Dehydra-decyclization of tetrahydrofurans to diene monomers over metal oxides

Ji, Yichen; Lawal, Ajibola; Nyholm, Andrew; Gorte, Raymond J.; Abdelrahman, Omar A.

doi:10.1039/d0cy01117g

Dehydra-decyclization of tetrahydrofurans to diene monomers over metal oxides

Journal Article · Fri Jul 24 00:00:00 EDT 2020 · Catalysis Science and Technology

DOI:https://doi.org/10.1039/d0cy01117g· OSTI ID:1644272

^[1]; Lawal, Ajibola ^[2]; Nyholm, Andrew ^[3]; Gorte, Raymond J. ^[4]; ^[5]

Univ. of Pennsylvania, Philadelphia, PA (United States); University of Massachusetts Amherst
Department of Chemical Engineering; University of Massachusetts Amherst; Amherst; USA
Univ. of Pennsylvania, Philadelphia, PA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States); Univ. of Delaware, Newark, DE (United States)
Univ. of Massachusetts, Amherst, MA (United States); Univ. of Delaware, Newark, DE (United States)

The dehydra-decyclization of tetrahydrofuran (THF) to butadiene was investigated over a series of metal oxide catalysts, where a common set of chemical pathways was identified. Alongside butadiene, propene is formed via a retro-Prins condensation as the main side product typically observed. Reaction occurred at similar temperatures on each of the oxides, but tetragonal zirconia (t-ZrO₂) and monoclinic zirconia (m-ZrO₂) were unique in showing high selectivity to butadiene (>90%). Near quantitative yields to butadiene could be achieved over t-ZrO₂ at 673 K and a WHSV of 0.93 g THF gcat^–1 h^–1. Through contact time studies, butadiene is determined to be a primary product. Methyl-substituted THF gave only moderate increases in rates and the products showed minimal isomerization of the carbon backbone. The t-ZrO₂ catalyst was found to be relatively stable with time on stream, experiencing coking as a likely source of deactivation. Complete regeneration of the catalyst was demonstrated through calcination alone, allowing for multiple regenerations with no irreversible loss in activity or selectivity. Lastly, the catalytic activity of zirconia was found to be structure insensitive, with t-ZrO₂ and m-ZrO₂ exhibiting similar initial activities; however, m-ZrO₂ was observed to deactivate much more rapidly.

View Accepted Manuscript (DOE)

Research Organization:: Catalysis Center for Energy Innovation, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001004

OSTI ID:: 1644272

Alternate ID(s):: OSTI ID: 1645147

Journal Information:: Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Vol. 10; ISSN 2044-4761; ISSN 2044-4753

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

Butanal Condensation Chemistry Catalyzed by Brønsted Acid Sites on Polyoxometalate Clusters Yang, Yifei; Lin, Fan; Tran, Honghi ChemCatChem, Vol. 9, Issue 2 https://doi.org/10.1002/cctc.201601042	journal	January 2017
Acidity and Catalytic Activity of MeAPSO-44 (Me = Co, Mn, Cr, Zn, Mg), SAPO-44, AIPO4-5, and AIPO4-14 Molecular Sieves in Methanol Dehydration Hocevar, S.; Batista, J.; Kaucic, V. Journal of Catalysis, Vol. 139, Issue 2 https://doi.org/10.1006/jcat.1993.1030	journal	February 1993
Isoprene by Prins Condensation over Acidic Molecular Sieves Dumitriu, E.; Trong On, D.; Kaliaguine, S. Journal of Catalysis, Vol. 170, Issue 1 https://doi.org/10.1006/jcat.1997.1745	journal	August 1997
Evidence for Oxidation of Ceria by CO2 Sharma, S.; Hilaire, S.; Vohs, J. M. Journal of Catalysis, Vol. 190, Issue 1 https://doi.org/10.1006/jcat.1999.2746	journal	February 2000
An Examination of Brønsted Acid Sites in H-[Fe]ZSM-5 for Olefin Oligomerization and Adsorption Kresnawahjuesa, O. Journal of Catalysis, Vol. 210, Issue 1 https://doi.org/10.1006/jcat.2002.3657	journal	August 2002
H-D Exchange of Simple Aromatics as a Measure of Brønsted-Acid Site Strengths in Solids Wang, Cong; Li, Sha; Mao, Xinyu Catalysis Letters, Vol. 148, Issue 11 https://doi.org/10.1007/s10562-018-2563-5	journal	September 2018
Plating on acrylonitrile–butadiene–styrene (ABS) plastic: a review Olivera, Sharon; Muralidhara, Handanahally Basavarajaiah; Venkatesh, Krishna Journal of Materials Science, Vol. 51, Issue 8 https://doi.org/10.1007/s10853-015-9668-7	journal	January 2016
Correlation between acidity and catalytic activity for the methanol dehydration over various aluminum oxides Sung, Dong Min; Kim, Yun Ha; Park, Eun Duck Research on Chemical Intermediates, Vol. 36, Issue 6-7 https://doi.org/10.1007/s11164-010-0201-y	journal	September 2010
ZrO2 Acting as a Redox Catalyst Kauppi, E. I.; Honkala, K.; Krause, A. O. I. Topics in Catalysis, Vol. 59, Issue 8-9 https://doi.org/10.1007/s11244-016-0556-4	journal	April 2016
Preparation and characterization of tetragonal ZrO2 Zhang, Y. -C.; Davison, S.; Brusasco, R. Journal of the Less Common Metals, Vol. 116, Issue 1 https://doi.org/10.1016/0022-5088(86)90238-9	journal	February 1986
Prins condensation of isobutylene and formaldehyde over Fe-silicates of MFI structure Dumitriu, Emil; Hulea, Vasile; Fechete, Ioana Applied Catalysis A: General, Vol. 181, Issue 1 https://doi.org/10.1016/S0926-860X(98)00366-4	journal	May 1999
Vapor-phase dehydration of C4 unsaturated alcohols to 1,3-butadiene Sun, Daolai; Arai, Shigenori; Duan, Hailing Applied Catalysis A: General, Vol. 531 https://doi.org/10.1016/j.apcata.2016.11.035	journal	February 2017
Selective production of 1,3-butadiene in the dehydration of 1,4-butanediol over rare earth oxides Wang, Yuchao; Sun, Daolai; Yamada, Yasuhiro Applied Catalysis A: General, Vol. 562 https://doi.org/10.1016/j.apcata.2018.05.029	journal	July 2018
Chemical and biological-based isoprene production: Green metrics Morais, Ana R. C.; Dworakowska, Sylwia; Reis, Alberto Catalysis Today, Vol. 239 https://doi.org/10.1016/j.cattod.2014.05.033	journal	January 2015
Catalytic consequences of acid strength in the conversion of methanol to dimethyl ether Carr, Robert T.; Neurock, Matthew; Iglesia, Enrique Journal of Catalysis, Vol. 278, Issue 1 https://doi.org/10.1016/j.jcat.2010.11.017	journal	February 2011
Adsorption of Small Alkanes on ZSM-5 Zeolites: Influence of Brønsted Sites Yeh, Yu-Hao; Gorte, Raymond J.; Rangarajan, Srinivas The Journal of Physical Chemistry C, Vol. 120, Issue 22 https://doi.org/10.1021/acs.jpcc.6b03855	journal	June 2016
Catalytic Pathways and Kinetic Requirements for Alkanal Deoxygenation on Solid Tungstosilicic Acid Clusters Lin, Fan; Chin, Ya-Huei Cathy ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01832	journal	September 2016
Mechanism of Isobutanal–Isobutene Prins Condensation Reactions on Solid Brønsted Acids Wang, Shuai; Iglesia, Enrique ACS Catalysis, Vol. 6, Issue 11 https://doi.org/10.1021/acscatal.6b02171	journal	October 2016
Renewable Isoprene by Sequential Hydrogenation of Itaconic Acid and Dehydra-Decyclization of 3-Methyl-Tetrahydrofuran Abdelrahman, Omar A.; Park, Dae Sung; Vinter, Katherine P. ACS Catalysis, Vol. 7, Issue 2 https://doi.org/10.1021/acscatal.6b03335	journal	January 2017
Ring Opening of Biomass-Derived Cyclic Ethers to Dienes over Silica/Alumina Kumbhalkar, Mrunmayi D.; Buchanan, J. Scott; Huber, George W. ACS Catalysis, Vol. 7, Issue 8 https://doi.org/10.1021/acscatal.7b01436	journal	July 2017
“Intelligent” Pt Catalysts Studied on High-Surface-Area CaTiO ₃ Films Lin, Chao; Foucher, Alexandre C.; Ji, Yichen ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b01278	journal	June 2019
Dehydra-Decyclization of Tetrahydrofuran on H-ZSM5: Mechanisms, Pathways, and Transition State Entropy Li, Sha; Abdelrahman, Omar A.; Kumar, Gaurav ACS Catalysis, Vol. 9, Issue 11 https://doi.org/10.1021/acscatal.9b03129	journal	September 2019
Biomass-Derived Butadiene by Dehydra-Decyclization of Tetrahydrofuran Abdelrahman, Omar A.; Park, Dae Sung; Vinter, Katherine P. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 5 https://doi.org/10.1021/acssuschemeng.7b00745	journal	March 2017
Process Design and Economic Analysis of Renewable Isoprene from Biomass via Mesaconic Acid Lundberg, Daniel J.; Lundberg, David J.; Zhang, Kechun ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 5 https://doi.org/10.1021/acssuschemeng.9b00362	journal	February 2019
Investigation of CO and CO ₂ Adsorption on Tetragonal and Monoclinic Zirconia Pokrovski, Konstantin; Jung, Kyeong Taek; Bell, Alexis T. Langmuir, Vol. 17, Issue 14 https://doi.org/10.1021/la001723z	journal	July 2001
Effects of Zirconia Phase on the Synthesis of Methanol over Zirconia-Supported Copper Jung, Kyeong Taek; Bell, Alexis T. Catalysis Letters, Vol. 80, Issue 1/2, p. 63-68 https://doi.org/10.1023/A:1015326726898	journal	January 2002
Review of old chemistry and new catalytic advances in the on-purpose synthesis of butadiene Makshina, Ekaterina V.; Dusselier, Michiel; Janssens, Wout Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/C4CS00105B	journal	January 2014
Quantitative carbon detector (QCD) for calibration-free, high-resolution characterization of complex mixtures Maduskar, Saurabh; Teixeira, Andrew R.; Paulsen, Alex D. Lab on a Chip, Vol. 15, Issue 2 https://doi.org/10.1039/C4LC01180E	journal	January 2015
Progress and prospects in catalytic ethane aromatization Xiang, Yizhi; Wang, Hui; Cheng, Jihong Catalysis Science & Technology, Vol. 8, Issue 6 https://doi.org/10.1039/C7CY01878A	journal	January 2018
Enhancing selectivity and efficiency in the electrochemical synthesis of adiponitrile Blanco, Daniela E.; Dookhith, Aaliyah Z.; Modestino, Miguel A. Reaction Chemistry & Engineering, Vol. 4, Issue 1 https://doi.org/10.1039/C8RE00262B	journal	January 2019
Dehydra-decyclization of 2-methyltetrahydrofuran to pentadienes on boron-containing zeolites Kumar, Gaurav; Liu, Dongxia; Xu, Dandan Green Chemistry, Vol. 22, Issue 13 https://doi.org/10.1039/D0GC00136H	journal	January 2020
Tire Rubber Recycling and Bioremediation: A Review Stevenson, Keri; Stallwood, Bethan; Hart, Adam G. Bioremediation Journal, Vol. 12, Issue 1 https://doi.org/10.1080/10889860701866263	journal	February 2008
Biodegradation of Natural Rubber and Related Compounds: Recent Insights into a Hardly Understood Catabolic Capability of Microorganisms Rose, K.; Steinbuchel, A. Applied and Environmental Microbiology, Vol. 71, Issue 6 https://doi.org/10.1128/AEM.71.6.2803-2812.2005	journal	June 2005
A Characterization Study of Reactive Sites in ALD-Synthesized WOx/ZrO2 Catalysts Wang, Cong; Mao, Xinyu; Lee, Jennifer Catalysts, Vol. 8, Issue 7 https://doi.org/10.3390/catal8070292	journal	July 2018

Similar Records

Selective dehydra-decyclization of cyclic ethers to conjugated dienes over zirconia

Journal Article · Tue Mar 29 00:00:00 EDT 2022 · Journal of Catalysis · OSTI ID:1977255

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Dehydra-decyclization of tetrahydrofurans to diene monomers over metal oxides

Citation Formats

References (34)

Similar Records

Related Subjects