Development of heterogeneous catalysts for the production of biomass-derived chemicals by selective C-O hydrogenolysis and deoxydehydration

Meeting Program — October 2016

Keiichi Tomishige
Kei­ichi Tomishige
Pro­fes­sor in the School of Engi­neer­ing,
Tohoku Uni­ver­si­ty


Keiichi Tomishige

Abstract — Chem­i­cal com­po­si­tion of the feed­stock from bio­mass and bio­mass-based build­ing blocks has much high­er oxy­gen con­tents than that from crude oil. It has been known that the tar­get prod­ucts such as monomers for the poly­mer syn­the­sis have com­par­a­tive­ly low­er oxy­gen con­tent, and the method­ol­o­gy for the decrease of the oxy­gen con­tent is more and more impor­tant. One of effec­tive meth­ods is the uti­liza­tion of the hydrogenol­y­sis of C-O bonds in the sub­strates. For exam­ple, C3-C6 sug­ar alco­hols (glyc­erol, ery­thri­tol, xyl­i­tol, and sor­bitol) are also regard­ed as promis­ing build­ing blocks in the bio­mass refin­ery. If the selec­tive hydrogenol­y­sis of the tar­get C-O bond among var­i­ous kinds of the C-O bonds is pos­si­ble, valu­able chem­i­cals such as diols, mono-ols, alka­nes can be pro­duced from bio­mass in high yield. ReOx-mod­i­fied Ir met­al cat­a­lyst (Ir-ReOx) is report­ed to be effec­tive to the selec­tive hydrogenol­y­sis of poly­ols and cyclic ethers in water sol­vent. Ir-ReOx/SiO2 cat­alyzes the hydrogenol­y­sis of glyc­erol to 1,3-propanediol. The hydrogenol­y­sis of ery­thri­tol over the cat­a­lyst pro­duces 1,4- and 1,3-butanediols. The selec­tive hydrogenol­y­sis of tetrahy­dro­fur­furyl alco­hol to 1,5-pentanediol also pro­ceeds using Ir-ReOx/SiO2. In addi­tion, the com­bi­na­tion of Ir-ReOx/SiO2 with H-ZSM-5 gives n-alka­nes and hexa­nols from cel­lu­lose, sug­ars, and sug­ar alco­hols in high yield with the total C-O hydrogenol­y­sis and with­out C-C bond dis­so­ci­a­tion and skele­tal iso­mer­iza­tion. Anoth­er inter­est­ing cat­a­lyst is ReOx-Pd/CeO2. The cat­a­lyst showed excel­lent per­for­mance for simul­ta­ne­ous hydrodeoxy­gena­tion of vic­i­nal OH groups in var­i­ous sub­strates. High yield (>99%), turnover fre­quen­cy, and turnover num­ber were obtained in the reac­tion of 1,4-anhydroerythritol to tetrahy­dro­fu­ran. This cat­a­lyst is also applic­a­ble to the con­ver­sion of sug­ar alco­hols mono-alco­hols and diols are obtained in high yields from sub­strates with even and odd num­bers of OH groups, respec­tive­ly. In addi­tion, ReOx-Au/CeO2 cat­alyzed the con­ver­sion of glyc­erol and ery­thri­tol to allyl alco­hol and 1,3-butadiene in high yield (91% and 81%), respec­tive­ly.

Biog­ra­phy — Kei­ichi Tomishige received his B.S., M.S. and Ph.D. from Grad­u­ate School of Sci­ence, Depart­ment of Chem­istry, The Uni­ver­si­ty of Tokyo with Prof. Y. Iwa­sawa. Dur­ing his Ph.D. course in 1994, he moved to Grad­u­ate School of Engi­neer­ing, The Uni­ver­si­ty of Tokyo as a research asso­ciate and worked with Prof. K. Fuji­mo­to. In 1998, he became a lec­tur­er, and then he moved to Insti­tute of Mate­ri­als Sci­ence, Uni­ver­si­ty of Tsuku­ba as a lec­tur­er in 2001. Since 2004 he has been an asso­ciate pro­fes­sor, Grad­u­ate School of Pure and Applied Sci­ences, Uni­ver­si­ty of Tsuku­ba. Since 2010, he is a pro­fes­sor, School of Engi­neer­ing, Tohoku Uni­ver­si­ty.
His research inter­ests are the devel­op­ment of het­ero­ge­neous cat­a­lysts for

  1. pro­duc­tion of bio­mass-derived chem­i­cals
  2. direct syn­the­sis of organ­ic car­bon­ates from CO2 and alco­hols
  3. steam reform­ing of bio­mass tar
  4. syn­gas pro­duc­tion by nat­ur­al gas reform­ing

He is Asso­ciate Edi­tor of Fuel Pro­cess­ing Tech­nol­o­gy (2014/2-), Edi­to­r­i­al board of Applied Catal­y­sis A:General (2009/4-), Edi­to­r­i­al advi­so­ry board of ACS Catal­y­sis (2013/11-), Inter­na­tion­al Advi­so­ry Board of Chem­SusChem (2015/1-) and Advi­so­ry Board of Green Chemistry(2016/8-).