Mechanistic study on the production of hydrogen peroxide in the anthraquinone process

Tomonori Nishimi, Takashi Kamachi, Kenji Kato, Tomio Kato, Kazunari Yoshizawa

研究成果: ジャーナルへの寄稿記事

22 引用 (Scopus)

抄録

Hydrogen peroxide is produced from hydrogen gas and air in industry by using the anthraquinone process. The mechanism for the production of hydrogen peroxide in this process is studied by using DFT calculations and reaction rate measurements. A hydrogen atom of anthrahydroquinone (AHQ) is directly abstracted by triplet dioxygen to produce a hydroperoxide radical (HOO·) and a 10-hydroxy-9-anthroxyl radical (AQH·), followed by subsequent hydrogen atom abstraction that leads to the formation of hydrogen peroxide and anthraquinone (AQ). Hydrogen atom abstraction was found to be the rate-determining step in this process. Tetrahydroanthrahydroquinone (THAHQ) is also used in this process in a similar way to AHQ, but a higher activation energy is required for the rate-determining step when THAHQ is used, which would lead to a 25-fold rate deacceleration compared with AHQ at 27 °C. The reactivities of AHQ and THAHQ are not significantly influenced by effects of side alkyl chain that is used in the industrial process for increasing the solubility of AHQ and AQ in working solution. The relative reaction rate of AHQ and THAHQ is measured under laboratory conditions. The computational results are consistent with an observed lower rate of the oxidation process of THAHQ.

元の言語英語
ページ(範囲)4113-4120
ページ数8
ジャーナルEuropean Journal of Organic Chemistry
発行部数22
DOI
出版物ステータス出版済み - 8 1 2011

Fingerprint

Anthraquinones
anthraquinones
hydrogen peroxide
Hydrogen Peroxide
Hydrogen
hydrogen atoms
Atoms
Reaction rates
reaction kinetics
Discrete Fourier transforms
Solubility
Activation energy
Gases
Oxygen
Oxidation
solubility
reactivity
industries
activation energy
Air

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry

これを引用

Mechanistic study on the production of hydrogen peroxide in the anthraquinone process. / Nishimi, Tomonori; Kamachi, Takashi; Kato, Kenji; Kato, Tomio; Yoshizawa, Kazunari.

:: European Journal of Organic Chemistry, 番号 22, 01.08.2011, p. 4113-4120.

研究成果: ジャーナルへの寄稿記事

Nishimi, Tomonori ; Kamachi, Takashi ; Kato, Kenji ; Kato, Tomio ; Yoshizawa, Kazunari. / Mechanistic study on the production of hydrogen peroxide in the anthraquinone process. :: European Journal of Organic Chemistry. 2011 ; 番号 22. pp. 4113-4120.
@article{6f0f94b034ac4333b9229156c1dcde59,
title = "Mechanistic study on the production of hydrogen peroxide in the anthraquinone process",
abstract = "Hydrogen peroxide is produced from hydrogen gas and air in industry by using the anthraquinone process. The mechanism for the production of hydrogen peroxide in this process is studied by using DFT calculations and reaction rate measurements. A hydrogen atom of anthrahydroquinone (AHQ) is directly abstracted by triplet dioxygen to produce a hydroperoxide radical (HOO·) and a 10-hydroxy-9-anthroxyl radical (AQH·), followed by subsequent hydrogen atom abstraction that leads to the formation of hydrogen peroxide and anthraquinone (AQ). Hydrogen atom abstraction was found to be the rate-determining step in this process. Tetrahydroanthrahydroquinone (THAHQ) is also used in this process in a similar way to AHQ, but a higher activation energy is required for the rate-determining step when THAHQ is used, which would lead to a 25-fold rate deacceleration compared with AHQ at 27 °C. The reactivities of AHQ and THAHQ are not significantly influenced by effects of side alkyl chain that is used in the industrial process for increasing the solubility of AHQ and AQ in working solution. The relative reaction rate of AHQ and THAHQ is measured under laboratory conditions. The computational results are consistent with an observed lower rate of the oxidation process of THAHQ.",
author = "Tomonori Nishimi and Takashi Kamachi and Kenji Kato and Tomio Kato and Kazunari Yoshizawa",
year = "2011",
month = "8",
day = "1",
doi = "10.1002/ejoc.201100300",
language = "English",
pages = "4113--4120",
journal = "Liebigs Annalen der Chemie",
issn = "1434-193X",
publisher = "Wiley-VCH Verlag",
number = "22",

}

TY - JOUR

T1 - Mechanistic study on the production of hydrogen peroxide in the anthraquinone process

AU - Nishimi, Tomonori

AU - Kamachi, Takashi

AU - Kato, Kenji

AU - Kato, Tomio

AU - Yoshizawa, Kazunari

PY - 2011/8/1

Y1 - 2011/8/1

N2 - Hydrogen peroxide is produced from hydrogen gas and air in industry by using the anthraquinone process. The mechanism for the production of hydrogen peroxide in this process is studied by using DFT calculations and reaction rate measurements. A hydrogen atom of anthrahydroquinone (AHQ) is directly abstracted by triplet dioxygen to produce a hydroperoxide radical (HOO·) and a 10-hydroxy-9-anthroxyl radical (AQH·), followed by subsequent hydrogen atom abstraction that leads to the formation of hydrogen peroxide and anthraquinone (AQ). Hydrogen atom abstraction was found to be the rate-determining step in this process. Tetrahydroanthrahydroquinone (THAHQ) is also used in this process in a similar way to AHQ, but a higher activation energy is required for the rate-determining step when THAHQ is used, which would lead to a 25-fold rate deacceleration compared with AHQ at 27 °C. The reactivities of AHQ and THAHQ are not significantly influenced by effects of side alkyl chain that is used in the industrial process for increasing the solubility of AHQ and AQ in working solution. The relative reaction rate of AHQ and THAHQ is measured under laboratory conditions. The computational results are consistent with an observed lower rate of the oxidation process of THAHQ.

AB - Hydrogen peroxide is produced from hydrogen gas and air in industry by using the anthraquinone process. The mechanism for the production of hydrogen peroxide in this process is studied by using DFT calculations and reaction rate measurements. A hydrogen atom of anthrahydroquinone (AHQ) is directly abstracted by triplet dioxygen to produce a hydroperoxide radical (HOO·) and a 10-hydroxy-9-anthroxyl radical (AQH·), followed by subsequent hydrogen atom abstraction that leads to the formation of hydrogen peroxide and anthraquinone (AQ). Hydrogen atom abstraction was found to be the rate-determining step in this process. Tetrahydroanthrahydroquinone (THAHQ) is also used in this process in a similar way to AHQ, but a higher activation energy is required for the rate-determining step when THAHQ is used, which would lead to a 25-fold rate deacceleration compared with AHQ at 27 °C. The reactivities of AHQ and THAHQ are not significantly influenced by effects of side alkyl chain that is used in the industrial process for increasing the solubility of AHQ and AQ in working solution. The relative reaction rate of AHQ and THAHQ is measured under laboratory conditions. The computational results are consistent with an observed lower rate of the oxidation process of THAHQ.

UR - http://www.scopus.com/inward/record.url?scp=79960582361&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79960582361&partnerID=8YFLogxK

U2 - 10.1002/ejoc.201100300

DO - 10.1002/ejoc.201100300

M3 - Article

SP - 4113

EP - 4120

JO - Liebigs Annalen der Chemie

JF - Liebigs Annalen der Chemie

SN - 1434-193X

IS - 22

ER -