Sub-ambient Conditions Research Articles

Sub-Ambient Performance of Potassium Sarcosinate for Direct Air Capture Applications: CO2 Flux and Viscosity Measurements

Absorption based direct air capture (DAC) technologies have garnered significant interest in recent years due to their scalability, competitive regeneration energy requirements, and low susceptibility to degradation. One of the key advantages of DAC lies in its flexible siting options and the potential to utilize low-value land. However, most of the research in this field has been focused on ambient climate zones (T > 20 °C), overlooking sub-ambient (−30 °C < T < 20 °C) regions, which comprise approximately 70 % of the Earth’s surface. To fully realize the potential of DAC, it is essential to understand how DAC solvents perform in these sub-ambient conditions before any large-scale deployment can be considered. Among DAC solvents of interest, potassium sarcosinate (K-SAR) has emerged as a promising candidate due to its high CO2 capacity, fast uptake kinetics, compatibility with contactor packing materials, low volatility, good thermal and oxidative stability, and competitive regeneration energy requirements compared to current industry standards. This paper characterizes the CO2 flux and viscosity of K-SAR at sub-ambient conditions and explores the potential of using ethylene glycol and triethylene glycol as additives to prevent solvent freezing in DAC applications. For 1 M K-SAR, the CO2 flux ranges between 1.3 × 10-5 and 8.0 × 10-5 mol m−2 s−1 across a temperature range of −5 °C to 45 °C. Ethylene glycol is shown to effectively suppress the freezing point of K-SAR below −30 °C with volumetric loadings of the additive as low as 0.1. A reaction model was developed to predict the CO2 flux for 1 M K-SAR at different temperatures, demonstrating good agreement between experimental and theoretical fluxes.

Heterostructure ZIF-8@MXene with sieving effect in mixed matrix membranes for CO2 separation

At the present time, the realm of gas separation membranes is predominantly centered on the development of membrane materials that simultaneously exhibit exceptional gas permeability and selectivity. Mixed Matrix Membranes (MMMs) hold significant promise in addressing the long-standing challenge of balancing membrane selectivity with permeability. By incorporating a molecular sieving mechanism, an enhanced gas separation process is achieved. In this research endeavor, single-layer MXene nanosheets serve as an ideal substrate for the direct growth of ZIF-8 nanoparticles, yielding heterogeneously structured nanofillers, coined ZIF-8@MXene. The composite filler, ZIF-8@MXene, maintains a two-dimensional lamellar structure reminiscent of MXene, while also integrating ZIF-8 nanoparticles with their optimal pore size of 3.4 Å. This optimal pore size efficiently facilitates the unimpeded passage of CO2 molecules through the channels, creating a preferential pathway. Conversely, N2 molecules encounter greater difficulty traversing these channels, effectively coupling the solubility-diffusion mechanism with the molecular sieving mechanism to enhance selectivity in gas separation processes. Consequently, the mixed matrix membrane exhibits a remarkable enhancement in gas selectivity. Particularly, under sub-ambient conditions (−20 °C), the PEO/ZIF-8@MXene-0.3 % membrane achieves an exceptional CO2/N2 selectivity of 294.1, accompanied by a high CO2 permeability of 115.58 Barrer. This outstanding performance surpasses the 2019 upper bound, underscoring the significant potential of heterostructured nanofillers to be harnessed in advancing various mixed matrix membranes (MMMs) towards high-performance gas separation capabilities.

Cold Temperature Direct Air CO2 Capture with Amine-Loaded Metal-Organic Framework Monoliths.

Zeolites, silica-supported amines, and metal-organic frameworks (MOFs) have been demonstrated as promising adsorbents for direct air CO2 capture (DAC), but the shaping and structuring of these materials into sorbent modules for practical processes have been inadequately investigated compared to the extensive research on powder materials. Furthermore, there have been relatively few studies reporting the DAC performance of sorbent contactors under cold, subambient conditions (temperatures below 20 °C). In this work, we demonstrate the successful fabrication of adsorbent monoliths composed of cellulose acetate (CA) and adsorbent particles such as zeolite 13X and MOF MIL-101(Cr) by a 3D printing technique: solution-based additive manufacturing (SBAM). These monoliths feature interpenetrated macroporous polymeric frameworks in which microcrystals of zeolite 13X or MIL-101(Cr) are evenly distributed, highlighting the versatility of SBAM in fabricating monoliths containing sorbents with different particle sizes and density. Branched poly(ethylenimine) (PEI) is successfully loaded into the CA/MIL-101(Cr) monoliths to impart CO2 uptakes of 1.05 mmol gmonolith-1 at -20 °C and 400 ppm of CO2. Kinetic analysis shows that the CO2 sorption kinetics of PEI-loaded MIL-101(Cr) sorbents are not compromised in the monoliths compared to the powder sorbents. Importantly, these monoliths exhibit promising working capacities (0.95 mmol gmonolith-1) over 14 temperature swing cycles with a moderate regeneration temperature of 60 °C. Dynamic breakthrough experiments at 25 °C under dry conditions reveal a CO2 uptake capacity of 0.60 mmol gmonolith-1, which further increases to 1.05 and 1.43 mmol gmonolith-1 at -20 °C under dry and humid (70% relative humidity) conditions, respectively. Our work showcases the successful implementation of SBAM in making DAC sorbent monoliths with notable CO2 capture performance over a wide range of sorption temperatures, suggesting that SBAM can enable the preparation of efficient sorbent contactors in various form factors for other important chemical separations.

Direct air CO2 capture using coal fly ash derived SBA-15 supported polyethylenimine

Designing an amine modified silica derived from coal fly ash (CFA) towards direct air CO2 capture (DAC) provides an economic way to manage increasing atmospheric CO2 concentration utilizing solid wastes. In this work, rod-like SBA-15 (SBA-15-R) and wheat-like SBA-15 (SBA-15-W) with distinct pore lengths are synthesized from CFA by controlling the synthesis conditions and then modified by PEI via the wet impregnation method. Their CO2 adsorption behaviors under sub-ambient conditions are investigated to explore their feasibility under aggressive conditions. The adsorbents with various silica morphologies exhibit distinctive CO2 adsorption performance under ambient and sub-ambient conditions. At 35°C under dry conditions, the CO2 adsorption capacity increases with amine loading. The CO2 adsorption capacity (qe) of SBA-15-W-PEI with long channels reaches the highest qe of 1.92 mmol/g with 70 wt.% PEI loading due to a large amount of strong chemisorption sites. Under the sub-ambient conditions (-20°C, 400 ppm), SBA-15-R-PEI30 with short channels having weaker CO2 diffusion resistance exhibits promising CO2 uptake of 0.83 mmol/g. These findings indicate that the ultra-dilute CO2 adsorption at ambient temperature requires an adsorbent with large amounts of adsorption sites, whereas the adsorbents for cold temperature application should reconcile amine loading with CO2 diffusion resistance inside pores. The co-adsorption of H2O and CO2 significantly improves CO2 capacity from 0.83 mmol/g and 1.92 mmol/g to 1.81 mmol/g and 3.48 mmol/g for SBA-15-R-PEI30 (-20°C, 400 ppm) and SBA-15-W-PEI70 (35°C, 400 ppm), respectively. Furthermore, the CFA derived SBA-15-PEI shows good cyclic stability during five consecutive TSA cycles. Preparing the amine silica adsorbents from coal fly ash potentially reduces the adsorbent cost of DAC devices. Moreover, the systematic exploration of amine silica adsorbents at a wide range of temperatures guides the design of high-performance CO2 adsorbents employed under various climatic conditions.

Li2 MnO3 : A Catalyst for a Liquid Cl2 Electrode in Low-Temperature Aqueous Batteries.

Li2 MnO3 has been contemplated as a high-capacity cathode candidate for Li-ion batteries; however, it evolves oxygen during battery charging under ambient conditions, which hinders a reversible reaction. However, it is unclear if this irreversible process still holds under subambient conditions. Here, the low-temperature electrochemical properties of Li2 MnO3 in an aqueous LiCl electrolyte are evaluated and a reversible discharge capacity of 302 mAh g-1 at a potential of 1.0V versus Ag/AgCl at -78 °C with good rate capability and stable cycling performance, in sharp contrast to the findings in a typical Li2 MnO3 cell cycled at room temperature, is observed. However, the results reveal that the capacity does not originate from the reversible oxygen oxidation in Li2 MnO3 but the reversible Cl2 (l)/Cl- (aq.) redox from the electrolyte. The results demonstrate the good catalytic properties of Li2 MnO3 to promote the Cl2 /Cl- redox at low temperatures.

The critical role of nanostructured carbon pores in supercapacitors

Carbon materials exist in several morphologies; however, the most famous one for supercapacitors electrode is the nanoporous carbon with large surface area (from 1500–2500 m2 g−1). For rapid charge/discharge in supercapacitors, alignment between the shape of the pores and the size of the solvated ions is necessary. Due to recent improvements focused on enhancing specific energy, power performance of supercapacitors is mostly ignored/compromised. In addition, the size and shape of the carbon pores are critical for the low-temperature performance of supercapacitors. This is because the interactions between carbon pore walls and the electrolyte affect its freezing/melting behavior and consequently the operation at sub-ambient conditions. In this review, we explain why nanostructuring of carbon pores is necessary for supercapacitors. Further, the latest progress in this research field, the trade-off between energy and power, and the processes at the interplay of pore/ion in non-aqueous and aqueous electrolytes have been discussed.

Subambient temperature swing adsorption utilizing cold energy from liquefied natural gas

This study proposes a CO2 capture process by temperature swing adsorption (TSA) using latent heat of evaporation for liquefied natural gas (LNG) as a cold energy source, which is currently unused and discarded into seawater. The proposed subambient process has several advantages: (1) the total energy cost can be saved by the LNG cold energy; (2) the equilibrium capacity of CO2 at subambient temperature can be increased substantially; and (3) water in the flue gas which would lead to deterioration of the adsorbent can be removed by a pretreatment step utilizing LNG cold energy. For the adsorbent in the TSA system, zeolite 13X, MIL-101, UiO-66, and CPL-1, which are considered effective for CO2 adsorption in the subambient, were considered and adsorption isotherm data were obtained at subambient conditions. Comparisons of these adsorbents were carried out using a rigorous dynamic model of the TSA process. It was found that CPL-1 gives a high recovery rate of 70% and purity of 95%. It was also found that the proposed system has the potential to capture up to 6% of the CO2 emitted from Japan.

Hydrogen Evolution upon Ammonia Borane Solvolysis: Comparison between the Hydrolysis and Methanolysis Reactions

Hydrogen (H2) production is a key challenge for green carbon-free sustainable energy. Among the H2 evolution methods from H-rich materials, ammonia borane (AB) solvolysis stands as a privileged source under ambient and sub-ambient conditions given its stability, non-toxicity, and solubility in protic solvents, provided suitable and optimized nanocatalysts are used. In this paper dedicated to Prof. Avelino Corma, we comparatively review AB hydrolysis and alcoholysis (mostly methanolysis) in terms of nanocatalyst performances and discuss the advantages and inconveniences of these two AB solvolysis methods including AB regeneration.

Elastomeric biodegradable starch/bentonite nanocomposites. Structure-thermo-mechanical correlation and degradation behavior

We developed layered silicate nanocomposite films based on corn starch (CS) and bentonite nanoclay, plasticized with glycerol. The films were elastomeric with stretchability of ca. 60–90 % and Tg = −75 to −85 °C. The nanocomposites were exfoliated if cbentonite < 2 wt%, and intercalated if cbentonite > 3 wt%. The exfoliated morphology induced thermal stability as shown by TGA. Interestingly, bentonite induced a reduction of Tg while increasing the Young's modulus E and reducing the extensibility. The fracture energy was a decreasing function of cbentonite except at 2.9 wt%, where the nanocomposite exhibited maximum Young's modulus and toughness, as demonstrated by the Ashby-style plot. The nanocomposite films were biodegradable in anaerobic and aerobic conditions, and in anaerobic conditions the intercalated nanocomposite of cbentonite = 2.9 wt% exhibited slower rate of degradation. These results provide insights into the development of bio-degradable elastomeric food packaging and coatings suitable for sub-ambient conditions.

Effects of Solid State Sulfonation of Poly(phenylene) on Mechanical Robustness and Proton Conductivity

To meet ever increasing demands for energy worldwide, advances in both energy storage and energy conversion must be meet. Fuel cells, especially polymer electrolyte fuel cells (PEMFCs), and vanadium redox batteries problems include electrolyte instability and fuel crossover. Nafion® is the industry standard, but several drawbacks include low selectivity due to it bicontinuous morphology, large water uptake, and production cost. Several alternative ionomers have been investigated, however post sulfonated diels alder poly(phenylene) membranes have shown ideal properties with respect to selectivity, mechanical robustness, ionic conductivity, and thermal transitions. A homogeneous sulfonation has limits due to swelling above an IEC of 2.2 This study focuses on a solid-state surface modification in dilute and sub-ambient conditions via direct immersion in a chlorosulfonic acid solution followed by an exchange with a monovalent counter-ion. Planned thermal and mechanical studies include defining degradation temperature, toughness, and Young’s modulus in the monovalent form. Further property determination includes assigning experimentally determined diffusion coefficients for water vapor, proton conductivity, gas, and liquid water. Both in plane and through plane conductivity measurements are planned to be done at different degrees of water saturation. Lastly, chemical composition and structure will be determined through Fourier transform infrared spectroscopy- attenuated total reflectance studies and transmission and grazing-incidence small-angle x-ray scattering. Future studies include evaluation of fuel cell performance and further phase analysis through transmission electron microscopy.

Sub-Ambient Temperature Direct Air Capture of CO2 using Amine-Impregnated MIL-101(Cr) Enables Ambient Temperature CO2 Recovery.

Due to the dramatically increased atmospheric CO2 concentration and consequential climate change, significant effort has been made to develop sorbents to directly capture CO2 from ambient air (direct air capture, DAC) to achieve negative CO2 emissions in the immediate future. However, most developed sorbents have been studied under a limited array of temperature (>20 °C) and humidity conditions. In particular, the dearth of experimental data on DAC at sub-ambient conditions (e.g., −30 to 20 °C) and under humid conditions will severely hinder the large-scale implementation of DAC because the world has annual average temperatures ranging from −30 to 30 °C depending on the location and essentially no place has a zero absolute humidity. To this end, we suggest that understanding CO2 adsorption from ambient air at sub-ambient temperatures, below 20 °C, is crucial because colder temperatures represent important practical operating conditions and because such temperatures may provide conditions where new sorbent materials or enhanced process performance might be achieved. Here we demonstrate that MIL-101(Cr) materials impregnated with amines (TEPA, tetraethylenepentamine, or PEI, poly(ethylenimine)) offer promising adsorption and desorption behavior under DAC conditions in both the presence and absence of humidity under a wide range of temperatures (−20 to 25 °C). Depending on the amine loading and adsorption temperature, the sorbents show different CO2 capture behavior. With 30 and 50 wt % amine loadings, the sorbents show weak and strong chemisorption-dominant CO2 capture behavior, respectively. Interestingly, at −20 °C, the CO2 adsorption capacity of 30 wt % TEPA-impregnated MIL-101(Cr) significantly increased up to 1.12 mmol/g from 0.39 mmol/g at ambient conditions (25 °C) due to the enhanced weak chemisorption. More importantly, the sorbents also show promising working capacities (0.72 mmol/g) over 15 small temperature swing cycles with an ultralow regeneration temperature (−20 °C sorption to 25 °C desorption). The sub-ambient DAC performance of the sorbents is further enhanced under humid conditions, showing promising and stable CO2 working capacities over multiple humid small temperature swing cycles. These results demonstrate that appropriately designed DAC sorbents can operate in a weak chemisorption modality at low temperatures even in the presence of humidity. Significant energy savings may be realized via the utilization of small temperature swings enabled by this weak chemisorption behavior. This work suggests that significant work on DAC materials that operate at low, sub-ambient temperatures is warranted for possible deployment in temperate and polar climates.

A membrane reflector, polymer hybrid infrared emitter for better radiative cooling performance

Due to the increasing power consumption for air-conditioning, the power-free passive radiative cooling technique has drawn great attentions in recent years. Blackbody-like broadband emitter and 8–13 μm selective emitter are the two major types of emitters used in current techniques. In this work, we put forward a new type of emitter which has high emissivity in the two atmospheric windows (8–13 μm & 16–25 μm) while maintaining high reflectance at other wavelengths. The proposed emitter has greater cooling potential than both selective and broadband emitters according to our calculations, expect for the extreme sub-ambient conditions. To approach this new emissive characteristic, based on PDMS film, we exploited the guided-mode resonance in the two-dimensional photonic crystal, which introduces a reflectance window between the two atmospheric windows. As the simulation results indicate, the emitter with structural optimization is able to achieve a temperature drop approaching 15 K for ambient temperature Ta = 300 K, non-radiative heat transfer coefficient hc = 2.0 W/m2/K and 3% solar absorption. We believe that it is the first attempt to exploit guided mode resonance in passive radiative cooling applications. Hopefully, this work may provide the researchers a new scheme in terms of the spectral property when designing radiative coolers.

Liquid structure and dynamics in the choline acetate:urea 1:2 deep eutectic solvent.

We report on the thermodynamic, structural, and dynamic properties of a recently proposed deep eutectic solvent, formed by choline acetate (ChAc) and urea (U) at the stoichiometric ratio 1:2, hereinafter indicated as ChAc:U. Although the crystalline phase melts at 36-38°C depending on the heating rate, ChAc:U can be easily supercooled at sub-ambient conditions, thus maintaining at the liquid state, with a glass-liquid transition at about -50°C. Synchrotron high energy x-ray scattering experiments provide the experimental data for supporting a reverse Monte Carlo analysis to extract structural information at the atomistic level. This exploration of the liquid structure of ChAc:U reveals the major role played by hydrogen bonding in determining interspecies correlations: both acetate and urea are strong hydrogen bond acceptor sites, while both choline hydroxyl and urea act as HB donors. All ChAc:U moieties are involved in mutual interactions, with acetate and urea strongly interacting through hydrogen bonding, while choline being mostly involved in van der Waals mediated interactions. Such a structural situation is mirrored by the dynamic evidences obtained by means of 1H nuclear magnetic resonance techniques, which show how urea and acetate species experience higher translational activation energy than choline, fingerprinting their stronger commitments into the extended hydrogen bonding network established in ChAc:U.

Dynamics of the sub-ambient gelation and shearing of solutions of P3HT and P3HT blends towards active layer formation in bulk heterojunction organic solar cells.

Organic solar cells (OSCs) containing an active layer consisting of a nanostructured blend of a conjugated polymer like poly(3-hexylthiophene) (P3HT) and an electron acceptor have the potential of competing against silicon-based photovoltaic panels. However, this potential is largely unfulfilled first due to interrelated production and stability issues of organic solar cells and second due to the unscalable nature of the generally employed spin coating process used for the fabrication of organic solar cells. Furthermore, alternatives to spin coating, especially relying on continuous polymer processing methods like extrusion and coating, cannot be readily applied due to the typically low shear viscosity and elasticity of polymer solutions making up the active layer. Recently, He et al. have reported that the gelation of P3HT with [6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) under sub-ambient conditions can provide a new route to the processing of the active layers of bulk heterojunction solar cells. Furthermore, increases in power conversion efficiencies (PCEs) of the P3HT/PC60BM active layer were determined to be possible under certain shearing and thermal histories of the P3HT/PC60BM gels. Here oscillatory and steady torsional flows were used to investigate the gel formation dynamics of P3HT with a recently proposed non-fullerene acceptor o-IDTBR under sub-ambient conditions and compared with the gelation behavior of P3HT/PC60BM blends. The rheological material functions as well as the gel strengths defined on the basis of linear viscoelastic material functions, characterized via small-amplitude oscillatory shearing, were observed to be functions of the P3HT and o-IDTBR concentrations, the solvent used and the shearing conditions. Overall, the P3HT gels which formed upon quenching to sub-zero temperatures were found to be stable during small-amplitude oscillatory shear (linear viscoelastic range) but broke down even at the relatively low shear rates associated with steady torsional flows, suggesting that the shearing conditions used during the processing of gels of P3HT and blends of P3HT with small molecule acceptors can alter the gel structure, possibly leading to changes in the resulting active layer performance.

Improving energy efficiency for a low-temperature CO2 separation process in natural gas processing

Conventional amine sweetening process is limited to treating gas with high content of CO2, due to significant energy demand for the regeneration of solvent and the compression of CO2 product for Enhanced Oil Recovery (EOR) or sequestration. Although distillation processes operating at sub-ambient conditions have been regarded as an economic and energy-efficient alternative to amine sweetening process, it is not straightforward to materialize the full benefits of the low temperature distillation process in practice because of complex design interactions existed. The distillation process for carbon dioxide separation operated at sub-ambient conditions are modeled with commercial simulator Aspen HYSYS®. A range of thermodynamic packages are screened for the selection of the most appropriate one to be used, while the validation of the process modeling is made with reference data. Understanding on the dependence of energy cost on the key design and operating variables is obtained with sensitivity studies, with which energy-efficient selection of column configurations and operating conditions throughout the process is made. Suggestion is also made for improving energy efficiency for the process without compromising separation process, by setting different operating pressure and introducing new configuration involving stream splitting and merging.

Au/CeO2-ZnO/Al2O3 as Versatile Catalysts for Oxidation Reactions: Application in Gas/Liquid Environmental Processes.

The present work showcases the versatility of nanogold systems supported on Zn-doped ceria when applied in two important environmental processes, the total CO oxidation, and the liquid phase oxidation of glucose to gluconic acid. In the CO oxidation the suitability of these materials is clearly demonstrated achieving full conversions even at sub-ambient conditions. Regarding the glucose oxidation our materials display high conversion values (always over 50%) and very importantly full or almost full selectivity toward gluconic acid—an added value platform chemical in the context of biomass upgrading routes. The key factors controlling the successful performance on both reactions are carefully discussed and compared to previous studies in literature. To our knowledge this is one of the very few works in catalysis by gold combining liquid and gas phase reactions and represents a step forward in the flexible behavior of nano gold catalysts.

Structures and dimensions of micelle-templated nanoporous silicas derived from swollen spherical micelles of temperature-dependent size

Subambient temperatures are employed in Pluronic-block-copolymer-templated syntheses of many large-pore silicas: SBA-15 (2-D hexagonal with cylindrical mesopores), FDU-12 (face-centered cubic with spherical mesopores), nanotubes and hollow nanospheres. Herein, the origin of a significant temperature dependence of the unit-cell parameter and pore diameter of silicas templated by swollen micelles of Pluronics under subambient conditions was elucidated. The temperature dependence of size of swollen spherical micelles of Pluronic F127 (EO106PO70EO106) in 2 M HCl solution was studied in 12–25 °C range using dynamic light scattering and was correlated with structure types, unit-cell sizes and pore sizes of silicas synthesized at four silica-precursor/Pluronic ratios with a swelling agent (toluene, ethylbenzene). The increase in size of swollen micelles with temperature decrease was paralleled by the increase in the unit-cell size and pore diameter, even if the micelle shape changed in the process of formation of the micelle-templated silica. The decrease in the silica-precursor/Pluronic F127 ratio at constant temperature triggered a succession of phases, including SBA-15 - nanotube sequence that may involve an intermediate nanotube bundle structure, which is uncommon and potentially useful. The temperature decrease also led to a succession of phases, including FDU-12 – SBA-15, hollow nanospheres – nanotube bundles, and nanotubes – SBA-15 sequences.

Development of Phase-Change-Based Thermally Modulated Fiber Sorbents

Microencapsulated phase change materials (μPCM) are combined with the metal–organic framework (MOF) UiO-66 and a cellulose acetate fiber support to introduce thermal modulation into CO2 capture devices operating in subambient conditions. μPCM particles are incorporated into sorbent fibers during the fiber spin dope preparation step and are observed to withstand the spinning and subsequent solvent exchange steps with little to no loss of thermal modulating properties as determined by differential scanning calorimetry (DSC). The spinning of this novel sorbent-μPCM fiber sorbent is the first instance of single step spinning of sorbents with a thermal modulator. It was found that μPCM weight loading as high as 75 wt % was attainable while maintaining spinable fibers. Breakthrough adsorption experiments and subsequent temperature profile analysis were collected to compare CO2 breakthrough capacity and heat release for sorbent systems with and without phase change materials incorporated. In adsorption modules w...

Simulation of Dual Mixed Refrigerant Natural Gas Liquefaction Processes Using a Nonsmooth Framework

Natural gas liquefaction is an energy intensive process where the feed is cooled from ambient temperature down to cryogenic temperatures. Different liquefaction cycles exist depending on the application, with dual mixed refrigerant processes normally considered for the large-scale production of Liquefied Natural Gas (LNG). Large temperature spans and small temperature differences in the heat exchangers make the liquefaction processes difficult to analyze. Exergetic losses from irreversible heat transfer increase exponentially with a decreasing temperature at subambient conditions. Consequently, an accurate and robust simulation tool is paramount to allow designers to make correct design decisions. However, conventional process simulators, such as Aspen Plus, suffer from significant drawbacks when modeling multistream heat exchangers. In particular, no rigorous checks exist to prevent temperature crossovers. Limited degrees of freedom and the inability to solve for stream variables other than outlet temperatures also makes such tools inflexible to use, often requiring the user to resort to a manual iterative procedure to obtain a feasible solution. In this article, a nonsmooth, multistream heat exchanger model is used to develop a simulation tool for two different dual mixed refrigerant processes. Case studies are presented for which Aspen Plus fails to obtain thermodynamically feasible solutions.

Ion-Exchanged SAPO-34 Membranes for Krypton-Xenon Separation: Control of Permeation Properties and Fabrication of Hollow Fiber Membranes.

Separation of radioisotope 85Kr from 136Xe is of importance in used nuclear fuel reprocessing. Membrane separation based on zeolite molecular sieves such as chabazite SAPO-34 is an attractive alternative to energy-intensive cryogenic distillation. We report the synthesis of SAPO-34 membranes with considerably enhanced performance via thickness reduction based upon control of a steam-assisted vapor-solid conversion technique followed by ion exchange with alkali metal cations. The reduction of membrane thickness leads to a large increase in Kr permeance from 7.5 to 26.3 gas permeation units (GPU) with ideal Kr/Xe selectivities >20 at 298 K. Cation-exchanged membranes show large (>50%) increases in selectivity at ambient or slight subambient conditions. The adsorption, diffusion, and permeation characteristics of ion-exchanged SAPO-34 materials and membranes are investigated in detail, with potassium-exchanged SAPO-34 membranes showing particularly attractive performance. We then demonstrate the fabrication of selective SAPO-34 membranes on α-alumina hollow fibers.