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At least 19 records

Comparison of microwave and conventional heating for CO 2 desorption from zeolite 13X

In this study, we investigate microwave irradiation as an alternative to conventional heating for temperature swing adsorption processes. The performance of microwave and conventional heating during sorbent regeneration was evaluated by measuring CO 2 desorption from zeolite 13X at different temperatures. Experimentally, a fixed bed of zeolite 13X was saturated by a 150 sccm flow of 15 % CO 2 at room temperature followed by sorbent regeneration under nitrogen at 55, 100, or 150 °C by applying either microwave irradiation or conventional heating. Microwaves reduced sorbent regeneration times by at least half compared to regeneration by conventional heating. Under conventional regeneration, desorption curves were resolved into two peaks representing physisorbed CO 2 (mass diffusion limited) at low temperature and bicoordinated CO 2 (thermally limited) with increasing temperature. Under microwave regeneration, only one desorption peak was observed suggesting that CO 2 desorption was limited by mass diffusion through the porous zeolite 13X structure, rather than by temperature. Depending on microwave power, apparent activation energy of the microwave-assisted regeneration was 15.8–18.1 kJ/mol, compared to 41.5 kJ/mol for conventional regeneration. The reduction in apparent activation energy is mainly attributed to selective microwave heating of CO 2 adsorption sites (Na + sites) resulting in greater steady state temperatures of Na + relative to framework atoms, suggesting greater heating efficiency due to microwaves compared to conventional heat transfer. Due to rapid cycling and efficient heat transfer to CO 2 sites on zeolite 13X, microwave regeneration is found to increase adsorption/desorption cycling productivity and potentially reduce the energy penalty of temperature swing capture.

54 ENVIRONMENTAL SCIENCES↗

Fabrication of yeast engineered porous 13X adsorbent layers for CO 2 capture

This study investigates a novel environmentally friendly coating technique using yeast fermentation to obtain super porous Zeolite 13X adsorbent layers through freeze-drying technique for CO 2 capture applications. Several mass ratios of sugar to yeast were used to control the porosity and pore sizes in the adsorbent layer. A unique peeling process was integrated to obtain foamy, hollow structures to have deeper layer accessibility of adsorbent for adsorption applications. These coated adsorbent layers were experimentally characterized as a function of the mass ratio of sugar to yeast and adsorbent solid fraction. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and Fourier-transform infrared spectroscopy (FT-IR) are used to analyze the coated layers. Here, the void fraction for coated samples is found to vary between 0.48 and 0.56, making the samples applicable for adsorption applications. Adsorption performance experiments are performed to test the coated samples' performance compared to 13X powder. Due to their simplistic fabrication, cost-effectiveness, rapid pore formation, and high adsorption capacity, these porous 13X layers hold potential for large-scale fabrication and CO 2 capture applications.

Adsorbent coating↗

Plasma catalytic non-oxidative methane conversion to hydrogen and value-added hydrocarbons on zeolite 13X

Non-thermal plasma has unfolded highly efficient, safe to operate novel routes for methane conversion to hydrogen. In this work, methane conversion is performed under atmospheric dielectric barrier discharge (DBD) plasma with and without 13X zeolite-based catalysts i.e., 13X, Ga/13X, Pd/13X, and Pd-Ga/13X. Experimental results indicate that the plasma catalytic process delivered almost twofold higher product yield than the plasma only route. The binary Pd-Ga catalyst possesses highest catalytic performance with about 40 % CH 4 conversion at an input flowrate of 5 cm 3 min -1 and 2W due to the formation of the Pd-Ga alloy, which acts as catalytic active centre for activating C–H bonds. Product yield can be tailored by the catalyst design where the bimetallic Pd-Ga/13X preferably favours the hydrocarbon formation while H 2 is the dominant product obtained over the Pd/13X. The cleavage of C–H bonds of methane molecule over the plasma only route is mainly governed by energetic electrons in the gaseous phase the catalyst activity, and plasma-catalyst synergism play a significant role in the plasma catalysis process. Further, the findings from this work provide significant insights into the methane activation for subsequent optimization of the methane conversion processes operated on floating production, storage, and offloading vessels (FPSOVs). Exploiting untapped offshore natural gas reserves, where conventional pipeline systems are less economical.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Isotope exchange of ND 3 on Pt catalyst-loaded 13X molecular sieve

During D-T fusion operations the capture, purification, and recycling of unburned tritium will be crucial, as the formation of tritium containing molecules require additional processing. Here, removing the tritium can require costly processing to be unbound from the tritium-containing molecules and improvements to these processes will be necessary moving forward. Existing techniques using sorbent material beds to remove tritium-containing molecules from process gas streams undergo repeated high-heat cycling which leads to diminished bed lifespans, necessitating replacement and associated downtime. This work demonstrates the capture and isotopic exchange technique of deuterated ammonia (ND3), used as a surrogate for tritium, at ambient temperature using a Pt catalyst-loaded 13X molecular sieve. Unmodified 13X molecular sieve is capable of adsorbing and retaining the ND3 however, incorporation of a catalyst facilitates the isotopic exchange of the hydrogen isotopes. The effluent gas streams were analyzed in conjunction with desorbed ammonia isotopologues post-exchange to verify these results. Isotopically exchanging and removing heavier hydrogen isotopes using this technique provides an alternative to traditional removal methods.

08 HYDROGEN↗

Evaluation of adsorption and mechanical strength of 13X zeolite mixtures with phyllosilicate binders using molecular dynamics simulation and positron annihilation spectroscopy

There is growing interest in developing zeolites with novel internal structures that have optimal adsorptive capacity and high mechanical strength, while offering advantages, such as being light weight. We integrate computational and experimental methods to explore the effect of binder/zeolite types, and weight percentages on the mechanical strength of 13X zeolite and adsorption capacities of N 2 , H 2 O, and CO 2 for additive manufacturing (AM) applications with the goal of maximizing both adsorption and strength. Zeolite 13X mixtures and phyllosilicate binders (either bentonite or kaolin) are combined using molecular dynamics (MD) simulations to create structures with various binder/zeolite weight percentages. Further, adsorption capabilities and mechanical strength are assessed using the grand canonical Monte Carlo (GCMC) and ReaxFF modules, respectively. Our modeling shows that an optimized zeolite/binder ratio for N 2 adsorption is around 15 wt% for kaolin and roughly 10 wt% for bentonite. The resulting parameters can be applied to facilitate macro-scale computational fluid dynamics (CFD) and finite element method (FEM) simulations of an AM zeolite structure. We also performed Positron Annihilation Lifetime Spectroscopy (PALS) measurements on zeolite samples to explore the effect of changes in the internal volume. The results show an inverse relationship between the free volume and the solid loading and adding a binder changes the morphology of the zeolite-binder compound and decreases open-volume area significantly.

36 MATERIALS SCIENCE↗

Microwave-induced selective decomposition of cellulose: Computational and experimental mechanistic study

Understanding microwave-material interactions will help facilitate the utilization of microwave technology in gasification and renewable energy production. In this study, cellulose was used as a model compound to simulate the organic matter in biomass, and its catalytic decomposition under a microwave (MW) field was studied to identify structural changes from the reaction. The study was conducted using a MW source coupled to a fixed-bed gas-flow reactor, mass spectroscopic, and Fourier transform infrared spectroscopy post-reaction analysis. Zeolite 13X was chosen as a microwave absorber to study the catalytic enhancement of the decomposition of cellulose. Density functional theory (DFT) was used to gain insights into the molecular transformations occurring in the presence of a static electric field, which was used to simulate the electric field component of the microwave electromagnetic radiation. Theoretical calculations demonstrated that both the positive and negative portion of the electric field interact with the permanent dipoles of the cellulose effecting the decomposition through the glycosidic bond breaking mechanism. The theoretical result was verified using infrared spectroscopic analysis of the pure cellulose during microwave heating. The theoretical calculations suggest only the positive electric field component may be active for the cellulose decomposition in the presence of Zeolite 13X. Physically mixing Zeolite 13X with the cellulose led to a significant enhancement in the decomposition rate of the glycosidic bond. Zeolite 13X enhanced the glycosidic O-C decomposition at lower MW power (lower temperatures), whereas the O-H functional group required higher MW power (higher temperature) for its decomposition. The DFT study coupled with the reaction studies revealed that the electric field polarizability is dependent upon both the direction and the orientation of the cellulose. Gas products revealed that applying 250 W of MW power led to the production of CO, H 2 , along with some CO 2 , CH 4 , and benzene at 305 °C. Finally, reaction under 500, 750, and 1000 W of power at constant temperature (305 °C) revealed that higher power led to the complete decomposition of cellulose to mostly CO, H 2 , and CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scaled-up fabrication of durable and porous adsorbent-coated minichannels on aluminum for CO 2 separation

A method was developed to fabricate zeolite 13X adsorbent-coated minichannels on aluminum for CO₂ adsorption applications in this study. It emphasizes the innovative use of aluminum as a substrate, which offers airtight assembly, paving the way for highly efficient adsorption systems. An optimized coating process was developed using a slurry of Zeolite 13X, yeast, sugar, and xanthan gum, resulting in durable and highly porous layers that enhance CO₂ capture performance. A PETG peeler was designed to remove the top layer of the yeast-engineered adsorbent coatings, revealing a super porous and foamy structure. The teeth of the peeler were designed and fabricated for high repeatability and rapid prototyping. Breakthrough experiments were conducted on the scaled-up adsorbent bed using gas mixtures of 80% CO₂, 20% N₂, and 20% CO₂, 80% N₂ to represent different industrial scenarios. The performance of the bed was evaluated at flow rates of 160 and 190 cm³ min -1 using a Raman Laser Gas Analyzer (RLGA), demonstrating stable adsorption without degradation across multiple cycles. Computational modeling of integral transport phenomena under the chosen experimental conditions was pursued using gPROMS ProcessBuilder™, and the modeling results were compared with those from the tests for adsorption time, which resulted in an error margin of 2% to 9% for the breakthrough time, confirming the easy reproducibility of the design through modeling. This research advances CO₂ capture technologies by providing an effective and scalable solution for producing aluminum-based adsorbent coated beds, supporting industrial carbon capture efforts.

CO2 capture↗

Analysis of energetics and economics of sub-ambient hybrid post-combustion carbon dioxide capture

Adsorption of CO 2 from post-combustion flue gas is one of the leading candidates for globally impactful carbon capture systems. In this report, work focused on understanding the opportunities and limitations of sub-ambient CO 2 capture processes utilizing a multistage separation process. A hybrid process design using a combination of pressure-driven separation of CO 2 from flue gas (e.g., adsorption- or membrane-based separation) followed by CO 2 -rich product liquefaction to produce high-purity (>99%) CO 2 at pipeline conditions is considered. The operating pressure of the separation unit is a key cost parameter and also an important process variable that regulates the available heat removal necessary to reach the sub-ambient operating conditions. The economic viability of applying pressure swing adsorption (PSA) processes using fiber sorbent contactors with internal heat management was found to be most influenced by the productivity of the adsorption system, with productivities as high as 0.015 mol CO2 /kg sorb -1 sec -1 being required to reduce costs of capture below $60/ton CO 2 captured. This analysis was carried out using a simplified two-bed process, and thus there is opportunity for further cost reduction with exploration of more complex cycle designs. Three exemplar fiber sorbents (MIL-101(Cr), UiO-66, and zeolite 13X) were considered for application in the sub-ambient process of PSA unit. Among the considered sorbents, zeolite 13X fiber composites were found to perform better at ambient temperatures as compared to sub-ambient. MIL-101(Cr) and UiO-66 fiber composites had improved purity, recovery, and productivity at colder temperatures reducing costs of capture as low as $61/ton CO 2 . Future economic improvement could be achieved by reducing the required operating pressure of the PSA unit and pushing the Pareto frontier closer to the final pipeline requirement via a combination of PSA cycle design and material selection.

42 ENGINEERING↗

Influence of Water, Vacuum, and Temperature on Surface Conditions of a Zeolite‐based Molecular Sieve

Molecular sieves such as zeolite-based materials are ubiquitous in industrial separation processes. However, there is a significant gap in understanding the surface properties and adsorption mechanisms for commercial zeolites, as most research focuses on pure zeolite powders rather than industrially relevant forms. Here, this work addresses this gap in understanding by employing advanced characterization techniques, including positron annihilation spectroscopy, X-ray diffraction, scanning electron microscopy, X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, liquid nitrogen sorption, and Fourier-transform infrared spectroscopy, to investigate the adsorption and desorption behavior of water in commercial zeolite 13X. Our research reveals insights into the pore-filling mechanisms, the impact of material binders on adsorption properties, and the dynamics of hydration and drying processes for zeolites. Monitoring changes on a minute scale allowed the distinction between fast and slow processes leading to sample drying. The identification of positronium bound to Na + ions indicated that water molecules remain in the vicinity of Na + ions after air-drying zeolite 13X. These findings highlight the importance of various environmental conditions in restoring zeolite properties to baseline after hydration, with significant implications for optimizing industrial processes. This work sets the direction for further research aimed at developing more efficient and robust separation techniques.

Beads Binder↗

DOE-VFP; Surface Engineered Multifunctional Zeolite Composite for Photodegradation of Per- and Polyfluoroalkyl substances (PFAS) in Aqueous Medium

Per- and Polyfluoroalkyl substances (PFAS) are widely used compounds proven to bioaccumulate and result in detrimental health effects. On October 18, 2021 the United States Environmental Pollution Agency (EPA) released a strategic roadmap to address PFAS that includes the investment in effective research that accelerates cleanup. Existing water treatment technologies for PFAS removal are based on adsorptive removal, are commonly single-use and result in pollutant-laden waste, leading to costly disposal processes. Here we proposed the development of a zeolite-TiO 2 composite for removal and degradation of PFAS. The composite is advantageous as it can be easily integrated into water treatment facilities, is multifunctional, and minimizes waste through regeneration. We studied the adsorptive capacity of zeolites 13X, 3A, 4A and 5A for an anionic PFAS surrogate, methyl orange (MO). Zeolite 3A showed the highest adsorptive capacity, followed by 4A, 5A, and 13X when incubated with 15 ppm MO for 3 hours. Depositing Au-nanospheres on the zeolites surface reduced MO adsorption for all zeolites. We also investigated the photodegradation capacity of TiO 2 , Fe 2 O 3 , Au-TiO 2 , and Au-Fe 2 O 3 , ranking their performance as TiO2 > Fe2O3 > Au-TiO 2 > Au-Fe 2 O 3 under 254 nm light in a 10 ppm MO solution. Our results highlight the favorable adsorption of small pore size zeolites for PFAS surrogates and the potential of TiO2 as a photocatalyst for PFAS degradation. We can further study and integrate the composite's components at our home institution. Other notable achievements of our VFP team includes the submission of two funding proposals, two poster presentations and one invited talk thus showcasing our progress.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Synthesis and Characterization of Silver-Modified Nanoporous Silica Materials for Enhanced Iodine Removal

In aquatic environments, the presence of iodine species, including radioactive isotopes like 129 I and I 2 , poses significant environmental and health concerns. Iodine can enter water resources from various sources, including nuclear accidents, medical procedures, and natural occurrences. To address this issue, the use of natural occurring nanoporous minerals, such as zeolitic materials, for iodine removal will be explored. This study focuses on the adsorption of iodine by silver-modified zeolites (13X-Ag, 5A-Ag, Chabazite-Ag, and Clinoptilolite-Ag) and evaluates their performance under different conditions. All materials were characterized using scanning electron microscopey (SEM), energy-dispersive X-ray spectroscopy (EDS), powdered X-ray diffraction (P-XRD), Fourier-transform infrared spectrometry (FTIR), and nitrogen adsorption studies. The results indicate that Chabazite-Ag exhibited the highest iodine adsorption capacity, with an impressive 769 mg/g, making it a viable option for iodine removal applications. 13X-Ag and 5A-Ag also demonstrated substantial adsorption capacities of 714 mg/g and 556 mg/g, respectively, though their behavior varied according to different models. In contrast, Clinoptilolite-Ag exhibited strong pH-dependent behavior, rendering it less suitable for neutral to slightly acidic conditions. Furthermore, this study explored the impact of ionic strength on iodine adsorption, revealing that Chabazite-Ag is efficient in low-salinity environments with an iodine adsorption capacity of 51.80 mg/g but less effective in saline conditions. 5A-Ag proved to be a versatile option for various water treatments, maintaining its iodine adsorption capacity across different salinity levels. In contrast, Clinoptilolite-Ag exhibited high sensitivity to ionic competition, virtually losing its iodine adsorption ability at a NaCl concentration of 0.1 M. Kinetic studies indicated that the pseudo-second-order model best describes the adsorption process, suggesting chemisorption mechanisms dominate iodine removal. Chabazite-Ag exhibited the highest initial adsorption rate with a k 2 value of 0.002 mg g -1 h -1 , emphasizing its superior adsorption capabilities. Chabazite and Clinoptilolite, naturally occurring minerals, provide eco-friendly solutions for iodine adsorption. Chabazite superior iodine removal highlights its value in critical applications and its potential for addressing pressing environmental challenges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation and Characterization of Materials for Low- to Intermediate-Temperature CO2 Adsorption

Global carbon dioxide emissions are rising and the use of fossil fuels in several sectors are the leading causes. As global population and economies continue to grow significantly, the most practical method of lowering such emissions is to capture CO2. Although other technologies are more developed, adsorption is very promising and has attracted much attention. To ensure this technology’s success, it is essential to have suitable CO2 adsorbent materials. In this work, several new hydrotalcites (HTs) with different initial concentrations of ion precursors were prepared for the first time by the co-precipitation method—it was possible to verify that the ion concentrations influence the characteristics of the materials. The prepared HTs were characterized by thermogravimetric analysis (TG), X-Ray diffraction (XRD), surface area measurements and temperature-programmed desorption of CO2 (TPD-CO2) to relate their CO2 capture capacity to their physicochemical properties; the CO2 adsorption equilibrium isotherms were determined at 35 and 300 °C for the prepared samples, as well as for some commercial materials: magnesium oxide, calcium oxide, aluminium oxide and Zeolite 13X. After determining which materials present the best CO2 adsorption capacity, these were submitted to adsorption-desorption cycles to study their stability. The main objective of the work was to prepare and study different CO2 adsorbents for processes that are carried out at low and intermediate temperatures. From the experimental results, it was possible to conclude that the Zeolite 13X showed the best capacity at 35 °C, 3.38 mmol·g−1 (@ pCO2 = 1 bar), and a prepared calcined HT (c-HT2) was the best at 300 °C, 0.97 mmol·g−1 (@ pCO2 = 1 bar). Moreover, it seems there is an optimum initial concentration of the ions’ solutions for the tested HTs, which depends on the final application—c-HT1 showed a better capacity at 35 °C and c-HT2 at 300 °C. From the adsorption-desorption cycles—performed at 35 and 300 °C with the best materials using a magnetic suspension microbalance at 1 bar of CO2 partial pressure —, a working cyclic capacity of 2.69 mmol∙g−1 was achieved by the Zeolite at 35 °C; in turn, c-HT2 showed a working cyclic capacity of 0.79 mmol∙g−1 at 300 °C.

Figueiredo, Anabela↗

Efficient SF 6 /N 2 separation at high pressures using a zirconium-based mesoporous metal–organic framework

Adsorptive separation of SF 6 /N 2 mixtures is an important issue since SF 6 is a significant greenhouse gas. Although separation performances should be evaluated under high pressure conditions to find an efficient adsorbent candidate for pressure swing adsorption (PSA) processes, no studies on metal–organic frameworks (MOFs) have focused on SF 6 /N 2 separation at high pressures above 1 bar. In this study, we evaluated the potential of three hydrothermally stable adsorbents, including two MOFs (UiO-66 and UiO-67) and zeolite-13X, for SF 6 /N 2 separation under normal PSA operation pressures (~10 bar). Interestingly, UiO-67 with a high surface area and large pore size exhibited very high SF6/N2 selectivity (30~37) at 10 bar as well as a significantly large SF6 working capacity (5.94 mmol g-1) between 10 bar and 1 bar. Moreover, UiO-67 showed facile regeneration at the ambient temperature as well as good cyclic adsorption and desorption behavior during 20 cycles. These results show that UiO-67 is a potential adsorbent for adsorptive SF 6 /N 2 separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discrepancy quantification between experimental and simulated data of CO 2 adsorption isotherm using hierarchical Bayesian estimation

Here, to quantitatively analyze the inconsistencies commonly observed between experimental and simulated adsorption isotherms, parameter estimation of adsorption isotherm models was conducted by hierarchical Bayesian estimation with parameter uncertainties being quantified as probability distributions. The estimation method was implemented using Markov Chain Monte Carlo (MCMC) to analyze multiple data sets obtained from different sources, including a publicly available database. To describe the discrepancies of experimental and simulated adsorption data, the simulation data was set as the reference to which experimental measurements were compared. We applied the proposed approach to analyze CO 2 adsorption isotherms that are measured and simulated on zeolite 13X and MIL-101(Cr). In these case studies, the discrepancy of CO 2 adsorption isotherm was successfully quantified between experimental measurements and predictions given by molecular simulations using Grand Canonical Monte Carlo (GCMC), where uncertainties were quantified as probability distributions. Furthermore, experimental data sets that agree well with the GCMC simulation have been identified, providing insights into experimental and measurement methods as well as choosing the right assumptions in the molecular simulation.

42 ENGINEERING↗

Near-cryogenic direct air capture using adsorbents

Direct air capture (DAC) of CO 2 is a key component in the portfolio of negative emissions technologies for mitigating global warming. However, even with the most potent amine sorbents, large-scale DAC deployment remains limited by high energy and capital costs. Recently, adsorbents relying on weak interactions with CO 2 have emerged as a potential alternative, thanks to their rapid adsorption kinetics and superior long-term stability, particularly under sub-ambient conditions (∼253 K). Despite these advantages, their use is hindered by the need for a water-removal process, location-specific constraints, and insufficient working capacity even in cold climates. In this study, we hypothesized that further reducing the adsorption temperature to a near-cryogenic range (160–220 K) could enable cost-effective DAC by utilizing the full potential of physisorbents. We primarily consider integrating DAC with a relatively untapped source of cold energy—liquified natural gas (LNG) regasification—to perform near-cryogenic DAC. From large-scale molecular simulations, Zeolite 13X and CALF-20 were identified as promising candidates. These materials were subsequently examined through experiments, including breakthrough analyses at 195 K. Their high CO 2 sorption capacity (4.5–5.5 mmol g −1 ), combined with a low desorption enthalpy and robust long-term stability, led to a threefold reduction in the levelized cost of capture (down to 68.2 USD per tonne CO 2 ). Estimates of the global LNG regasification resource suggest that LNG–DAC coupling could potentially enable the capture of 103–142 megatonnes of CO 2 annually as of 2050.

Kim, Seo-Yul [Georgia Institute of Technology, Atl↗

Effective CH4/N2 Separation using NU-1000 at High Pressures

Separation of methane (CH4) from other gases is of significant importance to reducing greenhouse gas emissions. In particular, the development and discovery of efficient adsorbents under pressure swing adsorption (PSA) conditions is a focus many research papers. We evaluated the potential of CH4/N2 separation performance using four adsorbents, including zirconium-based metal organic frameworks (NU-1000, UiO-66, and UiO-67) and a conventional adsorbent, zeolite-13X. Among them, NU-1000 presented high CH4/N2 selectivity (2.8) at 15 bar through ideal adsorbed solution theory because it has micro- and mesopores coupled with the large surface area, and a polar hydroxyl group along the pore surface. NU-1000 has a large CH4 working capacity (4.79) under PSA processes. These results demonstrated that NU-1000 is a sufficiently competitive adsorbent in PSA processes for CH4/N2 separation.

MOFs, NU-1000, separation↗