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At least 37 records · Page 2

Modelling the ejection of primary aerosols during the fast pyrolysis of biomass anisotropic particles

A model for the fast pyrolysis of anisotropic biomass particles is presented which considers bubbling dynamics within the liquid intermediate phase (metaplast) and aerosol ejection from this phase. The model employs the population balance equation and the method of moments to estimate the production rate and resultant size distribution of aerosol ejections, incorporating a detailed CRECK reaction mechanism, and considers the effect of anisotropic biomass microstructure on the intraparticle transport of mass and energy. Here, this study investigates the impact of particle size, heating rate (heat transfer coefficient), and lignocellulosic composition on aerosol ejection. The model predicts that, at high heating rates (convective heat transfer coefficient of 359 W/m 2 .K), aerosols can contribute over 20% to the heavy fraction yield in bio-oil for small particles (1 mm diameter, 4 mm length). The model can predict aerosol size distribution and surface area, indicating an average size of 20 μm for bubbles and 5 μm for aerosols during increased bubble production and aerosol ejection rates. These findings are consistent with prior experimental results and provide essential information for future modeling of extra-particle reactions of the aerosols as they progress through the reactor.

09 BIOMASS FUELS↗

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

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

09 BIOMASS FUELS↗

Recovery of value-added compounds through fast pyrolysis of apple pomace hydrochar

The environmental challenges associated with food production can be addressed via the thermochemical upcycling of agro-industrial biomass. Two such methods, hydrothermal carbonization (HTC) and pyrolysis, can be coupled to first reduce the water content of wet biomass wastes by producing a hydrochar (HC) via HTC and then a bio-oil via pyrolysis of the HC. However, HTC of biomass results in the formation of secondary char (SC), an amorphous tar-like mixture resulting from organic compounds released into the aqueous phase that adsorb, recondense and polymerize on the parent biomass. This study investigated how HTC temperature impacts the formation of SC from apple pomace and the SC’s subsequent impact on fast pyrolysis products. HCs were produced at temperatures of 175°C, 200°C, and 250°C. Lower HTC temperatures favor the formation of biorefinery platform chemicals such as 5-hydroxymethylfurfural and levulinic acid, while higher temperatures result in increased lignin degradation products (i.e., phenolics). HCs were subjected to fast pyrolysis before and after SC extraction in two analytical pyrolysis instruments. Fast pyrolysis of HC produced compounds similar to those found in SC, but with variations in CO and CO 2 emissions. In conclusion, the combination of SC extraction and fast pyrolysis demonstrates promise for recovering value-added compounds from agro-industrial waste biomass while retaining a solid char for fuel and carbon management.

09 BIOMASS FUELS↗

Electrocatalytic oxidation of hydrothermal liquefaction-derived aqueous phase for on-site wastewater treatment and H 2 production

Electrocatalytic oxidation (ECO) is a promising method for generating molecular hydrogen (H 2 ) while simultaneously treating the aqueous phase (AP) from hydrothermal liquefaction (HTL) of biomass-derived feedstocks such as algae, food waste, sludge, and wood. This study highlights the impact of HTL-AP composition on ECO performance, mainly activity, stability, and efficiency in a batch and flow electrolyzer. We demonstrated current efficiency (CE) for chemical oxygen demand (COD) removal ranges from 14% to 85% in the flow electrolyzer with electrode stability increasing from 20 to ≥2,800 h. Decreasing the applied potential enhances the CE. High ammonium content can accelerate deactivation, yet chloride ions appear to aid oxidation of organic compounds and enhanced anode stability. A preliminary energy and H 2 balance for an HTL sewage sludge plant shows that the HTL-AP contains sufficient COD to produce all the H 2 needs for bio-oil hydrotreating, with a 26% surplus available for other uses.

Electrolysis↗

Nonenergy Biomass Carbon Removal and Storage (BiCRS): Assessing Durability of Nongaseous Carbon Products Across Terrestrial Storage Fates

Biomass Carbon Removal and Storage, or BiCRS, pathways use plants or algae that remove carbon dioxide from the atmosphere through photosynthesis and store it underground or in long-lived products. While some BiCRS approaches generate an energy product, all BiCRS approaches generate a carbon product. A new subset of BiCRS approaches focus on the storage of these raw or converted carbon products for generation of carbon credits. However, the durability of these approaches is highly variable as carbon products vary widely in their “form” and the conditions of their “fate.” We organize our thinking about carbon products and their durability around these two primary axes. The durability of carbon product “forms” is mediated by chemical recalcitrance and ranges substantially across agricultural residues, municipal solid waste, woody biomass, and nongaseous products of thermochemical conversion (e.g., biochars and bio-oils). Meanwhile, terrestrial storage “fates” vary in the mechanism employed to stall decay, including surface storage, dry storage, shallow anoxic storage, and deep or geologic anoxic storage (or injection). Each mechanism has different implications for suitability with different feedstock forms as well as long-term risks. We present a framework for assessing durability of solid or liquid raw and conversion carbon products under terrestrial storage fates, highlighting knowns, unknowns, and research priorities moving forward.

09 BIOMASS FUELS↗

Establishing the Role of Metal, Interface, and Vacancy Sites in Pt/TiO 2 -Catalyzed Acetic Acid Hydrodeoxygenation

Catalytic hydrodeoxygenation (HDO) following catalytic fast pyrolysis (CFP) offers an approach to convert the vapor-phase product of biomass pyrolysis to a stable bio-oil product by reducing the oxygen content. Fundamental insights into the HDO of carboxylic acids, which are a corrosive and acidic CFP product, on promising catalyst materials, such as Pt/TiO 2 , are needed to inform the design of multifunctional HDO catalysts with improved carbon efficiency. In this contribution, density functional theory (DFT) calculations were used to assess the role of Pt-metal and Pt-TiO 2 -interface sites on acetic acid HDO (AA-HDO), and to determine the effect of interfacial oxygen vacancies at the Pt-TiO 2 interface, by calculating the reaction energetics for key AA-HDO surface intermediates and elementary steps on each site type. Pt-metal sites, modeled via Pt(111), preferred to form undesired decarboxylation products (CH 4 and CO 2 ), whereas Pt-TiO 2 -interface sites, modeled via an anatase-supported Pt nanowire, favored the formation of desired deoxygenation products (acetaldehyde and ethane). Interfacial-vacancy sites lowered the activation energy barrier for the first C-O bond-scission step in AA-HDO, predicted to be the rate-limiting step for AA-HDO at the Pt-TiO 2 interface in the absence of a vacancy. These atomistic insights reveal the importance of metal-metal oxide interface sites in AA-HDO selectivity and can be used to inform the rational design of improved HDO catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cycloalkane-rich sustainable aviation fuel production via hydrotreating lignocellulosic biomass-derived catalytic fast pyrolysis oils

Sustainable aviation fuel (SAF) produced from lignocellulosic biomass is emerging as an ideal alternative to conventional jet fuel for aviation sector decarbonization. Catalytic fast pyrolysis (CFP) can convert lignocellulosic biomass into relatively stable bio-oil that can be selectively transformed to various transportation fuels through hydroprocessing under conditions of different severities. In this contribution, two CFP oils produced from pine-based feedstocks over different types of catalysts (i.e., ZSM-5 and Pt/TiO 2 catalysts) were hydrotreated at 125 bar in a non-isothermal process with a maximum temperature of 385 °C over a sulfided NiMo/Al 2 O 3 catalyst to produce SAF with high cycloalkane concentrations of 89–92 wt%. Cycloalkanes are an important component of jet fuel with advantageous fuel properties, such as high energy density, low sooting, and potential for replacing aromatic hydrocarbons to provide good seal swelling properties. The hydrotreating process successfully converted 91–92% of the biogenic carbon in the CFP oil intermediates to liquid-phase hydrotreated products. Through distillation, 39–40 wt% of the hydrotreated oils were collected in the jet-fuel range as SAF fractions. The rest of the hydrotreated product could be valorized as fuels (e.g., diesel) or chemicals. The SAF fractions with oxygen contents below the detection limit (<0.01 wt%) met ASTM D7566 finished fuel blend and D4054 Tier 1 specifications with respect to density, lower heating value (LHV), volatility, flash point, and freeze point. These results indicate hydrotreating lignocellulosic biomass-derived CFP oil as a promising pathway to produce high-quality SAF rich in cycloalkanes. Continued research is required to increase the SAF yield by process improvements, such as increased CFP oil yields, and an enhanced production of SAF-range molecules via e.g., cracking of high-molecular weight compounds either during CFP or hydrotreating, as well as evaluation of a broader range of jet fuel properties and performance requirements.

09 BIOMASS FUELS↗

Introducing bioderived solvents for safer and more sustainable 19 F benchtop NMR analysis of pyrolysis oils

The development of increasingly sustainable analytical chemistry techniques is a growing area of research. Detailed knowledge of bio-oil composition is crucial for the wider use of this alternative, sustainable fuel product, whether by guiding and optimising the pyrolysis processes or for indicating appropriate upgrading methods. The oxygen-containing species in the oil are most important to analyse as they are key to the long-term stability and further processing of the oil. A common analytical method is derivatisation, inserting 19 F nuclei only into specific compounds in the sample, so that a sparser NMR spectrum of a subset of the compounds present can be acquired with even a benchtop NMR spectrometer. However, the derivatisation reactions themselves are not benign, with the most commonly used method relying on DMF throughout. While DMF is highly effective in facilitating the derivatisation reaction, it is not only harmful but increasingly restricted in use. By substituting DMF with ethyl lactate, the reaction is rendered safer and more sustainable. The change in solvent does not affect the NMR results, with estimates of total carbonyl content comparable with those produced by titration. The spectra acquired are detailed enough to also allow the quantification of the different carbonyl functional groups present. By switching to ethyl lactate, it is possible to increase the amount of water in the solvent mixture, further reducing the environmental impact, user risks and cost of the analytical method. By replacing harmful solvents with greener alternatives, benchtop NMR analyses of pyrolysis oils are increasingly safer to run, increasingly cheaper to run, and increasingly more accessible to a wide range of different users.

Tang, Bridget [Aston University, Birmingham (Unite↗

Uncertainty in determining carbon dioxide removal potential of biochar

A quantitative and systematic assessment of uncertainty in life-cycle assessment is critical to informing sustainable development of carbon dioxide removal (CDR) technologies. Biochar is the most commonly sold form of CDR to date and it can be used in applications ranging from concrete to agricultural soil amendments. Previous analyses of biochar rely on modeled or estimated life-cycle data and suggest a cradle-to-gate range of 0.20–1.3 kg CO 2 net removal per kg of biomass feedstock, with the range reported driven by differences in energy consumption, pyrolysis temperature, and feedstock sourcing. Herein, we quantify the distribution of CDR possible for biochar production with a compositional life-cycle inventory model paired with scenario-aware Monte Carlo simulation in a 'best practice' (incorporating lower transportation distances, high pyrolysis temperatures, high energy efficiency, recapture of energy for drying and pyrolysis energy requirements, and co-generation of heat and electricity) and 'poor practice' (higher transportation distances, lower pyrolysis temperatures, low energy efficiency, natural gas for energy requirements, and no energy recovery) scenarios. In the best-practice scenario, cradle-to-gate CDR (which is representative of the upper limit of removal across the entire life cycle) is highly certain, with a median removal of 1.4 kg of CO 2 e/kg biomass and results in net removal across the entire distribution. In contrast, the poor-practice scenario results in median net emissions of 0.090 kg CO 2 e/kg biomass. Whether this scenario emits (66% likelihood) or removes (34% likelihood) carbon dioxide is highly uncertain. The emission intensity of energy inputs to the pyrolysis process and whether the bio-oil co-product is used as a chemical feedstock or combusted are critical factors impacting the net carbon dioxide emissions of biochar production, together responsible for 98% of the difference between the best- and poor-practice scenarios.

54 ENVIRONMENTAL SCIENCES↗

Pilot-Scale Algal Oil Production

The main objective of the project is complete: development of a preliminary planning and design for a pilot-scale algal oil cultivation and processing facility, FEL-3 design with -5% / +15% cost estimate accuracy, and conversion of the algal oil to biofuel in an off-site existing bio-oil refinery. The design basis includes 10 tons per day of dried algae cultivated with CO 2 supplied by direct air capture, electricity supplied solar power, well water supply, zero liquid discharge, off-site extraction, and off-site conversion of oil to biofuel. The design and permitting package is an important milestone in the path to commercialization of algal biofuels and bioproducts as it provides the preliminary design, permitting path, long-term land lease, planning documents, and team needed for success in future engineering, construction, start-up and operations of a pilot-scale farm at a site in Paso Robles, CA. Outcomes of the business assessment include (i) identification of a product spectrum for economical algal biofuels using co-products with markets that are commensurate with production of 6-7 billion gallons per year of sustainable aviation fuel (SAF), renewable diesel, and renewable gasoline, (ii) a path toward near-term contribution of algae oil to SAF, and (iii) an approach for long-term operation of a pilot-scale farm.

09 BIOMASS FUELS↗

A Comprehensive Greenhouse Gas Assessment of Biomass-Based Carbon Dioxide Removal and Storage

Biomass-based Carbon Removal and Storage (BiCRS) is a suite of technological pathways that provide a relatively affordable and high-potential way to remove carbon dioxide from the atmosphere and simultaneously re-purpose residual biomass. BiCRS technologies are individually optimized to different biomass feedstocks, temperatures and oxygen, with the primary goal of capturing a high percentage of biomass-derived carbon dioxide and storing it in permanent below-ground storage (i.e. geologic storage), and a secondary goal of producing renewable energy. The current standard for BiCRS life cycle assessments does not account for greenhouse gas (carbon dioxide, methane and nitrous oxide) fluxes from surface soil amendment of BiCRS byproducts (e.g. char, ash) and their alternate fates. This is partly due to a paucity of empirical data due to the novelty of BiCRS conversion technologies, the range in feedstocks, and the heterogeneity of soils to which they might be amended. To fill this gap in in the life-cycle assessment and provide a realistic range of parameters for a soil amendment component of the BiCRS life cycle assessment, we conducted an incubation experiment to measure soil carbon changes, microbial respiration, methane fluxes, and nitrous oxide fluxes from two different soils amended with char- and ash- byproducts from biomass after gasification to hydrogen, fast pyrolysis to bio-oil, and torrefaction. Our results suggest that nitrous oxide and methane emission or consumption from BiCRS char amendments to soil are context dependent. Nitrous oxide emissions from amendments are higher in soils with higher pH, whereas some char amendments to low pH soil can reduce N 2 O emissions relative to control. In contrast, methane is emitted from BiCRS char amended to low pH soil, but consumed or neutral relative to control when amended to high pH soil. We present carbon and nitrogen mass balance throughout the experiment to help understand short-term durability of BiCRS chars and their counterfactuals, and preliminary suggestions for revisions to the broader BiCRS Measurement, Reporting, and Verification framework.

54 ENVIRONMENTAL SCIENCES↗

Development of Biofuel and Bioenergy Processes for Photosynthetic CO 2 Assimilation (CRADA Final Report)

In order to fully exploit algae carbon assimilation for fuels, a preqrequisite is high photosynthetic efficiency and carbon conversion to fuel precursors. In the context of this collaborative project between NLR and EMRE we aim to address aspects of both the biological constraints around photosynthesis-driven carbon assimilation flux as well as elements that bridge the gap between laboratory cultivation and meaningful outdoor deployment, building on the unique capabilities of NLR and EMRE’s algae bioengineering teams. The goal of this work is to improve our understanding of key cellular biochemistry, mass cultivation, and biomass conversion constraints that presently limit the potential bio-oil yield. The proposed first phase of this work will focus on biomass growth improvements by testing hypotheses for alleviating identified metabolic and photophysiological bottlenecks. The results of this work could inform decisions by stakeholders (e.g., industry, community, investors) on the design and deployment of a sustainable biofuel supply chain from algae.

09 BIOMASS FUELS↗

A Comprehensive Greenhouse Gas Assessment of Biomass-Based Carbon Dioxide Removal and Storage

Biomass with Carbon Removal and Sequestration (BiCRS) is a suite of technological pathways that provide a relatively affordable and high-potential way to remove carbon dioxide from the atmosphere and simultaneously re-purpose residual biomass. BiCRS technologies are individually optimized to different biomass feedstocks, temperatures and oxygen, with the goal of capturing a high percentage of biomass-derived carbon dioxide and storing it in permanent below-ground storage (i.e. geologic storage). The current standard for BiCRS life cycle assessments does not account for carbon dioxide, methane and nitrous oxide (CO 2 , CH 4 , and N 2 O) fluxes from surface soil amendment of BiCRS byproducts (e.g. char, ash) and their alternate fates. This is partly due to a paucity of empirical data due to the novelty of BiCRS conversion technologies, the range in feedstocks, and the heterogeneity of soils to which they might be amended. To fill this gap in in the life-cycle assessment (LCA) and provide a realistic range of parameters for a soil amendment component of the BiCRS LCA, we conducted an incubation experiment to measure soil carbon changes, microbial respiration, methane fluxes, and nitrous oxide fluxes from two different soils amended with char- and ash- byproducts from biomass after gasification to hydrogen, fast pyrolysis to bio-oil, and torrefaction.

54 ENVIRONMENTAL SCIENCES↗

Feasibility of using nuclear microreactor process heat for bioconversion and agricultural processes

Introduction There is a global goal to reduce greenhouse gas emissions by 43% by 2023. Nuclear microreactors, a subset of small modular reactors, offer a potential solution due to their compact size, transportability, and carbon-neutral power generation capabilities. Methods This study explores the feasibility of using heat from nuclear microreactors for bioconversion and agricultural processes, including transforming biomass into energy carriers and products such as syngas, bio-oil, and pasteurized milk. Operating requirements for gasification, pyrolysis, hydrothermal carbonization, hydrothermal liquefaction, hydrothermal gasification, ethanol production, anaerobic digestion, and pasteurization were obtained through a literature review. A Brayton cycle model based on the eVinci TM microreactor was developed to assess the feasibility of powering these processes using nuclear microreactor heat. Results and Discussion Exergetic efficiency values for high-temperature processes ranged from 72% to 100%, whereas lower-temperature processes ranged from 2% to 53%. These efficiencies depend on the available source temperature for each microreactor design. There were trade-offs between producing net power and using process heat, particularly for high-temperature processes. Three heat exchanger locations were considered: before the turbine (600 ℃ ), between the turbine and regenerator (370 ℃ ), and after the regenerator (192 ℃ ). High-temperature processes like gasification require temperatures too high for feasibility. Middle temperature processes are better suited to a heat exchanger between the turbine and regenerator, while also operable before the turbine. Lower-temperature processes like pasteurization and anaerobic digestion can use waste heat after the regenerator and do not impact power production. These findings are valuable for optimizing nuclear microreactor heat use and aligning with global climate initiatives.

09 BIOMASS FUELS↗

Synthetic and Biomass Alternate Fueling in Aviation

While transportation fueling can accommodate a broad range of alternate fuels, aviation fueling needs are specific, such as the fuel not freezing at altitude or become too viscous to flow properly or of low bulk energy density that shortens range. The fuel must also be compatible with legacy aircraft, some of which are more than 50 years old. Worldwide, the aviation industry alone uses some 85-95 billion gallons of hydrocarbon-based fossil fuel each year, which is about 10% of the transportation industry. US civil aviation alone consumes nearly 14 billion gallons. The enormity of the problem becomes overwhelming, and the aviation industry is taking alternate fueling issues very seriously. Biofuels (algae, cyanobacteria, halophytes, weeds that use wastelands, wastewater and seatwater), when properly sourced, have the capacity to be drop-in fuel replacements for petroleum fuels. As such, biojet from such sources solves the aviation CO2 emissions issue without the downsides of 'conventional' biofuels, such as competing with food and fresh water resources. Of the many current fundamental problems, the major biofuel problem is cost. Both research and development and creative engineering are required to reduce these biofuels costs. Research is also ongoing in several 'improvement' areas including refining/processing and biologics with greater disease resistance, greater bio-oil productivity, reduced water/nutrient requirements, etc. The authors' current research is aimed at aiding industry efforts in several areas. They are considering different modeling approaches, growth media and refining approaches, different biologic feedstocks, methods of sequestering carbon in the processes, fuel certification for aviation use and, overall, ensuring that biofuels are feasible from all aspects - operability, capacity, carbon cycle and financial. The authors are also providing common discussion grounds/opportunities for the various parties, disciplines and concerned organization to share both issues and potential ways for moving forward, and overall, trying to educate those concerned about the innate limitations of 'conventional' biofuels and the solutions provided by non-traditional feedstocks that used waste lands/water or saline/salt water have an immense capacity potential.

Hendricks, R. C.↗

Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified .. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and c~bon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes. Issues such as carbon sequestration and subsequent carbon balance of the closed system and identifying ideal process methods to achieve the highest quality products, whilst being energy friendly, will also be addressed.

McCoy, LaShelle E.↗

A Review: Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing. and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and carbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes.

McCoy, LaShelle E.↗