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Supercritical CO2 extraction was applied on fenugreek (Trigonella foenum-graecum L., Fabaceae) seeds with the aim to define optimal process conditions to obtain the maximal extract yields content of steroidal sapogenins. Central composite rotatable design (CCRD) combined with response surface methodology (RSM) was applied to determine optimal process conditions defined by the influence and interaction of pressure, temperature and time of extraction through consumption of SC CO2. Optimization experiments revealed that the pressure of 24.73 MPa, the temperature of 38.°C and the consumption of SC CO2 of 19.24 g/gDM were the best process conditions enabling the maximal yield of extract and gain of the highest content of sapogenins. The optimal values of pressure and temperature defined SC CO2 density of 885.47 kg/m3, which provided the maximal yield of the extract with the highest content of steroidal sapogenins. The achieved yield of extract at these conditions was 0.073g/gDM, with 0.774 mg/gDM diosgenin, 0.477 mg/gDM protodioscin, 0.713 mg/gDM sarsapogenin and 0.205 mg/gDM oleanolic and ursolic acid with a significant quantity of 2.475 mg/gDM in the obtained extract. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III45017]

The manganese carbonate catalyst, prepared by precipitation method, was used in transesterification of soybean oil under subcritical condition of methanol. Catalyst samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS). The triacylglycerol (TAG) conversion and fatty acid methyl esters (FAME) yield were determined using high performance liquid chromatography (HPLC). The transesterification was realized for 1 h using various working conditions: 0-3 wt.% of catalyst (based on the mass of oil), the mole ratio of methanol to oil from 13:1 to 27:1 and temperature ranging from 393 to 473 K. A maximum TAG conversion of 98.1% could be obtained at the optimal reaction conditions: 2 wt.% of catalyst, methanol/oil mole ratio of 21:1, for 1 h in a batch reactor at 453 K. Kinetic analysis showed that the model based on mass transfer and chemical reaction at the catalyst surface confirmed the experimental data. Using that kinetic expression, the effect of continuous transesterification was proposed and verified by a 360-h long realized experiment in a laboratory packed-bed reactor (PBR). Slow deactivation of the catalyst was caused by leaching of Mn in both biodiesel and glycerol phases and by blocking the active sites of the catalyst with organic compounds.

In this study, mixed system containing manganese carbonate (MnCO3) and zinc glycerolate (ZnGly) was synthesized, and tested as solid catalyst for transesterification of soybean oil and biodiesel production. The samples of MnCO3/ZnGly before and after usage for transesterification process were characterized using different techniques: determination of basic strength, determination of specific surface area according to Brunauer-Emmett-Teller (BET), measuring the mass change using thermal gravimetric analysis (TGA), investigating the solid phase content and presence of different specific elements and groups by X-Ray diffraction (XRD), the Fourier transform infrared (FT-IR) spectroscopy, the scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS). The effects of different working parameters of transesterification were also investigated: temperature (438-458K), duration of transesterification (0-3.5h), methanol to oil molar ratio (12:1-36:1) and used amounts of catalyst (1-5 mass%). The reusability and stability of MnCO3/ZnGly were analyzed and obtained results showed that MnCO3/ZnGly exhibited a good activity with 100% TG conversion and 81.5% FAME yield with fresh catalyst, and can give 95-100% TG conversion and 62-78% FAME yield after 13 repeated use of same amount of catalyst without regeneration processes. Content of Mn and Zn in biodiesel and glycerol was analyzed by ICP-AAS after each reuse of catalyst.

Currently, the catalytic efficiency and reusability of the solid base catalysts cannot meet the demand of industrial biodiesel production under low temperature. The purpose of this study is to define the kinetics of heterogeneous transesterification process which might be used for the prediction of the biodiesel synthesis at high temperature and pressure. The focus in this study was paid to recently reported data obtained with different catalysts used for biodiesel synthesis in a batch reactor at high temperatures. It was shown that three kinetic models that include: a) irreversible first order reaction; b) reaction with changeable order; and c) resistances of mass transfer and chemical reaction at active sites of the catalyst could be applied for predicting the effect of high temperature of the transesterification. The apparent reaction rate constant of the irreversible first order reaction was determined, as well as the parameters of the other two, more complicated kinetic models. The best agreement was obtained with the more complicated models and the mean relative percent deviation between calculated and experimentally determined triacylglycerols conversion for these kinetic models is between 3 and 10%. [Projekat Ministarstva nauke Republike Srbije, br. 45001]

The kinetic model, which was originally developed for sunflower oil methanolysis catalyzed by CaO.ZnO, was examined for several other calcium-based catalysts like neat CaO, quicklime and Ca(OH)2. This model including triacylglycerols mass transfer- and chemically-controlled regimes demonstrated a good agreement with the experimental data in terms of a high coefficient of determination (0.971±0.022) and acceptable mean relative percentage deviation (±15.9%). Hence, this model is recommended for modeling the kinetics of sunflower oil methanolysis over calcium-based catalysts under widely ranging reaction conditions. [Projekat Ministarstva nauke Republike Srbije, br. III 45001]

Vegetable oils are mainly esters of fatty acids and glycerol, which can be converted to fatty acid methyl esters (FAME), also known as biodiesel, by the transesterification reaction with methanol. In order to attain environmental benignity, a large attention has been focused in the last decades on utilizing heterogeneous catalysts for biodiesel production instead the homogenously catalyzed transesterification of vegetable oil. The pure CaO or CaO mixed with some other metal oxide due to its low solubility in methanol, FAME and glycerol, low cost and availability is one of the most promising among the proposed heterogeneous catalysts. Solid catalysts which contain CaO usually fulfill a number of important requirements, such as high activity at mild temperature, marginal leaching of Ca cations, long life activity, reusability in transesterification of vegetable oil and easy recovery from the final products of transesterification (FAME and glycerol). This review is focused to the recent application of pure CaO or CaO in complex catalyst structure and their use as heterogeneous base catalysts for biodiesel synthesis and suitability for industrial application. [Projekat Ministarstva nauke Republike Srbije, br. 45001]

The goal of this study was to prepare CaO.ZnO catalyst which contain small amount of K2CO3 and analyze its activity for biodiesel synthesis. Catalyst was prepared using the following procedure: CaO and ZnO (molar ratio of 1:2), water and K2CO3 (in various amounts) were mechanochemically treated and after milling heated at 700 oC in air atmosphere for obtaining mixed CaO•ZnO/xK2CO3 oxides (x = 0, 1, 2 and 4; mole of K2CO3 per 10 mole of CaO). All the samples were characterized by X-ray diffraction (XRD), inductively coupled plasma (ICP), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), infrared spectroscopy (FTIR), scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDS), particle size laser diffraction (PSLD) distribution, solubility measurement of Ca, Zn and K ions in methanol as well as by determination of their alkalinity (Hammett indicator method). Prepared CaO•ZnO/xK2CO3 composite powders were tested as catalysts for methanolysis of sunflower oil at 70ºC using molar ratio of sunflower oil to methanol of 1:10 and with 2 mas% of catalyst based on oil weight. The presence of K2CO3 in prepared samples was found to increase the activity of catalyst, and that such effect is caused by homogeneous-heterogeneous catalysis of biodiesel synthesis. [Projekat Ministarstva nauke Republike Srbije, br. 45001]

The kinetics of heterogeneous methanolysis of sunflower oil was studied at 60°C using mechanochemically synthesized CaO∙ZnO as catalyst. Influence of agitation speed, catalyst amount and methanol to oil molar ratio on the rate of reaction was analyzed. The rate of the process depends on the two resistances - mass transfer of triglycerides to the catalyst surface and chemical reaction on the catalyst surface, which are defined as the values of the overall triglyceride volumetric mass transfer coefficient, kmt,TG, and the effective pseudo first-order reaction rate constant, k, respectively. These kinetic parameters actually determine the value of the apparent reaction rate constant, kapp, whose change with time is defined with the change of triglyceride (TG) conversion. The kinetic model was proposed and the model parameters determined. [Projekat Ministarstva nauke Republike Srbije, br. 45001]