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Improving the odds and pace of successful biomass and waste carbon utilization technology scale-up is crucial to decarbonizing key industries such as aviation and materials within timelines required to meet global climate goals. In this perspective, we review deficiencies commonly encountered during scale-up to show that many nascent technology developers place too much focus on simply demonstrating that technologies work in progressively larger units ("profit") without expending enough up-front research effort to identify and derisk roadblocks to commercialization (collecting "information") to inform the design of these units. We combine this conclusion with economic and timeline data collected from technology scale-up and piloting operations at the National Renewable Energy Laboratory (NREL) to motivate a more scientific, risk-minimized approach to biomass and waste carbon upgrading scale-up. Our proposed approach emphasizes maximizing information collection in the smallest, most agile, and least expensive experimental setups possible, emulating the mentality embraced by R&D across the petrochemical industry. Key points are supported by examples of successful and unsuccessful scale-up efforts undertaken at NREL and elsewhere. We close by showing that the U.S. national laboratory system is uniquely well equipped to serve as a hub to facilitate effective scale-up of promising biomass and waste carbon upgrading technologies.
RESUMO
Lignin solvolysis from the plant cell wall is the critical first step in lignin depolymerization processes involving whole biomass feedstocks. However, little is known about the coupled reaction kinetics and transport phenomena that govern the effective rates of lignin extraction. Here, we report a validated simulation framework that determines intrinsic, transport-independent kinetic parameters for the solvolysis of lignin, hemicellulose, and cellulose upon incorporation of feedstock characteristics for the methanol-based extraction of poplar as an example fractionation process. Lignin fragment diffusion is predicted to compete on the same time and length scales as reactions of lignin within cell walls and longitudinal pores of typical milled particle sizes, and mass transfer resistances are predicted to dominate the solvolysis of poplar particles that exceed approximately 2â mm in length. Beyond the approximately 2â mm threshold, effectiveness factors are predicted to be below 0.25, which implies that pore diffusion resistances may attenuate observable kinetic rate measurements by at least 75 % in such cases. Thus, researchers are recommended to conduct kinetic evaluations of lignin-first catalysts using biomass particles smaller than approximately 0.2â mm in length to avoid feedstock-specific mass transfer limitations in lignin conversion studies. Overall, this work highlights opportunities to improve lignin solvolysis by genetic engineering and provides actionable kinetic information to guide the design and scale-up of emerging biorefinery strategies.
RESUMO
Oxymethylene dimethyl ethers (OMEs), CH3-(OCH2)n-OCH3, n = 1-5, possess attractive low-soot diesel fuel properties. Methanol is a key precursor in the production of OMEs, providing an opportunity to incorporate renewable carbon sources via gasification and methanol synthesis. The costly production of anhydrous formaldehyde in the typical process limits this option. In contrast, the direct production of OMEs via a dehydrogenative coupling (DHC) reaction, where formaldehyde is produced and consumed in a single reactor, may address this limitation. We report the gas-phase DHC reaction of methanol to dimethoxymethane (DMM), the simplest OME, with n = 1, over bifunctional metal-acid catalysts based on Cu. A Cu-zirconia-alumina (Cu/ZrAlO) catalyst achieved 40% of the DMM equilibrium-limited yield under remarkably mild conditions (200 °C, 1.7 atm). The performance of the Cu/ZrAlO catalyst was attributed to metallic Cu nanoparticles that enable dehydrogenation and a distribution of acid strengths on the ZrAlO support, which reduced the selectivity to dimethyl ether compared to a that obtained with a Cu/Al2O3 catalyst. The DMM formation rate of 6.1 h-1 compares favorably against well-studied oxidative DHC approaches over non-noble, mixed-metal oxide catalysts. The results reported here set the foundation for further development of the DHC route to OME production, rather than oxidative approaches.
RESUMO
Oxygenated biofuels provide a renewable, domestic source of energy that can enable adoption of advanced, high-efficiency internal combustion engines, such as those based on homogeneously charged compression ignition (HCCI). Of key importance to such engines is the cetane number (CN) of the fuel, which is determined by the autoignition of the fuel under compression at relatively low temperatures (550-800 K). For the plethora of oxygenated biofuels possible, it is desirable to know the ignition delay times and the CN of these fuels to help guide conversion strategies so as to focus efforts on the most desirable fuels. For alkanes, the chemical pathways leading to radical chain-branching reactions giving rise to low-temperature autoignition are well-known and are highly coincident with the buildup of reactive radicals such as OH. Key in the mechanisms leading to chain branching are the addition of molecular oxygen to alkyl radicals and the rearrangement and dissociation of the resulting peroxy radials. Prediction of the temperature and pressure dependence of reactions that lead to the buildup of reactive radicals requires a detailed understanding of the potential energy surfaces (PESs) of these reactions. In this study, we used quantum mechanical modeling to systematically compare the effects of oxygen functionalities on these PESs and associated kinetics so as to understand how they affect experimental trends in autoignition and CN. The molecules studied here include pentane, pentanol, pentanal, 2-heptanone, methylpentyl ether, methyl hexanoate, and pentyl acetate. All have a saturated five-carbon alkyl chain with an oxygen functional group attached to the terminal carbon atom. The results of our systematic comparison may be summarized as follows: (1) Oxygen functionalities activate C-H bonds by lowering the bond dissociation energy (BDE) relative to alkanes. (2) The R-OO bonds in peroxy radicals adjacent to carbonyl groups are weaker than corresponding alkyl systems, leading to dissociation of ROO⢠radicals and reducing reactivity and hence CN. (3) Hydrogen atom transfer in peroxy radicals is important in autoignition, and low barriers for ethers and aldehydes lead to high CN. (4) Peroxy radicals formed from alcohols have low barriers to form aldehydes, which reduce the reactivity of the alkyl radical. These findings for the formation and reaction of alkyl radicals with molecular oxygen explain the trend in CN for these common biofuel functional groups.
RESUMO
Lignocellulosic biomass has long been recognized as a potential sustainable source of mixed sugars for fermentation to biofuels and other biomaterials. Several technologies have been developed during the past 80 years that allow this conversion process to occur, and the clear objective now is to make this process cost-competitive in today's markets. Here, we consider the natural resistance of plant cell walls to microbial and enzymatic deconstruction, collectively known as "biomass recalcitrance." It is this property of plants that is largely responsible for the high cost of lignocellulose conversion. To achieve sustainable energy production, it will be necessary to overcome the chemical and structural properties that have evolved in biomass to prevent its disassembly.