Engineering topics
Hsu-Kim, Heileen
Publications and source records attributed to Hsu-Kim, Heileen.
Trace Element Sampling and Partitioning Modeling to Estimate Wastewater Composition and Treatment Performance at Coal Generators
The coal combusted at coal-fired power plants (CFPPs) contains several trace elements that impact human heath if released to the environment. Effective combinations of air pollution control devices (APCDs) and water pollution control devices (WPCDs) are critical to reducing these impacts. This work sampled pulverized CFPPs owned and operated by Louisville Gas & Electricity – Kentucky Utilities (LGE-KU) during baseload and cycling conditions. Next, an open-source and easy-to-implement trace element partitioning model was developed using publicly available datasets, literature studies of trace element partitioning, and sampling data to estimate trace element partitioning in APCDs to the gas, liquid, and solid phases exiting CFPPs. These estimates of the liquid phase trace element concentration in FGD wastewater were then used to estimate trace element behavior in WPCDs and evaluate treated wastewater effluent concentrations for compliance with the Effluent Limitation Guidelines (ELG) for the Steam Electric Generating Sector. Finally, cost estimates were developed for established and emerging wastewater treatment trains to identify the most cost-effective approaches for ELG compliance.
Nanoscale heterogeneity of arsenic and selenium species in coal fly ash particles: analysis using enhanced spectroscopic imaging and speciation techniques
Coal combustion byproducts are known to be enriched in arsenic (As) and selenium (Se). This enrichment is a concern during the handling, disposal, and reuse of the ash as both elements can be harmful to wildlife and humans if mobilized into water and soils. The leaching potential and bioaccessibility of As and Se in coal fly ash depends on the chemical forms of these elements and their association with the large variety of particles that comprise coal fly ash. The overall goal of this research was to determine nanoscale and microscale solid phase mineral associations and oxidation states of As and Se in fly ash. We utilized nanoscale 2D imaging (30–50 nm spot size) with the Hard X-ray Nanoprobe (HXN) in combination with microprobe X-ray capabilities (~5 μm resolution) to determine the As and Se elemental associations. Speciation of As and Se was also measured at the nano- to microscale with X-ray absorption spectroscopy. The enhanced resolution of HXN showed As and Se as either diffusely located around or comingled with Ca- and Fe-rich particles. The results also showed nanoparticles of Se attached to the surface of fly ash grains. Overall, a comparison of As and Se species across scales highlights the heterogeneity and complexity of chemical associations for these trace elements of concern in coal fly ash.
Crystal lattice defects in nanocrystalline metacinnabar in contaminated streambank soils suggest a role for biogenic sulfides in the formation of mercury sulfide phases
At mercury (Hg)-contaminated sites, streambank erosion can act as a main mobilizer of Hg into nearby waterbodies.
Functional Predictor Variables for the Leaching Potential of Arsenic and Selenium from Coal Fly Ash
The release of leachates from intact coal ash impoundments is a concern due to the enrichment and mobilization of toxic elements such as arsenic (As) and selenium (Se). This study aims to explore the intrinsic properties of coal fly ash that correlate with the relative leachability of As and Se. We performed leaching experiments with 52 fly ash samples collected from 15 different U.S. power plants and representing coal feedstocks from the three major domestic regions. We assessed the mobilization potential of As and Se in fly ash based on standardized leaching protocols and performed multivariate and lasso regression analyses to explore correlations of leachable As and Se contents with characteristics such as major element contents, loss on ignition, and pH. The results of regression models indicated that major elements (Fe, Ca, and Al) for a wide range of fly ashes can serve as predictor variables for the leaching potential of As but not for Se. LOI and pH were not important predictive variables in the models. Both regression approaches resulted in relatively strong fits for leachable As (correlation coefficient R 2 = 0.78 for both models) compared to models for leachable Se (R 2 = 0.49). Overall, these results suggest that correlation models combined with on-site elemental analysis with portable analyzers may enable a screening method for leachable As in coal ash.
Signatures of rare earth element distributions in fly ash derived from the combustion of Central Appalachian, Illinois, and Powder River basin coals
We report the distribution of Rare Earth elements (REE) in coal-derived fly ashes can have distinctive patterns when fly ashes are produced from different coals within or between basins, such as the Pennsylvanian Class F fly ashes from the Illinois and Central Appalachian basins. Both the Fire Clay coal and a blend of a number of eastern Kentucky coals show strong Gd peaks and an H-type distribution in the Upper Continental Crust-corrected plots. The Fire Clay coal-derived ash has a higher heavy REE concentration than the blended coal-derived ash. The Illinois Basin-derived fly as has an overall lower REE concentration than the latter ashes. Class C fly ash derived from Powder River Basin coals has, with the exception of an Eu peak, a flatter distribution of REE and an overall L-type or indistinct H- versus L-type distribution. The signatures of the REE in fly ashes may be useful in predicting their behavior in the extraction of the REE; simple extrapolations from the basic concentrations and the predicted extraction percentages for ashes from different basins are not necessarily indicative of the actual distribution of the extracted REE.
Microbe-Encapsulated Silica Gel Biosorbents for Selective Extraction of Scandium from Coal Byproducts
Establishing an inexpensive and environmentally friendly scandium (Sc) supply is critical for the development of clean energy technologies. However, refining Sc from Sc-bearing sources using current technologies poses economic and environmental challenges due to its low concentration relative to base metals and chemically similar lanthanides. In this work, we developed a biosorption-based flow-through process for extraction of Sc from low-grade feedstocks. A novel biosorbent material was synthesized by encapsulating Arthrobacter nicotianae, a bacterium that selectively adsorbs Sc, within a porous silica matrix. Through the use of several complementary microscopy techniques, we demonstrated a highly porous biosorbent structure with a high cell-loading density and a homogenous cell distribution. Batch adsorption assays revealed selective Sc adsorption over lanthanides and common based metals, with the exception of Fe(III), as evidenced by separation factors greater than 50. The MESG particles were packed into fixed-bed columns to enable adsorption under flow-through conditions, which demonstrated effective Sc extraction at flow rates up to 0.08 cm/s and high stability for reuse; greater than 95% of the adsorption capacity was maintained after 10 consecutive adsorption/desorption cycles. When applied to a lignite coal leachate, whose Fe content was depleted through pH-mediated precipitation, the MESG particles yielded Sc breakthrough at 30 bed volumes, whereas all other metals broke through after only a few bed volumes. Following desorption, an eluate with a 124-fold increase in Sc purity was achieved relative to the lignite leachate with Sc constituting 96.4% of the total REEs. This study established a rapid, facile, and scalable cell immobilization approach that enables the use of microbial biomass for Sc recovery from low-grade sources.
Data for "Relative Reactivity and Bioavailability of Mercury Sorbed to or Coprecipitated with Aged Iron Sulfides"
The potential for inorganic mercury (Hg) to be converted to methylmercury depends, in part, on the chemical form of Hg and its bioavailability to anaerobic microorganisms that can methylate Hg. In anaerobic settings, Hg can be associated with sulfide phases, including ferrous iron sulfide (FeS), which can sorb or coprecipitated with Hg. The objective of this study was to determine if the aging state of FeS alters the Hg coordination environment as well as the reactivity and bioavailability of sorbed and coprecipitated Hg species. FeS particles were synthesized with and without Hg2+ and aged in anaerobic conditions for multiple time frames spanning from 1 hour to 1 month. For FeS particles synthesized without Hg, Hg2+ was subsequently sorbed to the FeS for 1 day. Analysis of Hg speciation of these materials by X-ray absorption near edge spectroscopy revealed a predominance of 4-coodinate Hg-S species in the sorbed Hg-FeS solids and a mixture of 2- and 4-coordinate Hg-S in the coprecipitated Hg-FeS. The leaching potential of the Hg was assessed by exposing the particles to a solution of dissolved glutathione (a thiolate-based Hg chelator). As expected, the sorbed Hg-FeS released more soluble Hg compared to the co-precipitated Hg-FeS. However, when these particles were exposed to Desulfovibrio desulfuricans ND132 (a known Hg methylator), more Hg was methylated from the co-precipitated Hg-FeS than the sorbed Hg-FeS, consistent with expectations from the Hg-S coordination state and inconsistent with the selective leaching results. Overall, these results suggest that the bioavailability of particulate Hg cannot be easily discerned by leaching potential into bulk solution. Rather, bioavailability entails more subtle interactions at particle-cell interfaces and perhaps correlates with the local Hg-S coordination state in the particles. This data package contains data shown in the referenced publication, including all figures. Each figure is available in the respective *.csv file and a summary of all files are also included in the the xlsx file. Additional formatted data include X-ray diffraction data of the FeS solids are also available in a HPF format (Panalytical software), X-ray absorption spectroscopy data as *.prj files (Athena), and X-ray fluorescence data in its raw data form.
Distribution of rare earth elements in fly ash derived from the combustion of Illinois Basin coals
This study examined rare earth element (REE) trends for Illinois Basin coal-sourced fly ashes, with the goal of understanding the elemental composition and resource potential for various fly ash fractions. Illinois Basin coals have a high volatile C through A bituminous rank with a moderate ash content (slightly>12% ash (dry basis)), about 3% sulfur, and, in general, lower concentrations of hazardous and other trace elements than many Central Appalachian coals. Fly ash from the combustion of Illinois Basin coals tends to have a high Fe 2 O 3 content owing to the amount of pyrite in the feed coals. The rare earth element (REE) concentrations in Illinois Basin coal-sourced fly ashes are less than that for fly ashes from the combustion of Central Appalachian coals. The Upper continental crust-corrected fly ashes show an H-type enrichment, a positive Eu N /Eu N * , and, in some cases, a sharp Gd peak. For comparison, a suite of fly ashes from the combustion of a blend of eastern Kentucky coals had an H-type enrichment, a positive Eu N /Eu N * , but only a minimal Gd peak. In contrast, fly ash from the combustion of the Fire Clay coal, a REE-rich coal, had a negative Eu N /Eu N * and a sharp Gd peak. Finally, these results highlight the importance of feed coal composition on trace element contents of respective combustion fly ash fractions and also the unique REE enrichment patterns of the Illinois Basin fly ashes relative to the better studied fly ashes of eastern Kentucky and Central Appalachia.
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.
Separation of rare earth elements from mixed-metal feedstocks by micelle enhanced ultrafiltration with sodium dodecyl sulfate
Not provided.
Novel Membrane and Electrodeposition-Based Separation and Recovery of Rare Earth Elements from Coal Combustion Residues (Final Report)
This project developed a hydrometallurgical-based technology to extract and concentrate rare earth elements (REEs) from a representative group of coal combustion residuals (CCRs) from major coal sources in the United States. The approach for REE recovery comprises two general components: (1) Leaching of REEs from CCRs and (2) Separation of REEs from other major ions in the CCR leachate. The leaching step entails acid leaching with nitric or hydrochloric acid, and in some cases, pretreatment of CCRs with alkaline roasting prior to acid leaching. The follow-up REE recovery steps involve a series of membrane-based methods to separate and concentrate rare earth ions from other major ions in acid leachates of CCRs. These methods include liquid emulsion membranes, supported liquid membranes and electrodeposition with carbon nanotube electrochemical filters. The advantage of these separation approaches (relative to conventional approaches such as solvent extraction) is a reduction in the usage of solvents and other costly chemicals and a reduction of hazardous waste products that are challenges in conventional REE separation methods. In the testing of our process, we selected a representative set of CCR samples from our collection and performed a suite of characterization measurements (total REE content and major mineralogy). The major results of this work demonstrated that heated acid leaching could efficiently extract REEs from PRB-based coal fly ashes while the Appalachian and Illinois Basin CCRs required alkaline roasting with NaOH prior to acid leaching at room temperature. The supported liquid membrane (SLM) configuration and electrochemical deposition (ED) system yielded the most promising methods of REE recovery from the acid leachates of fly ash. Our most concentrated product to date comprised 1 wt.% (dry basis) REEs produced from an Appalachian-based fly ash leached and purified by SLM. The SLM separation process was more selective for heavy REEs over the light REEs. When SLM was combined with ED, preliminary results demonstrated that a final product of >2 wt.% REEs was possible.
Major element composition controls rare earth element solubility during leaching of coal fly ash and coal by-products
Coal combustion ash and pre-combustion coal refuse are currently under consideration as potential sources of rare earth elements. One of the early steps in recovering REEs from coal by-products is often acid leaching, which can result in low pH leachates with complex aqueous chemistry. The aim of this work was to understand the connection between REE solubility, pH, and major elemental components of leachates for coal by-products. To accomplish this, we investigated the effects of solids concentration (i.e., pulp density) and pH adjustment on REE solubility in acid leachates of coal fly ashes from the Powder River Basin (PRB) and Appalachian Basin in the United States, and a coal processing refuse from the Southwestern U.S. For PRB ashes, the concentrations of soluble REEs generally increased with increasing pulp density; however, at pulp density values above 80–100 g/L, the soluble REE concentrations in the leachates were markedly lower. Similarly, the soluble concentrations of other major solutes (Fe, Al, Si) that leached from PRB fly ashes were also non-linear with pulp density. These major elements tended to reach maximum concentration values at 60–70 g/L pulp density. In contrast, for the Appalachian fly ashes and the coal by-product, soluble concentrations of REE and major elements in leachates increased linearly with pulp density. Chemical equilibria calculations of mineral saturation indices indicated that trends in soluble REE concentrations could be explained by saturation conditions for Fe and Al-(hydr)oxides and possibly sulfate minerals, but not lanthanide hydroxides. Furthermore, pH adjustment of the acid leachates showed that REEs and many major solutes were removed from solution at pH values above 4.5, also consistent with Fe- and Al-(hydr)oxide precipitation. These results highlight the importance of understanding the chemical composition of leachates when designing REE recovery processes for low-grade geologic feedstocks and that precipitation of hydr(oxide) or sulfate minerals of major elements rather than discreet formation of REE mineral phases could be used for process optimization.
A biosorption-based approach for selective extraction of rare earth elements from coal byproducts
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 based on experimental data and modeling results. Two microbe immobilization systems (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. Life cycle analysis revealed that Si sol-gel based biosorption could be more environmental friendly than the prevailing REE production in China due to use of less toxic chemicals. However, fly ash sourced from Powder River Basin coals was neither profitable or environmentally sustainable, primarily due to low solublity of high-value scandium at an economical pulp density (100 ash/L). To further improve the proposed biotechnology, future research could focus on scandium recovery, leaching efficiency, and microbe carriers.