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At least 19 records

Next Generation Logistics Systems for Delivering Optimal Biomass Feedstocks to Biorefining Industries in the Southeastern U.S.

The diverse portfolio of biomass sources that is available in the Southeastern U.S., including a significant supply of pine “residue”, represents a valuable strategic position for the region. Through blends formulated based on critical properties, this project will take full advantage of the range in biomass properties afforded by the portfolio to produce a consistent, high-performance feedstock for the industry, while lowering cost. Key developments being targeted to enable this potential include whole-tree transport to a state-of-the-art merchandising depot that will further access biomass from ongoing, forest industry operations. The approach will more effectively utilize the tree and distribute cost, while minimizing in-woods contamination of the woody biomass component. To implement this vision, information on the chemical composition and changes that are induced during multiple preprocessing steps (size reduction, moisture removal, densification, etc.) is needed. New NIR sensor technology will be developed for online monitoring of important biomass properties. The data will be incorporated into a statistical process control platform to improve process efficiency and meet required specifications. Advanced process models are being developed to inform the techno-economic and life-cycle assessment of the program’s impact. The new system will ultimately reduce operational risks from supply chain disruptions, and allow operation of larger-scale biorefineries.

09 BIOMASS FUELS↗

Hot Water Extraction: Short Rotation Willow, Mixed Hardwoods, and Process Considerations

Short rotation woody crops (SRWC) like shrub willow are highly productive biomass resources of interest for energy and fuel applications. Hot water extraction (HWE) as an upgrading tool to enable the use of willow biomass in pellet applications has been proposed, and is of increasing interest. This study treats willow and mixes of willow and conventional mixed hardwood feedstock with HWE in a tumbling laboratory reactor to elucidate the effects of time, temperature, feedstock mixes, and other process considerations (water:biomass ratio, presteaming, counter-current processing) on mass removals and other extraction outcomes (e.g., sugar, acetate, and furan yields). Results demonstrated alignment of extraction outcomes with P-factor from 155 °C to 175 °C, with a good compromise of removed mass and co-product potential in the range from 575–800 P-factor. The preferred condition was chosen as 575 P-factor. HWE of mixes of willow and hardwood feedstocks showed a linear response of extraction outcomes to willow:hardwood ratios. Testing of water:biomass ratios demonstrated that this is a significant consideration, with each outcome being affected somewhat differently, and indicating that HWE is more diffusion dependent than expected. Presteaming shows little to no effect on extraction outcomes, while multi-stage cooks simulating counter-current operation indicate a significant potential value in counter-current extraction.

09 BIOMASS FUELS↗

Valorization of lignin from aqueous-based lignocellulosic biorefineries

An additional 100 million tons/year of lignin coproduct will result when lignocellulosic biomass is processed in biorefineries to fiber, sugars, biofuels, and bioproducts. This will double the amount of lignin already generated from pulping and paper production. Unlike pulping that results in lignosulphonate (88% of total) or Kraft lignin (9%), aqueous-based biorefining leaves behind non-sulfonated lignin and aromatic molecules. Furthermore, this new type of lignin provides opportunities for large volume agricultural uses such as controlled-release carriers and soil amendments as well as feedstocks for new chemistries that lead to molecular building blocks for the chemical industry and to precursors for sustainable aviation biofuels.

03 NATURAL GAS↗

CRISPR/Cas9 editing of p-COUMAROYL-CoA:MONOLIGNOL TRANSFERASE 1 in maize alters phenolic metabolism, lignin structure, and lignin-first biomass processing

Valorization of lignocellulosic biomass for sustainable production of high-value chemicals is challenged by the complexity of lignin, a phenolic biopolymer. Beyond the classical lignin monomers derived from p-coumaryl, coniferyl, and sinapyl alcohol, grass lignins incorporate substantial amounts of monolignol p-coumarates that are produced by p-COUMAROYL-CoA:MONOLIGNOL TRANSFERASE (PMT). Here, the CRISPR/Cas9-mediated mutation of ZmPMT1 in maize enabled the design of biomass depleted in p-coumaroylated lignin and enriched in guaiacyl lignin. Lignin-first biorefining of stem biomass from zmpmt1 mutants by reductive catalytic fractionation (RCF) generated a lignin oil depleted in carboxylates and enriched in guaiacyl-derived alcohols, which are desirable substrates for bio-based polyurethane synthesis. Furthermore, the reported lignin engineering in maize is a promising strategy for designing a dual-purpose crop, providing both food and feed, along with a renewable feedstock for the production of plant-based chemicals.

59 BASIC BIOLOGICAL SCIENCES↗

Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. Here, we demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents.

09 BIOMASS FUELS↗

Task 2.3: Continuous Counter-Current Chromatography

This task in the Separations Consortium focuses on the development of counter-current chromatography (CCC), which is an advanced liquid-liquid chromatography method. Today, CCC is primarily practiced in batch mode operation, but continuous operation will be required for at-scale deployment in a biorefinery setting. In this task, we are developing a continuous CCC process in collaboration with a company that builds CCC units. This work will be demonstrated on the biorefining challenge of lignin valorization. Specifically, we demonstrate use of continuous CCC for both monomer-monomer and monomer-oligomer separations in multiple lignin streams of relevance to the biorefining industry. Breakthroughs in this area would be useful for BETO goals in both sustainable aviation fuel and biochemicals production, including directly contributing to BETO's 2030 lignin valorization goal. Our approach includes developing new computational modeling approaches to optimize both batch and continuous CCC processes, experimental work to determine optimal solvent systems for multiple lignin streams sourced from BETO-funded projects and industrial collaborators, and techno-economic analysis and life cycle assessment to identify the most impactful areas to ultimately enable this approach in the biorefinery. This task overall will enable high-resolution, multi-component, continuous separations at scale, demonstrated on a grand challenge biorefining problem.

BIOMASS FUELS↗

Multicriteria-Based Selection of Microalgae Biorefineries: Biomass Composition Defines the Most Suitable Product Portfolios

The supply of microalgae-derived biofuels and bioproducts will be vital in a global-scale bioeconomy. As the diversity of microalgae strains and their compositional plasticity may yield a wide array of products of market interest, the design of effective biorefineries is a central aspect in the path to making microalgae-based products available in the market. In this way, the conversion of microalgae biomass should be planned to employ mature technologies, while maximizing economic and environmental benefits obtained from a diverse product portfolio. This study applied sequential, hybrid Multicriteria Decision Analyses (MCDA) to aid the decision-making process of outlining the most suitable biorefining pathways for specific compositional profiles. For this, the methodology simultaneously considered multiple technical, economic, and environmental criteria, such as market aspects for the main algae-derived products, potential reduction in greenhouse gas (GHG) emissions provided by the biobased alternatives, and technology readiness level of conversion routes, among others. The framework was tested using productivity and compositional data for 13 high-productivity summer strains cultivated under varying nutrient availability. The analysis pointed to compositional profile being a key driver in defining the core biorefining strategy of algae biomass, with lipid-to-carbohydrate ratios higher than roughly 1 warranting the preferential processing of lipids into hydrocarbon fuels with the remainder of the algae biomass compounds being sent to higher-value applications, such as carboxylic acids and renewable thermoplastic substitutes. An in-depth process simulation, techno-economic assessment (TEA), and life-cycle analysis (LCA) effort was carried out as a closing step to corroborate the results stemming from the proposed framework. This study validates the use of MCDAs as a screening method prior to implementing more time-consuming analysis techniques and makes a compelling case for this approach as a product selection tool on a wide range of algae species, thus helping establish species-agnostic (but composition-driven) biorefineries.

biofuels↗

Continuous hydrodeoxygenation of lignin to jet-range aromatic hydrocarbons

Sustainable aviation fuel (SAF) is essential to decrease the carbon footprint of the aviation industry. Although many strategies have been developed to provide the branched, aliphatic components of SAF, few viable strategies have been demonstrated to supply the aromatic and cycloalkane fraction of SAF at the necessary scale from bio-based feedstocks. Lignin is the largest natural source of renewable aromatic compounds, yet major challenges in deoxygenation have prevented its use as a feedstock for SAF. Here we report a continuous, two-stage catalytic process using molybdenum carbide to deoxygenate lignin from poplar into aromatic hydrocarbons with 87.5% selectivity towards aromatic hydrocarbons at 86% of the theoretical carbon recovery. This work demonstrates an effective approach to convert lignin into aromatic SAF blendstocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Editorial: Microorganisms for Consolidated 2nd Generation Biorefining

In the last few decades, lignocellulosic biomass has attracted substantial interest as a feedstock for fermentative production of fuels and other commodity chemicals due to its wide availability and low cost. However, lignocellulose has innate complexity and recalcitrance to biodegradation. In natural environments, effective plant biomass decay is obtained by synergistic activity of complex microbial communities.

59 BASIC BIOLOGICAL SCIENCES↗

Lignin Extraction and Condensation as a Function of Temperature, Residence Time, and Solvent System in Flow-through Reactors

Solvolytic extraction of lignin from biomass is a critical step in lignin-first biorefining, including the reductive catalytic fractionation (RCF) process. Key to optimal RCF processing is the ability to rapidly extract lignin from biomass at high delignification extents and transfer the lignin molecules to a catalyst surface in a time frame that minimizes lignin condensation reactions. Here, we use a flow-through reactor to study the effects of temperature (175-250 °C), residence time (9 to 36 min), and solvent composition (methanol and methanol-water) on lignin extraction and condensation. We evaluated three metrics at each condition: total delignification, delignification rate, and extent of condensation, the latter measured by a decrease in monomer yield for batch hydrogenolysis reactions of solvolysis liquor compared to batch RCF reactions. We observe that delignification is predominantly determined by temperature, while residence time dictates the lignin condensation extent. Moreover, the extent of both extraction and condensation increased in the methanol-water solvent system compared to that in the methanol system. Lignin extracted in methanol is stable up to 18-min residence times at or below 225 °C, while a majority of the lignin extracted in methanol-water is condensed with a 9-min residence time at 200 °C. These results can inform reactor designs and solvent selection for lignin-first biorefining processes that aim to physically separate the biomass and catalyst.

09 BIOMASS FUELS↗

Lignin Extraction and Condensation as a Function of Temperature, Residence Time, and Solvent System in Flow-through Reactors

Solvolytic extraction of lignin from biomass is a critical step in lignin-first biorefining, including the reductive catalytic fractionation (RCF) process. Key to optimal RCF processing is the ability to rapidly extract lignin from biomass at high delignification extents and transfer the lignin molecules to a catalyst surface in a time frame that minimizes lignin condensation reactions. Here, we use a flow-through reactor to study the effects of temperature (175–250 °C), residence time (9 to 36 min), and solvent composition (methanol and methanol–water) on lignin extraction and condensation. We evaluated three metrics at each condition: total delignification, delignification rate, and extent of condensation, the latter measured by a decrease in monomer yield for batch hydrogenolysis reactions of solvolysis liquor compared to batch RCF reactions. We observe that delignification is predominantly determined by temperature, while residence time dictates the lignin condensation extent. Moreover, the extent of both extraction and condensation increased in the methanol–water solvent system compared to that in the methanol system. Lignin extracted in methanol is stable up to 18-min residence times at or below 225 °C, while a majority of the lignin extracted in methanol–water is condensed with a 9-min residence time at 200 °C. These results can inform reactor designs and solvent selection for lignin-first biorefining processes that aim to physically separate the biomass and catalyst.

biorefining↗

NREL's Biochemical Conversion Pilot Plant Capabilities

NREL's biochemical conversion plant is a flexible pilot plant for testing a wide range of bio-based technologies for producing renewable fuels and byproducts. The biochemical conversion pilot plant is housed in the Integrated Biorefinery Research Facility located on the National Renewable Energy Laboratory's (NREL's) main campus. The facility provides industry partners the opportunity to test and develop their own biorefining technology using NREL equipment or rental equipment that can be brought into the plant. The pilot plant can process materials up to one dry ton per day in an integrated fashion using a variety of operating modes including batch, fed-batch, and continuous processing.

biochemical↗

Characterization and molecular simulation of lignin in Cyrene pretreatment of switchgrass

Biomass-derived solvents have been proposed as a novel pathway in biorefining for the realization of biofuels and bioproducts derived from lignocellulosic biomass. Cyrene derived from cellulose has recently been shown to have a high potential as a green organic solvent for pretreating poplar biomass. However, due to its high dynamic viscosity nature, high Cyrene concentration could cause negative effects on the sugar release of the pretreated biomass as well as driving up the operational cost of the lignin recovery. In this study, we combine experimental and computational approaches to examine the impact of Cyrene pretreatment with reduced Cyrene concentration under mild conditions on switchgrass lignin. Our experimental studies indicated correlation between pretreatment condition and recovery and structure modification of lignin. Switchgrass lignin extracted by Cyrene pretreatment possessed high preservation of β-O-4 ether inter-unit linkage, which could provide versatility in the integration of downstream lignin valorization into the modern biorefinery industries. Molecular modeling examining the solvation of switchgrass lignin polymer and the disaggregation of low-molecular weight lignin aggregates under pretreatment conditions indicated that a preferential interaction exists between Cyrene and lignin, which likely drives lignin release, and that the disruption of inter-lignin contacts can be modulated as a non-monotonic function of Cyrene : water ratio. Further, while Cyrene–lignin interactions permit the solubilization of lignin, simulations with proxy reactive-species reveal that changes to the diffusion of these reactive proxies and their localization near linkage sites under Cyrene conditions may inhibit chemical processes. In conclusion, the results indicated that loss of pretreatment efficacy caused by low Cyrene concentration could be compensated by prolonged pretreatment time and high catalyst dosage.

09 BIOMASS FUELS↗

Profitability, Scalability and Optimized Siting for Waste-to-Energy Supply Chains: A Case Study on Hydrothermal Liquefaction

Waste-to-Energy (WtE) conversion technologies have the potential to simultaneously reduce waste volumes, treatment-related emissions, and carbon intensity while producing valuable energy services. However, questions remain regarding under which conditions emerging WtE technologies are feasible to deploy. In this project, we develop an optimized siting method for WtE technologies to assess cost-effective WtE processor locations, throughput scales, and profitability. We apply the model using Hydrothermal Liquefaction (HTL) as an example WtE technology. We develop calibrated capital and operating expense cost curves based on literature data to study the techno-economic characteristics of WtE supply chains. Prior to solving the siting optimization, we analyze the model parameters to describe organic waste management system behavior under four different HTL deployment configurations: Co-Processing, where HTL plants send biocrude to existing conventional refineries via assumed pipelines; Co-Location, where biorefineries are co-located with HTL plants; and two alternative Standalone Biorefining cases, where distributed HTL plants transport biocrude intermediate via either assumed pipelines or trucking to centralized biorefineries. We also define and apply several feedstock gate fee calculations, representing different revenue distribution options, to investigate how bioproduct value could impact WtE supply chain economics in terms of waste producer and processor profit or cost reduction.

09 BIOMASS FUELS↗

Lignin-First Biorefinery Development

Cost-effective biomass fractionation is an enabling, grand challenge for biorefining, especially when both carbohydrates and lignin are targeted for valorization. The advent of Reductive Catalytic Fractionation (RCF) - an active stabilization approach that solubilizes lignin from biomass and catalytically depolymerizes it into a narrow slate of monomers and oligomers - represents a potential step forward for this important goal. In the Lignin-First Biorefinery Development project, we are employing techno-economic analysis (TEA) and life cycle assessment (LCA) to guide bench-scale R&D efforts towards cost-effective RCF-based biorefining. This project is critical to lignin valorization efforts and could enable the use of woody feedstocks in a traditional biochemical conversion context. To date, we have conducted the first rigorous TEA and LCA study of the RCF process, developed a flow-through system to separate biomass and the chemical catalyst in RCF chemistry, developed models for solvolysis chemistry and transport phenomena for poplar, and co-led an international, authoritative perspective on guidelines for the research community on how to best practice lignin-first biorefining. The primary challenges for the lignin-first RCF process going forward are catalyst stability, the need to utilize, recover, and recycle high boiling point solvents to lower RCF reactor pressure, and the challenge of operating RCF continuously - all of which are being directly tackled by this project.

biomass↗