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

Abstract

From oxidation over a FePcCl 16 -NH 2 -SiO 2 catalyst and tert-butyl hydroperoxide (TBHP) as oxidant, verbenone, a-pinene epoxide, and verbenol were obtained from a-pinene while carvone, limonene 1,2-epoxide and carveol were produced from limonene. TBHP decomposes into O 2 , tert-butanol, and di-tert-butyl peroxide (DTBP). With the aim to perform a batch-reactor conceptual design, a-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 a-pinene and limonene oxidations were exothermic and spontaneous at the selected reaction temperature. However, TBHP decomposition into O 2 , tert-butanol, and DTBP was an endothermic reaction.

Techno‐Economic Evaluation of d‐Limonene and α‐Pinene Separation from Citrus and Turpentine Oils

“…As most of the components of the essential oils are not included in the software databases, they were incorporated by the user, and the properties were determined by group contribution methods integrating the UNIFAC thermodynamic models and their modifications. Although some of these properties have already been compared with experimental reports in previous publications , it is not possible to do that comparison for all the compounds because there exist no extended reports of properties for them due to their low industrial availability.…”

“…As heterogeneous catalytic transformation of limonene and a-pinene have been reported with acetone as solvent [35], the extraction of orange oil was evaluated with this solvent for using the limonene dissolved in the organic solvent for its transformation. With this same objective, also ethanol was taken as extraction solvent.…”

“…As most of the components of the essential oils are not included in the software databases, they were incorporated by the user, and the properties were determined by group contribution methods integrating the UNIFAC thermodynamic models and their modifications. Although some of these properties have already been compared with experimental reports in previous publications [35], it is not possible to do that comparison for all the compounds because there exist no extended reports of properties for them due to their low industrial availability. The shortcut method by the DiSTillation-Winn-Underwood (DSTWU) block, based on the assumptions of constant relative volatilities and molar fluxes, was implemented to estimate the number of theoretical stages N 1) , external reflux ratio R, liquid distillate flow rate L D , reboiler duty Q N , and feeding stage N F .…”

Identification of the Crystalline Product of Liquid-Phase Oxidation of α-Pinene with Atmospheric Oxygen in the Presence of Cobalt (II) Stearate

“…: 26,20 (С9); 27,27 (С8); 27,81 (С4); 32,69 (С6); 38,89 (С5); 68,67 (С1); 72,33 (С7); 125,34 (С3); 134,48 (С2). Значения соответствуют опубликованным [1,19]. ИК-спектр, ν, см -1 : 3318 [(O-H, H)], 2840, 2886, 2934, 2973.…”

“…Процесс жидкофазного окисления кислородом воздуха терпеновых углеводородов хорошо изучен [2][3][4][5][6][7][8][9][10][11][15][16][17][18][19][20][21][22][23][24], однако сложно воспроизводим, т. к. окисление углеводородов относится к радикально-цепному и реакция может протекать в нескольких направлениях с образованием различных кислородсодержащих соединений. В настоящее время существует общепринятая схема радикально-цепного некаталитического окисления углеводородов [6,7,16,17]: сначала происходит зарождение цепи (стадия инициирования), далее продолжение процесса образования цепи с вырожденным разветвлением и обрыв цепи.…”