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This paper is a tribute to Dr Fred Munpton, the founder of the International Committee on Natural Zeolites (ICNZ), by one of his students, who later succeed him as president of the ICNZ. The tribute reflects on Dr. Mumpton's skills as an editor and his zeal for the study of natural zeolites.
The National Aeronautics and Space Administration (NASA) has developed a zeolite-based synthetic substrate, termed zeoponics. The zeoponic substrate (consisting of NH4(-) and K-exchanged clinoptilolite, synthetic apatite, and dolomite) provides all of the plant-essential nutrients through mineral dissolution and ion exchange, with only the addition of water. Previous studies have shown high productivity of wheat in zeoponic substrates; however, no experiments have been conducted on other crops. The objective of this study was to determine the productivity and nutrient uptake of radish (Raphanus sativus L.) grown in zeoponic substrates with three successive crops in the same substrate. Radish was chosen because of its sensitivities to NH4(+). Average fresh weights of edible roots were similar for radish grown in zeoponic substrates watered with deionized H2O (10.97 g/plant) and in potting mix control substrate irrigated with nutrient solution (10.92 g/plant). Average fresh weight production of edible roots for radish grown in same zeoponic substrate increased in yield over time with the lowest yield in the first crop (7.10 g/plant) and highest in the third crop (13.90 g/plant). The Ca plant tissue levels in radishes (1.8-2.9 wt. %) grown in zeoponic substrates are lower than the suggested sufficient range of 3.0-4.5 wt. % Ca; however, the Ca level is highest (2.9 wt. %) in radishes grown in the third crop in the same zeoponic substrates. The higher radish yield in the third crop was attributed to a reduction in an NH4(-) induced Ca deficiency that has been previously described for wheat grown in zeoponic substrates. The P levels in plant tissues of radish grown in the zeoponic substrates ranged from 0.94-1.15 wt. %; which is slightly higher than the sufficient levels of 0.3-0.7 wt. %. With the exception of Ca and P, other macronutrient and micronutrient levels in radish grown in zeoponic substrates were well within the recommended sufficient ranges. After three successive crops of radish growth, the zeoponic substrates had 52% of the original NH4(-)N and 78% of the original K remaining on zeolite exchange sites. Zeoponic substrates are capable of long-term productivity of radishes for space.
Efficient, regenerable sorbents for removal of H.sub.2 S from moderately high temperature (usually 200.degree. C.-550.degree.C.) gas streams comprise a porous, high surface area aluminosilicate support, suitably a zeolite, and most preferably a sodium deficient zeolite containing 1 to 20 weight percent of binary metal oxides. The binary oxides are a mixture of a Group VB or VIB metal oxide with a Group IB, IIB or VIII metal oxide such as V-Zn-O, V-Cu-O, Cu-Mo-O, Zn-Mo-O or Fe-Mo-O contained in the support. The sorbent effectively removes H.sub.2 S from the host gas stream in high efficiency and can be repetitively regenerated at least 10 times without loss of activity.
A synthetic soil/fertilizer for horticultural application having all the agronutrients essential for plant growth is disclosed. The soil comprises a synthetic apatite fertilizer having sulfur, magnesium and micronutrients dispersed in a calcium phosphate matrix, a zeolite cation exchange medium saturated with a charge of potassium and nitrogen cations, and an optional pH buffer. Moisture dissolves the apatite and mobilizes the nutrient elements from the apatite matrix and the zeolite charge sites.
A zeoponic plant growth system is defined as the cultivation of plants in artificial soils, which have zeolites as a major component. These systems: 1) can serve as a controllable and renewable fertilization system to provide plant growth nutrients; 2) can mitigate the adverse effects of contamination due to leaching of highly soluble and concentrated fertilizers; and 3) are being considered as substrates for plant growth in regenerative life-support systems for long-duration space missions. Batch-equilibrium studies of the dissolution and ion-exchange properties of mixtures of naturally-occurring Wyoming clinoptilolite (a zeolite) exchanged with K(+) or NH4(+); and synthetic hydroxyapatite were conducted to determine: 1) the plant availability of the macro-nutrients NH4-N, P, K, Ca, and Mg and 2) the effects of varying the clinoptilolite to hydroxyapatite ratio and the ratio of exchangeable cations (K(+) vs. NH4(+)) on clinoptilolite extraframework sites. The nutrients NH4-N (19.7 to 73.6 mg L(sup -1), P (0.57 to 14.99 mg L(sup- 1), K (14.8 to 104.9 mg L(sup -1), and Mg (0.11 to 6.68mg L(sup -1) are available to plants at sufficient levels. Solution Ca concentrations (0.47 to 3.40 mg L(sup -1) are less than optimal. Solution concentrations of NH4(+), K(+), Ca(2+), and Mg(2+) all decreased with increasing clinoptilolite to hydroxyapatite ratio in the sample. Solution concentrations of phosphorous initially increased, reached a maximum value and then decreased with increasing clinoptilolite to hydroxyapatite ratio in the sample. The NH4(+) -exchanged clinoptilolite is more efficient in dissolving synthetic hydroxyapatite than the K(+) -exchanged clinoptilolite. This suggests that NH4(+), which is less selective at clinoptilolite extraframework sites than K(+) is exchanged more readily by Ca(2+) and thereby enhances the dissolution of the synthetic hydroxyapatite.
Low temperature double-layer capacitor operation enabled by: - Base acetonitrile / TEATFB salt formulation - Addition of low melting point formates, esters and cyclic ethers center dot Key electrolyte design factors: - Volume of co-solvent - Concentration of salt center dot Capacity increased through higher capacity electrodes: - Zeolite templated carbons - Asymmetric cell designs center dot Continuing efforts - Improve asymmetric cell performance at low temperature - Cycle life testing Motivation center dot Benchmark performance of commercial cells center dot Approaches for designing low temperature systems - Symmetric cells (activated carbon electrodes) - Symmetric cells (zeolite templated carbon electrodes) - Asymmetric cells (lithium titanate/activated carbon electrodes) center dot Experimental results center dot Summary
Carbon Dioxide removal systems on submarines are compact and reliable. They use solubility chemistry. They spray a Carbon Dioxide adsorbing chemical directly into the air stream, and allow the liquid to settle. Carbon Dioxide removal systems on ISS are large and need repair. They use adsorption chemistry. They force air through a bed packed with granular zeolite, and heat the bed to desorb the Carbon Dioxide. The thermal cycles cause the zeolite to dust. New advances in additive manufacturing, and a better understanding of uid behavior in microgravity make it possible to expose a liquid directly to air in a microgravity environment. It is now practical to use submarine style solubility chemistry for atmosphere revitalization in space. It is now possible to develop space systems that achieve submarine levels of reliability. New developments in Ionic Liquid research make it possible to match the solubility performance characteristics of MEA used on submarines - with Ionic Liquids that do not release chemical vapors into the air. "Thirsty Walls" provide gentle, passive contact between ventilation air and Air Revitalization functions of temperature control, relative humidity control, and Carbon Dioxide removal. "Thirsty Walls" eliminates the need of large blowers and compressors that need to force air at high velocities through restrictive Air Revitalization hardware.
Design of advanced carbon dioxide removal systems begins with the study of sorbents. Specifically, new CO2 sorbents and desiccants need to be studied to enable greater productivity from existing and future spaceflight systems. This presentation will discuss the studies used as input for selecting future CO2 sorbent materials. Also, the adjoining issues of understanding the effects of water co-adsorption and material selection for desiccant beds will be discussed. Current sorbents for CO2 removal are based on 5A zeolites, but a transition to sorbents derived from 13X will be necessary as CO2 levels in cabin air become leaner. Unfortunately, these 13X zeolites are more susceptible to long-term performance loss due to water co-adsorption than 5A due at achievable regeneration temperatures. A study on how impactful the presence of trace water will be to the cyclic operation of small-scale beds will be discussed. Also, methods to recover the performance of beds in a space environment after a major moisture adsorption event will be discussed. The information obtained from the water co-adsorption studies will play a major part in selecting a CO2 sorbent for advanced removal systems. Pellet structural properties play another major role in the selection process. One factor for long-term, hands-off operation of a system is pellet integrity. Maintaining integrity means preventing pellet fracture and the generation of fines due to various thermal and mechanical means which would eventually clog filters or damage downstream systems. Either of these problems require significant shutdowns and maintenance operations and must be avoided. Therefore, study of high-integrity pellets and design of new pellets will be discussed.
The 1-D axially dispersed plug flow model is a mathematical model widely used for the simulation of adsorption processes. Lumped mass transfer coefficients such as the Glueckauf linear driving force (LDF) term and the axial dispersion coefficient are generally obtained by fitting simulation results to the experimental breakthrough test data. An approach is introduced where these parameters, along with the only free parameter in the energy balance equations, are individually fit to specific test data that isolates the appropriate physics. It is shown that with this approach this model provides excellent simulation results for the C02 on zeolite SA sorbent/sorbate system; however, for the H20 on zeolite SA system, non-physical deviations from constant pattern behavior occur when fitting dispersive experimental results with a large axial dispersion coefficient. A method has also been developed that determines a priori what values of the LDF and axial dispersion terms will result in non-physical simulation results for a specific sorbent/sorbate system when using the one-dimensional axially dispersed plug flow model. A relationship between the steepness of the adsorption equilibrium isotherm as indicated by the distribution factor, the magnitude of the axial dispersion and mass transfer coefficient, and the resulting non-physical behavior is derived. This relationship is intended to provide a guide for avoiding non-physical behavior by limiting the magnitude of the axial dispersion term on the basis of the mass transfer coefficient and distribution factor.
As a coating made of highly porous zeolite materials, the Molecular Adsorber Coating (MAC) was developed to capture outgassed molecular contaminants, such as hydrocarbons and silicones. For spaceflight applications, the adsorptive capabilities of the coating can alleviate on-orbit outgassing concerns on or near sensitive surfaces and instruments within the spacecraft. Similarly, this sprayable paint technology has proven to be significantly beneficial for ground-based space applications, in particular, for vacuum chamber environments. This presentation describes the application of the MAC technology for the James Webb Space Telescope (JWST) at NASA Johnson Space Center (JSC). The coating was used as a mitigation tool to entrap outgassed contaminants, specifically silicone-based diffusion pump oil, from within JSCs cryogenic optical vacuum chamber test facility called Chamber A. This presentation summarizes the background, fabrication, installation, chemical analysis test results, and future plans for the MAC technology, which was effectively used to protect the JWST test equipment from vacuum chamber contamination. As a coating made of highly porous zeolite materials, the Molecular Adsorber Coating (MAC) was developed to capture outgassed molecular contaminants, such as hydrocarbons and silicones. For spaceflight applications, the adsorptive capabilities of the coating can alleviate on-orbit outgassing concerns on or near sensitive surfaces and instruments within the spacecraft. Similarly, this sprayable paint technology has proven to be significantly beneficial for ground-based space applications, in particular, for vacuum chamber environments. This presentation describes the application of the MAC technology for the James Webb Space Telescope (JWST) at NASA Johnson Space Center (JSC). The coating was used as a mitigation tool to entrap outgassed contaminants, specifically silicone-based diffusion pump oil, from within JSCs cryogenic optical vacuum chamber test facility called Chamber A. This presentation summarizes the background, fabrication, installation, chemical analysis test results, and future plans for the MAC technology, which was effectively used to protect the JWST test equipment from vacuum chamber contamination.
There is abundant evidence for liquid water on early Mars, but the debate remains whether early Mars was warm and wet or cold and icy with punctuated periods of melting. To further investigate the hypothesis of a cold and icy early Mars, we collected rocks and sediments from the Collier and Diller glacial valleys in the Three Sisters volcanic complex in Oregon. We analyzed rocks and sediments with X-ray diffraction (XRD), scanning and transmission electron microscopies with energy dispersive spectroscopy (SEM, TEM, EDS), and visible, short-wave infrared (VSWIR) and thermal-IR (TIR) spectroscopies to characterize chemical weathering and sediment transport through the valleys. Here, we focus on the composition and mineralogy of the weathering products and how they compare to those identified on the martian surface. Phyllosilicates (smectite), zeolites, and poorly crystalline phases were discovered in pro- and supra-glacial sediments, whereas Si-rich regelation films were found on hand samples and boulders in the proglacial valleys. Most phyllosilicates and zeolites are likely detrital, originating from hydrothermally altered units on North Sister. TEM-EDS analyses of the <2 um size fraction of glacial flour samples demonstrate a variety of poorly crystalline (i.e., no long-range crystallographic order) phases: iron oxides, devitrified volcanic glass, and Fe-Si-Al phases. The CheMin XRD on the Curiosity rover in Gale crater has identified significant amounts of X-ray amorphous materials in all samples measured to date. The amorphous component is likely a combination of silicates, iron oxides, and sulfates. Although we have not yet observed amorphous sulfate in the samples from Three Sisters, the variety of poorly crystalline weathering products found at this site is consistent with the variable composition of the X-ray amorphous component identified by CheMin. We suggest that these amorphous phases on Mars could have formed in a similarly cold and icy environment.
To improve the increasing CO 2 levels on Earth, technology for carbon capture and utilization must be efficient and cost effective. One major contributor of atmospheric CO 2 is post-combustion flue gas, which can contain up to 20% CO 2 . Scrubbing this CO 2 could reduce the environmental impact of this common industrial process. In off-Earth environments, capturing and utilizing CO 2 from space resources is useful for crewed spaceflight life support. Specifically, the Bosch process, which produces water and carbon powder by reacting CO 2 and hydrogen, is a possible in-situ resource utilization (ISRU) architecture for the Moon and Mars. The Rapid Cycle Temperature Swing Adsorption (RC-TSA) pump is an innovative technology designed to capture CO 2 efficiently. The RC-TSA leverages a stacked plate geometry to cycle multiple zeolite-coated beds. The thin layers allow for rapid heat transfer of the zeolite coating, which improves performance over previously tested pump designs. The design is favorable for scalability and manufacturability, which are forward work. Initial testing of the sorption pump using a simulated flue gas environment shows favorable breakthrough capacities and reduced cycle times. Results show promise for on- and off-Earth applications, such as a Martian surface and crewed spaceflight environments.
Conversion of methanol and dimethyl ether to high-octane gasoline catalyzed by beta zeolite (BEA) provides an opportunity for the production of high-quality fuels from renewable carbon sources (e.g., gasified biomass). Recent research demonstrated that a Cu-modified BEA zeolite catalyst (Cu/BEA) offered advantages over the unmodified BEA catalyst due to multifunctional Cu species that enabled incorporation of co-fed H2, reactivation of light alkanes, and reduction of products from the aromatic hydrocarbon pool. The shift in hydrocarbon pool chemistry has the potential to influence the identity and relative composition of surface carbon species that are often linked to deactivation. A detailed understanding of these carbon species is important to develop an effective and efficient regeneration procedure that can enable the transition from fundamental catalyst development to commercial application. Here, we applied complementary ex situ and in situ characterization techniques to compare the structures of surface carbon species on post-reaction Cu/BEA and unmodified BEA catalysts. Both catalysts contained acyclic and aromatic hydrocarbons along with graphitic carbon species. However, the post-reaction Cu/BEA catalyst had a lower polycyclic aromatic content, and further, the graphitic species were more hydrogenated and defective. It was also found that the presence of Cu promoted carbon removal at lower temperatures than for unmodified BEA through activation of O2 by Cu during thermal oxidation. The fundamental insight into the composition of surface carbon species enabled the design of an effective and efficient regeneration strategy for the DME homologation reaction over Cu/BEA, resulting in full recovery of the catalyst activity.
NREL’s thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient and economical route to completely biogenic pyrolysis-based fuel precursors, potential fuels, and value-added chemicals depending on catalyst choice and process conditions. In this approach, biomass vapors are generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce conditioned vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled with a custom pyrolyzer system designed to produce consistent composition pyrolysis vapors as feed to the DCR. The coupled system is shown below (Figure 1). Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available and laboratory modified zeolite-based catalysts. Upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and micro distillation to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. Measured process parameters identified from technoeconomic process analysis included achieving oil oxygenate contents of 20% or less, carbon-conversion efficiencies of 30% or more, and catalyst coking rates of 10% or less. A proprietary modified zeolite catalyst from Johnson Matthey produced oils that met these requirements. Using the DCR equipped with a proprietary nozzle system, a second approach focused on reducing the carbon intensity of petroleum-derived hydrocarbon fuels by FCC co-processing these CFP oils with petroleum vacuum gas oil (VGO) to produce biogenic carbon containing fuels. The vapor-phase upgrading results demonstrated for the first time the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The co-processing results demonstrated the feasibility of using CFP oils with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.
Disclosed are passive NOx adsorbers and methods for synthesizing the same. Small-pore zeolitic materials with practical loadings of transition metals atomically dispersed in the micropores are described herein. Also demonstrated are simple and scalable synthesis routes to high loadings of atomically dispersed transition metals in the micropores of a small-pore zeolite.
Bimetallic catalysts for the hydrodeoxygenation (HDO) conversion of lignin into useful hydrocarbons are provided. The catalysts are bifunctional bimetallic ruthenium catalysts Ru-M/X+Y comprising a metal M such as iron (Fe), nickel (Ni), copper (Cu) or zinc (Zn), zeolite Y and cation X+ (e.g. H+) associated with zeolite Y.
Sampling uranium hexafluoride (UF6) for the determination of enrichments by destructive analysis (DA) is a critical component in the International Atomic Energy Agency’s layered safeguards approach for uranium processing facilities. Typically, gram-quantity UF6 samples are collected during inspections and stored under tag-and-seal until transportation to an off-site analytical laboratory. The shipping times can be long, and evolving restrictions on radioactive/corrosive materials shipments may increasingly limit the IAEA’s ability to transport UF6 samples easily. Pacific Northwest National Laboratory has developed a low-cost UF6 sampling technology called Single-Use Destructive Assay (SUDA) that addresses these challenges, as well as provides DA sample geometries that can be tailored for different analytical methods, including potential on-site analyses. The SUDA samplers, along with a unique holder, are designed for direct attachment to existing taps at uranium processing facilities, allowing gaseous UF6 to come into direct contact with a zeolite film. The SUDA technology features the ability to capture uranium in a more easily shipped and handled form as the solid, more stable, and relatively less hazardous hydrated uranyl fluoride (UO2F2•nH2O), which is formed through the controlled hydrolysis of UF6. We have recently simulated uranium collection under enrichment plant sampling conditions to further improve our understanding of SUDA sampling. Presented here is our recent work on measuring the relationship between sampling conditions and uranium collection, which includes control of the uranium-mass-to-zeolite ratio and assessing variable UF6 gas and sampling parameters that can affect collection using the SUDA sampler.