44 Search Results

Sulfur dioxide (SO₂) is a harmful acidic gas generated from power plants and fossil fuel combustion and represents a significant health risk and threat to the environment. Benzimidazole-linked polymers (BILPs) have emerged as a promising class of porous solid adsorbents for toxic gases because of their chemical and thermal stability as well as the chemical nature of the imidazole moiety. The performance of BILPs in SO₂ capture was examined by synergistic experimental and theoretical studies. BILPs exhibit a significantly high SO₂ uptake of up to 8.5 mmol g^–1 at 298 K and 1.0 bar. The density functional theory (DFT) calculationsmore » predict that this high SO₂ uptake is due to the dipole–dipole interactions between SO₂ and the functionalized polymer frames through O₂S(δ⁺)···N(δ^–)-imine and O=S=O(δ^–)···H(δ⁺)-aryl and intermolecular attraction between SO₂ molecules (O=S=O(δ^–)···S(δ⁺)O₂). Moderate isosteric heats of adsorption (Q_st ≈ 38 kJ mol^–1) obtained from experimental SO₂ uptake studies are well supported by the DFT calculations (≈40 kJ mol^–1), which suggests physisorption processes enabling rapid adsorbent regeneration for reuse. Repeated adsorption experiments with almost identical SO₂ uptake confirm the easy regeneration and robustness of BILPs. Moreover, BILPs possess very high SO₂ adsorption selectivity at low concentration over carbon dioxide (CO₂), methane (CH₄), and nitrogen (N₂): SO₂/CO₂, 19–24; SO₂/CH₄, 118–113; SO₂/N₂, 600–674. This study highlights the potential of BILPs in the desulfurization of flue gas or other gas mixtures through capturing trace levels of SO₂.« less

Since the 2000, there have been numerous investigations into electrical energy storage types that use ocean thermal-to-electricity conversion techniques. Field tests have demonstrated that this technology is feasible for UUVs with long-term missions of over 3,000 km per deployment. Nonetheless, the energy generated by this method is not sufficient to meet the energy requirements of Unscrewed Underwater Vehicles (UUVs). The objective of this study is to design a highly effective ocean thermal gradient energy system to support long-term missions of a UUV. To enhance the performance of the thermal gradient energy system, we have developed a hybrid type (buoyancy regulationmore » and electrical storage). Phase Change Material (PCM)-based energy harvesting system to facilitate efficient UUV operations. A prototype of the hydraulic-to-electric conversion system was implemented, and experimental findings indicate that the hybrid system successfully delivers hydraulic energy for buoyancy change and improved efficiency of hydraulic-to-electric energy conversion, demonstrating its potential as a promising technology for supporting long-term UUV missions.« less

In this study, biorefinery residues and biomass ash were used to develop sulfonated carbon-based solid-acid catalysts to enhance xylan hydrolysis. Here, metals extracted from the biomass ash were impregnated into a carbon support prepared from biorefinery residues to synthesize sulfonated ash-impregnated carbon-based catalyst. Metals present in the ash most probably are responsible for the increased acid density in the catalyst. Using this catalyst, 11.4 % xylose yield was produced, an increase of 171 % over the yield obtained from a catalyst without ash impregnation. Using a xylan-to-catalyst ratio of 1:2, 72.9 % xylose yield was obtained, comparable to using 0.5more » wt% sulfuric acid under the same reaction condition. Moreover, this catalyst significantly inhibited xylose dehydration, only forming 11.3 % furfural compared to that generated using dilute acid. Hence, these results show the potential for using biomass ash as a metal source to increase the number of acid sites in solid-acid catalysts used for biomass pretreatment.« less

Our industrial client (Geo40) has developed and deployed a process to remove silica from geothermal fluids and produce a high-margin specialty colloidal silica product comparable to those of market leaders. Geo40 now wishes to explore opportunities to extend their mineral extraction operations to other elements that are present in these brines. Geo40 has identified cesium (Cs) that is present in Ohaaki brines (pH ~8–8.5) at parts per million levels and could be sold to customers if it could be produced at an attractive price. With support from the Department of Energy’s (DOE’s) Geothermal Technologies Office, a simple and highly cost-effectivemore » magnetic nanofluid method for extraction of rare earth elements (REEs) from geothermal brine solutions has been developed and demonstrated at the laboratory bench scale at Pacific Northwest National Laboratory (PNNL). Core shell sorbent particles are produced using an iron oxide core particle, which is used to anchor and grow a surrounding adsorbent shell functionalized with a chelating ligand that selectively binds REEs. We extended PNNL’s work by exploring new sorbent shells that are highly selective for Cs. Uptake of Cs was measured as a function of exposure time by analyzing solution samples extracted from batch sorption tests.« less

Hypothesis: The precipitation and dissolution of aluminum-bearing mineral phases in aqueous systems often proceed via changes in both aluminum coordination number and connectivity, complicating molecular-scale interpretation of the transformation mechanism. Here, the thermally induced transformation of crystalline sodium aluminum salt hydrate, a phase comprised of monomeric octahedrally coordinated aluminate which is of relevance to industrial aluminum processing, has been studied. Because intermediate aluminum coordination states during melting have not previously been detected, it is hypothesized that the transition to lower coordinated aluminum ions occurs within a highly disordered quasi-two-dimensional phase at the solid-solution interface. Experiments and simulations: In this work,more » in situ X-ray diffraction (XRD), Raman and ²⁷Al nuclear magnetic resonance (NMR) spectroscopy were used to monitor the melting transition of nonasodium aluminate hydrate (NSA, Na₉[Al(OH)₆]₂·3(OH)·6H₂O). A mechanistic interpretation was developed based on complementary classical molecular dynamics (CMD) simulations including enhanced sampling. A reactive forcefield was developed to bridge speciation in the solution and in the solid phase. Findings: In contrast to classical dissolution, aluminum coordination change proceeds through a dynamically stabilized ensemble of intermediate states in a disordered layer at the solid-solution interface. In both melting and dissolution of NSA, octahedral, monomeric aluminum transition through an intermediate of pentahedral coordination. The intermediate dehydroxylates to form tetrahedral aluminate (Al(OH)$$_4^–$$) in the liquid phase. This coordination change is concomitant with a breaking of the ionic aluminate-sodium ion linkages. The solution phase Al(OH)$$_4^–$$ ions subsequently polymerize into polynuclear aluminate ions. However, there are some differences between bulk melting and interfacial dissolution, with the onset of the surface-controlled process occurring at a lower temperature (~30 °C) and the coordination change taking place more gradually as a function of temperature. This work to determine the local structure and dynamics of aluminum in the disordered layer provides a new basis to understand mechanisms controlling aluminum phase transformations in highly alkaline solutions.« less

Thermal gradient energy-generation technologies for powering unmanned underwater vehicles (UUVs) or autonomous sensing systems in the ocean are mainly in the research development phase or commercially available at a limited scale, and salinity-gradient energy-generation technologies have not been adequately researched yet. The demand for self-powered UUVs suitable for long-term deployments has been growing, and further research related to small-scale ocean gradient energy systems is needed. In this study, we conducted a comprehensive review about harvesting energy from ocean thermal or salinity gradients for powering UUVs, focusing on gliders and profiling floats. Thermal gradient energy systems for UUVs based on phasemore » change materials (PCM) cannot provide the energy required for powering autonomous sensing systems because of the systems’ low energy conversion efficiency. Besides reducing energy consumption by developing more efficient electrical-mechanical systems, enhancing the thermal conductivity of the PCMs may help address this challenge by increasing the power generation rate of the UUVs. Several other emerging technologies, such as thermoelectric generators, shape memory alloys, and small-scale thermodynamic cycle systems, have shown potential for powering UUVs, but they are still only at the laboratory testing or conceptual design phase. The most advanced power generation technologies based on salinity gradients, reverse electrodialysis and pressure-retarded osmosis, are still not economically viable for large-scale deployment, mainly because of the high cost of the components required to operate in harsh saline environments. Our feasibility evaluation showed that existing salinity gradient power generation technologies are not directly feasible for powering UUVs in the open ocean.« less

Pacific Northwest National Laboratory (PNNL), in collaboration with Parker and Hannifin, is developing a compact, inexpensive, and highly sensitive and selective surface acoustic wave sensor coated with fluorophillic sorbent for detecting fluorocarbon leaks from HVAC systems. Having a highly effective sorbent sensitive to fluorocarbon refrigerant vapors provides a means to develop a sensing device for leak detection. Surface acoustic wave (SAW) sensors with a gas sensing film deposited between the delay lines or on the interdigital transducer have been used to detect gas and vapor molecules in harsh environments with high sensitivity. As part of this project, PNNL screened severalmore » sorbent materials that are shown to be selective towards fluorocarbon refrigerant (R32) molecule. The identified sorbent materials were synthesized, characterized, and tested towards R32 using various spectroscopic technique. Next, the sorbent material was coated on a SAW sensor as a thin film using vapor deposition and drop coating methods. The coated thin film was further characterized and tested towards the detection of pure R32 and R32 in ambient air at room temperature to demonstrate the SAW response towards R32 in presence of other competing gases and vapors in air.« less

Rare earth elements (REE) are critical materials having a wide variety of applications such as generating and storing renewable energy. Extracting rare earth metals from geothermal brines is a very challenging problem due to the low concentrations of these elements and engineering challenges with traditional chemical separations methods involving packed sorbent beds or membranes that would impede large volumetric flow rates of geothermal fluids transitioning through the geothermal power plant. We are demonstrating a simple and highly cost-effective nanofluid-based method for extracting rare earth metals from geothermal brines. Core-shell composite nanoparticles that contain a magnetic iron oxide core surrounded bymore » a shell made of metal-organic framework (MOF) sorbent functionalized with chelating ligands are produced to selectively extract rare earth elements. Baseline values of the important parameters including rare earth metal concentration and price, adsorbent need, cost and lifetime have been identified. This information together with a flowsheet model were used to estimate the operating and capital costs of the extraction process. A techno-economic performance analysis of extraction systems using a modified In-MOF as the adsorbent showed potential to generate a promising internal rate of return (IRR) higher than 16%. Sensitivity analysis has been done on some key parameters such as REE concentration and price and adsorbent cost to reveal their impacts on IRR.« less

Renewable power generated from wave energy has faced technological and cost barriers to entry into utility-scale electricity markets. As an alternative, the production of chemical fuels, such as ammonia (NH3) which has high energy density (11.5 MJ/L) and facile storage properties, may open wave energy to new markets including ocean exploration and transportation. The electrochemical method has been studied to synthesize NH3 from air and water at ambient conditions. Based on some recent work on the electrochemical synthesis of NH3, it is possible to achieve an overall conversion efficiency of 10% from wave energy to NH3 through an electrochemical reactionmore » between air and water. If all the recoverable wave energy in the United States (1170 TWh/yr) is used to produce renewable NH3 fuel replacing hydrocarbon fuels, this can help reduce over 300 million tons of CO2 emission every year. Several potential application scenarios at sea have been proposed for renewable NH3 fuel including production and storage for marine shipping and seasonal energy storage for Arctic exploration. Liquefied NH3 has much higher energy density, both gravimetric and volumetric, than a variety of batteries but the energy efficiency of NH3 is lower than modern batteries such as Li-ion. The Levelized cost of storing NH3 prepared using electric energy is less than $0.2/kWh and the storage time can exceed 10,000 hours which indicates that NH3 can be a promising energy storage solution to make use of abundant wave energy. However, there are some safety and environmental concerns involved in the usage of NH3 at sea. The challenges in the electrochemical catalyst for the NH3 synthesis and how molecular simulation may help to screen electrocatalyst with high efficiency and selectivity were also briefly discussed.« less

A novel sorbent-based separation process has been developed to selectively remove target molecules from the real fast pyrolysis (FP) pine bio-oils. Specifically, zeolitic molecular sieves and functionalized polymeric resins were found to effectively reduce carbonyl content and carboxylic acid number of a real pine fast pyrolysis bio-oils, therefore enhance bio-oil stability and preserve down-stream catalyst. Our results provide the first-time evidence on the potential effectiveness of sorption technology strategy for dealing with real FP bio-oils, reducing the carbonyl-rich FP oils from 7.5 mmolg-1 down to 4 mmolg-1 at 40 ?, which has potential to enable bio-oil stabilization and enhance operationmore » stability for down-stream upgrading/hydrotreating processes.« less