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Krypton Concentration using HZ-PAN

Idaho National Laboratory (INL) has developed and tested engineered sorbents to separate and capture volatile fission products such iodine, xenon (Xe), and krypton (Kr) from off-gas streams. As noble gases, Xe and Kr can be difficult to capture and separate. Historically, cryogenic distillation has been used to execute the separation. However, performing this separation from bulk air streams is expensive and can pose significant hazards. INL has successfully developed two different sorbents for Xe and Kr capture, silver mordenite polyacrylonitrile and hydrogen mordenite polyacrylonitrile (HZ-PAN). Adsorption studies to date successfully separated and captured Kr from carrier gas streams, but those studies focused primarily on initial separation and capture. Successful utilization in a used nuclear fuel (UNF) reprocessing facility, however, requires further concentration of the Kr to minimize long term storage volumes. This study focuses on the concentration of Kr utilizing HZ PAN as the concentrating media. Concentrating Kr during desorption is ideal for two reasons: one, to produce Kr that can be used for commercial and research applications, or two, to minimize the volume of the radioactive gaseous waste stream for disposal. This report investigates the Kr concentrating potential of HZ-PAN by running multiple Kr adsorption-desorption cycles, collecting the desorbed effluent from a saturated HZ-PAN column, and loading it onto a fresh column. This study demonstrates that four adsorption-desorption cycles can transform a 150 ppmv Kr stream into a 37.5% Kr stream, an overall concentration factor of 2497. Each concentration step results in successively smaller volumes desorbed, reducing volume by a factor of approximately 40,000. Depending on the operational goals, during desorption one could collect smaller volume fractions of high concentration Kr (~ 67%). This demonstration should be considered proof-of-concept. Further refinement is necessary to develop optimum operating schemes to integrate into UNF off-gas treatment.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗

Prioritizing Off-Gas Metrics: A Guide for Comparable Off-Gas Capture Testing

The Material Recovery and Waste Form Development (MRWFD) off-gas team had a workshop, hosted by Idaho National Laboratory (INL), to align goals and expectations for off-gas research. The workshop included team members from four national laboratories. The workshop focused on defining distinct R&D phases with specific metrics, outlining standard test and measurement protocols for Iodine and Krypton/Xenon sorbents, brainstorming approaches to future disruptive technologies, and recognizing parameters with more inherent risk, requiring more rigorous evaluation. This report will serve as a guide for future off-gas work. Its purpose is to foster efficient collaboration across diverse research facilities and invite direct comparison of materials and results.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Development of Engineered Metal-Organic Framework (MOF) materials for perfluorooctane sulfonate (PFOS) Remediation

In this project, an engineered form of a Metal-Organic Framework (MOF) based material is developed for the removal of perfluorooctane sulfonate (PFOS) for real-world applications. The powdered MOF material has been demonstrated at the Pacific Northwest National Laboratory (PNNL) to selectively capture PFOS from distilled (DI) water with a large performance advantage over granulated activated carbon (GAC). In this project, the powdered material was transformed into an engineered form (using a polymer) to demonstrate PFOS adsorption capacity in tap water. PNNL developed and processed the MOF material in the engineering form (granules). After thorough characterization and stability testing, these engineered MOF granules were provided to an industrial collaborator, AVANTech, LLC, for testing and demonstration of continuous, long-term PFOS removal from tap water. The preliminary results showed PFOS sorption capacities at parts per billion (ppb) concentrations in tap water under a flow system. Also provided insight into sorbent-based material utilization in a continuous flow system. Further studies are required to optimize and understand sorption in such industrial-scale applications.

36 MATERIALS SCIENCE↗

Recovery of Rare Earths, Precious Metals and other Critical Materials from Geothermal Waters with Advanced Sorbent Structures - CRADA 355 (Abstract)

The ability to recover valuable trace level minerals from geothermal brines using high-performance solid-phase sorbents will be explored and developed. A compressive range of sorbent materials will be screened for application to metal extraction from geothermal brines. Preferred sorbents from extraction of trace levels of rare earths (REs), precious metals (PMs), and other critical/strategically valuable materials (CMs) such as Zn, Mn, Te, Sc, Se and U from geothermal brines will be identified. For the preferred sorbents PNNL will determine the volumes they are capable of providing efficient extraction from. The thermal and chemical limits (including, acid, sulfur, salt) for performance of the preferred sorbent materials will be determined; with a target of at least 125°C and perhaps as high as 400° C. Sorbent form factors (including, packed bed, membrane, mats) that can function efficiently and be installed cost effectively in geothermal energy plants will be assessed for chemical and economic viability. Material regeneration and cyclic utilization will be demonstrated, targeting hundreds to thousands of cycles. Options for recovery and purification (including, selective separation of heavy REs) of collected materials will be explored. A techno-economic analysis (TEA) will be performed to assess the best approach to provide a value-added extraction process for geothermal energy systems. The sorbent materials and engineering analysis will be applicable to other industrial processes in which secondary recovery of valuable materials could provide economic benefit.

15 GEOTHERMAL ENERGY↗

Pilot Testing of a Highly Efficient Pre-combustion Sorbent-based Carbon Capture System

TDA developed and demonstrated a highly efficient pre-combustion carbon capture system. The overall objective of this work was to develop a new sorbent-based pre-combustion carbon capture technology for Integrated Gasification Combined Cycle (IGCC) power plants. In this project our goal was to demonstrate the techno-economic viability of the new technology by 1) demonstrating it in large-scale slipstream tests, and 2) carrying out a high fidelity engineering and cost analysis. TDA’s process used an advanced physical adsorbent that selectively removes CO 2 from coal-derived synthesis gas above the dew point of the gas at temperatures as high as 300°C. The sorbent consists of a mesoporous carbon whose surface was grafted with functional groups that remove CO 2 via a well-known acid-base interaction. As documented in bench-scale experiments and field tests with actual coal gas, the sorbent achieved a very high capacity for CO 2 at temperatures as high as 300°C. The sorbent bound CO 2 more strongly than common physical adsorbents, providing the chemical potential needed for the high temperature operation. However, because CO 2 does not form a true covalent bond with the surface sites (as is the case with chemical absorbents), the sorbent regeneration could be carried out with only a very small energy input. The heat input to regenerate our sorbent was only 4.9 kcal per mol of CO 2 , which is much lower than that for chemical absorbents (e.g., 29.9 kcal/mol CO 2 for sodium carbonate) and was similar to the requirements of physical solvents (e.g., 4 kcal/mol CO 2 for Selexol TM ). Because the sorbent operates above the dew point of the synthesis gas (unlike the Selexol TM process), a higher power cycle efficiency can be achieved. With previous DOE/NETL funding (Contract No. DE-FE-0000469), we demonstrated the techno-economic viability of the technology in bench-scale tests and slipstream demonstrations at the National Carbon Capture Center (NCCC), Wilsonville, Alabama and Wabash River IGCC plant in Terra Haute, Indiana. We demonstrated a stable working CO 2 capacity for over 11,650 cycles with simulated synthesis gas. We also evaluated its performance with actual synthesis gas in two test campaigns at the Wabash River IGCC Plant, Terre Haute, IN and the National Carbon Capture Center (NCCC), Wilsonville, AL. The slipstream tests clearly showed that the actual coal gas constituents and potential contaminants (e.g. trace metals, halides, tars) had no effect on the sorbent’s ability to remove CO 2 (the same sorbent beds were used in both field tests with no sign of deactivation for 2,000 cycles with over 26,750 SCF of gas treated). As expected, due to the high temperature CO 2 removal capability and low energy needed to regenerate the sorbent, the power cycle efficiency with our process was greater than 34% on a higher heating value (HHV) basis; in comparison, the same IGCC plant equipped with the Selexol TM solvent for carbon capture can only achieve 31.4% HHV efficiency. The capital cost for an IGCC system with TDA’s process is estimated as $2,417/kW e , which is 12% lower than that of the IGCC/ Selexol TM process. The levelized cost for electricity including the transport, storage and monitoring (TS&M) cost for CO 2 was calculated as $\$ $92.9/MWh (lowest reported to our knowledge), which is much better than the $105.2/MWh estimated for the IGCC/ Selexol TM process. In this project (DE-FE0013105), TDA Research, in collaboration with our partners Gas Technology Institute (GTI), Illinois Clean Coal Institute (ICCI), University of California, Irvine (UCI), University of Alberta (UOA), Siemens, NCCC and Sinopec advanced the technical maturity of the technology; scaling it up by a factor of 100. We optimized the reactor design using computational fluid dynamics (CFD); using adsorption modeling we improved the pressure swing adsorption (PSA) cycle sequence. We carried out two field test campaigns with a fully-equipped 0.1 MW e prototype unit (for a total of 844 hours) using actual synthesis gas to prove the viability of the new technology. A successful 30 day (707 hrs) evaluation was completed at NCCC under air blown gasification conditions. We demonstrated 97.3% carbon capture at 1,500 SLPM, 93% carbon capture at 1,800 SLPM, and 90% carbon capture at 2,100 SLPM in the NCCC tests. We also demonstrated the system for 137 hours at a Sinopec petrochemical plant under oxygen blown gasification, demonstrating 86% carbon capture at 2,660 SLPM. In collaboration with University of California, Irvine (UCI), we completed a techno-economic analysis (TEA) for TDA’s warm gas cleanup technology integrated to IGCC power plant. The net plant efficiencies (on a coal HHV basis) for the warm gas cleanup cases were estimated to be 34.0% for E-GasTM gasifier, 34.4% for GE gasifier, 33.4 for the Shell gasifier and 34.2 for the TRIG TM gasifier (Cases 2, 4, 6 and 8 in this study) with a catalytic combustor for CO 2 purification, which are significantly higher than those for the Cold Gas Case, or an increase of as much as 12% in the heat rate for Case 2, 6% for Case 4, 9% for Case 6, and 9% for Case 8. The 1st year cost of electricity with the transport, storage and monitoring (TS&M) costs for the CO 2 included was $\$ $129.2/MWh for the E-GasTM gasifier Warm Gas Cleanup Case, $\$ $131.9/MWh for the GE gasifier Warm Gas Cleanup Case, $\$ $146.8/MWh for the Shell Gasifier Warm Gas Cleanup Case, and $\$ $129.9/MWh for the TRIG TM gasifier Warm Gas Cleanup Case. For comparison, the costs for the baseline Cold Gas CO 2 removal with Selexol for the different gasifiers were: $\$ $146.6/MWh for the E-Gas TM gasifier, $\$ $142.2/MWh for the GE gasifier, $\$ $159.0/MWh for the Shell gasifier and $\$ $144.3/MWh for the TRIG TM gasifier. In summary, the costs for our system were 7 to 12% lower than the corresponding Cold Gas Cleanup cases. The results of this techno-economic analysis suggested that TDA’s high temperature PSA-based Warm Gas Clean-up Technology can make a substantial improvement in the IGCC plant thermal performance for achieving near zero CO 2 emissions for E-Gas TM , GE, Shell and TRIG TM gasifier based IGCC power plants. The capital expenses were estimated to be lower than that of Selexol’s™. Taken together, the higher net plant efficiency and lower capital and operating costs resulted in substantial reduction in the cost of carbon capture for the IGCC plant equipped with TDA’s high temperature PSA-based carbon capture system. Finally, in collaboration with Gas Technology Institute (GTI) we completed the environmental health and safety assessment for TDA’s warm gas carbon capture technology.

01 COAL, LIGNITE, AND PEAT↗

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↗

Polydiallylammonium-Polysulfone Multiblock Copolymers for Moisture-Swing Direct Air Capture of Carbon Dioxide

Polysulfones are an important class of materials for a variety of applications due to their excellent strength and thermal stability. Quaternary ammonium polymers are also useful materials due to their ion exchange properties, and such materials with alkaline counterions have been used to capture carbon dioxide (CO 2 ) from ambient air through a moisture-driven mechanism. Herein, we design sulfone-based multiblock copolymers containing ammonium functionalities and demonstrate their potential for CO 2 capture. Specifically, a series of multiblock copolymers containing both polydiallyldimethylammonium (PDADMA) and polysulfone (PSf) blocks were synthesized. PSf blocks provide mechanical integrity, while the PDADMA blocks enable the direct air capture of CO 2 . Multiblock copolymers were synthesized at high yield, and PDADMA(OH)-PSf copolymer films with good flexibility and strength were formed with IECs of 424 μmol/g (17 mol % PDADMA(OH)), 1407 μmol/g (44 mol % PDADMA(OH)), and 1726 μmol/g (50 mol % PDADMA(OH)). Thermogravimetric analysis was used to determine that all films are thermally stable up to 345 °C. Differential scanning calorimetry revealed that the 17 and 44 mol % functionalized PDADMA(OH)-PSf multiblock copolymers showed one T g at 185 °C and 50 mol % PDADMA(OH)-PSf polymer showed a T g at 183 °C and a second T g at 16 °C. Atomic force microscopy showed that the multiblock polymers exhibit disordered phase separation. Furthermore, the copolymer materials displayed moisture-swing direct air capture of CO 2 , opening up pathways to utilize polymer architecture and chemistry to tailor the properties of promising sorbents.

42 ENGINEERING↗

Phase field-volumetric lattice Boltzmann model of ion uptake in porous nuclear waste form materials under continuous flow

The flow field within the mesopores of sorbent particles plays a crucial role in radionuclide diffusion and ion uptake kinetics, thus, impacting the overall performance of porous nuclear waste form materials. To fundamentally understand the influence of microstructures and material properties on the radionuclide absorption and retention processes requires a coupled multi-physics model that considers the advection and diffusion within the flow field, the reaction at liquid-solid interfaces, and finally, the solid-state diffusion within a complex nanoporous medium. Here, this study employs the volumetric lattice Boltzmann method (VLBM) to accurately and efficiently calculate the steady state velocity field inside the mesopores of sorbent particles. The obtained velocity field is then utilized to calculate the advection of ions in the steady flow. A phase field (PF) model of ion uptake is used to describe the reaction occurring at the solid-liquid interface and diffusion inside the porous medium. The integrated PF-VLBM model is verified in terms of the mass conservation and numerical efficiency and validated qualitatively with experimental observation data. Then, it is applied to study the influence of thermodynamic and kinetic properties, as well as flow field conditions on the ion uptake kinetics. The numerical results demonstrate that the ion uptake kinetics in porous particles has three distinct stages, which is in agreement with the observations in continuous flow experiments. In the first stage, the kinetics is predominantly controlled by the flow field and ion diffusivity in the liquid phase. The kinetics in the second stage is primarily governed by ion diffusivity in the solid phase. In the third stage the system reaches a dynamic equilibrium with a net zero uptake flux at the interface. It is also found that porous structures significantly affect the efficiency and capacity of ion uptake. The simulation results can help to understand the physics behind the observed ion uptake kinetics in experiments and to facilitate the development of constitutive equations that can account for heterogeneous microstructures in engineering performance codes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Design and characterization of hierarchical aluminosilicate composite materials for Cs entrapment: Adsorption efficiency tied to microstructure

The growing quantity of nuclear waste and the serious threats to the environment challenge researchers to innovate and target new waste form technologies. In the past decades, considerable efforts have been devoted to developing highly selective sorbents followed by safe disposal with the assurance of chemical stability and robust retention performance. Zeolite-containing geopolymers are regarded as a possible 2-in-1 material able to both capture and sequester elements such as Cs in bed fixed column application perspective. Here, these composites show promise for combining extraction properties of zeolite powder due to its crystalline structure (high capacity and selective adsorption), with the tunable microstructure and the shaping feasibility of the geopolymer binder. For the development of materials devoted to Cs immobilization, porous zeolite/geopolymer composites were prepared by dispersing NaY zeolite particles in a geopolymer binder. The influence of the structural properties of such composites on their ability to entrap a large amount of Cs by an ionic exchange process was notably studied. Composites' compositions, porosities, morphologies and crystallinity were analyzed by scanning electron microscopy coupled with energy dispersive x-ray spectroscopy (SEM-EDX), x-ray diffraction analysis (XRD) and nitrogen adsorption/desorption studies. Experimental Cs sorption in batch mode was used to follow the ionic exchange phenomenon in these materials. Along with 5 wt% amount of zeolite in geopolymer improves the Cs adsorption performance offering multiple new adsorption sites. Additionally, the geopolymer mesopores are beneficial facilitating the access of Cs and its role as a binder is advantageous to tailor granular hierarchical structure for safer industrial application.

36 MATERIALS SCIENCE↗

Liquid Sorption-Enhanced Haber–Bosch Process

The use of a liquid sorbent in a traditional Haber-Bosch process enables significant improvements in energy efficiency and potential cost savings for arguably the most important chemical process on the planet. The approach presented in this report employs an incompressible liquid sorbent that absorbs and releases ammonia (NH 3 ) under specific conditions. To achieve this, we investigate reactions of ammonia and pure phosphoric acid (H 3 PO 4 , PA), which rapidly neutralize to form an equilibrated solution of monoammonium phosphate (MAP) and diammonium phosphate (DAP) that functions as a reversible and regenerable sorbent. Through intimate contact of the gas-phase Haber-Bosch reaction mixture with this liquid absorbent, complete equilibrium uptake may be achieved in an appropriately sized separator, and facile separation occurs through the use of independent liquid and gas phases. Following depressurization and release of the ammonia product, only the incompressible fluid needs to be repressurized and returned to the reactor. This study documents proof-of-concept absorption and desorption experiments carried out in 75 mL batch reactors, predominantly charged with precise MAP and DAP mixtures that equilibrate at process-relevant temperatures and pressures. We then assemble the first thermodynamic relationships that underlie this advantaged separation strategy, validated by reactive force field (ReaxFF) interatomic potential simulations, and benchmarked with traditional separation routes via process modeling and technoeconomic analysis. The scale of energy consumption in the century-old Haber-Bosch process is massive, and the elegant liquid sorption approach reported here offers opportunities to enhance its energy efficiency for the next frontier of ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Structured Adsorbent Architectures for Transformative Carbon Dioxide Capture Performance (Final Report)

Svante is a world leader at using solid sorbents for low-cost Carbon Dioxide (CO 2 ) capture, a technology which is recognized as critical in meeting the dual mandates of energy security/reliability and the mitigation of man-made CO 2 emissions. Svante has been developing proprietary adsorbent material compositions, forming them into structured laminates, developing and optimizing process cycles, and system design for efficient capture of CO 2 from post-combustion flue gases of thermal power plants and industrial facilities. The deployment of first-generation CO 2 capture technology has been significantly hampered by high costs and energy penalties, among other barriers. Second generation CO 2 capture technologies (including the Mark I variant of Svante’s Veloxotherm™ adsorption-based technology), utilizing single adsorbent architecture, show promise for reducing the barriers to deploying CO 2 capture plants in commercially meaningful numbers. The objective of this project was to evaluate the Recipient’s transformational (Mark-II) VeloxoTherm™ Technology via the development and bench-scale testing of an advanced structured adsorbent, including novel Bi-layer, laminated adsorbent structures and segmented beds. Svante selected, synthesized, and characterized tailored solid adsorbents for computational modeling, advanced structured adsorbent development, process simulations, and dynamic bench scale (~1-10 kg/day CO 2 captured) testing using an existing single-bed VeloxoTherm™ Station (VTS) coupled with a natural gas-fired boiler. Segmented beds used the in-house, multi-bed Process Demonstration Unit (PDU) to demonstrate key performance indicators (KPIs), such as recovery, product purity, regeneration energy, and the integrated system's productivity in lifetime analysis. Segmented beds were used at a 1 tonne per day (TPD) unit at an industrial site to provide bench-scale validation of performance in an industrial setting. Svante was developing and optimizing the post-combustion CO 2 adsorption technology architectures, including the Bi-layer and segmented laminated adsorbent structure design, integrated rapid cycle temperature swing adsorption (RC-TSA) cycle, flow path architecture, and adsorbent bed construction and packaging (including gas porting) to progress towards achievement of DOE’s Transformational CO 2 Capture goals of 95% CO 2 purity and a cost of electricity at least 30% lower than a supercritical Pulverized Coal (PC) power plant with CO 2 capture, or approximately $30 per tonne of CO 2 captured ready for demonstration by 2030. The main requirements to reach the DOE target cost of carbon capture below $30/MT using Rapid-Cycling Temperature Swing Adsorption (RC-TSA) are as follows: (1) Increased capacity at different CO 2 concentrations, (2) Increased sorbents cycle life, (3) Increased O 2 resistance, and (4) Decreased steam requirement to extract 1 kg of CO 2 .

20 FOSSIL-FUELED POWER PLANTS↗