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Simonetti, Dante A.

Publications and source records attributed to Simonetti, Dante A..

9 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Lanthanum induced lattice strain improves hydrogen sulfide capacities of copper oxide adsorbents

This work probes the effects of La on reactions involving CuO sorbents and H 2 S in gaseous streams. La-CuO sorbents with nominal La/Cu atomic ratios of 1:2 achieved higher capacities (27 and 36 g H 2 S per 100 g sorbent) compared to CuO sorbents (25 g H 2 S per 100 g sorbent). Here, comparison of the La-CuO sorbents using energy dispersive x-ray spectroscopy and La L 3 -edge XAS suggested that increased capacity resulted from more uniform dispersion of La within the CuO phase (3.3 wt.% vs. 1.0 wt.% La). X-Ray absorption near edge structure analysis suggested more electron-rich Cu species in La-CuO samples, while extended X-ray absorption fine structure modeling showed an increase in single-scattering path lengths for neighboring and near-neighbor atoms. These changes suggest that La induces strain in the Cu-O lattice, thereby increasing H 2 S capacity by reducing energy barriers associated with surface reactions between oxygen atoms and adsorbed H 2 S molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Buffer-free process cycle for CO 2 sequestration and carbonate production from brine waste streams with high salinity

A method includes: (1) using a chelating agent, extracting divalent ions from a brine solution as complexes of the chelating agent and the divalent ions; (2) using a weak acid, regenerating the chelating agent and producing a divalent ion salt solution; and (3) introducing carbon dioxide to the divalent ion salt solution to induce precipitation of the divalent ions as a carbonate salt. Another method includes: (1) combining water with carbon dioxide to produce a carbon dioxide solution; (2) introducing an ion exchanger to the carbon dioxide solution to induce exchange of alkali metal cations included in the ion exchanger with protons included in the carbon dioxide solution and to produce a bicarbonate salt solution of the alkali metal cations; and (3) introducing a brine solution to the bicarbonate salt solution to induce precipitation of divalent ions from the brine solution as a carbonate salt.

Sant, Gaurav↗
DOE OSTI2021

Predicting zeolites’ stability during the corrosion of nuclear waste immobilization glasses: Comparison with glass corrosion experiments

During the long-term corrosion of nuclear waste glasses under nuclear waste disposal conditions, the precipitation of zeolitic phases has been linked to a delayed acceleration in glass corrosion (known as “Stage III”). Hence, predicting the thermodynamic propensity for zeolites to form upon the dissolution of nuclear waste glasses is key to ensure their long-term performance. Here, we compile a unified, internally-consistent thermodynamic database “clay20” to estimate the stability of clay and feldspar phases relevant to nuclear waste immobilization glasses, including beidellite(Mg, Ca, Na, K), kaolinite, montmorillonite(Mg, Ca, Na, K), nontronite(Mg, Ca, Na, K), saponite(Ca, Na, K), and albite. Based on this, we report a geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. We show that this approach offers a realistic description of the stability of the secondary phases forming during the dissolution of two archetypical model nuclear glasses (namely, the International Simple Glass, ISG, and WVUTh-203) under conditions relevant to nuclear waste disposal (T = 90°C, p = 1 bar) as a function of pH. We find that the formation of silica and clay secondary phases is thermodynamically favored at low pH (pH < 10), whereas, in contrast, zeolite (analcime) and calcium–silicate–hydrate phases are favored at high pH (pH > 10.5). This suggests that thermodynamics (i.e., not solely kinetics) plays a key role in determining the range of solution pH wherein stage III corrosion may occur, i.e., when zeolite formation is favored.

Zhen-Wu, Bi Yun↗
DOE OSTI2020

Implementation of Ion Exchange Processes for Carbon Dioxide Mineralization Using Industrial Waste Streams

Sequestration of CO 2 within stable mineral carbonates (e.g., CaCO 3 ) represents an attractive emission reduction strategy because it offers a leakage-free alternative to geological storage of CO 2 in an environmentally benign form. However, the pH of aqueous streams equilibrated with gaseous streams containing CO 2 (pH < 4) are typically lower than that which is required for carbonate precipitation (pH > 8). Traditionally, alkalinity is provided by a stoichiometric reagent (e.g., NaOH) which renders these processes environmentally hazardous and economically unfeasible. This work investigates the use of regenerable ion-exchange materials to induce alkalinity in CO 2 -saturated aqueous solutions such that the pH shift required for mineralization occurs without the need for stoichiometric reagents. Na + -H + exchange isotherms (at [H + ] = 10 −8 –10 −1 M) and rates were measured for 13X and 4A zeolites and TP-207 and TP-260 organic exchange resins in batch equilibrium and fixed-bed exchange experiments, respectively. At solutions equilibrated with CO 2 at 1.0 atm (pH = 3.9), H + exchange capacities for the materials were similar (1.7–2.4 mmol H + /g material) and resulted in pH increases from 3.9 to greater than 8.0. Multi-component mixtures using Ca 2+ and Mg 2+ cations (at 10 −3 –10 −1 M) in CO 2 -saturated water were used to probe competitive ion exchange. The presence of divalent cations in solution inhibited H + exchange, reducing capacities to as low as 0.2 mmol H + /g for both resins and zeolites. Dynamic H + exchange capacities in fixed-bed ion exchange columns were similar to equilibrium values for resins (∼1.5 mmol/g) and zeolites (∼0.8 mmol/g) using inlet solutions that were equilibrated with gaseous streams of CO 2 at 1.0 atm. However, exchange kinetics were limited by intraparticle diffusion as indicated by the increased rate parameters with increasing inlet flow rates (20–160 cm 3 min −1 ). Experimental calcite precipitation from mixing the alkaline CO 3 2− -rich water solution obtained from the ion-exchange column with a simulated liquid waste stream solution achieved thermodynamic maximum yields. The results from these studies indicate that ion exchange processes can be used as an alternative to the addition of stoichiometric bases to induce alkalinity for the precipitation of CaCO 3 , thereby opening a pathway toward sustainable and economic mineralization processes.

42 ENGINEERING↗
DOE OSTI2020

Insights into Copper Sulfide Formation from Cu and S K edge XAS and DFT studies

An understanding of the fundamentals of the reaction between CuO with trace amounts of H 2 S to form CuS products is critical for the optimal utilization of this process in sulfur removal applications. Unfortunately, CuS is a complex material, featuring various Cu 2-x S compounds (with 0 ≤ x ≤ 1), distorted crystal phases, and varying electronic structures and coordination environments of Cu and S ions. In this work, we combine ex situ and in situ X-ray absorption spectroscopy (XAS) at S and Cu K edges, fixed bed sorption experiments, DFT simulations, and other characterization techniques to speciate the CuS products formed at different temperatures (298–383 K) and from CuO sorbents with different crystallite sizes (2.8–40 nm). The results of our analysis identify the formation of a distorted CuS layer at the surface of CuO crystals with disulfide groups with shorter Cu–S bonds and higher delocalization of the positive charge of the Cu center into (S 1– )2. This distorted CuS layer dominates the XAS signal at lower temperatures (298–323 K) and at the initial stages of sulfidation at higher temperatures (353 and 383 K) where conversion is low (<40%). First-principles atomistic simulations confirm the thermodynamic favorability of the formation of surface (S 1– )2 on both CuO (111) and ($\bar{1}11$) surfaces, providing further support for our experimental observations. Furthermore, these simulations reveal that the presence of disulfide bonds stabilized surface hydroxyl groups, leading to lower Gibbs Free Energies of their surface migration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗