Heterogeneous catalysis is in recent focus of research for biodiesel production from vegetable oils because of advantages such as easy separation and reuse of catalysts, although homogeneous catalysis is most commonly used method. The aim of this study was preparation of γ-Al 2 O 3 supported by modified sol-gel procedure, synthesis of the KI/Al 2 O 3 catalyst and testing its activity in the transesterification of sunflower oil with methanol. Influences of different process parameters on conversion of sunflower oil to methyl esters were examined. The gained results implicate that the potassium iodide incorporation into/ /onto the structure of γ-Al 2 O 3 significantly influences textural and structural properties of the catalyst. Additionally, the catalyst basic strength is increased and all together those properties are positively affecting the activity of the catalyst in the reaction of transesterification of sunflower oil with methanol. The impregnation of alumina with potassium iodide resulted in the additional formation of basic catalytically active sites. The surface properties of the catalyst have an essential impact on its catalytic performance. Under relatively mild process conditions and relatively short reaction time, the usage of the KI/Al 2 O 3 catalyst resulted in very high conversion to fatty acids methyl esters (i.e., 99.99%).

The influence of the physicochemical properties of a series of CaO catalysts activated at different temperatures on the biodiesel production was investigated. These catalysts show dissimilar yields in the transesterification of triglycerides with methanol. We have found significant relationships between structural properties (the type of the pore system, the typical CaO crystal phase and the sizes of crystallites (up to 25 nm), the minimal weight percentage of CaO phase, the total surface basicity and potential existence of two types of basic active sites) of CaO prepared and activated by means of thermal treatment at highest temperature and catalytic efficiency. Benefits of this catalyst are short contact time, standard operating temperature and atmospheric conditions, relatively low molar ratios and small catalyst loading. These all together resulted in a very high biodiesel yield of high purity. The properties of different biodiesel (obtained with the use of the prepared CaO catalyst) blends with different diesel and biodiesel ratios indicate that the higher the fraction of biodiesel fuel the better the achieved fuel properties according to the EU standards. A significant reduction of CO 2 and CO emissions and only a negligible NO x increase occurred when blends with an increased biodiesel portion was used. The use of biodiesel derived blends, and the eventual complete replacement of fossil fuels with biodiesel as a renewable, alternative fuel for diesel engines, would greatly contribute to the reduction of greenhouse gas emissions.

In this contribution, the preparation of hierarchically structured ETS-10-based catalysts exhibiting notably higher activity in the conversion of triolein with methanol compared to microporous titanosilicate is presented. Triolein, together with its unsaturated analog trilinolein, represent the most prevalent triglycerides in oils. The introduction of mesopores by post-synthetic treatment with hydrogen peroxide and a subsequent calcination step results in the generation of an additional active surface with Brønsted basic sites becoming accessible for triolein and enhancing the rate of transesterification. The resulting catalyst exhibits a comparable triolein conversion (≈73%) after 4 h of reaction to CaO (≈76%), which is reportedly known to be highly active in the transesterification of triglycerides. In addition, while CaO showed a maximum conversion of 83% after 24 h, the ETS-10-based catalyst reached 100% after 8 h, revealing its higher stability compared to CaO. The following characteristics of the catalysts were experimentally addressed – crystal structure (X-ray diffraction, transmission electron microscopy), crystal shape and size (scanning electron microscopy, laser diffraction), textural properties (N2 sorption, Hg porosimetry), presence of hydroxyl groups and active sites (temperature-programmed desorption of NH3 and CO2, 29Si magic angle spinning nuclear magnetic resonance (NMR)), mesopore accessibility and diffusion coefficient of adsorbed triolein (pulsed field gradient NMR), pore interconnectivity (variable temperature and exchange spectroscopy experiments using hyperpolarized 129Xe NMR) and oxidation state of Ti atoms (electron paramagnetic resonance). The obtained results enabled the detailed understanding of the impact of the post-synthetic treatment applied to the ETS-10 titanosilicate with respect to the catalytic activity in the heterogeneously catalyzed transesterification of triglycerides.

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