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Kinetics of the Epoxide Ring Opening Reactions

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Kinetics of the Epoxide Ring Opening Reactions processes Article Soybean Oil Epoxidation: Kinetics of the Epoxide Ring Opening Reactions Elio Santacesaria 1,* , Rosa Turco 2 , Vincenzo Russo 2 , Riccardo Tesser 2 and Martino Di Serio 2 1 CEO of Eurochem Engineering Ltd., 20139 Milano, Italy 2 NICL—Department of Chemical Science, University of Naples Federico II, 80126 Naples, Italy; [email protected] (R.T.); [email protected] (V.R.); [email protected] (R.T.); [email protected] (M.D.S.) * Correspondence: [email protected] Received: 7 July 2020; Accepted: 9 September 2020; Published: 11 September 2020 Abstract: The epoxide ring opening reaction (ROR) can be considered as the most important side reaction occurring in the epoxidation of soybean oil reaction network. This reaction consistently reduces the selectivity to epoxidized soybean oil (ESBO). The reaction is also important for producing polyols and lubricants. In this work, the reaction was studied in different operative conditions to evaluate the effect on ROR rate respectively: (i) The Bronsted acidity of the mineral acid (H2SO4 or H3PO4), used as catalyst for promoting the oxidation with hydrogen peroxide of formic to performic acid, that is, the reactant in the epoxide formation; (ii) the concentration of the nucleophilic agents, normally present during the ESBO synthesis like HCOOH, HCOOOH, H2O, H2O2; (iii) the stirring rate that changes the oil–water interface area and affects the mass transfer rate; (iv) the adopted temperature. Many different kinetic runs were made in different operative conditions, starting from an already epoxidized soybean oil. On the basis of these runs two different reaction mechanisms were hypothesized, one promoted by the Bronsted acidity mainly occurring at the oil–water interface and one promoted by the nucleophilic agents, in particular by formic acid. As it will be seen, the kinetic laws corresponding to the two mentioned mechanisms are quite different and this explain the divergent data reported in the literature on this subject. All the kinetic runs were correctly interpreted with a new developed biphasic kinetic model. Keywords: epoxides; soybean oil; hydrogen peroxide; kinetics; ring opening reaction 1. Introduction The epoxide ring opening reaction (ROR) of epoxidized vegetable oils has been intensively studied by many researchers interested in the production of polyols [1] or to the use as lubricants [2] or as intermediates for polyurethanes production [3]. In this case the scope is to find a good catalyst for promoting the reaction in a short time. On the contrary, in the epoxidation of vegetable oils (Prileschajew reaction [4]), ROR is an undesired side reaction lowering the yield in the production of epoxidized vegetable oils and the studies are, therefore, focused to hinder the reaction as much as possible. An example of epoxidation reaction network can be summarized as follows: H2O2 + HCOOH HCOOOH + H2O (1) Processes 2020, 8, 1134; doi:10.3390/pr8091134 www.mdpi.com/journal/processes Article Soybean Oil Epoxidation: Kinetics of the Epoxide Ring Opening Reactions Elio Santacesaria 1,*, Rosa Turco 2, Vincenzo Russo 2, Riccardo Tesser 2 and Martino Di Serio 2 1 CEO of Eurochem Engineering LtD., 20139 Milano, Italy 2 NICL—Department of Chemical Science, University of Naples Federico II, 80126 Naples, Italy; [email protected] (R.T.); [email protected] (V.R.); [email protected] (R.T.); [email protected] (M.D.S.) * Correspondence: [email protected] Received: 7 July 2020; Accepted: 9 September 2020; Published: 11 September 2020 Abstract: The epoxide ring opening reaction (ROR) can be considered as the most important side reaction occurring in the epoxidation of soybean oil reaction network. This reaction consistently reduces the selectivity to epoxidized soybean oil (ESBO). The reaction is also important for producing polyols and lubricants. In this work, the reaction was studied in different operative conditions to evaluate the effect on ROR rate respectively: (i) The Bronsted acidity of the mineral acid (H2SO4 or H3PO4), used as catalyst for promoting the oxidation with hydrogen peroxide of formic to performic acid, that is, the reactant in the epoxide formation; (ii) the concentration of the nucleophilic agents, normally present during the ESBO synthesis like HCOOH, HCOOOH, H2O, H2O2; (iii) the stirring rate that changes the oil–water interface area and affects the mass transfer rate; (iv) the adopted temperature. Many different kinetic runs were made in different operative conditions, starting from an already epoxidized soybean oil. On the basis of these runs two different reaction mechanisms were hypothesized, one promoted by the Bronsted acidity mainly occurring at the oil–water interface and one promoted by the nucleophilic agents, in particular by formic acid. As it will be seen, the kinetic laws corresponding to the two mentioned mechanisms are quite different and this explain the divergent data reported in the literature on this subject. All the kinetic runs were correctly interpreted with a new developed biphasic kinetic model. Keywords: epoxides; soybean oil; hydrogen peroxide; kinetics; ring opening reaction 1. Introduction The epoxide ring opening reaction (ROR) of epoxidized vegetable oils has been intensively studied by many researchers interested in the production of polyols [1] or to the use as lubricants [2] or as intermediates for polyurethanes production [3]. In this case the scope is to find a good catalyst for promoting the reaction in a short time. On the contrary, in the epoxidation of vegetable oils (Prileschajew reaction [4]), ROR is an undesired side reaction lowering the yield in the production of epoxidized vegetable oils and the studies are, therefore, focused to hinder the reaction as much as possible.Processes 2020 An, 8 ,example 1134 of epoxidation reaction network can be summarized as follows: 2 of 23 H2O2 + HCOOH HCOOOH + H2O (1) (2) (2) and according to our previous insights [5,6]; Processesand according 2020, 8, x FOR to our PEER previous REVIEW insights [5,6]; 2 of 23 Processes 2020, 8, x FOR PEER REVIEW 2 of 23 Processes 2020, 8, x; doi: FOR PEER REVIEW www.mdpi.com/journal/processes (3) (3) (3) TheThe sequence ofof reactionreaction isis the the same same if if acetic acetic acid acid is usedis used instead instead of formicof formic acid. acid. As itAs can it becan seen, be The sequence of reaction is the same if acetic acid is used instead of formic acid. As it can be seen,according according to this to mechanism, this mechanism, the oxirane the oxirane cleavage cleavage step occurs step inoccurs series in with series the with epoxidation the epoxidation reaction seen, according to this mechanism, the oxirane cleavage step occurs in series with the epoxidation reactionand is promoted and is promoted by a Bronsted by a Bronsted acid environment. acid environment. Considering Con thatsidering the reaction that the of reaction formic toof performicformic to reaction and is promoted by a Bronsted acid environment. Considering that the reaction of formic to performicacid is catalyzed acid is catalyzed by mineral by acids, mineral such acids, as sulfuric such as or sulfuric phosphoric or phosphoric acid, the sameacid, the catalyst same seemscatalyst to performic acid is catalyzed by mineral acids, such as sulfuric or phosphoric acid, the same catalyst seemspromote to alsopromote the ring also opening the ring side opening reaction. side It reaction. is important It is toimportant point out to that point reaction out that (1) occursreaction in the(1) seems to promote also the ring opening side reaction. It is important to point out that reaction (1) occursaqueous in phase,the aqueous where phase, the mineral where acid the is mineral dissolved, acid while is dissolved, epoxide while rings areepoxide dissolved rings in are the dissolved oil phase. occurs in the aqueous phase, where the mineral acid is dissolved, while epoxide rings are dissolved inTherefore, the oil phase. it is reasonableTherefore, it to is assume reasonable that to reaction assume (3) that occurs reaction at the (3) wateroccurs/oil at interfacethe water/oil as suggested interface in the oil phase. Therefore, it is reasonable to assume that reaction (3) occurs at the water/oil interface asby suggested us in two ofby ourus in previous two of worksour previous [5,6] and works also by[5,6] other and authors also by [7 –other11] Then, authors considering [7–11] Then, that as suggested by us in two of our previous works [5,6] and also by other authors [7–11] Then, consideringreaction (3) isthat deleterious reaction (3) to obtainis deleterious epoxidized to obtain products epoxidized at high yield, products a detailed at high study yield, dealing a detailed with considering that reaction (3) is deleterious to obtain epoxidized products at high yield, a detailed studythe kinetics dealing of thiswith reaction the kinetics can be of useful this inreaction order tocan find be the useful best operativein order conditionsto find the and best to operative minimize study dealing with the kinetics of this reaction can be useful in order to find the best operative conditionsthe negative and influence to minimize of this the reaction. negative Diff influenceerent studies of this have reaction. already Different been performed, studies onhave the already subject, conditions and to minimize the negative influence of this reaction. Different studies have already beeninvestigating performed, the on influence
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