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At least 415 records · Page 23

The significance of biomass densification in biological-based biorefineries: A critical review

Replacing fossil fuels with renewable biofuels derived from lignocellulosic biomass is an important aspect of addressing environmental challenges and developing a sustainable industrial society. Densification overcomes the problems of low bulk density and poor flowability of biomass and has been commercialized for producing solid biofuels, but the overall impact of densification on biological-based biorefineries that primarily target liquid fuels (e.g., ethanol) is still under investigation. Herein, this review provides a thorough summary of the application of densified biomass in biological-based biorefineries. First, the effects of densification parameters as well as variables of biomass materials on the densified products’ quality are reviewed, and different commonly used densification technologies are also discussed and compared. Then, the discussion focuses on the physiochemical modifications of biomass caused by densification that may influence further pretreatment and/or enzymatic hydrolysis in biorefineries. Industrial pelleting has been generally shown to exhibit positive/neutral effects on the enzymatic hydrolysis of multiple biomass feedstocks after pretreatments, indicating the viability of using pellets as starting feedstocks in biorefineries. Densification causes structural disruption of biomass, which may facilitate further biochemical conversions. Integrating biomass densification in the feedstock supply chain is feasible for large-scale biorefineries to overcome the techno-economic barriers and become profitable. Suggestions are presented for the efficiency enhancement and cost reduction in densification-based biorefineries. To enable wider applications, it is now the time to employ more demo and full-scale activities in different regions of the world pushing the research and innovation of densification integrated within biorefining.

09 BIOMASS FUELS↗

A percolating path to green iron

About 1.9 gigatons of steel is produced every year, emitting 8% (3.6 gigatons) of global CO 2 in the process. More than 50% of the CO 2 emissions come from a single step of steel production, known as ironmaking. Hydrogen- based direct reduction (HyDR) of iron oxide to iron has emerged as an emission-free ironmaking alternative. However, multiple physical and chemical phenomena ranging from nanometers to meters inside HyDR reactors alter the microstructure and pore networks in iron oxide pellets, in ways that resist gaseous transport of H 2 /H 2 O, slow reaction rates, and disrupt continuous reactor operation. Using synchrotron nano X-ray computed tomography and percolation theory, we quantify the evolution of pores in iron oxide pellets and demonstrate how nanoscale pore connectivity influences micro- and macroscale flow properties such as permeability, diffusivity, and tortuosity. Our modeling framework connects disparate scales and offers opportunities to accelerate HyDR.

hydrogen↗

Fiber Sorbents – A Versatile Platform for Sorption-Based Gas Separations

Increasing demand for high-purity fine chemicals and a drive for process intensification of large-scale separations have driven significant work on the development of highly engineered porous materials with promise for sorption-based separations. While sorptive separations in porous materials offer energy-efficient alternatives to longstanding thermal-based methods, the particulate nature of many of these sorbents has sometimes limited their large-scale deployment in high-throughput applications such as gas separations, for which the necessary high feed flow rates and gas velocities accrue prohibitive operational costs. These processability limitations have been historically addressed through powder shaping methods aimed at the fabrication of structured sorbent contactors based on pellets, beads or monoliths, commonly obtained as extrudates. These structures overcome limitations such as elevated pressure drops commonly recorded across powder adsorption beds but often accrue thermal limitations arising from elevated particle density and aggregation, which ultimately cap their maximum separation performance. Furthermore, the harsh mechanical strain to which powder particles are subjected during contactor fabrication, in the form of extrusion/compression forces, can result in partial pore occlusion and framework degradation, further limiting their performance. Here, we present the development of porous fiber sorbents as an alternative sorbent contactor design capable of addressing sorbent processability limitations while enabling an array of performance-maximizing heat integration capabilities. This new sorbent form factor leverages pre-existing know-how from hollow fiber spinning to produce fiber-shaped sorbent contactors through the phase inversion of known polymers in a process known as dry-jet/wet quenching. The process of phase inversion allows microporous sorbent particles to be latched onto a macroporous polymer matrix under mild processing conditions, thus making it compatible with soft porous materials prone to amorphization under traditional pelletization conditions. Sorbent fibers can be created with different geometries through control of the spinning apparatus and process, offering the possibility to produce monolithic and hollow fibers alike, the latter of which can be integrated with thermalization fluid flows. In this Account, we summarize our progress in the field of fiber sorbents from both design and application standpoints. We further guide the reader through the evolution of this field from the early inceptive work on zeolite hollow fibers to recent developments on MOF fibers. We highlight the versatile nature of fiber sorbents, both from the composition, fabrication and structure points of view, and further demonstrate how fiber sorbents offer alternative paths in tackling new and challenging chemical separation challenges like direct air capture (DAC), with a final perspective on the future of the field.

36 MATERIALS SCIENCE↗

High Thermoelectric Performance in 2D Sb 2 Te 3 and Bi 2 Te 3 Nanoplate Composites Enabled by Energy Carrier Filtering and Low Thermal Conductivity

Thermoelectrics are an important class of materials with great potential in alternative energy applications. In this study, two-dimensional (2D) nanoplates of the layered chalcogenides, Sb 2 Te 3 and Bi 2 Te 3 , are synthesized and composites of the two are investigated for their thermoelectric properties. The two materials, Sb 2 Te 3 and Bi 2 Te 3 , were synthesized as hexagonal, 2D nanoplates via a colloidal polyol route. The as-synthesized Sb 2 Te 3 and Bi 2 Te 3 vary drastically from one another in their lateral and vertical dimensions as revealed by scanning electron microscopy and atomic force microscopy. The single crystalline nanoplate nature is deduced by high-resolution transmission electron microscopy and selected area electron diffraction. Nanoplates have well-defined hexagonal facets as seen in the scanning and transmission electron microscopy images. The nanoplates were consolidated as an anisotropic nanostructured pellet via spark plasma sintering. Preferred orientation observed in the powder X-ray diffraction pattern and scanning electron microscopy images of the fractured pellets confirm the anisotropic structure of the nanoplates. Thermoelectric properties in the parallel and perpendicular directions were measured, revealing strong anisotropy with a significant reduction to thermal conductivity in the perpendicular direction due to increased phonon scattering at nanoplate interfaces. All compositions, except that of the 25% Bi 2 Te 3 nanoplate composite, behave as degenerate semiconductors with increasing electrical resistivity as the temperature increases. The Seebeck coefficient is also increased dramatically in the nanocomposites, the highest reaching 210 μV/K for 15% Bi 2 Te 3 . The increase in Seebeck is attributed to energy carrier filtering at the nanoplate interfaces. Overall, these enhanced thermoelectric properties lead to a drastic increase in the thermoelectric performance in the perpendicular direction, with zT ~ 1.26, for the 15% Bi 2 Te 3 nanoplate composite at 450 K.

36 MATERIALS SCIENCE↗

The quest for safer nuclear fuels

Here, to increase the safety and performance of nuclear reactors, researchers are working on developing ‘accident tolerant’ fuels. Ideally, these fuel pellets will be less susceptible to swelling and be more resistant to extreme heat. This led chemists to develop uranium dioxide (UO 2 ) doped with divalent elements, E 2+ . These dopants can introduce vacancies into the lattice that lead to larger grain sizes, which create longer pathways for fission gasses to migrate out of the grains. In undoped fuel, fission gas build-up at grain boundaries causes the fuel pellet to swell. Therefore, having larger grains that slow fission gas migration into grain boundaries is highly desired. Divalent Cr 2+ ions are a commonly explored dopant for UO 2 fuels. These materials have larger grain sizes while maintaining the dissolution kinetics of undoped UO 2 , making their long-term storage and disposal paths similarly safe. Atomistic models have suggested that Mn 2+ is a conceivable alternative doping material, with the potential to increase the sizes of grains even more than Cr 2+ dopants. As such, experimental studies are required to understand the physical chemistry and reactivity of these potential fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Air separation via two-step solar thermochemical cycles based on SrFeO 3-δ and (Ba,La) 0.15 Sr 0.85 FeO 3-δ perovskite reduction/oxidation reactions to produce N 2 : rate limiting mechanism(s) determination

Two-step solar thermochemical cycles based on reversible reactions of SrFeO 3–δ and (Ba,La) 0.15 Sr 0.85 FeO 3–δ perovskites were considered for air separation. The cycle steps encompass (1) the thermal reduction of SrFeO 3–δ or (Ba,La) 0.15 Sr 0.85 FeO 3–δ perovskites driven by concentrated solar irradiation and (2) oxidation in air to remove O 2 and produce N 2 . Rate limiting mechanisms were examined for both reactions using a combination of isothermal and non-isothermal thermogravimetry for temperature-swings between 673 and 1373 K, heating rates of 10, 20, and 50 K min –1 , and O 2 pressure-swings between 20% O 2 /Ar and 100% Ar at atmospheric pressure. Evolved O 2 and associated lag due to transport behavior were measured with gas chromatography and used with measured sample temperatures to predict equilibrium compositions from a compound energy formalism thermodynamic model. Measured and predicted chemical equilibrium changes in deviation from stoichiometry were compared. Rapid chemical kinetics were observed as the samples equilibrated rapidly for all conditions, indicative that heat and mass transfer were the rate limiting mechanisms. Furthermore, the effects of bulk diffusion (or gas diffusion through the bed or pellet) were examined using pelletized and loose powdered samples and determined to have no discernable impact.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting Thermal Excursions During in situ Oxidative Regeneration of Packed Bed Catalytic Fast Pyrolysis Catalyst

Ex situ catalytic fast pyrolysis (CFP) uses a secondary reactor to upgrade biomass pyrolysis vapors to stabilized CFP oils with reduced oxygen content. In one configuration, the secondary reactor is operated as a packed-bed swing reactor system which allows coke-deactivated beds to be decarbonized in situ while other beds remain online for vapor upgrading. In situ decarbonization must be done carefully to avoid irreversible deactivation and/or physical degradation of catalyst pellets. Given that packed bed reactors are well known to have poor heat transfer characteristics, this is a critical issue impacting scaleability and commercial viability of the technology. To predict thermal excursions during regeneration, finite element computational models have been built to assist in scaling up oxidative decarbonization of a Pt/TiO2 CFP catalyst (0.5 mm spheres) from a bench scale packed bed with 100 g of catalyst to a pilot scale packed bed with 2 kg of catalyst and internal cooling tubes. Based on transient measurements of outlet temperature and effluent CO2 concentration, and using an assumed coke profile and activation energy, this paper demonstrates that specific combinations of effective thermal conductivity and wall heat transfer coefficient can fit bench scale oxidative regeneration data equally well. For the upscaled 2 kg bed, four bench-scale “best fit” parameter pairs give different predictions for location and magnitude of thermal excursions, with the maximum computed bed temperature gradients ranging from 30 °C cm-1 to as high as 3000 °C cm-1. The larger the fraction of heat removal by conduction through the cooling tubes, the greater the differences between the parameter pairs. The modelling results presented in this paper cast doubt on the industrial viability of the proposed combination of catalyst, bed and regeneration process, and point to the need for alternate reactor designs. However, there is considerable uncertainly in some of the key model parameters. The reliability of model predictions can be increased by adding more temperature measurements at key bed locations, testing additional variations in process conditions, performing careful bed dissections to determine the true coke profile, and perhaps most importantly, directly measuring the effective thermal conductivity of the catalyst pellets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Overdriven-detonation states produced by spherically diverging waves

A series of experiments are currently underway at the Detonation Science and Technology group, within Los Alamos National Laboratory, to study the overdriven-detonation states achievable in energetic materials as a result of detonation-wave interactions. A multi-component, energetic-material array was designed to study the amplification of velocity and pressure states produced by spherically diverging detonation waves in pentaerythritol tetranitrate (PETN) output charges. The unique geometry provides a low-jitter, highly controlled series of interactions between three independent-detonation inputs. Streak-camera imaging was performed on the output face of PETN pellets ranging in thickness from 2.5 – 10 mm to characterize the resulting breakout profile. Additionally, photonic Doppler velocimetry (PDV) measurements were collected at the output-pellet surface to determine simultaneity within the system. Detonation-wave velocities upwards of 16 mm/µs were measured, as compared to a steady-state detonation velocity of 7.9 mm/µs for the PETN pressing density investigated. Finally, additional experiments are being conducted to measure the pressure amplification generated at key areas of interaction.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Methods to determine the radiated power in SPI-mitigated disruptions in JET

Here we present techniques for evaluating the radiated power in JET disruptions. Disrupting plasmas are shown to have non-axisymmetric radiation profiles, motivating the re-evaluation of the standard techniques for calculating the total radiated power at JET using bolometry. Four single-channel bolometers at different toroidal locations are exploited to quantify the radiation asymmetry. Toroidal radiation peaking factors integrated over the entire disruption of up to 1.5 have been observed when varying the quantity of neon in pellets used in disruptions mitigated by shattered pellet injection. Using synthetic bolometer diagnostics developed with the Cherab spectroscopy modeling framework, we can estimate the systematic error on total power calculations for relevant radiation profiles and improve estimates of the total radiated power. We show that the component of the systematic error on the total power due to the poloidal radiation profile can be reduced from 70% to 10% with suitable assumptions about the structure of the poloidal profile.

47 OTHER INSTRUMENTATION↗

Control of internal transport barriers in magnetically confined tokamak burning plasmas

The initiation, termination, and control of internal transport barriers associated with E × B flow shear near local minima of magnetic shear are examined for burning plasmas to determine if the positive feedback loops between profiles, instability, transport, and flow shear operate in regimes with fusion self-heating. A five-field transport model for the evolution of profiles of density, ion and electron temperature, ion and electron fluctuations, and radial electric field is utilized to examine the efficacy of controls associated with external inputs of heat and particles, including neutral beam injection, RF, pellets, and gas puffing. The response of the plasma to these inputs is studied in the presence of self-heating. The latter is affected by the external inputs and their modification of profiles and is, therefore, not an external control. Provided sufficient external power is applied, internal transport barriers can be created and controlled, both in ion and electron channels. Barrier control is sensitive to the locations of power deposition and pellet ablation, as well as temporal sequencing of external inputs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The Use of High-Density UN Fuel in Heat-Pipe Microreactors

Heat-pipe microreactors (HPMRs) are very small-scale nuclear reactors that employ heat pipes (HPs) for heat removal. HPMRs can be easily integrated with other forms of renewable energies, can be used for emergency responses to disaster relief zones, can be deployed in remote locations not connected to the grid, and can be removed from sites and replaced by new ones. HPMRs can also be used for space missions as HPs do not rely on gravity for heat transfer. Conventional fuel materials, such as uranium oxide (UO 2 ) and uranium oxycarbide (UCO), are currently considered in most existing HPMR designs, but ceramic uranium nitride (UN) fuel that has high uranium density, high thermal conductivity, and high melting point may become a better fuel candidate. Through neutronics calculations, this paper assesses the impact of using UN fuel in HPMRs with two different neutron spectra (fast and thermal) and two different fuel forms [traditional solid fuel pellets and TRi-structural-ISOtropic (TRISO) fuel compacts]. It was concluded that retrofitting HPMRs with UN fuel has the potential to reduce the initial 235 U enrichment requirement by ~3 wt% (to keep the same cycle length) or increase the cycle length (by keeping the same initial 235 U enrichment), which enables more compact and transportable HPMR core designs. However, using UN fuel decreases the control element worth [by up to 20% for the Special Purpose Reactor (SPR) and 5% for HP-MR] and is up to 80% more costly. Increasing 15 N enrichment can further decrease the initial 235 U enrichment requirement and increase the control element worth but is more costly. In conclusion, compared to fast-spectrum HPMRs fueled with solid pellet fuels, retrofitting UN fuel is more suitable for thermal-spectrum HPMRs fueled with TRISO fuel compacts, where the neutron spectrum hardening caused by using UN is less significant.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Accelerated Fuel Qualification of Fast Modular Reactor Fuel in a Thermal Reactor: Modeling and Simulation Paired with Irradiation Testing

The accelerated fuel qualification (AFQ) methodology is applied by simulating accelerated fuel tests of the General Atomics Electromagnetic Systems’ fuel system for its 44-MW(electric) gas-cooled, fast-spectrum fast modular reactor (FMR). This fuel is comprised of UO 2 pellets in SiGA® cladding, a silicon carbide ceramic matrix composite. Fast reactors, like the FMR, offer many benefits, including high fuel utilization and flexibility, but may require a lengthy material design process if tests are performed using fast neutron irradiation alone. A thermal neutron irradiation can instead be used to rapidly test how well key components of the current material models extend to high burnup. Thermal neutrons produce a different radial power distribution within the pin than fast neutrons. However, the temperature and burnup values for the two neutron types are comparable, and the differences between the simulated fuel responses are relatively small, demonstrating the weak sensitivity of the physics-based fuel model calculations on the neutron type and the irradiation rate. Furthermore, the deformation of the SiGA cladding saturates after about 1 displacement per atom for both neutron spectra. In an accelerated fuel test, the irradiation time required to reach the target fuel burnup can be reduced by a factor of 3 by using a small rodlet with a 45% smaller pellet diameter while maintaining the same linear power. Therefore, the time for data collection up to high burnup can be significantly reduced while maintaining the same temperature profile, which largely determines the material response. Tests of fuel rodlets of standard and compact size will be carried out in the Idaho National Laboratory’s Advanced Test Reactor (ATR), including full size and compact rodlets with varying gap sizes. By applying physics-based mechanistic modeling and simulation in accordance with the AFQ methodology, this type of compact rodlet testing in a thermal test reactor captures the necessary phenomena to test fuel material models up to high burnup and to simulate the expected impact of fast neutron radiation on the fuel in FMR operations. Finally, this approach to testing fast reactor fuels in existing thermal test reactors, paired with advanced physics-based mechanistic modeling and simulation, is expected to be applicable to a range of advanced fuels and will decrease the overall fuel qualification timeframe from decades to years.

Advanced test reactor (ATR)↗

$\mathrm{EBR-II MOX}$ Fuel Characterization Enabling ARES Phase I Testing

Pretransient characterization was performed for the Experimental Breeder Reactor II (EBR-II) mixed-oxide (MOX) fuel pellets from the SPA-2/-2B Operational Reliability Testing collaboration between Japan and the United States. Continued collaboration under the Advanced Reactor Experiments for Sodium Fast Reactor Fuels project will investigate the transient performance of these rods in the Transient Reactor Test facility at Idaho National Laboratory in the MOXTOP-THOR experiment. The results will fill a gap in existing transient performance data for MOX as these rods have a peak burnup of 14.3 at. % (~134.4 GWd/t) in the EBR-II. Fuel pellet properties were gathered from available resources and their irradiation and decay history evaluated. Further reactor physics calculations were performed to support the experiment design, reactor operations, and safety analyses necessary to enable the programmatic success of this effort. Of the three irradiated fuel pins, two will undergo transient testing, and all three will undergo post-irradiation examination. The methodology development and analysis activities utilized we report enable current experiment design work and provide the pathway through which measured data of this type can be further evaluated.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Development of advanced vacuum technologies for extending plasma pulse duration on EAST

Advanced vacuum technologies, including pumping, fueling and wall conditioning, have been successfully developed or upgraded to efficiently control the fuel and impurity particles to extend the plasma pulse duration in the experimental advanced superconducting tokamak (EAST). To improve the particle exhaust rate cryopumps with a 60% increase in pumping speed and ∼2 times increase in saturation capacity have been developed, and molecular pumps with a ∼30% increase in pumping speed have been upgraded. In order to monitor the molecular pump status while avoiding bearing faults and overload accidents, a fault detection system has been built which can offer an early warning to avoid more losses within the fusion device. A series of fueling technologies have been developed including gas injection system, supersonic molecular beam injector, pellet injector (PI), massive gas injector and shattered pellet injector, installed at the midplane and divertor positions at different ports to improve fueling uniformity and efficiency. Meanwhile, routine wall conditioning such as electric and hot N 2 baking, ion cyclotron wall conditioning and glow discharge cleaning have been successfully developed to remove the impurity particles from the inner component and materials. The low Z material wall coating and real-time powder injection during plasma discharge are also designed and applied to further improve particle control capability. Finally, by using these advanced vacuum related technologies, good vacuum (<2 × 10 −6 Pa) and wall conditions are realized, and the fuel and impurity particles can be effectively and stably controlled, which promotes the achievement of the record plasma of ∼1056 s pulse duration with the line-averaged electron density of 1.8 × 10 19 m −3 on EAST. They provide a very important reference for vacuum system design and operation for future fusion devices.

EAST↗

Routes to high-performance operation in Wendelstein 7-X: turbulence suppression with shaping of the density profile

Steep density gradients generally lead to improved plasma performance in the neoclassically optimized stellarator W7-X. This is evident in the global energy confinement time as well as in the ion temperature and can be explained by a strong reduction of the ion temperature gradient turbulence. Such conditions can experimentally be realized by several methods: injection of cryogenic hydrogen pellets, appropriate combination of neutral beam and electron cyclotron resonance heating (ECRH) and, in some cases, with low power of ECRH after preconditioning of the first wall. The duration of the improved phases is determined by the ability to sustain the steep density gradient, by technical limitations of the involved systems and, eventually, by the plasma stability. This paper gives an overview of relevant experimental results and presents example discharges where the improved confinement conditions could be extended to multiple seconds: up to 4 s using neutral beam injection and from 14 to 40 s with steady state pellet injection. In these plasmas the turbulent thermal diffusivity is reduced by a factor of 3 to 4 in a broad radial range, which allows high ion temperatures of up to 3 keV at the densities of about 1.5 • 10 20 m −3 .

high performance plasma↗

Runaway electron seed formation at reactor-relevant temperature

Systematic variation of the pre-disruption core electron temperature (T e ) from 1 to 12 keV using an internal transport barrier scenario reveals a dramatic increase in the production of ‘seed’ runaway electrons (REs), ultimately accessing near-complete conversion of the pre-disruption current into sub-MeV RE current. Injected Ar pellets are observed to ablate more intensely and promptly as T e rises. At high T e , the observed ablation exceeds predictions from published thermal ablation models. Simultaneously, the thermal quench (TQ) is observed to significantly shorten with increasing T e —a surprising result. While the reason for the shorter TQ is not yet understood, candidate mechanisms include: insufficiently accurate thermal ablation models, enhanced ablation driven by the seed RE population, or significant parallel heat transport along stochastic fields. Kinetic modeling that self-consistently treats the plasma cooling via radiation, the induced electric field, and the formation of the seed RE is performed. Including the combined effect of the inherent dependence of hot-tail RE seeding on T e together with the shortened TQ, modeling recovers the progression towards near-complete conversion of the pre-disruption current to RE current as T e rises. Measurement of the HXR spectrum during the early current quench (CQ) reveals a trend of decreasing energy with pre-disruption T e . At the very highest T e (≈ 12 keV), ≈ 100% conversion of the thermal current to runaway current is found. The energy of this peculiar RE beam is inferred to be sub-MeV as it emits vanishingly few MeV hard x-rays (HXRs). These measurements demonstrate novel TQ dynamics as Te is varied and illustrate the limitations of treating the RE seed formation problem without considering the inter-related dependencies of the pellet ablation, radiative energy loss, and resultant variations of the TQ duration. Finally, if the observed shortening of the TQ with increasing T e extends to fusion-grade plasmas, than their propensity to form large quantities of RE seeds at high T e may be far worse than previously thought. Positively, the high T e scenario in DIII-D produces REs so prodigiously that it can serve as a meaningful new platform for demonstrating RE avoidance techniques.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗