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Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)

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.

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.

Characterization of Molecules in Degraded Lignin

Scientific Achievement A novel evaporation/ionization method [(-)ESI/NaOH] for mass spectrometric characterization of lignin degradation products yields only the deprotonated molecule for each compound, with no bias or fragmentation. Significance and Impact This methodology will allow highly detailed molecular-level characterization of processed lignin, enabling the development of reaction product-specific catalysts for efficient conversion

• f biomass lignin to fuel molecules.

Haupert LJ, Owen BC, Marcum CL, Jarrell TM, Pulliam CJ, Amundson LM, Narra P, Aqueel MS, Parsell TH, Abu-Omar MM, Kenttämaa HI (2012) Characterization of processed lignin and the lignome by using atmospheric pressure ionization tandem mass

• spectrometry. Fuel , 95:634-641.

Work was performed at Purdue University

Research Details

• Twelve individual lignin degradation model compounds were subjected to positive and

negative ion mode APCI and ESI under traditional and novel experimental conditions.

• Using negative ion mode ESI with NaOH dopant, both individual model compounds and their

mixtures yielded only one product ion (the deprotonated molecule) per compound, confirming the suitability of this method for tandem mass spectrometric characterization of mixtures.

• Valuable structural information was obtained on the deprotonated molecules by MSn (n =

iterations of 2 to 7 times) experiments involving multiple ion isolation and collision-activated dissociation steps.

100 200 300 400 500 600 700 m/z 20 40 60 80 100 20 40 60 80 100 93 95 71 151 355 211 109 155 357 269 647 683 319 75

(-)APCI/CHCl3 (-)ESI/NaOH [M+Cl]- [M-H]- Fragment ions

Model compounds relevant to lignin can be ionized without fragmentation.

Guaiacylglycerol-β-guaiacylether

Ferrous ion co-catalyst targets multiple chemistries of cell wall during dilute acid pretreatment of biomass

Scientific Achievement Revealed that acid-ferrous ion-assisted 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.

Wei H, Donohoe BS, Vinzant TB, Ciesielski PN, Wang W, Gedvilas LM, Zeng Y, Johnson DK, Ding SY, Himmel ME, Tucker MP (2011). Biotechnol Biofuels 4:48. Work was performed at the National Renewable Energy Lab (NREL)

• We observed concomitant increases in solubilized sugars in the hydrolysate and reducing

sugars in the (insoluble) biomass residues and digestibility in residues after acid/ Fe2+ pretreatments .

• Fourier transform Raman spectroscopy showed that major peaks representing the C-O-C

and C-H bonds in cellulose are significantly attenuated by Fe2+ ions.

• Prussian blue staining indicated that Fe2+ ions associate with both cellulose/xylan and

lignin in pretreated corn stover samples.

• Electron microscopy analysis revealed the delamination and fibrillation of the cell wall by

Fe2+ ions.

Scanning electron microscope (SEM) images of dilute acid/Fe2+-pretreated corn stover

Research Details

High yields of furfural starting from intact biomass

Scientific Achievement Demonstrated the kinetics of maleic acid as a dual-function catalyst for both depolymerization of hemi- cellulose from intact biomass and selective conversion of the solubilized pentoses to furfural Significance and Impact Provides a simple “one-pot” catalytic conversion of about 20% dry mass of biomass to a useful chemical and potential building block for hydrocarbon fuels Research Details

Eurick S. Kim, Liu Shuo, Mahdi M. Abu-Omar and Nathan S. Mosier, Energy & Fuels 2012, 26, 1298- 1304 Work was performed at Purdue University

+

Biomass Lignin & Cellulose Xylose ≥ 80% yield filter furfural ≥ 70% yield

Maleic acid 160 C, 20 min Maleic acid 200 C, 10 min

• Maleic acid fractionated intact biomass (switchgrass, corn stover and poplar) to produce

furfural at high yields (>70%).

• Kinetic and thermodynamic properties were determined for the reactions involved in

transforming xylose to furfural.

• A catalyst based on readily available Pd/C has been developed for the transformation of

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- twisted short regions to form Research Details

High-Temperature Behavior of Cellulose I Matthews J.F., et al. J. Phys. Chem. B 2011 115(10) pg. 2155-2166 Conversion of cellulose Iα to Iβ via a high temperature intermediate (I-HT) and

• ther cellulose phase transformations

Matthews J.F., Himmel M.E., Crowley M.F. Cellulose 2012 19(1) pg. 297-306 Work was performed at NREL

• Cellulose at high temperature is difficult to study experimentally, but our simulations

provide molecular explanations consistent with all experimental data

• New hydrogen bonds between layers cause the local straightening of cellulose

microfibrils, and make a hydrogen transfer pathway to the surface from the interior

• Phase transformations of cellulose crystals can occur with heating, and our

simulations suggest why these transformations proceed in one direction only

Crystal structure Twist develops immediately At high T, H-bonds form between layers

TEM analysis of Maleic Acid pretreated Lignin Mutants

Scientific Achievement

TEM micrographs reveal the dramatic impact of maleic acid pretreatment on cell wall architecture when applied to biomass with modified (high S) lignin composition (D)

Significance and Impact

This evidence suggests that the cell wall architecture of high S lignin feedstocks will yield to pretreatment at lower severities and therefore lower costs

Research Details

– fah1-2 C4H F5H (high S) mutants exhibit a less dense middle lamella – pretreatment caused extensive dislocation of cells at the middle lamella – pretreatment caused delamination within the secondary cell walls – pretreatment caused nano-fibrillation at the cell lumen surface – these physical properties of biomass cell wall deconstruction are highly correlated with conversion yields A B C D

WT, untreated WT, maleic acid pretreated fah 1-2 C4H F5H, untreated fah 1-2 C4H F5H, maleic acid pretreated

Peter Ciesielski, Bryon Donohoe - NREL Clint Chapple, Nate Mosier - Purdue cell lumen 2º cell wall 1º cell wall middle lamella nano-fibrillation dislocation delamination

Production of C5 and C6 furfurals from lignocellulosic biomass in the microwave using cheap and abundant aluminum catalyst

Scientific Achievement

Demonstrated the use of AlCl36H2O 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- 70% of the biomass (cellulose plus xylose) to platform chemicals that can be upgraded to liquid fuels. The products are recovered by liquid-liquid separation and the catalyst can be recycled multiple times without loss of activity.

Research Details

Yu Yang , Chang-wei Hu, and Mahdi M Abu-Omar Green Chem. 2012,14, 509-513; ChemSusChem 2012, 5, 405-410. Work was performed at Purdue University

• Al3+

(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 moderate and high yields, respectively.

• The reaction is complete in less than 30 minutes under microwave heating at 160-180 C.
• The catalyst is cheap, abundant, and can be recycled multiple times without loss of
• activity. Al3+

(aq) can be obtained by dissolving soda cans in basic solution.

• The kinetics of glucose conversion to HMF indicates that Al3+

(aq) catalyzes glucose

isomerization to fructose followed by the latter’s dehydration to give HMF.

corn stover pine wood grass poplar 10 20 30 40 50 60 70

Yield (%) HMF furfural

High Performance Liquid Chromatography Combined with Tandem Mass Spectrometry for Analysis of Degraded Lignin

Scientific Achievement A novel high-performance liquid chromatography (HPLC) method compatible with (-)ESI/ NaOH ioni- zation and high-resolution tandem mass spectro- metry (MS3) allows analysis of isomeric (see below) and isobaric lignin degradation products. Significance and Impact This methodology significantly improves the ability to characterize complex mixtures that arise from lignin upon degradation, facilitating the develop- ment of reaction product-specific procedures for efficient conversion of biomass lignin to fuel.

Owen BC, Haupert LJ, Jarrell TM, Marcum CL, Parsell TH, Abu-Omar MM, Bozell JJ, Black SK, Kenttämaa HI (2012) High-performance liquid chromatography/high-resolution multiple stage tandem mass spectrometry using negative ion mode hydroxide-doped electrospray ionization for the characterization of lignin degradation

• products. Anal. Chem., 84:6000-6007.

Work was performed at Purdue University

Research Details

• Three different reversed-phase HPLC columns were tested by using 12 lignin

degradation model compounds and their known mixtures.

• A solvent gradient system was developed by testing several buffer salts and

their concentrations in the mobile phase.

• The HPLC method was coupled with an ion trap mass spectrometer using negative ion

ion mode ESI with NaOH dopant to characterize an organosolv oak lignin sample.

• Several molecules in the sample, including isomers, were identified by using MS3

experiments involving multiple ion isolation and collision-activated dissociation steps.

A molecule identified in organosolv oak lignin sample by HPLC/(-)ESI/high-resolution MS3 .

Envisioning the transition to a next-generation biofuels industry in the Midwest

Scientific Achievement

Feed vs. Fuel is a US Midwest issue; done wisely, both can be produced economically and sustainably

Significance and Impact

−Biomass sorghum annuals produce the same amount of biomass as Miscanthus with the same amount of nitrogen. −Annuals have an advantage in the Corn Belt in initiating the industry; perennials will extend the range −Retrofitting existing ethanol facilities is a far more reasonable approach than building biorefineries where crops don’t exist −Rail infrastructure is in place, but biomass would increase load at least 3-fold; greatest need is an integration of advanced biofuels at farm or Coop levels

Research Details

−This research on the development of a Midwest biofuels industry was created from existing public information and the perspectives of leading bioenergy scientists

Dweikat, I., Weil, C.F., Moose, S.P., Kochian, L., Mosier, N.S., Ileleji, K.E., Brown, P.J., Peer, W.A., Murphy, A.S., Taheripour, F., McCann, M.C., Carpita, N.C. Envisioning the transition to a next-generation biofuels industry in the Midwest. BioFPR, 6, 376-386 (2012). Work was performed at Purdue Univ., Univ. of Nebraska-Lincoln, Univ. of Illinois- Urbana, and Cornell Univ.

Ethanol Plants

Rail Shuttle Transfer Stations