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DOE OSTI2023

Laboratory investigation of hydraulic fracturing in granitic rocks using active and passive seismic monitoring

SUMMARY Knowledge of the fracturing processes can be important for the optimization of pressurized fluid injection operations in the deep underground rock mass. Active and passive seismic monitoring techniques have been used in the field for tracking or mapping the propagating hydraulic fracture. Although both these monitoring techniques provide valuable information about the generated fracture network, it is difficult for either technique to comprehensibly identify the different processes associated with hydraulic fracturing. The combined active and passive monitoring has the potential for better characterization of the complex hydraulic fracturing phenomena. In this study, laboratory hydraulic fracturing experiments with combined active and passive seismic monitoring were conducted on true triaxially loaded Barre granite cubes with different fluid injection rates. The seismic inelastic fracturing was detected by 16 passive acoustic emission sensors, where 3678 and 2370 seismic source events were detected for the high and low injection rate experiments, respectively. For active monitoring, strong variations in the attributes of signals were observed which were transmitted through four source–receiver pairs, placed both perpendicular and parallel to the generated hydraulic fracture. Positive velocity changes were observed for active sensor pairs with ray paths passing through the generated hydraulic fracture indicating fluid permeation, whereas isolated dry deformation was characterized by a slight but permanent velocity decrease. Compared to velocity, the energy of the active signals was 1–2 orders of magnitude more sensitive to different hydraulic fracturing processes. However, the sensitivity and signatures of the active signal attributes were found to be dependent on the frequency range and direction of ray path with respect to the location of the generated fracture network. Using the coupled evaluation of the active and passive signals we were able to systematically identify various hydraulic fracturing processes including: (1) aseismic deformation, (2) fracture initiation and fluid permeation, (3) pressure build-up, (4) fracture propagation and (5) pressure release and leak-off. The results of this study showed that combining the respective advantages of active and passive seismic techniques and using both of them to monitor the failure processes can facilitate a more comprehensive understanding and better control of the hydraulic stimulations in subsurface operations.

Geochemistry & Geophysics↗

DOE OSTI2023

LTE-P-8 Gas permeability

A procedure for the measurement of gas permeability of an anion exchange membrane (AEM). During the course of the electrochemical reaction, low gas permeation of hydrogen and oxygen through the membrane is crucial to run the process efficiently. The gas permeation rate can be measured using (A) pressure permeation cell, (B) electrochemical monitoring cell, (C) microelectrode and (D) in-situ measurement in MEA. The process relies on a chronoamperometric technique to accurately measure the gas permeation rate across the membrane.

08 HYDROGEN↗

DOE OSTI2020

Zeolite Membrane Reactor for Pre-Combustion Carbon Dioxide Capture (Final Scientific/Technical Report)

Water-gas shift (WGS) reaction followed by carbon dioxide (CO 2 ) separation is a critical step in the integrated gasification combined cycle (IGCC) process for fossil-fuel-fired electrical power generation with CO 2 capture. To intensify the IGCC process hydrogen-permselective zeolite membrane reactor offers promise to replace the conventional energy-intensive fixed-bed reactors and solvent-based CO 2 capture units. The objectives of this project were to develop a bench-scale zeolite membrane reactor (total membrane area: 932 cm 2 for a 21-tube membrane bundle) for the water-gas-shift reaction of raw syngas from an oxygen-blown coal-gasifier for H 2 production with simultaneous CO 2 separation at the capability of about 2 kilograms H 2 per day (equivalent to 2 kW IGCC power plant) and to demonstrate significant progress toward achieving overall performance goal of 90% CO 2 capture rate with 95% CO 2 purity at the cost of electricity 30% less than the baseline carbon capture approaches. This report summarizes results obtained in this project on scaling up the zeolite membrane reactor by a factor of 200 in membrane area, tests of the bench-scale zeolite membrane reactor for the water-gas-shift reaction at high temperature and high-pressure, and techno-economic analysis of the integration of the zeolite membrane reactor in IGCC power plant for the electrical generation with CO 2 capture. With effective pore modification by catalytic cracking deposition of MDES (methyldiethoxysilane), fabrication of MFI-type zeolite membranes was successfully scaled-up from a lab-scale disk type to bench-scale multiple-tube bundles on low-cost alumina supports. A Co-Mo based sour shift catalyst was evaluated and used in the zeolite membrane reactors for water-gas-shift reaction. The reaction kinetic and gas-permeation equations were developed and employed in mathematic models to guide/predict experiments/performance of zeolite membrane reactors for water-gas shift reaction. Multiple-tube zeolite membrane bundles and reactors were designed, fabricated and tested for gas separation and water-gas-shift reactions with real raw syngas from a coal-fired gasifier operated at high temperature and pressure. The zeolite membrane reactors demonstrated good long-term thermal and chemical stability and constant H 2 permeance (>300 GPU) together with a Knudsen selectivity (~4.7) for H 2 over CO 2 in the field test (cumulative time >28 hours) with high-sulfur coal-derived syngas. The zeolite-membrane-reactor integrated IGCC process was designed using the performance experimentally measured by the University of Cincinnati team with a single-tube zeolite membrane reactor that offers a CO conversion >98% with more than 90% of CO 2 and H 2 captured. With the above integrative approaches, a techno-economic analysis for a cost-benefit comparison was performed to uncover features that determine the power output, capital expenditure, operating expenditure, cost of electricity and cost of CO 2 capture in a 550-MW zeolite-membrane-reactor integrated IGCC process. The integration of the zeolite membrane reactor in IGCC could provide a significant reduction of 80% and 27% in the power consumption for Selexol™ Acid Gas Removal and CO 2 compression, respectively, which lowers the total auxiliary power consumption by 12.5%. However, the low pressure required at permeate stream for maintaining the driving force of hydrogen permeation through the zeolite membrane costs a huge power in permeate compressor, compensating the power consumption reduction achieved with the membrane reactor. Thus, for coal-fired IGCC for electricity generation with 90% CO 2 captured, the integration of the membrane reactor could provide a CO conversion ~99% and a significant drop in cost-of-electricity using zeolite membrane with H 2 permeance >600 GPU and the H 2 /CO 2 selectivity over 70.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2020

MAX phase materials and MXenes as hydrogen barrier coatings

Hydrogen and its isotopes play an important role in nuclear applications, but their permeation and radioactivity lead to degradation of materials. Therefore, hydrogen isotope permeation barriers are an important supporting technology. Unfortunately, most permeation barriers that perform well in the laboratory fail when placed in radiation environments. The goal of this work is to begin the development of next generation permeation barriers with materials known to have good stability under neutron irradiation, and then tailor their composition and structure to maximize their barrier properties. In particular MAX phase materials and their two-dimensional analogues (MXenes) have been chosen due their excellent stability under neutron irradiation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Comparative Energetics of Various Membrane Distillation Configurations and Guidelines for Design and Operation

This paper presents a comparative performance study of single-stage desalination processes with major configurations of membrane distillation (MD) modules. MD modules covered in this study are (a) direct contact MD (DCMD), (b) vacuum MD (VMD), (c) sweeping gas MD (SGMD), and (d) air gap MD (AGMD). MD-based desalination processes are simulated with rigorous theoretical MD models supported by molecular thermodynamic property models for the accurate calculation of performance metrics. The performance metrics considered in MD systems are permeate flux and energy efficiency, i.e., gained output ratio (GOR). A general criterion is established to determine the critical length of these four MDs (at fixed width) for the feasible operation of desalination in a wide range of feed salinities. The length of DCMD and VMD is restricted by the feed salinity and permeate flux, respectively, while relatively large AGMD and SGMD are allowed. The sensitivity of GOR flux with respect to permeate conditions is investigated for different MD configurations. AGMD outperforms other configurations in terms of energy efficiency, while VMD reveals the highest permeate production. With larger MD modules, utilization of thermal energy supplied by the hot feed for evaporation is in the order of VMD > AGMD > SGMD > DCMD. Simulation results highlight that energy efficiency of the overall desalination process relies on the efficient recovery of spent for evaporation, suggesting potential improvement in energy efficiency for VMD-based desalination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1972

Physical electronics and surface physics

Current analytical and experimental investigations of the influence of surface processes on the rate of permeation of gases through solids are summarized. A brief description is presented of an analytical model that provides an approximate prediction of the dependence of the permeation rate on the rates of surface processes relative to the rate of the diffusion process. Results of experiments indicate that the desorption process of hydrogen from various materials is influenced by surface impurities to the degree that substantial changes in the spatial distribution of the desorbed molecules are observed when the impurities are varied. Except possibly for H-Nb, the permeation measurements indicate that the desorption process is not influenced to the degree that detectable changes in the permeation rates are observed when the impurities and temperatures are varied. On the basis of analysis, it is unlikely that the desorption process will be the rate-controlling step under the conditions of the present experiments.

Stickney, R. E.↗

NASA NTRS1995

On-line removal of volatile fatty acids from CELSS anaerobic bioreactor via nanofiltration

The CELSS (controlled ecological life support system) resource recovery system, which is a waste processing system, uses aerobic and anaerobic bioreactors to recover plants nutrients and secondary foods from the inedible biomass. The anaerobic degradation of the inedible biomass by means of culture of rumen bacteria,generates organic compounds such as volatile fatty acids (acetic, propionic, butyric, VFA) and ammonia. The presence of VFA in the bioreactor medium at fairly low concentrations decreases the microbial population's metabolic reactions due to end-product inhibition. Technologies to remove VFA continuously from the bioreactor are of high interest. Several candidate technologies were analyzed, such as organic solvent liquid-liquid extraction, adsorption and/or ion exchange, dialysis, electrodialysis, and pressure driven membrane separation processes. The proposed technique for the on-line removal of VFA from the anaerobic bioreactor was a nanofiltration membrane recycle bioreactor. In order to establish the nanofiltration process performance variables before coupling it to the bioreactor, a series of experiments were carried out using a 10,000 MWCO tubular ceramic membrane module. The variables studied were the bioreactor slurry permeation characteristics, such as, the permeate flux, VFA and the nutrient removal rates as a function of applied transmembrane pressure, fluid recirculation velocity, suspended matter concentration, and process operating time. Results indicate that the permeate flux, VFA and nutrients removal rates are directly proportional to the fluid recirculation velocity in the range between 0.6 to 1.0 m/s, applied pressure when these are low than 1.5 bar, and inversely proportional to the total suspended solids concentration in the range between 23,466 to 34,880. At applied pressure higher than 1.5 bar the flux is not more linearly dependent due to concentration polarization and fouling effects over the membrange surface. It was also found that the permeate flux declines rapidly during the first 5 to 8 hours, and then levels off with a diminishing rate of flux decay.

Colon, Guillermo↗

NASA NTRS1994

Permeability of membranes to amino acids and modified amino acids: mechanisms involved in translocation

The amino acid permeability of membranes is of interest because they are one of the key solutes involved in cell function. Membrane permeability coefficients (P) for amino acid classes, including neutral, polar, hydrophobic, and charged species, have been measured and compared using a variety of techniques. Decreasing lipid chain length increased permeability slightly (5-fold), while variations in pH had only minor effects on the permeability coefficients of the amino acids tested in liposomes. Increasing the membrane surface charge increased the permeability of amino acids of the opposite charge, while increasing the cholesterol content decreased membrane permeability. The permeability coefficients for most amino acids tested were surprisingly similar to those previously measured for monovalent cations such as sodium and potassium (approximately 10(-12)-10(-13) cm s-1). This observation suggests that the permeation rates for the neutral, polar and charged amino acids are controlled by bilayer fluctuations and transient defects, rather than partition coefficients and Born energy barriers. Hydrophobic amino acids were 10(2) more permeable than the hydrophilic forms, reflecting their increased partition coefficient values. External pH had dramatic effects on the permeation rates for the modified amino acid lysine methyl ester in response to transmembrane pH gradients. It was established that lysine methyl ester and other modified short peptides permeate rapidly (P = 10(-2) cm s-1) as neutral (deprotonated) molecules. It was also shown that charge distributions dramatically alter permeation rates for modified di-peptides. These results may relate to the movement of peptides through membranes during protein translocation and to the origin of cellular membrane transport on the early Earth.

Review↗

NASA NTRS2009

Nano-Pervaporation Membrane with Heat Exchanger Generates Medical-Grade Water

A nanoporous membrane is used for the pervaporation process in which potable water is maintained, at atmospheric pressure, on the feed side of the membrane. The water enters the non-pervaporation (NPV) membrane device where it is separated into two streams -- retentate water and permeated water. The permeated pure water is removed by applying low vapor pressure on the permeate side to create water vapor before condensation. This permeated water vapor is subsequently condensed by coming in contact with the cool surface of a heat exchanger with heat being recovered through transfer to the feed water stream.

Tsai, Chung-Yi↗

NASA NTRS2014

Towards Co-evolution of Membrane Transport and Metabolism

Protocellular boundaries were inextricably connected to the metabolism they encapsulated: to be inheritable, early metabolism must have led to an increased rate of growth and division of vesicles and, similarly, transport through vesicle boundaries must have supported the evolution of metabolism. Even though explaining how this coupling emerged and evolved in the absence of the complex machinery of modern cells is one of the key issues in studies on the origin of life, little is known about the biochemical and biophysical processes that might have been involved. This gap in our knowledge is a major impediment in efforts to construct scenarios for the origin of life and laboratory models of protocells. A combination of experimental and computational studies carried out by us and our collaborators is aimed at helping to close this gap. Properties of membranes might have contributed to the selection of RNA as an early biopolymer. A kinetic mechanism was proposed (Sacerdote & Szostak, 2005) in which ribose was supplied more quickly than other aldopentoses to primordial cells for preferential incorporation of ribonucleotides into nucleic acids. This proposal is based on a finding that ribose permeates membranes an order of magnitude faster than its diastereomers, arabinose and xylose. Our computer simulations, which yield permeation rates in excellent agreement with experiment, and kinetic modeling explain this phenomenon in terms of inter- and intramolecular interactions involving exocyclic hydroxyl groups attached to carbon atoms of the pyranose ring (Wei and Pohorille, 2009). They also constrain scenarios for the formation of the earliest nucleic acids (Wei and Pohorille, 2013). In one scenario, sugars permeate protocellular walls and subsequently are used to synthesize nucleic acids inside protocells. As long as this process proceeds at the rate faster than 6x10(exp -3)/s, ribose derivatives will be available for synthesis easier than their diastereomers. If nucleosides or their activated derivatives are synthesized outside protocells and subsequently transported across protocellular membranes the kinetic mechanism does not apply because all diastereomers, which have their sugars in the furanose rather than pyranose form, permeate the membrane at approximately the same rate. Properties of membranes might have been also coupled to metabolism involving peptides. Recently, Adamala and Szostak (2013) have shown that a dipeptide inside fatty-acid vesicles catalyzes the formation of another dipeptide that binds to vesicle walls and, by doing so, promotes their growth at the expense of other vesicles. This coupling of metabolism, permeability of vesicles and their growth is the first demonstration of evolutionary advantage imparted by small, membrane-bound peptides. Building on this work we have calculated the rate at which different blocked amino acids are delivered to a protocell for synthesis of dipeptides. We have further shown that the dipeptides are located at the water-membrane interface rather than in the center of the bilayer. On these basis it is anticipated that other dipeptides containing aromatic, but not necessarily hydrophobic amino acids (e.g. tyrosine) could have the same catalytic effects. Insight from these studies allows for estimating the rate of vesicle growth and the rates of dipeptide synthesis required to keep the system in balance. These results, in combination with our earlier studies, lead to a general scenario for evolution from membrane-bound dipeptides to ion channels in the origin of life.

Metabolism↗

DOE OSTI2020

Technical Performance of Refractory Liners for Molten Chloride Salt Thermal Energy Storage Systems

A chloride-based molten-salt system that uses a ternary blend of MgCl2/KCl/NaCl is investigated to provide higher temperature thermal energy storage capability. Despite higher thermal stability, molten chlorides present several unique challenges, including the design of internal refractory-ceramic liners to prevent the corrosion and thermal stress of alloy tank shells. This work discusses issues and potential solutions related to containment of molten chloride salt, specifically the optimization of the refractory material at the molten salt interface (hot face). The down-selected hot face candidate limits permeation of salt through the material and forms a highly stable secondary surface phase in equilibrium with the molten salt. A mortar is created using the corrosion resistant hot face brick. Brick and mortar composite are subjected to mechanical stress/strain analysis, in order to calculate composite material properties and better inform thermomechanical models. The U.S. Department of Energy Generation 3 (DOE Gen3) program seeks to develop higher efficiency CSP plants that can provide cost-competitive, flexible power in the U.S. electric grid. The proposed Gen3 Liquid Pathway CSP plant closely resembles the configuration of current nitrate salt power towers with two-tank storage (Gen2). The differences between Gen2 and Gen3 include the types of compatible materials used in salt storage tank construction. Stainless steel loses strength at Gen3 temperatures, and although nickel superalloys would be capable of withstanding sustained high temperatures, these materials are prohibitively expensive at scale. Uninsulated tank shells also pose a significant risk as common steels are highly susceptible to chemical attack from molten chloride salt. To address these concerns, refractory-ceramic based containment materials are proposed to line the inside of the hot and cold storage tanks. In doing so, stainless or carbon steel shells may be used in construction depending on the level of insulation provided. The composition of the internal liner requires careful consideration to maximize the efficacy of multiple parameters including corrosion resistance, strength at operating temperature, durability, and cost. This is particularly true for the material at the interface with the salt, known as the "hot face", which is responsible for protecting the insulating layers between the tank shell and the hot face brick layer. The molten salt in this system is superheated over 300 °C above its freeze temperature. Therefore, unlike other industrial processes which use refractory-lined vessels, it is not expected that a freeze plane will develop in the hot face. Therefore, the hot face must be designed to withstand chemical corrosion and inhibit permeation of molten salt into the insulating layers. A down selection was performed to identify a hot face candidate best equipped to maintain thermal, mechanical, and chemical integrity when exposed to molten salt over extended periods of time. Long-duration chemical capability experiments were conducted with the down selected hot face refractory fully immersed in molten chloride salt for up to 3000 hours. The average salt penetration does not exceed 100 microns. When extrapolated to 20 and 30 years of continuous exposure, the expected salt penetration depth is approximately 2.0 mm and 2.9 mm, respectively. A magnesium-rich secondary phases develops at the salt/refractory interface. X-ray diffraction identifies the material as forsterite (Mg2SiO4), which is reported to form synthetically in molten chloride salt solutions. These results suggest the selected hot face will adequately inhibit salt permeation. While there is optimism that the hot face brick will inhibit salt permeation, mortar joints are typically the weakest point of a refractory brick liner. From a thermochemical perspective, differing thermal expansion coefficients may result in the mortar and brick to grow independent of each other, creating gaps through which molten salt can penetrate. To address this issue, NREL has developed an in-house mortar composed of the down selected hot face brick that has been shown to be compatible with the salt. Compressive stress/strain analyses have been performed on the brick/ mortar composites to generate stress/strain curves. Modulus of elasticity and Poisson's ratio of the composite may be calculated from the stress/strain curves, in order to provide more representative data to finite element mechanical models for accurate approximation of stress on the tank shell and the amount of thermal expansion expected within the tank liner.

41 EE - Solar Energy Technologies Office (EE-4S)↗

DOE OSTI2022

High-Temperature Ceramic-Carbonate Dual-Phase Membrane Reactor for Pre-combustion Carbon Dioxide Capture (Final Scientific/Technical Report)

Arizona State University, in collaboration with University of South Carolina, worked on a project aimed at development of a new high temperature, high pressure CO 2 perm-selective membrane reactor for water-gas-shift reaction (WGS) with simulated gasifier syngas to produce a high concentration H 2 stream with CO 2 capture. The membrane reactor is made of a CO 2 semi-permeable ceramic-carbonate dual-phase (CCDP) membrane with high CO 2 perm-selectivity/permeance and thermal/mechanical stability for application in WGS reaction. The objectives of this project were to (1) synthesize the chemically/thermally stable tubular CCDP membranes with CO 2 permeance and selectivity (with respect to H 2 , CO or H 2 O) larger than 6.5×10-7 mol/m2·s·Pa and 500, respectively; (2) establish CCDP membrane reactor setup and study high pressure CO 2 permeation and WGS reaction with CO 2 capture using the setup; and (3) identify conditions for WGS in the CCDP membrane reactor that produce CO 2 and H 2 streams with purity of >99% and >90% respectively at CO conversion >95% and overall carbon capture >90%. The work in this project included both membrane development and membrane reactor process study. The membrane development efforts were focused on investigating a H 2 S resistant and highly oxygen-ionic conducting metal oxide material and membrane for CO 2 separation, fabrication of tubular samaria-doped-ceria/molten-carbonate CCDP membrane with high mechanical strength, and experimental and modeling study of high-pressure CO 2 permeation of the CCDP membranes. Mathematical models were developed to describe WGS in the CCDP membrane reactor without a catalyst or packed with a commercial high temperature WGS catalyst. Experiments on WGS in the CCDP membrane reactor with the commercial WGS catalyst, guided by the model analysis, were performed to identify optimum conditions for achieving the CO conversion, carbon capture, and the purity of the H 2 and CO 2 streams mentioned above. At 30 atm feed pressure, 750°C operation temperature, space velocity of 250 h-1, and with steam sweep, a single-stage CCDP membrane reactor with average CO 2 permeation flux of 0.5 cm3(STP)/min.cm2 can achieve CO 2 conversion of 95% and overall carbon capture of 94%, and produce CO 2 and H 2 streams with dry-based purity of >99% and 92% respectively. The project also included process design and techno-economic analysis (TEA) for a CCDP membrane reactor process for WGS reaction with CO 2 capture for a 550 MW coal-fired IGCC power plant, and its comparison with the conventional fixed-bed reactor system for WGS with follow-up CO 2 capture by an amine absorption process. The target performance for the reactor for WGS with CO 2 capture includes CO conversion >95%, hydrogen stream purity >90%, CO 2 stream purity >95%, and total carbon capture >90%. The CCDP membrane developed in this project can achieve the performance target, without subsequent CO 2 capture process at the optimum conditions identified in this project. The outcome of the process design and TEA analysis shows that the membrane reactor for WGS with in-situ CO 2 capture has an operating cost about 40% lower than that for the conventional fixed-bed reactor with a separate amine absorption process for CO 2 capture. However, the capital cost of the membrane reactor process is about twice that of the conventional process because of the higher cost of the CCDP membrane. Modeling analysis shows that a membrane reactor using a CCDP membrane with higher CO 2 permeance (about three times the current value) can deliver the targeted performance for WGS reaction with CO 2 capture at a much higher space velocity and lower membrane surface area to catalyst volume ratio, leading to a smaller catalyst amount and/or membrane area and hence significantly reduced membrane reactor capital costs.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2021

Kraft black liquor concentration with graphene oxide membranes: Process simulations and technoeconomic analysis

Abstract Black liquor (BL) dewatering by multi‐effect evaporation in the kraft papermaking process is highly energy‐intensive. It was previously shown that graphene oxide (GO) nanofiltration membranes can remove lignin, other organics, and inorganic salts from BL while exhibiting stability in caustic BL conditions. Here, we design and simulate several candidate dewatering processes and evaluate their technoeconomic characteristics. All processes concentrate BL from 15 to 30 wt% solutes while producing aqueous permeate. Two process options were analyzed—option A including “last‐mile” permeate treatment to reduce solutes to 0.2 wt%, and option B excluding this treatment and producing a 3–4 wt% solutes stream. These processes were simulated in custom‐built ASPEN Plus flowsheets interfaced with Microsoft Excel and MATLAB. All processes deliver large (>40%) energy savings. Detailed technoeconomic analysis showed that option A processes are profitable in mills equipped with condensing turbines, but unprofitable with only purchased fuel savings. Option B processes are profitable in both situations, but require the caustic permeate to be utilized in other kraft process units. They are also profitable with electricity generation when operated at smaller scales matching the requirements of other process units. Monte‐Carlo sensitivity analysis shows that Option A can yield median 20‐year NPVs up to ~$10MM and Option B up to ~$25MM. Overall, GO membrane‐based BL dewatering is economically promising, assuming successful slipstream piloting and scale‐up campaigns. It would have immediate sustainability benefits from large energy savings, and broader implications for biorefinery processes due to the ability to fractionate biomass feedstock components under harsh conditions.

Wang, Zhongzhen↗

DOE OSTI2021

Toward predictive permeabilities: Experimental measurements and multiscale simulation of methanol transport in Nafion

A polymer membrane's permeability to solutes determines its suitability for various applications: a permeability value is essential for predicting performance in diverse contexts. Using aqueous methanol permeation through Nafion as an example, we describe a methodology for determining membrane permeability that accounts for boundary layer effects and the possibility of swelling. For the materials and apparatus used herein, analysis of a permeance measurement and computational fluid dynamics simulations show that the mass transfer boundary layer is on the order of ones to tens of microns. Additionally, the data are used to develop and validate a multiscale model describing solute permeation through a hydrated membrane as a series of physical mechanistic steps: reversible adsorption from solution at the membrane interface, diffusion driven by a concentration gradient within the membrane, and reversible desorption into solution at the opposite membrane interface. The validated model is used to predict methanol transport across a solar-driven CO 2 reduction device and to assess the impact of polymer changes on the measured value. The approach of combining experimental data, computational fluid dynamics, and the mechanistic multiscale model is expected to provide more accurate analysis of membrane permeation data in cases with polymer swelling or unusual device geometries, among others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Penetrant competition and plasticization in membranes: How negatives can be positives in natural gas sweetening

Membranes are attractive for upgrading natural gas; however, the gas permeation processes through membranes are challenging to control. The coexistence of condensable H 2 S and CO 2 typically causes membrane performance to decline under practical feed conditions, due to uncontrolled penetrant competition and undesired plasticization of the membrane polymer matrix. In this paper, we report a strategy to successfully transform these apparent negatives, i.e. plasticization and penetrant competition, into positives that boost the natural gas sweetening efficiency of membranes greatly. Our strategy is to disperse engineered metal organic framework (MOF) fillers into designed polymer matrices to form hybrid membranes, which promote the permeation of both H 2 S and CO 2 but hinder CH 4 permeation. Moreover, uniformly dispersed MOF fillers also significantly alter the plasticization responses of polymer matrices, enabling controlled plasticization benefits. Ultimately, we illustrate a highly tunable MOF-polymer hybrid membrane platform that meets the diverse natural gas sweetening requirements under aggressive conditions.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Performance characterization of nanofiltration, reverse osmosis, and ion exchange technologies for acetic acid separation

A major obstacle to widespread implementation of bio-based fuels and chemicals is the lack of efficient and costeffective separation methods. To purify acetic acid produced by biochemical conversion of biomass via anaerobic digestion, this work employs two commonly used separation technologies: (1) ion-exchange (IX) resin and (2) pressure-driven membranes. This study tested five commercially available strong- and weak-base anion-exchange resins and five commercially available nanofiltration (NF) and reverse osmosis (RO) membranes. The pH of the feed solution significantly affected adsorption capacity. At pH 6.3, a strong-base IX resin (IRN-78) performed best (95.1% acetate removal). With strong-base IX resins, the Langmuir isotherm model fit well, whereas for weak-base IX resins, the Freundlich isotherm provided a better fit. A pseudo-second-order kinetic model fit well for both IRN-78 and IRA-67. Regarding membrane separation, RO (BW30XFR membrane) achieved the highest rejection (98.6% acetate rejection), whereas an NF membrane (NF*) achieved the best combination of permeate flux (105 L/(h∙m 2 )) and rejection (83.1% acetate rejection). For membrane performance, the experimental data were fit using the solution diffusion model. Increased pH in the feed solution lowered permeate flux but increased acetic acid rejection. Finally, then the acetic acid concentration in the feed solution increased, both permeate flux and acetic acid rejection decreased for membrane NF*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Computational Fluid Dynamics Analysis of the Molten Salt Tritium Transport Experiment Test Section

Tritium, a radionuclide produced through neutron capture by lithium and other elements (beryllium and fluoride) in molten salts, presents unique challenges to radionuclide release. This is true for both fusion energy breeder blankets and molten salt fission reactors. The fundamental understanding of tritium transport is crucial to the safe design and operation of these reactors. The Molten Salt Tritium Transport Experiment (MSTTE), currently under construction at Idaho National Laboratory, aims to investigate tritium transport phenomena using a forced-convection fluoride salt loop. This loop is designed to study various transport mechanisms, such as permeation through metals and gas-liquid interactions, and is intended to support future research on tritium extraction units. A critical aspect of the MSTTE loop design is ensuring a fully developed velocity profile before the fluid reaches the permeation test section where measurements are made. This study employs computational fluid dynamics to model the salt flow behavior within the MSTTE permeation test section. A realizable k-ε turbulent model with enhanced wall treatment is used to simulate the single-phase, vertical upward flow of molten salt FLiNaK under isothermal conditions. The simulation results indicated flow distortion and underdeveloped profiles at all planned flow rates within the test section due to the 85-deg sharp bend. To address this issue, a reduced diameter with a reducer and expander and a flow conditioner are investigated to achieve fully developed flow. The analysis showed that the flow conditioner successfully corrected the flow profile, achieving fully developed behavior at a flow rate of 50 liters per minute (LPM). In conclusion, this research enhances our understanding of flow dynamics in molten salt systems and contributes to optimizing tritium transport control technologies.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Dynamic control of molecular transport MXene transistor membranes

Controlled spatial confinement and surface properties of lamellar 2D nanomaterial membranes could enhance many precision separation processes. Traditionally, researchers view channel dimensions, surface properties, and permeation rates of these membranes as intrinsic properties that cannot be modulated in operando. We report that gate voltage applied to the conducting laminar MXene membrane can modulate the permeation rate of ions and neutral solutes, as well as its effective size rejection. In operando wide-angle x-ray scattering measurements reveal that these changes are not driven by electrically induced variations in the d spacing of the MXene layers. Instead, experimental data and continuum electrokinetic modeling reveal that ion transport through the MXene channels is primarily affected by Donnan equilibrium at the membrane-solution interface. We also report a strong increase in the permeation rates through the membrane under a low-frequency ac voltage gating regime that we attribute to diffusioosmotic flow oscillations induced in the membrane. Overall, MXene “transistor” membranes provide a previously unidentified approach to dynamic control of molecular separations.

Pendse, Aaditya [Lawrence Livermore National Labor↗