Parameters affecting thermal risk through a kinetic model under adiabatic condition: Application to liquid-liquid reaction system
Introduction
Energy sector and chemical industry still depend on the use of fossil raw materials. As example, Speight [1] reported that 90% of organic chemicals are produced from natural gas or petroleum. Recently, academies, industries and public authorities have put a great effort to develop new processes and new chemicals using renewable feedstock.
The use of vegetable oils, as a renewable feedstock, for the production of chemicals or biofuels is a good illustration of this effort. The worldwide production of vegetable oil is increasing since 1975 [2]. The part of production for industrial uses also increases and not only for biodiesels [3]. Vegetable oils can be considered as platform molecules [[4], [5], [6]].
Among the different functionalization of vegetable oils, there is the epoxidation of vegetable oils. Epoxidized vegetable oils are important chemicals for the production of non-isocyanate polyurethanes [[7], [8], [9], [10], [11], [12], [13]], biolubricants [[14], [15], [16], [17], [18]], plasticizers [19,20] or stabilizers for polymers. Several routes for the production of epoxidized vegetable oils exist. One of the more eco-friendly methods is the use of oxygen or hydrogen peroxide [21], however, the research on catalyst is still ongoing [[22], [23], [24], [25], [26], [27], [28]]. The use of enzymes is an alternative that is being more and more applied [[29], [30], [31], [32], [33], [34], [35], [36]].
For these reasons, at the industrial scale, the Prileschajew oxidation is the most used process [[37], [38], [39], [40], [41]]. Prileschajew oxidation is a liquid-liquid process where a percarboxylic acid is produced in situ in the aqueous phase from the perhydrolysis reaction, and diffused into the organic phase to epoxide the unsaturated groups of the vegetable oils. Solubility in the organic phase and reactivity of percarboxylic acid are higher compared to hydrogen peroxide. However, one of the main drawbacks of this reaction system is the risk of thermal runaway induced by several consecutive exothermic reactions [[42], [43], [44], [45], [46], [47], [48]].
The aforementioned articles have studied thermal risks and/or thermal instabilities of this chemical system. Nevertheless, none of them has built a kinetic model under adiabatic conditions, including secondary reactions as the decomposition of peroxide species. This work proposes to fill this gap by building a kinetic model for the epoxidation of cottonseed oil by peracetic acid produced in situ. The benefit of such model compared to the zero-order approach [49] is that one can estimate the safety parameters at different initial operating conditions.
Based on this model, safety parameters such as the time to maximum rate under adiabatic conditions, TMRad, and the adiabatic temperature rise, ΔTad, are estimated. These safety parameters are necessary to make a thermal risk assessment because while the latter represents the severity of a thermal risk, the former signifies its probability. The influence of reactant, catalyst concentrations and the initial temperature on these safety parameters are studied in the current work.
Section snippets
Chemicals
To perform the experiments in the Advanced Reactive System Screening Tool (ARSST) system, the following chemicals were used: distilled water, hydrogen peroxide (33 wt %, VWR International), acetic acid (>99%, Alfa Aesar GmbH & Co.) and cottonseed oil (ThermoFisher Scientific GmbH).
Experiments performed in ARSST
ARSST system is a calorimeter which can work under near-adiabatic conditions by using the principle of heat loss compensation [[7], [8], [9], [10],17,42,49]. It yields critical experimental knowledge of the rates of
Kinetics
Epoxidation of vegetable oils by Prileschajew oxidation is a liquid-liquid reaction system, where peracetic acid (PAA) is produced in the aqueous phase from the perhydrolysis reaction. Then, PAA diffuses to the organic phase to epoxidize the unsaturated groups.
Different side reactions, such as decomposition of peroxide species (hydrogen peroxide and PAA) or ring-opening reactions by different nucleophiles, can occur. Fig. 1 shows the different reactions occurring in the aqueous phase. As shown
Conclusions
Epoxidation of vegetable oils is an important process for polymer industries, because epoxidized vegetable oils can be seen as platform molecules. In industry, Prileschajew oxidation is used, which consists of the in situ production of a percarboxylic acid in the aqueous phase. This percarboxylic acid diffuses to the organic phase to epoxidize the unsaturated groups. Several studies have built kinetic model under isothermal or isoperibolic conditions, and other studies have stressed their
Acknowledgement
The authors thank the Maitrise des Risques et Environementaux and Chimie Fine et Ingénierie departments.
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2023, Industrial Crops and ProductsCitation Excerpt :The epoxidation for Canola oil has taken 1 h while Canola biodiesel has taken 30 min (Somidi et al., 2016). Epoxidation of vegetable oils is done by the oxidation of Prileschajew by involving the in situ production of percarboxylic acid from hydrogen peroxide and the corresponding carboxylic acid (Leveneur et al., 2018). The metallic catalysts are more prominent than the inorganic catalyst.