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Rare earth elements (REE) play a critical role in the global economy. The concern about the REE supply challenge has stimulated global interest in recovering REE from alternative non-conventional REE sources such as coal fly ash. In this paper, sequential extraction, physical separations and hydrothermal alkaline treatment were explored for characterization and enrichment of REE from coal fly ash. Seven-step sequential extraction of coal fly ash has demonstrated that 86.1% of total REE were associated with the glassy phase of the fly ash, with the remaining REE mainly distributed in the organic and sulfides phase (8.3%), the exchangeable phase (3.7%), and the carbonates phase (1.5%). A process combining physical separations, namely, particle size separation and magnetic separation, and hydrothermal alkaline treatment was proposed for enrichment of REE from coal fly ash. The optimal hydrothermal alkaline treatment condition was determined. It was demonstrated that NaOH concentration, solid-to-liquid ratio, temperature, and reaction duration had significant influence on ash dissolution in NaOH solution. Grinding could also enhance ash dissolution during subsequent hydrothermal alkaline treatment. REE were enriched from coal fly ash from 325 mg/kg to 877 mg/kg via the proposed process under optimal hydrothermal alkaline treatment conditions.

Reference standard NIST SRM 1633b and FA 345, a fly ash sample from an eastern U.S. coal power plant, were analyzed to determine and quantify the mineralogical association of rare earth elements (REE). These analyses were completed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and a scanning electron microscope, equipped with an energy-dispersive X-ray spectrometer (SEM-EDS). Internal standardization was avoided by quantifying elemental concentrations by normalizing to 100% oxides. Mineral grains containing elevated REE concentrations were found in diverse chemical environments, but were most commonly found in regions where Al and Si were predominant. Dividing the spot analyses into time segments yielded plots that showed the REE content changing over time as individual mineral grains were being ablated. SEM-EDS images of FA 345 confirmed the trends that were found in the LA-ICP-MS results. Small grains of apatite, monazite, or zircon were frequently observed as free mineral grains or embedded in amorphous aluminosilicate glass and were not associated with ferrous particles. This finding is consistent with previous reports that magnetic enrichment may be an effective way of concentrating non-magnetic REE phases. Furthermore, aggressive mechanical and chemical-based separation schemes will be required to separate and recover REE from aluminosilicate glass.

Rare earth elements (REE) are of strategic importance because they find numerous applications in various sectors of the global economy. The concern about the REE supply challenge has led to increasing interest and research in the recovery of REE from end-of-life products and secondary sources such as coal and coal by-products. The work reported here was focused on examining the technical feasibility of physical separation techniques for the enrichment of REE from coal and coal by-products. Particle size, magnetic and density separations were performed on coal, coal ash, clay and shale samples. It was found that the samples responded to particle size separation differently. For all ash samples, higher REE concentrations were found in the finer fractions. For the clay and shale samples, however, the REE concentrations decrease as the particle size reduces possibly because RE minerals were not effectively released by grinding. Magnetic separation showed that REE are enriched in non-magnetic fractions for all ash samples. All samples responded similarly to density separation. Among the three methods, density separation showed the highest enrichment of REE. A combination of these methods is recommended. Finally, correlations between elements were demonstrated, which leads to the classification of three groups containing mainly Al/Si, Fe and Ca, respectively. REE are strongly associated with the Al/Si group.

Coal contains trace amounts of rare earth elements (REE). They are either in the form of discrete minerals or chemically bound to organic matter. Methods of distinguishing the organic and inorganic associations of REE in coal have been mostly based on the correlations between the REE concentrations and the ash yields. Quantitative characterization of organically associated REE is still very challenging. In this work, we confirm the existence of organically-associated REE in coal and present an approach to quantifying its mass fraction. The coal sample used in this study was a cleaned low-ash coal collected from a coal preparation plant in Kentucky, USA and originally from the central Appalachian basin coal region. The results from particle size and density separations of the coal suggested that the REE are associated with both organic and inorganic matters. It was found that as the ash yield increases, both the total REE concentration on the whole coal basis and the LREE/HREE ratio increase, while the total REE concentration on the ash basis reduces dramatically. The results also suggested that the organic matter is relatively enriched in HREE. Based on these observation and findings, a method was developed to quantitatively determine the distribution of REE in the organic and inorganic phases of the coal. It was found that the total REE concentrations in the organic and inorganic phases are 31 ppm and 1141 ppm, respectively. The results also showed that in the low-ash Appalachian coal sample used in this work, 25% of the REE is associated with the organic matter. The method developed in this work for quantitative evaluation of the organic/inorganic mode of occurrence may be applied to other coal samples and for many other trace elements in coals.

The concentrations of rare earth elements in Alberta, Canada oil sands and six oil sand waste streams were determined using inductively coupled plasma mass spectrometry (ICP–MS). The results indicate that the rare earth elements (REEs) are largely concentrated in the tailings solvent recovery unit (TSRU) sample compared to the oil sand itself. The concentration of lanthanide elements is ∼1100 mg/kg (1100 ppm or 0.11 wt %), which represents a >20× increase in the concentration compared to the oil sand itself and a >7× increase compared to the North American Shale Composite (NASC). The process water, which is used to extract the oil from oil sands, and the water fraction associated with the different waste streams had very low concentrations of REEs that were near or below the detection limits of the instrument, with the highest total concentration of REEs in the water fraction being less than 10 μg/L (ppb). Size and density separations were completed, and the REEs and other potentially interesting and valu...

We have utilized an environmentally friendly synthesis approach for the accelerated growth of a selective inorganic membrane on a polymeric hollow fiber support for postcombustion carbon capture. Specifically, continuous defect-free ZIF-8 thin films were grown and anchored using continuous flow synthesis on the outer surface of porous supports using water as solvent. These membranes demonstrated CO2 permeance of 22 GPU and the highest reported CO2/N2 selectivity of 52 for a continuous flow synthesized ZIF-8 membrane.

The supply and price of rare earth elements (REEs) have become a concern to many countries in the world, which has led to renewed interest in exploration and recovery of REEs from secondary or waste sources. Potential high REE waste sources that are of particular interest are coal mining, preparation, combustion, and other fossil energy by-products, including those from natural gas production. In this work, we have examined a set of five solid samples from the treatment of produced and flowback water containing elevated concentrations of barium. In order to confirm the correct concentrations of Eu, we studied these materials using sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), which is capable of resolving species of nearly identical masses, including Eu and BaO. While the use of quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) for the REE analysis of most geological sample matrices should pose no problem, the presence of large amounts of Ba, as encountered in water treatment solids from natural gas produced and flowback samples may require SF-ICP-MS for accurate determination of all REEs.

Recovering aqueous rare earth elements (REEs) from domestic water sources is one key strategy to diminish the U.S.'s foreign reliance of these precious commodities. Herein, we synthesized an array of porous, amine-epoxy monolith and particle REE recovery sorbents from different polyamine, namely tetraethylenepentamine, and diepoxide (E2), triepoxide (E3), and tetra-epoxide (E4) monomer combinations via a polymer-induced phase separation (PIPS) method. The polyamines provided -NH2 (primary amine) plus -NH (secondary amine) REE adsorption sites, which were partially reacted with C-O-C (epoxide) groups at different amine/epoxide ratios to precipitate porous materials that exhibited a wide range of apparent porosities and REE recoveries/affinities. Specifically, polymer particles (ground monoliths) were tested for their recovery of La3+, Nd3+, Eu3+, Dy3+, and Yb3+ (Ln3+) species from ppm-level, model REE solutions (pH ≈ 2.4, 5.5, and 6.4) and a ppb-level, simulated acid mine drainage (AMD) solution (pH ≈ 2.6). Screening the sorbents revealed that E3/TEPA-88 (88% theoretical reaction of -NH2 plus -NH) recovered, overall, the highest percentage of Ln3+ species of all particles from model 100 ppm- and 500 ppm-concentrated REE solutions. Water swelling (monoliths) and ex situ, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) (ground monoliths/particles) data revealed the high REE uptake by the optimized particles was facilitated by effective distribution of amine and hydroxyl groups within a porous, phase-separated polymer network. In situ DRIFTS results clarified that phase separation, in part, resulted from polymerization of the TEPA-E3 (N-N-diglycidyl-4-glycidyloxyaniline) species in the porogen via C-N bond formation, especially at higher temperatures. Most importantly, the E3/TEPA-88 material cyclically recovered >93% of ppb-level Ln3+ species from AMD solution in a recovery-strip-recovery scheme, highlighting the efficacy of these materials for practical applications.

We have utilized an environmentally friendly synthesis approach for the accelerated growth of a selective inorganic membrane on a polymeric hollow fiber support for postcombustion carbon capture. Specifically, continuous defect-free ZIF-8 thin films were grown and anchored using continuous flow synthesis on the outer surface of porous supports using water as solvent. These membranes demonstrated CO

The interfacial forces that control colloid stability in aqueous and non-aqueous systems are functions of the polar and apolar properties of the medium. This study presents a complete empirical and theoretical description of the forces and energies between a glass microsphere and a glass surface in aqueous and non-aqueous n-decane solutions that were amended systematically to enhance various colloidal interactions. Force data were measured using colloid probe atomic force microscopy (AFM) and both classical DLVO and extended-DLVO (XDLVO) theories were used to calculate the free energy of each system. The successes and failures of each theory in predicting force data were evaluated and the results indicate the importance of minor amounts of impurities, especially in the non-aqueous solutions, which impart measurable electrostatic charges on the colloidal particles. Data were also collected in a complex non-aqueous solution (commercial motor oil) and the recorded forces were significantly different compared to data collected in n-decane; long-range repulsive forces were measured by AFM. These results document the significance of aqueous impurities in non-aqueous systems which will likely dominate interactions between colloids in natural systems. Our results also indicate that DLVO and XDLVO theory predict colloidal interactions in aqueous systems. However these theories are unable to predict colloid stability in natural and chemically complex non-aqueous media.

The results of experiments designed to test the hypothesis that near-surface molecular structure of iron oxide minerals influences adhesion of dissimilatory iron reducing bacteria are presented. These experiments involved the measurement, using atomic force microscopy, of interaction forces generated between Shewanella oneidensis MR-1 cells and single crystal growth faces of iron oxide minerals. Significantly different adhesive force was measured between cells and the (001) face of hematite, and the (100) and (111) faces of magnetite. A role for electrostatic interactions is apparent. The trend in relative forces of adhesion generated at the mineral surfaces is in agreement with predicted ferric site densities published previously. These results suggest that near-surface structure does indeed influence initial cell attachment to iron oxide surfaces; whether this is mediated via specific cell surface-mineral surface interactions or by more general interfacial phenomena remains untested. (C) 2005 American Institute of Physics. United States. Department of Energy. Office of Health and Environmental Research - Financial Assistance Grant No. DE-FC09-96-SR18546 University of Georgia Research Foundation, Inc. National Science Foundation (U.S.) - Grant No. EAR 01-03053 Published version