Details

Autor(en) / Beteiligte

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

Titel

Mechanistic Study on the Production of Hydrogen Peroxide in the Anthraquinone Process

Ist Teil von

• European Journal of Organic Chemistry, 2011-08, Vol.2011 (22), p.4113-4120

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2011

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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 ed by triplet dioxygen to produce a hydroperoxide radical (HOO·) and a 10‐hydroxy‐9‐anthroxyl radical (AQH·), followed by subsequent hydrogen atom ion that leads to the formation of hydrogen peroxide and anthraquinone (AQ). Hydrogen atom ion 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. Reaction mechanisms for the autoxidation step of the anthraquinone process have been studied. The proposed mechanism is that the hydrogen atom of anthrahydroquinone is ed by dioxygen to produce a hydroperoxide radical, followed by subsequent hydrogen atom ion, leading to the formation of hydrogen peroxide and anthraquinone.