Synthesis and application of lanthanum aluminate perovskites obtained from aluminum saline slags as catalysts for dry reforming of methane and other environmental uses
Authors:   , Muñoz Alvear Helir Joseph 
Published: September 2024

In this work, the aluminum was successively extracted from saline slags using an acidic medium (HCl or citric acid). The aluminum solutions obtained were used as precursors in the synthesis of lanthanum aluminate perovskite supports (LaAlO3), and various synthesis methods, including MOF-gel precursor, Pechini, and modified citrate, were evaluated to obtain the perovskite. The parameters in the synthesis of lanthanum aluminate were studied, and the physicochemical properties of the resulting functional materials were characterized, with the purpose to optimize the synthesis process and choose the most promising materials. The chosen materials were evaluated, either as catalytic supports or as catalysts, for the dry reforming of methane or the degradation of carbofuran (CBF) in water doped with synthetic dissolved natural organic matter (NOM). The catalytic behavior was compared with that of catalysts prepared by conventional methods and using commercial aluminum saline. The first two chapters of this thesis correspond to the introduction and focus on the theory related to the subject. The First Chapter (I) refers to lanthanum aluminate perovskite, its physicochemical parameters, synthesis methods, and some of its applications. This chapter focuses on the review of studies from the past ten years related to all the synthesis methods employed in the preparation of lanthanum aluminate. It discusses the synthetic challenges, advantages, and limitations associated with these methods, as well as the most significant catalytic applications. The Second Chapter (II) is related to Ni-perovskites-based catalysts for the dry reforming of methane. This chapter delves into the thermodynamic and kinetic aspects of the DRM, highlighting that the properties of A and B can affect catalytic performance. It discusses recent advancements in the substituting of the B cation to enhance catalytic efficiency through synergistic effects. Similarly, the substitution of cation A is explored for its ability to control acid- base properties and the consequent impact on coke formation and deposition. The chapter also reviews progress in improving the low textural properties of perovskites, either directly or by deposition of the perovskites on a support. Finally, new lines of research focused on softening DRM reaction conditions and promoting the process at lower temperatures are also highlighted. The next three chapters (Chapter III to Chapter V) are related to the results and analysis of the experimental part developed in this work. Chapter III is related with a novel and simple strategy developed for synthesizing the pure perovskite phase of lanthanum aluminate (LaAlO3). This involves the calcination of a highly porous, dry MOF precursor gel, which is prepared using commercial precursors, and its subsequent application in the dry reforming of methane. This study revealed that the textural properties of the materials can be modulated by the solvothermal treatment time. Additionally, it identified the main factors that contribute to enhancing the catalytic performance in the dry reforming of methane (DRM) using the Ni/LaAlO3 catalyst. Chapter IV corresponds to the first synthesis of nickel-modified lanthanum aluminate (Ni/LaAlO3) perovskite catalysts using aluminum extracted from saline slag via acid leaching with HCl or citric acid. Three preparation methods (Pechini, modified citrate, and metal–organic gel) were evaluated to obtain the pure lanthanum aluminate (LaAlO3) phase. This study also investigated the effects of several factors, with some variations observed depending on the methodology used. The most promising materials were evaluated as catalytic supports for Ni active sites in the dry reforming of methane. The catalytic performance of the catalysts was compared with a reference catalyst prepared by a conventional method and using commercial aluminum salt. The annex in this document is related to this part of the study. Given the novelty of preparing lanthanum aluminate perovskite from HCl- and citric acid-extracted aluminum from saline slag, and due to the resulting enhancement in the physicochemical properties of the final functional materials, a patent application has been submitted (details provided in the annex). Chapter V corresponds to the first synthesis of LayAl1–xCuxO3–δ perovskite catalysts using Al extracted from saline slag residue (previously extracted with HCl). This study investigates the effect of parameters such as the La/Al molar ratio during the synthetic process. The best catalyst was used to optimize the degradation of carbofuran (CBF) in water doped with synthetic dissolved natural organic matter (NOM) using the Fenton-like catalytic wet peroxide oxidation (CWPO) approach. Lastly, this work investigates the optimal conditions for maximizing pesticide degradation. Finally, Chapter VI corresponds to the general conclusions that can be obtained from this work.