Parameters affecting thermal risk through a kinetic model under adiabatic condition: Application to liquid-liquid reaction system

doi:10.1016/j.tca.2018.05.024

Thermochimica Acta

Volume 666, 10 August 2018, Pages 10-17

https://doi.org/10.1016/j.tca.2018.05.024 Get rights and content

Highlights

•
A kinetic model for complex chemical system under adiabatic condition was developed.
•
ΔT_ad and TMR_ad in presence of several exothermic reactions were determined.
•
Thermal risk assessment for the epoxidation of vegetable oil were performed.

Abstract

Risk of thermal runaway for epoxidation is not negligible and should be analyzed and assessed. In industry, epoxidation of vegetable oils is carried out by the oxidation of Prileschajew, involving the in situ production of percarboxylic acid from hydrogen peroxide and the corresponding carboxylic acid. Different research groups have developed kinetic models under isothermal or isoperibolic mode for this liquid-liquid reaction system. Nevertheless, none of them have built a kinetic model under adiabatic mode. Such kinetic model under adiabatic condition is important to evaluate the thermal risk of a process.

During this study, a kinetic model was built for the epoxidation of cottonseed oil by peracetic acid by using ARSST system, which works under near-adiabatic condition. This kinetic model can fit the experimental reaction temperature. Then, based on this model, the influence of different inlet parameters (i.e. initial temperature and concentrations) on safety parameters, i.e., Time-to-Maximum rate under adiabatic conditions and adiabatic temperature rise was investigated.

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, TMR_ad, and the adiabatic temperature rise, ΔT_ad, 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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Citation 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.
Biolubricants are emerging as an alternate option to petroleum-based lubricants and seeking the attention of researchers worldwide due to their biodegradability, renewability, and non-toxic nature. The presence of various acids such as oleic acid, ricinoleic acid, and linoleic acid enables the conversion of vegetable oil into biolubricants with desired lubricating properties. The addition of nanoparticles may ensure good anti-wear properties and proper viscosity of biolubricants. Transesterification, epoxidation, and estolide formation are the main method of the synthesis of the biolubricants from vegetable oil. This paper reviews the state–of–art development of the biolubricants, vegetable oil as feedstock for the biolubricants, and physico-chemical properties of biolubricants for better lubrication considering the improvement in chemical properties and methods of production. Chemical modification and the use of nanomaterial to improve the quality of the biolubricants have been reviewed in this paper. This paper will provide complete insight into the recent development of biolubricants to researchers working in the field of tribology and lubrication.

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Parameters affecting thermal risk through a kinetic model under adiabatic condition: Application to liquid-liquid reaction system

Highlights

Abstract

Introduction

Section snippets

Chemicals

Experiments performed in ARSST

Kinetics

Conclusions

Acknowledgement

Renew. Sustain. Energy Rev.

Mater. Today

Bioresour. Technol.

Appl. Catal. B

Ind. Crops Prod.

Catal. Today

Enzyme Microb. Technol.

J. Mol. Catal. B: Enzym.

Chem. Phys. Lipids.

Chem. Eng. Sci.

J. Taiwan Inst. Chem. E

Chem. Eng. J.

Chem. Eng. J.

Org. Process Res. Dev.

Process Saf. Environ. Prot.

J. Loss Prev. Process Ind.

Chem. Eng. Process.: Process Intensif.

Org. Process Res. Dev.

Chem. Eng. Sci.

Chem. Eng. Sci.

Chem. Eng. Sci.

Thermochim. Acta.

J. Chem. Thermodyn.

Environmental Organic Chemistry for Engineers

A global overview of vegetable oils, with reference to biodiesel

Rep. IEA Bioenergy

From petrochemical polyurethanes to biobased polyhydroxyurethanes

Macromolecules

Vegetable oils as platform chemicals for polymer synthesis

Eur. J. Lipid Sci. Technol.

Carbonation of vegetable oils: influence of mass transfer on reaction kinetics

Ind. Eng. Chem. Res.

Non-isocyanate polyurethanes: synthesis, properties, and applications

Polym. Adv. Technol.

Sustainable routes to polyurethane precursors

Green Chem.