Rebeca Sánchez-Vázquez

Low-grade oils and fats: Effect of several impurities on biodiesel production over sulfonic acid heterogeneous catalysts

Different lipidic wastes and low-grade oils and fats have been characterized and evaluated as feedstocks for the acid-catalyzed production of FAME. The characterization of these materials has revealed significant contents of free fatty acids, Na, K, Ca, Mg, P, unsaponifiable matter and humidity. Arenesulfonic acid-functionalized SBA-15 silica catalyst has provided yields to FAME close to 80% in the simultaneous esterification-transesterification of the different feedstocks, regardless of their nature and properties, using methanol under the following reaction conditions: 160 °C, 2 h, methanol to oil molar ratio of 30, 8 wt.% catalyst loading, and 2000 rpm stirring rate. Nevertheless, reutilization of the catalyst is compromised by high levels of impurities, especially because of deactivation by strong interaction of unsaponifiable matter with the catalytic sites. The conditioning of these materials by aqueous washing in the presence of cationic-exchange resin Amberlyst-15, followed by a drying step, resulted in a lower deactivation of the catalyst.

Zr-containing hybrid organic-inorganic mesoporous materials:hydrophobic acid catalysts for biodiesel production

Zirconium‐containing periodic mesoporous organosilicas (Zr‐PMOs) with varying framework organic content have been synthesized through a direct synthesis method. These materials display the excellent textural properties of the analogous inorganic solid acid Zr‐SBA‐15 material. However, the substitution of silica by organosilicon species provides a strong hydrophobic character. This substitution leads to meaningful differences in the environment surrounding the zirconium metal sites, leading the modification of the catalytic properties of these materials. Although lower metal incorporation is accomplished in the final materials, leading to a lower population of metal sites, hydrophobisation leads to an impressive beneficial effect on the intrinsic catalytic activity of the zirconium sites in biodiesel production by esterification/transesterification of free fatty acid ‐containing feedstock. Moreover, the catalytic activity of the highly hybridised materials is hardly affected in presence of large amounts of water, confirming their very good water‐tolerance. This makes Zr‐PMO materials interesting catalysts for biodiesel production from highly acidic water‐containing feedstock.

Isosorbide Production from Sorbitol over Heterogeneous Acid Catalysts: Screening and Kinetic Study

The catalytic performance of two types of heterogeneous acid catalysts—sulfonic acid-functionalized materials and aluminum containing zeolites,—in the dehydration of sorbitol to isosorbide, in solventless and autogenous pressure conditions, has been studied. Catalysts screening evidenced strong differences between sulfonic acid-based materials and acid zeolites in terms of catalytic performance. Whereas sulfonic materials, such as Amberlyst-70 and SBA-15-Pr-SO3H, showed a very high catalytic activity, zeolites with beta structure evidenced good catalytic performance together with minimized promotion of side reactions (production of non-desired sorbitans, humins, etc.). Kinetic studies performed at different temperatures, adjusting to a Langmuir–Hinshelwood type model, allowed correlating the physicochemical properties of the acid materials with their catalytic performance in sorbitol dehydration. Thus, the analysis of initial selectivity through kinetic constants comparison indicated that commercial beta zeolite with a Si/Al ratio of 19 is the most selective catalyst for the production of isosorbide, though following a slower kinetics than the sulfonic materials. Furthermore, an equivalent hierarchical beta zeolite has been synthesised and evaluated, resulting in a slight improvement of the catalytic performance, in terms of both yield and selectivity to isosorbide. This improvement is attributed to the superior textural properties.