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At least 37 records · Page 2

Eudicot Nutshells: Cell-Wall Composition and Biofuel Feedstock Potential

Nutshells are the recalcitrant and membranous layers that encompass and provide protection to the seed of a fruit. Rich in lignin, these are often waste products of the food industry and are a potential energy-dense feedstock for biorefineries to convert to biofuels. Here, assessing their potential requires an understanding of the relative amounts of cellulose, hemicelluloses, and lignin, the composition and structure of the lignin, and a saccharifiability assessment, all provided here. In the context of understanding the general character of phylogenetically diverse eudicot species, we provide a chemical analysis of the lignin in the shells of commonly eaten nuts and detail the chemical composition of their lignins. Particularly striking observations include the >40% levels of Klason lignins in the nutshells from macadamia, pecan, and Brazil nut and lignin compositions ranging from <1% syringyl (S) in macadamia to 77% S in pistachio and essentially 0% p-hydroxyphenyl (H) in mango to as high as 7.5% H in walnut. Novel units in the lignin polymer (such as the hydroxystilbenes recently discovered in macaúba and coconut shell lignins) were not evident in any of the samples, but the series provided such a range of compositions that it aided more detailed assignment.

NMR↗

Production of chitosan-based composite film reinforced with lignin-rich lignocellulose nanofibers from rice husk

Lignocellulosic nanofibers (LCNFs), implying lignin-containing cellulose fibers, maintain the properties of both lignin and cellulose, which are hydrophobic and hydrophilic, respectively. The presence of hydrophobic lignin in LCNFs is expected to be an economical and attractive option that can improve the thermal and mechanical properties of polymers. Thus, this study was conducted to produce lignin-rich LCNFs from sugar-rich waste obtained from rice husks after acidic pretreatment. The LCNFs were produced from the lignin-rich solid fractions obtained after pretreatment and enzymatic hydrolysis, which were then incorporated as an additive into a chitosan-based film. The variations in lignin content in the range of approximately 50.6%-66.8% in differently obtained LCNFs gave significantly different optical strengths and mechanical properties. These controllable processes may allow for customized film formation. Additionally, the glucose-rich liquid fractions obtained after pretreatment and enzymatic hydrolysis were used as a substrate for ethanol fermentation to achieve total utilization of rice husk biomass waste. In conclusion, the lignin-rich biomass fraction holds promise as a suitable material for chitosan-LCNF film and has the potential to increase the economic feasibility of the biomaterial industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Co-Hydrotreatment of Yellow Greases and the Water-Insoluble Fraction of Pyrolysis Oil. Part I: Experimental Design to Increase Kerosene Yield and Reduce Coke Formation

Here, this paper reports the co-hydrotreatment of Biomass Technology Group commercial pyrolysis oil water-insoluble (WIS) phase (also known as pyrolytic lignin) and yellow greases (waste cooking oil), aiming to produce sustainable aviation fuels (SAFs). We use a sulfided NiMo/Al 2 O 3 blend with 16 wt % WIS and a central composite experimental design to identify processing conditions increasing kerosene yield and reducing coke formation. The input variables were: (1) reaction temperature (320, 350, and 380 °C), (2) initial hydrogen pressure (5, 6, and 7 MPa), and (3) amount of catalyst (0.7, 1.0, and 1.3 g). The hydrotreated oily phases were distilled to obtain gasoline (<150 °C), kerosene (150–250 °C), diesel (250–350 °C), and residual oil (>350 °C). The reaction temperature is the main factor affecting the yield of gaseous, solid, and liquid products. Meanwhile, a higher initial hydrogen pressure and catalyst loading increased the yield of kerosene and other distillates and decreased the coke formation. A high temperature correlated with a lower content of oxygenates in kerosene cuts. Based on our experimental results, we propose to conduct hydrotreatment studies at 380 °C, initial H 2 pressure of 7 MPa, and 1.3 g of catalyst. Under the identified conditions, it was possible to improve the kerosene yield to more than 20 wt % and reduce the yield of coke to close to 2.0 wt %. The chemical composition and fuel properties of the gasoline, kerosene, and diesel cuts were thoroughly analyzed. The content of aromatics and phenols in the kerosene fraction produced at the conditions identified in this project exceeded the recommended values for SAFs. New strategies (such as blending and more intense hydrotreatment to remove oxygenated compounds) need to be implemented to reduce the content of these molecules in our final product.

09 BIOMASS FUELS↗

Cell Free and Immobilization Technologies (CFIT)

Today, several key factors negatively impact the production of fuels and chemicals from renewable sources. Common hindrances in the biological production of biochemicals are: (1) end-product or intermediate toxicity to the microbial biocatalyst, (2) the diversion of carbon to biomass formation, and (3) co-production of undesired byproducts. A particularly attractive alternative is to eliminate the biocatalyst entirely and instead operate the desired metabolic pathways in isolation, thus circumventing the roadblocks of biological toxicity, lower yields, and lack of specificity. However, cell-free enzyme systems still suffer from low productivities owing in part to the effects of free diffusion of intermediates, lack of long term enzyme stability, cofactor cost or inefficient recycling rates, and finally, the cost of enzyme production/purification. This project represents a new effort to propose innovative and cost competitive routes to producing biochemicals from a variety of feedstocks using cell free approaches. These routes will help reduce the current risk and cost associated with classical cell free production. Cell free technologies show promise for application to the production of toxic/inhibitory products or products difficult to separate from microbial growth media and can help reduce the production barriers in multiple areas of biological conversion of feedstocks to biochemicals. More specifically, we are developing new technologies and routes that could be used to produce high value biochemicals such as 2,3 BDO and terpenes (among many others) from biomass derived C5/C6 sugars or lignin but also from waste byproducts such as glycerol. This project will lead to significant innovation and also lead to new concepts and rational design of pathways and enzymes. Within this project, we will develop new metabolic enzyme cascades that will represent natural or artificial combinations of enzymes to produce the desired biochemicals from a variety of feedstocks. We are also developing basic design principals for constructing synthetic metabolons, using fusion proteins and synthetic protein scaffolds, to promote substrate channeling and stability while conserving peak activity. Additionally, our efforts include a techno economic analysis (TEA) of cell free approaches to provide the sensitivities of the process to enzyme loading, activity, pH, reactor volumes, cofactor recycling rates. Finally, we are focusing on further increasing stability, operating lifetime and efficiency of the pathway enzymes by immobilization on support surfaces. We are also focus on immobilizing pathway enzymes or combinations of enzymes on several different conducting polymers and evaluate the effect on stability and operating lifetime. As more combinations become available we will conduct a more systematic study of the means of immobilizing these enzymes. This preliminary work will enable the in-depth study of cofactor recycling at these interfaces using mediators for electron transfer. Taken together, these approaches will enable process intensification, continuous operation, lower capital and separations costs and end-product flexibility, and thus has the potential to contribute significantly to BETO's goals of cost competitive biofuels and bioproducts. To date we have demonstrated 1) the conversion of pyruvate to 2,3 BDO (4 enzymes with cofactor recycling, no additional cofactors needed) at >100g/L (>3g/L/h) using our enzyme tethering approach, 2) Generated mutants of a key redox enzyme with >180- fold improvement in NADH utilization over WT to >85% of NADPH utilization. 3) Produced mevalonate at >10g/L from glucose, limonene at >10g/L from mevalonate and more than >5g/L from glucose with crude enzyme preparations and complete cofactor recycling. 4) successfully generated fully active cross-linked aggregates (CLEAs) of NOX, a cofactor-regenerating water-forming oxidase that is key to our process with increased stability 5) Engineered and identified enzymes able to use the biomimetic cofactor NMN and synthesized new synthetic cofactors.

biocatalysis↗

Challenges and Opportunities in Biological Funneling of Heterogeneous and Toxic Substrates Beyond Lignin

Significant developments in the understanding and manipulation of microbial metabolism have enabled the use of engineered biological systems toward a more sustainable energy and materials economy. While developments in metabolic engineering have primarily focused on the conversion of carbohydrates, substantial opportunities exist for using these same principles to extract value from more heterogeneous and toxic waste streams, such as those derived from lignin, biomass pyrolysis, or industrial waste. Funneling heterogeneous substrates from these streams toward valuable products, termed biological funneling, presents new challenges in balancing multiple catabolic pathways competing for shared cellular resources and engineering against perturbation from toxic substrates. Solutions to many of these challenges have been explored within the field of lignin valorization. This perspective aims to extend beyond lignin to highlight the challenges and discuss opportunities for use of biological systems to upgrade previously inaccessible waste streams.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Enabling Partnership between South Carolina and NREL for Advancing Opportunities in Plastics Recycling Research (EPSCOR for Plastics Recycling)

Proposal Objectives: 1. Utilize depolymerization/fractionation techniques to recover highly processable and reactive feedstocks for polymer synthesis from lignin. 2. Synthesize lignin‐derived non‐isocyanate polyurethane, epoxy, and polyamide using non‐ toxic, biobased route designed for chemical recycling. Characterize resulting materials. 3. Design a high‐yielding chemical recycling process for as‐synthesized materials yielding usable building blocks for many generations of polymer synthesis. 4. Optimize chemical recycling of PET waste for the synthesis of lignin‐based polymers. Compare properties to commercial materials. 5. Optimize reaction conditions and recycling steps to facilitate enhanced sustainability of the synthetic steps and final properties of materials. 6. Complete a lifecycle assessment of lignin utilization and chemical recycling to compare their environmental performance to that of materials produced from virgin material. Identify hot spots and benefits using the chemical recycling process.

36 MATERIALS SCIENCE↗

Reductive catalytic fractionation of agricultural residue and energy crop lignin and application of lignin oil as antimicrobials

Cheap and abundant waste from bioethanol and agricultural processing industries are an alluring alternative feedstock for biorefineries. In this work, we employ reductive catalytic fractionation (RCF) to depolymerize, over Ru/C powder and Ru/Al 2 O 3 pellets, five herbaceous biomass feedstocks, namely corn stover, miscanthus, switchgrass, sugarcane bagasse, and wheat straw into phenolic monomers with high yields (~40 wt.% based on total (Klason + acid soluble) lignin and > 50 wt.% when stabilized using aldehydes), leaving behind a carbohydrate pulp residue. Interestingly, a polar solvent is sufficient to solubilize and fragment the lignin polymer into monomers without any catalyst. Here, contrary to woody biomass, where the monomer yields are positively correlated with the S-content of lignin, principal component analysis indicates that the monomer yields from herbaceous biomass depend on the content of lignin crosslinker – ferulate. Using NMR, we further identify α – 6 C-C linked oligomers formed from condensation reactions, explaining the unexpected low monomer yields of high β-O-4 herbaceous biomass. Recyclability experiments indicate that catalyst deactivation occurs through sintering, leaching, and fouling. Lignin oil from herbaceous biomass exhibits bacteriostatic effects against Staphylococcus aureus, highlighting a potential application in functional food development and as food or feed preservative.

09 BIOMASS FUELS↗

Comparison of Mechanical Properties of Lignin/High-Density Polyethylene (HDPE) Composites and Wood/HDPE Composites

Lignin is a plant-derived, the second most abundant natural polymer, and a waste byproduct of the pulp industry. Incorporation of lignin into plastic composites using scalable approaches is commercially favored and low carbon-cost. Potential end applications for lignin plastic composites (LPCs) could be found in buildings and furniture where wood plastic composites (WPCs) are used in various components. This study compares the mechanical properties of LPCs and WPCs, aiming at the examination of the viability of the use of LPCs as alternative materials to WPCs in the building industry. Sodium ligninsulfonate (SLS)-based LPC blended with high-density polyethylene (HDPE) (45 wt.%) and maleic anhydride grafted polyethylene (MAPE) as a compatibilizer (5 wt.%) reached flexural strength (35.17 and 30.92 MPa respectively) and moduli (2.87 and 1.79 GPa respectively) comparable to benchmarking WPCs. Lignin dealkaline (LD)-based LPC exhibited higher ultimate strain but lower strength than SLS-based LPC, probably due to fragmentation during the post-sulfite treatment steps.

cellulose and other wood products↗

Nonthermal hydrogen plasma-enabled ambient, fast lignin hydrogenolysis to valuable chemicals and bio-oils

The reduction of fossil fuel resources and the ongoing surge in global energy demand have captured the interest of researchers worldwide, prompting a focus on developing renewable energy sources. For this reason, biomass conversion has emerged as a crucial pathway for renewable fuel production. Lignin, constituting 10–35% of woody biomass, represents a significant and largely untapped sustainable feedstock. Despite the potential of lignin, a substantial portion of this lignocellulosic residue remains unused, with approximately 60% considered waste. This study addresses the challenge of underutilized lignin by introducing an innovative approach to its hydrogenolysis. Despite their potential, existing hydrogenolysis methods face obstacles such as complexity, high cost, and the need for high temperatures or pressures. Herein we report a noncatalytic nonthermal hydrogen plasma method for lignin hydrogenolysis, conducted under ambient temperature and pressure conditions. Our method proves to be highly effective in breaking lignin bonds, achieving complete conversion, and generating valuable gaseous and bio-oil products including methane and aromatic dimers and monomers obtained from guaiacyl and syringyl units within the lignin structure. Our results showed an increase in gaseous products, especially methane, and aromatic monomer yields, as well as a reduction in total bio-oil and biochar yields and lignin functional groups by increasing reaction time, input power, and H2 partial pressure. This research confirms the considerable promise of utilizing noncatalytic nonthermal hydrogen plasma-assisted hydrogenolysis as an effective technique for producing gaseous and liquid fuels from lignin.

Pishva, Parsa↗

Reductive amination cascades in cell‐free and resting whole cell formats for valorization of lignin deconstruction products

Abstract The selective introduction of amine groups within deconstruction products of lignin could provide an avenue for valorizing waste biomass while achieving a green synthesis of industrially relevant building blocks from sustainable sources. Here, we built and characterized enzyme cascades that create aldehydes and subsequently primary amines from diverse lignin‐derived carboxylic acids using a carboxylic acid reductase (CAR) and an ω‐transaminase (TA). Unlike previous studies that have paired CAR and TA enzymes, here we examine multiple homologs of each of these enzymes and a broader set of candidate substrates. In addition, we compare the performance of these systems in cell‐free and resting whole‐cell biocatalysis formats using the conversion of vanillate to vanillyl amine as model chemistry. We also demonstrate that resting whole cells can be recycled for multiple batch reactions. We used the knowledge gained from this study to produce several amines from carboxylic acid precursors using one‐pot biocatalytic reactions, several of which we report for the first time. These results expand our knowledge of these industrially relevant enzyme families to new substrates and contexts for environmentally friendly and potentially low‐cost synthesis of diverse aryl aldehydes and amines.

Biotechnology & Applied Microbiology↗

Energy-Efficient Microbial Electrochemical Lignin and Alkaline Hydroxide Recovery from DMR Black Liquor

Black liquor is a complex waste stream generated from the fast-expanding biorefinery industry, and the high management cost has been known as a major development barrier. In this work, we demonstrated a rationally designed 4-chamber microbial electrolysis process that was capable of recovering the value-added lignin, NaOH, and H2 products while removing waste organics from the Deacetylation and Mechanical Refining (DMR) black liquor, which could potentially reduce the disposal cost by up to 40%. The lab-scale MEC achieved 52% organic removal from a highly concentrated feedstock (28,960 ± 212 mg/L COD) and recovered 83.2 mM NaOH under a small voltage application (1.2 V). Lignin recovery was observed to be as high as 13.98 +/- 0.28 g/L, and 0.35 L/L/day H2 was produced with a faradaic efficiency of 93.5%. This work provided a good example on how complex liquid waste stream can be valorized via multi-functional microbial electrochemical technology, and how the traditionally unfavored pH gradient in an electrochemical reactor can be manipulated for lignin precipitation and alkaline recovery at the same time. The versatility and good performance in concurrent contaminants removal, lignin precipitation, H2 production and NaOH recovery demonstrate a good potential for microbial electrolysis in black liquor treatment.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Towards functionalized lignin and its derivatives for high-value material applications

In pursuit of low-carbon development, the production of diverse functional materials from renewable resources, especially lignocellulosic biomass, is of vital importance. Lignin is a major component of lignocellulose, and it is nature's only true high-volume aromatic polymer, which has the advantages of biodegradability, biocompatibility, and low acquisition cost. After modification by a variety of physicochemical strategies, it can be applied as an alternative to basic industrial materials, including polyurethanes, phenolic, and epoxy resins, which stands comparably to conventional synthetic polymers in terms of both performance and reduced cost. To further unlock the potential of lignin, an alluring opportunity is the exploitation of lignin for high-value materials, especially nanomaterials, that find extensive applications in energy and environment areas. This review provides a systematic summary and perspective of research that has been devoted to lignin transformation to high-value materials, ranging from industrially well-established engineering materials to the recently emerged nanomaterials that were used for energy and environment applications. Latest cutting-edge innovations on lignin modification, controlled depolymerization, and assembly during the last five years are summarized. Structure-function relationships of lignin materials in terms of their specific applications are analyzed. Furthermore, challenges and future opportunities for lignin conversion to high-value materials are also provided. We wish this review will stimulate further advances in lignin based high-value materials, and promote “waste” into “wealth”.

36 MATERIALS SCIENCE↗

Manufacturing of Continuous Microporous Polymeric Fibers for Separation Applications

Polyolefin plastic waste, particularly polypropylene, is one of the most prevalent components in the plastic waste stream generated globally. However, only a small fraction of this waste is recycled and reintegrated into second applications. These materials have significant embedded energy that could be used for additional productivity if recycled properly. Therefore, there is a critical need to develop scalable processing techniques with high throughput to effectively recycle it. We report the continuous manufacturing of microporous fibers using waste polypropylene plastic and melt-processable lignin, a plant biomass constituent produced as a byproduct in paper mills or biorefineries, as a template to create pores. Further, these filaments with hierarchical porosity─created by controlled microphase separation during high-speed extensional flow followed by removal of lignin─exhibit exceptional capillary action for hydrophobic liquids. The resulting porous fibers can be used for various separation applications. For example, the oil uptake of the fibers is 9.59 ± 0.82 g/g for applications in oil recovery in bodies of water. In addition, polyethylenimine infiltration within these nanoporous fibers introduces cyclic room temperature sorption and thermal desorption potential of acidic gases such as CO 2 in a bench-scale experiment. The fibers exhibit multiple cycles of CO 2 absorption, with a range of 0.15 to 0.17 mmol/g. Thus, these polyethylenimine-infiltered nanoporous polypropylene fibers can also be used in removing acidic gases from a gas mixture.

36 MATERIALS SCIENCE↗

Lignin-derived electrochemical energy materials and systems

Electrochemical energy storage systems such as supercapacitors, rechargeable batteries and fuel cells have been proven the most effective technologies for energy conversion, storage, and management at different scales. Although a large number of electrochemical energy technologies have been developed in the past and they will continue to be optimized in terms of cost, lifetime, and performance, there is a substantial growing demand for advanced electrochemical energy systems. To deploy these advanced systems, the electrode and electrolyte materials with higher performance, longer life, and lower cost, must be developed. Lignin is the second most abundant natural polymer after cellulose, a byproduct from emerging cellulosic biorefineries, and a waste product from pulp and paper industries. Numerous researches have successfully demonstrated that lignin from different sources can be used as precursors or feedstocks for preparing high-performance electrochemical energy materials and components such as electrodes, electrolytes, membrane separators, and additives. Moreover, techno-economic analyses indicate that it is possible to prepare cost-effective carbons from lignin at engineering scales, compared to current carbon products. These facts suggest that scalable conversion of lignin into high-value energy materials will offer a promising pathway to not only promote the utilization and valorization of lignin but also boost the development of the advanced electrochemical energy systems. This review presents state of the arts of renewable energy materials derived from various lignin and their applications in electrochemical energy systems with emphasis on supercapacitors, rechargeable batteries, and fuel cells. Meanwhile, this article also aims to carve out the critical barriers for lignin-derived high-performance materials for energy applications, intending to identify viable approaches for synthesis of sustainable new energy materials.

09 BIOMASS FUELS↗

Designing a Dynamic Material via Interlocking Kraft Lignin with Ultrahigh Molecular Weight Poly(ethylene oxide)

The environmental issues stemming from plastic waste and the excessive use of petroleum-based chemicals are both concerning and urgent. To effectively address this problem, we need to adopt a comprehensive approach involving developing more sustainable and renewable materials. These materials should be capable of demonstrating similar or even better performance than functional polymers synthesized from petroleum-based chemicals. Our research aims to develop more sustainable materials by leveraging the intrinsic characteristics of a natural polymer, lignin, a byproduct of the biorefinery industries. We utilized the three-dimensional branching structure of lignin as a material framework. We employed an approach to co-reactive melt processing of kraft lignin with aliphatic flexible chains of soft cross-linkers through the reaction of the cross-linker epoxy chain ends with lignin functional groups. Our study demonstrates that the interlocked structure formed from the co-blending of kraft lignin with ultrahigh molecular weight poly(ethylene oxide) and the cross-linking of lignin chains through a solvent-free process can manipulate the macromolecular interactions and relaxation. This manipulation results in materials that exhibit a wide range of thermomechanical properties and self-healing and shape memory effects, with drastically improved stiffness in a single material. We have explored the fundamental understanding of the macromolecular chain relaxation dynamics originating from the interlocking structure formation. In conclusion, this investigation utilized various techniques, including thermal, mechanical, rheology, and quasi-elastic neutron scattering.

36 MATERIALS SCIENCE↗

Recovery of p -Hydroxybenzoic Acid from Cu-Catalyzed Alkaline Hydrogen Peroxide Pretreatment of Hybrid Poplar

p-Hydroxybenzoic acid (pHBA) is present in some hardwood biomass feedstocks as an ester attached to the polymeric lignin subunits. Here, we report the isolation and recovery of pHBA from alkaline liquor waste streams obtained from fractionation of hybrid poplar using the “Cu-AHP process”. This process features two stages: alkaline pre-extraction (AP) of the biomass and copper-catalyzed alkaline hydrogen peroxide pretreatment. On a biomass scale of 100 g, 0.5 g of pHBA with a purity of 96% was obtained after decolorization and crystallization. The scalability of the purification process was demonstrated by using liquor obtained from the first-stage AP with 900 g of poplar biomass to afford 3.5 g of crystalline pHBA with 97% purity. Altogether, these results show that pHBA may be isolated and purified from waste streams generated in the two-stage Cu-AHP process without any alteration of the process conditions or impact on carbohydrate and lignin fractionation.

09 BIOMASS FUELS↗