Intensifying the oxidation of isopropylbenzene

Koshel, G. N.; Смирнова, Е. В.; Курганова, Е. А.; Ekimova, I. D.; Lebedeva, N. V.; Koshel, S. G.; Плахтинский, В. В.

doi:10.1134/s2070050410030086

Cited by 6 publications

(4 citation statements)

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“…As demonstrated in the earlier study [3], the reuse of N HPI separated from the oxidation products does not lead to any significant changes in the main…”

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confidence: 74%

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Liquid-phase oxidation of isopropylbenzene in the presence of N-hydroxyphthalimide

et al. 2012

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96Alkylarene oxidations are the key reactions in the promising methods of obtaining various oxygen con taining organic compounds, namely, alkylphenols and aliphatic ketones, which are widely used in the synthe sis of valuable polymers.Among these reactions, the cumene method of producing phenol and acetone [1] and the simulta neous synthesis of styrene and propylene oxide (Hal con process) [2] have been investigated in detail and widely commercialized. The basic step of these pro cesses is the initiated liquid phase oxidation of isopro pylbenzene or ethylbenzene into the corresponding hydroperoxide. The economic characteristics of the overall process depend directly on the efficiency of this step. It is, therefore, necessary to optimize the oxida tion conditions so as to increase the conversion of the initial hydrocarbon into the hydroperoxide (including through employment of an efficient catalyst) without affecting a high hydroperoxide selectivity and chang ing the existing technology.Kinetic studies of the liquid phase oxidation of iso propylbenzene demonstrated that N hydroxyphthal imide (N HPI) at a concentration of 2-3 wt % increases the hydrocarbon oxidation rate by a factor of 2 relative to the oxidation rate under the standard pro cess conditions. At 120-130°C, the isopropylbenzene conversion is 40-50% in 2-3 h with a hydroperoxide selectivity of 90-95% [3]. Thus, N HPI intensifies the process by increasing the reaction rate and hydrocar bon conversion without reducing the high hydroper oxide selectivity. Considering that phenol is produced in great amounts, this intensification provides means to markedly improve the efficiency of the process.In order to confirm the appropriateness of employ ing N HPI and its structural analogues as agents accelerating the oxidation of isopropylbenzene, we calculated, using the PM3 (unrestricted open shell Hartree-Fock) method, the reactivity index, specifi cally, the difference between the energy of the singly occupied molecular orbital (|E SOMO |) of the substrate (isopropylbenzene) radical and the same energy of the nitrogen containing compound (NC) (|ΔE SOMO |).Japanese researchers [4] recommend to select the catalytic systems, in which the difference between the E SOMO values from 0 to 10 eV, preferably, 0-4 eV. This approach will allow the suitability of a catalyst and the process rate to be estimated a priori, providing a basis for further technological investigation. The |ΔE SOMO | values for the systems examined here fall in the 1-1.5 eV range; therefore, N HPI and its structural analogues are usable in the liquid phase oxidation of isopropyl benzene.N HPI is known to accelerate the oxidation of alkanes, alkylbenzenes, alcohols, ethers, and acetals into oxygen containing compounds (such as ketones and carboxylic and dicarboxylic acids) [5]. It is believed that, in these oxidation processes, the inter action of N HPI with the initiator radical or with the peroxy radical of an oxidizer yields the N oxyphthal imide radical (N OPIR) that is capable of selectively sub...

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“…As demonstrated in the earlier study [3], the reuse of N HPI separated from the oxidation products does not lead to any significant changes in the main…”

mentioning

confidence: 74%

“…At 120-130°C, the isopropylbenzene conversion is 40-50% in 2-3 h with a hydroperoxide selectivity of 90-95% [3]. Thus, N HPI intensifies the process by increasing the reaction rate and hydrocar bon conversion without reducing the high hydroper oxide selectivity.…”

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confidence: 97%

Liquid-phase oxidation of isopropylbenzene in the presence of N-hydroxyphthalimide

et al. 2012

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“…In recent years, N-hydroxyphthalimide (NHPI) has attracted much attention because of its nontoxicity, ease of preparation by phthalic anhydride and hydroxylamine, and high activity towards various types of organic substrates [12,13]. Therefore, the use of this compound as a catalyst allows ones to increase the conversion of oxidised hydrocarbon by 2-3 times with selectivity of its hydroperoxide formation over 90% [2,14].…”

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confidence: 99%

Forecasting of catalytic activity of phthalimide compounds in the process of liquid-phase aerobic oxidation of alkylaromatic hydrocarbons

Kabanova,

Kurganova,

Frolov

et al. 2024

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The authors calculated the single occupied molecular orbital energies of the substrate radical and the phthalimide catalyst radical by the Hartree-Fock quantum chemical method (PM7). According to the research, low numerical values of ∆Esomo characterise N-hydroxyphthalimide derivatives containing electron-donating substituents in their structure and possess high catalytic activity. Application of such compounds allows ones to intensify essentially the process of alkylaromatic hydrocarbons aerobic liquid-phase oxidation with preservation of feedstock conversion high parameters and selectivity of its hydroperoxide formation. The calculated data are in good agreement with the experimentally obtained data. Hence, the proposed method can be used to evaluate the catalytic activity of phthalimide compounds with respect to a wide range of aromatic hydrocarbons.

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“…The liquid-phase initiated oxidation of substituted mononuclear arenes is an industrial way of obtaining the corresponding hydroperoxides used in many areas. One way of improving the efficiency of this process that allows an increase in the conversion of initial hydrocarbons to hydroperoxides while maintaining their high selectivity is to use N-hydroxyphthalimide (NHPI) as a homogeneous catalyst [1][2][3]. The use of NHPI and its alkyl-substituted analogs in oxidation allows to increase the conversion of hydrocarbons by 2-3 times, relative to standard conditions, while maintaining high selectivity to form hydroperoxides [4].…”

Section: Introductionmentioning

confidence: 99%

Correlation between the Thermodynamic and Kinetic Parameters of the Oxidation Reactions of Substituted Mononuclear Arenes in the Presence of N-Hydroxyphthalimide

Соловьев

Курганова

Фролов

et al. 2019

Russ. J. Phys. Chem.

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The effect the structure of substituted mononuclear arenes has on the thermodynamic functions of reactions during their oxidation in the presence of N-hydroxyphthalimide is studied. The relationship between the free energy of the oxidation of cumene, isopropyl-m-xylene, isopropyl-o-xylene, isopropyl-pxylene, m-cymene, p-cymene, and cyclohexylbenzene and its rate at 363-413 K is studied. There is a strong correlation between the free energy of hydrogen abstraction from a tertiary carbon atom with an N-hydroxyphthalimide radical, the rate constant of this reaction, and rate of oxidation for different isomers of the same hydrocarbon, making it possible to predict their relative oxidability.

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Intensifying the oxidation of isopropylbenzene

Cited by 6 publications

References 2 publications

Liquid-phase oxidation of isopropylbenzene in the presence of N-hydroxyphthalimide

Liquid-phase oxidation of isopropylbenzene in the presence of N-hydroxyphthalimide

Forecasting of catalytic activity of phthalimide compounds in the process of liquid-phase aerobic oxidation of alkylaromatic hydrocarbons

Correlation between the Thermodynamic and Kinetic Parameters of the Oxidation Reactions of Substituted Mononuclear Arenes in the Presence of N-Hydroxyphthalimide

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