Kinetics and Mechanisms of C-C Forming and C-O Cleavage Reactions of Interests in Bio-oil Upgrading

Meeting Program — September 2013

Daniel E. Resas­co
Uni­ver­si­ty of Okla­homa
Nor­man, OK

Abstract — Bio-oil pro­duced by fast pyrol­y­sis of lig­no­cel­lu­losic bio­mass has attract­ed con­sid­er­able atten­tion as an inter­me­di­ate liq­uid prod­uct towards the pro­duc­tion of fuels. How­ev­er its chem­i­cal insta­bil­i­ty, high vis­cos­i­ty, and cor­ro­sive­ness lim­it their process­abil­i­ty and stor­age. One of the great­est chal­lenges in the upgrad­ing of bio-oil is the accel­er­at­ed degra­da­tion that occurs when the con­densed liq­uid is sub­se­quent­ly heat­ed for frac­tion­a­tion or oth­er pro­cess­ing. Cat­alyt­ic upgrad­ing is an attrac­tive strat­e­gy that can be used to opti­mize car­bon effi­cien­cy and min­i­mize hydro­gen usage. Impor­tant reac­tions for this upgrad­ing include:

  • For­ma­tion of C-C bonds to extend the car­bon back­bone of short oxy­genates to the desired gasoline/diesel range via aldol con­den­sa­tion and ketoniza­tion in aque­ous phase
  • Incor­po­ra­tion of short car­bon frag­ments (C1-C3) into the aro­mat­ic ring of phe­no­lic com­pounds via alky­la­tion in bipha­sic sys­tems
  • Deoxy­gena­tion of the result­ing prod­ucts to mono­func­tion­al com­pounds or hydro­car­bons in the liq­uid phase.

We have inves­ti­gat­ed the kinet­ics and reac­tion mech­a­nisms of these reac­tions on dif­fer­ent cat­a­lysts, includ­ing met­als sup­port­ed on reducible oxides (e.g. Ru/TiO2); acidic cat­a­lysts (HY, H-beta zeo­lites), sup­port­ed met­al cat­a­lysts (Cu, Ni, Ru, Pd sup­port­ed on car­bon nan­otubes) and amphiphilic nanopar­ti­cle cat­a­lysts that are able sta­bi­lize water/oil emul­sions and to con­duct reac­tions at the liquid/liquid inter­face to ben­e­fit from the dif­fer­ences in sol­u­bil­i­ty exhib­it­ed by the reac­tants (bio-oil) and prod­ucts (bio-fuels) and achieve con­tin­u­ous reaction/separation.

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Daniel_ResascoBiog­ra­phy — Daniel E. Resas­co is a Pro­fes­sor of Chem­i­cal, Bio­log­i­cal, and Mate­ri­als Engi­neer­ing at the Uni­ver­si­ty of Okla­homa. He holds the D. Bourne endowed Chair. He received his PhD from Yale Uni­ver­si­ty in 1983. He is author of more than 200 pub­li­ca­tions and 35 indus­tri­al patents in the areas of het­ero­ge­neous catal­y­sis and car­bon nan­otubes and has received more than 8,000 cita­tions. He has been a Pres­i­den­tial Pro­fes­sor, S. Wil­son Pro­fes­sor, and in the last few years he was award­ed the Okla­homa Chemist of the Year award by the Amer­i­can Chem­i­cal Soci­ety, the Yale Sci­ence and Engi­neer­ing Asso­ci­a­tion award, and the Regents Award for Supe­ri­or Research. He is the founder of South­West Nan­otech­nolo­gies, a com­mer­cial car­bon nan­otube pro­duc­er that oper­ates in Nor­man, OK. He has been Edi­tor of the Jour­nal of Catal­y­sis, and has been a mem­ber of the edi­to­r­i­al board of Applied Catal­y­sis and Jour­nal of Catal­y­sis.