Catalyst and reactor design considerations for selective production of acids by oxidative cleavage of alkenes and unsaturated fatty acids with H2O2

Yun, Danim; Zhang, Zhongyao; Flaherty, David W.

doi:10.1039/d2re00160h

Catalyst and reactor design considerations for selective production of acids by oxidative cleavage of alkenes and unsaturated fatty acids with H₂O₂

Journal Article · Fri Jun 10 00:00:00 EDT 2022 · Reaction Chemistry & Engineering

DOI:https://doi.org/10.1039/d2re00160h· OSTI ID:1902737

^[1]; Zhang, Zhongyao ^[2]; Flaherty, David W. ^[2]

Univ. of Illinois at Urbana-Champaign, IL (United States); University of Illinois
Univ. of Illinois at Urbana-Champaign, IL (United States)

Oxidative cleavage of alkenes and unsaturated fatty acids with hydrogen peroxide gives an efficient and sustainable process to obtain mono- and di-acids for polymers and lubricants with fewer safety risks and less environmental impact than processes that utilize ozone or other inorganic oxidizers (e.g., permanganate, dichromate, etc.). Guided by insight into the mechanisms for competing reaction pathways (i.e., epoxidation of alkene on W–(η²-O₂) complexes vs. H₂O₂ decomposition) and the apparent kinetics derived from kinetic experiments, here, we postulate that W-based heterogeneous catalysts can provide high performance and stable operations at low H₂O₂ concentrations. Semi-batch reactors with continuous introduction of H₂O₂ solutions offer the means to maintain low H₂O₂ concentrations while providing sufficient quantities of H₂O₂ to satisfy the reaction stoichiometry. We derived simple kinetic model equations for the epoxidation, ring-opening, oxidative cleavage, and oxidation steps and fit theses equations to batch experimental data to obtain kinetic parameters. Furthermore, this kinetic model describes the concentration profiles of reactant, oxidant, and products well as shown by agreement with experimental data. Further predictions of the optimal H₂O₂ feed rate for semi-batch operation utilized by the proposed rate expressions and the reactor design equations suggest that low H₂O₂ feed rate increases selectivity towards oxidative cleavage products and selective use of H₂O₂ for oxidative cleavage pathway. Comparisons of oxidative cleavage of 4-octene in batch and semi-batch reactors show that semibatch reactors with optimized molar feed rates of H₂O₂ increased oxidative cleavage product selectivities (76% to 99%; with an increase in butyric acid selectivity from 1% to 55%) and H₂O₂ selectivity (3% to 30%). In addition, semibatch reaction conditions used avoid H₂O₂-mediated dissolution of W-atoms from the catalyst. Analysis of these findings suggest that solid oxide catalysts will be effective for continuous oxidative cleavage reactions if deployed within fixed-bed reactors that allow for distributed introduction of reactants and therefore low in situ concentrations of H₂O₂.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0018420

OSTI ID:: 1902737

Alternate ID(s):: OSTI ID: 1873449

Journal Information:: Reaction Chemistry & Engineering, Journal Name: Reaction Chemistry & Engineering Journal Issue: 9 Vol. 7; ISSN 2058-9883

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Toward Replacing Ethylene Oxide in a Sustainable World: Glycolaldehyde as a Bio‐Based C ₂ Platform Molecule Faveere, William H.; Van Praet, Sofie; Vermeeren, Benjamin Angewandte Chemie International Edition, Vol. 60, Issue 22 https://doi.org/10.1002/anie.202009811	journal	December 2020
Fatty Acids and their Derivatives as Renewable Platform Molecules for the Chemical Industry Biermann, Ursula; Bornscheuer, Uwe T.; Feussner, Ivo Angewandte Chemie International Edition, Vol. 60, Issue 37 https://doi.org/10.1002/anie.202100778	journal	May 2021
Fe-Catalyzed One-Pot Oxidative Cleavage of Unsaturated Fatty Acids into Aldehydes with Hydrogen Peroxide and Sodium Periodate Spannring, Peter; Yazerski, Vital; Bruijnincx, Pieter C. A. Chemistry - A European Journal, Vol. 19, Issue 44 https://doi.org/10.1002/chem.201301371	journal	September 2013
Effect of H ₂ O ₂ addition mode on enzymatic removal of phenol from wastewater in the presence of polyethylene glycol Wu, Jiangning; Bewtra, J. K.; Biswas, N. The Canadian Journal of Chemical Engineering, Vol. 72, Issue 5 https://doi.org/10.1002/cjce.5450720515	journal	October 1994
Gold‐catalyzed synthesis of dicarboxylic and monocarboxylic acids Kulik, Anna; Janz, Alexander; Pohl, Marga‐Martina European Journal of Lipid Science and Technology, Vol. 114, Issue 11 https://doi.org/10.1002/ejlt.201200027	journal	August 2012
Surface hydrophobicity and acidity effect on alumina catalyst in catalytic methanol dehydration reaction: Hydrophobicity and acidity effect on DME production Osman, Ahmed I.; Abu-Dahrieh, Jehad K.; Rooney, David W. Journal of Chemical Technology & Biotechnology, Vol. 92, Issue 12 https://doi.org/10.1002/jctb.5371	journal	September 2017
Transition-metal Catalyzed Oxidative Cleavage of Unsaturated Fatty Acids Rüsch, M.; Klaas, Gen.; Bavaj, P. Fett Wissenschaft Technologie/Fat Science Technology, Vol. 97, Issue 10 https://doi.org/10.1002/lipi.19950971002	journal	January 1995
Characterizations of Iron-Containing MCM-41 and Its Catalytic Properties in Epoxidation of Styrene with Hydrogen Peroxide Wang, Ye; Zhang, Qinghong; Shishido, Tetsuya Journal of Catalysis, Vol. 209, Issue 1 https://doi.org/10.1006/jcat.2002.3607	journal	July 2002
Introduction to Catalysis No authors listed Organometallic Chemistry and Catalysis https://doi.org/10.1007/978-3-540-46129-6_16	book
Synthesis of azelaic acid and suberic acid from Vernonia galamensis oil Ayorinde, Folahan O.; Osman, Gamal; Shepard, Robert L. Journal of the American Oil Chemists' Society, Vol. 65, Issue 11 https://doi.org/10.1007/BF02542380	journal	November 1988
Permanganate oxidation of oleic acid using emulsion technology Garti, Imissim; Avni, Eitan Journal of the American Oil Chemists' Society, Vol. 58, Issue 8 https://doi.org/10.1007/BF02665593	journal	August 1981
Effect of postharvest period on sugars, organic acids and fatty acids composition in commercially sold medlar (Mespilus germanica 'Dutch') fruit Glew, Robert H.; Ayaz, F. Ahmet; Sanz, Carlos European Food Research and Technology, Vol. 216, Issue 5 https://doi.org/10.1007/s00217-002-0654-3	journal	March 2003
Catalytic oxidation of fatty acids. II. Epoxidation and oxidative cleavage of unsaturated fatty acid esters containing additional functional groups Khlebnikova, Tatiana B.; Pai, Zinaida P.; Fedoseeva, Larisa A. Reaction Kinetics and Catalysis Letters, Vol. 98, Issue 1 https://doi.org/10.1007/s11144-009-0054-9	journal	September 2009
Catalytic oxidation of olefins and alcohols with hydrogen peroxide in a two-phase system giving mono- and dicarboxylic acids Pai, Z. P.; Tolstikov, A. G.; Berdnikova, P. V. Russian Chemical Bulletin, Vol. 54, Issue 8 https://doi.org/10.1007/s11172-006-0047-z	journal	August 2005
New Environmentally Friendly Oxidative Scission of Oleic Acid into Azelaic Acid and Pelargonic Acid Godard, Anaïs; De Caro, Pascale; Thiebaud-Roux, Sophie Journal of the American Oil Chemists' Society, Vol. 90, Issue 1 https://doi.org/10.1007/s11746-012-2134-7	journal	August 2012
Sustainable Process for Production of Azelaic Acid Through Oxidative Cleavage of Oleic Acid Benessere, Vincenzo; Cucciolito, Maria E.; De Santis, Augusta Journal of the American Oil Chemists' Society, Vol. 92, Issue 11-12 https://doi.org/10.1007/s11746-015-2727-z	journal	October 2015
Liquid-phase catalytic oxidation of unsaturated fatty acids Noureddini, H.; Kanabur, M. Journal of the American Oil Chemists' Society, Vol. 76, Issue 3 https://doi.org/10.1007/s11746-999-0236-7	journal	March 1999
Acorn (Quercus spp.) as a novel source of oleic acid and tocopherols for livestock and humans: discrimination of selected species from Mediterranean forest Akcan, T.; Gökçe, R.; Asensio, M. Journal of Food Science and Technology, Vol. 54, Issue 10 https://doi.org/10.1007/s13197-017-2740-3	journal	June 2017
The oxidation of oleic acid by permanganate in oil in water emulsion Garti, Nissim; Avni, Eitan Colloids and Surfaces, Vol. 4, Issue 1 https://doi.org/10.1016/0166-6622(82)80087-5	journal	January 1982
The role of peroxymetallation in selective oxidative processes Mimoun, H. Journal of Molecular Catalysis, Vol. 7, Issue 1 https://doi.org/10.1016/0304-5102(80)85001-2	journal	January 1980
Alumina-catalyzed alkene epoxidation with hydrogen peroxide Mandelli, Dalmo; van Vliet, Michiel C. A.; Sheldon, Roger A. Applied Catalysis A: General, Vol. 219, Issue 1-2 https://doi.org/10.1016/S0926-860X(01)00693-7	journal	October 2001
Optimization of cyclohexene epoxidation with dilute hydrogen peroxide and silica-supported titanium catalysts Fraile, José M.; Garcı́a, José I.; Mayoral, José A. Applied Catalysis A: General, Vol. 245, Issue 2 https://doi.org/10.1016/S0926-860X(02)00643-9	journal	June 2003
Practical dihydroxylation and C–C cleavage of unsaturated fatty acids Oakley, Michael A.; Woodward, Simon; Coupland, Keith Journal of Molecular Catalysis A: Chemical, Vol. 150, Issue 1-2, p. 105-111 https://doi.org/10.1016/S1381-1169(99)00213-7	journal	December 1999
Alumina-catalyzed epoxidation of unsaturated fatty esters with hydrogen peroxide Sepulveda, Jorge; Teixeira, Sergio; Schuchardt, Ulf Applied Catalysis A: General, Vol. 318 https://doi.org/10.1016/j.apcata.2006.11.004	journal	February 2007
Monomeric and dimeric oxido–peroxido tungsten(VI) complexes in catalytic and stoichiometric epoxidation Amini, Mojtaba; Haghdoost, Mohammad Mehdi; Bagherzadeh, Mojtaba Coordination Chemistry Reviews, Vol. 268 https://doi.org/10.1016/j.ccr.2014.01.035	journal	June 2014
Effect of semi-batch reactor configuration on aromatic hydroxylation reactions Callanan, Linda H.; Burton, Robert M.; Mullineux, John Chemical Engineering Journal, Vol. 180 https://doi.org/10.1016/j.cej.2011.11.033	journal	January 2012
Carbon black-polydopamine-ruthenium composite as a recyclable boomerang catalyst for the oxidative cleavage of oleic acid Gámez, Sebastián; de la Torre, Ernesto; Gaigneaux, Eric M. Chemical Engineering Journal, Vol. 427 https://doi.org/10.1016/j.cej.2021.131820	journal	January 2022
Use of semibatch reactor technology for the investigation of reaction mechanism and kinetics: Heterogeneously catalyzed epoxidation of fatty acid esters Perez-Sena, Wander Y.; Wärnå, Johan; Eränen, Kari Chemical Engineering Science, Vol. 230 https://doi.org/10.1016/j.ces.2020.116206	journal	February 2021
The biorefinery concept: Using biomass instead of oil for producing energy and chemicals Cherubini, Francesco Energy Conversion and Management, Vol. 51, Issue 7 https://doi.org/10.1016/j.enconman.2010.01.015	journal	July 2010
Economic risk assessment using Monte Carlo simulation for the production of azelaic acid and pelargonic acid from vegetable oils De Leon Izeppi, Gerardo Antonio; Dubois, Jean-Luc; Balle, Antonin Industrial Crops and Products, Vol. 150 https://doi.org/10.1016/j.indcrop.2020.112411	journal	August 2020
Kinetic and spectroscopic evidence for reaction pathways and intermediates for olefin epoxidation on Nb in *BEA Bregante, Daniel T.; Priyadarshini, Pranjali; Flaherty, David W. Journal of Catalysis, Vol. 348 https://doi.org/10.1016/j.jcat.2017.02.008	journal	April 2017
Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites Tan, Jun Zhi; Bregante, Daniel T.; Torres, Chris Journal of Catalysis, Vol. 405 https://doi.org/10.1016/j.jcat.2021.11.029	journal	January 2022
A combined experimental and DFT study of active structures and self-cycle mechanisms of mononuclear tungsten peroxo complexes in oxidation reactions Jin, Peng; Wei, Donghui; Wen, Yiqiang Journal of Molecular Structure, Vol. 992, Issue 1-3 https://doi.org/10.1016/j.molstruc.2011.02.023	journal	April 2011
“Drop-in” fuel production from biomass: Critical review on techno-economic feasibility and sustainability Kargbo, Hannah; Harris, Jonathan Stuart; Phan, Anh N. Renewable and Sustainable Energy Reviews, Vol. 135 https://doi.org/10.1016/j.rser.2020.110168	journal	January 2021
Ruthenium catalysed oxidation without CCl4 of oleic acid, other monoenic fatty acids and alkenes Zimmermann, François; Meux, Eric; Mieloszynski, Jean-Luc Tetrahedron Letters, Vol. 46, Issue 18 https://doi.org/10.1016/j.tetlet.2005.03.052	journal	May 2005
Alkene Epoxidations with H ₂ O ₂ over Groups 4–6 Metal-Substituted BEA Zeolites: Reactive Intermediates, Reaction Pathways, and Linear Free-Energy Relationships Ayla, E. Zeynep; Potts, David S.; Bregante, Daniel T. ACS Catalysis, Vol. 11, Issue 1 https://doi.org/10.1021/acscatal.0c03394	journal	December 2020
Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H ₂ O ₂ over Tungsten Oxide Catalysts Yun, Danim; Ayla, E. Zeynep; Bregante, Daniel T. ACS Catalysis, Vol. 11, Issue 5 https://doi.org/10.1021/acscatal.0c05393	journal	February 2021
Consequences of Confinement for Alkene Epoxidation with Hydrogen Peroxide on Highly Dispersed Group 4 and 5 Metal Oxide Catalysts Bregante, Daniel T.; Thornburg, Nicholas E.; Notestein, Justin M. ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.7b03986	journal	February 2018
Impact of Specific Interactions Among Reactive Surface Intermediates and Confined Water on Epoxidation Catalysis and Adsorption in Lewis Acid Zeolites Bregante, Daniel T.; Flaherty, David W. ACS Catalysis, Vol. 9, Issue 12 https://doi.org/10.1021/acscatal.9b03323	journal	October 2019
The Use of Ultra- and Nanofiltration Techniques in Homogeneous Catalyst Recycling Dijkstra, Harm P.; van Klink, Gerard P. M.; van Koten, Gerard Accounts of Chemical Research, Vol. 35, Issue 9 https://doi.org/10.1021/ar0100778	journal	June 2002
Alkylated Polyethyleneimine/Polyoxometalate Synzymes as Catalysts for the Oxidation of Hydrophobic Substrates in Water with Hydrogen Peroxide Haimov, Adina; Cohen, Hagai; Neumann, Ronny Journal of the American Chemical Society, Vol. 126, Issue 38 https://doi.org/10.1021/ja046349u	journal	September 2004
Periodic Trends in Olefin Epoxidation over Group IV and V Framework-Substituted Zeolite Catalysts: A Kinetic and Spectroscopic Study Bregante, Daniel T.; Flaherty, David W. Journal of the American Chemical Society, Vol. 139, Issue 20 https://doi.org/10.1021/jacs.7b01422	journal	May 2017
Oxidative cleavage of 1,2-diols to carboxylic acids by hydrogen peroxide Venturello, Carlo; Ricci, Marco The Journal of Organic Chemistry, Vol. 51, Issue 9 https://doi.org/10.1021/jo00359a042	journal	May 1986
Opposite regioselectivity in the epoxidation of geraniol and linalool with molybdenum and tungsten peroxo complexes Arcoria, Antonio; Ballistreri, Francesco Paolo; Tomaselli, Gaetano Andrea The Journal of Organic Chemistry, Vol. 51, Issue 12 https://doi.org/10.1021/jo00362a037	journal	June 1986
Efficient Oxidative Cleavage of Olefins to Carboxylic Acids with Hydrogen Peroxide Catalyzed by Methyltrioctylammonium Tetrakis(oxodiperoxotungsto)phosphate(3−) under Two-Phase Conditions. Synthetic Aspects and Investigation of the Reaction Course Antonelli, Ermanno; D'Aloisio, Rino; Gambaro, Mario The Journal of Organic Chemistry, Vol. 63, Issue 21 https://doi.org/10.1021/jo980481t	journal	October 1998
Hydration of γ-Alumina in Water and Its Effects on Surface Reactivity Lefèvre, Grégory; Duc, Myriam; Lepeut, Patrick Langmuir, Vol. 18, Issue 20 https://doi.org/10.1021/la025651i	journal	October 2002
Oleic Acid Oxidation Using Hydrogen Peroxide in Conjunction with Transition Metal Catalysis Turnwald, S. E.; Lorier, M. A.; Wright, L. J. Journal of Materials Science Letters, Vol. 17, Issue 15, p. 1305-1307 https://doi.org/10.1023/A:1006532314593	journal	January 1998
Conversion of Oleic Acid to Saturated Fatty Acids in Severn Estuary Sediments Rhead, M. M.; Eglinton, G.; Draffan, G. H. Nature, Vol. 232, Issue 5309 https://doi.org/10.1038/232327a0	journal	July 1971
The shape of water in zeolites and its impact on epoxidation catalysis Bregante, Daniel T.; Chan, Matthew C.; Tan, Jun Zhi Nature Catalysis, Vol. 4, Issue 9 https://doi.org/10.1038/s41929-021-00672-4	journal	September 2021
Efficient ruthenium-catalysed oxidative cleavage of methyl oleate with hydrogen peroxide as oxidant Behr, Arno; Tenhumberg, Nils; Wintzer, Andreas RSC Adv., Vol. 3, Issue 1 https://doi.org/10.1039/C2RA22370H	journal	January 2013
Chemically catalyzed oxidative cleavage of unsaturated fatty acids and their derivatives into valuable products for industrial applications: a review and perspective Enferadi Kerenkan, Amir; Béland, François; Do, Trong-On Catalysis Science & Technology, Vol. 6, Issue 4 https://doi.org/10.1039/C5CY01118C	journal	January 2016
Sodium stannate promoted double bond cleavage of oleic acid by hydrogen peroxide over a heterogeneous WO ₃ catalyst Li, Xiukai; Choo Ping Syong, Joel; Zhang, Yugen Green Chemistry, Vol. 20, Issue 15 https://doi.org/10.1039/C8GC00949J	journal	January 2018
Recent trends in the development of sustainable catalytic systems for the oxidative cleavage of cycloalkenes by hydrogen peroxide Cousin, Tony; Chatel, Gregory; Kardos, Nathalie Catalysis Science & Technology, Vol. 9, Issue 19 https://doi.org/10.1039/C9CY01269A	journal	January 2019
Heteroatom substituted zeolite FAU with ultralow Al contents for liquid-phase oxidation catalysis Bregante, Daniel T.; Tan, Jun Zhi; Sutrisno, Andre Catalysis Science & Technology, Vol. 10, Issue 3 https://doi.org/10.1039/C9CY01886G	journal	January 2020
Influence of solvent structure and hydrogen bonding on catalysis at solid–liquid interfaces Potts, David S.; Bregante, Daniel T.; Adams, Jason S. Chemical Society Reviews, Vol. 50, Issue 22 https://doi.org/10.1039/D1CS00539A	journal	January 2021
Regio- and stereoselective terpene epoxidation using tungstate-exchanged takovites: a study of phase purity, takovite composition and stable catalytic activity Levecque, Pieter; Poelman, Hilde; Jacobs, Pierre Physical Chemistry Chemical Physics, Vol. 11, Issue 16 https://doi.org/10.1039/b820336a	journal	January 2009
Transition metal-catalyzed oxidative double bond cleavage of simple and bio-derived alkenes and unsaturated fatty acids Spannring, Peter; Bruijnincx, Pieter C. A.; Weckhuysen, Bert. M. Catalysis Science & Technology, Vol. 4, Issue 8 https://doi.org/10.1039/c3cy01095c	journal	January 2014
Environmentally friendly catalytic methods Clark, James H.; Macquarrie, Duncan J. Chemical Society Reviews, Vol. 25, Issue 5 https://doi.org/10.1039/cs9962500303	journal	January 1996
Organic reactions in strong alkalis. Part V. Alkali fusion of epoxides and ethers Ansell, M. F.; Shepherd, I. S.; Weedon, B. C. L. Journal of the Chemical Society C: Organic https://doi.org/10.1039/j39710001840	journal	January 1971
Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis Zope, B. N.; Hibbitts, D. D.; Neurock, M. Science, Vol. 330, Issue 6000 https://doi.org/10.1126/science.1195055	journal	September 2010
Valorization of Biomass: Deriving More Value from Waste Tuck, C. O.; Perez, E.; Horvath, I. T. Science, Vol. 337, Issue 6095, p. 695-699 https://doi.org/10.1126/science.1218930	journal	August 2012
Self-Assembled Complexes of Non-cross-linked Amphiphilic Polymeric Ligands with Inorganic Species: Highly Active and Reusable Solid-Phase Polymeric Catalysts Yamada, Yoichi M. A. CHEMICAL & PHARMACEUTICAL BULLETIN, Vol. 53, Issue 7 https://doi.org/10.1248/cpb.53.723	journal	January 2005

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