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At least 127 records · Page 7

Advances in ionic liquid recycling for lignocellulosic biomass pretreatment

Ionic liquids (ILs) are promising solvents for the pretreatment of lignocellulosic biomass due to their ability to disrupt cellulose, hemicellulose, and lignin structures. However, large-scale implementation requires the development of efficient recovery and recycling methods. This review provides a comprehensive analysis of the recyclability potential of ILs used in biomass pretreatment, emphasizing their mechanisms, recent innovations, and ongoing challenges. We begin by discussing the structural diversity and tunability of ILs, which underlie their effectiveness in biomass deconstruction. The distinct roles of IL anions and cations in dissolving specific biomass components are systematically presented and compared. Advances in IL recycling techniques, including antisolvent precipitation methods, membrane separation, and distillation, are critically examined, with attention to how mechanistic insights can inform the design of more efficient and selective recovery strategies. Despite progress, significant challenges remain to scaling up IL-based biomass processing, including high cost, environmental concerns, and impact of biomass-derived impurities (e.g., lignin residues, sugars, proteins) on IL purity and functionality after reuse. We also review the applicability of different ILs based on life cycle assessments and techno-economic analyses. Lastly, we identify critical research gaps and propose future directions, including the design and development of next-generation ILs with improved recyclability, reduced toxicity, and enhanced economic viability for industrial-scale applications.

36 MATERIALS SCIENCE↗

Effects of nitrogen fertilization and bioenergy crop type on topsoil organic carbon and total Nitrogen contents in middle Tennessee USA

Nitrogen (N) fertilization affects bioenergy crop growth and productivity and consequently carbon (C) and N contents in soil, it however remains unclear whether N fertilization and crop type individually or interactively influence soil organic carbon (SOC) and total N (TN). In a three-year long fertilization experiment in switchgrass (SG: Panicum virgatum L.) and gamagrass (GG: Tripsacum dactyloides L.) croplands in Middle Tennessee USA, soil samples (0–15cm) were collected in plots with no N input (NN), low N input (LN: 84 kg N ha -1 yr -1 in urea) and high N input (HN: 168 kg N ha -1 yr -1 in urea). Besides SOC and TN, the aboveground plant biomass was also quantified. In addition to a summary of published root morphology data based on a separated mesocosm experiment, the root leachable dissolved organic matter (DOM) of both crops was also measured using archived samples. Results showed no significant interaction of N fertilization and crop type on SOC, TN or plant aboveground biomass (ABG). Relative to NN, HN (not LN) significantly increased SOC and TN in both crops. Though SG showed a 15–68% significantly higher ABG than GG, GG showed a 9.3–12% significantly higher SOC and TN than SG. The positive linear relationships of SOC or TN with ABG were identified for SG. However, GG showed structurally more complex and less readily decomposed root DOM, a larger root volume, total root length and surface area than SG. Collectively, these suggested that intensive N fertilization could increase C and N stocks in bioenergy cropland soils but these effects may be more likely mediated by the aboveground biomass in SG and root chemistry and morphology in GG. Future studies are expected to examine the root characteristics in different bioenergy croplands under the field fertilization experiment.

54 ENVIRONMENTAL SCIENCES↗

Thermomechanical Separation of Biogenic and Non-biogenic Carbon from Non-Recyclable MSW

The effective separation of biogenic and non-biogenic carbon from non-recyclable municipal solid waste (n-MSW) presents a significant challenge in the United States. Currently, there are no efficient methods available to address this issue, hindering the potential for maximizing waste utilization and reducing landfilling rates. This project aims to develop and implement a combine thermomechanical separation techniques to separate biogenic and non-biogenic carbon within n-MSW, ultimately facilitating greater resource recovery and enhancing the efficiency and environmental impact of waste management practices.

09 - BIOMASS FUELS↗

Biomass char gasification kinetic rates compared to data, including ash effects

This investigation provides both experimental and theoretical analyses of biomass char gasification kinetics over 1150–1350 °C in the environment of CO 2 , H 2 O and combinations of these reactants. The experimental data include continuous measurements of particle mass, external and internal temperatures, shape, and size with periodic but not continuous measurements of char porosity, pore size distribution, and pore surface area. The model describes heterogeneous char gasification for poplar wood, corn stover and switchgrass in different shapes and industrially relevant sizes (12.5 mm and smaller). Nonlinear least-squares regression produces optimized power-law model parameters for global kinetics that describe biomass char gasification with respect to both CO 2 and H 2 O separately and in combination. A single set of kinetic parameters describes reaction rates for all three fuels. Model simulations agree with measured data at all stages of char conversion even though the observed mass loss rates change significantly with conversion. In conclusion, the change in rate with conversion depends strongly on ash content, and this investigation provides a simple and theoretically based reaction rate expression that includes the effect of inert ash occupying an increasing portion of the reactive surface with increased conversion.

09 BIOMASS FUELS↗

Community structure and function during periods of high performance and system upset in a full-scale mixed microalgal wastewater resource recovery facility

Microalgae have the potential to exceed current nutrient recovery limits from wastewater, enabling water resource recovery facilities (WRRFs) to achieve increasingly stringent effluent permits. The use of photobioreactors (PBRs) and the separation of hydraulic retention and solids residence time (HRT/SRT) further enables increased biomass in a reduced physical footprint while allowing operational parameters (e.g., SRT) to select for desired functional communities. However, as algal technology transitions to full-scale, there is a need to understand the effect of operational and environmental parameters on complex microbial dynamics among mixotrophic microalgae, bacterial groups, and pests (i.e., grazers and pathogens) and to implement robust process controls for stable long-term performance. Here, we examine a full-scale, intensive WRRF utilizing mixed microalgae for tertiary treatment in the US (EcoRecover, Clearas Water Recovery Inc.) during a nine-month monitoring campaign. We investigated the temporal variations in microbial community structure (18S and 16S rRNA genes), which revealed that stable system performance of the EcoRecover system was marked by a low-diversity microalgal community (D INVSIMPSON = 2.01) dominated by Scenedesmus sp. (MRA = 55 %-80 %) that achieved strict nutrient removal (effluent TP < 0.04 mg·L -1 ) and steady biomass concentration (TSS monthly avg . = 400–700 mg·L −1 ). Operational variables including pH, alkalinity, and influent ammonium (NH 4 + ), correlated positively (p < 0.05, method = Spearman) with algal community during stable performance. Further, the use of these parameters as operational controls along with N/P loading and SRT allowed for system recovery following upset events. Importantly, the presence or absence of bacterial nitrification did not directly impact algal system performance and overall nutrient recovery, but partial nitrification (potentially resulting from NO 2 − accumulation) inhibited algal growth and should be considered during long-term operation. The microalgal communities were also adversely affected by zooplankton grazers (ciliates, rotifers) and fungal parasites (Aphelidium), particularly during periods of upset when algal cultures were experiencing culture turnover or stress conditions (e.g., nitrogen limitation, elevated temperature). Altogether, the active management of system operation in order to maintain healthy algal cultures and high biomass productivity can result in significant periods (>4 months) of stable system performance that achieve robust nutrient recovery, even in winter months in northern latitudes (WI, USA).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Disposition of Solids from Hydrothermal Liquefaction of Biomass: Current Understanding, Research Gaps, and Opportunities

Characteristics of solid residuals generated during hydrothermal liquefaction (HTL) of biomass are reported to establish disposition options for these residuals to reduce liability or barriers to commercialization of HTL. HTL solids from pilot scale are reported and compared to existing HTL solids literature for a variety of biomass feedstocks and HTL configurations, noting differences among literature HTL solids due to solids collection methods. Reported analyses include CHNOS, moisture, ash, inorganics by Inductively Coupled Plasma (ICP), and High Heating Value (HHV). HTL solids are determined to be substantially compatible with U.S. Environmental Protection Agency (EPA) disposal regulations within existing data. Disposition and valorization routes are identified, yet combustion as valorization is determined to be not economically beneficial. Further, research gaps are identified, which include the need for future research to be performed on HTL solids that are representative of a continuous, commercializable flowsheet; verification that specific HTL solids meet EPA disposal requirements; exploration of valorization options; and the need for invention of continuous HTL solids separations/management.

09 BIOMASS FUELS↗

Regional variability of dust single scattering albedo due to mineral composition

Nearly all Earth System Models (ESMs) assume globally homogeneous dust aerosols, neglecting regional variations of the imaginary refractive index (IRI) due to varying mineral composition. This has led to a range of single scattering albedo (SSA) and direct radiative forcing (DRF) estimates, as models assign global properties using dust measurements from different regions. We use model and observational data to assess to what extent regionally varying mineral composition affects visible-band SSA and short-wave DRF of dust. We run global simulations with NASA GISS ModelE2.1, using optical properties for minerals based on laboratory-derived empirical relationships between dust IRI at visible wavelengths and the mineral content of iron oxides. When allowing mineral variations instead of homogeneous dust, we find regional differences in dust SSA up to ~0.06 and consequent variations in DRF up to ~6 and ~5 W/m2, at surface and top-of-atmosphere respectively. We compare model SSA with AERONET inversion data (Version 3.0, Level 2), filtered by aerosol size and optical properties to identify pure dust scenes. To investigate possible contamination by biomass burning aerosols, we use the dataset of Schuster et al. (2016, doi:10.5194/acp-16-1565-2016), who separately calculated the contribution of iron oxides and carbonaceous species to AERONET extinction and absorption optical depths. Our results show that: (1) the range of observed SSA (even without carbonaceous species) is larger than that resulting from homogeneous dust; (2) residual amounts of fine mode black and brown carbon may affect AERONET SSA even in seasons with limited biomass burning; (3) model SSA from our mineral scheme exceeds the AERONET range, possibly due also to an uncertain treatment of goethite. In summary, homogeneous dust cannot explain the variability of observed SSA, so regionally varying optical properties based on mineral content are necessary. Higher accuracy in soil mineralogy maps is needed to better reproduce SSA variations at regional scales. Also, distinct soil maps for hematite and goethite are required, given the high sensitivity of model SSA to their extreme optical properties.

V. Obiso↗

Integrated low carbon H 2 conversion with in situ carbon mineralization from aqueous biomass oxygenate precursors by tuning reactive multiphase chemical interactions

Meeting our rising demand for clean energy carriers such as H 2 from renewable biomass resources is challenged by the co-emission of CO 2 and CH 4 . To address this challenge, we design novel reactive separation pathways that integrate multiphase chemical reactions by harnessing Ca and Mg bearing minerals as a sorbent to capture CO 2 released during the hydrothermal deconstruction of aqueous biomass oxygenates to produce H 2 and solid carbonates via low temperature aqueous phase reforming and thermodynamically downhill carbon mineralization. Earth abundant catalysts such as Ni/Al 2 O 3 are effective in producing H 2 yields as high as 79% and 74% using ethylene glycol and methanol in the presence of Ca(OH) 2 as an alkaline sorbent, without contaminating or deactivating the catalyst. H 2 yields with in situ carbon mineralization using a Ni or Pt/Al 2 O 3 catalyst are enhanced based on the following order of reactivity: acetate < glycerol < methanol < formate < ethylene glycol. These studies demonstrate that the multiphase chemical interactions can be successfully tuned to enhance H 2 yields through the selective cleavage of C–C bonds using Ni/Al 2 O 3 catalysts to deconstruct biomass oxygenates for producing H 2 and CO 2 , and in situ carbon mineralization by harnessing abundant alkaline materials, as demonstrated using ladle slag. This approach unlocks new scientific possibilities for harnessing multiple emissions including abundant organic-rich wastewater streams and alkaline industrial residues to co-produce low carbon H 2 and carbonate-bearing materials for use in construction by using renewable solar thermal energy resources.

09 BIOMASS FUELS↗

Advanced one-pot deconstruction and valorization of lignocellulosic biomass into triacetic acid lactone using Rhodosporidium toruloides

Abstract Background Rhodosporidium toruloides is capable of co-utilization of complex carbon sources and robust growth from lignocellulosic hydrolysates. This oleaginous yeast is therefore an attractive host for heterologous production of valuable bioproducts at high titers from low-cost, deconstructed biomass in an economically and environmentally sustainable manner. Here we demonstrate this by engineering R. toruloides to produce the polyketide triacetic acid lactone (TAL) directly from unfiltered hydrolysate deconstructed from biomass with minimal unit process operations. Results Introduction of the 2-pyrone synthase gene into R. toruloides enabled the organism to produce 2.4 g/L TAL from simple media or 2.0 g/L from hydrolysate produced from sorghum biomass. Both of these titers are on par with titers from other better-studied microbial hosts after they had been heavily engineered. We next demonstrate that filtered hydrolysates produced from ensiled sorghum are superior to those derived from dried sorghum for TAL production, likely due to the substantial organic acids produced during ensiling. We also demonstrate that the organic acids found in ensiled biomass can be used for direct synthesis of ionic liquids within the biomass pretreatment process, enabling consolidation of unit operations of in-situ ionic liquid synthesis, pretreatment, saccharification, and fermentation into a one-pot, separations-free process. Finally, we demonstrate this consolidation in a 2 L bioreactor using unfiltered hydrolysate, producing 3.9 g/L TAL. Conclusion Many steps involved in deconstructing biomass into fermentable substrate can be combined into a distinct operation, and directly fed to cultures of engineered R. toruloides cultures for subsequent valorization into gram per liter titers of TAL in a cost-effective manner.

59 BASIC BIOLOGICAL SCIENCES↗

Cyanobacterial photosystem II reaction center design in tobacco chloroplasts increases biomass in low light

Abstract The D1 polypeptide of the photosystem II (PSII) reaction center complex contains domains that regulate primary photochemical yield and charge recombination rate. Many prokaryotic oxygenic phototrophs express two or more D1 isoforms differentially in response to environmental light needs, a capability absent in flowering plants and algae. We report that tobacco (Nicotiana tabacum) plants carrying the Synechococcus (Synechococcus elongatus PCC 7942) low-light mutation (LL-E130Q) in the D1 polypeptide (NtLL) acquire the cyanobacterial photochemical phenotype: faster photodamage in high light and significantly more charge separations in productive linear electron flow in low light. This flux increase produces 16.5% more (dry) biomass under continuous low-light illumination (100 μE m−2 s−1, 24 h). This gain is offset by the predicted lower photoprotection at high light. By contrast, the introduction of the Synechococcus high-light mutation (HL-A152S) into tobacco D1 (NtHL) has slightly increased photoprotection, achieved by photochemical quenching, but no apparent impact on biomass yield compared to wild type under the tested conditions. The universal design principle of all PSII reaction centers trades off energy conversion for photoprotection in different proportions across all phototrophs and provides a useful guidance for testing in crop plants. The observed biomass advantage under continuous low light can be transferred between evolutionarily isolated lineages to benefit growth under artificial lighting conditions. However, removal of the selective marker gene was essential to observe the growth phenotype, indicating growth penalty imposed by use of the particular spectinomycin-resistance gene.

Zhang, Yuan (ORCID:0000000291785207)↗

Multiphase Processing of the Water-Soluble and Insoluble Phases of Biomass Burning Organic Aerosol

Biomass burning is one of the most significant sources of organic aerosol in the atmosphere. Biomass burning organic aerosol (BBOA) has been observed to undergo liquid– liquid phase separation (LLPS) to give core–shell morphology with the hydrophobic phase encapsulating the hydrophilic phase, potentially impacting the evolution of light-absorbing components, i.e., brown carbon (BrC), through multiphase processes. Here, we demonstrate how multiphase processing differs between the watersoluble (i.e., hydrophilic) and insoluble (i.e., hydrophobic) phases of BBOA in terms of reactive uptake of ozone in a coated-wall flow tube. Effects of relative humidity (RH) and ultraviolet (UV) irradiation were investigated. Experimental timeseries were used to inform simulations using multilayer kinetic modeling. Among non-irradiated thin films, the uptake coefficient was greatest for the water-soluble phase at 75% RH (3 × 10 –5 , corresponding to a diffusion coefficient of BrC, D BrC , of 3 × 10 –9 cm 2 s –1 ) and least for the same phase at 0% RH (1 × 10 –5 , corresponding to D BrC of 1 × 10 –10 cm 2 s –1 ). The uptake coefficient for the water-insoluble phase fell between these two (about 1.5 × 10 –5 ), regardless of RH, and the corresponding D BrC increased only slightly (8 × 10 –10 cm 2 s –1 at 0% RH to 9 × 10 –10 cm 2 s –1 at 75% RH). The uptake coefficients of both phases at 0% RH decreased significantly after UV irradiation, consistent with a transition from viscous liquid to solid and supported by qualitative microscopy observations. Modeling multiphase ozone oxidation of primary BrC components in the atmosphere demonstrated, first, that LLPS may extend the lifetime of water-soluble BBOA encapsulated by water-insoluble species by a factor of 1.5 at moderate to high RH and, also, that UV irradiation may extend the lifetime of both phases by more than a factor of 2.5.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Summary Report of the Reactive CO 2 Capture: Process Integration for the New Carbon Economy Workshop

Decarbonization of our global economy is required to limit planetary warming to +1.5⁰C above pre-industrial levels, an ambitious goal set into motion by the Paris agreement. Given the scale and urgency, the solution demands international, cross-sector advancements spanning policy, social responsibility, and technology, with emphasis on step changes over incremental changes. To that end, technological revolutions that disrupt the status quo need to be envisioned and enacted. One potential technological revolution is the production of fuels, chemicals, and materials from carbon dioxide (CO 2 ) as the starting feedstock, leveraging renewable energy as the driving force. Over the past decades, significant research, development, and deployment has occurred on technologies for capturing CO 2 from point sources or the air and utilizing this CO 2 as a working fluid or as a chemical reactant; however, most of this work has been siloed in these two categories. Recently, an emerging field has started to explore the direct integration of CO 2 capture and conversion technologies as a means to reduce overall energy demand (i.e., avoid energy penalty of CO 2 desorption/regeneration of capture media) and capital expense through process intensification. This strategy represents an opportunity to leapfrog forward this technological revolution. However, the field is in its infancy and the technologies are at an early stage of development, thus it is critically important to define and assess the value proposition of this strategy relative to alternatives (e.g., separated capture and conversion technologies, fuels and chemicals derived from renewable feedstocks like biomass, and industrial electrification) to chart a path forward. To identify next steps, we organized a workshop titled “Reactive CO 2 Capture: Process Integration for the New Carbon Economy” which was held in Golden, Colorado, February 18–19, 2020. The focus of this workshop was to discuss approaches for merging CO 2 capture and CO 2 conversion/utilization systems into what we denoted as an integrated "reactive capture" strategy. By our definition, reactive capture of CO 2 is the coupled process of capturing CO 2 from a mixed gas stream and converting it into a valuable product without going through a purified CO 2 intermediate (see full definition in the Introduction section). This report seeks to summarize feedback from the approximately 125 participants and subject matter experts in attendance from academia, industry, U.S. Department of Energy (DOE), and DOE national laboratories. The workshop agenda is included in Appendix A and the full list of attendees can be found in Appendix B. To elucidate a path forward, we first asked the attendees to define what success would look like for reactive capture in the short term (0–5 years), midterm (5–10 years), and long term (10+ years) and then asked them to answer four questions related to how we could achieve that success: (1) What are the key barriers and challenges to success? (2) What are needed activities to overcome barriers and challenges? (3) What opportunities will arise from these activities? (4) What is a target outcome and what metrics need to be met?

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Hydrogen from Carbonaceous Waste Material - Hydrogen Fuel Cells Prize Phase 2 Voucher: Cooperative Research and Development (Final Report)

NLR conducted a conceptual design study for scaling up biomass conversion technology from Green Fortress Engineering (GFE). GFE has proprietary technology where cellulosic biomass is thermally converted to a tar-free syngas. A ceramic membrane separation unit (MSU) previously developed with NLR can extract high-purity hydrogen from the syngas. The energy content of the retentate stream is sufficient to power the process with a gas-powered genset. Design details including mass and energy balances, process and instrumentation diagrams (P&ID), and major equipment schedules were delivered.

08 HYDROGEN↗

Optical variability and pigment biomass in the Sargasso Sea as determined using deep-sea optical mooring data

A 9-month time series of optical data, composed of three separate deployments, from the Biowatt 1987 deep-sea mooring located in the oligotrophic waters of the Sargasso Sea at 32 deg N, 70 deg W, is presented. These data were analyzed using several biooptical models for the purpose of providing a continuous estimate of the spectral diffuse attenuation coefficient and pigment biomass. Results of the first 70-day deployment demonstrate the utility of optical observations as proxy measures of biological parameters, and facilitate a preliminary analysis of the temporal variations and a comparison of the present biooptical observations with concurrent physical observations. Biooptical properties exhibit variation in response to physical forcings, such as diel variations of incident solar irradiance, episodic wind forcing, advective mesoscale eddy layer depth, and succession of phytoplankton. The mooring data are discussed in the context of contemporaneous shipboard observations as well as in terms of future ocean satellite observations.

Smith, R. C.↗

Stepwise allomorphic transformations by alkaline and ethylenediamine treatments on bamboo crystalline cellulose for enhanced enzymatic digestibility

Efficient modification and decrystallization of cellulose Iβ in lignocellulosic biomass are potential ways to overcome biomass recalcitrance and facilitates enzymatic degradation. Herein, we have treated moso bamboo and microcrystalline cellulose separately by either alkali or ethylenediamine (EDA) treatments, as well as using both in succession. The pretreatments successfully transformed the initial cellulose Iβ allomorph into cellulose II, III I , and cellulose III II . Crystal structures and crystallinities were determined by Rietveld X-ray diffraction and CP/MAS 13 C NMR. Comparatively, the samples that were sequentially treated by EDA and NaOH had low crystallinity (~50%), larger d-spacings of ~4.4 Å for the hydrophobic (110) planes, and less condensed microfibrillar aggregation. The factors simultaneously contributed to as high enzymatic hydrolysis yield as 89.5% and 91.7% respectively, followed by the yields of mercerized cellulose II and cellulose III II allomorph. Here, the stepwise allomorphic transformations may provide new strategies on improving efficiency of saccharification process and biomass utilization.

59 BASIC BIOLOGICAL SCIENCES↗

LDRD Macromolcule Radiolysis Poster

Moving toward a circular carbon economy depends on enabling reuse of carbon-based macromolecules and increased recycling of waste products into higher value products. Macromolecules are challenging to valorize into products easily converted into liquid fuel or chemical feedstocks, due to their large and sometimes heterogeneous network of polymeric bonds. The novel aspect of this project is to show a proof of principle that radiolysis of macromolecules using “waste” radiation from energy production in the presence of radical capping donors presents an attractive opportunity to break down complex macromolecules into smaller molecules while controlling re-polymerization. This approach offers a new, cost-efficient way to utilize “waste” radiation and heat byproducts of nuclear energy production to convert a simple mixture of complex molecules into a complex mixture of small molecules, to be utilized as an energy source by the fuel industry, or to create value-added feedstocks for new polymers or commodity chemicals. Ionizing radiation can be harnessed to convert energy to molecules, adding value to low-value macromolecules as they are broken down into smaller, more easily separated feedstocks or fuels to be converted to a value-added product. This project will test 2 hypotheses. Hypothesis 1: Macromolecular materials that comprise biomass and coal or other macromolecules can be infused with radical capping donors (RCDs), and gamma irradiation of the resulting mixtures will produce ensembles of lower-molecular weight chemicals that can be more easily separated. If this expectation is realized, the conversion chemistry can be optimized by adjusting the feedstock composition, irradiation time, and choice of RCD.

02 - PETROLEUM↗

Catalytic Fast Pyrolysis for Chemicals: Cooperative Research and Development, CRADA Number CRD-16-00637 (Final Report)

The purpose of this partnership between the ExxonMobil Chemical Company and NREL is to advance the state of the art for converting biomass to liquid hydrocarbons using catalytic fast pyrolysis (CFP), with particular emphasis on directing and improving yields of such liquid hydrocarbons for uses in commodity chemical markets. CFP of biomass is a promising route for the production of renewable fuels and chemicals, and the key driver for economic viability is carbon yield to valuable products. The majority of prior CFP work has been targeted at fuel production, but this CRADA seeks to pursue routes to chemical co-products, thereby enhancing the overall economic viability of CFP. This project is beneficial to the public because it advances a technology that could one day provide renewable fuels and chemicals to our economy, thus improving the sustainability of our transportation and chemical manufacturing sectors.

09 BIOMASS FUELS↗