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

Transcription

1 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 DIRECTINS 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.

2 Sample Preparation for Biomass Biomaterials Microscopy ptimized and standardized a set of hybrid biological and materials science sample preparation techniques to enable consistently high quality multiscale microscopy analysis of biomass. Provides a single go to reference for the field that shares details and tips that are not possible to fully convey in the typical manuscript methods section. Facilitates direct, quantitative comparison between samples prepared and imaged by these methods. NREL s Biomass Surface Characterization Laboratory (BSCL) is a leader in multi scale microscopic structural analysis of biomass conversion processes. C3Bio enabled a critical transition in the BSCL workflow to include quantitative image analysis as the final goal of all imaging efforts. The impact quantitative image analysis has had on informing sample prep and image acquisition is reflected in this chapter. a thermocouple vacuum chamber water(convec, on(pla/ orm( b condenser( chamber sample chambers c C 2 cylinder drying chamber hot(and(cold(water( a" b controllers deionized' water' water(chiller water(heater staining' solu+on' staining' bath''' mul+2grid' holder' Donohoe, B. S.; Ciesielski, P. N.; and Vinzant, T. B. PRESERVATIN AND PREPARATIN F LIGNCELLULSIC BIMASS SAMPLES FR MULTI SCALE MICRSCPY ANALYSIS, In: Michael E. Himmel (ed.), Biomass Conversion: Methods and Protocols, Methods in Molecular Biology, 908, (2012). [ / _4] Work was performed at NREL

3 Tandem Mass Spectrometric Analysis of Degraded Cellulose Demonstrated that chloride anion attachment/atmospheric pressure ionization generates only one ion for each carbohydrate in a mixture and that multistage tandem mass spectrometry can be used to determine the ions structures. Allows more detailed characterization of mixtures of pyrolyzed and otherwise degraded cellulose than before. Used linear quadrupole ion trap and a variety of ionization methods to ionize pure carbohydrates After identification of the best ionization method, examined known mixtures of carbohydrates Measured tandem mass spectra up to MS 4 to gather useful structural information from the fragmentation patterns of the carbohydrates Relative Abundance [M+ 35 Cl] Xylose Fructose [C 6 H 9 5 ] [M+ 35 Cl] Fructose m/z Vinueza, N.R., Gallardo, V.A., Klimek, J.F., Carpita, N., and Kenttämaa, H.I. ANALYSIS F CARBHYDRATES BY ATMSPHERIC PRESSURE CHLRIDE ANIN ATTACHMENT TANDEM MASS SPECTRMETRY, Fuel, 105, (2013). Work was performed at Purdue University [M+ 35 Cl] Cellobiose Chloride anion attachment mass spectrum for a mixture of three compounds ( 35 Cl and 37 Cl Isotopes facilitate Identification) Isolation of ion of m/z 377 followed by fragmentation

4 Fe III (PP) Catalyst for HMF xidation to FDCA A porphyrin based porous organic polymer (PP) loaded with Fe 3+ catalyst is a thermally stable and recyclable catalyst for oxidation of hydroxymethylfurfural (HMF) to 2,5 furandicarboxylic acid (FDCA) in water using molecular oxygen. In C3Bio, we have shown that maleic acid catalysis converts glucose in non crystalline polymers in biomass to HMF. Saha et al achieved quantitative conversion of HMF with >85% selectivity in water under mild reaction conditions. The catalyst retained Fe(III) oxidation state after catalysis and metal does not leach into solution. FDCA is a promising replacement for petroleumderived terephthalic acid for polyester production Time, h Characterization of the catalyst showed uniform nanospheres of dimension nm which self assemble to larger sizes. Hydroxymethyl group ( CH 2 H) of HMF oxidized first followed by oxidation of CH group. The data support a hypothesis that the reaction progresses via a free radical chain mechanism with the formation of peroxyl radical in the catalytic cycle. HMF conversion and product distribution, % H CH CH CH HC HC CH CH Before catalysis After catalysis Saha, B.; Gupta, D.; Abu mar, M. M.; Modak, A.; and Bhaumik, A. PRPHYRIN BASED PRUS RGANIC PLYMER SUPPRTED IRN(III) CATALYST FR EFFICIENT AERBIC XIDATIN F 5 HYDRXYMETHYLFURFURAL INT 2,5 FURANDICARBXYLIC ACID. Journal of Catalysis, 299, (2013). [ /j.jcat ] Work was performed at Purdue University and University of Delhi. Catalyst was prepared by collaborator at Indian Association for the Cultivation of Science.

5 3D Electron Tomography of Pretreated Biomass Informs Atomic Modeling of Cellulose Microfibrils Using 3D electron tomography and novel computational analysis tools, we modeled and quantified the macromolecular architecture of thermochemically treated biomass. This study produced the first measurements of cellulose microfibril curvature. We investigated the significance of this parameter by construction and evaluation of atomic models that exhibited the geometry obtained from the microscopy data. ur results and analyses have elucidated new relationships between the nanostructure and energetics of plant cellulose that may be exploited in catalytic conversion processes. Tomographic subvolumes showing space curves fit to cellulose microfibrils (scale bars 10 nm) riginal atomic Energy minimized The radius of curvature of the microfibrils was measured from the fitted curves. Atomistic models were constructed using the extracted geometric parameters. Kink defects were predicted in the atomic models when the fibril was bent about certain crystallographic directions. coordinates atomic coordinates Ciesielski, P. N.; Matthews, J. F.; Tucker, M. P.; Beckham, G. T.; Crowley, M. F.; Himmel, M. E.; Donohoe, B. S. 3D ELECTRN TMGRAPHY F PRETREATED BIMASS INFRMS ATMIC MDELING F CELLULSE MICRFIBRILS. ACS Nano, 7, DI: /nn Work performed at the National Renewable Energy Laboratory Averagae radius of curvature (nm)

6 Catalytic cleavage and hydrodeoxygenation of lignin models A combined Zn/Pd/C catalyst effectively cleaved the lignin β 4 linkage and subsequently hydrodeoxygenated the aromatic fragments without loss of aromatic functional groups. The catalyst is robust and fully recyclable without the need for additional zinc. The β 4 linkage is the most abundant repeating subunit of the lignin macromolecule. Devising a catalyst that can selectively cleave this type of ether linkage and undergo hydrodeoxygenation provides a means of unzipping the very complex polymeric structure into smaller, manageable molecules that have higher energy value. In a typical experiment: substrate, 5 wt% Zn/Pd/C, and methanol (15 ml) were added to a dry glass sleeve, placed into a stainless steel Parr reactor and sealed. While stirring, the mixture was purged with UHP grade H 2 for ca. 1 2 min., pressurized with H 2 ( psi, bar), and heated to 150⁰C. The monomeric lignin surrogate substrates were 4 (hydroxymethyl) 2 methoxyphenol, 4 hydroxy 3 methoxybenzaldehyde, and 4 (methoxymethyl) 2 methoxyphenol. The dimeric lignin surrogate was guaiacylglycerol β guaiacyl. Reaction products were characterized using HPLC coupled to an LQIT mass spectrometer equipped with an ESI source using negative ion mode. Parsell TH, wen BC, Klein I, Jarrell TM, Marcum CL, Haupert LJ, Amundson LM, Kenttämaa HI Ribeiro F, Miller JT, Abu mar MM. Cleavage and hydrodeoxygenation (HD) of C bonds relevant to lignin conversion using Pd/Zn synergistic catalysis. Chem. Sci., 4, (2013). [ /C2SC21657D] Work was performed at Purdue University and Argonne National Lab

7 Cobalt Catalyzed xidative Cleavage of Lignin Models G models of lignin are slow to react. However, we developed a new catalyst that transforms both S and G subunits lignin models into benzoquinones in high yields. Lignin, a macromolecule of syringyl L i g n i n M o d e l s (S) and guaiacyl (G) subunits, is an underused product of biorefinery operations. ptimal reaction conditions for the conversion of lignin models to quinones were determined. Internal ligand and aliphatic base on the ligand allow for a much stronger catalytic activity. This methodology is highly applicable to the oxidative cleavage of lignin. Previous studies from our laboratory showed that G lignin models undergo oxidation in presence of Co salen catalyst and a hindered base in 50% yield. This new unsymmetrical Co salen catalyst oxidizes each of the lignin primary units. The catalyst contains an internal nitrogen ligand (needed for S and G subunits) and an internal bulky base (needed for G subunit). An efficient protecting group free strategy for the synthesis of lignin models has also been developed. H i g h V a l u e C h e m i c a l s Cedeno, D.; Bozell, J. J.; Tetrahedron Lett. 2012, 53, Biannic, B.; Bozell, J. J. manuscript in preparation Work was performed at: University of Tennessee, Center for Renewable Carbon

8 Selective cobalt catalyzed oxidations of biorefinery lignin New processes promote oxidation of both general types of aromatic structure in lignin models (S and G) that are verified in oxidation of actual biorefinery lignin samples (organosolv and extracted kraft) without compromising yield. Instead of burning biorefinery waste lignin as a $0.05/lb fuel, we have identified processes that position lignin as a chemical feedstock, opening new opportunities in biobased chemical production H!"#$%&#' ()*+,& "%, %*+&.%/("%&+0%&"%#$1( *& 2 3&45' %* 5( *&6 ' 7& In order to assess the involvement of the sterically hindered base, we studied the interaction between DIPEA and Co(salen) using NMR and UV vis spectroscopy Although S subunit models from guaiacyl unit models were easily converted into their corresponding p quinones, the same approach with vanillyl alcohol, a model of the G subunit, gave the corresponding 2 methoxybenzoquinone in only 21% yield. G models are more difficult to oxidize than S models because formation of the key phenoxy radical is slower. Molecular modeling studies (DFT) have provided new insight into the mechanism and its control Mass spectrometry development at Purdue has identified new products resulting from lignin oxidation 28 Diana C, and Bozell JJ. Catalytic oxidation of para substituted phenols with cobalt Schiff base complexes/2 selective conversion of syringyl and guaiacyl lignin models to benzoquinones. Tetrahedron Letters 53, (2012). Work was performed at the University of Tennessee, Knoxville Center for Renewable Carbon

9 Solvent free methods for making biomass derived acetals Demonstrated solvent free synthesis of acetals prepared from furfural and glycerol using a variety of common Lewis acids and solid acids Acetals are produced in high yields under mild reaction conditions, allowing for a new route for the utilization of glycerol. Acetal products are potentially useful synthetic platforms and potential fuel additives Reactions between furfural and glycerol are performed at 100 C with a fivefold excess of furfural, allowing for yields up to 90% The addition of a dry stream of nitrogen purging the headspace improves yields and allows for a reduced excess of furfural The novel reaction methods are applicable to crude glycerol Acetal products were successfully hydrogenated and acetylated, and the resulting material tested as fuel additives in biodiesel Wegenhart, Benjamin L.; Liu, Shuo; Thom, Melanie; Stanley, David; and Abu mar, Mahdi M. SLVENT FREE METHDS FR MAKING ACETALS DERIVED FRM GLYCERL AND FURFURAL AND THEIR USE AS A BIDIESEL FUEL CMPNENT, ACS Catalysis, 2, (2012). [ /cs300562e] Work was performed at Purdue University