Зависимоcть активности и процесса in situ формирования ненанесенных сульфидных никель-вольфрамовых катализаторов совместного превращения пиридина и нафталина от содержания серы

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Abstract

Ненанесенные сульфидные никель-вольфрамовые катализаторы получены in situ из соответствующих маслорастворимых соединений-прекурсоров и элементной серы в реакционных смесях нафталин–пиридин различного состава при 380°C, 5.0 МПа Н2, 5 ч и содержании Ni и W, соответственно, 7.3×10–5 и 1.5×10–4 моль. Установлено, что состав продуктов гидрирования нафталина и гидродеазотирования пиридина зависит от состава реакционной смеси и количества элементной серы, вводимой для in situ формирования сульфидных катализаторов. При полной конверсии нафталина с ростом содержания пиридина в смеси (от 0.5 до 9 мас.%) доля декалинов в продуктах снижается от 97 до 71 мас.% при мольном соотношении в катализаторе S/W, равном 4, и от 97 до 51 мас.% при S/W, равном 10. С увеличением мольного соотношения нафталин/пиридин от 0.5 до 60 наблюдали снижение степени превращения пиридина от 100 до 91% (при S/W, равном 4 мольн.) и от 100 до 81% (при S/W, равном 10 мольн.). Показано, что увеличение содержания серы способствует формированию более дисперсных частиц сульфида вольфрама, характеризующихся высокой степенью промотирования атомами никеля[1].

 

[1] Дополнительные материалы доступны в электронном виде по DOI статьи: 10.31857/S0028242124050054

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About the authors

Мария Игоревна Князева

Институт нефтехимического синтеза им. А. В. Топчиева РАН

Author for correspondence.
Email: knyazeva@ips.ac.ru
ORCID iD: 0000-0001-9054-0905

к. х. н.

Russian Federation, 199991, Москва

Айгуль Фанисовна Зиниатуллина

Институт нефтехимического синтеза им. А. В. Топчиева РАН

Email: knyazeva@ips.ac.ru
ORCID iD: 0000-0001-5902-0194
Russian Federation, 199991, Москва

Татьяна Сергеевна Кучинская

Институт нефтехимического синтеза им. А. В. Топчиева РАН

Email: knyazeva@ips.ac.ru
ORCID iD: 0000-0002-2908-0353
Russian Federation, 199991, Москва

Антон Львович Максимов

Институт нефтехимического синтеза им. А. В. Топчиева РАН

Email: knyazeva@ips.ac.ru
ORCID iD: 0000-0001-9297-4950

д. х. н., чл.- корр. РАН

Russian Federation, 199991, Москва

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3. Fig. 1. Dependence of the composition of naphthalene hydrogenation products on the pyridine content in the reaction mixture at S/W ratios of (a) 4/1 mol. and (b) 10/1 mol. (380°C, 5.0 MPa H2, 5 h, 7.3×10-5 mol Ni, 1.5×10-4 mol W).

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4. Fig. 2. Dependence of the composition of pyridine conversion products on the molar ratio of naphthalene/pyridine in the reaction mixture at S/W ratio: (a) 4/1 mol; (b) 10/1 mol. (380°C, 5.0 MPa H2, 5 h, 7.3×10-5 mol Ni, 1.5×10-4 mol W).

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5. Fig. 3. Diffractograms of catalyst samples formed in situ (380°C, 5.0 MPa H2, 5 h, 7.3×10-5 mol Ni, 1.5×10-4 mol W, naphthalene/pyridine = 3/1 mol%): 1 - NiW_4; 2 - NiW_10.

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6. Fig. 4. Microphotographs of catalyst samples formed in situ (380°C, 5.0 MPa H2, 5 h, 7.3×10-5 mol Ni, 1.5×10-4 mol W, naphthalene/pyridine = 3/1 mol): a, b, c - NiW_4; d, e, f - NiW_10.

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7. Fig. 5. Deconvolution of the spectra of (a)W4f, (b) Ni2p and (c) S2p levels of NiW_10 catalyst.

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