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The MnCO3/Na silicate (Mn/Na/Si mole ratio of 4.65:1:1.65) catalyst in the form of solid particles with diameter of 0.99–1.99 mm was used as a catalyst for transesterification of soybean oil in batch autoclave at different conditions: 388–468 K, methanol-to-oil mole ratio 12:1–30:1, catalyst amount based on the mass of oil 0–12.5 %. The complete triacylglycerols (TAG) conversion and high yield of fatty acid methyl ester (FAME) was obtained after 1 h at 458 K, methanol-to-oil mole ratio 30:1 and 10 % of catalyst. Kinetics of transesterification process was analyzed by three models: the simple first order irreversible reaction rate, as well as two more complex models recently reported in literature. The catalyst reuse in transesterification process was tested and the average values of 99.0 % of TAG conversion and 97.5 % of FAME yield were obtained after 8 consecutive runs. Different techniques were used to characterize fresh and used MnCO3/Na silicate catalyst. The determined amounts of leached Na (

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 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]

The problem of sulfur compounds conversion, particularly heterocyclic compounds, from the middle fraction of crude oil (light gas oil) was analyzed and will be published in several articles in the Chemical Industry Journal. Published data in the literature, covering the conversion of tiophene, benzothiophene and dibenzothiophene are presented in the first paper of this series with the goal of comparing and critically analyzing their usage for reactor calculation.

The performed investigations were directed toward the analysis of the performance and activity of the fresh and regenerated Cyanamid HDS 20C catalyst in a laboratory batch reactor (2 dm3) for the HDS of the diesel fraction (light gas oil, LGO). Testing of the regenerated catalyst was performed with light gas oil (LGO) of different characteristics. The determined values of the reaction rate constant were compared to some published data in the literature for the HDS of specific sulfur compounds as well as the values of the activation energy. The rates of deactivation of the fresh and regenerated catalyst actually existed compared to some other results recently published in the literature. However, such an observed differences were not sufficient to derive a relation which could be used for the determination of the rate of catalyst deactivation.

The kinetic model originally developed for quicklime-catalyzed methanolysis of sunflower oil was tested for another three calcium-based catalysts, namely, neat CaO, Ca(OH)2, and CaO·ZnO. This model includes the changing reaction mechanism and the triacylglycerol (TAG) mass transfer. The applicability and generalization capability of this model for heterogeneous methanolysis reaction catalyzed by calcium-based catalysts was evaluated. As indicated by the high coefficient of determination and the relatively small mean relative percentage deviation, the model was a reliable predictor of the time variation of TAG conversion degree in the sunflower oil methanolysis over all four calcium-based catalysts within the ranges of the reaction conditions applied. This model is recommended in general for describing the kinetics of sunflower oil methanolysis over calcium-based catalysts. [ABSTRACT FROM AUTHOR]

A heterogeneous catalyst, ZnO supported on alumina/silica, was synthesized by the sol-gel method. The prepared catalysts were employed for methanolysis of sunflower oil. Effects of various supports as well as calcination temperature were evaluated following the kinetics of the reaction. Simple first-order irreversible and reversible reaction models were applied to determine the reaction rate constant. The results proved that under optimized conditions the catalyst exhibited good activity in the methanolysis of sunflower oil and the kinetics of the methanolysis process could be expressed by the first-order reversible reaction model. For other catalysts with lower activity, the first-order irreversible reaction model could be successfully applied to describe well the process kinetics. [ABSTRACT FROM AUTHOR]

Abstract: Kinetics and selectivity of supercritical carbon dioxide (SC CO2) extraction of Helichrysum italicum flowers were analyzed at pressures in the range of 10–20MPa and temperatures of 40°C and 60°C (density of SC CO2 from 290 to 841kg/m3) and also at 10MPa and 40°C using flowers with different moisture contents (10.5% and 28.4%). Increased moisture content of H. italicum flowers resulted in enchased solubility of solute enabling decrease of SC CO2 consumption necessary for achieving desired extraction yield. The most abundant compounds in the supercritical extracts are sesquiterpenes and waxes while monoterpenes and sesquiterpenes are the main constituents of essential oil obtained by hydrodistillation. The optimal set of working parameters with respect to extraction yield, SC CO2 consumption and chemical composition of extract were defined related to moisture content of raw material and SC CO2 density. [Copyright &y& Elsevier]

The MnCO3/Na silicate (Mn/Na/Si mole ratio of 4.65:1:1.65) catalyst in the form of solid particles with diameter of 0.99-1.99 mm was used as a catalyst for transesterification of soybean oil in batch autoclave at different conditions: 388-468 K, methanol-to-oil mole ratio 12:1-30:1, catalyst amount based on the mass of oil 0-12.5 %. The complete triacylglycerols (TAG) conversion and high yield of fatty acid methyl ester (FAME) was obtained after 1 h at 458 K, methanol-to-oil mole ratio 30:1 and 10 % of catalyst. Kinetics of transesterification process was analyzed by three models: the simple first order irreversible reaction rate, as well as two more complex models recently reported in literature. The catalyst reuse in transesterification process was tested and the average values of 99.0 % of TAG conversion and 97.5 % of FAME yield were obtained after 8 consecutive runs. Different techniques were used to characterize fresh and used MnCO3/Na silicate catalyst. The determined amounts of leached Na (<500 ppm) and Mn (<20 ppm) in biodiesel phase implied that the homogeneous-heterogeneous process influences the catalyst selectivity, whereby leached Na enables the complete transformation of TAG to FAME. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Highlights: [•] Mechanochemical synthesis of CaO·ZnO catalyst and its testing in methanolysis of virgin sunflower and used vegetable oil. [•] Determination of heterogeneous methanolysis kinetics and kinetic parameters evaluation. [•] Definition of the overall volumetric mass transfer coefficient as a function of triglycerides conversion. [•] Proposal of the kinetic model to describe the heterogeneous methanolysis kinetics. [ABSTRACT FROM AUTHOR]

Abstract: A difficulty of biodiesel synthesis based on alkaline catalysts obviously exists if free fatty acids (FFAs) content in vegetable oil is above 0.5wt.%. In this study, the ferric sulfate supported on silica (Fe2(SO4)3/SiO2) was synthesized, activated (at different temperature: 120–600°C) and tested for heterogeneous esterification of FFA (oleic acid) present in sunflower oil (5wt.%). The catalyst samples were characterized by BET, TG/DTG, XRD and FTIR analyses. Obtained results showed that catalyst activated at 500°C for 2h in air atmosphere gave the maximal conversion of oleic acid (∼97%). Repeated use of catalyst without additional catalyst treatment or re-activation indicated that catalyst posses desired stability and activity. A pseudo-homogeneous kinetic model was proposed with good agreement between calculated and experimental data. [Copyright &y& Elsevier]

Abstract: The goal of present work was to investigate and explain kinetics and mass transfer phenomena occurring during the SFE from the mixture of two plants with different initial composition. The extractions from pure clove, oregano and thyme as well as from clove/oregano (C/O) and clove/thyme (C/T) mixtures with various initial compositions of plant material were carried out using supercritical CO2 at 10MPa and 40°C. The results indicated that presence of light compounds in supercritical CO2 originated from the oregano leaves or thyme at the beginning of extraction process increases the extraction rate of compounds from clove bud. Only small added amounts of oregano or thyme to clove bud (C/O – 90:10%, w/w; or C/T – 84:16%, w/w) in the starting plant mixture had the same effect resulted in the similar and the highest increase of the extraction rate and had negligible influence on total extraction yield compared to extract isolated from pure clove. Different mathematical models were used for simulation of experimental data which showed that the highest increase of the solubility of extractable compounds in supercritical CO2 as well as the highest mass transfer rate in the solid phase during extractions existed during extraction from C/O (90:10, w/w) and C/T (84:16, w/w) mixtures. Decrease of SC CO2 consumption or shorter time of extraction necessary for achieving desired extract yield in the case of SFE of the clove buds could be important for industrial-scale application. [Copyright &y& Elsevier]

Abstract: The kinetics of Ca(OH)2-catalyzed methanolysis of sunflower oil was studied at a moderate temperature (60°C), a methanol-to-oil molar ratio (6:1) and different catalyst amounts (from 1% to 10% based on oil weight). The methanolysis process was shown to involve the initial triglyceride (TG) mass transfer controlled region, followed by the chemical reaction controlled region in the latter period. The TG mass transfer limitation was caused by the low available active specific catalyst surface due to the high adsorbed methanol concentration. Both the TG mass transfer and chemical reaction rates increased with increasing the catalyst amount. [Copyright &y& Elsevier]

Abstract: The supercritical carbon dioxide (SFE) extraction of Dalmatian sage (Salvia officinalis L.) was investigated and compared to extraction performed by Soxhlet ethanol–water (70:30) mixture extraction (SE) and hydrodistillation (HD). The supercritical extraction allowed isolation of wide spectrum of phytochemicals, while other applied methods were limited to either volatiles (HD) or high molecular compounds isolation (SE). The kinetics of the supercritical extraction and fractionation within the pressure range of 10–30MPa at 50°C were also analyzed as well as the chemical compositions of total extract and partial or differential fractions isolated at different CO2 consumption. Volatile fraction could be isolated at low pressure and low CO2 consumption, whereby the pressures between 10 and 15MPa followed by increased CO2 consumption were favourable for obtaining desired selectivity of diterpenes which contain compounds with expressed antioxidative characteristics. [Copyright &y& Elsevier]

Abstract: The methanolysis of sunflower oil was studied in the presence of CaO previously calcined at various temperatures and the optimal temperature for CaO calcination was determined. The sigmoidal process kinetics was explained by the initial triglyceride (TG) mass transfer controlled region, followed by the chemical reaction controlled region in the latter reaction period. The TG mass transfer limitation was due to the small available active specific catalyst surface, which was mainly covered by adsorbed molecules of methanol. In the later phase, the adsorbed methanol concentration decreased, causing the increase of both the available active specific catalyst surface and the TG mass transfer rate, and the chemical reaction rate become smaller than the TG mass transfer rate. [Copyright &y& Elsevier]

Abstract: The kinetics of the sunflower oil methanolysis process was studied at lower temperatures (10–30°C). The sigmoidal kinetics of the process was explained by the mass transfer controlled region in the initial heterogenous regime, followed by the chemical reaction controlled region in the pseudo-homogenous regime. A simple kinetic model, which did not require complex computation of the kinetic constants, was used for simulation of the TG conversion and the FAME formation in the latter regime: the fast irreversible second-order reaction was followed by the slow reversible second-order reaction close to the completion of the methanolysis reaction. The mass transfer was related to the drop size of the dispersed (methanol) phase, which reduced rapidly with the progress of the methanolysis reaction. This was attributed to the formation of the emulsifying agents stabilizing the emulsion of methanol drops into the oil. [Copyright &y& Elsevier]