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HPW supported on ammonium hexafluorosilicate modified Hβ: Efficient catalysts for ethylene glycol and methyl tert‐butyl ether reaction with high selectivity and stability

A series of HPW supported on ammonium hexafluorosilicate (AHFs) modified Hβ (30HPW/Hβ‐Si(x)) was successfully prepared. After Hβ zeolite was pretreated with 0.1 mol·L−1 AHF's solution, the Brønsted/Lewis ratio of Hβ‐Si(0.1) increased compared with those of Hβ, and the strong acid density of 30H...

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Published in:Applied organometallic chemistry 2023-08, Vol.37 (8), p.n/a
Main Authors: Jiang, Hui, Wang, Hefang, Ma, Xiaofei, Shao, Kai, Wang, Cui
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description A series of HPW supported on ammonium hexafluorosilicate (AHFs) modified Hβ (30HPW/Hβ‐Si(x)) was successfully prepared. After Hβ zeolite was pretreated with 0.1 mol·L−1 AHF's solution, the Brønsted/Lewis ratio of Hβ‐Si(0.1) increased compared with those of Hβ, and the strong acid density of 30HPW/Hβ‐Si(0.1) decreased compared with those of 30HPW/Hβ respectively. Strong acidic sites and Lewis acid sites are catalytic sites for by‐products diisobutene and ethylene glycol oligomers, which deposited on the catalyst result in the deactivation of catalysts. According to the results of characterization, the internal Si‐OH groups of Hβ (strong acidity sites) were filled with silicon of AHFs. The extraframework aluminum (strong acid sites) was removed by the H+, which is the hydrolysis of AHFs. In addition, the hydrophobicity of 30HPW/Hβ‐Si(0.1) was also improved compared with that of 30HPW/Hβ due to the SiO2/Al2O3 ratio of Hβ increased after treatment by 0.1 mol·L−1 AHFs solution. The 30HPW/Hβ‐Si(0.1) maintained an 80% conversion of methyl tert‐butyl ether and 100% selectivity to ethylene glycol mono‐tert‐butyl ether and DBE ethylene glycol bis‐tert‐butyl ether with 336 h of time on stream. HPW supported on ammonium hexafluorosilicate (AHFs) modified Hβ was prepared. The internal Si‐OH groups of Hβ were filled with silicon of AHFs, and the extraframework aluminum was removed by the H+ produced by hydrolysis of AHFs. The medium/strong acid density of 30HPW/Hβ‐Si(0.1) decreased compared to 30HPW/Hβ.
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After Hβ zeolite was pretreated with 0.1 mol·L−1 AHF's solution, the Brønsted/Lewis ratio of Hβ‐Si(0.1) increased compared with those of Hβ, and the strong acid density of 30HPW/Hβ‐Si(0.1) decreased compared with those of 30HPW/Hβ respectively. Strong acidic sites and Lewis acid sites are catalytic sites for by‐products diisobutene and ethylene glycol oligomers, which deposited on the catalyst result in the deactivation of catalysts. According to the results of characterization, the internal Si‐OH groups of Hβ (strong acidity sites) were filled with silicon of AHFs. The extraframework aluminum (strong acid sites) was removed by the H+, which is the hydrolysis of AHFs. In addition, the hydrophobicity of 30HPW/Hβ‐Si(0.1) was also improved compared with that of 30HPW/Hβ due to the SiO2/Al2O3 ratio of Hβ increased after treatment by 0.1 mol·L−1 AHFs solution. The 30HPW/Hβ‐Si(0.1) maintained an 80% conversion of methyl tert‐butyl ether and 100% selectivity to ethylene glycol mono‐tert‐butyl ether and DBE ethylene glycol bis‐tert‐butyl ether with 336 h of time on stream. HPW supported on ammonium hexafluorosilicate (AHFs) modified Hβ was prepared. The internal Si‐OH groups of Hβ were filled with silicon of AHFs, and the extraframework aluminum was removed by the H+ produced by hydrolysis of AHFs. 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After Hβ zeolite was pretreated with 0.1 mol·L−1 AHF's solution, the Brønsted/Lewis ratio of Hβ‐Si(0.1) increased compared with those of Hβ, and the strong acid density of 30HPW/Hβ‐Si(0.1) decreased compared with those of 30HPW/Hβ respectively. Strong acidic sites and Lewis acid sites are catalytic sites for by‐products diisobutene and ethylene glycol oligomers, which deposited on the catalyst result in the deactivation of catalysts. According to the results of characterization, the internal Si‐OH groups of Hβ (strong acidity sites) were filled with silicon of AHFs. The extraframework aluminum (strong acid sites) was removed by the H+, which is the hydrolysis of AHFs. In addition, the hydrophobicity of 30HPW/Hβ‐Si(0.1) was also improved compared with that of 30HPW/Hβ due to the SiO2/Al2O3 ratio of Hβ increased after treatment by 0.1 mol·L−1 AHFs solution. The 30HPW/Hβ‐Si(0.1) maintained an 80% conversion of methyl tert‐butyl ether and 100% selectivity to ethylene glycol mono‐tert‐butyl ether and DBE ethylene glycol bis‐tert‐butyl ether with 336 h of time on stream. HPW supported on ammonium hexafluorosilicate (AHFs) modified Hβ was prepared. The internal Si‐OH groups of Hβ were filled with silicon of AHFs, and the extraframework aluminum was removed by the H+ produced by hydrolysis of AHFs. The medium/strong acid density of 30HPW/Hβ‐Si(0.1) decreased compared to 30HPW/Hβ.</abstract><cop>Chichester</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/aoc.7167</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0002-1935-3178</orcidid><orcidid>https://orcid.org/0009-0005-0230-5021</orcidid><orcidid>https://orcid.org/0009-0006-1805-9504</orcidid><orcidid>https://orcid.org/0009-0008-2243-2767</orcidid><orcidid>https://orcid.org/0000-0001-8946-2727</orcidid></addata></record>
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subjects Aluminum oxide
ammonium hexafluorosilicate
Catalysts
Chemistry
Ethylene glycol
ethylene glycol bis‐tert‐butyl ether
ethylene glycol mono‐tert‐butyl ether
HPW
Hydrophobicity
Lewis acid
Silicon dioxide
title HPW supported on ammonium hexafluorosilicate modified Hβ: Efficient catalysts for ethylene glycol and methyl tert‐butyl ether reaction with high selectivity and stability
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