The synthesis of fatty acid ethyl esters (FAEE) from Jatropha curcas L. oil was studied in a batch reactor and a continuous centrifugal contactor separator (CCCS) using sodium ethoxide as the catalyst. The effect of relevant process variables like rotational speed, temperature, catalyst concentration, and molar ratio of ethanol to oil was investigated. Maximum yield of FAEE was 98 mol% for both the batch (70°C, 600 rpm, 0.8% w/w of sodium ethoxide) and CCCS reactor configuration (60°C, 2100 rpm, 1% w/w of sodium ethoxide, oil feed 28 mL/min). The volumetric production rate of FAEE in the CCCS at optimum conditions was 112 kgFAEE/m3liquid · min.Practical applications: The Jatropha curcas L. shrub produces a non‐edible oil in yields up to 1.5 ton/(ha. y), which is known to be suitable for biodiesel synthesis. We here report an experimental study on the synthesis of jatropha biodiesel using ethanol instead of methanol as the alcohol source. Ethanol is accessible from biomass by fermentation and as such a green alternative for methanol. In addition, it is more readily available in developing countries than methanol. Biodiesel synthesis was performed in a CSSS, a continuous device that integrates reaction and separation. The device has potential to be applied in small scale mobile biodiesel technology due to its compact size, robustness, flexibility in operation, and high volumetric productivities.

The synthesis of fatty acid methyl esters (FAME) from sunflower oil and methanol was studied in a continuous centrifugal contactor separator (CCCS) using sodium methoxide as the catalyst. The effect of relevant process variables like oil and methanol flow rate, rotational speed and catalyst concentration was investigated and modelled using non-linear regression. Good agreement between experiments and model were obtained. At optimised conditions (oil flow rate of 31 mL/min, rotational speed of 34 Hz, catalyst concentration of 1.2%w/w and a methanol flow rate of 10 mL/min), the FAME yield was 94 mol% at a productivity of 2470 kg FAME /m 3 reactor .h. Proof of principle for the synthesis and subsequent refining of FAME in a cascade of two CCCS devices was also obtained. Relevant properties of the refined FAME obtained using this technology were determined and were shown to meet the ASTM specifications.Practical application: Synthesis and refining of sunflower biodiesel was successfully performed in a cascade of two CSSS devices. Besides for large scale biodiesel production, this technology has particularly potential to be applied in small mobile biodiesel units due to the compact size, robustness, flexibility in operation, and high volumetric productivity of the CCCS devices.

An experimental study to modify Sterculia foetida L. oil (STO) or the corresponding methyl esters (STO FAME) to branched ester derivatives is reported. The transformations involve conversion of the cyclopropene rings in the fatty acid chains of STO through various catalytic as well as stoichiometric reactions. Full conversion of the cyclopropene rings was obtained using Diels-Alder chemistry involving cyclopentadiene in water at 408C without the need for a catalyst. Olefin metathesis reactions were performed using a Grubbs 2nd generation catalyst and cyclopropene ring conversion was !99 and 54 mol% with 2,3-dimethyl-2-butene and 1-octene, respectively. Oxidation reactions were performed using established epoxidation (Sharpless) and dihydroxylation (Prilezhaev) protocols using aqueous hydrogen peroxide as the oxidant. For both reactions, full conversion of the cyclopropene rings was obtained at RT to yield the corresponding a,b-unsaturated ketone in good selectivities. Rearrangement reactions of the cyclopropene rings to the corresponding conjugated diene were successfully performed using homogeneous and heterogeneous palladium catalysts. Excellent conversions (!99%) were obtained using homogeneous palladium catalyst in a biphasic cyclohexane-water mixture (1:1) at 908C. Relevant cold flow properties of all products were determined and compared to crude STO and STO FAME. Best results were obtained for the metathesis products of STO with 1-octene, with a cloud point (CP) and pour point (PP) of À128C.Practical applications: The S. foetida L. tree produces a tropical oil with high potential to be converted to various oleochemical products. The oil contains cyclopropene rings in the fatty acid chains which are known to be very reactive and as such excellent starting materials for various chemical modification reactions. We here report an experimental study on the modifications of STO into novel branched ester derivatives which are prospective products for a range of applications. Examples are the use as cold-flow improvers for biodiesel or biolubricants (ester derivatives with long, aliphatic branches), as reactive building block material for resin, coatings and/or packaging application (derivatives containing unsaturated (cyclic) structures in the fatty acid chains). Abbreviations: APT, attached proton test; 1, methyl esters of STO; 2, methyl esters of Diels-Alder reaction products; 3a, product of metathesis reaction of STO with 2,3-dimethyl-2-butene; 3b, product of metathesis reaction of STO with 1-octene; 4a, methyl esters of 3a; 4b, methyl esters of 3b; 5, product of epoxidation reaction; 6, product of hydroxylation reaction; 7, product of 1,4-addition reaction of STO with noctylMgBr; 8, methyl esters of 7; 9, methyl esters of rearrangement