Significance of the structural properties of CaO catalyst in the production of biodiesel: An effect on the reduction of greenhouse gases emission

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 CO2 and CO emissions and only a negligible NOx 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 gases emissions.</jats:p

Influence of alumina addition on structural and catalytic properties of sulphated zirconia in isomerization of n-hexane

New binary catalytic systems based on sulphated zirconia-alumina were synthesized by controlled hydrolysis of alkoxides using relative molar ratios of constituents 1:1, 1:2 and 1:3 in favour of zirconia. The obtained differences in the final catalytic material?s properties may be related to organic precursor memory effect, the applied calcinations temperatures and used alumina contents. The addition of alumina to zirconia affected the structural and surface properties stabilizing bare zirconia by means of slower phase transformation of tetragonal zirconia crystal phase into monoclinic one, further resulting in smaller crystallites sizes and higher surface density of acidic function (sulphates). The best alumina impact on physico-chemical properties was achieved when the highest amount of alumina (e.g. 50%) and lower calcination temperature (500?C) were used, causing relatively high steady-state activity in isomerization of n-hexane at reaction temperature 250 ?C. On the other hand, higher calcination temperature (600 ?C) played a role in the genesis of greater sulphate density. Catalytic activity and selectivity are expressed as a complex synergistic function of relative density of acid sites together with positive status of other optimized physico-chemical properties of the catalytic material (by activation and calcination temperatures).</jats:p

Variations in the composition of essential oils of selected Artemisia species as a function of soil type

Five Artemisia species (seven A. alba Turra samples and twelve samples of each four remaining species: A. absinthium L., A. annua L., A. vulgaris L. and A. scoparia Waldst. &amp; Kit.) from Serbia were studied from the aspect of essential oil chemical composition, and potential correlations between essential oil composition with soil type determined using World Reference Base for Soil Resources (WRB). A great variety in essential oil composition was observed for A. alba, A. absinthium and A. vulgaris samples, while in the case of A. annua, as well as A. scoparia, the composition of the examined essential oils was more uniform. Principal component analysis (PCA) and agglomerative hierarchical clustering (AHC) showed that there is no significant effect of soil type on the Artemisia essential oil composition while Mantel test showed that there is a correlation between samples within A. vulgaris, as well as A. scoparia and the geographical distances of the localities from which these samples were collected.</jats:p

Synthesis of biodiesel from sunflower oil over potassium loaded alumina as heterogeneous catalyst: The effect of process parameters

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-Al2O3 support by modified sol-gel procedure, synthesis of the KI/Al2O3 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-Al2O3 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/Al2O3 catalyst resulted in very high conversion to fatty acids methyl esters (i.e. 99.99 %). [Projekat Ministarstva nauke Republike Srbije, br. 172061 i br. TR 34008

Synthesis of highly active ETS-10-based titanosilicate for heterogeneously catalyzed transesterification of triglycerides

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.</jats:p

Active Heterogeneous CaO Catalyst Synthesis from Anadara granosa

Heterogeneous catalysts are often used at large to produce biodiesel from non-edible vegetable crude oils such as Jatropha curcas oil (JCO). In this study, an active heterogeneous CaO catalyst was synthesized from a tropical biodiversity seashells Anadara granosa (A.granosa). The catalytic efficiency of A.granosa CaO was investigated in transesterification of JCO as biodiesel. The A.granosa CaO catalyst was synthesized using ‘Calcination – hydration – dehydration’ protocol. The spectral characterization of the catalyst were investigated by employing FT-IR, SEM, BET and BJH spectrographic techniques. The experimental design was executed with four reaction parameters that include catalyst concentration (CC), methanol ratio (MR), transesterification time (TT) and reaction temperature (RT). The JCO transesterification reactions as well as impact of reaction parameters on the Jatropha biodiesel yield (JBY) were analyzed. The sufficiency of the experimental results conformed through sequential validation tests, as a result, an average of 96.2% JMY was noted at optimal parametric conditions, CC of 3wt. %, TT of 120 min, MR of 5 mol. and RT of 60ºC at a constant agitation speed of 300rpm. An average JMY of 87.6% was resulted from the A.granosa CaO catalyst during their recycling and reuse studies up to third reuse cycle