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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; USDOE
OSTI Identifier:
1671015
Alternate Identifier(s):
OSTI ID: 1778306
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:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 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. https://doi.org/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. https://doi.org/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. https://doi.org/10.1016/j.apcatb.2020.119424. https://www.osti.gov/servlets/purl/1671015.
@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}
}

Works referenced in this record:

Towards Quantitative Catalytic Lignin Depolymerization
journal, April 2011

  • Roberts, Virginia. M.; Stein, Valentin; Reiner, Thomas
  • Chemistry - A European Journal, Vol. 17, Issue 21, p. 5939-5948
  • DOI: 10.1002/chem.201002438

Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass
journal, September 2007

  • Huber, George W.; Corma, Avelino
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7184-7201
  • DOI: 10.1002/anie.200604504

Upgrading Pyrolysis Oil over Ni/HZSM-5 by Cascade Reactions
journal, January 2012

  • Zhao, Chen; Lercher, Johannes A.
  • Angewandte Chemie International Edition, Vol. 51, Issue 24
  • DOI: 10.1002/anie.201108306

Conversion of biomass to selected chemical products
journal, January 2012


Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals
journal, September 2007

  • Chheda, Juben N.; Huber, George W.; Dumesic, James A.
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7164-7183
  • DOI: 10.1002/anie.200604274

Competitive liquid biofuels from biomass
journal, January 2011


Historical Developments in Hydroprocessing Bio-oils
journal, May 2007

  • Elliott, Douglas C.
  • Energy & Fuels, Vol. 21, Issue 3, p. 1792-1815
  • DOI: 10.1021/ef070044u

Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes
journal, May 2011


Reaction pathways in the liquid phase alkylation of biomass-derived phenolic compounds
journal, November 2014

  • González-Borja, Miguel Ángel; Resasco, Daniel E.
  • AIChE Journal, Vol. 61, Issue 2
  • DOI: 10.1002/aic.14658

Improving carbon retention in biomass conversion by alkylation of phenolics with small oxygenates
journal, December 2012


Selective catalytic hydroalkylation and deoxygenation of substituted phenols to bicycloalkanes
journal, April 2012


Solvent-determined mechanistic pathways in zeolite-H-BEA-catalysed phenol alkylation
journal, January 2018


Aqueous Phase Hydroalkylation and Hydrodeoxygenation of Phenol by Dual Functional Catalysts Comprised of Pd/C and H/La-BEA
journal, November 2012

  • Zhao, Chen; Song, Wenji; Lercher, Johannes A.
  • ACS Catalysis, Vol. 2, Issue 12
  • DOI: 10.1021/cs300418a

Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy
journal, June 2017

  • Zhao, Zhenchao; Shi, Hui; Wan, Chuan
  • Journal of the American Chemical Society, Vol. 139, Issue 27
  • DOI: 10.1021/jacs.7b02153

Role of Keto Intermediates in the Hydrodeoxygenation of Phenol over Pd on Oxophilic Supports
journal, January 2015

  • de Souza, Priscilla M.; Rabelo-Neto, Raimundo C.; Borges, Luiz E. P.
  • ACS Catalysis, Vol. 5, Issue 2
  • DOI: 10.1021/cs501853t

Effect of Zirconia Morphology on Hydrodeoxygenation of Phenol over Pd/ZrO 2
journal, November 2015

  • de Souza, Priscilla M.; Rabelo-Neto, Raimundo C.; Borges, Luiz E. P.
  • ACS Catalysis, Vol. 5, Issue 12
  • DOI: 10.1021/acscatal.5b01501

Hydrodeoxygenation of Phenol over Pd Catalysts. Effect of Support on Reaction Mechanism and Catalyst Deactivation
journal, February 2017

  • de Souza, Priscilla M.; Rabelo-Neto, Raimundo C.; Borges, Luiz E. P.
  • ACS Catalysis, Vol. 7, Issue 3
  • DOI: 10.1021/acscatal.6b02022

Steric Effect and Evolution of Surface Species in the Hydrodeoxygenation of Bio-Oil Model Compounds over Pt/HBEA
journal, January 2016


Effects of Carbohydrates on the Hydrodeoxygenation of Lignin-Derived Phenolic Compounds
journal, November 2014

  • Dwiatmoko, Adid Adep; Lee, Sangheon; Ham, Hyung Chul
  • ACS Catalysis, Vol. 5, Issue 1
  • DOI: 10.1021/cs501567x

Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds
journal, April 2013

  • Wang, Huamin; Male, Jonathan; Wang, Yong
  • ACS Catalysis, Vol. 3, Issue 5
  • DOI: 10.1021/cs400069z

Deoxyalkylation of guaiacol using haggite structured V 4 O 6 (OH) 4
journal, January 2019

  • Yan, Fei; Wen, Zhe; Wu, Kai
  • Catalysis Science & Technology, Vol. 9, Issue 8
  • DOI: 10.1039/C9CY00024K

Alkylation of phenol with cyclohexene over solid acids: Insight in selectivity of O- versus C-alkylation
journal, May 2005


Liquid-phase alkylation of phenol with long-chain olefins over WO/ZrO solid acid catalysts
journal, August 2005


High Surface Area Nafion Resin/Silica Nanocomposites:  A New Class of Solid Acid Catalyst
journal, January 1996

  • Harmer, Mark A.; Farneth, William E.; Sun, Qun
  • Journal of the American Chemical Society, Vol. 118, Issue 33
  • DOI: 10.1021/ja9541950

Functional assessment of the strength of solid acid catalysts
journal, May 2009


Hydrolysis of Triglycerides Using Solid Acid Catalysts
journal, May 2009

  • Ngaosuwan, Kanokwan; Lotero, Edgar; Suwannakarn, Kaewta
  • Industrial & Engineering Chemistry Research, Vol. 48, Issue 10
  • DOI: 10.1021/ie8013988

Preparation of Glycerol Carbonate Esters by using Hybrid Nafion-Silica Catalyst
journal, June 2013


C O cleavage of diphenyl ether followed by C C coupling reactions over hydrophobized Pd/HY catalysts
journal, December 2019

  • Scaldaferri, Cristiane A.; Warakunwit, Puridej; Pasa, Vânya M. D.
  • Applied Catalysis B: Environmental, Vol. 259
  • DOI: 10.1016/j.apcatb.2019.118081

Structure and orientation of phenols chemisorbed on .gamma.-alumina
journal, September 1972

  • Taylor, D. R.; Ludlum, K. H.
  • The Journal of Physical Chemistry, Vol. 76, Issue 20
  • DOI: 10.1021/j100664a017

Hydronium-Ion-Catalyzed Elimination Pathways of Substituted Cyclohexanols in Zeolite H-ZSM5
journal, October 2017

  • Hintermeier, Peter H.; Eckstein, Sebastian; Mei, Donghai
  • ACS Catalysis, Vol. 7, Issue 11
  • DOI: 10.1021/acscatal.7b01582