論文 / 著書情報
Article / Book Information
題目(和文)

高難度選択酸化反応用Fe含有ゼオライト触媒に関する研究

Title(English)

Study on Fe-containing zeolite catalysts for extremely difficult selectiveoxidation reactions

著者(和文)

XiaoPeipeiAuthor(English)

PEIPEI XIAO

出典(和文)

学位:博士(工学),学位授与機関:東京工業大学,
報告番号:甲第10979号,授与年月日:2018年9月20日,
学位の種別:課程博士,
審査員:野村 淳子,鎌田 慶吾,本倉 健,庄子 良晃,横井 俊之

Citation(English)

Degree:Doctor (Engineering),Conferring organization: Tokyo Institute of Technology,
Report number:甲第10979号,
Conferred date:2018/9/20,
Degree Type:Course doctor,Examiner:,,,,

学位種別(和文)

博士論文

Category(English)

Doctoral Thesis

種別(和文)

審査の要旨

Type(English)

Exam Summary

Powered by T2R2 (Science Tokyo Research Repository)

（博士課程）論文審査の要旨及び審査員
報告番号甲第号
氏

主査

論文審査
審 査 員

審査員

名

学位申請者氏名
職

名

野村淳子

准教授

鎌田慶吾

准教授

本倉健

准教授

庄子良晃

准教授

Xiao Peipei
氏

名

横井俊之

職

名

准教授

審査員

論文審査の要旨（2000 字程度）

This thesis is entitled “Study on Fe-containing zeolite catalysts for extremely difficult selectiveoxidation reactions” and the approaches to obtain highly active Fe-containing zeolites catalysts for
extremely difficult selective oxidation reactions, including direct conversion of methane to methanol(MTM) and benzene to phenol (BTP) with H2O2 are addressed.
In Chapter 1, which was named the “Introduction”, the research background was described todemonstrate the importance of the thesis.
Chapter 2 entitled “Direct synthesis of phenol by hydroxylation of benzene with hydrogen peroxideover Fe-containing MFI zeolite catalysts” explored the role of different Fe species on Fe-containing MFI
zeolites by different methods. Directly synthesized Fe-silicalite-1 achieved better catalytic performance
than the post synthesis ones in BTP reaction. The formation of isolated and oligomeric extra framework Fespecies played a key role for achieving high yield of phenol. Moreover, post-alkaline treatment wasadvantageous to the formation of mesopores and oligomeric Fe species on the extra framework, thus thehighest phenol yield of 7.6% was achieved.
Chapter 3 entitled “Dramatic impacts of the distribution of Fe species in Fe-silicalite-1 zeolites andsolvent on liquid-phase methane conversion to methanol with H2O2” investigated Fe distribution inFe-silicalite-1 zeolites using TPAOH as OSDA with or without Na cations. Fe-sillicalite-1 zeolites
synthesized without Na cations showed more uniform Fe distribution than those synthesized with Nacations. Sulfolane was useful to improve the production of methanol and its stability during MTM reaction.
The use of sulfolane in water with an appropriate proportion led to an extremely high methanol production
with a high selectivity. Fe-silicalite-1 zeolites synthesized using TPAOH as OSDA without Na cations
showed better catalytic performance than those with Na cations possibly due to the position of Fe species.
Chapter 4 entitled “The influence of iron and aluminum location in MFI zeolites on the catalytic
performance in hydroxylation of benzene to phenol and methane to methanol with H2O2” discussed Fedistribution in Fe-ZSM-5 zeolites using TPAOH as OSDA with and without Na cations. Fe-ZSM-5 zeolites
synthesized without Na cations (FZ(T)x) displayed more uniform Fe distribution than those synthesizedwith Na cations (FZ(TN)y). In general, FZ(T)x zeolites showed better catalytic performance than FZ(TN)yin both BTP and MTM reactions. The introduction of Al in FZ(T)x zeolites improved the catalyticperformance in BTP and MTM reactions, but in FZ(TN)y zeolites, the catalytic performance was not
obviously increased possibly due to the location of iron and aluminum.
In Chapter 5 entitled “Alkaline treatment on as-synthesized and calcined Fe-silicalite-1 andFe-ZSM-5 zeolites for hydroxylation of benzene to phenol with H2O2” the influence of desilication onFe-ZSM-5 and Fe-silicalite-1 zeolites was researched. Both template and aluminum can prevent
desilication and protect the crystal structure. Alkaline treatment was an effective post modification methodto affect both the porosity of the zeolite and the nature of Fe species. The increased porosity improved thetransport properties, reduced diffusion resistance and increased the active Fe species.
In Chapter 6 entitled “Direct synthesis of Fe-containing MWW zeolite for direct hydroxylation ofbenzene to phenol and methane to methanol with H2O2” the effects of calcination temperature on thecatalytic performance of Fe-MWW and Fe, Al-MWW were discovered. High temperature calcination toremove OSDA was beneficial to produce more isolated and oligomeric Fe species on the extra frameworkfor Fe-MWW, thus activate the catalytic performance. But the presence of Al in Fe, Al-MWW dispersed Feand high temperature calcination produced the FeAlOx species, which may be not beneficial to thecatalytic performance. In addition, increasing the calcination temperature to prepare H-type zeolite mademore seriously Fe aggregation for both Fe-MWW and Fe, Al-MWW, thus decrease the catalyticperformance.
Chapter 7 entitled “Iron- and copper-exchanged Beta zeolite catalysts for hydroxylation of benzene
to phenol and methane to methanol with H2O2” included Fe and/ or Cu exchanged Beta catalysts withvaried metal contents. Fe-Cu/Beta catalysts showed dramatically high catalytic activity due to thesynergetic effect. 6Fe-6Cu/Beta achieved the highest phenol yield of 10.5 % in BTP reaction and MeOH
yield of 720 µmol in MTM reaction. The catalytic stability in the BTP reaction was investigated. The
synergetic effect was influenced by the metallic states instead of the content.
Chapter 8 entitled “Summary” gave a summary based on the whole thesis.
On a whole, this thesis satisfies the academic level of doctor of engineering.
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