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Title: Alkylation of lignin-derived aromatic oxygenates with cyclic alcohols on acidic zeolites

Abstract

Moderately strong BAS and spacious microporous environments (i.e., large-pore acidic zeolites HBEA and HY) are important criteria for efficient alkylation of phenols with cyclic alcohols and alkenes, while very strong BAS appear to be responsible for catalyst deactivation. BAS confined in HBEA and HY pores show substantially higher turnover frequencies compared to solids without molecularly sized pore constraints. HBEA favors the formation of mono-alkylates, while enhanced formation of di-alkylates is observed on HY. Dehydration of alcohols always dominates over the alkylation at the onset of the reaction. Carbenium ions, the direct electrophile for aromatic oxygenates, are produced mainly from the adsorption and protonation of olefins. The present study shows that for the alkylation of phenols and cyclic alcohols in apolar liquids, the alcohol concentration should be kept low to avoid the formation of unreactive surface dimers and mitigate their inhibitory effects on olefin adsorption and protonation.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2];  [3]
  1. Technische Univ. Munchen, Garching (Germany)
  2. Yangzhou Univ. (China); Technische Univ. Munchen, Garching (Germany)
  3. Technische Univ. Munchen, Garching (Germany); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1671015
Report Number(s):
PNNL-SA-155226
Journal ID: ISSN 0926-3373
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis B: Environmental
Additional Journal Information:
Journal Volume: 281; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
alkylation; phenol; aromatic oxygenates; zeolites; reaction pathways

Citation Formats

Liu, Yuanshuai, Cheng, Guanhua, Baráth, Eszter, Shi, Hui, and Lercher, Johannes A. Alkylation of lignin-derived aromatic oxygenates with cyclic alcohols on acidic zeolites. United States: N. p., 2020. Web. doi:10.1016/j.apcatb.2020.119424.
Liu, Yuanshuai, Cheng, Guanhua, Baráth, Eszter, Shi, Hui, & Lercher, Johannes A. Alkylation of lignin-derived aromatic oxygenates with cyclic alcohols on acidic zeolites. United States. doi:10.1016/j.apcatb.2020.119424.
Liu, Yuanshuai, Cheng, Guanhua, Baráth, Eszter, Shi, Hui, and Lercher, Johannes A. Thu . "Alkylation of lignin-derived aromatic oxygenates with cyclic alcohols on acidic zeolites". United States. doi:10.1016/j.apcatb.2020.119424.
@article{osti_1671015,
title = {Alkylation of lignin-derived aromatic oxygenates with cyclic alcohols on acidic zeolites},
author = {Liu, Yuanshuai and Cheng, Guanhua and Baráth, Eszter and Shi, Hui and Lercher, Johannes A.},
abstractNote = {Moderately strong BAS and spacious microporous environments (i.e., large-pore acidic zeolites HBEA and HY) are important criteria for efficient alkylation of phenols with cyclic alcohols and alkenes, while very strong BAS appear to be responsible for catalyst deactivation. BAS confined in HBEA and HY pores show substantially higher turnover frequencies compared to solids without molecularly sized pore constraints. HBEA favors the formation of mono-alkylates, while enhanced formation of di-alkylates is observed on HY. Dehydration of alcohols always dominates over the alkylation at the onset of the reaction. Carbenium ions, the direct electrophile for aromatic oxygenates, are produced mainly from the adsorption and protonation of olefins. The present study shows that for the alkylation of phenols and cyclic alcohols in apolar liquids, the alcohol concentration should be kept low to avoid the formation of unreactive surface dimers and mitigate their inhibitory effects on olefin adsorption and protonation.},
doi = {10.1016/j.apcatb.2020.119424},
journal = {Applied Catalysis B: Environmental},
number = ,
volume = 281,
place = {United States},
year = {2020},
month = {8}
}

Journal Article:
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This content will become publicly available on August 13, 2021
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