Detection and capture of toxic nitrogen oxides (NOx) is important for emissions control of exhaust gases and general public health. The ability to directly electrically detect trace (0.5–5 ppm) NO2 by a metal–organic framework (MOF)-74-based sensor at relatively low temperatures (50 °C) is demonstrated via changes in electrical properties of M-MOF-74, M = Co, Mg, Ni. The magnitude of the change is ordered Ni > Co > Mg and explained by each variant's NO2 adsorption capacity and specific chemical interaction. Ni-MOF-74 provides the highest sensitivity to NO2; a 725× decrease in resistance at 5 ppm NO2 and detection limit <0.5 ppm, levels relevant for industry and public health. Furthermore, the Ni-MOF-74-based sensor is selective to NO2 over N2, SO2, and air. Linking this fundamental research with future technologies, the high impedance of MOF-74 enables applications requiring a near-zero power sensor or dosimeter, with the active material drawing <15 pW for a macroscale device 35 mm2 with 0.8 mg MOF-74. This represents a 104–106× decrease in power consumption compared to other MOF sensors and demonstrates the potential for MOFs as active components for long-lived, near-zero power chemical sensors in smart industrial systems and the internet of things.
Iodine detection is crucial for nuclear waste clean-up and first responder activities. For ease of use and durability of response, robust active materials that enable the direct electrical detection of I2 are needed. Herein, a large reversible electrical response is demonstrated as I2 is controllably and repeatedly adsorbed and desorbed from a series of metal-organic frameworks (MOFs) MFM-300(X), each possessing a different metal center (X = Al, Fe, In, or Sc) bridged by biphenyl-3,3′,5,5′-tetracarboxylate linkers. Impedance spectroscopy is used to evaluate how the different metal centers influence the electrical response upon cycling of I2 gas, ranging from 10× to 106× decrease in resistance upon I2 adsorption in air. This large variation in electrical response is attributed not only to the differing structural characteristics of the MOFs but also to the differing MOF morphologies and how this influences the degree of reversibility of I2 adsorption. Interestingly, MFM-300(Al) and MFM-300(In) displayed the largest changes in resistance (up to 106×) yet lost much of their adsorption capacity after five I2 adsorption cycles in air. On the other hand, MFM-300(Fe) and MFM-300(Sc) revealed more moderate changes in resistance (10-100×), maintaining most of their original adsorption capacity after five cycles. This work demonstrates how changes in MOFs can profoundly affect the magnitude and reversibility of the electrical response of sensor materials. Tuning both the intrinsic (resistivity and adsorption capacity) and extrinsic (surface area and particle morphology) properties is necessary to develop highly reversible, large signal-generating MOF materials for direct electrical readout for I2 sensing.
The removal of silica, ubiquitous in produced and industrial waters, by novel mixed oxides is investigated in this present study. We have combined the advantage of high selectivity hydrotalcite (HTC, (Mg6Al2(OH)16(CO3)·4H2O)), with large surface area of active alumina (AA, (Al2O3)) for effective removing of the dissolved silica from cooling tower water. The batch test results indicated the combined HTC/AA is a more effective method for removing silica from CTW than using each of HTC or AA separately. The silica uptake was confirmed by Fourier transform infrared (FTIR), and Energy dispersive spectroscopy (EDS). Results indicate HTC/AA effectively removes silica from cooling tower water (CTW), even in the presence of large concentrations of competing anions, such as Cl−, NO3− HCO3−, CO32− and SO42−. The Single Path Flow Through (SPFT) tests confirmed to rapid uptake of silica by combined HTC/AA during column filtration. The experimental data of silica adsorption fit best to Freundlich isotherm model.
Water shortages are a growing global problem. Reclamation of industrial and municipal wastewater will be necessary in order to mitigate water scarcity. However, many operational challenges, such as silica scaling, prevent large scale water reuse. Previously, our team at Sandia has demonstrated the use of selective ion exchange materials, such as calcinated hydrotalcite (HTC, (Mg 6 Al 2 (OH) 16 (CO 3 )*4H 2 O)), for the low cost removal of silica from synthetic cooling tower water. However, it is not currently know if calcinated HTC has similar capabilities in realistic applications. The purpose of this study was to investigate the ability of calcinated HTC to remove silica from real cooling tower water. This was investigated under both batch and continuous conditions, and in the presence of competing ions. It was determined that calcinated HTC behaved similarly in real and synthetic cooling tower water; the HTC is highly selective for the silica even in the presence of competing cations. Therefore, the data concludes that calcinated HTC is a viable anti-scaling pretreatment for the reuse of industrial wastewaters.
Fresh water scarcity is going to be a global great challenge in the near future because of the increasing population. Our water resources are limited and, hence, water treatment and recycling methods are the only alternatives for fresh water procurement in the upcoming decades. Water treatment and recycling methods serve to remove harmful or problematic constituents from ground, surface and waste waters prior to its consumption, industrial supply, or other uses. Scale formation in industrial and domestic installations is still an important problem during water treatment. In water treatment, silica scaling is a real and constant concern for plant operations. The focus of this study is on the viability of using a combination of catechol and active carbon to remove dissolved silica from concentrated cooling tower water (CCTW). Various analytical methods, such as ICP-MS and UV-vis, were used to understand the structure-property relationship between the material and the silica removal results. UV-Vis indicates that catechol can react with silica ions and form a silica-catecholate complex. The speciation calculation of catechol and silica shows that catechol and silica bind in the pH range of 8 – 10; there is no evidence of linkage between them in neutral and acidic pHs. The silica removal results indicate that using ~4g/L of catechol and 10g/L active carbon removes up to 50% of the dissolved silica from the CCTW.
The study of mineral-water interfaces is of great importance to a variety of applications including oil and gas extraction, gas subsurface storage, environmental contaminant treatment, and nuclear waste repositories. Understanding the fundamentals of that interface is key to the success of those applications. Confinement of water in the interlayer of smectite clay minerals provides a unique environment to examine the interactions among water molecules, interlayer cations, and clay mineral surfaces. Smectite minerals are characterized by a relatively low layer charge that allows the clay to swell with increasing water content. Montmorillonite and beidellite varieties of smectite were investigated to compare the impact of the location of layer charge on the interlayer structure and dynamics. Inelastic neutron scattering of hydrated and dehydrated cation-exchanged smectites was used to probe the dynamics of the interlayer water (200-900 cm-1 spectral region) and identify the shift in the librational edge as a function of the interlayer cation. Molecular dynamics simulations of equivalent phases and power spectra, derived from the resulting molecular trajectories, indicate a general shift in the librational behavior with interlayer cation that is generally consistent with the neutron scattering results for the monolayer hydrates. Both neutron scattering and power spectra exhibit librational structures affected by the location of layer charge and by the charge of the interlayer cation. Divalent cations (Ba2+ and Mg2+) characterized by large hydration enthalpies typically exhibit multiple broad librational peaks compared to monovalent cations (Cs+ and Na+), which have relatively small hydration enthalpies.
The National Water, Energy and Carbon Sequestration simulation model (WECSsim) is being developed to address the question, 'Where in the current and future U.S. fossil fuel based electricity generation fleet are there opportunities to couple CO{sub 2} storage and extracted water use, and what are the economic and water demand-related impacts of these systems compared to traditional power systems?' The WECSsim collaborative team initially applied this framework to a test case region in the San Juan Basin, New Mexico. Recently, the model has been expanded to incorporate the lower 48 states of the U.S. Significant effort has been spent characterizing locations throughout the U.S. where CO{sub 2} might be stored in saline formations including substantial data collection and analysis efforts to supplement the incomplete brine data offered in the NatCarb database. WECSsim calculates costs associated with CO{sub 2} capture and storage (CCS) for the power plant to saline formation combinations including parasitic energy costs of CO{sub 2} capture, CO{sub 2} pipelines, water treatment options, and the net benefit of water treatment for power plant cooling. Currently, the model can identify the least-cost deep saline formation CO{sub 2} storage option for any current or proposed coal or natural gas-fired power plant in the lower 48 states. Initial results suggest that additional, cumulative water withdrawals resulting from national scale CCS may range from 676 million gallons per day (MGD) to 30,155 MGD depending on the makeup power and cooling technologies being utilized. These demands represent 0.20% to 8.7% of the U.S. total fresh water withdrawals in the year 2000, respectively. These regional and ultimately nation-wide, bottom-up scenarios coupling power plants and saline formations throughout the U.S. can be used to support state or national energy development plans and strategies.
Radioactive iodine, 129I, a component of spent nuclear fuel, is of particular concern due to its extremely long half-life, its potential mobility in the environment and its effects on human health. In the spent fuel reprocessing scheme under consideration, the 129I is released in gaseous form and collected using Ag-loaded zeolites such as Ag-mordenite. The 129I can react with the Ag to form insoluble AgI. We have investigated the use of low temperature-sintering glass powders mixed with either AgI or AgI-zeolite to produce dense waste forms that can be processed at 500°C, where AgI volatility is low. These mixtures can contain up to 20 wt% crushed AgI-mordenite or up to 50 wt% AgI. Both types of waste forms were found to have the high iodine leach resistance in these initial studies.
Concerns over rising concentrations of greenhouse gases in the atmosphere have resulted in serious consideration of policies aimed at reduction of anthropogenic carbon dioxide (CO2) emissions. If large scale abatement efforts are undertaken, one critical tool will be geologic sequestration of CO2 captured from large point sources, specifically coal and natural gas fired power plants. Current CO2 capture technologies exact a substantial energy penalty on the source power plant, which must be offset with make-up power. Water demands increase at the source plant due to added cooling loads. In addition, new water demand is created by water requirements associated with generation of the make-up power. At the sequestration site however, saline water may be extracted to manage CO2 plum migration and pressure build up in the geologic formation. Thus, while CO2 capture creates new water demands, CO2 sequestration has the potential to create new supplies. Some or all of the added demand may be offset by treatment and use of the saline waters extracted from geologic formations during CO2 sequestration. Sandia National Laboratories, with guidance and support from the National Energy Technology Laboratory, is creating a model to evaluate the potential for a combined approach to saline formations, as a sink for CO2 and a source for saline waters that can be treated and beneficially reused to serve power plant water demands. This presentation will focus on the magnitude of added U.S. power plant water demand under different CO2 emissions reduction scenarios, and the portion of added demand that might be offset by saline waters extracted during the CO2 sequestration process.
In an effort to address the potential to scale up of carbon dioxide (CO{sub 2}) capture and sequestration in the United States saline formations, an assessment model is being developed using a national database and modeling tool. This tool builds upon the existing NatCarb database as well as supplemental geological information to address scale up potential for carbon dioxide storage within these formations. The focus of the assessment model is to specifically address the question, 'Where are opportunities to couple CO{sub 2} storage and extracted water use for existing and expanding power plants, and what are the economic impacts of these systems relative to traditional power systems?' Initial findings indicate that approximately less than 20% of all the existing complete saline formation well data points meet the working criteria for combined CO{sub 2} storage and extracted water treatment systems. The initial results of the analysis indicate that less than 20% of all the existing complete saline formation well data may meet the working depth, salinity and formation intersecting criteria. These results were taken from examining updated NatCarb data. This finding, while just an initial result, suggests that the combined use of saline formations for CO{sub 2} storage and extracted water use may be limited by the selection criteria chosen. A second preliminary finding of the analysis suggests that some of the necessary data required for this analysis is not present in all of the NatCarb records. This type of analysis represents the beginning of the larger, in depth study for all existing coal and natural gas power plants and saline formations in the U.S. for the purpose of potential CO{sub 2} storage and water reuse for supplemental cooling. Additionally, this allows for potential policy insight when understanding the difficult nature of combined potential institutional (regulatory) and physical (engineered geological sequestration and extracted water system) constraints across the United States. Finally, a representative scenario for a 1,800 MW subcritical coal fired power plant (amongst other types including supercritical coal, integrated gasification combined cycle, natural gas turbine and natural gas combined cycle) can look to existing and new carbon capture, transportation, compression and sequestration technologies along with a suite of extracting and treating technologies for water to assess the system's overall physical and economic viability. Thus, this particular plant, with 90% capture, will reduce the net emissions of CO{sub 2} (original less the amount of energy and hence CO{sub 2} emissions required to power the carbon capture water treatment systems) less than 90%, and its water demands will increase by approximately 50%. These systems may increase the plant's LCOE by approximately 50% or more. This representative example suggests that scaling up these CO{sub 2} capture and sequestration technologies to many plants throughout the country could increase the water demands substantially at the regional, and possibly national level. These scenarios for all power plants and saline formations throughout U.S. can incorporate new information as it becomes available for potential new plant build out planning.
Reprocessing nuclear fuel releases gaseous radio-iodine containing compounds which must be captured and stored for prolonged periods. Ag-loaded mordenites are the leading candidate for scavenging both organic and inorganic radioiodine containing compounds directly from reprocessing off gases. Alternately, the principal off-gas contaminant, I2, and I-containing acids HI, HIO3, etc. may be scavenged using caustic soda solutions, which are then treated with bismuth to put the iodine into an insoluble form. Our program is focused on using state-of-the-art materials science technologies to develop materials with high loadings of iodine, plus high long-term mechanical and thermal stability. In particular, we present results from research into two materials areas: (1) zeolite-based separations and glass encapsulation, and (2) in-situ precipitation of Bi-I-O waste forms. Ag-loaded mordenite is either commercially available or can be prepared via a simple Ag+ ion exchange process. Research using an Ag+-loaded Mordenite zeolite (MOR, LZM-5 supplied by UOP Corp.) has revealed that I2 is scavenged in one of three forms, as micron-sized AgI particles, as molecular (AgI)x clusters in the zeolite pores and as elemental I2 vapor. It was found that only a portion of the sorbed iodine is retained after heating at 95o C for three months. Furthermore, we show that even when the Ag-MOR is saturated with I2 vapor only roughly half of the silver reacted to form stable AgI compounds. However, the Iodine can be further retained if the AgI-MOR is then encapsulated into a low temperature glass binder. Follow-on studies are now focused on the sorption and waste form development of Iodine from more complex streams including organo-iodine compounds (CH3I). Bismuth-Iodate layered phases have been prepared from caustic waste stream simulant solutions. They serve as a low cost alternative to ceramics waste forms. Novel compounds have been synthesized and solubility studies have been completed using competing groundwater anions (HCO3-, Cl- and SO42-). Distinct variations in solubility were found that related to the structures of the materials.
Expansion of uranium mining in the United States is a concern to some environmental groups and sovereign Native American Nations. An approach which may alleviate some problems is to develop inherently safe in situ uranium recovery ('ISR') technologies. Current ISR technology relies on chemical extraction of trace levels of uranium from aquifers that, once mined, can still contain dissolved uranium and other trace metals that are a health concern. Existing ISR operations are few in number; however, high uranium prices are driving the industry to consider expanding operations nation-wide. Environmental concerns and enforcement of the new 30 ppb uranium drinking water standard may make opening new mining operations more difficult and costly. Here we propose a technological fix: the development of inherently safe in situ recovery (ISISR) methods. The four central features of an ISISR approach are: (1) New 'green' leachants that break down predictably in the subsurface, leaving uranium, and associated trace metals, in an immobile form; (2) Post-leachant uranium/metals-immobilizing washes that provide a backup decontamination process; (3) An optimized well-field design that increases uranium recovery efficiency and minimizes excursions of contaminated water; and (4) A combined hydrologic/geochemical protocol for designing low-cost post-extraction long-term monitoring. ISISR would bring larger amounts of uranium to the surface, leave fewer toxic metals in the aquifer, and cost less to monitor safely - thus providing a 'win-win-win' solution to all stakeholders.