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

Journal Article · · Green Chemistry
DOI:https://doi.org/10.1039/c5gc02164b· OSTI ID:1387601
 [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)
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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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001004
OSTI ID:
1387601
Journal Information:
Green Chemistry, Journal Name: Green Chemistry Journal Issue: 5 Vol. 18; ISSN GRCHFJ; ISSN 1463-9262
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (22)

Selective Production of Renewable para -Xylene by Tungsten Carbide Catalyzed Atom-Economic Cascade Reactions journal January 2018
Synthesis of 1,4-Cyclohexanedimethanol, 1,4-Cyclohexanedicarboxylic Acid and 1,2-Cyclohexanedicarboxylates from Formaldehyde, Crotonaldehyde and Acrylate/Fumarate journal May 2018
Selective Production of Renewable para -Xylene by Tungsten Carbide Catalyzed Atom-Economic Cascade Reactions journal January 2018
Synthesis of 1,4-Cyclohexanedimethanol, 1,4-Cyclohexanedicarboxylic Acid and 1,2-Cyclohexanedicarboxylates from Formaldehyde, Crotonaldehyde and Acrylate/Fumarate journal May 2018
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
Excellent Performances of Dealuminated H-Beta Zeolites from Organotemplate-Free Synthesis in Conversion of Biomass-derived 2,5-Dimethylfuran to Renewable p -Xylene journal October 2018
Zeolite and zeotype-catalysed transformations of biofuranic compounds journal January 2016
Heterogeneous Diels–Alder catalysis for biomass-derived aromatic compounds journal January 2017
Advances in porous and nanoscale catalysts for viable biomass conversion journal January 2019
A solvent-free, one-step synthesis of sulfonic acid group-functionalized mesoporous organosilica with ultra-high acid concentrations and excellent catalytic activities journal January 2018
Catalytic conversion of 5-hydroxymethylfurfural to some value-added derivatives journal January 2018
Chiral phosphoric acid-catalyzed asymmetric C(sp 3 )–H functionalization of biomass-derived 2,5-dimethylfuran via two sequential Cope-type rearrangements journal January 2019
Efficient conversion of 5-hydroxymethylfurfural to high-value chemicals by chemo- and bio-catalysis journal January 2018
A Zr-Al-Beta zeolite with open Zr( iv ) sites: an efficient bifunctional Lewis–Brønsted acid catalyst for a cascade reaction journal January 2019
Highly selective production of renewable p -xylene from bio-based 2,5-dimethylfuran and ethylene over Al-modified H-Beta zeolites journal January 2019
Ultrafast flow chemistry for the acid-catalyzed conversion of fructose journal January 2019
Synthesis of functionalized tetrahydrofuran derivatives from 2,5-dimethylfuran through cascade reactions journal January 2019
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

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
bio-inspired
biofuels (including algae and biomass)
catalysis (heterogeneous)
catalysis (homogeneous)
hydrogen and fuel cells
materials and chemistry by design
synthesis (novel materials)
synthesis (scalable processing)
synthesis (self-assembly)