Center for Direct Catalytic Conversion of Biomass to Biofuels - PowerPoint PPT Presentation

Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio) C3Bio develops transformational knowledge and technologies for the direct conversion of plant lignocellulosic biomass to advanced (drop-in) biofuels and other biobased products, currently derived from oil, by the use of new chemical catalysts and thermal treatments. RESEARCH PLAN AND DIRECTIONS We will maximize the energy and carbon efficiencies of advanced biofuels production by the design of both thermal and chemical conversion processes and the biomass itself. Impacts are to more than double the carbon captured into fuel molecules and expand the product range to alkanes and other energy-rich fuels.

Characterization of Molecules in Degraded Lignin Scientific Achievement Fragment (-)APCI/CHCl 3 93 A novel evaporation/ionization method 100 ions 80 Guaiacylglycerol- β -guaiacylether [(-)ESI/NaOH] for mass spectrometric 95 60 71 characterization of lignin degradation products 151 [M+Cl] - 40 355 20 211 109 155 yields only the deprotonated molecule for each 357 269 647 683 0 319 compound, with no bias or fragmentation. 100 [M-H] - 80 (-)ESI/NaOH Significance and Impact 60 This methodology will allow highly detailed 40 20 75 molecular-level characterization of processed 0 100 200 300 400 500 600 700 lignin, enabling the development of reaction m/z Model compounds relevant to lignin can be product-specific catalysts for efficient conversion ionized without fragmentation. of biomass lignin to fuel molecules. Haupert LJ, Owen BC, Marcum CL, Research Details Jarrell TM, Pulliam CJ, Amundson - Twelve individual lignin degradation model compounds were subjected to positive and LM, Narra P, Aqueel MS, Parsell negative ion mode APCI and ESI under traditional and novel experimental conditions. TH, Abu-Omar MM, Kenttämaa HI (2012) Characterization of - Using negative ion mode ESI with NaOH dopant, both individual model compounds and their processed lignin and the lignome mixtures yielded only one product ion (the deprotonated molecule) per compound, confirming by using atmospheric pressure the suitability of this method for tandem mass spectrometric characterization of mixtures. ionization tandem mass - Valuable structural information was obtained on the deprotonated molecules by MS n (n = spectrometry. Fuel , 95 :634-641. iterations of 2 to 7 times) experiments involving multiple ion isolation and collision-activated Work was performed at Purdue University dissociation steps.

Ferrous ion co-catalyst targets multiple chemistries of cell wall during dilute acid pretreatment of biomass Scientific Achievement Scanning electron microscope (SEM) images of Revealed that acid-ferrous ion-assisted dilute acid/Fe 2+ -pretreated corn stover pretreatment increases solubilization and enzymatic digestion of both cellulose and xylan to monomers. It targets multiple chemistries in plant cell wall polymer networks, including the C- O-C and C-H bonds in cellulose. Significance and Impact Identified several essential factors that contribute to ferrous ion-enhanced efficiency during dilute acid pretreatment of biomass. Research Details - We observed concomitant increases in solubilized sugars in the hydrolysate and reducing Wei H, Donohoe BS, Vinzant sugars in the (insoluble) biomass residues and digestibility in residues after acid/ Fe 2+ TB, Ciesielski PN, Wang W, pretreatments . Gedvilas LM, Zeng Y, Johnson DK, Ding SY, Himmel ME, - Fourier transform Raman spectroscopy showed that major peaks representing the C-O-C Tucker MP (2011) . Biotechnol and C-H bonds in cellulose are significantly attenuated by Fe 2+ ions. Biofuels 4:48. - Prussian blue staining indicated that Fe 2+ ions associate with both cellulose/xylan and lignin in pretreated corn stover samples. Work was performed at the National Renewable Energy Lab - Electron microscopy analysis revealed the delamination and fibrillation of the cell wall by (NREL) Fe 2+ ions.

High yields of furfural starting from intact biomass Scientific Achievement Lignin & Xylose Biomass Demonstrated the kinetics of maleic Cellulose ≥ 80% yield acid as a dual-function catalyst for Maleic acid both depolymerization of hemi- 160  C, 20 min + cellulose from intact biomass and selective conversion of the solubilized pentoses to furfural Significance and Impact filter Provides a simple “one - pot” catalytic Maleic acid 200  C, 10 min conversion of about 20% dry mass of biomass to a useful chemical and potential building block for furfural hydrocarbon fuels ≥ 70% yield Research Details Eurick S. Kim, Liu Shuo, Mahdi M. Abu-Omar and - Maleic acid fractionated intact biomass (switchgrass, corn stover and poplar) to produce Nathan S. Mosier, Energy furfural at high yields (>70%). & Fuels 2012 , 26 , 1298- - Kinetic and thermodynamic properties were determined for the reactions involved in 1304 transforming xylose to furfural. Work was performed at - A catalyst based on readily available Pd/C has been developed for the transformation of Purdue University furfural to methyltetrahydrofuran, immiscible with water.

Understanding cellulose at high temperature Scientific Achievement Determined the structure and dynamics of cellulose at high temperature (225 ° C) in atomic detail using molecular simulation Significance and Impact Cellulose at high temperature locally straightens due to changes in hydrogen bond patterns, which causes easily degraded highly- Crystal structure Twist develops At high T, H-bonds twisted short regions to form immediately form between layers Research Details High-Temperature Behavior of Cellulose I - Cellulose at high temperature is difficult to study experimentally, but our simulations Matthews J.F., et al. J. Phys. Chem. provide molecular explanations consistent with all experimental data B 2011 115(10) pg. 2155-2166 - New hydrogen bonds between layers cause the local straightening of cellulose Conversion of cellulose Iα to Iβ via a high temperature intermediate (I-HT) and microfibrils, and make a hydrogen transfer pathway to the surface from the interior other cellulose phase transformations Matthews J.F., Himmel M.E., Crowley M.F. - Phase transformations of cellulose crystals can occur with heating, and our Cellulose 2012 19(1) pg. 297-306 simulations suggest why these transformations proceed in one direction only Work was performed at NREL

TEM analysis of Maleic Acid pretreated Lignin Mutants A B Scientific Achievement middle lamella TEM micrographs reveal the dramatic 1º cell wall impact of maleic acid pretreatment on cell wall architecture when applied to biomass with modified (high S) lignin composition (D) 2º cell wall Significance and Impact This evidence suggests that the cell wall cell lumen architecture of high S lignin feedstocks will yield to pretreatment at lower severities and WT, untreated fah 1-2 C4H F5H, untreated therefore lower costs C D Research Details nano-fibrillation – fah1-2 C4H F5H (high S) mutants exhibit a less dense middle lamella – pretreatment caused extensive dislocation of dislocation cells at the middle lamella – pretreatment caused delamination within the delamination secondary cell walls – pretreatment caused nano-fibrillation at the cell lumen surface – these physical properties of biomass cell wall WT, maleic acid pretreated fah 1-2 C4H F5H, maleic acid pretreated deconstruction are highly correlated with Peter Ciesielski, Bryon Donohoe - NREL conversion yields Clint Chapple, Nate Mosier - Purdue

Production of C5 and C6 furfurals from lignocellulosic biomass in the microwave using cheap and abundant aluminum catalyst Scientific Achievement Demonstrated the use of AlCl 3  6H 2 O in biphasic medium as an effective and recyclable catalyst for the conversion of lignocellulosic biomass variants (corn stover, pine wood, poplar, and switch grass) to hydroxymethylfurfural (HMF) and furfural (Ff). Significance and Impact Provides in a single catalytic step, conversion of 60- HMF 70 furfural 70% of the biomass (cellulose plus xylose) to platform 60 chemicals that can be upgraded to liquid fuels. The 50 products are recovered by liquid-liquid separation and 40 Yield (%) the catalyst can be recycled multiple times without 30 loss of activity. 20 10 Research Details 0 corn stover pine wood grass poplar - Al 3+ (aq) affects the hydrolysis of intact biomass (switch grass, corn stover, pine wood and poplar) into soluble sugars and their subsequent dehydration to produce HMF and Ff in Yu Yang , Chang-wei Hu, and moderate and high yields, respectively. Mahdi M Abu-Omar - The reaction is complete in less than 30 minutes under microwave heating at 160-180  C. Green Chem. 2012 , 14 , 509-513; - The catalyst is cheap, abundant, and can be recycled multiple times without loss of ChemSusChem 2012 , 5 , 405-410. activity. Al 3+ (aq) can be obtained by dissolving soda cans in basic solution. Work was performed at Purdue - The kinetics of glucose conversion to HMF indicates that Al 3+ (aq) catalyzes glucose University isomerization to fructose followed by the latter’s dehydration to give HMF.