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Title: Role of Silica Support in Phosphoric Acid Catalyzed Production of p-Xylene from 2,5-Dimethylfuran and Ethylene

Abstract

p-Xylene is a commodity chemical of industrial importance for terephthalic acid production, for which renewable sourcing from naturally abundant lignocellulosic biomass is highly desired. Previous work demonstrated that phosphoric acid stabilized on siliceous zeolite supports (e.g., P-BEA, P-SPP) exhibits high selectivity toward p-xylene (>97%) from 2,5-dimethylfuran (DMF) and ethylene. However, the effect of the support and the contribution of heterogeneous versus homogeneous phosphoric acid on the observed catalytic behavior in the solvated reaction system have not been addressed. Here, we determine the phosphoric acid catalytic activity for DMF conversion and its selectivity to p-xylene when it is supported on a silica support as well as in the absence of a support. Specifically, phosphoric acid catalysis was studied in three different scenarios: (1) phosphoric acid was added in the liquid reaction mixture in the absence of any solid support, (2) phosphoric acid was added in the liquid reaction mixture along with inert silica support including siliceous zeolite (i.e., allowing for phosphoric acid–support assembly to proceed in the reaction mixture), and (3) phosphoric acid was first impregnated on the siliceous zeolite support and then the preassembled supported phosphoric acid catalyst was added in the liquid reaction mixture. We found that the reactionmore » rate and selectivity to p-xylene are different in the above scenarios reflecting the effect of the solid support on the catalytic performance of phosphoric acid. In scenario 1, a low concentration of phosphoric acid (1.7 mM) in the absence of any solid support exhibited high selectivity to p-xylene (80% selectivity to p-xylene at 60% conversion of DMF), which decreased with increasing acid concentration. The selectivity to p-xylene and activity of phosphoric acid significantly increased by adding a silica support into the reaction system (scenario 2). Furthermore, this improvement was attributed to phosphoric acid partial association with the surface of the silica support under the reaction conditions (in situ catalyst assembly). Phosphoric acid predeposited on siliceous zeolite supports (e.g., P-BEA, P-SPP) synthesized via impregnation prior to the reaction (scenario 3) catalyzed the reaction heterogeneously without noticeable leaching and exhibited the highest activity and selectivity to p-xylene, suggesting an important role of the silica support and the need to ensure that phosphoric acid acts as a heterogeneous catalyst in order to accomplish selective conversion of DMF to p-xylene.« less

Authors:
 [1];  [2]; ORCiD logo [1]; ORCiD logo [3];  [4]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [5]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Massachusetts, Amherst, MA (United States); Univ. of Delaware, Newark, DE (United States)
  2. Univ. of Delaware, Newark, DE (United States); Univ. of Minnesota, Minneapolis, MN (United States)
  3. Univ. of Massachusetts, Amherst, MA (United States); Northwest Univ., Shanxi (China)
  4. Univ. of Massachusetts, Amherst, MA (United States)
  5. Univ. of Delaware, Newark, DE (United States); Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkins Univ., Laurel, MD (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1865837
Grant/Contract Number:  
SC0001004
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Industrial and Engineering Chemistry Research
Additional Journal Information:
Journal Volume: 59; Journal Issue: 51; Journal ID: ISSN 0888-5885
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Hydrocarbons; Silica; Catalysts; Mixtures; Selectivity

Citation Formats

Gulbinski, Jason, Ren, Limin, Vattipalli, Vivek, Chen, Huiyong, Delaney, Jonathan, Bai, Peng, Dauenhauer, Paul, Tsapatsis, Michael, Abdelrahman, Omar A., and Fan, Wei. Role of Silica Support in Phosphoric Acid Catalyzed Production of p-Xylene from 2,5-Dimethylfuran and Ethylene. United States: N. p., 2020. Web. doi:10.1021/acs.iecr.0c04493.
Gulbinski, Jason, Ren, Limin, Vattipalli, Vivek, Chen, Huiyong, Delaney, Jonathan, Bai, Peng, Dauenhauer, Paul, Tsapatsis, Michael, Abdelrahman, Omar A., & Fan, Wei. Role of Silica Support in Phosphoric Acid Catalyzed Production of p-Xylene from 2,5-Dimethylfuran and Ethylene. United States. https://doi.org/10.1021/acs.iecr.0c04493
Gulbinski, Jason, Ren, Limin, Vattipalli, Vivek, Chen, Huiyong, Delaney, Jonathan, Bai, Peng, Dauenhauer, Paul, Tsapatsis, Michael, Abdelrahman, Omar A., and Fan, Wei. 2020. "Role of Silica Support in Phosphoric Acid Catalyzed Production of p-Xylene from 2,5-Dimethylfuran and Ethylene". United States. https://doi.org/10.1021/acs.iecr.0c04493. https://www.osti.gov/servlets/purl/1865837.
@article{osti_1865837,
title = {Role of Silica Support in Phosphoric Acid Catalyzed Production of p-Xylene from 2,5-Dimethylfuran and Ethylene},
author = {Gulbinski, Jason and Ren, Limin and Vattipalli, Vivek and Chen, Huiyong and Delaney, Jonathan and Bai, Peng and Dauenhauer, Paul and Tsapatsis, Michael and Abdelrahman, Omar A. and Fan, Wei},
abstractNote = {p-Xylene is a commodity chemical of industrial importance for terephthalic acid production, for which renewable sourcing from naturally abundant lignocellulosic biomass is highly desired. Previous work demonstrated that phosphoric acid stabilized on siliceous zeolite supports (e.g., P-BEA, P-SPP) exhibits high selectivity toward p-xylene (>97%) from 2,5-dimethylfuran (DMF) and ethylene. However, the effect of the support and the contribution of heterogeneous versus homogeneous phosphoric acid on the observed catalytic behavior in the solvated reaction system have not been addressed. Here, we determine the phosphoric acid catalytic activity for DMF conversion and its selectivity to p-xylene when it is supported on a silica support as well as in the absence of a support. Specifically, phosphoric acid catalysis was studied in three different scenarios: (1) phosphoric acid was added in the liquid reaction mixture in the absence of any solid support, (2) phosphoric acid was added in the liquid reaction mixture along with inert silica support including siliceous zeolite (i.e., allowing for phosphoric acid–support assembly to proceed in the reaction mixture), and (3) phosphoric acid was first impregnated on the siliceous zeolite support and then the preassembled supported phosphoric acid catalyst was added in the liquid reaction mixture. We found that the reaction rate and selectivity to p-xylene are different in the above scenarios reflecting the effect of the solid support on the catalytic performance of phosphoric acid. In scenario 1, a low concentration of phosphoric acid (1.7 mM) in the absence of any solid support exhibited high selectivity to p-xylene (80% selectivity to p-xylene at 60% conversion of DMF), which decreased with increasing acid concentration. The selectivity to p-xylene and activity of phosphoric acid significantly increased by adding a silica support into the reaction system (scenario 2). Furthermore, this improvement was attributed to phosphoric acid partial association with the surface of the silica support under the reaction conditions (in situ catalyst assembly). Phosphoric acid predeposited on siliceous zeolite supports (e.g., P-BEA, P-SPP) synthesized via impregnation prior to the reaction (scenario 3) catalyzed the reaction heterogeneously without noticeable leaching and exhibited the highest activity and selectivity to p-xylene, suggesting an important role of the silica support and the need to ensure that phosphoric acid acts as a heterogeneous catalyst in order to accomplish selective conversion of DMF to p-xylene.},
doi = {10.1021/acs.iecr.0c04493},
url = {https://www.osti.gov/biblio/1865837}, journal = {Industrial and Engineering Chemistry Research},
issn = {0888-5885},
number = 51,
volume = 59,
place = {United States},
year = {Mon Dec 14 00:00:00 EST 2020},
month = {Mon Dec 14 00:00:00 EST 2020}
}

Works referenced in this record:

From Biomass-Derived Furans to Aromatics with Ethanol over Zeolite
journal, October 2016


Spontaneous nucleation and growth of pure silica zeolite-? free of connectivity defects
journal, January 1996


Highly Selective Production of p -Xylene from 2,5-Dimethylfuran over Hierarchical NbO x -Based Catalyst
journal, December 2017


Biobased Terephthalic Acid Technologies: A Literature Review
journal, April 2014


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


Biomass-Derived Renewable Aromatics: Selective Routes and Outlook for p -Xylene Commercialisation
journal, September 2016


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


Synthesis of Self-Pillared Zeolite Nanosheets by Repetitive Branching
journal, June 2012


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


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


Production of p -xylene from bio-based 2,5-dimethylfuran over high performance catalyst WO 3 /SBA-15
journal, January 2017


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


Synthesis of p -Xylene from Ethylene
journal, September 2012


Alternative Approaches for p -Xylene Production from Starch: Techno-Economic Analysis
journal, June 2014


Catalytic fast pyrolysis of glucose with HZSM-5: The combined homogeneous and heterogeneous reactions
journal, March 2010


H-D Exchange of Simple Aromatics as a Measure of Brønsted-Acid Site Strengths in Solids
journal, September 2018


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


Synthesis of ethylene glycol and terephthalic acid from biomass for producing PET
journal, January 2016


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


Effect of acidity of ZSM-5 zeolite on conversion of ethanol to propylene
journal, May 2011