One-Pot Tandem Catalytic Epoxidation—CO2 Insertion of Monounsaturated Methyl Oleate to the Corresponding Cyclic Organic Carbonate

Conversion of unsaturated fatty acids, FAMEs or triglycerides into the corresponding cyclic organic carbonates involves two reaction steps—double-bond epoxidation and CO2 insertion into the epoxide—that are generally conducted separately. We describe an assisted-tandem catalytic protocol able to carry out carbonation of unsaturated methyl oleate in one-pot without isolating the epoxide intermediate. Methyl oleate carbonate was obtained in 99% yield and high retention of cis-configuration starting from methyl oleate using hydrogen peroxide and CO2 as green reagents, in a biphasic system and in the presence of an ammonium tungstate ionic liquid catalyst with KBr as co-catalyst.

Experimental investigation on n-butanol/methyl oleate dual fuel RCCI combustion in a single cylinder engine at high-load condition

Reactivity controlled compression ignition (RCCI) engines have a high thermal efficiency as well as low emissions of soot and nitrogen oxides (NOx). However, there is a conflict between combustion stability and harmful emissions at high engine load. Therefore, this work presented a novel approach for regulating n-butanol/methyl oleate dual fuel RCCI at high engine load in attaining lower pollutant emissions while maintaining stable combustion and avoiding excessive in-cylinder pressure. The tests were conducted on a single cylinder engine under rated speed and 90% full load. In this study, n-butanol was selected as a low-reactivity fuel for port injection, and n-butanol/methyl oleate blended fuel was used for in-cylinder direct injection. Combustion and emission characteristics of the engine were first investigated with varied ratios of n-butanol port injection (PFI) and direct injection (DI). Results showed that as the ratio of n-butanol PFI and DI rose, the peak cylinder pressure and heat release rate increased, while NOx and soot emissions reduced, and carbon monoxide (CO) and hydrocarbon (HC) emissions increased under most test conditions. When RNBPI = 40% and RNBDI = 20%, the soot and NOx emissions of the engine were near the lowest values of all test conditions, yet the peak in-cylinder pressure and fuel consumption could not increase significantly. Therefore, the possibility of optimizing the combustion process and lowering emissions by adjusting the pilot injection strategy was investigated utilizing these fuel injection ratios. The results revealed that with an appropriate pilot injection ratio and interval, the peak in-cylinder pressure and NOx emission were definitely reduced, while soot, CO, and HC emissions did not significantly increase.

Slug flow as tool for selectivity control in the homogeneously catalysed solvent-free epoxidation of methyl oleate

Catalytic oxidation of sustainable raw materials like unsaturated fats and oils, or fatty acids and their esters, lead to biobased, high-value products. Starting from technical grade methyl oleate, hydrogen peroxide as a green oxidant produces only water as by-product. A commercially available, cheap water-soluble tungsten catalyst is combined with Aliquat® 336 as a phase-transfer agent in solvent-free reaction conditions. In this study, we first report the transfer of this well-known batch system into continuous mode. The space–time yield is improved from 0.08 kg/L.h in batch to 1.29 kg/L.h in flow mode. The improved mass transfer and reduced back mixing of the biphasic liquid–liquid slug flow allows for selectivity control depending on physical parameters of slug flow namely volumetric phase ratio, volumetric flow rate, and slug length. Even though the product, methyl 9,10-epoxystearate is obtained at a maximum selectivity of only 58% in flow mode, higher space time yield combined with possible reactant recycling in flow mode offers a promising avenue of research. This work analyses the use of slug flow parameters as tools for controlling selectivity towards oxidation products of methyl oleate.