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119 records · Page 7

Challenges and Advances in Aqueous Processing of Corn Stover Pellets into High Concentration Slurries

Significant progress has occurred in developing combined enzyme hydrolysis and fermentation technologies for transforming lignocellulosic feedstocks into ethanol and other bioproducts. Various routes described in the literature show that low carbon footprint processes efficiently convert the cellulose and hemicellulose fractions of pretreated corn stover, wood chips, and sugarcane bagasse to sugars and to ethanol.Combinations of different pretreatments at high or low pH or in liquid hot water, followed by enzyme hydrolysis and fermentation or direct conversion of cellulose to ethanol (i.e., by consolidated bioprocessing)have been demonstrated. These successes have brought the need to preparing the feedstock – before it enters the biorefinery – into focus. This paper summarizes recent developments in liquefying corn stover,before pretreatment, so that slurries with yield stresses below 200 Pa are obtained and a “pumpable” corn stover slurry results at initial solids loadings of up to 300 g/L. The manner in which corn stover pellets are combined with water and enzyme in an agitated bioreactor is described, and properties that define slurry behavior are presented. Implications on biorefinery operations are explained in terms of particle properties and the preprocessing of corn stover as well as the team approach used to obtain these results.

Wassgren, Carl↗

Composition-Preserving Extraction and Characterization of Biomass Extrinsic and Intrinsic Inorganic Compounds

The inorganic content of biomass impairs size reduction tool life and the conversion process. Conventional ash extraction relies on furnace combustion that inevitably alters the inorganic compounds due to oxidation and decomposition. This study developed composition-preserving methods for extracting and analyzing extrinsic and intrinsic inorganic compounds. Comprehensive characterization was carried out on selected biomass feedstocks, including corn stover, pine residue, and pine anatomical fractions, to reveal their inorganic species and morphology. The extrinsic inorganic compounds were found to be dominated by quartz, along with other minor minerals, such as albite, microcline, and gehlenite, and have particle sizes ranging from tens to hundreds of micrometers. Among the pine anatomical fractions, the needles contain the highest intrinsic silicon content while the bark trapped the most extrinsic minerals. By correlation of the total ash and extrinsic inorganic contents to the wear behavior, both the extrinsic and intrinsic inorganic compounds were concluded to have made significant contributions to the wear process. Finally, the results here validated a new approach to characterize inorganic compounds in biomass and provided fundamental insights for their potential impact on preprocessing tool wear.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accuracy of genomic prediction in switchgrass ( Panicum virgatum L.) improved by accounting for linkage disequilibrium

Switchgrass is a relatively high-yielding and environmentally sustainable biomass crop, but further genetic gains in biomass yield must be achieved to make it an economically viable bioenergy feedstock. Genomic selection (GS) is an attractive technology to generate rapid genetic gains in switchgrass, and meet the goals of a substantial displacement of petroleum use with biofuels in the near future. In this study, we empirically assessed prediction procedures for genomic selection in two different populations, consisting of 137 and 110 half-sib families of switchgrass, tested in two locations in the United States for three agronomic traits: dry matter yield, plant height, and heading date. Marker data were produced for the families’ parents by exome capture sequencing, generating up to 141,030 polymorphic markers with available genomic-location and annotation information. We evaluated prediction procedures that varied not only by learning schemes and prediction models, but also by the way the data were preprocessed to account for redundancy in marker information. More complex genomic prediction procedures were generally not significantly more accurate than the simplest procedure, likely due to limited population sizes. Nevertheless, a highly significant gain in prediction accuracy was achieved by transforming the marker data through a marker correlation matrix. Our results suggest that marker-data transformations and, more generally, the account of linkage disequilibrium among markers, offer valuable opportunities for improving prediction procedures in GS. Furthermore, some of the achieved prediction accuracies should motivate implementation of GS in switchgrass breeding programs.

59 BASIC BIOLOGICAL SCIENCES↗

Chapter 4: "Waste"-to-Energy for Decarbonization - Transforming Nut Shells Into Carbon-Negative Electricity

This chapter presents a study demonstrating waste pistachio nut shells as a renewable feedstock for climate-friendly electricity generation via industrial gasification technology. The study includes biomass feedstock characterization (i.e., pistachio waste critical material attributes), process variability (i.e., bulk material handling), and overall operational reliability and conversion performance through extended testing. Additionally, techno-economic analysis (TEA) and life cycle assessment (LCA) were performed to assess the economic feasibility and environmental impact of the technology to transform agricultural waste to biopower. For processing pistachio waste material, among critical material attributes, fines content in the biomass (<1/4") had the largest potential to reduce the operating time of the gasifiers due to plugging. Pelletizing fines and co-feeding them with the mixed pistachio waste increased the average feed density, feed rate, and biochar production. Compared to pine wood chips, mixed pistachio waste yielded higher biochar quantity but slightly reduced quality. In general, a systematic Quality by Design methodology is the preferred approach for designing preprocessing and material conveyance systems, where a downstream technology (end user) for the produced intermediate is specified at the outset. TEA results show that the biochar production rate and selling price had an overwhelming impact on the modeled Minimum Electricity Selling Price (MESP), which ranged from 35.5 to 39.9 cents/kWh for the cases studied (16 h/day operational basis). Moreover, LCA results show that the valorization of pistachio shells for biopower generation is a "carbon negative" process that can help decarbonize the U.S. electricity grid. The specific carbon intensity was -0.29 to -0.71 kg CO2e/kWh, compared to 0.45 kg CO2e/kWh for the average U.S. electricity mix. Biochar production from pistachio waste as a potential means for carbon sequestration was a significant driver for the LCA. The highly stable biochar permanently sequesters a considerable fraction of biochar carbon in the ground, more than enough to offset the life cycle emissions, and can be a complementary climate change mitigation strategy.

bio-char↗

Enhancing the flowability of woody biomass slurries in wet biorefineries

Feeding wet lignocellulosic biomass (e.g., softwood and hardwood) slurries into high-pressure, high-temperature reactors at an industrially relevant scale presents significant challenges, such as process equipment plugging. Here, in this study, we investigate the possibility of improving the flowability of biomass slurries in an industrial scale wet biorefinery by tuning the physical and chemical characteristics of the biomass particles. To understand the effects of the chemical characteristics of woody biomass on flowability, cellulose pulp particles are produced from pulp sheets via knife milling, pelletizing, and crumbling. These cellulose pulp particles are processed for acid hydrolysis dehydration (AHDH) at one –tonne-per day pilot scale. The levulinic acid yield (a product of cellulose AHDH) and the flowability of the biomass particles are compared using market pulp, 1 mm crumbled pine softwood, a blend of 2 mm hammer-milled pine softwood with 10 wt.% bark, and 2 mm hammer-milled hardwood material with 10 wt.% bark (to represent forest residues). The results indicate that the presence of hemicellulose and lignin influences the flowability of lignocellulosic feedstocks. Crumbled wood particles show poor flowability at the pilot scale, while the presence of fine materials (less than 0.7 mm) and bark improves the flowability of biomass slurries without affecting the organic acid yields (based on C6 carbohydrate content).

09 - BIOMASS FUELS↗

Evaluation of Agricultural Equipment Manufacturing for a Bio-Based Economy

This report provides the analysis results of agricultural and preprocessing equipment and manufacturing requirements to support the mobilization of the Billion Ton projections utilizing the conventional supply chain logistics. This report discusses the number of required agricultural machinery and their market values, the drivers and barriers of the transition in agricultural equipment, the potential economic impacts to the US associated with expansion of these equipment manufacturing and the factors that impact the transition in agricultural machinery to support the growth of a large-scale biofuel and bio-products industry in short and long terms. Short and long terms refer to the early development and mature development phases of the cellulosic biofuels industry in the United States.

09 BIOMASS FUELS↗

Performance assessment of dilute-acid leaching to improve corn stover quality for thermochemical conversion

Lignocellulosic biomass is a sustainable energy source that can help meet the increasing demand for biofuels in the United States. However, the quality and availability of such feedstocks greatly affects their suitability for downstream conversion. This work reports the effects of dilute-acid leaching at various solid loadings, temperatures and acid loadings on the quality of a traditional biochemical feedstock, corn stover, as a potential feedstock for thermochemical conversions. At 5 wt% solids, dilute-acid leaching was observed to effectively remove 97.3% of the alkali metals and alkaline earth metals that can negatively affect degradation pathways during pyrolysis and result in greater yield of non-condensable gases. In addition, up to 98.4% of the chlorine and 88.8% of the phosphorus, which can cause equipment corrosion and foul upgrading catalysts, respectively, were removed. At 25°C in the absence of acid, only 6.8% of the alkali metals and alkaline earth metals were removed; however 88.0% of chloride was still removed. The ratio of alkaline/acidic ash species has been suggested to proportionately relate to slagging in biopower applications. The initial alkali/acid ratio of the ash species present in the untreated corn stover was 0.38 (significant slagging risk). At 5 wt% solids, this ratio was decreased to 0.18 (moderate slagging risk) at 0 wt% acid and 90°C, and was decreased to 0.07, 0.08 and 0.06 at 0.5 wt% acid at 25°C, 50°C and 90°C, respectively (little or no slagging risk). Increasing the acid loading to 1.0% only slightly decreased the measured alkali/acid ratio of remaining ash species. Lastly, the results presented here show that a water wash or dilute-acid preprocessing step can improve corn stover quality for pyrolysis, hydrothermal liquefaction and biopower.

09 BIOMASS FUELS↗

Interparticle Characterization of Mechanical Biomass Particle-Particle and Particle-Wall Interactions

The biomass materials industry faces significant challenges in managing material variability and its impact on storage and handling systems. Physical properties such as moisture content, particle size, and density fluctuate considerably, leading to operational issues like bridging and ratholing that disrupt material flow. These variations create a complex cascade effect throughout the process chain, affecting transportation, storage, and conversion processes. The economic consequences of this variability manifest in increased operational costs, maintenance requirements, and system downtime. Environmental factors further complicate the situation, as weather conditions and seasonal availability influence material properties and system performance. Engineers employ specialized equipment design, material characterization protocols, and pre-processing steps like size reduction and homogenization to address these challenges. A critical knowledge gap exists between continuous-level constitutive models and particle-scale behavior. This project developed a novel device to quantify interparticle mechanics between biomass particles, measuring friction and adhesion forces between particles and wall materials. The research focused on corn stover and southern pine forest residue, creating a comprehensive database of particle interactions. This breakthrough enables direct application in particle-based computational modeling, advancing the field's understanding of biomass handling characteristics and supporting the development of more reliable and efficient storage and handling systems. The project's outcomes contribute significantly to understanding biomass's mechanical and flow characteristics, particularly how variability at the particle level affects larger-scale handling operations. This knowledge is crucial for engineering feedstock supply systems that consistently meet quality and cost specifications for various conversion processes. The innovative experimental setup developed through this research represents a significant advancement in biomass characterization methodology. Providing precise measurements of particle-level interactions establishes a foundation for more accurate predictive modeling of bulk material behavior. This enhanced understanding of fundamental particle mechanics enables engineers to anticipate better and address handling challenges before they manifest in full-scale operations. This research opens new avenues for optimizing biomass handling systems through data-driven design approaches. The comprehensive database of particle interactions serves as a valuable resource for future research and development efforts, potentially leading to more efficient and cost-effective biomass processing solutions. This advancement in particle-level mechanics could revolutionize how biomass handling systems are designed and operated, contributing to more sustainable and reliable renewable energy production.

09 BIOMASS FUELS↗

The effects of physical and chemical preprocessing on the flowability of corn stover

Continuous and reliable feeding of biomass is essential for successful biofuel production. However, the challenges associated with biomass solids handling are commonly overlooked. In this study, we examine the effects of preprocessing (particle size reduction, moisture content, chemical additives, etc.) on the flow properties of corn stover. Compressibility, flow properties (interparticle friction, cohesion, unconfined yield stress, etc.), and wall friction were examined for five corn stover samples: ground, milled (dry and wet), acid impregnated, and deacetylated. The ground corn stover was found to be the least compressible and most flowable material. The water and acid impregnated stovers had similar compressibilities. Yet, the wet corn stover was less flowable than the acid impregnated sample, which displayed a flow index equivalent to the dry, milled corn stover. The deacetylated stover, on the other hand, was the most compressible and least flowable examined material. However, all of the tested stover samples had internal friction angles >30°, which could present additional feeding and handling challenges. All of the ''wetted'' materials (water, acid, and deacetylated) displayed reduced flowabilities (excluding the acid impregnated sample), and enhanced compressibilities and wall friction angles, indicating the potential for added handling issues; which was corroborated via theoretical hopper design calculations. All of the ''wetted'' corn stovers require larger theoretical hopper outlet diameters and steeper hopper walls than the examined ''dry'' stovers.

09 BIOMASS FUELS↗

An experiment-informed discrete element modelling study of knife milling for flexural biomass feedstocks

A discrete element method (DEM) based approach is used to study the relationships between material attributes (MAs), processing parameters (PPs), and quality attributes (QAs) for the knife milling of maize stalks. An approximate DEM shape model was conceptualized based on real maize stalks and calibrated based on experimental bending test data for flexural properties (elastic bending stiffness, elastic bending angle limit, elastoplastic ratio, etc.). DEM simulations of maize stalk comminution in a Jordan Reduction Solutions (“JRS”) knife mill were performed to investigate the relationships between the MAs (maize stalk size and breakage stress limit), PPs (impeller rotational speed), and QAs (mass throughput and output particle size distribution (PSD)). The DEM results suggest that stalk length has little influence on mass throughput and PSD, whilst stalks with larger cross sections tend to generate larger sizes of milled particles given the same breakage stress limit. Both the DEM and experimental results show that faster impeller rotation (or higher power) does not necessarily generate higher throughput or smaller output PSD, especially for maize stalks of higher breakage stress limit. The correlations between these MAs, PPs and QAs are found highly stochastic, though breakage stress limit dictates mass throughput, regardless of stalk size. The DEM-predicted output particle size tended to match the experimental data with coarse PSDs based on sieve size but showed weakened fidelity with finer material, indicating the potential for further model improvement.

09 BIOMASS FUELS↗

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗