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.     

TiO2/Al2O3 membrane reactor equipped with a methanol recovery unit to produce palm oil biodiesel

In this study, the central composite design of the response surface methodology was employed to investigate the effects of reaction temperature, catalyst concentration and cross flow circulation velocity on the production of biodiesel in a TiO₂/Al₂O₃ membrane reactor. High‐quality palm oil biodiesel was produced by combination of alkali transesterification and separation processes in the ceramic membrane reactor. The optimum conditions for the conversion of palm oil to biodiesel in the ceramic membrane reactor were as follows: 70°C reaction temperature, 1.12 wt% catalyst concentration and 0.211 cm s^{? 1} cross flow circulation velocity. The physical and chemical properties of the produced biodiesel were determined and compared with the standard specifications. Copyright © 2010 John Wiley & Sons, Ltd.     

High-pressure phase equilibrium measurements and thermodynamic modeling for the systems involving CO2, ethyl esters (oleate,stearate, palmitate) and acetone

The aim of this work was to study the phase behavior of systems involving carbon dioxide (CO₂), fatty acid ethyl esters (ethyl oleate, ethyl stearate and ethyl palmitate) and acetone at high pressures. The phase behavior involving these components is an important step regarding the design and optimization of industrial processes based on supercritical conditions, such as biodiesel production and fatty esters fractionation involving supercritical and/or pressurized solvents. In addition, supercritical CO₂ can offer an interesting alternative for glycerol separation in water-free biodiesel purification processes. The binary systems investigated in this work were CO₂ + ethyl oleate, and CO₂ + ethyl stearate and these were compared with the CO₂ + ethyl palmitate system. The ternary CO₂ + ethyl palmitate + acetone was also investigated at two different ethyl palmitate to acetone molar ratios of (1:1) and (1:3). The static synthetic method using a variable-volume view cell was employed to obtain the experimental data in the temperature range of 303.15–353.15 K. Vapor–liquid (VL), liquid–liquid (LL) and vapor–liquid–liquid (VLL) phase transitions were observed in these systems. In the binary systems, the solubility increased with the presence of unsaturation and decreased with the number of carbon atoms in the fatty ester chain. Addition of acetone as well as ethanol eliminated the liquid–liquid immiscibility and reduced the pressure transitions, therefore increasing the solubility of the ester in supercritical CO₂. The experimental data sets for the binary and ternary systems were successfully modeled using the Peng–Robinson equation of state with the classical van der Waals quadratic mixing rule (PR-vdW2) and Wong-Sandler (PR-WS) mixing rule. Both models showed good performance in the phase equilibrium correlations and in predictions for the binary and ternary systems.     

Non-catalytic production of fatty acid ethyl esters from soybean oil with supercritical ethanol in a two-step process using a microtube reactor

This work reports the production of fatty acid ethyl esters (FAEE) from the transesterification of soybean oil in supercritical ethanol in a continuous catalyst-free process using different reactor configurations. Experiments were performed in a microtube reactor with experimental simulation of two reactors operated in series and a reactor with recycle, both configurations at a constant temperature of 573 K, pressure of 20 MPa and oil to ethanol mass ratio of 1:1. Results show that the configurations studied with intermediate separation of glycerol afford higher conversions of vegetable oil to its fatty acid ethyl ester derivatives when compared to the one-step reaction, with relatively low decomposition of fatty acids (<3.0 wt%).     

A Comparison of the Migration of ‘Spiked’ and ‘Intrinsic’ Substances from Paper and Board into Raisins and into Tenax as a Food Simulant

Four samples of paper and board (P/B) of a type used for packaging dry foods were subjected to migration experiments using raisins and the polymeric powder Tenax as a food simulant. The P/B samples contained only low levels of diisopropylnaphthalene (DiPN) and diisobutyl phthalate (DiBP), and so, experiments were also conducted after spiking the P/B with added model substances. These were o‐xylene, acetophenone, dodecane, benzophenone, DiPN and DiBP. Migration experiments into raisins and Tenax were conducted for 10 days at 40°C. Migration levels depended strongly on the nature of the substance. Migration from spiked P/B samples was more extensive (as a percentage of that available) than migration of intrinsic migratable substances, and so, studying spiked samples tends to be conservative. It is considered likely that this is because of binding of substances, especially aromatics with pi‐electrons such as DiPN and DiBP, to active sites on the surface of P/B fibres, resulting in non‐linear absorption isotherms. However, further work would be needed to prove this conclusively. Considering the results overall and also that raisins packed in P/B can have a shelf life of up to 1 year at ambient temperatures, the test results using Tenax as a food simulant are considered to be appropriate without application of a correction factor. Copyright © 2014 John Wiley & Sons, Ltd.     

Do phosphoric acid esters affect the immediate enamel bond strengths?

Purpose: To investigate the effects of phosphoric acid esters (PAEs)-containing primers on the micro-tensile bond strengths (MTBS) of etched enamel, the micro-morphologies of the resin–enamel interfaces, and the enamel surfaces.

Materials and Methods: Thirty-three bovine incisors were used in this study. After the labial enamel surfaces were highly polished, they were etched, water sprayed, and air-dried. Afterward, the enamel surfaces were treated with or without (control) one of three PAEs-containing primers (40%MDP, Ivoclar Vivadent; Resulcin AquaPrime A + B, DMG; Xeno V, Dentsply), water sprayed, and air-dried. Subsequently, an adhesive Heliobond (Ivoclar Vivadent) was applied and resin composite (Core Build-up, Bisco) was placed incrementally. They were prepared into multiple beams of about 1 × 1 × 8 mm for MTBS tests. The enamel surfaces and resin–enamel interfaces were analyzed by SEM and TEM. The data were analyzed by two-way ANOVA and LSD test.

Results: Using PAEs-containing primers could increase the enamel MTBS (p < 0.05). The primer MDP produced higher MTBS than the primer Resulcin AquaPrime A + B and Xeno V. The SEM findings revealed the primed enamel surfaces were covered with a thin or glue-like layer of monomer-calcium salts of PAEs and the residual enamel crystallites, and various micro-porosities were detected within the hybrid layers. The TEM findings revealed the hydroxyapatite crystallites were tightly covered by the adhesive, the adhesive mixed with resin composite, or sparse irregular enamel crystallites.

Conclusion: The application of PAEs-containing primers on the etched enamel substrate could significantly increase the immediate enamel bond strengths. However, this effect was dependent on the individual PAEs-containing primer used.     

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.     

Solubilization Behavior of Phorbol Esters from Jatropha Oil in Surfactant Micellar Solutions

Phorbol esters (PEs) are important toxic compounds found in Jatropha curcas oil and pressed seeds. These compounds are tumor promoters; thus, their removal prior to further utilization of the pressed seed is important. This work aimed to investigate the solubilization behavior of PEs and Jatropha oil in nonionic [effect of the ethylene oxide number (EON), carbon‐chain length and temperature] and anionic (NaCl addition) surfactant systems. The results reveal that an increase in the EON of the nonionic surfactant molecules, rather than an increase in the carbon‐chain length, enhances PE solubilization. The hydrophile‐lipophile balance (HLB) value was correlated with PE solubilization for nonionic surfactant solutions. The solubilization of PEs decreased slightly with increasing temperature, in contrast to solubilization of the oil. Moreover, the mole fraction of PE solubilized in the micelle decreased with increasing electrolyte concentration in anionic surfactant solutions. The solubilization behavior of PEs in both nonionic and anionic solutions indicates that PE acts more like a polar compound than a nonpolar compound. In addition, the PEs in nonionic micelles are likely located in the palisade region (i.e., between the head group and the first few carbon atoms of the tail), whereas those in anionic micelles are likely near the outer core of the head group. This finding suggests that a nonionic surfactant with a higher EON has a greater potential to extract PE from Jatropha seeds. If an anionic surfactant is combined as co‐surfactant, a small amount of electrolyte should be added to increase PE solubilization.