Reaction Kinetics, Mechanisms and Catalysis

, Volume 127, Issue 2, pp 787–801 | Cite as

Formation and transformation of nitroso compounds of ketoxime isomers in ketone ammoximation catalyzed by hollow titanium silicalite

  • Shengjian ZhangEmail author
  • Hong Zhao
  • Xiaoyong Wang
  • Shu Luo
  • Yuanqing Shi
  • Yingxian Zhao
  • Liyan Ying
  • Jie Chen


2-Nitrosopropane as the isomer of acetoxime was first found in ammoxidation of acetone with hydrogen peroxide catalyzed by hollow titanium silicalite (HTS). Experimental investigation indicates that the formation of 2-nitrosopropane was closely related to the pore size and surface acidity of HTS zeolite and significantly affected by reaction conditions, and further revealed that once formed, this isomer could be easily converted into main product acetoxime and also turned into by-product 2-nitropropane in the presence of excess hydrogen peroxide or O2. Based on the experimental results in combination with the analysis of reaction mechanism, it was suggested that the pathways of acetone ammoxidation catalyzed by HTS could involve both hydroxylamino intermediate and imino intermediate. The former was dominant in the production of acetone oxime, while the latter was mainly responsible for the formation of 2-nitropropane. In the latter case, an acetone first reacted with ammonia to form an imine and then interacted with an active center of Ti-OOH on catalyst to generate an unstable 2-nitrosopropane.


Hollow titanium silicalite Ketone ammoximation Mechanism pathway Imine Nitroso propane 



The support of the Zhejiang Province Natural Science Foundation of China (Granted No. LY13B030003) is greatly acknowledged.

Supplementary material

11144_2019_1597_MOESM1_ESM.docx (102 kb)
Supplementary material 1 (DOCX 101 kb)


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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.Ningbo Institute of TechnologyZhejiang UniversityNingboPeople’s Republic of China
  2. 2.Ningbo Siming Chemical Co., LtdNingboPeople’s Republic of China

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