Kinetic Study and Modeling of Peroxypropionic Acid Synthesis from Propionic Acid and Hydrogen Peroxide Using Homogeneous Catalysts

Abstract

This article describes a kinetic study of the perhydrolysis of propionic acid with sulfuric acid at various molar reactant ratios (PA-H2O2 from 0.4 to 2.05), reaction temperatures (from 30 to 60 °C), and catalyst concentrations (from 0 to 1.41 M). The influence of water and acidic catalysts were taken into account to develop a suitable kinetic model. The system is nonideal, mainly due to the presence of the strong electrolyte (i.e., H2SO4), and a parameter was introduced to describe the nonideality. The kinetic and thermodynamic parameters determined by nonlinear regression analysis were statistically well identified. The standard enthalpy change of reaction was estimated to −4.17 kJ·mol-1, and the activation energy of the reaction was estimated to 44.2 kJ·mol-1.

Synthesis of peroxypropionic acid from propionic acid and hydrogen peroxide over heterogeneous catalysts

“…Fig. 1 confirms that the perhydrolysis kinetics of propionic acid in the absence of an added catalyst is slow, but propionic acid itself is able to act as a catalyst, therefore some conversion was noticeable [6]. However, one can observe that there is a significant effect of sulfuric acid even at low concentrations (0.001 and 0.004 M), implicating that there is no clear threshold value for the added catalyst concentration.…”

“…It was decided to investigate the perhydrolysis of propionic acid; the choice of peroxypropionic acid is due to its higher stability compared to peroxyacetic acid. In a previous contribution [6], it was demonstrated that the kinetics of propionic acid perhydrolysis, catalyzed by sulfuric acid, is dependent on Brønsted concentration.…”

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

“…Below this catalyst loading, the perhydrolysis of propionic acid due to the protolysis of the carboxylic acids occurs [7]. The change of the catalyst loading in the range 10.24-18.25 g/L does not influence the kinetics of H 2 O 2 decomposition at 50°C (Fig.…”

“…This reaction occurs at acidic pH [5][6][7], and is traditionally catalyzed by sulfuric acid. 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).…”

Simultaneous desulfurization and denitrogen of liquid fuels using two functionalized group ionic liquids

“…(1) [2,19,33,34]. The carboxylic acid itself can also dissociate H + , which is able to act as a catalyst to accelerate the forming rate of -COOOH [19].…”