Liquid Phase Selective Catalytic Oxidation of Oleic Acid to Azelaic Acid Using Air and Transition Metal Acetate Bromide Complex

Abstract

Industrially important di‐carboxylic acids are synthesized from mono‐carboxylic unsaturated and unsaturated fatty acids. In this study, the aim is to perform the simultaneous catalytic oxidative C=C cleavage of oleic acid (OA) to azelaic acid and pelargonic acid, and oxidation of the terminal methyl group in pelargonic acid to azelaic acid using cobalt‐ and manganese‐acetate as catalyst, hydrogen bromide as co‐catalyst and air in acetic acid at elevated pressure (2.8–5.8 barg) and temperature (353–383 K). Oxygen solubility is determined under varying pressure, temperature and OA loading. The effect of OA loading, pressure and temperature on OA conversion and azelaic acid selectivity is studied by varying one variable at a time; however, the presence of the synergistic effect of the catalyst and co‐catalyst is investigated by central composite design assisted response surface methodology. Oxidation of terminal methyl group in saturated fatty acid is also confirmed by the oxidation of stearic acid to octadecanedioic acid using identical oxidation conditions of OA. Oxidation products of fatty acids are quantified by gas chromatographic analysis. The innovation of the work is thus the ability of the catalytic system to perform a total oxidation of a terminal methyl group of the hydrocarbon chain. OA oxidation kinetics relating to catalyst and co‐catalyst concentration along with oxygen solubility at elevated temperature and pressure is established. The frequency factor and activation energy for OA oxidation is determined using the Arrhenius equation.

Oxidative Cleavage of Fatty Acid Derivatives for Monomer Synthesis

“…Many catalysts have been applied to this type of reaction [37][38][39][40]. For example, a niobium oxide catalyst has been recently used in the oxidative cleavage of methyl linoleate to obtain aldehydes as a major product.…”

Synthesis, Characterization, and the Potential for Closed Loop Recycling of Plant Oil-Based PA X.19 Polyamides

“…To be even more sustainable, full use of available bio-based carbon should be achieved for the synthesis of plant oil-based polyamides. The use of cobalt and manganese salts together with hydrogen bromide, for example, enables the full use of bio-based carbon for the synthesis of azelaic acid. , In this one-pot reaction, the byproduct pelargonic acid is oxidized to form azelaic acid, reaching 100% atom efficiency. Another method for the synthesis of linear aliphatic diacids with 100% atom efficiency is isomerizing methoxycarbonylation.…”

Spongy titanosilicate promotes the catalytic performance and reusability of WO3 in oxidative cleavage of methyl oleate

“…Some researchers turned to use hydrogen peroxide (H 2 O 2 ) as an oxidant for this reaction [10][11][12] as H 2 O 2 is environmentally benign and produces water as the only by-product. Some transition metal containing catalysts, [13][14][15][16] such as H 2 WO 4 @Al-MCM-41, 12 BaFeO 3Àd , 17,18 Ru(OH) x /g-Al 2 O 3 19 and VO@TiO 2 20 have been proved efficient in catalyzing this reaction with H 2 O 2 as oxidant. Among them, tungsten containing catalysts such as tungsten oxide (WO 3 ), WO 3 nanoparticles, 24 tungstic acid, 25 tungstates and supported WO 3 [26][27][28][29][30] have shown the best catalytic performance.…”