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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Simultaneous optimization of simulated moving bed adsorption and distillation for 2,3‐butanediol recovery

Abstract A combined simulated moving bed (SMB) and distillation separation scheme is developed to recover 2,3‐butanediol (BDO) from a dilute fermentation broth. The scheme was integrated into a lignocellulosic biorefinery that produces hydrocarbon fuels from corn stover with BDO as an intermediate. BDO recovery is one of the most challenging processes in this biorefinery; and given the high associated energy duties, direct distillation is considered cost‐prohibitive. An alternative separation is SMB adsorption in nanoporous materials, which can reject 90% of the water and reduce subsequent distillation costs. Rigorous models were used to optimize the SMB and distillation simultaneously. The separation can be added to the biorefinery while keeping the projected minimum fuel selling price (MFSP) below $0.66 USD (US dollars) per liter gasoline‐equivalent ($2.50/GGE, gallon gasoline equivalent). Finally, sensitivity analyses were conducted to assess the effects of cost and lifetime of the adsorbent, titer concentration, and BDO purity.

09 BIOMASS FUELS↗
DOE OSTI2023

Towards the sustainable conversion of corn stover into bioenergy and bioproducts through biochemical route: Technical, economic and strategic perspectives

Corn stover (CS) is one of the most abundant agricultural wastes and is ubiquitous around the world that is left over after grain harvest and accounts for 47–50% dry mass of the total grain yield. The global CS yield is 1661.25 million tons/year, which is 27.2% of the total agricultural waste. CS consists of about 34.5% stems, 32.3% leaves, 14.3% husks, 12.3% cobs and 6.6% flowers, with up to 45% cellulose, 30% hemicellulose and 20% lignin. Further, due to its favorable economic and environmental potential, CS is considered an ideal raw material for producing biofuels and biobased chemicals, which can largely be divided into carbohydrate and lignin platforms. However, the techno-economic perspectives of CS-based biorefineries have remained questionable due to the inadequate supply chain logistics, lack of cost-effective conversion technologies, limited scale-up of the product-specific technologies, and lower competitiveness in the market compared to their counterparts, such as sugar and starch-based biorefineries. While CS is converted by thermochemical and biochemical approaches, the latter is considered to be more sustainable for its selective conversion under mild conditions using microorganisms. This review aimed to critically discuss the latest research and developments on the biochemical conversion of CS into biofuels and chemicals. In particular, this paper covers the market potential of biofuels and chemicals to which CS can make a significant contribution, technological developments in the microbial conversion of CS, major biofuels and chemicals produced from CS-derived carbohydrates and lignin, and the technoeconomic perspectives of CS-based biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2024

Techno-economic and life-cycle analysis of strategies for improving operability and biomass quality in catalytic fast pyrolysis of forest residues

Many of the challenges faced by the first commercial biorefineries were associated with feedstock handling, quality, and cost. Strategies are needed to enable further expansion of biorefineries and meet the growing demand for bio-based fuels and products. Here, we examine 2 key feedstock challenges and mitigation strategies in the context of a catalytic fast pyrolysis (CFP) biorefinery: (1) the operability of the feed system, which may be improved by modifying the minimum particle size fed to the reactor, and (2) the quality of the biomass, which may be improved by employing air classification to remove undesirable material and increase fuel yields. We conduct techno-economic analysis (TEA) and life-cycle analysis for these strategies, employing a discrete event simulation model for biomass preprocessing combined with a series of correlations developed from literature data and a rigorous CFP conversion model. Our results highlight the importance of balancing increased cost and material losses from preprocessing against improved operability and fuel yields. Economics and sustainability were optimized when operating at the lowest minimum particle size, emphasizing the importance of minimizing material losses while maintaining the operability of the process. Economically, additional costs and material losses from air classification could be acceptable due to improved biomass conversion, and an optimum air classification speed was identified; however, the fuel GHG emissions were minimized when air classification was not used. Valorizing material removed during preprocessing as a coproduct could improve economics and sustainability, decreasing the burden of material losses.

09 - BIOMASS FUELS↗
DOE OSTI2021

Machine Learning Reduced Order Model for Cost and Emission Assessment of a Pyrolysis System

Biomass pyrolysis is a promising approach for producing economic and environmentally-friendly fuels and bioproducts. Biomass pyrolysis experiments show that feedstock properties have a significant impact on product yields and composition. Scientists are developing detailed chemical reaction mechanisms to capture the relationships between biomass composition and pyrolysis yields. These mechanisms can be computationally intensive. In this study, we investigate the use of a machine learning reduced order model (ROM) for assessing the costs and emissions of a pyrolysis biorefinery. Here, we developed a Kriging-based ROM to predict pyrolysis yields of 314 feedstock samples based on the results of a detailed chemical kinetic pyrolysis mechanism. The ROM is integrated into a chemical process model for calculating mass and energy yields in a commercial-scale (2000 tonne/day) biorefinery. The ROM estimated biofuel yields of 65 to 130 gallons per ton of dry biomass. This results in biofuel minimum fuel-selling prices of $2.62 to $5.43 per gallon and emissions of -13.62 to 145 kg of CO 2 per MJ. The ROM achieved an average mean square error of 1.8e-20 and a mean absolute error of 0.53%. These results suggest that ROMs can facilitate rapid feedstock screening for biorefinery systems.

09 BIOMASS FUELS↗
DOE OSTI2025

Greenhouse Gas Accounting Procedures in Low Carbon Fuel Policies Overlook the Spatial Variability of Miscanthus-Derived Sustainable Aviation Fuel

Low carbon fuel policies such as the U.S. Renewable Fuel Standard (RFS), Canada Clean Fuel Regulations (CFR), and California Low Carbon Fuel Standard (LCFS) as well as the 45Z tax credit are intended to reduce greenhouse gas (GHG) emissions from transportation. Cellulosic feedstocks, optimized biorefineries, and favorable farming locations can significantly reduce biofuel carbon intensity (CI). Despite advances in field-to-fuel GHG monitoring and flexibility in resource allocation within biorefineries (e.g., governing net electricity production), rigid CI accounting procedures in current policies may limit CI responsiveness across candidate sites and processing facilities. Here, this work examines a hypothetical biomass-to-sustainable aviation fuel (SAF) pathway using miscanthus and alcohol-to-jet (i) to demonstrate how GHG accounting requirements drive estimates of biofuel CIs and (ii) to explore potential CI and financial implications of scenario-specific life cycle assessment (LCA). Results demonstrate that GHG accounting using the CFR/LCFS can reasonably account for distinct levels of net electricity production by a biorefinery, but only the CFR yields similar CI sensitivity to spatially explicit factors (feedstock CI, grid electricity CI) as scenario-specific LCA: most GHG accounting frameworks do not capture CI variation across candidate sites in the United States. Ultimately, this work demonstrates the importance of LCA methodological specifications in low carbon fuel policies and tax credits.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2021

Controlling Bacterial Contamination During Fuel Ethanol Fermentation Using Thermochemically Depolymerized Lignin Bio-Oils

Lactic acid bacteria (LAB) contamination during fuel ethanol fermentation can lead to significant economic loses. To circumvent this, fuel ethanol plants add antibiotics prophylactically, but their overuse has resulted in the emergence of antibiotic-resistant LAB strains. Lignin is a sustainable biopolymer that can be found as a waste product from lignocellulosic biorefineries. Technical lignins and their smaller phenolic subunits have been shown to exhibit broad-spectrum antimicrobial properties, but there is a lack of demonstrations of lignin derivatives with highly selective properties in the literature. Here, corn stover lignin from a biorefinery was oxidatively depolymerized using an environmentally benign organic oxidant, peracetic acid, into a bio-oil that has selective antimicrobial properties against LAB and not yeasts. The resulting bio-oil demonstrated up to 90% inhibition of commercially sampled LAB (including antibiotic-resistant strains) at 4 mg ml-1 with no inhibition against an industrial yeast strain. These antimicrobial properties of the bio-oil are attributed to larger unidentified lignin oligomers, compared to monolignols, that have a membrane damaging mode of action. Using the bio-oil (4 mg ml-1) during simultaneous saccharification and fermentation (SSF) of raw corn starch showed no inhibition of enzymatic activity, and in LAB contaminated fermentations the bio-oil treatments showed an 8% increase in ethanol yields at higher bacterial contamination ratios (l : 100 yeast to LAB, CFU per ml). This study illustrates the efficacy of using lignin bio-oil as an antibiotic replacement during fuel ethanol fermentation and demonstrates the highly selective antimicrobial properties of lignin oligomers, which creates a viable lignin valorization strategy for biorefineries.

bio-oil↗
DOE OSTI2022

Technoeconomic evaluation of recent process improvements in production of sugar and high-value lignin co-products via two-stage Cu-catalyzed alkaline-oxidative pretreatment

Abstract Background A lignocellulose-to-biofuel biorefinery process that enables multiple product streams is recognized as a promising strategy to improve the economics of this biorefinery and to accelerate technology commercialization. We recently identified an innovative pretreatment technology that enables of the production of sugars at high yields while simultaneously generating a high-quality lignin stream that has been demonstrated as both a promising renewable polyol replacement for polyurethane applications and is highly susceptible to depolymerization into monomers. This technology comprises a two-stage pretreatment approach that includes an alkaline pre-extraction followed by a metal-catalyzed alkaline-oxidative pretreatment. Our recent work demonstrated that H 2 O 2 and O 2 act synergistically as co-oxidants during the alkaline-oxidative pretreatment and could significantly reduce the pretreatment chemical input while maintaining high sugar yields (~ 95% glucose and ~ 100% xylose of initial sugar composition), high lignin yields (~ 75% of initial lignin), and improvements in lignin usage. Results This study considers the economic impact of these advances and provides strategies that could lead to additional economic improvements for future commercialization. The results of the technoeconomic analysis (TEA) demonstrated that adding O 2 as a co-oxidant at 50 psig for the alkaline-oxidative pretreatment and reducing the raw material input reduced the minimum fuel selling price from $1.08/L to $0.85/L, assuming recoverable lignin is used as a polyol replacement. If additional lignin can be recovered and sold as more valuable monomers, the minimum fuel selling price (MFSP) can be further reduced to $0.73/L. Conclusions The present work demonstrated that high sugar and lignin yields combined with low raw material inputs and increasing the value of lignin could greatly increase the economic viability of a poplar-based biorefinery. Continued research on integrating sugar production with lignin valorization is thus warranted to confirm this economic potential as the technology matures.

09 BIOMASS FUELS↗
DOE OSTI2023

Techno-Economic Case Study: Low-Temperature Conversion Performance Based on Isolated Anatomical Fractions of Corn Stover

This report summarizes analysis conducted to support a case study under the Feedstock-Conversion Interface Consortium (FCIC) focused on techno-economic analysis (TEA) modeling to quantify the yield and cost ramifications for processing isolated anatomical fractions of corn stover through a low-temperature conversion (biochemical pathway) biorefinery. It is hypothesized that different individual anatomical fractions of corn stover vary in composition and recalcitrance, such that processing each fraction on its own e.g. through dedicated campaigns may enable economic benefits relative to processing the whole stover material. To investigate this concept, we worked with FCIC researchers to obtain data on compositional analysis, as well as processing conditions and yields, for conversion of whole corn stover plus three individual anatomical fractions (cobs, husks, and stalks) across key steps of the biorefinery conversion process within FCIC research scope, namely pretreatment and enzymatic hydrolysis. After running the data through the TEA models, fractionated cobs and husks achieved higher fuel yields and lower minimum fuel selling prices than whole corn stover, but stalks fared worse than whole stover on both metrics. The most direct takeaway from this assessment is that a biorefinery would stand to benefit economically from maximizing the use of cob and husk fractions while avoiding or minimizing the use of stalks, though recognizing practical constraints with this approach in maintaining an equivalent processing capacity (fixed at 2,000 dry metric tonne per day in all cases).

09 BIOMASS FUELS↗
DOE OSTI2022

Enabling Production of Algal Biofuels by Techno-Economic Optimization of Co-Product Suites

Recent techno-economic analysis (TEA) has underscored that for algal biofuels to be cost competitive with petroleum fuels, co-products are necessary to offset the cost of fuel production. The co-product suite must scale with fuel production while also maximizing value from the non-fuel precursor components. The co-product suite also depends on algal biomass composition, which is highly dynamic and depends on environmental conditions during cultivation. Intentional shifts in composition during cultivation are often associated with reduced biomass productivity, which can increase feedstock production costs for the algae-based biorefinery. The optimal algae-based biorefinery configuration is thus a function of many factors. We have found that comprehensive TEA, which requires the construction of process models with detailed mass and energy balances, along with a complete accounting of capital and operating expenditures for a commercial-scale production facility, provides invaluable insight into the viability of a proposed biorefinery configuration. This insight is reflected in improved viability for one biorefining approach that we have developed over the last 10 years, namely, the Combined Algal Processing (CAP) approach. This approach fractionates algal biomass into carbohydrate-, lipid-, and protein-rich fractions, and tailors upgrading chemistry to the composition of each fraction. In particular, transitioning from valorization of only the lipids to a co-product suite from multiple components of high-carbohydrate algal biomass can reduce the minimum fuel selling price (MFSP) from more than $8/gallon of gasoline equivalent (GGE) to $2.50/GGE. This paper summarizes that progress and discusses several surprising implications in this optimization approach.

09 BIOMASS FUELS↗
DOE OSTI2022

Techno‐economic assessment of single‐stream feedstock logistics supply chain for corn stover and grain

Abstract The state‐of‐technology for corn stover harvest is a multi‐pass system that collects the stover after grain harvest. An alternative is a single‐stream system where the grain and stover are harvested as a bulk material co‐stored and preserved by anerobic fermentation, and finally, co‐transported to a biorefinery. In the present work, four single‐pass whole‐plant bulk systems were compared with a conventional multi‐pass bale system. The single‐stream systems consisted of the harvest of corn grain and a portion of the stover fraction. Four machine configurations were simulated. This work predicted that a multi‐pass bale system would result in a material cost of 111.80 $2021 Mg –1 stover DM delivered to the biorefinery gate. Alternatively, the lowest cost single‐stream system was the self‐propelled forage harvester (SPFH) configured with the whole‐plant header, which delivered feedstock for 74.76 $2021 Mg stover DM –1 . In addition to machine configuration, a sensitivity analysis was performed to understand important drivers of feedstock cost. These analyses revealed that feedstock cost increased with moisture content, fertilizer price, and biorefinery size, and decreased with harvest season length, crop yield, and grower participation. This work demonstrated that single‐stream systems could reduce corn stover feedstock costs in comparison with state‐of‐technology systems. © 2022 The Authors. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.

09 BIOMASS FUELS↗
DOE OSTI2022

A System Level Analysis of Ethanol Upgrading to Middle Distillates

We systematically study the upgrading of ethanol toward middle distillates with desired properties. To survey the large design space, we introduce a novel superstructure-based optimization framework integrating process design and fuel formulation. We show that biorefineries that produce middle distillates by upgrading lignocellulosic ethanol can have an energy return on investment (EROI) greater than 1. Additionally, we show that technological improvements can lead to significant increases in EROI. Furthermore, trade-offs between fuel properties and biorefinery profitability are established, showing how process economics are strongly influenced by fuel properties. In the case of diesel, the feasibility of producing high cetane number biofuels is demonstrated, coupled with a discussion of the technological requirements and costs to produce these superior fuels. It is also shown that the minimum fuel selling price (MFSP) can be reduced by increasing the biorefinery complexity. Lastly, we discuss the possibility of satisfying current and projected middle distillates demand in the U.S. using biofuels produced by ethanol upgrading, and we estimate the potential CO2 mitigation of these technologies.

09 BIOMASS FUELS↗
DOE OSTI2024

Economic and environmental sustainability of bio-based HMF production and recovery from lignocellulosic biomass

5-Hydroxymethyl furfurals (HMF) is one of the versatile platform chemicals. However, green routes to produce it directly from lignocellulosic biomass are lacking. A significant amount of HMF produced during the hydrothermal valorization of lignocellulosic biomass is considered undesired and ends up in a waste stream. The study transformed the undesired byproduct into a valuable coproduct by advancing the existing biofuel production process. A detailed economic and environmental sustainability analysis of the integrated biorefinery design was performed. The evaluation showed that the biorefinery could afford a maximum feedstock purchasing price of $\$115.17$ per MT and produce HMF with a minimum selling price of $\$4.54$ per kg which is ~75% lower than the commercial price of HMF. The median global warming potential of HMF was estimated to be 3.92 kg CO 2 -eq. per kg HMF which was ~32% less than its counterpart bio-based p-xylene. Diverse coproducts produced in the biorefinery using transgenic feedstock positively impacted sustainability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Integrating catalytic fractionation and microbial funneling to produce 2-pyrone-4,6-dicarboxylic acid and ethanol

Replacing biorefinery designs that use stepwise fractionation, depolymerization, and conversion processes with designed tandem process steps can greatly reduce a biorefinery's operating costs and environmental impact. Reductive Catalytic Fractionation (RCF) is a highly efficient lignin-first approach that combines biomass fractionation and lignin depolymerization to generate a hydrogenolysis oil and pulp. The oil is composed of a complex mixture of phenolic monomers, dimers, and oligomers. Intergrating this chemical deconstruction process with microbial funneling of phenolics can simplify the product mixture and make high-value products. We applied RCF to poplar biomass in a biomass-to-bioproduct processing chain in which the phenolics were funneled to 2-pyrone-4,6-dicarboxylic acid (PDC) by an engineered strain of Novosphingobium aromaticivorans DSM12444. The pulp was enzymatically digested and the glucose and xylose was funneled to ethanol by an engineered strain of Saccharomyces cerevisiae GLBRCY945. By combining biomass fractionation and lignin depolymerization we removed a costly processing step that directly translated into a 29% reduction in the minimum selling price of PDC. This work combines experimentation with process modeling of an integrated biorefinery design to show how utilizing tandem process steps can significantly reduce operating expenses and environmental impact of upgrading lignocellulosic biomass to a portfolio of high value products.

Sener, Canan [Great Lakes Bioenergy Research Cente↗
DOE OSTI2026

Solvent selection for a biomass-to-bioproduct pipeline through integrated reductive catalytic fractionation and microbial funneling

The growing significance of lignin-first biorefineries, which focus on upgrading the aromatics resulting from lignin depolymerization, presents opportunities for bioproduct synthesis using microbial strains capable of funneling a diverse array of phenolics into a single commodity chemical. In this study, we evaluated a biomass-to-bioproduct pipeline involving the reductive catalytic fractionation (RCF) of poplar biomass followed by biological funneling with a Novosphingobium aromaticivorans strain that produces 2-pyrone-4,6-dicarboxylic acid (PDC), a potential bioplastic precursor. Considering the impact of solvent on RCF reactor operating pressure, and the potential inhibitory effects of solvent on downstream microbial funneling, we performed an analysis of six pure solvents, namely methanol, ethanol, isopropanol, isobutanol, 1,4-dioxane and ethylene glycol, and different variations of their aqueous mixtures comprising 5 to 50 vol% water. For each pure solvent and solvent/water system, we measured phenolic monomer yields in the RCF process and PDC yields from the phenolic monomers. We then developed correlation models that relate phenolic monomer yields from RCF-derived samples to Hansen solubility parameters to determine solvent descriptors that contribute to high yields. Furthermore, we developed an integrated biorefinery system to estimate the minimum selling price (MSP) of PDC and the associated carbon footprint to identify solvent systems with better costs and sustainability metrics. These analyses resulted in the 50 vol% methanol/water system being identified as optimal because it reduces RCF reactor pressure and is compatible with microbial funneling with N. aromaticivorans. This solvent system produced 63 g PDC per kg biomass (264 g PDC per kg lignin) from 85 g phenolic monomers per kg biomass at a reduced reactor pressure of 48 bar (reduced by 26% compared to our previous poplar-to-PDC pipeline). The MSP for this system is $\$$13.98 per kg of purified PDC (carbon footprint of 1.47 kg CO 2 e per kg), which is about 24% lower than a previously described poplar-to-PDC pipeline and 46% lower than a lignin-to-PDC pipeline that used pure methanol as the solvent. The results from this study illustrate improvements that can be made in lignocellulosic biorefineries that are compatible with the hybrid chemical and biological processes needed to gain value from lignin.

Sripada, Sarada [Great Lakes Bioenergy Research Ce↗
DOE OSTI2024

yuyao-jia/Bio-based_HMF_coproduction

5-Hydroxymethyl furfurals (HMF) is one of the versatile platform chemicals. However, green routes to produce it directly from lignocellulosic biomass are lacking. A significant amount of HMF produced during the hydrothermal valorization of lignocellulosic biomass is considered undesired and ends up in a waste stream. The study transformed the undesired byproduct into a valuable coproduct by advancing the existing biofuel production process. A detailed economic and environmental sustainability analysis of the integrated biorefinery design was performed. The evaluation showed that the biorefinery could afford a maximum feedstock purchasing price of $115.17 per MT and produce HMF with a minimum selling price of $4.54 per kg which is ∼75% lower than the commercial price of HMF. The median global warming potential of HMF was estimated to be 3.92 kg CO2-eq. per kg HMF which was ∼32% less than its counterpart bio-based p-xylene. Diverse coproducts produced in the biorefinery using transgenic feedstock positively impacted sustainability.

Jia, Yuyao↗
DOE OSTI2022

Techno-economic assessment for the production of algal fuels and value-added products: opportunities for high-protein microalgae conversion

Abstract Background Microalgae possess numerous advantages for use as a feedstock in producing renewable fuels and products, with techno-economic analysis (TEA) frequently used to highlight the economic potential and technical challenges of utilizing this biomass in a biorefinery context. However, many historical TEA studies have focused on the conversion of biomass with elevated levels of carbohydrates and lipids and lower levels of protein, incurring substantial burdens on the ability to achieve high cultivation productivity rates relative to nutrient-replete, high-protein biomass. Given a strong dependence of algal biomass production costs on cultivation productivity, further TEA assessment is needed to understand the economic potential for utilizing potentially lower-cost but lower-quality, high-protein microalgae for biorefinery conversion. Results In this work, we conduct rigorous TEA modeling to assess the economic viability of two conceptual technology pathways for processing proteinaceous algae into a suite of fuels and products. One approach, termed mild oxidative treatment and upgrading (MOTU), makes use of a series of thermo-catalytic operations to upgrade solubilized proteins and carbohydrates to hydrocarbon fuels, while another alternative focuses on the biological conversion of those substrates to oxygenated fuels in the form of mixed alcohols (MA). Both pathways rely on the production of polyurethanes from unsaturated fatty acids and valorization of unconverted solids for use as a material for synthesizing bioplastics. The assessment found similar, albeit slightly higher fuel yields and lower costs for the MA pathway, translating to a residual solids selling price of $899/ton for MA versus $1033/ton for MOTU as would be required to support a $2.50/gallon gasoline equivalent (GGE) fuel selling price. A variation of the MA pathway including subsequent upgrading of the mixed alcohols to hydrocarbon fuels (MAU) reflected a required solids selling price of $975/ton. Conclusion The slight advantages observed for the MA pathway are partially attributed to a boundary that stops at oxygenated fuels versus fungible drop-in hydrocarbon fuels through a more complex MOTU configuration, with more comparable results obtained for the MAU scenario. In either case, it was shown that an integrated algal biorefinery can be economical through optimal strategies to utilize and valorize all fractions of the biomass.

09 BIOMASS FUELS↗
DOE OSTI2023

Liquefaction of different corn stover fractions assisted by enzyme-biomass deconstruction

Recalcitrant properties of different sources of lignocellulosic biomass represent challenges in materials processing within a biorefinery, as well as enzyme efficient deconstruction to fermentable sugars. Limitations include lignin derived enzyme inhibitors, enzyme inhibition by hydrolysis products, and resistance to mixing due to rheological properties of lignocellulosic particulates at high solids loadings. Consequently, we examined conditions that might be used to achieve liquid slurries (i.e., liquefaction) at solids loadings of 300 g/L before the material enters the biorefinery through a pretreatment step. This work explores enzyme-assisted liquefaction in a fed-batch process using the commercial enzymes Celluclast 1.5L or Ctec-2 at 1FPU/g or 3 FPU/g of dry solids, basis. Corn stover pellets were fed into a 1 L stirred bioreactor containing enzyme solution over a 5-hour period until reaching 30% solids loading (dry wgt / vol basis). After 6, 24 and 96 hours from the start of the run, samples were taken and characterized with respect to their sugar composition, rheology, water absorption and enzyme activity. Slurries with dramatically reduced yield stresses were achieved for corn stover. Yield stresses of 178±7 Pa (3 FPU, Celluclast 1.5L) and 79±6 Pa (3FPU, Ctec-2) were measured for corn stover at 24 hours, compared to 6,000 Pa for samples without enzyme.Yield stress was 155± 29 Pa (3FPU, Ctec-2) and 257 ± 72 Pa (1 FPU, Celluclast 1.5L) for corn cobs at 24 hours.A profile based on 6, 24 and 96h of yield stress measurements and sugar conversion is presented. Enzyme activity is measured and the impact of liquefaction on an integrated processing in a biorefinery operation is discussed.

Gutierrez, Diana↗
DOE OSTI2024

Catalytic Approaches to C–O Activation in Biorenewable Feedstocks

The carbon present in biomass (the largest renewable source on the planet) continues to tempt us as a possible replacement for the carbon we currently obtain from fossil fuels. As we have recently reviewed, the challenges of extracting chemically useful feedstocks from biorenewables, and, especially, cellulosics, is largely under-developed relative to the maturity of the technologies for deriving industrially useful chemicals from petroleum. This ultimately boils down to problems in functionalization catalysis (for oil) versus defunctionalization (for cellulosics). The technology gap for achieving the selective defunctionalization of cellulosic feedstocks is much larger than it is for petroleum functionalization. This assessment suggests that the problem is not that bio-renewable feedstocks are fundamentally flawed from an economic and chemical sustainability perspective, but that we lack the technologies for deoxygenating cellulosic to more valuable chemicals. Bozell and Petersen have argued that integrated biorefineries will require a suite of products for viability (in analogy to an integrated petroleum refinery). These products will range from low-value high-volume energy related products (i.e. fuels) to high-value low-volume compounds focused on specialty markets and pharmaceuticals. The latter, although less impactful in terms of volume, is a critical economic component of the future integrated biorefinery. Our review was stimulated by their assessment of the state of the biorefinery and focused on the available chemistries for achieving low-volume high-value outcomes. To help fill this technology gap, we seek new catalytic technologies for synthesizing high-value chemicals from cellulosics and take the view that the inherent chirality of C 6 O 6 feedstocks will provide valuable materials for specialty and pharmaceutical applications, but only if one can achieve site-selective reactions that don’t denude the stereochemistry inherent to the sugars. Eliminative methods are less desirable as this deoxygenation scheme removes multiple stereocenters. The research plan outlined herein seeks methods for site-selective deoxygenation reactions that lead to high value specialty/pharma products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗