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At least 541 records · Page 30

Systems Based Approaches for Thermochemical Conversion of Biomass to Bioenergy and Bioproducts

Auburn’s Center for Bioenergy and Bioproducts conducts research on production of synthesis gas for use in power generation and the production of liquid fuels. The overall goal of our gasification research is to identify optimal processes for producing clean syngas to use in production of fuels and chemicals from underutilized agricultural and forest biomass feedstocks. This project focused on construction and commissioning of a bubbling-bed fluidized-bed gasifier and subsequent shakedown of the gasification and gas cleanup system. The result of this project is a fully commissioned gasification laboratory that is conducting testing on agricultural and forest biomass. Initial tests on forest biomass have served as the foundation for follow-up studies on gasification under a more extensive range of temperatures, pressures, and oxidant conditions. The laboratory gasification system consists of a biomass storage tank capable of holding up to 6 tons of biomass; a biomass feeding system, with loss-in-weight metering system, capable of feeding biomass at pressures up to 650 psig; a bubbling-bed fluidized-bed gasification reactor capable of operating at pressures up to 650 psig and temperatures of 1500oF with biomass flowrates of 80 lb/hr and syngas production rates of 37 scfm; a warm-gas filtration system; fixed bed reactors for gas conditioning; and a final quench cooling system and activated carbon filtration system for gas conditioning prior to routing to Fischer-Tropsch reactors, or storage, or venting. This completed laboratory enables research to help develop economically feasible technologies for production of biomass-derived synthesis gases that will be used for clean, renewable power generation and for production of liquid transportation fuels. Moreover, this research program provides the infrastructure to educate the next generation of engineers and scientists needed to implement these technologies.

09 BIOMASS FUELS↗

Thermochemical Interactions Between Yttria-Stabilized Zirconia and Molten Lunar Regolith Simulants

Oxygen produced through in-situ resource utilization (ISRU) is critical to maintaining a permanent human presence on the lunar surface. Molten regolith electrolysis and carbothermal reduction are two promising ISRU techniques for generating oxygen directly from lunar regolith, which is primarily a mixture of oxide minerals; however, both processes require operating temperatures of 1600 C to melt lunar regolith and dissociate the molten oxides. These conditions limit the use of many oxide refractory materials, such as Al2O3 and MgO, due to rapid degradation resulting from reactions between the refractory materials and molten lunar regolith. Yttria-stabilized zirconia (YSZ) is shown here to be a promising refractory oxide to provide containment of molten regolith while demonstrating limited reactivity. This work focuses on corrosion studies of YSZ powders and dense YSZ crucibles in contact with molten lunar maria and highlands regolith simulants at 1600 C. The interactions between YSZ and molten regolith are characterized using SEM/EDS, XRD, and EBSD. A FactSage thermochemical model is created to compare with the experimental results. These combined analyses suggest that lunar maria regolith will degrade YSZ faster than lunar highlands regolith due to the lower viscosity of the maria regolith. The feasibility of long-term molten regolith containment with YSZ is discussed based on the YSZ powder and crucible results.

Kevin Yu↗

Recycling of Printed Circuit Boards to Recover Critical Materials

The printed circuit board (PCB), a central component of most electronic devices, represents a significant fraction of the electronic product waste stream. The complex composition of PCBs, consisting of metals, polymers, and fiberglass, requires specialized recovery steps to reclaim valuable and critical materials and the safe disposal of brominated compounds. In this review paper, we describe the current state of critical material recovery and traditional recycling technologies and identify key obstacles to large-scale implementation. Metals present at high concentrations, such as copper, lead, and iron, are conventionally recovered from PCBs using hydrometallurgical, pyrometallurgical, or electrometallurgical processes. Hydrometallurgical methods achieve high selectivity through chemical leaching but pose significant challenges for effluent and reagent recovery. Pyrometallurgical methods facilitate rapid metal separation through smelting but require substantial energy and may release harmful gases. Electrometallurgical techniques produce high-purity metals but are constrained by pretreatment requirements and the consumption of energy. The non-metallic fraction of PCB waste is recycled using thermochemical conversion, microwave-aided heating, and direct recycling of epoxy–fiberglass composites, enabling material or energy recovery. The recovered polymer from direct recycling may have reduced mechanical strength and poor compatibility with new polymer matrices, and the resulting products from the thermal conversion suffer from incomplete conversion, degradation of quality, and residual contamination, as compared to synthetic polymers. Recent process developments have focused on extracting rare earth and supply-critical materials present at lower concentrations in the waste stream. The literature on existing and emerging approaches for recycling PCB wastes is reviewed to identify sustainable, economically viable, and environmentally responsible strategies for the recovery and reuse of critical materials from waste streams.

36 MATERIALS SCIENCE↗

Understanding the structure and composition of recalcitrant oligosaccharides in hydrolysate using high-throughput biotin-based glycome profiling and mass spectrometry

Novel Immunological and Mass Spectrometry Methods for Comprehensive Analysis of Recalcitrant Oligosaccharides in AFEX Pretreated Corn Stover. Lignocellulosic biomass is a sustainable alternative to fossil fuel and is extensively used for developing bio-based technologies to produce products such as food, feed, fuel, and chemicals. The key to these technologies is to develop cost competitive processes to convert complex carbohydrates present in plant cell wall to simple sugars such as glucose, xylose, and arabinose. Since lignocellulosic biomass is highly recalcitrant, it must undergo a combination of thermochemical treatment such as Ammonia Fiber Expansion (AFEX), dilute acid (DA), Ionic Liquid (IL) and biological treatment such as enzyme hydrolysis and microbial fermentation to produce desired products. However, when using commercial fungal enzymes during hydrolysis, only 75–85% of the soluble sugars generated are monomeric sugars, while the remaining 15–25% are soluble recalcitrant oligosaccharides that cannot be easily utilized by microorganisms. Previously, we successfully separated and purified the soluble recalcitrant oligosaccharides using a combination of charcoal and celite-based separation followed by size exclusion chromatography and studies their inhibitory properties on enzymes. We discovered that the oligosaccharides with higher degree of polymerization (DP) containing methylated uronic acid substitutions were more recalcitrant towards commercial enzyme mixtures than lower DP and neutral oligosaccharides. Here, we report the use of several complementary techniques that include glycome profiling using plant biomass glycan specific monoclonal antibodies (mAbs) to characterize sugar linkages in plant cell walls and enzymatic hydrolysate, matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) using structurally-informative diagnostic peaks offered by negative ion post-secondary decay spectra, gas chromatography followed by mass spectrometry (GC–MS) to characterize oligosaccharide sugar linkages with and without derivatization. Since oligosaccharides (DP 4–20) are small, it is challenging to mobilize these molecules for mAbs binding and characterization. To overcome this problem, we have applied a new biotin-coupling based oligosaccharide immobilization method that successfully tagged most of the low DP soluble oligosaccharides on to a micro-plate surface followed by specific linkage analysis using mAbs in a high-throughput system. This new approach will help develop more advanced versions of future high throughput glycome profiling methods that can be used to separate and characterize oligosaccharides present in biomarkers for diagnostic applications.

59 BASIC BIOLOGICAL SCIENCES↗

Hydrogen production by water decomposition using a combined electrolytic-thermochemical cycle

A proposed dual-purpose power plant generating nuclear power to provide energy for driving a water decomposition system is described. The entire system, dubbed Sulfur Cycle Water Decomposition System, works on sulfur compounds (sulfuric acid feedstock, sulfur oxides) in a hybrid electrolytic-thermochemical cycle; performance superior to either all-electrolysis systems or presently known all-thermochemical systems is claimed. The 3345 MW(th) graphite-moderated helium-cooled reactor (VHTR - Very High Temperature Reactor) generates both high-temperature heat and electric power for the process; the gas stream at core exit is heated to 1850 F. Reactor operation is described and reactor innards are illustrated. A cost assessment for on-stream performance in the 1990's is optimistic.

Farbman, G. H.↗

Thermochemistry of dense hydrous magnesium silicates

Recent experimental investigations under mantle conditions have identified a suite of dense hydrous magnesium silicate (DHMS) phases that could be conduits to transport water to at least the 660 km discontinuity via mature, relatively cold, subducting slabs. Water released from successive dehydration of these phases during subduction could be responsible for deep focus earthquakes, mantle metasomatism and a host of other physico-chemical processes central to our understanding of the earth's deep interior. In order to construct a thermodynamic data base that can delineate and predict the stability ranges for DHMS phases, reliable thermochemical and thermophysical data are required. One of the major obstacles in calorimetric studies of phases synthesized under high pressure conditions has been limitation due to the small (less than 5 mg) sample mass. Our refinement of calorimeter techniques now allow precise determination of enthalpies of solution of less than 5 mg samples of hydrous magnesium silicates. For example, high temperature solution calorimetry of natural talc (Mg(0.99) Fe(0.01)Si4O10(OH)2), periclase (MgO) and quartz (SiO2) yield enthalpies of drop solution at 1044 K to be 592.2 (2.2), 52.01 (0.12) and 45.76 (0.4) kJ/mol respectively. The corresponding enthalpy of formation from oxides at 298 K for talc is minus 5908.2 kJ/mol agreeing within 0.1 percent to literature values.

Bose, Kunal↗

Technology for Electrically Enhanced Thermochemical Hydrogen (TEETH)

This is the Final Technical Report for the TEETH project. The TEETH concept couples high-temperature solar-thermochemical water splitting (TCWS) with electrochemical H 2 pumping through a proton conducting membrane (PCM) and capitalizes on the benefits of the individual technologies to synergistically providing new benefits. That is, TEETH is a coupled thermochemical/electrochemical process to produce H 2 from steam using solar energy. This approach is thermodynamically equivalent to other hybrid electrolytic processes but is unique in that the equilibrium of the reaction is driven forward by close coupling an electrically driven proton-conducting-membrane to the H 2 -producing reoxidation step. The process uniquely provides and benefits from the necessary H 2 /steam separation and, also unlike other hybrid processes, benefits thermodynamically from the use of readily generated high pressure steam. The concept also satisfies the objectives of previous concepts: 1) decreasing the reduction enthalpy (the reduction temperature), of the working metal-oxide (MO); 2) eliminating the need for a windowed receiver; and 3) widening the scope of material candidates, while also obviating the need for electrical connections to the working MO and avoiding the use of aqueous electrolytes and hydrated redox species (there is no liquid phase), without increasing mechanical complexity.

08 HYDROGEN↗

Characterisation of sludge for pyrolysis conversion process based on biomass composition analysis and simulation of pyrolytic properties

Highlights: • Characterisation of different types sewage sludge for pyrolytic properties. • Developed analytical procedure to categorise and quantify composition of sludge. • Observed qualitative similarity and quantitative variation on properties of sludge. • Correlated organic components with thermochemical properties of sludge. • Coupled model compounds selection and composition analysis for simulation study. - Abstract: Pyrolytic behaviour of sludge is highly complex and obscure because of its heterogeneous and diverse composition. Therefore, an analytical procedure is proposed to categorise and quantify the main constituents in sludge. In addition, a simulation study of sludge characteristics is carried out to complement the composition analysis and to improve our understanding on the relationship between composition of sludge and its corresponding properties. Different types of sludge samples were collected at different treatment stages from four Water Reclamation Plants in Singapore in two separate batches. Model compounds are selected to represent components identified and are used in simulation of pyrolytic properties of sludge. Constituents of sludge are adequately categorised, quantified and characterised in this study. Qualitative similarities and quantitative variations on characteristics of different sludge samples were identified. Comparison among the samples collected with the simulation provided insights on how differences in organic composition of sludge affected its properties.

09 BIOMASS FUELS↗

Engineering Database of Liquid Salt Thermophysical

The purpose of this report is to provide a review of thermophysical properties and thermochemical characteristics of candidate molten salt coolants, which may be used as a primary coolant within a nuclear reactor or heat transport medium from the Very High Temperature Reactor (VHTR) to a processing plant; for example, a hydrogen-production plant. Thermodynamic properties of four types of molten salts, including LiF-BeF 2 (67 and 33 mol%, respectively; also known as FLiBe), LiF-NaF-KF (46.5, 11.5, and 52 mol%, also known as FLiNaK), and KCl-MgCl 2 (67 and 33 mol%), and sodium nitrate-sodium nitrite-potassium nitrate (NaNO 3 –NaNO 2 –KNO 3 , 7-49-44 mol%, also known as Hitec® salt) have been investigated. Limitations of existing correlations to predict density, viscosity, specific heat capacity, surface tension, and thermal conductivity were identified. The impact of thermodynamic properties on the heat transfer, especially the Nusselt number, was also discussed. Stability of the molten salts with structural alloys and their compatibility with the structural alloys was studied. Nickel and high temperature alloys with dense Ni coatings are effectively inert to corrosion in fluorides, but not so in chlorides. Of the chromium containing alloys, Hastelloy N appears to have the best corrosion resistance in fluorides, while Haynes 230 was the most resistant in chloride. In general, alloys with increasing carbon and chromium content are increasingly subject to corrosion by the fluoride salts FLiBe and FLiNaK due to attack and dissolution of the intergranular chromium carbide. Future research to obtain needed information was identified.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermodynamic analysis of alternate energy carriers, hydrogen and chemical heat pipes

The paper discusses the production concept and efficiency of two new energy transmission and storage media intended to overcome the disadvantages of electricity as an overall energy carrier. These media are hydrogen produced by water-splitting and the chemical heat pipe. Hydrogen can be transported or stored, and burned as energy is needed, forming only water and thus obviating pollution problems. The chemical heat pipe envisions a system in which heat is stored as the heat of reaction in chemical species. The thermodynamic analysis of these two methods is discussed in terms of first-law and second-law efficiency. It is concluded that chemical heat pipes offer large advantages over thermochemical hydrogen generation schemes on a first-law efficiency basis except for the degradation of thermal energy in temperature thus providing a source of low-temperature (800 K) heat for process heat applications. On a second-law efficiency basis, hydrogen schemes are superior in that the amount of available work is greater as compared to chemical heat pipes.

Cox, K. E.↗

Primordial or Secondary? Testing Models of Debris Disk Gas with ALMA

The origin and evolution of gas in debris disks are still not well understood. Secondary gas production from cometary material or a primordial origin have been proposed. So far, observations have mostly concentrated on CO, with only a few C observations available. We overview the C and CO content of debris disk gas and test the state of the-art models. We use new and archival Atacama Large Millimeter/submillimeter Array (ALMA) observations of CO and C I emission, complemented by C II data from Herschel, for a sample of 14 debris disks. This expands the number of disks with ALMA measurements of both CO and C I by 10 disks. We present new detections of C I emission toward three disks: HD 21997, HD 121191, and HD 121617. We use a simple disk model to derive gas masses and column densities. We find that current state-of-the-art models of secondary gas production overpredict the C 0 content of debris disk gas. This does not rule out a secondary origin, but might indicate that the models require an additional C removal process. Alternatively, the gas might be produced in transient events rather than a steady-state collisional cascade. We also test a primordial gas origin by comparing our results to a simplified thermochemical model. This yields promising results, but more detailed work is required before a conclusion can be reached. Our work demonstrates that the combination of C and CO data is a powerful tool to advance our understanding of debris disk gas.

Radiative transfer↗

A Thermally-Conductive Martian Core and Implications for Its Dynamo Cessation

Mars experienced a dynamo process that generated a global magnetic field ~4.3 (or earlier) to 3.6 billion years ago (Ga). The cessation of this dynamo strongly affected Mars’ history and is expected to be linked to thermochemical evolution of Mars’ iron-rich liquid core, which is strongly influenced by its thermal conductivity. Here, we directly measured thermal conductivities of solid iron-sulfur alloys to pressures relevant to the Martian core and temperatures to 1023 Kelvin. Our results show that a Martian core with 16 weight % sulfur has a thermal conductivity of ~19 to 32 Watt meter −1 Kelvin −1 from its top to the center, much higher than previously inferred from electrical resistivity measurements. Our modeled thermal conductivity profile throughout the Martian deep-mantle and core indicates a ~4- to 6-fold discontinuity across the core-mantle boundary. The core’s efficient cooling resulting from the depth-dependent, high conductivity diminishes thermal convection and forms thermal stratification, substantially contributing to cessation of Martian dynamo.

Wen-Pin Hsieh↗

Machine-Learned Manifold-Based Models for Large Eddy Simulation of Turbulent Combustion

Reduced-order manifold combustion models are commonly used to lower the cost of reacting Large Eddy Simulations (LES) and may be derived either from physical principles as in flamelet models or from data-driven methods like Principal Component Analysis (PCA). In either case, neural networks are increasingly used as part of these models to provide a nonlinear mapping between a small set of pre-defined variables that parameterize the manifold and outputs of interest, such as reaction rates. In this work, we propose a new manifold-based modeling approach that combines the definition of the manifold-parameterizing variables (linear combinations of species), the nonlinear mapping to the outputs, and closure of filtered quantities for LES into the structure of a single neural network. This allows the process used to train the neural network to simultaneously optimize both the functional form of the model and the identities of the inputs to the model. The new approach can flexibly incorporate thermochemical data from any combustion system; if trained on data from 1D flames it can be interpreted as an optimized flamelet model, but it can also be used to learn models from data from more complex configurations. This work presents a priori evaluations of the new approach in both contexts. Evaluation using data from 1D premixed flames demonstrates the physical interpretability of the manifold variables generated by the new approach. Evaluation using data from direct numerical simulations of turbulent flames shows improved predictions relative to either flamelet or PCA-based models in a more complex configuration.

47 OTHER INSTRUMENTATION↗

Mild Biomass Liquefaction Process for Economic Production of Stabilized Refinery-Ready Bio-oil

Southern Research (SR) in cooperation with U.S. Department of Energy (DOE), Bioenergy Technology Office (BETO), investigated a biomass liquefaction process for economic production of stabilized refinery-ready bio-oil. The project was awarded by DOE under a Funding Opportunity Announcement (DE-FOA-0000686) for Bio-oil Stabilization and Commoditization that intended to evaluate the feasibility of using bio-oil as a potential feedstock in an existing petroleum refinery. SR investigated Topic Area 1 of the FOA at Technology Readiness Level 2-3 to develop thermochemical liquefaction technologies for producing a bio-oil feedstock from high-impact biomass that can be utilized within a petroleum refinery. Bio-oil obtained from fast pyrolysis of biomass is a green intermediate that can be further upgraded into a biofuel for blending in a petroleum refinery using a hydro-deoxygenation (HDO) route. Co-processing pyrolysis bio-oil in a petroleum refinery is an attractive approach to leverage the refinery’s existing capital. However, the petroleum industry is reluctant to accept pyrolysis bio-oil because of a lack of a standard definition for an acceptable bio-oil feedstock in existing refinery processes. Also per BETO’s multiyear program plan, fast pyrolysis-based bio-fuel is presently not cost competitive with petroleum-based transportation fuels. SR aims to develop and demonstrate a cost-effective low-severity thermal liquefaction and hydrodeoxygenation (HDO) process to convert woody biomass to stabilized bio-oils that can be directly blended with hydrotreater input streams in a petroleum refinery for production of gasoline and/or diesel range hydrocarbons. The specific project objectives are to demonstrate the processes at laboratory scale, characterize the bio-oil product and develop a plan in partnership with a refinery company to move the technology towards commercialization.

09 BIOMASS FUELS↗

Potential synergies of drop-in biofuel production with further co-processing at oil refineries

Drop-in biofuels have been defined as functionally equivalent to petroleum-based transportation fuels and are fully compatible with the existing petroleum infrastructure. They will be essential in sectors such as aviation if we are to achieve emission reduction and climate mitigation goals. Currently, 'conventional' drop-in biofuels, which are primarily based on upgrading of lipids / oleochemicals, are the only significant source of commercial volumes of drop-in biofuels. However, the necessary increased, future volumes will likely come from 'advanced' drop-in biofuels based on biomass feedstocks such as forest and agriculture residues. Biocrudes / bio-oils produced from lignocellulosic feedstocks using thermochemical technologies such as gasification, pyrolysis, and hydrothermal liquefaction need to be further upgraded to drop-in biofuels. However, advanced drop-in biofuels have been slow to reach commercial maturity due to significant technical challenges, high capital costs, and the challenge of generally lower oil prices. It is likely that the co-processing of drop-in biofuels with conventional petroleum refining could considerably reduce capital costs. Initially, co-processing is likely to be established through the upgrading of conventional / oleochemical feedstocks (lipids). Lipids are readily available in large volumes (global production in 2017 was ~185 million metric tonnes) and can be more easily integrated into oil-refinery processes. In contrast, lignocellulose-derived biocrudes / bio-oils are not yet available in significant volumes and are more complex to co-process in a refinery. The likely strategies for co-processing of oleochemicals (lipids) and bio-oil and biocrude feedstocks based on different insertion points within the refinery infrastructure are discussed.

09 BIOMASS FUELS↗

Open-cycle thermochemical energy storage for building space heating: Practical system configurations and effective energy density

Salt-hydrate thermochemical materials (TCM) are promising candidates for energy storage systems for building space heating due to their high theoretical energy density and the need for low regeneration temperature. However, water vapor is required to drive the hydration process of the TCM reactor, which poses a challenge during winter when water vapor is typically scarce. Using indoor air directly lowers the building's humidity to an unconformable level in practice, while the cold outdoor air contains limited moisture. Here we consider different integration strategies for open-cycle TCM reactors in buildings and develop a model to simulate their thermal performance across diverse buildings and climates, specifically for building space heating. The potential energy densities and the levelized cost of storage of the TCM reactor are evaluated in practical scenarios to demonstrate the load-shifting potential of TCM systems for heating applications. We use a strontium chloride (SrCl 2 )-based composite as the baseline and explore the impact of various reactor and material changes to the energy density and levelized cost of storage.

25 ENERGY STORAGE↗

Thermochemical conversion of waste plastics with coal and biomass to generate value-added products

Co-gasification of waste plastic and waste coal/biomass in steam was investigated to evaluate the effects of operating conditions and low-cost catalyst compositions of coal ash on syngas production and tar mitigation. The results demonstrate the benefits of waste plastic conversion with coal or biomass. A better understanding of these processes will facilitate the development of more accurate kinetic models for industrial-scale chemical recycling.

co-gasification↗