Technological Aspects of Chemoenzymatic Epoxidation of Fatty Acids, Fatty Acid Esters and Vegetable Oils: A Review

Abstract

Abstract:The general subject of the review is analysis of the effect of technological parameters on the chemoenzymatic epoxidation processes of vegetable oils, fatty acids and alkyl esters of fatty acids. The technological parameters considered include temperature, concentration, amount of hydrogen peroxide relative to the number of unsaturated bonds, the amounts of enzyme catalysts, presence of solvent and amount of free fatty acids. Also chemical reactions accompanying the technological processes are discussed together with different technological options and significance of the products obtained.

Chemistry and Catalytic Performance of Pyridyl‐Benzimidazole Oxidomolybdenum(VI) Compounds in (Bio)Olefin Epoxidation

“…The olefins Ole and LinOle are model substrates for fatty‐acid methyl esters (FAMEs), which are produced from vegetable oils by transesterification . Epoxidized FAMEs have widespread use, for example, as solvents, lubricants, PVC stabilizers and plasticizers, and as intermediates in the production of polyurethane polyols, cosmetics, and pharmaceuticals . Traditionally, at the industrial level, plant oils and their derivatives are epoxidized under homogeneous conditions by using the Prilezhaev reaction, involving peracids generated in situ by the reaction of organic acids with hydrogen peroxide in the presence of a mineral‐acid catalyst , , .…”

“…Epoxidized FAMEs have widespread use, for example, as solvents, lubricants, PVC stabilizers and plasticizers, and as intermediates in the production of polyurethane polyols, cosmetics, and pharmaceuticals . Traditionally, at the industrial level, plant oils and their derivatives are epoxidized under homogeneous conditions by using the Prilezhaev reaction, involving peracids generated in situ by the reaction of organic acids with hydrogen peroxide in the presence of a mineral‐acid catalyst , , . Environmental and safety concerns associated with this stoichiometric process have motivated the search for alternative catalytic methods that employ more convenient oxidants.…”

Epoxidized vegetable oil and bio‐based materials as PVC plasticizer

“…proved that hydrogen peroxide deactivate oxalate oxidase during the oxidation of oxalate to carbon dioxide. In addition, Milchert et al . reviewed the effect of different parameters on chemoenzymatic epoxidation process of vegetable oils.…”

Deep Eutectic Solvents Enable More Robust Chemoenzymatic Epoxidation Reactions

“…[7] One challenge to be faced in the synthesis of epoxidized esters is the hydrolytic activity of the enzymes, which leads to epoxidized fatty acids in the presence of water.T herefore, if epoxidized esters such as epoxidized vegetable oils are desired, particulara ttention has to be paid to the exclusion of trace amounts of water.Very recently,w er eported that lipase Gf rom Penicillieum camembertii exhibited no activity towards triglycerides,w hich made it ap romising catalystf or the direct epoxidation of epoxidizedt riglycerides. [8] Unfortunately,h owever,l ipase Gw as not very robust under the reactionc onditions, which limited its practical applicability.I nspired by av ery recent contribution, [9] we decided to evaluate some natural deep eutectic solvents (DESs) as stabilizers for lipase G. In af irst set of experiments,w ecompared different DESs as reaction media for the chemoenzymatic epoxidation of glyceryl trioleate (GT) to epoxidizedg lyceryl trioleate (EGT) (Figure 1). Notably,t he acid number of the GT used in this study was comparably high (1 mg (KOH) per gram of GT corresponding to an oleic acid concentrationi nG To fc a.…”