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At least 973 records · Page 54

From ash to oxides: Recovery of rare-earth elements as a step towards valorization of coal fly ash waste

Coal fly ash (CFA) is both a valuable waste material and a potential source of environmental contamination. The inclusion of metals such as rare-earth elements offer a possible incentive towards waste valorization if the metals can be extracted and recovered in an economical manner. Rare-earth elements (REEs) have many technological applications and are critically important in the manufacture of electric vehicles, communication devices, and industrial magnets. However, the global supply of rare-earth elements has faced shortages and price shocks. Current methods for separating and isolating individual rare-earth elements use large amounts of energy and organic solvents, raising concerns over environmental impacts. These factors have led to the investigation of nontraditional sources and separation techniques for these elements. Here, we describe a column-based system that uses a newly developed ligand-associated organosilica sorbent to concentrate and separate rare-earth elements from fly ash leachate. The fly ash used in this study originally contained 0.024 wt% rare-earth elements and the final oxide powder after enrichment contained > 10 wt% rare-earth elements, which is a enrichment of > 400 times. This process requires no additional organic solvents after the sorbent media has been synthesized, offering an alternative to the current standard using solvent extraction for rare-earth element recovery.

42 ENGINEERING↗

Evaluation of mixed #3–7 plastic waste from material recovery facilities (MRFs) in the United States

Plastic recycling rates are still low in the United States (U.S.), with less than 10% of municipal solid waste (MSW) plastic being recycled. Most unrecycled plastics are identified by Resin Identification Codes (RIC) from #3–7, which are commonly destined for landfill or waste-to-energy facilities (WTE). Therefore, the composition and quality of outbound bales containing #3–7 plastics were assessed to understand the potential to increase recycling rates. Three bales were sourced from three different Material Recovery Facilities (MRFs) located in the United States. Each bale was manually sorted and characterized for quality and performance via multiple plastic characterization techniques. Considerable differences in bale composition were observed between MRFs, which correlated with the technology used by each MRF in the sorting process. The differences were substantial in the residual levels of poly(ethylene terephthalate) (PET) and high-density polyethylene (HDPE), which are highly desired for mechanical recycling processes and not expected in #3–7 plastics bales. Traditional recycling processes including washing, extrusion, and injection molding of the sorted material were employed prior to the physical, thermal, and molecular characterization. Despite differences in bale composition by plastic type, some polymer properties were similar across MRFs. Here, this research suggests that landfill-diverted mixed plastic waste can be utilized in the mechanical recycling of currently unrecycled materials, as processes can be designed to work with consistent polymer properties. It also highlights the need to upgrade the sorting systems to prevent waste feedstocks, which can be recycled with current technologies, from contaminating other plastic streams or reach landfills.

36 MATERIALS SCIENCE↗

Production of high-quality polyethylene (PE) films from post-consumer shrink wrap with solvent targeted recovery and precipitation (STRAP)

The solvent-targeted recovery and precipitation (STRAP™) process separates polymers from contaminants present in the feedstock. In this work, we demonstrate the recyclability of a post-consumer waste (PCW) shrink wrap that contains inks, adhesives, and paper using STRAP. We produced a clear rPE cast film from the PCR shrink wrap with no visual contamination from paper or inks. STRAP decreased the ash content from 0.96 wt% to 0.24 wt%. A techno-economic analysis (TEA) shows that a STRAP plant processing 50,000 metric tons annually of shrink wrap waste (purchased at $\$0.25$/kg) containing 85 wt% PE can achieve an IRR of 16.2% when selling rPE at $\$1.30$/kg, an IRR of 10.7% with an rPE price of $\$1.00$/kg, or an IRR of 3.79% with an rPE price of $\$0.70$/kg. Furthermore, the life cycle assessment (LCA) shows a 64% reduction in global warming potential (kg CO 2 equivalent) when compared to the production of virgin LDPE. As a result, this work shows how feedstocks with insoluble impurities can be recycled using STRAP on a large scale.

Radkevich, Elizaveta [University of Wisconsin-Madi↗

Environmental Life Cycle Assessment of small water resource recovery facilities: Comparison of mechanical and lagoon systems

Small water resource recovery facilities (WRRFs) serving communities with populations of less than 10,000 people account for 70% of centralized wastewater treatment systems in the United States. Here, with growing interest globally in improving the sustainability of these systems, this study evaluated the environmental life cycle impact and land use tradeoffs of different lagoon and mechanical WRRFs across the diverse climate of Nebraska. Life cycle inventory including construction and operations was collected for 35 existing systems representing a range of commonly used mechanical WRRFs: oxidation ditch, extended aeration, and sequencing batch reactors, and lagoon treatment systems: complete retention, irrigation, and controlled discharge lagoons.

42 ENGINEERING↗

Real-Time Detection of Hydrogen and Ammonia Isotopologues for Impurity Removal and Recovery of Tritium

To accommodate gas measurements for impurity removal and recovery of tritium, a silver-coated optical or waveguide is employed for collecting Raman scattered signals to determine relative hydrogen and ammonia isotopologue populations in real time. The data and results presented here demonstrate an analytical methodology for the analysis of four ammonia and three hydrogen isotopologues in a hydrogen–deuterium exchange reaction by gas phase Raman spectroscopy. Standard chemometric modeling techniques effectively unravel the signatures of the isotopologues involved observed here; however, a sophisticated quantum chemical approach supports the spectral assignments. An interpretation of the data presented here can emphasize the practicality and reliability of the gaseous monitoring system in complex chemical environments for the hydrogen fuel economy as well as the more distant energy source from a facility that handles tritium. There are still considerable concerns about the measurement of tritium in isotope separation and radiological impurities from gas processing. A common impurity in gas processing is ammonia, which can form readily in the presence of nitrogen and tritium. Substituted ammonia (NQ 3 ), where Q = H, D, or T, is traditionally removed through getters or diffusers along with other non-hydrogen contaminants. A preferable analytical approach is noninvasive and can be deployed for real-time process evaluation in radiological environments.

Ammonia↗

A Review of Lattice-Boltzmann Models Coupled with Geochemical Modeling Applied for Simulation of Advanced Waterflooding and Enhanced Oil Recovery Processes

To maintain economic profit and improve the oil production efficiency after the primary and secondary production phase, advanced waterflooding techniques such as low salinity waterflooding in carbonate reservoirs have been investigated in numerical simulations, laboratory experiments, and field pilot tests. Multiple underlying mechanisms have been proposed based on these studies, and they are still under debate. Various numerical modeling approaches are introduced, but there exists a lack of a pore-scale comprehensive modeling scheme to fully understand the processes. Lattice-Boltzmann method (LBM) is a type of numerical fluid flow modeling technique that shows capabilities and flexibilities in modeling pore-scale fluid flow to integrate physical–chemical processes within complex structures. The intrinsic feature of LBM makes it a promising framework for simulating advanced waterflooding due to its flexibility, accuracy, and parallel efficiency. LBM works either by itself for solving reactive transport problems or by coupling with a third-party reaction solver. This review mainly introduces the LBM fluid flow and reactive transport capabilities and the concept and modeling approaches to simulate advanced waterflooding techniques. Meanwhile, an evaluation of the coupled LBM models for enhanced oil recovery (EOR) simulations is discussed with future research challenges and directions concluded.

02 PETROLEUM↗

Silver(I) Supported Liquid Membranes for Selective Ethylene Recovery from Mixed-Gas Streams of Tandem CO 2 Electrolysis

Large-scale olefin separations from unreacted paraffins and other byproduct gases are primarily done by energy-intensive cryogenic distillation processes at refineries. Silver(I) supported liquid membranes (Ag SLMs) can be implemented at smaller production scales of ethylene (C 2 H 4 ), a critical industrial chemical, such as its electrocatalytic (EC) production from CO 2 . Challenges of EC C 2 H 4 production mainly stem from reducing gases like hydrogen (H 2 ), where the redox reactions pertinent to Ag(I) facilitators diminish olefin transport. Herein we report that aqueous Ag(I) solution in a composite Ag SLM can operate in mixed-gas conditions containing H 2 gas utilizing reduced titania compounds, such as titanium(III) oxide (Ti 2 O 3 ). Embedding Ti 2 O 3 in the polydimethylsiloxane layer of Ag SLM assisted in selectively separating C 2 H 4 from mixed-gas feed streams related to CO 2 electrolysis containing H 2 . The direct exposure of a mixed-gas stream containing C 2 H 4 , CO 2 , CO, N 2 , and CH 4 with as high as 50 vol % H 2 maintained excellent C 2 H 4 separations for 7 days of continuous operation. The Ag SLM provided effective separations of C 2 H 4 from CO (at detection limits), CH 4 (selectivity ratio (α) = 20–30), and H 2 (α = ∼20), but C 2 H 4 from CO 2 (α = 2–4) revealed a slightly lower separation. These data show that aqueous Ag(I) solution(s) used in the SLMs can separate C 2 H 4 for extended periods, even under highly reducing gas conditions. Also, we report C 2 H 4 recovery from the gas mixture produced in the EC CO 2 reduction process. In conclusion, the Ag SLM gave C 2 H 4 selective separation from a five-component complex mixed-gas stream, relevant to tandem CO 2 electrolysis.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Engineering Calcium-Bearing Mineral/Hydrogel Composites for Effective Phosphate Recovery

Effectively recovering phosphate from wastewater streams and reutilizing it as a nutrient will critically support sustainability. Here, to capture aqueous phosphate, we developed novel mineral-hydrogel composites composed of calcium alginate, calcium phosphate (CaP), and calcium silicate (CSH) (CaP + CSH/Ca-Alg). The CaP + CSH/Ca-Alg composites were synthesized by dripping a sodium alginate (Na-Alg) solution with ionic precursors into a calcium chloride bath. To change the mineral seed’s properties, we varied the calcium bath concentrations and the ionic precursor (sodium dibasic phosphate (NaH 2 PO 4 ) and/or sodium silicate (Na 2 SiO 3 )) amounts and their ratios. The added CSH in the mineral-hydrogel composites resulted in the release of calcium and silicate ions in phosphate-rich solutions, increasing the saturation ratio with respect to calcium phosphate within the mineral-hydrogel composites. The CSH addition to the mineral-hydrogel composites doubled the phosphate removal rate while requiring lesser initial amounts of Ca and P materials for synthesis. Furthermore, by incorporating both CSH and CaP mineral seeds in composites, we achieved a final concentration of 0.25 mg-P/L from an initial 6.20 mg-P/L. Moreover, the mineral-hydrogel composites can remove phosphate even under CaP undersaturated conditions. This suggests their potential to be a widely applicable and environmentally-sustainable treatment and recovery method for nutrient-rich wastewater.

42 ENGINEERING↗

Cast Film Production with Polyethylene Recycled from a Post-Industrial Printed Multilayer Film by Solvent-Targeted Recovery and Precipitation

The solvent-targeted recovery and precipitation (STRAP) process separates and recovers the constituent resins in multilayer plastic packaging films by selective polymer dissolution. In this work, three different experimental methods were considered to recover a polyethylene (PE) resin from a printed multilayer film by STRAP. The methods consisted of (1) a filter bag system, (2) a Soxhlet extraction, and (3) a jacketed dissolution vessel. Cast films were produced with the PE recovered from each method and were analyzed for color, mechanical properties, and number of impurities. High-quality recycled PE cast films can be produced by increasing the solvent to plastic ratio, including a filter pore size of 100 μm, and optimizing temperature control in STRAP. Furthermore, this study demonstrates that STRAP polymers can be recycled back into plastic films, enabling the potential circularity of these packaging materials.

36 MATERIALS SCIENCE↗

High-Sensitivity NO 2 Gas Sensor: Exploiting UV-Enhanced Recovery in a Hexadecafluorinated Iron Phthalocyanine-Reduced Graphene Oxide

Monitoring ultralow nitrogen dioxide (NO 2 ) concentrations is crucial for air quality management and public health. However, the existing NO 2 gas sensors have several defects, like high cost and power consumption, and exhibit poor selectivity. This study addresses these challenges by presenting a novel hexadecafluorinated iron phthalocyanine-reduced graphene oxide (FePcF 16 -rGO) covalent hybrid sensor for NO 2 detection. This innovative approach, which overcomes the limitations of fabrication cost, energy efficiency, and gas selectivity, is a significant step forward in gas sensor technology. The sensor demonstrates exceptional sensitivity toward ultralow NO 2 concentrations (15.14% response for 100 ppb) with a rapid 60 s UV light-induced recovery. Additionally, the sensor exhibits high selectivity for NO 2 , achieving a limit of detection (LOD) of 8.59 ppb. This approach paves the way for developing cost-effective, energy-efficient, and miniature NO 2 monitoring devices for improved environmental monitoring and enhanced safety in workplaces where NO 2 exposure is a concern.

36 MATERIALS SCIENCE↗

Effects of Recovery Conditions and Aggregation Mechanisms on the Chemical and Physical Properties of Hybrid Poplar and Corn Stover Lignins

Heterogeneity in the physical properties and processing behavior of lignins recovered from biorefining process streams can hinder their effective utilization and industrial valorization. This work investigates lignin recovery by acidification from alkaline pretreatment liquors of varying sources (corn stover and hybrid poplar), compositions, solid contents, and incubation temperatures prior to filtration. Recovered lignins were characterized for filtration performance, mass yield, chemical composition, particle size and morphology, and color. A transition temperature was identified corresponding to marked shifts in lignin physical properties and was a function of the solid content and liquor source. Filtration below this temperature yielded slow-filtering, dark, brittle lignins with smoother particle surfaces, whereas precipitation above this threshold yielded fast-filtering, lighter, powdery lignins with rougher particle surfaces. The impact of temperature and concentration on universal cluster aggregation mechanisms was proposed to explain the differences between lignin particle properties and filtration behavior.

Aggregation↗

Techno-Economic and Life Cycle Assessments for Sustainable Rare Earth Recovery from Coal Byproducts using Biosorption

Coal byproducts could be a promising feedstock to alleviate the supply risk of critical rare earth elements (REEs) due to their abundance and REE content. Herein, we investigated the economic and environmental potential of producing REEs from coal fly ash and lignite through an integrated process of leaching, biosorption, and oxalic precipitation on the basis of experimental data and modeling results. Two microbe immobilization systems (polyethylene glycol diacrylate (PEGDA) microbe beads and Si sol–gels) were examined for their efficiency in immobilizing Arthrobacter nicotianae to selectively recover REEs. Techno-economic analysis revealed that North Dakota lignite could be a profitable feedstock when Si sol–gel is used due to its high cell loading and REE adsorption capacity as well as high reuse cycles. Life cycle analysis revealed that Si sol–gel-based biosorption could be more environmental friendly than the prevailing REE production in China due to the use of less toxic chemicals. However, fly ash sourced from Powder River Basin coals was neither profitable nor environmentally sustainable, primarily due to low solubility of high-value scandium at an economical pulp density (100 g ash/L of acid solution). To further improve the proposed biotechnology, future research could focus on scandium recovery, leaching efficiency at a high pulp density, and reuse cycles of the immobilized microbes.

01 COAL, LIGNITE, AND PEAT↗

Recovery of p -Hydroxybenzoic Acid from Cu-Catalyzed Alkaline Hydrogen Peroxide Pretreatment of Hybrid Poplar

p-Hydroxybenzoic acid (pHBA) is present in some hardwood biomass feedstocks as an ester attached to the polymeric lignin subunits. Here, we report the isolation and recovery of pHBA from alkaline liquor waste streams obtained from fractionation of hybrid poplar using the “Cu-AHP process”. This process features two stages: alkaline pre-extraction (AP) of the biomass and copper-catalyzed alkaline hydrogen peroxide pretreatment. On a biomass scale of 100 g, 0.5 g of pHBA with a purity of 96% was obtained after decolorization and crystallization. The scalability of the purification process was demonstrated by using liquor obtained from the first-stage AP with 900 g of poplar biomass to afford 3.5 g of crystalline pHBA with 97% purity. Altogether, these results show that pHBA may be isolated and purified from waste streams generated in the two-stage Cu-AHP process without any alteration of the process conditions or impact on carbohydrate and lignin fractionation.

09 BIOMASS FUELS↗

Enhanced Recovery of Critical Minerals and Geological Hydrogen in The Mine of the Future

invited perspective article: The rapid demand for critical minerals (CMs) and hydrogen (H2) necessitates innovative solutions beyond conventional mining. This study explores enhanced mineral recovery (EMR) and geological hydrogen production (GeoH2) by leveraging the Earth’s subsurface as a reactive platform. Using ultramafic rocks and engineered fluids, the approach simultaneously mobilizes critical resources and produces H2 through natural processes like serpentinization. This paradigm offers a transformative pathway to secure essential materials and diversify energy resources, setting a foundation for the Terrestrial Mine of the Future

Yan, Keju↗

Mild pH-decoupling aqueous flow battery with practical pH recovery

Establishing a pH difference between the two electrolytes (pH decoupling) of an aqueous redox flow battery (ARFB) enables cell voltages exceeding the 1.23 V thermodynamic water-splitting window, but acid–base crossover penalizes efficiency and lifetime. Here we employ mildly acidic and mildly alkaline electrolytes to mitigate crossover, achieving high round-trip energy efficiency with open circuit voltage >1.7 V. We implemented an acid–base regeneration system to periodically restore electrolytes to their initial pH values. The combined system exhibited capacity fade rate <0.07% per day, round-trip energy efficiency >85% and approximately 99% Coulombic efficiency during stable operation for over a week. Cost analysis shows that the tolerance of acid–base crossover could be increased if the pH-decoupling ARFB achieved a higher voltage output and lower resistance. Finally, this work demonstrates principles for improving lifespan, rate capability and energy efficiency in high-voltage pH-decoupling ARFBs and pH recovery concepts applicable for pH-decoupling systems.

25 ENERGY STORAGE↗

Recovery of high specific activity molybdenum-99 from accelerator-induced fission on low-enriched uranium for technetium-99m generators

Abstract A new process was developed to recover high specific activity (no carrier added) 99 Mo from electron-accelerator irradiated U 3 O 8 or uranyl sulfate targets. The process leverages a novel solvent extraction scheme to recover Mo using di(2-ethylhexyl) phosphoric acid following uranium and transuranics removal with tri- n -butyl phosphate. An anion-exchange concentration column step provides a final purification, generating pure 99 Mo intended for making 99 Mo/ 99m Tc generators. The process was demonstrated with irradiated uranium targets resulting in more than 95% 99 Mo recovery and without presence of fission products or actinides in the product.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Structure-performance correlations of cross-linked boronic acid polymers as adsorbents for recovery of fructose from glucose–fructose mixtures

Recovery of bio-oxygenates from reaction mixtures is one of the major challenges for future bio-refineries. Isolation of fructose produced by isomerization of glucose presents a typical example at a very early stage of the value chain. Here, we propose to recover fructose from a solution containing a mixture of glucose and fructose by adsorption on polymers bearing phenylboronate moieties. p-Vinylphenylboronic acid was polymerized with various cross-linkers, namely polar aliphatic, low-polarity aliphatic, and aromatic. The cross-linker content was in the range 5–40 mol%. The polymers exhibit high capacities for fructose, with a maximum loading of up to 1 mol Fru mol B -1 . Fructose loading depends significantly on the length and content of cross-linker, as well as pre-treatment of the polymer. In general, the maximum fructose capacity correlates with the swelling ability of the polymers, since phenylboronate moieties become available for adsorption upon swelling. In contrast, maximum glucose loadings are much lower, in the range 0.1–0.3 mol Glu mol B -1 , and depend only slightly on the type of cross-linker. The structures of the glucose and fructose complexes and the kinetics of their uptake were studied by in situ MAS NMR. Efficient desorption of fructose was observed in acidic medium, and more importantly, using CO 2 . The structures of the polymers after repeated adsorption and desorption remain unchanged, as confirmed by solid-state NMR. Adsorption-assisted isomerization of glucose catalyzed by soluble carbonates was also studied. A 56% yield of fructose was achieved after 8 successive cycles of reaction and adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗