Selective ammonia oxidation over ZSM-5 zeolite: Impact of catalyst's support porosity and type of deposited iron species

[EN] In the presented studies an influence of different parameters, such as zeolite sample porosity, form of used iron source ([Fe-3(OAc)(6)O(H2O)(3)](+)oligocations or FeSO4 solutions) and method of iron species deposition (ion-exchange, impregnation), on the catalytic activity in the process of the selective catalytic oxidation of ammonia (NH3-SCO) was studied. Conventional and mesoporous ZSM-5 zeolites, obtained by desilication and modified with iron species, were analysed with respect to their textural, surface and crystalline properties (N-2-sorption, HRTEM, SEM, XRD) as well as the form of introduced Fe species (UV-vis-DRS). Ion-exchange with [Fe-3(OAc)(6)O (H2O)(3)](+) oligocations and impregnation with these oligocations and FeSO4 solutions were found as the most effective methods of the zeolite samples activation for NH3-SCO.This work was carried out in the frame of project No. 0670/IP3/2016/74 from the Polish Ministry of Science and Higher Education in the years 2016-2019. Part of the work was performed in the frame of project No. 2012/05/B/ST5/00269from the National Science Centre (Poland). U. D. acknowledges to the Spanish Government by the funding (MAT2017-82288-C2-1-P). The authors would like to acknowledge to Clariant Company for the providing of the HMFI zeolite material for the presented research.Borcuch, A.; Rutkowska, M.; Marzec, A.; Kowalczyk, A.; Michalik, M.; Moreno, J.; Díaz Morales, UM.... (2020). Selective ammonia oxidation over ZSM-5 zeolite: Impact of catalyst's support porosity and type of deposited iron species. Catalysis Today. 348:223-229. https://doi.org/10.1016/j.cattod.2019.08.054S223229348Weckhuysen, B. M., & Yu, J. (2015). Recent advances in zeolite chemistry and catalysis. Chemical Society Reviews, 44(20), 7022-7024. doi:10.1039/c5cs90100fVerboekend, D., & Pérez-Ramírez, J. (2011). Design of hierarchical zeolite catalysts by desilication. Catalysis Science & Technology, 1(6), 879. doi:10.1039/c1cy00150gRutkowska, M., Pacia, I., Basąg, S., Kowalczyk, A., Piwowarska, Z., Duda, M., … Chmielarz, L. (2017). Catalytic performance of commercial Cu-ZSM-5 zeolite modified by desilication in NH 3 -SCR and NH 3 -SCO processes. Microporous and Mesoporous Materials, 246, 193-206. doi:10.1016/j.micromeso.2017.03.017Góra-Marek, K., Brylewska, K., Tarach, K. A., Rutkowska, M., Jabłońska, M., Choi, M., & Chmielarz, L. (2015). IR studies of Fe modified ZSM-5 zeolites of diverse mesopore topologies in the terms of their catalytic performance in NH3-SCR and NH3-SCO processes. Applied Catalysis B: Environmental, 179, 589-598. doi:10.1016/j.apcatb.2015.05.053Macina, D., Piwowarska, Z., Góra-Marek, K., Tarach, K., Rutkowska, M., Girman, V., … Chmielarz, L. (2016). SBA-15 loaded with iron by various methods as catalyst for DeNOx process. Materials Research Bulletin, 78, 72-82. doi:10.1016/j.materresbull.2016.02.026Rutkowska, M., Duda, M., Macina, D., Górecka, S., Dębek, R., Moreno, J. M., … Chmielarz, L. (2019). Mesoporous Beta zeolite functionalisation with FexCry oligocations; catalytic activity in the NH3SCO process. Microporous and Mesoporous Materials, 278, 1-13. doi:10.1016/j.micromeso.2018.11.003Miller, J. T., Glusker, E., Peddi, R., Zheng, T., & Regalbuto, J. R. (1998). Catalysis Letters, 51(1/2), 15-22. doi:10.1023/a:1019072631175Kowalczyk, A., Borcuch, A., Michalik, M., Rutkowska, M., Gil, B., Sojka, Z., … Chmielarz, L. (2017). MCM-41 modified with transition metals by template ion-exchange method as catalysts for selective catalytic oxidation of ammonia to dinitrogen. Microporous and Mesoporous Materials, 240, 9-21. doi:10.1016/j.micromeso.2016.11.002Chmielarz, L., & Jabłońska, M. (2015). Advances in selective catalytic oxidation of ammonia to dinitrogen: a review. RSC Advances, 5(54), 43408-43431. doi:10.1039/c5ra03218kThommes, M., Kaneko, K., Neimark, A. V., Olivier, J. P., Rodriguez-Reinoso, F., Rouquerol, J., & Sing, K. S. W. (2015). Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure and Applied Chemistry, 87(9-10), 1051-1069. doi:10.1515/pac-2014-1117Qi, G., & Yang, R. T. (2005). Selective catalytic oxidation (SCO) of ammonia to nitrogen over Fe/ZSM-5 catalysts. Applied Catalysis A: General, 287(1), 25-33. doi:10.1016/j.apcata.2005.03.00

Influence of iron aggregation on the catalytic performance of desilicated MFI in the DeNO(x) process

[EN] In the present study, an influence of the iron aggregation in conventional and micro-mesoporous MFI on their catalytic activity in the NO reduction with ammonia (DeNO(x) process) was studied. Modification of MFI zeolite properties was done by the desilication in the presence of NaOH and TPAOH (tertapropylammonium hydroxide). In the next step, the samples were modified with iron by ion-exchange with the use of a conventional solution of Fe cations (FeSO4) and a solution of iron triple-metallic aggregates (oligocations) ([Fe-3(OAc)(6)O(H2O)(3)](+)). Both of the applied modification techniques (desilication and modification with Fe-3 oligocations) increased the catalytic activity of the MFI zeolite in the DeNO(x) process. This increased catalytic activity was connected with changes in sample porosity, Si/Al ratio, topology, as well as aggregation and dispersion of iron species on the catalyst surface, which was investigated by N-2-sorption, XRD, ICP, NMR, HRTEM and UV-vis-DRS techniques.This work was carried out in the frame of project No. 0670/IP3/2016/74 from the Polish Ministry of Science and Higher Education in the years 2016-2019 and in the frame of project No. 2012/05/B/ST5/00269 from the National Science Centre (Poland). U. D. acknowledges to the Spanish Government by the funding (MAT2017-82288-C2-1-P).Rutkowska, M.; Borcuch, A.; Marzec, A.; Kowalczyk, A.; Samojeden, B.; Moreno, J.; Díaz Morales, UM.... (2020). Influence of iron aggregation on the catalytic performance of desilicated MFI in the DeNO(x) process. Microporous and Mesoporous Materials. 304:1-8. https://doi.org/10.1016/j.micromeso.2018.09.015S1830

Synthesis and characterisation of coating polyurethane cationomers containing fluorine built-in hard urethane segments

Polyurethane cationomers were synthesised in the reaction of 4,4’-methylenebis(phenyl isocyanate) with polyoxyethylene glycol (M = 2,000) or poly(tetrafluoroethyleneoxide-co-difluoromethylene oxide) α,ω-diisocyanate and N-methyl diethanolamine. Amine segments were built-in to the urethane-isocyanate prepolymer in the reaction with 1-bromobutane or formic acid, and then they were converted to alkylammonium cations. The obtained isocyanate prepolymers were then extended in the aqueous medium that yielded stable aqueous dispersions which were applied on the surfaces of test poly(tetrafluoroethylene) plates. After evaporation of water, the dispersions formed thin polymer coatings. 1H, 13C NMR and IR spectral methods were employed to confirm chemical structures of synthesised cationomers. Based on 1H NMR and IR spectra, the factors κ and α were calculated, which represented the polarity level of the obtained cationomers. The DSC, wide angle X-ray scattering and atom force microscopy methods were employed for the microstructural assessment of the obtained materials. Changes were discussed in the surface free energy and its components, as calculated independently according to the method suggested by van Oss–Good, in relation to chemical and physical structures of cationomers as well as morphology of coating surfaces obtained from those cationomers. Fluorine incorporated into cationomers (about 30%) contributed to lower surface free energy values, down to about 15 mJ/m2. That was caused by gradual weakening of long-range interactions within which the highest share is taken by dispersion interactions