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Rh-Catalyzed Hydroformylation of 1,3-Butadiene and Pent-4-enal to Adipaldehyde in CO2-Expanded Media
dc.contributor.author | Tenorio, Maria-José | |
dc.contributor.author | Chaudhari, Raghunath V. | |
dc.contributor.author | Subramaniam, Bala | |
dc.date.accessioned | 2021-05-24T15:21:15Z | |
dc.date.available | 2021-05-24T15:21:15Z | |
dc.date.issued | 2019-10-25 | |
dc.identifier.citation | Ind. Eng. Chem. Res. 2019, 58, 22526−22533 | en_US |
dc.identifier.uri | http://hdl.handle.net/1808/31646 | |
dc.description.abstract | The 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.publisher | American Chemical Society | en_US |
dc.rights | Copyright © 2019 American Chemical Society | en_US |
dc.subject | Hydroformylation | en_US |
dc.subject | Hydrocarbons | en_US |
dc.subject | Catalysts | en_US |
dc.subject | Syngas | en_US |
dc.subject | Selectivity | en_US |
dc.title | Rh-Catalyzed Hydroformylation of 1,3-Butadiene and Pent-4-enal to Adipaldehyde in CO2-Expanded Media | en_US |
dc.type | Article | en_US |
kusw.kuauthor | Tenorio, Maria-José | |
kusw.kuauthor | Chaudhari, Raghunath V. | |
kusw.kuauthor | Subramaniam, Bala | |
kusw.kudepartment | Chemical and Petroleum Engineering | en_US |
kusw.kudepartment | Center for Environmentally Beneficial Catalysis | en_US |
dc.identifier.doi | 10.1021/acs.iecr.9b05184 | en_US |
dc.identifier.orcid | https://orcid.org/0000-0002-1972-1620 | en_US |
dc.identifier.orcid | https://orcid.org/0000-0001-5361-1954 | en_US |
kusw.oaversion | Scholarly/refereed, publisher version | en_US |
kusw.oapolicy | This item meets KU Open Access policy criteria. | en_US |
dc.rights.accessrights | openAccess | en_US |