Thermodynamic Analysis of α‐Pinene and Limonene Allylic Oxidation over a FePcCl16‐NH2‐SiO2 Catalyst

• Published in: Chemical engineering & technology Vol. 41; no. 1; pp. 124 - 133
• Main Authors: Becerra, Jaime-Andrés, Villa, Aída-Luz
• Format: Journal Article
• Language: English
• Published: Frankfurt Wiley Subscription Services, Inc 01-01-2018
• Subjects: Butanol; Butyl hydroperoxide; Catalysis; Catalysts; Decomposition; Decomposition reactions; Design standards; Endothermic reactions; Enthalpy; Entropy of formation; Exothermic reactions; Free energy; Gibbs free energy; Limonene oxidation; Oxidation; Silicon dioxide; Specific heat; Thermodynamic analysis; Vaporization; α‐Pinene oxidation
• ISSN: 0930-7516; 1521-4125
• DOI: 10.1002/ceat.201700118

From oxidation over a FePcCl16‐NH2‐SiO2 catalyst and tert‐butyl hydroperoxide (TBHP) as oxidant, verbenone, α‐pinene epoxide, and verbenol were obtained from α‐pinene while carvone, limonene 1,2‐epoxide and carveol were produced from limonene. TBHP decomposes into O2, tert‐butanol, and di‐tert‐butyl peroxide (DTBP). With the aim to perform a batch‐reactor conceptual design, α‐pinene and limonene oxidation was thermodynamically analyzed. Standard enthalpy and entropy of formation, liquid heat capacity, enthalpy of reaction and vaporization, and Gibbs free energy were determined by group contribution methods using Aspen Plus® simulation. Although the results depend on the method, it was found that α‐pinene and limonene oxidations were exothermic and spontaneous at the selected reaction temperature. However, TBHP decomposition into O2, tert‐butanol, and DTBP was an endothermic reaction.
The thermodynamic properties of terpenes estimated by different models depend on the applied group contribution method. The α‐pinene and limonene allylic oxidations over FePcCl16‐NH2‐SiO2 and tert‐butyl hydroperoxide are exothermic and spontaneous; however, the tert‐butyl hydroperoxide decomposition into oxygen and tert‐butanol and di‐tert‐butyl peroxide is an endothermic reaction.