Investigation of propene oxidation to acrolein by the method of ultralow conversion: A new mechanism of the reaction

被引:6
|
作者
Panov, Gennady I. [1 ]
Parfenov, Mikhail V. [1 ]
Starokon, Eugeny V. [1 ]
Kharitonov, Alexandr S. [1 ]
机构
[1] Boreskov Inst Catalysis, Dept Heterogeneous Catalysis, Pr Lavrentieva 5, Novosibirsk 630090, Russia
关键词
Propene oxidation; Acrolein; Multicomponent catalysts; Method of ultralow conversion; Allyl alcohol; Allyl radical; Allyl hydroxylation mechanism; Intermediate products; BISMUTH MOLYBDATE CATALYST; C-H BOND; SELECTIVE OXIDATION; ACTIVE-CENTERS; AMMOXIDATION MECHANISMS; PROPYLENE OXIDATION; PHASE COOPERATION; SITE ISOLATION; MOVNBTEO M1; M2; PHASES;
D O I
10.1016/j.jcat.2018.09.033
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Investigation of reaction mechanisms by identifying the intermediates released into the gas phase is most effective at low conversion of reactants, ideally approaching zero. However, conversions below 0.5-1% are rarely used, due to the difficulty of analysis of low-concentration products. The mechanism of the title reaction is a subject of long-term discussion. We studied the mechanism using an original ultralow conversion (ULC) method. The idea is to perform the analysis of products after their preliminary accumulation in a suitable absorbent at the reactor outlet. This allows decreasing conversion by 2-3 orders of magnitude. The ULC experiments were conducted with a Bi-Mo catalyst at 100-250 degrees C and with propene conversion down to 0.001%. A new so-called allyl hydroxylation mechanism was revealed. A key step is the hydroxylation of the CH3 group to form an allyl alcohol intermediate, which is further oxidized to acrolein. The mechanism explains all reaction features and was confirmed by experiments at 350 degrees C. (C) 2018 Elsevier Inc. All rights reserved.
引用
收藏
页码:315 / 323
页数:9
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