Comparison of Box-Behnken, Face Central Composite and Full Factorial Designs in Optimization of Hempseed Oil Extraction by n-Hexane: a Case Study

Statistical multivariate methods like Box-Behnken, face central composite and full factorial designs (BBD, FCCD and FFD, respectively) in combination with the response surface methodology (RSM) were compared when applied in modeling and optimization of the hempseed oil (HSO) extraction by n-hexane. The effects of solvent-to-seed ratio, operation temperature and extraction time on HSO yield were investigated at the solvent-to-seed ratio of 3:1, 6.5:1 or 10:1 mL/g, the extraction temperature of 20, 45 or 70 °C and the extraction time of 5, 10 or 15 min. All three methods were efficient in the statistical modeling and optimization of the influential process variables and led to almost the same optimal process conditions and predicted HSO yield. Having better statistical performances and being economically advantageous over the FFD with repetition, the BBD or FCCD combined with the RSM is recommended for the optimization of liquid-solid extraction processes

Triethanolamine as an efficient cosolvent for biodiesel production by cao-catalyzed sunflower oil ethanolysis: An optimization study

Triethanolamine was applied as an efficient „green“ cosolvent for biodiesel production by CaO-catalyzed ethanolysis of sunflower oil. The reaction was conducted in a batch stirred reactor and optimized with respect to the reaction temperature (61.6-78.4 °C), the ethanol-to-oil molar ratio (7:1-17:1) and the cosolvent loading (3-36 % of the oil weight) by using a rotatable central composite design (RCCD) combined with the response surface methodology (RSM). The optimal reaction conditions were found to be: the ethanol-to-oil molar ratio of 9:1, the reaction temperature of 75 °C and the cosolvent loading of 30 % to oil weight, which resulted in the predicted and actual fatty acid ethyl ester (FAEE) contents of 98.8 % and 97.9±1.3 %, respectively, achieved within only 20 min of the reaction. Also, high FAEE contents were obtained with expired sunflower oil, hempseed oil and waste lard. X-ray diffraction analysis (XRD) was used to understand the changes in the CaO phase. The CaO catalyst can be used without any treatment in two consecutive cycles. Due to the calcium leaching into the product, an additional purification stage must be included in the overall process.Supplementary material: [http://cherry.chem.bg.ac.rs/handle/123456789/3798

Supplementary data for article: Đokić-Stojanović, D. R.; Todorović, Z. B.; Troter, D. Z.; Stamenković, O. S.; Veselinović, L. M.; Zdujić, M. V.; Manojlović, D. D.; Veljković, V. B. Triethanolamine as an Efficient Cosolvent for Biodiesel Production by Cao-Catalyzed Sunflower Oil Ethanolysis: An Optimization Study. Hemijska Industrija 2019, 73 (6), 351–362. https://doi.org/10.2298/HEMIND190822033D

Supplementary material for: [https://doi.org/10.2298/HEMIND190822033D]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/3797

Heterogeno katalizovana etanoliza suncokretovog ulja u prisustvu polietilen glikola, etil acetata i dietil etra kao kosolvenata

A heterogeneous reaction process using propylene glycol (PEG), ethyl acetate and diethyl ether as cosolvents for the transesterification of sunflower oil with ethanol in the presence of calcium oxide as a catalyst has been developed. Significant results were obtained with propylene glycol as a cosolvent. Under determined reaction conditions (CaO concentration, based on the oil weight 1.3736 mol∙dm-3; temperature 70°C; and ethanol-to-oil molar ratio 12:1), the conversion of sunflower oil to fatty acid ethyl esters (FAEE) exceeded 98% after 120 min, which was 2 times faster than transesterification of sunflower oil without a cosolvent. After initially enhanced ethanolysis, after 180 min ethyl acetate and diethyl ether negatively influenced the reaction rate and the FAEE yield.U radu je opisana heterogena transesterifikacija suncokretovog ulja sa etanolom i kalcijum oksidom kao katalizatorom u prisustvu polietilen glikola (PEG), etil acetata i dietil etra kao kosolvenata. Najpovoljniji rezultati su dobijeni sa polietilen glikolom kao kosolventom gde je, pod određenim reakcionim uslovima (koncentracija CaO, računata u odnosu na masu ulja 1.3736 mol∙dm-3, temperatura 70°C i molarni odnos etanol:ulje 12:1), konverzija suncokretovog ulja u etil estre masnih kiselina (FAEE) dostigla vrednost od 98% nakon 120 minuta, što je 2 puta brže od transesterifikacije suncokretovog ulja bez prisustva kosolventa. Etil acetat i dietil etar poboljšavaju reakciju etanolize na početku, ali, kako reakcija napreduje, posle 180 minuta, njihovo prisustvo u reakcionoj smeši negativno utiče na brzinu reakcije i prinos etil estrara masnih kiselina (FAEE)

Influence of various cosolvents on the calcium oxide-catalyzed ethanolysis of sunflower oil

Ten organic solvents (triethanolamine, diethanolamine, ethylene glycol, methyl ethyl ketone, n-hexane, triethylamine, ethylene glycol dimethyl ether, glycerol, tetrahydrofuran and dioxane) were applied as cosolvents in the CaO-catalyzed ethanolysis of sunflower oil performed in a batch stirred reactor under the following reaction conditions: temperature 70 °C, ethanol-to-oil mole ratio 12:1, initial catalyst concentration 1.374 mol·L -1 and amount of cosolvent 20 % based on the oil amount. The main goals were to assess the effect of the used cosolvents on the synthesis of fatty acid ethyl esters (FAEE) and to select the most efficient one with respect to the final FAEE content, reaction duration and safety profile. In the absence of any cosolvent, the reaction was rather slow, providing a FAEE content of only 89.7±1.7 % after 4 h. Of the tested cosolvents, diethanolamine, triethanolamine and ethylene glycol significantly accelerated the ethanolysis reaction, whereby the last two provided a final FAEE content of 93.1±2.1 and 94.1±1.5 %, respectively, within 0.5 h. However, because of its safety profile, triethanolamine was selected as the best cosolvent for the ethanolysis of sunflower oil catalyzed by calcined CaO

[Kontinualni postupci dobijanja biodizela]

Continuous biodiesel production on laboratory and industrial scale was analyzed, with focus on their advantages and disadvantages. Attention was paid to specific characteristics of industrial processes in order to point out the advanced technologies. The well-known base-catalyzed continuous biodiesel production processes are related to problems caused by the immiscibility of the reactants (alcohol and oil), application of relatively high operating temperature (usually the boiling temperature of alcohol or one near it) and obtained yield of methyl ester yields lower than desired. One way to overcome these problems is to employ special reactor design favoring the emulsion process and increasing the overall rate of biodiesel production process, even at room temperature and atmospheric pressure. The second way is to apply heterogeneous catalysts in continuous processes, which will probably be the optimal approach to economically justified and environmentally friendly biodiesel production

Утицај концентрације раствора и степена полимеризације карбоксиметилцелулозе на садржај гаса у реактору са вибрационом мешалицом

Gas holdup was investigated in a gas-liquid and gas-liquid-solid reciprocating plate column (RPC) under various operation conditions. Aqueous carboxymethylcellulose (sodium salt, CMC) solutions were used as the liquid phase, the solid phase was spheres placed into interplate spaces, and the gas plase was air. The gas holdup in the RPC was influenced by: the vibration intensity, i.e., the power consumption, the superficial gas velocity, the solids content and the rheological properties of the liquid phase. The gas holdup increased with increasing vibration intensity and superficial gas velocity in both the two- and three-phase system. With increasing concentration of the CMC PP 50 solution (Newtonian fluid), the gas holdup decreased, because the coalescence of the bubbles was favored by the higher liquid viscosity. In the case of the CMC PP 200 solutions (non-Newtonian liquids), the gas holdup depends on the combined influence of the rheological properties of the liquid phase, the vibration intensity and the superficial gas velocity. The gas holdup in the three-phase systems was greater than that in the two-phase ones under the same operating conditions. Increasing the solids content has little influence on the gas holdup. The gas holdup was correlated with the power consumption (either the time-averaged or total power consuption) and the superficial gas velocity

Purification technologies for crude biodiesel obtained by alkali-catalyzed transesterification

For commercial application, the ester product of alkali-catalyzed transesterification of vegetable oil or animal fats should be refined after glycerol separation by settling to fulfill the biodiesel standard specifications. This crude biodiesel, after neutralization and methanol removal, should be further cleaned by either one of the following methods: wet washing, dry washing, membrane extraction or using ion liquids. This paper presents a review on the traditional (wet and dry washing) and novel (membrane separation technology and usage of ion liquids) methods of crude biodiesel purification. It also provides a comparison of crude biodiesel purification methods. Each method has its advantages and disadvantages, which should be carefully analyzed when choosing the proper one for refining crude biodiesel