Kinetic study of decomposition of peroxypropionic acid in liquid phase through direct analysis of decomposition products in gas phase

Leveneur, Sébastien; Salmi, Tapio; Musakka, Niko; Wärnå, Johan

doi:10.1016/j.ces.2006.12.040

Cited by 14 publications

(17 citation statements)

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“…49,59,60 The first decomposition route produces water and carbon dioxide. With a temperature increase, a second decomposition route should not be neglected which is the decomposition into formic acid and oxygen.…”

Section: Resultsmentioning

confidence: 99%

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Kinetic modeling strategy for an exothermic multiphase reactor system: Application to vegetable oils epoxidation using Prileschajew method

et al. 2015

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Epoxidation of cottonseed oil by peroxyformic acid (PFA) was studied in a semibatch calorimeter. This liquid-liquid reaction system is composed of different exothermic steps. Thus, a kinetic modeling strategy to diminish the number of parameters to estimate was developed by investigating each reaction system: PFA synthesis and decomposition, ringopening and epoxidation. A thermal study was conducted by determining heat capacity of the different organic species, and by analyzing the evolution of global heat-transfer coefficient with the reaction extent. The epoxidation reaction was performed in a semibatch reactor under isoperibolic mode within an initial temperature range of 50-708C, an organic phase of 30-34 wt %, a formic acid molar flow rate of 0.02-0.05 mol/min and an addition time of 25-50 min. The interfacial mass transfer was supposed to be faster than the intrinsic reaction kinetics suppressing the use of mass transfer correlation. Nonlinear regression was used to estimate the kinetic and thermal parameters. The kinetic parameters of epoxidation of the three different fatty acids, namely oleic, linoleic, and its intermediate were estimated. The reaction enthalpy of epoxidation was estimated to 2230 6 3.8 kJ/mol, and the reaction enthalpy of ring-opening was measured to be 290 kJ/mol by Tian-Calvet calorimeter.Kinetic modeling of vegetable oils epoxidation by peroxycarboxylic acids formed in situ in batch and semibatch reactor system has been described by several research groups. This system is complex due to the presence of several consecutive steps. Different approaches have been done such as:Taking into account mass transfer parameters using different correlations or by estimating them, this model is called two-phase kinetic model. Frequently, only carboxylic and peroxycarboxylic acids mass-transfer coefficients were taken into account. [24][25][26] Pseudohomogeneous model by assuming fast mass transfer compared to reaction kinetics, this leads to a simplification of the mass balance equations. [27][28][29][30][31][32] Establishing the mass balance only on the organic phase and assuming steady-state approach on peroxycarboxylic acids formation. 13,[33][34][35][36][37][38][39][40] The advantage of that approach is that graphical method can be used to determine epoxidation rate constants, but one neglects ring-opening reaction. This model is called homogeneous model.Some authors have focused their study only on the ringopening reactions system in batch or semibatch reactor. One can distinguish the two following approaches:Only considering the organic phase and using a pseudofirst-order approach. 41-43 Figure 1. Simplified mechanism of the Prileschajew oxidation of vegetable oils.

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Section: Resultsmentioning

confidence: 99%

“…Decomposition of peroxycarboxylic acid follows a firstorder kinetics 59,60 and can be expressed in both cases as…”

Section: Kinetic Equationsmentioning

confidence: 99%

Kinetic modeling strategy for an exothermic multiphase reactor system: Application to vegetable oils epoxidation using Prileschajew method

et al. 2015

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“…In our previous studies [9,11] no decomposition of hydrogen peroxide was noticed due to Brønsted acidity in either sulfuric acid or sulfonic groups bearing by the resins. For that reason Lewis acid sites in such materials can be considered to be responsible for the decomposition of hydrogen peroxide.…”

Section: Resultsmentioning

confidence: 93%

“…From our previous study [9,11], the kinetics of propionic acid perhydrolysis is demonstrated to be dependant on the Brønsted acid sites in the cases of homogeneous and heterogeneous catalysis. One should keep in mind that the goal is to check the stability of hydrogen peroxide towards aluminosilicate materials in an acidic environment by studying the reaction of perhydrolysis.…”

Section: Apparatus and Experimental Proceduresmentioning

confidence: 96%

“…This reaction was selected because spontaneous decomposition of hydrogen peroxide or peroxycarboxylic acids is negligible [8][9][10] in traditional experimental conditions (pH: 1-3; and temperature: 20-50°C); and configurational diffusion can be neglected because the size of the reactant molecules is smaller compared to the pore size of the materials used (Table 1). Thus, by using heterogeneous catalysts for this reaction, only decomposition due to the solid acid catalyst can occur.…”

Section: Scheme 1 Applications Of H 2 O 2 In Fine Chemical Reactionsmentioning

confidence: 99%

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Stability of hydrogen peroxide during perhydrolysis of carboxylic acids on acidic heterogeneous catalysts

et al. 2010

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This paper describes a study of the stability of hydrogen peroxide in the presence of different aluminosilicate materials, in connection with an investigation of carboxylic acid perhydrolysis. During the reaction, aluminosilicate materials such as H-b zeolites, mesoporous material H-MCM-41 and alumina initiate the decomposition of hydrogen peroxide. The reason of the spontaneous decomposition of H 2 O 2 is related to the partial dealumination of these zeolites. However, in the case of experiments carried out with H-ZSM-5 zeolite catalysts, a slight catalytic effect on the perhydrolysis and no spontaneous decomposition of hydrogen peroxide were noticed. The use of cation exchange resins as catalysts is more kinetically beneficial than H-ZSM-5 zeolite catalysts.

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Thermal risk assessment of vegetable oil epoxidation

Leveneur

Estel

Crua

2015

J Therm Anal Calorim

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This article describes thermal risks assessment of vegetable oil epoxidation by peroxycarboxylic acid. It is a liquid-liquid system where several exothermic reactions occur.Acetic acid was used as the carboxylic acid, and oleic acid was chosen as a model molecule because it is a common fatty acid in the triglyceride molecule. Differential scanning calorimetry (DSC) and accelerating rate calorimetry (ARC) were used to determine safety criteria such as the final temperature (TFinal), TD24 and time-to-maximum-rate under adiabatic condition (TMRad). We found that the calculation of TMRad based on DSC data could be incorrect when assuming a zero order kinetic reaction. By using a process temperature of 70°C, the extrapolated final temperature was found to be 544°C from DSC experiments, TD24 was estimated to 20°C based on ARC experiment and TMRad was calculated to 164 min from ARC experiments. These criteria indicate that the process can lead to full accumulation of peroxides species. Therefore we recommend that vegetable oil epoxidation by peroxycarboxylic acid should not be performed in batch reactor, but in semi-batch mode.

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Kinetic study of decomposition of peroxypropionic acid in liquid phase through direct analysis of decomposition products in gas phase

Cited by 14 publications

References 1 publication

Kinetic modeling strategy for an exothermic multiphase reactor system: Application to vegetable oils epoxidation using Prileschajew method

Kinetic modeling strategy for an exothermic multiphase reactor system: Application to vegetable oils epoxidation using Prileschajew method

Stability of hydrogen peroxide during perhydrolysis of carboxylic acids on acidic heterogeneous catalysts

Thermal risk assessment of vegetable oil epoxidation

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