DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Lewis acid zeolites for tandem Diels–Alder cycloaddition and dehydration of biomass-derived dimethylfuran and ethylene to renewable p-xylene

Abstract

In this work, Lewis acid zeolites including Zr-, Sn-, and Ti-BEA were examined for tandem [4 + 2] Diels–Alder cycloaddition of 2,5-dimethylfuran (DMF) and ethylene to oxanorbornene with subsequent dehydration to produce biorenewable p-xylene. Zr-BEA (Si/Zr = 168) exhibited superior performance with improved recalcitrance to deactivation, which was attributed to its low activity for the hydrolysis of DMF to 2,5-hexanedione and subsequent condensation. Zr-BEA also achieved the highest selectivity to p-xylene of 90% at 99% conversion of DMF. For low catalyst loading within a three-phase reactor, the reaction rate to form p-xylene was linearly proportional to the number of Lewis acid sites, while high catalyst loading exhibited zero order dependence on Lewis acid sites. A maximum achievable reaction rate was shown to be consistent with a transition in rate-limiting reactions from dehydration of oxanorbornene, the Diels–Alder product, to the Diels–Alder cycloaddition of DMF and ethylene.

Authors:
 [1];  [1];  [2];  [2];  [3];  [4];  [1]
  1. Univ. of Massachusetts, Amherst, MA (United States); Univ. of Delaware, Newark, DE (United States); Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
  2. Univ. of Delaware, Newark, DE (United States); Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Pennsylvania, Philadelphia, PA (United States)
  3. Univ. of Delaware, Newark, DE (United States); Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
  4. Univ. of Delaware, Newark, DE (United States); Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1387601
Grant/Contract Number:  
SC0001004
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 18; Journal Issue: 5; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); biofuels (including algae and biomass); bio-inspired; hydrogen and fuel cells; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Chang, Chun-Chih, Je Cho, Hong, Yu, Jingye, Gorte, Ray J., Gulbinski, Jason, Dauenhauer, Paul, and Fan, Wei. Lewis acid zeolites for tandem Diels–Alder cycloaddition and dehydration of biomass-derived dimethylfuran and ethylene to renewable p-xylene. United States: N. p., 2015. Web. doi:10.1039/c5gc02164b.
Chang, Chun-Chih, Je Cho, Hong, Yu, Jingye, Gorte, Ray J., Gulbinski, Jason, Dauenhauer, Paul, & Fan, Wei. Lewis acid zeolites for tandem Diels–Alder cycloaddition and dehydration of biomass-derived dimethylfuran and ethylene to renewable p-xylene. United States. https://doi.org/10.1039/c5gc02164b
Chang, Chun-Chih, Je Cho, Hong, Yu, Jingye, Gorte, Ray J., Gulbinski, Jason, Dauenhauer, Paul, and Fan, Wei. Tue . "Lewis acid zeolites for tandem Diels–Alder cycloaddition and dehydration of biomass-derived dimethylfuran and ethylene to renewable p-xylene". United States. https://doi.org/10.1039/c5gc02164b. https://www.osti.gov/servlets/purl/1387601.
@article{osti_1387601,
title = {Lewis acid zeolites for tandem Diels–Alder cycloaddition and dehydration of biomass-derived dimethylfuran and ethylene to renewable p-xylene},
author = {Chang, Chun-Chih and Je Cho, Hong and Yu, Jingye and Gorte, Ray J. and Gulbinski, Jason and Dauenhauer, Paul and Fan, Wei},
abstractNote = {In this work, Lewis acid zeolites including Zr-, Sn-, and Ti-BEA were examined for tandem [4 + 2] Diels–Alder cycloaddition of 2,5-dimethylfuran (DMF) and ethylene to oxanorbornene with subsequent dehydration to produce biorenewable p-xylene. Zr-BEA (Si/Zr = 168) exhibited superior performance with improved recalcitrance to deactivation, which was attributed to its low activity for the hydrolysis of DMF to 2,5-hexanedione and subsequent condensation. Zr-BEA also achieved the highest selectivity to p-xylene of 90% at 99% conversion of DMF. For low catalyst loading within a three-phase reactor, the reaction rate to form p-xylene was linearly proportional to the number of Lewis acid sites, while high catalyst loading exhibited zero order dependence on Lewis acid sites. A maximum achievable reaction rate was shown to be consistent with a transition in rate-limiting reactions from dehydration of oxanorbornene, the Diels–Alder product, to the Diels–Alder cycloaddition of DMF and ethylene.},
doi = {10.1039/c5gc02164b},
journal = {Green Chemistry},
number = 5,
volume = 18,
place = {United States},
year = {2015},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 125 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

On the Diels-Alder Approach to Solely Biomass-Derived Polyethylene Terephthalate (PET): Conversion of 2,5-Dimethylfuran and Acrolein into p-Xylene
journal, September 2011

  • Shiramizu, Mika; Toste, F. Dean
  • Chemistry - A European Journal, Vol. 17, Issue 44
  • DOI: 10.1002/chem.201101580

A DFT study of the acid-catalyzed conversion of 2,5-dimethylfuran and ethylene to p-xylene
journal, January 2013


Derivatives of 7-oxabicyclo[2.2.1]heptane in nature and as useful synthetic intermediates
journal, November 1999


p- Xylene Formation by Dehydrative Aromatization of a Diels–Alder Product in Lewis and Brønsted Acidic Zeolites
journal, October 2014

  • Nikbin, Nima; Feng, Shuting; Caratzoulas, Stavros
  • The Journal of Physical Chemistry C, Vol. 118, Issue 42
  • DOI: 10.1021/jp506027f

p -Xylene Oxidation to Terephthalic Acid: A Literature Review Oriented toward Process Optimization and Development
journal, June 2013

  • Tomás, Rogério A. F.; Bordado, João C. M.; Gomes, João F. P.
  • Chemical Reviews, Vol. 113, Issue 10
  • DOI: 10.1021/cr300298j

Rapid synthesis of Sn-Beta for the isomerization of cellulosic sugars
journal, January 2012

  • Chang, Chun-Chih; Wang, Zhuopeng; Dornath, Paul
  • RSC Advances, Vol. 2, Issue 28
  • DOI: 10.1039/c2ra21381h

Diels–Alder cycloaddition of 2-methylfuran and ethylene for renewable toluene
journal, January 2016


Synthesis and Verification of Biobased Terephthalic Acid from Furfural
journal, February 2015

  • Tachibana, Yuya; Kimura, Saori; Kasuya, Ken-ichi
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08249

Al-free Zr-zeolite beta as a regioselective catalyst in the Meerwein–Ponndorf–Verley reaction
journal, January 2003

  • Zhu, Yongzhong; Chuah, Gaikhuan; Jaenicke, Stephan
  • Chem. Commun., Issue 21
  • DOI: 10.1039/B309191K

Current Technologies, Economics, and Perspectives for 2,5-Dimethylfuran Production from Biomass-Derived Intermediates
journal, February 2015


Probing Lewis Acid Sites in Sn-Beta Zeolite
journal, February 2013

  • Roy, Sounak; Bakhmutsky, Kevin; Mahmoud, Eyas
  • ACS Catalysis, Vol. 3, Issue 4
  • DOI: 10.1021/cs300599z

Production of p -Xylene from Biomass by Catalytic Fast Pyrolysis Using ZSM-5 Catalysts with Reduced Pore Openings
journal, October 2012

  • Cheng, Yu-Ting; Wang, Zhuopeng; Gilbert, Christopher J.
  • Angewandte Chemie International Edition, Vol. 51, Issue 44
  • DOI: 10.1002/anie.201205230

Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural
journal, May 2014

  • Pacheco, J. J.; Davis, M. E.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 23
  • DOI: 10.1073/pnas.1408345111

Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p -Xylene
journal, April 2012

  • Williams, C. Luke; Chang, Chun-Chih; Do, Phuong
  • ACS Catalysis, Vol. 2, Issue 6
  • DOI: 10.1021/cs300011a

Elucidation of Diels–Alder Reaction Network of 2,5-Dimethylfuran and Ethylene on HY Zeolite Catalyst
journal, December 2012

  • Do, Phuong T. M.; McAtee, Jesse R.; Watson, Donald A.
  • ACS Catalysis, Vol. 3, Issue 1
  • DOI: 10.1021/cs300673b

Mechanistic Study of Alcohol Dehydration on γ-Al 2 O 3
journal, July 2012

  • Roy, Sounak; Mpourmpakis, Giannis; Hong, Do-Young
  • ACS Catalysis, Vol. 2, Issue 9
  • DOI: 10.1021/cs300176d

Bio-Ethanol Based Ethylene
journal, May 2009


Computational Study of p -Xylene Synthesis from Ethylene and 2,5-Dimethylfuran Catalyzed by H-BEA
journal, September 2014

  • Li, Yi-Pei; Head-Gordon, Martin; Bell, Alexis T.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 38
  • DOI: 10.1021/jp506664c

Experimental and computational study of the ring opening of tricyclic oxanorbornenes to polyhydro isoindole phosphonates
journal, January 2010

  • Claeys, Diederica D.; Stevens, Christian V.; Roman, Bart I.
  • Organic & Biomolecular Chemistry, Vol. 8, Issue 16
  • DOI: 10.1039/c002926b

Catalysis of Diels–Alder reactions by zeolites
journal, January 1986


Green and sustainable manufacture of chemicals from biomass: state of the art
journal, January 2014


Synthesis of p -Xylene from Ethylene
journal, September 2012

  • Lyons, Thomas W.; Guironnet, Damien; Findlater, Michael
  • Journal of the American Chemical Society, Vol. 134, Issue 38
  • DOI: 10.1021/ja307612b

Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels–Alder Products
journal, March 2015

  • Patet, Ryan E.; Nikbin, Nima; Williams, C. Luke
  • ACS Catalysis, Vol. 5, Issue 4
  • DOI: 10.1021/cs5020783

The effect of oxide acidity on HMF etherification
journal, January 2014

  • Luo, Jing; Yu, Jingye; Gorte, Raymond J.
  • Catal. Sci. Technol., Vol. 4, Issue 9
  • DOI: 10.1039/C4CY00563E

Selective Production of Aromatics from Alkylfurans over Solid Acid Catalysts
journal, January 2013

  • Wang, Dong; Osmundsen, Christian M.; Taarning, Esben
  • ChemCatChem, Vol. 5, Issue 7, p. 2044-2050
  • DOI: 10.1002/cctc.201200757

Ultra-selective cycloaddition of dimethylfuran for renewable p-xylene with H-BEA
journal, January 2014

  • Chang, Chun-Chih; Green, Sara K.; Williams, C. Luke
  • Green Chem., Vol. 16, Issue 2
  • DOI: 10.1039/C3GC40740C

Catalytic dehydration of bioethanol to ethylene: Pilot-scale studies and process simulation
journal, December 2011

  • Kagyrmanova, A. P.; Chumachenko, V. A.; Korotkikh, V. N.
  • Chemical Engineering Journal, Vol. 176-177
  • DOI: 10.1016/j.cej.2011.06.049

The HfCl4-Mediated Diels–Alder Reaction of Furan
journal, November 2002


Production of p -Xylene from Biomass by Catalytic Fast Pyrolysis Using ZSM-5 Catalysts with Reduced Pore Openings
journal, October 2012

  • Cheng, Yu-Ting; Wang, Zhuopeng; Gilbert, Christopher J.
  • Angewandte Chemie, Vol. 124, Issue 44
  • DOI: 10.1002/ange.201205230

The HfCl4-Mediated Diels—Alder Reaction of Furan.
journal, April 2003

  • Hayashi, Yujiro; Nakamura, Masahiko; Nakao, Shigehiro
  • ChemInform, Vol. 34, Issue 13
  • DOI: 10.1002/chin.200313107

Works referencing / citing this record:

Selective Production of Renewable para -Xylene by Tungsten Carbide Catalyzed Atom-Economic Cascade Reactions
journal, January 2018


Selective Production of Renewable para -Xylene by Tungsten Carbide Catalyzed Atom-Economic Cascade Reactions
journal, January 2018

  • Dai, Tao; Li, Changzhi; Li, Lin
  • Angewandte Chemie International Edition, Vol. 57, Issue 7
  • DOI: 10.1002/anie.201710074

Synthesis of 1,4-Cyclohexanedimethanol, 1,4-Cyclohexanedicarboxylic Acid and 1,2-Cyclohexanedicarboxylates from Formaldehyde, Crotonaldehyde and Acrylate/Fumarate
journal, May 2018

  • Hu, Yancheng; Zhao, Zhitong; Liu, Yanting
  • Angewandte Chemie International Edition, Vol. 57, Issue 23
  • DOI: 10.1002/anie.201801287

Renewable p -Xylene from 2,5-Dimethylfuran and Ethylene Using Phosphorus-Containing Zeolite Catalysts
journal, January 2017


Glucose Isomerization and Epimerization over Metal‐Organic Frameworks with Single‐Site Active Centers
journal, February 2019


A Simple and Mild Approach for the Synthesis of p -Xylene from Bio-Based 2,5-Dimethyfuran by Using Metal Triflates
journal, March 2017


Catalytic Transformation of Cellulose and Its Derivatives into Functionalized Organic Acids
journal, June 2018


Zeolite and zeotype-catalysed transformations of biofuranic compounds
journal, January 2016

  • Li, Hu; Yang, Song; Riisager, Anders
  • Green Chemistry, Vol. 18, Issue 21
  • DOI: 10.1039/c6gc02415g

Highly selective production of renewable p -xylene from bio-based 2,5-dimethylfuran and ethylene over Al-modified H-Beta zeolites
journal, January 2019

  • Zhao, Rongrong; Xu, Lulu; Huang, Shengjun
  • Catalysis Science & Technology, Vol. 9, Issue 20
  • DOI: 10.1039/c9cy01113g

Synthesis of functionalized tetrahydrofuran derivatives from 2,5-dimethylfuran through cascade reactions
journal, January 2019

  • Li, J.; Muller, E.; Pera-Titus, M.
  • Green Chemistry, Vol. 21, Issue 10
  • DOI: 10.1039/c9gc01060b

Synergistic effect of acidity and extraframework position in faujasite on renewable p -xylene production
journal, May 2018


5-Hydroxymethylfurfural (HMF) in Organic Synthesis: A Review of its Recent Applications Towards Fine Chemicals
journal, July 2019