CH4 oxidation to oxygenates with N2O over iron-containing Y zeolites: Effect of preparation

doi:10.1016/j.cjche.2018.05.021

Chinese Journal of Chemical Engineering ›› 2018, Vol. 26 ›› Issue (10): 2064-2069.DOI: 10.1016/j.cjche.2018.05.021

• Catalysis, Kinetics and Reaction Engineering • 上一篇下一篇

CH₄ oxidation to oxygenates with N₂O over iron-containing Y zeolites: Effect of preparation

Jing Zhu, Lisong Fan, Lina Song, Fengqiu Chen, Dangguo Cheng

Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

收稿日期:2018-04-02 修回日期:2018-04-24 出版日期:2018-10-28 发布日期:2018-11-14
通讯作者: Dangguo Cheng,E-mail address:dgcheng@zju.edu.cn
基金资助:
Support by the National Key R&D Program of China (2016YFA0202900), the National Natural Science Foundation of China (21622606), the Natural Science Foundation of Zhejiang Province (LR18B060001), Basic Research Project of Sinopec Group (415025) and the Fundamental Research Funds for the Central Universities.

CH₄ oxidation to oxygenates with N₂O over iron-containing Y zeolites: Effect of preparation

Jing Zhu, Lisong Fan, Lina Song, Fengqiu Chen, Dangguo Cheng

Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

Received:2018-04-02 Revised:2018-04-24 Online:2018-10-28 Published:2018-11-14
Contact: Dangguo Cheng,E-mail address:dgcheng@zju.edu.cn
Supported by:
Support by the National Key R&D Program of China (2016YFA0202900), the National Natural Science Foundation of China (21622606), the Natural Science Foundation of Zhejiang Province (LR18B060001), Basic Research Project of Sinopec Group (415025) and the Fundamental Research Funds for the Central Universities.

摘要/Abstract

摘要： Developing effective iron-incorporated zeolites and determining their active centers for the direct oxidation of CH₄ to oxygenates have remained challenging topics so far. In this paper, we successfully prepare the highly-dispersed iron supported Y zeolites by a facile solid-state ion-exchange method with ferrocene, which was conducted under water-free conditions followed by a series of calcination. Moreover, extra-framework dinuclear Fe²⁺ complexes are identified as so-called active α-iron sites on zeolites. ICP-OES, N₂ adsorption-desorption test, X-ray diffraction, solid-state ²⁷Al NMR, N₂O titration, TEM, EPR and ⁵⁷Fe Mössbauer spectra were carried out to characterize properties of sample structure, acid sites, as well as the supported iron species. Characterization results indicate that high-temperature treatments have no effect on the typical structure feature of zeolites. Compared with catalysts synthesized by conventional impregnation, the samples prepared by the facile approach possess abundant dinuclear Fe²⁺ complexes but no Fe₂O₃ bulks and show weak acidity. These lead to a higher oxygenate selectivity in CH₄ oxidation to oxygenates. Remarkably, the oxygenate (HCHO and CH₃OH) selectivity of 6.5% at 375℃ can be eventually obtained.

关键词: Ferrocene, Iron-containing zeolites, Preparation, Distributions, Partial oxidation

Abstract: Developing effective iron-incorporated zeolites and determining their active centers for the direct oxidation of CH₄ to oxygenates have remained challenging topics so far. In this paper, we successfully prepare the highly-dispersed iron supported Y zeolites by a facile solid-state ion-exchange method with ferrocene, which was conducted under water-free conditions followed by a series of calcination. Moreover, extra-framework dinuclear Fe²⁺ complexes are identified as so-called active α-iron sites on zeolites. ICP-OES, N₂ adsorption-desorption test, X-ray diffraction, solid-state ²⁷Al NMR, N₂O titration, TEM, EPR and ⁵⁷Fe Mössbauer spectra were carried out to characterize properties of sample structure, acid sites, as well as the supported iron species. Characterization results indicate that high-temperature treatments have no effect on the typical structure feature of zeolites. Compared with catalysts synthesized by conventional impregnation, the samples prepared by the facile approach possess abundant dinuclear Fe²⁺ complexes but no Fe₂O₃ bulks and show weak acidity. These lead to a higher oxygenate selectivity in CH₄ oxidation to oxygenates. Remarkably, the oxygenate (HCHO and CH₃OH) selectivity of 6.5% at 375℃ can be eventually obtained.

Key words: Ferrocene, Iron-containing zeolites, Preparation, Distributions, Partial oxidation

Jing Zhu, Lisong Fan, Lina Song, Fengqiu Chen, Dangguo Cheng. CH₄ oxidation to oxygenates with N₂O over iron-containing Y zeolites: Effect of preparation[J]. Chinese Journal of Chemical Engineering, 2018, 26(10): 2064-2069.

Jing Zhu, Lisong Fan, Lina Song, Fengqiu Chen, Dangguo Cheng. CH₄ oxidation to oxygenates with N₂O over iron-containing Y zeolites: Effect of preparation[J]. Chin.J.Chem.Eng., 2018, 26(10): 2064-2069.

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CH₄ oxidation to oxygenates with N₂O over iron-containing Y zeolites: Effect of preparation

CH₄ oxidation to oxygenates with N₂O over iron-containing Y zeolites: Effect of preparation

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