Renewable production of phthalic anhydride from biomass-derived furan and maleic anhydride

Meeting Program — January 2014

 
Eyas Mah­moud†, Don­ald A. Wat­son‡ and Raul F. Lobo†
†Catal­y­sis Cen­ter for Ener­gy Inno­va­tion
Depart­ment of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing
Uni­ver­si­ty of Delaware
Newark, DE 19716 USA
 
‡Depart­ment of Chem­istry and Bio­chem­istry
Uni­ver­si­ty of Delaware
Newark, DE 19716 USA

 
Abstract — A route to renew­able phthal­ic anhy­dride (2-benzofuran-1,3-dione) from bio­mass-derived furan and male­ic anhy­dride (furan-2,5-dione) is inves­ti­gat­ed. Furan and male­ic anhy­dride were con­vert­ed to phthal­ic anhy­dride in two reac­tion steps: Diels Alder cycload­di­tion fol­lowed by dehy­dra­tion. Excel­lent yields for the Diels-Alder reac­tion between furan and male­ic-anhy­dride were obtained at room tem­per­a­ture and sol­vent-free con­di­tions (SFC) yield­ing 96% exo-4,10-Dioxa-tricyclo[5.2.1.0]dec-8-ene-3,5-dione (oxanor­bornene dicar­boxylic anhy­dride) after 4 hrs of reac­tion. It is shown that this reac­tion is resis­tant to ther­mal run­away because its reversibil­i­ty and exother­mic­i­ty. The dehy­dra­tion of the oxanor­bornene was inves­ti­gat­ed using mixed-sul­fon­ic car­boxylic anhy­drides in methane­sul­fon­ic acid (MSA). An 80% selec­tiv­i­ty to phthal­ic anhy­dride (87% selec­tiv­i­ty to phthal­ic anhy­dride and phthal­ic acid) was obtained after run­ning the reac­tion for 2 hrs at 298 K to form a sta­ble inter­me­di­ate fol­lowed by 4 hrs at 353 K to dri­ve the reac­tion to com­ple­tion. The struc­ture of the inter­me­di­ate was deter­mined. This result is much bet­ter than the 11% selec­tiv­i­ty obtained in neat MSA using sim­i­lar reac­tion con­di­tions.
 
Biog­ra­phy — Eyas Mah­moud, recip­i­ent of the AIChE SCI Schol­ar award, grad­u­at­ed sum­ma cum laude from from the Uni­ver­si­ty of Penn­syl­va­nia with a B.S.E.in Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing in 2011. Since then he received the NSF Grad­u­ate Research Fel­low­ship (GRFP) and went on to pur­sue a Ph.D. in the Depart­ment of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing from the Uni­ver­si­ty of Delaware, under the super­vi­sion of Pro­fes­sor Raul F. Lobo. His the­sis work focus­es on the renew­able pro­duc­tion of aro­mat­ics from bio­mass-feed­stocks. Recent­ly, he has pub­lished work on the renew­able pro­duc­tion of phthal­ic anhy­dride from furan and male­ic anhy­dride by using mixed sul­fon­ic-car­boxylic anhy­drides.