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dc.contributor.authorTenorio, Maria-José
dc.contributor.authorChaudhari, Raghunath V.
dc.contributor.authorSubramaniam, Bala
dc.date.accessioned2021-05-24T15:21:15Z
dc.date.available2021-05-24T15:21:15Z
dc.date.issued2019-10-25
dc.identifier.citationInd. Eng. Chem. Res. 2019, 58, 22526−22533en_US
dc.identifier.urihttp://hdl.handle.net/1808/31646
dc.description.abstractThe homogeneous hydroformylation of pent-4-enal, the preferred aldehyde intermediate from 1,3-butadiene hydroformylation, was systematically investigated with Rh catalyst complexes in neat and CO2-expanded toluene media at 40–80 °C, syngas partial pressures ranging from 5–50 bar, and different ligand/Rh ratios. At similar operating conditions, the TOFs are generally greater with Rh/DIOP relative to a Rh/TPP catalyst. On both catalyst complexes, the chemoselectivity toward the dialdehydes ranges from 75%–100%, with the maximum adipaldehyde selectivity reaching approximately 75% (n/i ∼ 3) at 60 °C, 10 bar syngas, and molar DIOP/Rh ratio of 2.5. By using CO2-expanded toluene, the regioselectivity toward the adipaldehyde (desired product), and therefore its yield, is significantly enhanced. Interestingly, even with the simple Rh/TPP catalyst complex, adipaldehyde selectivity of up to 85% (n/i ∼ 5.6) is achieved at 60 °C, 10 bar syngas, and 50 bar CO2. The beneficial effects of CO2-expanded media are attributed to the facile tunability of the H2/CO ratio in such a phase with a fixed syngas feed composition. This approach to accelerate pent-4-enal hydroformylation to form adipaldehyde could also help in overcoming equilibrium limitations typically associated with the catalytic isomerization of pent-3-enal (the dominant product from 1,3-butadiene hydroformylation) to pent-4-enal (the preferred isomer).en_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsCopyright © 2019 American Chemical Societyen_US
dc.subjectHydroformylationen_US
dc.subjectHydrocarbonsen_US
dc.subjectCatalystsen_US
dc.subjectSyngasen_US
dc.subjectSelectivityen_US
dc.titleRh-Catalyzed Hydroformylation of 1,3-Butadiene and Pent-4-enal to Adipaldehyde in CO2-Expanded Mediaen_US
dc.typeArticleen_US
kusw.kuauthorTenorio, Maria-José
kusw.kuauthorChaudhari, Raghunath V.
kusw.kuauthorSubramaniam, Bala
kusw.kudepartmentChemical and Petroleum Engineeringen_US
kusw.kudepartmentCenter for Environmentally Beneficial Catalysisen_US
dc.identifier.doi10.1021/acs.iecr.9b05184en_US
dc.identifier.orcidhttps://orcid.org/0000-0002-1972-1620en_US
dc.identifier.orcidhttps://orcid.org/0000-0001-5361-1954en_US
kusw.oaversionScholarly/refereed, publisher versionen_US
kusw.oapolicyThis item meets KU Open Access policy criteria.en_US
dc.rights.accessrightsopenAccessen_US


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