New technological solutions in the production of high quality cyclohexanone

Abstract

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 Formation and Structure of Transition State During "Chair" to "Boat" Transition of Cyclohexanone

“…Вместе с тем наименьшая энергия этой конформации является причиной ее наименьшей реакционной способности из всех конформаций циклогексанона в реакциях окисления [9]. Так как окисление циклогексанона в процессе окисления циклогексана -основная причина снижения селективности [1][2][3][4][10][11][12][13][14], исследование закономерностей переходов циклогексанона в более реакционноспособные конформации представляется достаточно актуальным. Поскольку наиболее вероятен переход циклогексанона из конформации «кресло» в конформацию «ванна», обладающую меньшей энергией из всех прочих конформаций кетона [5][6][7][8][9], в настоящей работе были изучены закономерности конформационного перехода «кресло»-«ванна».…”

Heterogeneous catalytic condensation of propanal

“…1,2 In petrochemistry, aldol condensation is an important tool for the production of fuel components and conversion of the biomass to valuable monomers and intermediate products. [3][4][5][6][7] The products of aldol condensation of lower aldehydes serve as intermediates for the synthesis of additives to diesel fuel, aromatizing agents, and plasticizers for building blocks. 8 These reactions occur, as a rule, under mild conditions and do not need a sophisticated technical equipment.…”