Experiments and Kinetic Modeling on the Co/Mn/Br Catalyzed Oxidation of Prehnitene to Mellophanic Acid in the Liquid Phase

Abstract

Mellophanic acid (MPA) was prepared by liquidphase oxidation of prehnitene (PR) using Co/Mn/Br as the catalyst and acetic acid/water as the solvent in this work. The effects of temperatures and catalyst concentration and ratio on the yield of MPA and trimellitic acid (TMA) were investigated. It was found that improving reaction temperatures can significantly enhance the yield of MPA, and the higher ratio of Mn and concentration of Br in the catalyst is beneficial to increase the yield of both MPA and TMA. Based on the complex radical chain mechanism of hydrocarbon oxidation, the reaction pathway of PR oxidation was proposed and a lumped kinetic model including the most important intermediates and final products was established. The number of kinetic model parameters was much reduced through the Hammett structure−reactivity relationship. The model reliability was confirmed by comparisons with experimental data. Hopefully, the results obtained in this work can bring insights into the liquid-phase oxidation of other polyalkyl aromatic hydrocarbons.

Kinetic Modeling of Homogenous Catalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

“…Fortunately, it can be obtained from the expression of the model that the reaction rate constants are insensitive to the composition of the catalyst, except k 1 and k b . Other hydrocarbon oxidation, such as p -xylene oxidation and m -xylene oxidation, also confirmed the validation of this kind of model simplification method . Fitting six sets of experiments simultaneously yields the 17 rate constants listed in the Table .…”

“…Other hydrocarbon oxidation, such as p-xylene oxidation and m-xylene oxidation, also confirmed the validation of this kind of model simplification method. 21 Fitting six sets of experiments simultaneously yields the 17 rate constants listed in the Table 1. They can share the parameters k 2 through k 6 , and only k 1 and k b need to be adjusted as the alterable parameter, which not only reduces the difficulty of estimating the model parameters but also improves the reliability of these model parameters.…”

“…Therefore, there are still some barriers to the commercial viability of heterogeneous catalysts. For the production of FDCA, the most industrially promising process is the Amoco Mid-Century (MC) process based on Co/Mn/Br homogeneous catalysis that has been extensively used in the commercial production of a variety of aromatic dicarboxylic acids, such as via paraxylene (PX) oxidation to produce PTA. , Due to the limited solubility in acetic acid, FDCA can be separated from the solution by filtering and the Co/Mn/Br catalyst can be easily recovered and recycled . Specifically, Avantium has successfully utilized the MC process to produce FDCA at its pilot demonstration factory in Geleen, The Netherlands .…”

Biosourced Aromatic Derivatives in the Upcycling of Recycled PET: Mellophanic Dianhydride as a Chain Extender

“…Mellophanic dianhydride (MEDA) is currently synthesized starting from fossil sources (Figure a). − Recently, a synthesis from bio-based dimethylfuran and maleic anhydride has been proposed (Figure b), and the process includes an oxidation step performed with potassium permanganate . To the best of our knowledge, MEDA is actually used only in the preparation of polyimides. , …”