Heterogeneously catalysed partial oxidation of cyclohexane in supercritical carbon dioxide

Armbruster, Udo

doi:10.1016/j.apcata.2004.01.017

Cited by 15 publications

(3 citation statements)

References 29 publications

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“…Oxidation of I to olone in a continuous process in sc-CO 2 , using supported metal (M = Fe, Co, Mn) oxide catalysts and zeolite-immobilized metal complexes gives substantially lower yields than the conventional batch process. 307 Since new largescale processes for adipic acid are likely to require innovations in several areas, not just an alternative solvent use, it is unlikely that simply addition of CO 2 to a conventional process could provide substantial green and economic benefits. Industrial CO 2 -based oxidation processes have not yet been realized.…”

Section: Direct One-step Conversion Of Cyclohexane To Adipic Acidmentioning

confidence: 99%

Transiting from Adipic Acid to Bioadipic Acid. 1, Petroleum-Based Processes

Bart

Cavallaro

2014

Ind. Eng. Chem. Res.

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Adipic acid, which is a very important commodity chemical, is traditionally manufactured industrially by an aged and unsustainable multistep process that involves homogeneous catalysts, aggressive oxidants (concentrated nitric acid) and the production of large quantities of the greenhouse gas nitrous oxide. Much research and development into alternative and cleaner process routes to adipic acid have been carried out over the past 70 years. Improved reaction schemes have invoked variations in fossil raw materials (from benzene and phenol to cyclohexane, cyclohexanol, cyclohexanone, cyclohexene, butadiene, and adiponitrile, etc.), oxidants (O 2 , air, H 2 O 2 , t-BuOOH, ozone), catalysts (homogeneous, heterogeneous, phase transfer, biomimetic) and reaction conditions (low temperature, atmospheric pressure, and solvent-, metal-, halide-, and corrosion-free). No single proposed alternative pathwaysome of which are purely academicsimultaneously addresses the problems of petrochemical origin, toxic starting materials or reagents, generation of environmentally incompatible byproducts, use of forcing reaction conditions, and cost in an entirely satisfactory manner, despite very intense efforts. Recently, more benign bio-based reaction pathways have been proposed starting from renewables, such as glucose or vegetable oils (which will be discussed in Part 2 of this series).

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Section: Direct One-step Conversion Of Cyclohexane To Adipic Acidmentioning

confidence: 99%

Transiting from Adipic Acid to Bioadipic Acid. 1, Petroleum-Based Processes

Bart

Cavallaro

2014

Ind. Eng. Chem. Res.

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“…For the commercial processes, cobalt (as acetate or palmitate) is the usual catalyst with molecular oxygen as the oxidant, and the product formed is an approximately equimolar mixture of cyclohexanol and cyclohexanone. Other catalyst systems using oxygen as the oxidant, such as iron and ruthenium catalyst, nanostructured iron and cobalt catalyst, immobilized cobalt catalyst, polymer-supported cobaltous palmitate, and cobalt salen complex supported on silica have been reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

Heteronuclear Macrocyclic Iron−Copper Complex Catalyst Covalently Bonded to Modified Alumina Catalyst for Oxidation of Cyclohexane

Kishore

Kumar

2007

Ind. Eng. Chem. Res.

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In this paper, we report the synthesis of FeCuL 1 and FeCuL 2 complexes of 2,6-diformyl-4-methylphenol and 1,2-phenylenediamine (L 1 ) and 2,6-diformyl-4-methylphenol and 1,3-diaminopropane (L 2 ). The FeCuL 1 complex has been covalently bonded to alumina and used as a catalyst for the oxidation of cyclohexane. The complex catalyst thus-prepared was found to be thermally stable and was completely characterized by CHN, scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDAX), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), and NMR spectroscopy. The oxidation of cyclohexane has been carried out using molecular oxygen without any solvent, coreactant, or cocatalyst in the temperature range (398-483 K) with cyclohexanone as the only product. The GC-MS of the product formed showed the total conversion was as much as 7.7%. In order to explain the experimental data, a possible reaction mechanism has been proposed and rate constants (assuming single phase) at different temperatures were determined using an optimal curve fitting by applying genetic algorithm. The rate constants thus-determined were found to be functions of temperature only. From experiments carried out at different temperatures, we found that, for every rate constant, an Arrhenius-type relation could be established.

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“…Various catalysts have been developed and among them, cobalt (as acetate or palmitate) is the most commonly used catalyst with molecular oxygen as the oxidant, and the products formed are about equimolar mixture of cyclohexanol and cyclohexanone. Other catalyst systems using oxygen as oxidant such as iron and ruthenium catalyst,8 nanostructured iron and cobalt catalyst,10 immobilized cobalt catalyst,11 polymer supported cobaltous palmitate,12 and cobalt salen complex supported on silica13 have been reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

Kinetic study of oxidation of cyclohexane using complex catalyst

Kishore

Kumar

2007

AIChE Journal

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With an effort to use a multimetallic catalyst system for oxidation of cyclohexane using oxygen, a binuclear monometallic macrocyclic ZrZr complex was prepared and covalently bonded to modified alumina support. The complex catalyst thus prepared was found to be thermally stable and was completely characterized by CHN, SEM‐EDAX, TGA, and FTIR analysis. We carried out liquid phase oxidation of cyclohexane using molecular oxygen without any solvent, coreactant, or cocatalyst at considerably mild reaction conditions (150°C, 27 atm) with extremely high selectivity. The GC‐MS of the liquid product formed showed the total conversion of as much as 19% having cyclohexanone and cyclohexanol in the ratio of 16:1. To explain the experimental data, a possible reaction mechanism has been proposed and rate constants (assuming single phase) at different temperatures were determined using an optimal curve fitting by applying genetic algorithm. We showed that the steady state approximation cannot be assumed, and for the pressure range studied (7–35 atm), the rate constants thus determined were found to be a function of temperature only. From experiments carried out at different temperatures, we found that for every rate constant, an Arrhenious type relation could be established. © 2007 American Institute of Chemical Engineers AIChE J, 2007

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Heterogeneously catalysed partial oxidation of cyclohexane in supercritical carbon dioxide

Cited by 15 publications

References 29 publications

Transiting from Adipic Acid to Bioadipic Acid. 1, Petroleum-Based Processes

Transiting from Adipic Acid to Bioadipic Acid. 1, Petroleum-Based Processes

Heteronuclear Macrocyclic Iron−Copper Complex Catalyst Covalently Bonded to Modified Alumina Catalyst for Oxidation of Cyclohexane

Kinetic study of oxidation of cyclohexane using complex catalyst

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