Forestry residues have immense potential as alternative feedstocks to petroleum, yet their inherent complexity remains a major challenge to widespread use. Pairing the temporal rhythms of plant biology with biorefinery performance is critical to industrial-scale biorefinery development. Here, we provide the first report of a techno-economic analysis (TEA) and life cycle assessment (LCA) for a model integrated reductive catalytic fractionation (RCF)-molten salt hydrolysis process for forestry residues varying in tree part, species, and phenophase. All forestry residues resulted in net-negative greenhouse gas (GHG) emissions vs. comparable petroleum feedstocks, with GHG emissions potentially reduced >4.0 & times; through composition-based feedstock selection (e.g., harvesting American beech bark in spring vs. summer). Moreover, American beech twigs/branchlets and bark in leafed and emergence phenophases, respectively, had 7.9 & times; lower predicted phenolic minimum selling prices (MSPs) vs. other feedstocks and MSPs within the current global phenolic market range. Hemicellulose content and RCF yield emerged as key parameters impacting GHG emissions and biorefinery revenue, identifying hardwood twigs/branchlets in the leafed phenophase as optimal biofeedstocks. Biorefinery expenses were dominated by purchased equipment, raw materials, and utility costs, highlighting essential areas for future study. Notably, RCF reactor pressures drove 85-90% of equipment costs, but sensitivity analysis revealed that decreasing the pressure 20% could reduce the phenol MSP 4-fold. Structural carbohydrate dynamics were also investigated using a two-step acid hydrolysis method to resolve tissue- and species-level patterns in biomass composition throughout the year to enable harvest optimization based on TEA/LCA findings. Ultimately, elucidating the impact of biofeedstock dynamics on biorefinery performance enables harvest optimization, informed engineering design, and progress towards an expanded bioeconomy.

The widespread reliance on fossil-derived linear alkylbenzene sulfonates (LAS) in surfactant formulations presents significant sustainability and biodegradability challenges. We report a synthetic route to oleo-furan sulfonate (OFS) and branched sulfonate surfactants derived from a hybrid of renewable biomass and polyolefin plastics waste carbon. Plastics-derived paraffins were obtained via catalytic hydrogenolysis and subsequently oxidized using non-thermal atmospheric plasma. The resulting oxygenated paraffins, rich in mid-chain ketones and alcohols, were selectively reduced to mono-alcohols using sodium borohydride. These plastics-derived hydroxy paraffins were then coupled with biomass-derived 2-furoic acid to produce furoates and olefins, which were sulfonated to yield unique oleo-furan and branched sulfonate surfactants. The resulting surfactants exhibited superior performance, including a low critical micelle concentration (CMC) of 591 ppm and a Krafft temperature below 0 degrees C, surpassing not only previously synthesized OFS but also commercial LAS and sodium lauryl sulfates (SLS). This work offers a blueprint for producing high-value specialty surfactants from hybrid waste feedstocks and contributes to the advancement of circular, high-performance surfactant technologies.

Renewable feedstocks are a critical component of sustainability and resource security efforts, and feedstock selection is vital for the improved biorefinery production of fuels, chemicals, and materials. A major hurdle for feedstock selection is the inherent heterogeneity and variability among biofeedstocks. Herein, based on knowledge convergence among tree physiological ecology, wood science, and chemical engineering, we present a harvest optimization strategy to maximize lignin valorization in carbon-neutral forestry residues, elucidating the influence of canopy phenophase on possible valorization avenues. This study provides the first report on how tree part, species, and phenophase impact lignin content and deconstruction yields and distributions. Notably, harvesting during the leafed phenophase can double or triple phenolic yields compared to other times of year, offering a simple yet effective strategy to enhance lignin valorization and overall biorefinery production.

Lignin is a promising renewable feedstock to produce chemicals, fuels, and materials, yet a major challenge for lignocellulosic biorefineries is the significant variation in lignin content and structure. Traditional lignin characterization approaches require time-intensive, wet laboratory procedures, highlighting the need for rapid and reliable characterization methods to quantify lignin content and deconstruction products. This study presents a noninvasive, preharvest approach to determine lignin content, total phenolic monomer yield, and syringyl/guaiacyl (S/G) unit ratios in tree biomass from reductive catalytic fractionation (RCF) utilizing the optical properties of stemflow dissolved organic matter (DOM) as a proxy. A significant relationship between fluorescent signatures in stemflow DOM and constituent-specific composition (bark, twigs/branchlets, foliage) is identified, and stepwise multiple linear regression models showcase stemflow DOM component utilization to estimate lignin content, total phenolic monomer yield, and S/G ratio. Unlike traditional approaches, stemflow fluorescence can be quantified preharvest and pretransportation, enabling early lignin screening and prediction of deconstruction performance and product distribution. This stemflow fluorescence approach, harnessing the characterization of DOM in natural processes, is a higher-throughput, lower-cost screening method that could be a critical solution for biorefineries to overcome challenges due to biomass variability and facilitate feedstock screening, process optimization, and output product prediction.

Discovering high-performance molecules and processes to produce them relies on expert knowledge and intuition, often requiring extensive laboratory work with many failures. Being able to predict the chemical properties of new molecules while considering the full cycle from design to environmental fate, early in the discovery phase, would streamline the process significantly. Synthetic insecticides, while effective at enhancing crop yields, pose significant risks such as biodiversity loss, pest resistance, and environmental persistence. This underscores the need for a sustainable agricultural framework, one exemplified by environmentally friendly insecticides that balance efficacy with ecological safety. This study employs a structure-directed molecular design approach to predict carbamate insecticide structures derived from renewable platform molecules. We generated and identified potential furan-based carbamates with predicted reduced ecological impact using computational tools and predictive ecological frameworks. We then utilized reaction patterns to systematically explore chemical space and generate novel bioactive structures and found that hydrogenated furan derivatives possess an improved sustainability profile. We next synthesized and evaluated ten of these molecules. Among them, methyl N-[(furan-2-yl)methyl] carbamate and methyl N-{[5-(methoxymethyl)oxolan-2-yl]methyl} carbamate exhibited high insecticidal activity against lesser mealworm beetle (Alphitobius diaperinus) with reduced ecological impact, demonstrating a sweet spot between potency and biodegradability. Our methodology paves the way for accelerated and targeted discovery of next-generation sustainable pest management solutions and, more generally, for designing innovative biobased chemicals.

Correction for ‘Reductive catalytic fractionation of agricultural residue and energy crop lignin and application of lignin oil in antimicrobials’ by Elvis Osamudiamhen Ebikade et al. , Green Chem. , 2020, 22 , 7435–7447, https://doi.org/10.1039/D0GC02781B.

Developing a process that performs the lignocellulosic biomass fractionation under milder conditions simultaneously with the depolymerization and/or the upgrading of all fractions is fundamental for the economic viability of future lignin-first biorefineries. The molten salt hydrates (MSH) with homogeneous or heterogeneous catalysts are a potential alternative to biomass pretreatment that promotes cellulose's dissolution and its conversion to different platform molecules while keeping the lignin reactivity. This review investigates the fractionation of lignocellulosic biomass using MSH to produce chemicals and fuels. First, the MSH properties and applications are discussed. In particular, the use of MSH in cellulose dissolution and hydrolysis for producing high-value chemicals and fuels is presented. Then, the biomass treatment with MSH is discussed. Different strategies for preventing sugar degradation, such as biphasic media, adsorbents, and precipitation, are contrasted. The potential for valorizing isolated lignin from the pretreatment with MSH is debated. Finally, challenges and limitations in utilizing MSH for biomass valorization are discussed, and future developments are presented.

Production of sustainable aviation fuels (SAFs) can significantly reduce the aviation industry's carbon footprint. Current pathways that produce SAFs in significant volumes from ethanol and fatty acids can be costly, have a relatively high carbon intensity (CI), and impose sustainability challenges. There is a need for a diversified approach to reduce costs and utilize more sustainable feedstocks effectively. Here, we map out catalytic synthesis routes to convert furanics derived from the (hemi)cellulosic biomass to alkanes and cycloalkanes using automated network generation with RING and semiempirical thermochemistry calculations. We find >100 energy-dense C8-C16 alkane and cycloalkane SAF candidates over 300 synthesis routes; the top three are 2-methyl heptane, ethyl cyclohexane, and propyl cyclohexane, although these are relatively short. The shortest, least endothermic process chemistry involves C-C coupling, oxygen removal, and hydrogen addition, with dehydracyclization of the heterocyclic oxygens in the furan ring being the most endothermic step. The global warming potential due to hydrogen use and byproduct CO2 is typically 0.7-1 kg CO2/kg SAF product; the least CO2 emitting routes entail making larger molecules with fewer ketonization, hydrogenation, and hydrodeoxygenation steps. The large number of SAF candidates highlights the rich potential of furanics as a source of SAF molecules. However, the structural dissimilarity between reactants and target products precludes pathways with fewer than six synthetic steps, thus necessitating intensified processes, integrating multiple reaction steps in multifunctional catalytic reactors.

Globally, less than 0.5% of postconsumer textile waste is recycled, with the majority incinerated or ending up in landfills. Most postconsumer textiles are mixed fibers, complicating mechanical recycling due to material blends and contaminants. Here, we demonstrate the chemical conversion of postconsumer mixed textile waste using microwave-assisted glycolysis over a ZnO catalyst followed by solvent dissolution. This approach electrifies the process heat while allowing rapid depolymerization of polyester and spandex to their monomers in 15 minutes. A simple solvent dissolution enables the separation of cotton and nylon. We assess the quality of all components through extensive material characterization, discuss their potential for sustainable recycling, and provide a techno-economic analysis of the economic feasibility of the process.

With the continuous increase in food production to support the growing population, ensuring agricultural sustainability using crop-protecting agents, such as pesticides, is vital. Conventional pesticides pose significant environmental risks, prompting the need for eco-friendly alternatives. This study reports the synthesis of new amide-based insecticidal active ingredients from biomass-derived monomers, specifically furfural and vanillin. The process involves reductive amination followed by carbonylation. The synthesis of the furfural-based carbamate yield reaches a cumulative 88 %, with catalysts Rh/Al 2 O 3 and La(OTf) 3 being recyclable at each stage. Insecticidal activity assessments reveal that the furfural carbamate exhibits competitive performance, achieving an LC 50 of 254.22  μ g/cm 2 , compared to 251.25  μ g/cm 2 for carbofuran. Ecotoxicity predictions indicate significantly lower toxicity levels toward non-target aquatic and terrestrial species. The importance of the low octanol-water partition coefficient of the biobased carbamate, attributed to the oxygen heteroatom and electron density of the furan ring, is discussed in detail. Building on these promising results, the synthesis strategy was extended to six other biobased aldehydes, resulting in a diverse portfolio of biomass-derived carbamates. A techno-economic analysis reveals a minimum selling price of 11.1 $/kg, only half that of comparable carbamates, demonstrating the economic viability of these new biobased insecticides.

Intensified lauric acid self-ketonization and its impact on biolubricant base oil production.

Neo acids are highly branched carboxylic acids currently produced from fossil fuels. In this work, we report a strategy to synthesize renewable neo acids with tailored molecular architecture from biomass-derived monomers.

Food waste is a profound challenge as 17% of global food production (i.e., 931 million tons) ends up as waste yearly. A cost-effective strategy is the extraction of high-value phenolic acids from food waste, but their downstream purification is challenging owing to their similar chemical nature, high boiling points, and low concentrations in complex mixtures. Herein, we propose separating target phenolics using molecular imprinted polymers. The stability of the monomer-template complex during the synthesis is critical in optimizing the polymer selectivity and performance. COnductor like Screening MOdel for Real Solvents (COSMO-RS) and Hansen Solubility Parameters in Practice (HSPiP) computations were used to screen the interaction of 28 monomers and 13 porogenic solvents with chlorogenic acid as the target molecule. Experiments revealed that itaconic acid, the functional monomer, and tetrahydrofuran (THF), the synthesis solvent, provide the highest reported separation factor. The polymer exhibits superior selectivity towards chlorogenic acid in concentrated solutions of up to 1 mg/mL, and its high sensitivity to various functionalities enables the effective separation of all target phenolic acids. The polymer's performance was evaluated in different extraction solvents, and Fourier transform infrared (FTIR) studies revealed polymer-solvent interaction as the critical factor influencing its performance. The application of the polymer in purifying up to 92% chlorogenic acid from coffee beans and potato peel waste extractives is demonstrated, and its reusability is evaluated. In contrast to the current industrial purification methodology that produces mixtures, the proposed technology provides at least eleven times higher economic value and 95% less carbon emissions based on lab-scale techno-economic analysis.

The rising demand for linear alkylbenzene surfactants (LAS) poses an environmental threat as LAS are industrially produced from petroleum using corrosive acid catalysts.

Enormous efforts have been made to convert biomass to liquid fuels and products catalytically. Long molecules with a suitable structure are ideal precursors for fuels and value-added products. Here, a C21 oxygenate was synthesized for the first time in one step through aldol condensation of furfural and acetone over the amine-functionalized zirconium-based metal-organic framework (MOF), UiO-66-NH2. Structural changes of UiO-66-NH2 were investigated to improve the yield and evaluate the role of the ligand, cluster node, defectiveness, modulator, surface area, and textural properties on the product distribution. We demonstrate the possibility of making long-chain oxygenates without using vegetable oil-derived fatty acids toward 100% waste biomass-derived renewable fuels, lubricants, and surfactants.

There are few reports of microbial deconstruction or functionalization of the recalcitrant backbone of polyolefins. However, microbes can utilize polyolefin deconstruction products, including n-alkanes. Here, we combined chemical catalysis with bioconversion to valorize polyethylene (PE) deconstruction products. High-density PE (HDPE) was deconstructed via hydrogenolysis over a ruthenium on carbon catalyst. The resulting n -alkane mixture (C 4 -C 35 ) was utilized as a feedstock for microbial consortia derived from soil from local recycling plants. We found two consortia that utilized the PE-deconstruction product mix as a sole carbon source. We adapted the consortia on a commercially-available n -alkane mix to reduce the number of species present and enrich for enhanced alkane utilization. Both resulting enriched consortia utilized the PE-deconstruction product mix more effectively than the original (parent) consortia. The predominant metabolite produced by both enriched consortia was a C 16 -C 16 wax ester. Wax esters have considerable industrial value, with the longer chain lengths (C 32 -C 36 ) having the highest value. We identified two Rhodococcus aetherivorans strains that grow well on C 24 , indicating this species is important for the functionalization of long-chain alkanes. This work demonstrates that enriched consortia from plastic-enriched environments can be combined with chemical catalysis to valorize polyethylene. Synopsis Chemical catalysis can be used to deconstruct polyethylene waste material to produce a mixture of alkanes. Enriched environmental microbial consortia can valorize these polyethylene deconstruction products via functionalization that preserves the alkane chain length thus minimizing CO 2 production.

The incentive to reduce greenhouse gas (GHG) emissions has motivated the development of lignocellulosic biomass conversion technologies, especially those associated with the carbohydrate fraction. However, improving the overall biomass valorization necessitates using lignin and understanding the impact of different tree parts (leaves, bark, twigs/branchlets) on the deconstruction of lignin, cellulose, and hemicellulose toward value-added products. In this work, we explore the production of chemicals from a yellow poplar-based integrated biorefinery. Yellow poplar (Liriodendron tulipifera L.) is an ideal candidate as a second-generation biomass feedstock, given that it is relatively widespread in the eastern United States. Herein, we evaluate and compare how the different proportions of cellulose, hemicellulose (xylan), and lignin among leaves, bark, and twigs/branchlets of yellow poplar, both individually and as a composite mix, influence the life-cycle GHG model of a yellow poplar biorefinery. For example, the processing GHG emissions were reduced by 1,110 kg carbon dioxide (CO2)-eq, 654 kg CO2-eq, and 849 kg CO2-eq per metric ton of twigs/branchlets, leaves, and bark, respectively. Finally, a sensitivity analysis illustrates the robustness of this biorefinery to uncertainties of the feedstock xylan/glucan ratio and carbon content.

Branched benzene lubricant and branched cyclic lubricant base oils were synthesized from lignin-derived monomers and aldehyde by hydroxyalkylation/alkylation and hydrodeoxygenation in high yields.

A review of thermal and thermocatalytic valorization of food waste into biobased platform chemicals. A detailed summary of process level and fundamental kinetic insights are provided towards upgrading FW to useful products for a circular economy.