex-GDR) formed during the reaction. The experiments on the so-called depletive oxidation [18] were performed in an integral reactor. A CO ow in argon was passed through the catalyst layer, i.e. this occurred in the absence of an oxidizing agent from the gas phase. The process was controlled on the basis of the CO2 concentration at the reactor outlet. The behaviour of the catalysts during ozone decomposition in the presence of nitrogen oxides was investigated using an integral pulse reactor. At its inlet, 20 cm3 of nitrogen oxides with a concentration of 68 vol.% were injected. The formation of nitrates on the catalyst surface was controlled by an FTIR (Brucker) spectrometer.

3. Experimental results Fig. 2 shows the temperature dependencies of the conversion degrees of ozone, CO and benzene on the two catalysts. Evidently, the ilmenite catalyst has a higher catalytic activity at lower temperatures. It should be noted that when molecular oxygen is used on both catalysts oxidation of benzene and CO begins only at 150200 C. Hence during OZCO, the temperature of catalyst efciency is lower by 100 150 C. Table 1 shows the activation energies and rate constants calculated per gram of catalyst and unit surface. Obviously, ozone decomposition proceeds with a relatively high activation energy. During oxidation of benzene and carbon monoxide on an ilmenite catalyst, the activation energy is lower than is the case of the spinel catalyst. The rate constants per gram ilmenite are higher than those per gram spinel and the highest rate constant corresponds to ozone decomposition. The rate constant per unit spinel surface area is higher probably because of the higher concentration of active sites. However, if we accept the activation energy as a measure of the catalyst activity, then ilmenite is the more active catalyst with respect to the reactions under consideration. This is in agreement with the results in a previous paper [12] dealing with catalytic oxidation of benzene with molecular oxygen on analogous catalysts, however, at high temperatures.

Fig. 2. Temperature dependencies of the conversion degrees of ozone, CO and benzene on the catalysts investigated.

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Table 1 Kinetic parameters of the reactions on the catalysts investigated Catalysts Reaction Ozone decomposition (30 C) NiMnO3 Reaction ratea (mol/g s) Activation energy (kJ/mol) NiMn2 O4 Reaction ratea (mol/g s) Activation energy (kJ/mol)
a

CO oxidation by O3 (40 C) 1.86108 (0.42109 ) 26 3.23109 (0.65109 ) 48

C6 H6 oxidation by O3 (30 C) 8.76108 (2.00109 ) 34 4.14108 (8.28109 ) 50

2.63106 (0.60107 ) 44 2.09106 (4.18107 ) 40

Values in parenthesis are in mol/m2 s.

Fig. 3. Results on so-called depletive oxidation on the samples at 30 C.

Fig. 3 presents the results of depletive oxidation of CO over the two catalysts. It is evident that the active oxygen content is higher in the case of ilmenite. The curves in Fig. 3 are of an overshot response type which indicates that the regeneration of active sites on the surface is the rate-controlling step of the reaction [19]. It is known [4] that when ozone is formed by air, a denite amount of nitrogen oxides is present in the gas phase and they block the ozone decomposition. In the present investigations the ilmenite catalyst has a higher resistivity with respect to nitrogen oxides in the gas phase, as is shown in Fig. 4. Nitrate groups poisoning the catalyst are formed on its surface. The same has been observed with both catalysts (Fig. 5). Bielanski and Haber [20] have divided the oxides into three groups: (1) oxides on which oxygen is adsorbed mainly in the form of electron-rich species (oxides of Ni, Mn and Co); (2) oxides on which oxygen

Fig. 4. Results from the experiments on pulse poisoning of the catalysts by nitrogen oxides during the reaction of ozone decomposition.

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where R is the organic compound or CO and M represents the metal ion. Comparison of the results shows that the decomposition of ozone on the two catalysts leads to the formation of active oxygen. According to our opinion the O form is the most probable one and this leads to a sharp drop in the temperature needed for complete oxidation of benzene and its removal from the gas mixture.

4. Conclusions
Fig. 5. IR spectra of the samples after the poisoning by nitrogen oxides.

is adsorbed in the form of species less rich in electrons, such as O2 (oxides of Zn and Ti) and oxides which do not adsorb oxygen (oxides of Mo and W). The rst group of oxides, to which the oxides used in the present work belong, are characterized by a high concentration of electron-donor centres, due to which the electron-rich species O and O2 are formed during oxygen adsorption. It is supposed that the O provides the complete oxidation [2023]. It is established that O interacts with CO forming CO2 radicals [24]. In our earlier investigation we observed that when CO/O3 /O2 is passed through CeO2 , no radicals originating from CO appeared, i.e. O3 is the only constituent of the gas mixture that can react with the surface. This means that the decomposition of ozone precedes the oxidation of CO, i.e. the EleyRideal mechanism is possible. The existence of O has not been observed experimentally, but is logically suggested. The general form of the reactions taking place is O3 + Z ZO + O2 O3 + ZO Z + 2O2 (1) (2)

On the basis of the experimental results obtained and their interpretation it can be concluded that NiMnO3 and NiMn2 O4 have a high activity with respect to the reactions of ozone decomposition and CO and C6 H6 oxidation in the presence of ozone at temperature close to the room temperatures, i.e they are appropriate for the OZCO process. The sample with an ilmenite structure shows in all cases a higher catalytic activity. The surface oxygen of NiMnO3 is more reactive at room temperature than in the case of NiMn2 O4 . The initial hypothesis according to which with the two metal cations in octahedral coordination the catalyst activity is higher and the stability towards catalytic poisons is enhanced has proved to be correct. It should be noted that a catalyst (NiMnO3 ) has been synthesized which is able to decompose ozone at room temperature and to activate the organic molecule to a degree permitting catalytic oxidation by ozone at room temperature. In addition, this catalyst shows a relatively high stability with respect to the poisoning by nitrogen oxides during the reaction of ozone decomposition. References
[1] A. Naydenov, D. Mehandjiev, Complete oxidation of benzene on MnO2 by ozone, Appl. Catal. 97 (1993) 1722. [2] A. Naydenov, D. Mehandjiev, Comparative study of the catalytic oxidation of CO and benzene with molecular oxygen and ozone, in: Proceedings of the 8th International Symposium on Heterogeneous Catalysis, Varna, 59 October 1996, Part I, pp. 383387. [3] A. Naydenov, D. Mehandjiev, Decrease of the temperature of catalytical oxidation of CO by ozone on Co3 O4 , C. r. LAcad. Bulg. Sci. 6 (1998) 50.

Writing these reactions so as to present the changes in oxidation state of the metal ions, one obtains Mn+ + O3 Mn+1 O + O2 Mn+1 O + R Mn+ + RO Mn+1 O + O3 Mn+ + 2O2 Mn+1 O + O2 Mn+1 O3 (3) (4) (5) (6)

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