Effect of TiO<sub>2</sub> on Pd/La<sub>2</sub>O<sub>3</sub>-CeO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> Systems during Catalytic Oxidation of Methane in the Presence of H<sub>2</sub>O and SO<sub>2</sub>
Ralitsa Velinova,
Silviya Todorova,
Daniela Kovacheva,
Hristo Kolev,
Yordanka Karakirova,
Pavel Markov,
Katerina Tumbalova,
Georgi Ivanov,
Anton Naydenov
Affiliations
Ralitsa Velinova
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria
Silviya Todorova
Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria
Daniela Kovacheva
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria
Hristo Kolev
Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria
Yordanka Karakirova
Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria
Pavel Markov
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria
Katerina Tumbalova
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria
Georgi Ivanov
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria
Anton Naydenov
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria
New results on the effect of TiO2 on Pd/La2O3-CeO2-Al2O3 systems for catalytic oxidation of methane in the presence of H2O and SO2 have been received. Low-temperature N2-adsorption, XRD, SEM, HRTEM, XPS, EPR and FTIR techniques were used to characterize the catalyst. The presence of Ce3+ on the catalytic surface and in the volume near the lantana was revealed by EPR and XPS. After aging, the following changes are observed: (i) agglomeration of the Pd-clusters (from 8 nm to 12 nm); (ii) transformation of part of the TiO2 from anatase to larger particles of rutile; and (iii)—the increase in PdO/Pd—ratio above its optimum. The modification by Ti of the La2O3-CeO2-Al2O3 system leads to higher resistance towards the presence of SO2 most likely due to the prevailing formation of unstable surface sulfites instead of thermally stable sulfates. Based on kinetic model calculations, the reaction pathway over the Pd/La2O3-CeO2-TiO2-Al2O3 catalyst follows the Mars–van Krevelen mechanism. For evaluation of the possible practical application of the obtained material, a sample of Pd/La2O3-CeO2-TiO2-Al2O3, supported on rolled aluminum-containing stainless steel (Aluchrom VDM®), was prepared and tested. Methane oxidation in an industrial-scale monolithic reactor was simulated using a two-dimensional heterogeneous reactor model.
