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At least 109 records · Page 6

Metaproteomics reveals enzymatic strategies deployed by anaerobic microbiomes to maintain lignocellulose deconstruction at high solids

Economically viable production of cellulosic biofuels requires operation at high solids loadings—on the order of 15 wt%. To this end we characterize Nature’s ability to deconstruct and utilize mid-season switchgrass at increasing solid loadings using an anaerobic methanogenic microbiome. This community exhibits undiminished fractional carbohydrate solubilization at loadings ranging from 30 g/L to 150 g/L. Metaproteomic interrogation reveals marked increases in the abundance of specific carbohydrate-active enzyme classes. Significant enrichment of auxiliary activity family 6 enzymes at higher solids suggests a role for Fenton chemistry. Stress-response proteins accompanying these reactions are similarly upregulated at higher solids, as are β-glucosidases, xylosidases, carbohydrate-debranching, and pectin-acting enzymes—all of which indicate that removal of deconstruction inhibitors is important for observed undiminished solubilization. Our work provides insights into the mechanisms by which natural microbiomes effectively deconstruct and utilize lignocellulose at high solids loadings, informing the future development of defined cultures for efficient bioconversion.

09 BIOMASS FUELS↗

Engineering Innovations, Challenges, and Opportunities for Lignocellulosic Biorefineries: Leveraging Biobased Polymer Production

Alternative polymer feedstocks are highly desirable to address environmental, social, and security concerns associated with petrochemical-based materials. Lignocellulosic biomass (LCB) has emerged as one critical feedstock in this regard because it is an abundant and ubiquitous renewable resource. LCB can be deconstructed to generate valuable fuels, chemicals, and small molecules/oligomers that are amenable to modification and polymerization. However, the diversity of LCB complicates the evaluation of biorefinery concepts in areas including process scale-up, production outputs, plant economics, and life-cycle management. We discuss aspects of current LCB biorefinery research with a focus on the major process stages, including feedstock selection, fractionation/deconstruction, and characterization, along with product purification, functionalization, and polymerization to manufacture valuable macromolecular materials. We highlight opportunities to valorize underutilized and complex feedstocks, leverage advanced characterization techniques to predict and manage biorefinery outputs, and increase the fraction of biomass converted into valuable products.

59 BASIC BIOLOGICAL SCIENCES↗

Center for Lignocellulose Structure and Formation (CLSF)

Lignocellulose is the carbon- and energy-rich material synthesized by plants when they make secondary cell walls, e.g. in woody tissues. Plants annually convert gigatons of atmospheric CO 2 into these complex and useful biomaterials that comprise over half of all biological carbon on Earth. This biological conversion helps to reduce atmospheric CO 2 that contributes to climate change while generating renewable plant cell walls that are used commercially on a massive scale in the paper, timber and textile industries. Recent technical developments open new possibilities for use of modified wood and cellulose fibers as large-scale alternatives to steel, plastics, and other nonrenewable materials with high carbon footprints and energy inputs, as well as for generation of biofuels and bio-hydrogen. Despite the utility of plant-based biomaterials, many physical and biological aspects of cell wall structure and formation remain obscure, and this limits the current scope for engineering these renewable resources for greater utility.

09 BIOMASS FUELS↗

Nanostructural Analysis of Enzymatic and Non-enzymatic Brown Rot Fungal Deconstruction of the Lignocellulose Cell Wall†

Brown rot (BR) decay mechanisms employ carbohydrate-active enzymes (CAZymes) as well as a unique non-enzymatic chelator-mediated Fenton (CMF) chemistry to deconstruct lignocellulosic materials. Unlike white rot fungi, BR fungi lack peroxidases for lignin deconstruction, and also lack some endoglucanase/cellobiohydrolase activities. The role that the CMF mechanism plays in “opening up” the wood cell wall structure in advance of enzymatic action, and any interaction between CMF constituents and the selective CAZyme suite that BRs possess, is still unclear. Expression patterns for CMF redox metabolites and lytic polysaccharide monooxygenase (LPMO–AA9 family) genes showed that some LPMO isozymes were upregulated with genes associated with CMF at early stages of brown rot by Gloeophyllum trabeum. In the structural studies, wood decayed by the G. trabeum was compared to CMF-treated wood, or CMF-treated wood followed by treatment with either the early-upregulated LPMO or a commercial CAZyme cocktail. Structural modification of decayed/treated wood was characterized using small angle neutron scattering. CMF treatment produced neutron scattering patterns similar to that of the BR decay indicating that both systems enlarged the nanopore structure of wood cell walls to permit enzyme access. Enzymatic deconstruction of cellulose or lignin in raw wood samples was not achieved via CAZyme cocktail or LPMO enzyme action alone. CMF treatment resulted in depolymerization of crystalline cellulose as attack progressed from the outer regions of individual crystallites. Multiple pulses of CMF treatment on raw wood showed a progressive increase in the spacing between the cellulose elementary fibrils (EFs), indicating the CMF eroded the matrix outside the EF bundles, leading to less tightly packed EFs. Peracetic acid delignification treatment enhanced subsequent CMF treatment effects, and allowed both enzyme systems to further increase spacing of the EFs. Moreover, even after a single pulse of CMF treatment, both enzymes were apparently able to penetrate the cell wall to further increase EF spacing. The data suggest the potential for the early-upregulated LPMO enzyme to work in association with CMF chemistry, suggesting that G. trabeum may have adopted mechanisms to integrate non-enzymatic and enzymatic chemistries together during early stages of brown rot decay.

59 BASIC BIOLOGICAL SCIENCES↗

Renewable Schiff-Base Ionic Liquids for Lignocellulosic Biomass Pretreatment

Growing interest in sustainable sources of chemicals and energy from renewable and reliable sources has stimulated the design and synthesis of renewable Schiff-base (iminium) ionic liquids (ILs) to replace fossil-derived ILs. In this study, we report on the synthesis of three unique iminium-acetate ILs from lignin-derived aldehyde for a sustainable “future” lignocellulosic biorefinery. The synthesized ILs contained only imines or imines along with amines in their structure; the ILs with only imines group exhibited better pretreatment efficacy, achieving >89% sugar release. Various analytical and computational tools were employed to understand the pretreatment efficacy of these ILs. This is the first study to demonstrate the ease of synthesis of these renewable ILs, and therefore, opens the door for a new class of “Schiff-base ILs” for further investigation that could also be designed to be task specific.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Material Extrusion Additive Manufacturing of Wood and Lignocellulosic Filled Composites

Wood and lignocellulosic-based material components are explored in this review as functional additives and reinforcements in composites for extrusion-based additive manufacturing (AM) or 3D printing. The motivation for using these sustainable alternatives in 3D printing includes enhancing material properties of the resulting printed parts, while providing a green alternative to carbon or glass filled polymer matrices, all at reduced material costs. Previous review articles on this topic have focused only on introducing the use of natural fillers with material extrusion AM and discussion of their subsequent material properties. This review not only discusses the present state of materials extrusion AM using natural filler-based composites but will also fill in the knowledge gap regarding state-of-the-art applications of these materials. Emphasis will also be placed on addressing the challenges associated with 3D printing using these materials, including use with large-scale manufacturing, while providing insight to overcome these issues in the future.

36 MATERIALS SCIENCE↗

A Techno-economic Analysis for Integrating an Electrochemical Reactor into a Lignocellulosic Biorefinery for Production of Industrial Chemicals and Hydrogen

In this study, we present a techno-economic analysis for integrating an electrochemical reactor into a lignocellulosic biorefinery for the purpose of converting biorefinery lignin to higher-value industrial chemicals with co-generation of hydrogen. We consider how the electrochemical reactor impacts the manufacturing costs for producing biofuel and determine a break-even value for the lignin oxidation product stream, which is the minimum lignin conversion product stream value that renders the cost to produce biofuel the same as in the typical biorefinery concept. We conclude that at low extents of lignin conversion, the break-even product stream value is likely too high for the process to be feasible. However, at higher extents of lignin conversion, the break-even product stream value may be between 1.00 and 2.00/kg, depending on capital cost and other manufacturing costs like depreciation. Here the potential markets for the biomass conversion products include resin manufacturing, where the products would compete with petroleum-derived resin precursors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The critical role of lignin in lignocellulosic biomass conversion and recent pretreatment strategies: A comprehensive review

Heterogeneity and rigidity of lignocellulose causing resistance to its deconstruction have provided technical and economic challenges in the current biomass conversion processes. Lignin has been considered as a crucial recalcitrance component in biomass utilization. An in-depth understanding of lignin properties and their influences on biomass conversion can provide clues to improve biomass utilization. Also, utilization of lignin can significantly increase the economic viability of biorefinery. Recent lignin-targeting pretreatments have aimed not only to overcome recalcitrance for biomass conversion but also to selectively fractionate lignin for lignin valorization. Numerous studies have been conducted in biomass characteristics and conversion technologies, and the role of lignin is critical for lignin valorization and biomass pretreatment development. In this review, we provide a comprehensive review of lignin-related biomass characteristics, the impact of lignin on the biological conversion of biomass, and recent lignin-targeting pretreatment strategies. The desired lignin properties in biorefinery and future pretreatment directions are also discussed.

09 BIOMASS FUELS↗

Process design and techno-economic analysis for bio-based graphite and liquid hydrocarbons production from lignocellulosic biomass

The worldwide demand for graphite, as the main anode material for Li-ion batteries, is expected to double by 2028 since it supports the use of electricity, including transient renewable sources, for energy storage, sustainable mobility, and automation. However, the dependence on non-renewable and external resources jeopardizes the world supply chain. This study explores the technical and economic performance of transforming lignocellulosic biomass into biographite and fuel-grade hydrocarbons through pyrolysis bio-oil upgrading. According to simulation results, the total power demand for the biorefinery reached 10,784 kWh per tonne of biographite, of which 36 % can be supplied by the heat integration network and power plant. Sensitivity and risk analyses were conducted to evaluate the economics, with process yields identified as the most relevant indicators to the minimum selling price (MSP). The analysis revealed a promising cost-competitive range for biographite MSP against fossil-based graphite (medium quality synthetic graphite Chinese market price ~$\$$4.2/kg). Case D, which includes biofuels as a byproduct, presents the best metrics, reaching a MSP of $\$$3.3/kg of anode-grade biographite with a profit margin of 27 %. While including biofuels in the product slate provides the best economic performance, the uncertainty associated with the big capital investment makes its risk 13 % higher to attain an IRR >20 % than the case in which biographite is produced as a standalone product. Overall, this study demonstrates that integrated biorefineries can produce a cost-competitive bio-based anode material for Li-ion batteries.

09 BIOMASS FUELS↗

Use of a Lewis acid, a Brønsted acid, and their binary mixtures for the hydrothermal liquefaction of lignocellulose

The main objective of the present study is to investigate the effect of a Lewis acid, Brønsted acid, and their combined use on the hydrothermal liquefaction of lignocellulosic biomass. Hydrothermal liquefaction of teak wood was conducted at 250, 300 and 350 °C for 15, 30 and 60 min. Hydrothermal liquefaction of teak wood was carried out at 300 °C for 30 min (the best optimum conditions) without and with the use of Mg(ClO 4 ) 2 , HClO 4 , and HClO 4 /Mg(ClO 4 ) 2 at various loadings (2–10 mmol/15 g wood). The highest bio-oil yield was obtained with the non-catalytic run. All tested catalysts have negative effect on bio-oil yields. The bio-oil yields generally decreased with increasing the catalyst loadings. The deoxygenation degree in bio-oils changed depending on the type of catalyst and loading. A high degree of de-oxygenation took place with Mg(ClO 4 ) 2 catalysts. An increased catalyst loading led to decreased aromatic contents of bio-oils catalyzed by either Mg(ClO 4 ) 2 or HClO 4 . The use of a catalyst increased total naphtha fractions in bio-oils. The highest heating value of the bio-oil was estimated to be approximately 30 MJ/kg. Gas chromatography–mass spectrometry analysis revealed that the bio-oils from the non-catalytic and catalytic runs contained aldehydes, ketones, phenols, acids, esters and alcohols. Furthermore, the relative yields of the oxygenated compounds were affected by catalyst type.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidation of phenolic compounds during autothermal pyrolysis of lignocellulose

Fast pyrolysis is traditionally defined as the rapid decomposition of organic material in the absence of oxygen to produce primarily a liquid product known as bio-oil. However, the introduction of small amounts of oxygen to the process holds prospects of internally generating the energy needed for pyrolysis. The present study investigates the partial oxidation of lignin-derived compounds during pyrolysis, which generates both carbon oxides and aromatic carbonyl compounds. Analysis of lignin derived phenolic compounds was performed to determine if the composition had changed under oxidative conditions. NMR analyses indicates aromatic carbonyls increased under oxidative conditions, with a corresponding decrease in phenolic hydroxyl groups. Finally, model phenolic compounds were pyrolyzed to help understand the role of partial oxidation during autothermal pyrolysis of lignocellulosic biomass.

09 BIOMASS FUELS↗

A consolidated bioprocess design to produce multiple high-value platform chemicals from lignocellulosic biomass and its technoeconomic feasibility

5-Hydroxymethyl furfural (HMF) and furfurals are DOE-listed platform chemicals that can be derived from the renewable carbon in the lignocellulosic biomasses and have the potential to replace petroleum-derived alter- natives. High substrate cost and use of expensive solvents limit the economic feasibility of bio-based HMF production on an industrially relevant scale. The study presents an experimental optimized condition that maximizes the chemical-free production of HMF and furfurals without lowering the yield of total fermentable sugars from Saccharum bagasse. Hydrothermal pretreatment at 210 °C for 15 min yielded approximately 10%, 12%, and 46% of HMF, furfurals, and fermentable sugars per gram of dry biomass, respectively. Additionally, the study proposes a consolidated bioprocess model to produce and recover four high-value bioproducts i.e., HMF, furfurals, ethanol, and acetic acid based on the experimental results and evaluates its technoeconomic feasibility considering HMF as the main product. The minimum selling price (MSP) of HMF was estimated to be 930.6 USD/ t which is competitive with its petroleum-derived precursor alternative p-xylene (1,113 USD/t). The sensitivity analysis performed for the process parameters suggests that pretreatment cost and revenues from coproducts immensely influence the MSP of HMF. The preliminary technoeconomic analysis performed on the consolidated bioprocess design indicates that additional revenue streams from diversified coproducts in biorefineries aid in lowering the MSP of high-value bioproducts.

09 BIOMASS FUELS↗

Effects of different pelleting technologies and parameters on pretreatment and enzymatic saccharification of lignocellulosic biomass

Densification of lignocellulosic biomass is beneficial for its logistics, and in some situations, also for its application in biorefineries. In this study, industrial pellets and laboratory-made pellets produced at different die temperatures (90, 125 °C) from wheat straw, beech, and pine were pretreated (by dilute acid and alkali) and enzymatically hydrolyzed to study the effects of pelleting on pretreatment and sugar yield. The results showed that industrial pelleting positively affected sugar yield of the three biomasses for both acid and alkaline pretreatments, while laboratory pelleting affected sugar yield differently related to pretreatment types and biomass species. Pelleting disturbed biomass cell wall structure and affected the stability of hemicellulose and β-O-4' linkages in lignin. The extent of hemicellulose solubility during acid pretreatment and the amount of lignin β-O-4' ether linkages present in acid pretreated substrates could serve as indicators of the effect of pelleting on sugar yield. The structural modifications caused by pelleting and their effects on the enzymatic sugar yield correlate tightly to pelleting technology, pretreatment method, and biomass species. As a result, the discrepant effects between industrial and laboratory pelleting on sugar yield observed in this study should be considered when designing future studies.

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↗

Cost of Deconstruction Depots for Diversified, Waste-Based Lignocellulosic Sugars Using Distillable Solvents

Transitioning to a bioeconomy that makes use of low-emission and waste feedstocks requires greater flexibility to accommodate seasonal variations and mitigate long-term storage challenges, such as material loss and fire risk. To achieve this goal, biomass deconstruction technologies must efficiently handle diverse feedstocks. Here, we assess the cost of using butylaminea distillable solventto deconstruct 22 different biomass feedstocks: 7 herbaceous, 9 woody, 4 food processing residues, and 2 blends. Lignocellulosic sugar production costs, based on current empirical data, range from $1.3 to 6.1/kg, suggesting that substantial improvements are required to compete with conventional sugars. The high solvent loading (850 g/kg of whole slurry) is a process bottleneck. Lowering the solvent loading to 59 g/kg of whole slurry, demonstrated in an L-scale reactor using poplar biomass, reduces the minimum sugar selling price by 33%. Solvent loading and recovery, solid loading, sugar yield, enzyme use, and delivered biomass cost all play key roles in reaching sugar production costs of $0.45-0.79/kg. Strategic feedstock blending to maximize carbohydrate content, process optimization to improve conversion efficiency, and the selection of low-cost feedstocks are important to advancing feedstock-flexible biorefineries.

TEA↗

Understanding Electrochemical Alcohol Hydrogenolysis Enabled by Carbonyl Reduction in Lignocellulosic Biomass-Derived Aromatic Oxygenates

Molecules derived from lignocellulosic biomass are oxygenates with multiple oxygen-containing functional groups, such as hydroxyl and carbonyl groups. Therefore, the ability to selectively reduce a specific oxygenate group is essential for the reductive upgrading of such molecules. Previous studies on electrochemical biomass conversion have shown that alcohol hydrogenolysis, which involves cleavage of the σ(C–O alcohol ) bond, is extremely challenging for furfural and 5-hydroxymethylfurfural (HMF) derivatives, including furfuryl alcohol, 5-methylfurfuryl alcohol (MFA), and 2,5-bis(hydroxymethyl)furan (BHMF). In contrast, HMF itself undergoes alcohol hydrogenolysis relatively easily in acidic aqueous media. Considering that the only structural difference between HMF and BHMF or MFA is the presence of a carbonyl group, this observation raises the question of whether the carbonyl group in HMF facilitates alcohol hydrogenolysis. In this study, we designed systematic experiments to provide a coherent explanation of when and how a carbonyl group enables hydrogenolysis of a copresent alcohol group. Specifically, we show that alcohol hydrogenolysis in HMF proceeds via reduction of the carbonyl group to a ketyl radical, followed by a spin-center shift (SCS) through extended π conjugation. We also elucidate the effect of pH on the selectivity between carbonyl hydrogenation and alcohol hydrogenolysis, both of which share the ketyl radical intermediate. This mechanistic understanding enhances our ability to predict and control alcohol hydrogenolysis in the reductive upgrading of biomass-derived oxygenates.

alcohols↗

Genomic and functional analyses of fungal and bacterial consortia that enable lignocellulose breakdown in goat gut microbiomes

Abstract The herbivore digestive tract is home to a complex community of anaerobic microbes that work together to break down lignocellulose. These microbiota are an untapped resource of strains, pathways and enzymes that could be applied to convert plant waste into sugar substrates for green biotechnology. We carried out more than 400 parallel enrichment experiments from goat faeces to determine how substrate and antibiotic selection influence membership, activity, stability and chemical productivity of herbivore gut communities. We assembled 719 high-quality metagenome-assembled genomes (MAGs) that are unique at the species level. More than 90% of these MAGs are from previously unidentified herbivore gut microorganisms. Microbial consortia dominated by anaerobic fungi outperformed bacterially dominated consortia in terms of both methane production and extent of cellulose degradation, which indicates that fungi have an important role in methane release. Metabolic pathway reconstructions from MAGs of 737 bacteria, archaea and fungi suggest that cross-domain partnerships between fungi and methanogens enabled production of acetate, formate and methane, whereas bacterially dominated consortia mainly produced short-chain fatty acids, including propionate and butyrate. Analyses of carbohydrate-active enzyme domains present in each anaerobic consortium suggest that anaerobic bacteria and fungi employ mostly complementary hydrolytic strategies. The division of labour among herbivore anaerobes to degrade plant biomass could be harnessed for industrial bioprocessing.

59 BASIC BIOLOGICAL SCIENCES↗