Ethanolysis of waste cottonseed oil over lithium impregnated calcium oxide: Kinetics and reusability studies

A series of Li/CaO catalysts has been prepared by impregnating 0.5–5.0 wt% Li in CaO by wet chemical method. Prepared Li/CaO catalysts have been characterized by powder X-ray diffraction, scanning electron and transmission electron microscopy and Brunauer–Emmett–Teller (BET) surface area studies, in order to establish the structure and surface morphology of the catalyst. Hammett indicator test study was performed to determine the basic strength of the Li/CaO catalysts. The prepared Li/CaO catalysts have been employed as a heterogeneous catalyst for the transesterification of waste cottonseed oil (having 2.8 wt% free fatty acid contents) with ethanol. Under optimal reaction conditions viz., ethanol/oil molar ratio of 12:1, catalyst to oil weight fraction of 5% and 65 °C reaction temperature, 98% fatty acid ethyl ester yield was obtained in 2.5 h of reaction duration. Under the optimized reaction conditions, the pseudo first order constant and Arrhenius activation energy were found to be 0.03 min⁻¹ and 70.0 kJ mol⁻¹, respectively. Further Li/CaO catalyst was also found to be effective for the ethanolysis and methanolysis of vegetable oils having up to 3.4 wt% free fatty acids. The use of 3-Li/CaO catalyst is advantageous considering that it not only utilizes waste cottonseed oil as a feedstock, but also renewable and nontoxic alcohol, ethanol, for the biodiesel production.     

Biodiesel production from olive–pomace oil of steam-treated alperujo

Recently interest has been revived in the use of plant-derived waste oils as renewable replacements for fossil diesel fuel. Olive–pomace oil (OPO) extracted from alperujo (by-product of processed olives for olive oil extraction), and produced it in considerable quantities throughout the Mediterranean countries, can be used for biodiesel production. A steam treatment of alperujo is being implemented in OPO extraction industry. This steam treatment improves the solid–liquid separation by centrifugation and facilitates the drying for further extraction of OPO. It has been verified that the steam treatment of this by-product also increases the concentration of OPO in the resulting treated solid, a key factor from an economic point of view. In the present work, crude OPO from steam-treated alperujo was found to be good source for producing biodiesel. Oil enrichment, acidity, biodiesel yield and fatty acid methyl ester composition were evaluated and compared with the results of the untreated samples. Yields and some general physicochemical properties of the quality of biodiesel were also compared to those obtained with other oils commonly used in biodiesel production. As for biodiesel yield no differences were observed. A transesterification process which included two steps was used (acid esterification followed by alkali transesterification). The maximum biodiesel yield was obtained using molar ratio methanol/triglycerides 6:1 in presence of sodium hydroxide at a concentration of 1% (w/w), reaction temperature 60 °C and reaction time 80 min. Under these conditions the process gave yields of about 95%, of the same order as other feedstock using similar production conditions.     

Mass transfer simulation of biodiesel synthesis in microreactors

A coupled nonlinear mathematical model for the mass transfer of the species involved in the transesterification reaction between soybean oil and methanol in a parallel plates geometry microreactor is presented. The set of partial differential equations that governs the concentration profile of these species were obtained from the general mass balance equation for the case of isothermal flow and steady state with constant physical properties. The velocity profile was obtained from the Navier-Stokes equations assuming fully developed stratified laminar flow for two immiscible Newtonian fluids, with a plane interface between them, based on experimental observation of this flow pattern. The second order kinetic equations for the species were developed assuming homogeneous and reversible chemical reactions and these equations were written as source terms in the main equations. The mathematical model was solved using the hybrid method known as Generalized Integral Transform Technique (GITT). The simulation results were critically compared with those obtained by using the COMSOL multiphysics platform, showing a good agreement between the hybrid and fully numerical simulations. The effects of governing parameters such as residence time, temperature and microreactor dimensions were investigated. It was observed that higher triglycerides conversion rates occurred at higher temperatures and residence times and lower microreactor depths.     

Biodiesel Production Using a Carbon Solid Acid Catalyst Derived from β‐Cyclodextrin

A novel carbon solid acid catalyst was prepared by incomplete hydrothermal carbonization of β‐cyclodextrin into small polycyclic aromatic carbon sheets, followed by the introduction of –SO₃H groups via sulfonation with sulfuric acid. The physical and chemical properties of the catalyst were characterized in detail. The catalyst simultaneously catalyzed esterification and transesterification reactions to produce biodiesel from high free fatty acid (FFA) containing oils (55.2 %). For the as‐prepared catalyst, 90.82 % of the oleic acid was esterified after 8 h, while the total transesterification yield of high FFA containing oils reached 79.98 % after 12 h. By contrast, the obtained catalyst showed comparable activity to biomass (such as sugar, starch, etc.)‐based carbon solid acid catalyst while Amberlyst‐15 resulted in significantly lower levels of conversion, demonstrating its relatively high catalytic activity for simultaneous esterification and transesterification. Moreover, as the catalyst can be regenerated, it has the potential for use in biodiesel production from oils with a high FFA content.     

Lipase-Catalyzed Synthesis of Fatty Acid Pyridylcarbinol Ester for the Analysis of Seed Lipids

Numerous derivatives of fatty acids (FA), including esters of methanol/3‐hydroxymethylpyridine or dimethyloxazoline, are used for the analysis of FAs in biological specimens. Picolinyl derivatives are frequently prepared for structural determination by gas chromatography–mass spectrometry (GC‐MS) since they provide characteristic fragments. The ester can be prepared by chemical methods‐multistep methodologies or basic transesterification. Microbial lipases catalyze a number of transesterification reactions, and their catalytic activities are often stable at extreme conditions. Although these characteristic features may be useful in the application of typical FA structure analysis by picolinyl ester, detailed studies have not been reported. To address the problems, a simple and quantitative methodology for the synthesis of picolinyl esters from lipids has been developed. It involves the transesterification with Novozym 435 (Novozymes Biopharma US Inc., Franklinton, USA), resin‐immobilized lipase from Candida antartica in toluene. Mild reaction conditions allow for complete derivatization of perilla seed oil in 30 min at 50 °C. The procedure was further studied with various TAGs and fatty wax from 17 plants. The optimized procedure was as follows; 1 mg lipid and 20 mg catalyst in 2 mL toluene at 50 °C for 1 h. Quantitative analysis of marker FAs was performed with the proposed method. The results coincided well with those from potassium t‐butoxide‐catalyzed reaction. The optimized method, however, was not applicable for the determination of some epoxy FAs, fatty wax, and parinaric acid.     

Biodiesel Production Using Calcined Waste Filter Press Cake from a Sugar Manufacturing Facility as a Highly Economic Catalyst

For the first time, a low cost, high performance and environmentally friendly heterogeneous catalyst derived from waste filter press cake (FPC) from a sugar manufacturing facility was used for the production of biodiesel. This industrial waste was calcined in air at 900 °C for 2 h to convert it into an active CaO‐based catalyst (FPC‐HT). In addition, the calcium oxide nanoparticles (FPC‐NAC) were synthesized by surfactant‐hydration treatment of FPC‐HT. The synthesized catalysts were characterized by XRD, FTIR, SEM, TEM and BET analysis. These calcium oxide catalysts were used for a transesterification reaction between canola oil and methanol to produce biodiesel. The results show that the FPC‐NAC has higher catalytic activity than FPC‐HT under optimized reaction conditions. Therefore, this economic catalyst is able to catalyze the transesterification of canola oil to its methyl esters in 1.5 h with yields above 96 %.     

Production and Emulsifying Effect of Polyglycerol and Fatty Acid Esters with Varying Degrees of Esterification

Esters with acyl groups can be formed by the esterification of polyglycerol. The purpose of the present study was to produce fatty acid esters [hexanoic (caproic), octanoic (caprylic), decanoic (capric), dodecanoic (lauric), tetradecanoic (myristic), hexadecanoic (palmitic), octadecanoic (stearic)] and polyglycerol (average number‐of degrees of polymerization of 5) with varying degrees of esterification and to examine their emulsifying properties. A number of fundamental catalysts of polyglycerol acylation reactions by methyl esters of carboxylic acid were studied, and sodium methoxide was found to be the best choice. The temperature rate of transesterification increased from 180 to 220 °C with the fatty acid chain alkyl residue. Synthesized mono‐, di‐, tri‐, tetra‐, and heptaesters of various fatty acids and polyglycerol provided the highest hydroxyl values from 15 to 815 mg KOH g^?1 and saponification values from 82 to 321 mg KOH g^?1. The emulsifying properties were assessed for all polyglycerol and fatty acid esters, with results showing maximum emulsifying effect for tri‐ and tetraesters of capric, lauric, and caprylic acids. Regardless of the hydrophilic–lipophilic balance value (HLB) of polyglycerol esters and carboxylic acid, a 4:1 ratio of sunflower oil to water formed a water‐in‐oil type emulsion. When mixing oil and water in a 1:1 ratio, mono‐ and diesters of polyglycerol formed an oil‐in‐water type emulsion, heptaesters formed a water‐in‐oil type emulsion, and tri‐ and tetraesters formed both of types of emulsions, depending on the length of the acid hydrocarbon radicals.     

Acid Value,Polar Compounds and Polymers as Determinants of the Efficient Conversion of Waste Frying Oils to Biodiesel

The cost of starting materials for the production of biodiesel is typically 75 % of the final retail price. Oils previously used for frying, waste frying oils (WFO), are a very suitable resource. Repetitive use of oil for frying foods involves high temperature, moisture and aeration for extended periods. The most important deterioration processes triggered by these conditions are hydrolysis and oxidation. In this study, 24 WFO samples of different origins were analyzed and classified as potential starting materials for biodiesel production using three quality parameters representing the main factors that affect the conversion of WFO. These parameters were: acid value, content of polar compounds and content of polymers, which varied in the ranges from 0.2 to 7.6, 14.9 to 43.2 and 0.9 to 15.2 %, respectively. Ester content obtained using conventional transesterification (TE) for WFO conversion decreased with increased levels of WFO deterioration determined by any of the three parameters noted above. TE products obtained had ester content between 81.4 and 95.7 %. Total ester content of a WFO sample with relatively low %AV could be increased to 96.5 % using a two-stage base catalysis TE. Finally, conversion of WFO samples resulted in ester contents of 89.0 and 91.3 %, respectively, when transesterified by conventional TE. After blending up to 10 % with refined oil, the ester content achieved was near 96.5 %. Thus, the blending represents an alternative for obtaining a product with suitable ester content.     

Transesterification of canola oil as biodiesel over Na/Zr-SBA-15 catalysts: Effect of zirconium content

A series of mesoporous Zr-SBA-15-supported Na catalysts was prepared and applied to the heterogeneous catalysis of canola oil transesterification. The effects of Si/Zr ratio, reaction time, and percentage of Na loading on the conversion to fatty acid methyl esters (FAME) were studied. The dependence of the textural structure and chemical properties of Zr-SBA-15 supports on Zr content was investigated using small-angle X-ray diffraction, Brunauer–Emmett–Teller analysis, transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy. The results obtained from FTIR and TEM indicate that the incorporation of Zr atoms into the SBA-15 structure facilitated the formation of Brönsted acid sites and decreased the particle size of Na species. Catalysts with a higher Zr content enhanced the FAME yield. The optimum conditions determined were as follows: reaction temperature of 70 °C, 15 wt.% Na, reaction time of 6 h, and 12% catalyst content (wt.% oil) with a methanol/oil molar ratio of 6:1. The optimum conditions resulted in a FAME yield of up to 99%.