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New technological solutions in the production of high quality cyclohexanone

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Objectives. The intensification of modern large-tonnage Russian technologies requires a deep investigation into the theoretical foundations of these processes and searching for ways that would significantly reduce the time and cost of their development, as well as to ensure the access of high-quality products on the world market. The aim of the work was to study the options regarding technological changes in the process of obtaining cyclohexanone at two stages: 1) oxidate (cyclohexane oxidation product after the stage of neutralization and removal of the main amount of unreacted cyclohexane) saponification and 2) end product rectification. The changes should ensure the high quality of the product without requiring significant energy and investment costs.

Methods. Studies of heterophase alkaline hydrolysis with NaOH solutions were carried out at 30–80 °C in the presence of and without a phase transfer catalyst (PTC) (saponification conditions in the industry are 70 °C). The homophase process was studied in the presence of KOH at 120 °C (industrial conditions for raw cyclohexanone rectification are 90–130 °C) on artificial mixtures based on industrial samples of the oxidate with the addition of model substances (oxygencontaining impurities with a main substance content of no less than 95%). Analysis of the initial and obtained products was carried out using gas-liquid chromatography and chromatographymass spectrometry.

Results. The totality of the obtained data provides theoretical justification for the fact: 50– 70% of esters and unsaponifiable impurities can be removed by using heterophase alkaline saponification in industrial environments. The post-treatment of crude cyclohexanone by rectification in the presence of KOH decreases the ester number by a factor of 3–5, however, the number of cyclohexanone condensation products in the bottom sharply increases. The amount of these substances varies from 10 to 20 kg/t of cyclohexanone depending on compliance with the conditions. In the presence of PTC, the conversion of esters at the saponification stage is 95–100%, aldehydes 100%, and unsaturated ketones 80%.

Conclusions. If the proposed technology for saponification in the presence of PTC is adopted there will be no need to use an alkali during the process of cyclohexanone rectification. This makes the process more stable, reduces the losses of cyclohexanone, reduces the amount of tars, and normalized indicators of cyclohexanone quality are attained.

About the Authors

S. V. Levanova
Samara State Technical University
Russian Federation

Svetlana V. Levanova, Dr. of Sci. (Chemistry), Professor of the Chair “Technology of Organic and Petrochemical Synthesis”

244, Molodogvardeiskaya ul., Samara 443100, Russia

E. A. Martynenko
Samara State Technical University
Russian Federation

Evgeniya A. Martynenko, Cand. of Sci. (Chemistry), Researcher of the Chair “Chemical Technology of Oil and Gas Refining”

244, Molodogvardeiskaya ul., Samara 443100, Russia

A. A. Morgun
Samara State Technical University
Russian Federation

Alena A. Morgun, Master’s Degree Candidate, Engineer of the Chair “Technology of Organic and Petrochemical Synthesis”

244, Molodogvardeiskaya ul., Samara 443100, Russia

I. L. Glazko
Samara State Technical University
Russian Federation

Ilya L. Glazko, Cand. of Sci. (Chemistry), Associate Professor of the Chair “Technology of Organic and Petrochemical Synthesis”

244, Molodogvardeiskaya ul., Samara 443100, Russia

A. B. Sokolov
Samara State Technical University
Russian Federation

Alexander B. Sokolov, Cand. of Sci. (Chemistry), Associate Professor of the Chair “Technology of Organic and Petrochemical Synthesis”

244, Molodogvardeiskaya ul., Samara 443100, Russia


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Supplementary files

1. Scheme of an industrial process for cyclohexanone isolation and purification with the suggested optimization options.
Type Исследовательские инструменты
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For citation:

Levanova S.V., Martynenko E.A., Morgun A.A., Glazko I.L., Sokolov A.B. New technological solutions in the production of high quality cyclohexanone. Fine Chemical Technologies. 2019;14(5):21-30.

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