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Browsing by Author "Zhang, Wencai"

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    Acid Leaching of Rare Earth Elements from Coal and Coal Ash: Implications for Using Fluidized Bed Combustion To Assist in the Recovery of Critical Materials
    Honaker, Rick; Zhang, Wencai; Werner, Joshua (American Chemical Society, 2019-07-18)
    High temperature pretreatment of coal-based mineral matter in an oxidizing environment significantly enhances the leaching characteristics of rare earth elements (REEs). A research study has found that the temperatures used in fluidized-bed combustion (FBC) of coal to produce electricity are near optimum for pre-treating the associated mineral matter prior to leaching to maximize the recovery of critical materials. Tests were performed on representative samples collected from preparation plants treating West Kentucky No. 13, Illinois No. 6, and Fire Clay coal seam sources as well as fly ash and bed ash samples from two FBC power plants. Acid leaching tests using 1.2M HCl at 75℃ were performed on both the coal and the FBC ash samples. Prior to leaching, the coal samples were pretreated at temperatures of 600℃, 750℃, and 900℃ in an oxidizing environment to study the effect on leaching characteristics. The results showed that pretreatment at 600℃ for 2 hours resulted in a significant increase in REE recovery from a range of 20-40% to about 80% for all coal sources. The leaching kinetics are characterized by a quick release of rare earth elements within the first few minutes of the process. For the West Kentucky No. 13 coal source, about 75% of REEs were leached in the first 15 min from the 1.4-1.8 specific gravity (SG) fraction that was calcined at 600℃. Additionally, the leaching kinetics of the major contaminant, i.e., Fe, were much lower than the REEs, which significantly benefits the efficiency of leaching and the downstream upgrading processes. REE leaching characteristics of the FBC ash samples were similar to that of the calcined coals. Mineralogy characterization showed that the degree of crystallinity for both the calcined coal and FBC samples were similar to the original associated mineral matter, which provided evidence for the advantage of using the FBC by- products as REE feedstocks over pulverized coal boilers that utilize temperatures greater than 1200℃. These findings were used to develop a conceptual flowsheet that incorporates FBC technology and its typical combustion environment to enhance the feasibility of recovering critical materials from coal-based sources.
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    A Comprehensive Review of Rare Earth Elements Recovery from Coal-Related Materials
    Zhang, Wencai; Noble, Christopher Aaron; Yang, Xinbo; Honaker, Rick (MDPI, 2020-05-17)
    Many studies have been published in recent years focusing on the recovery of rare earth elements (REEs) from coal-related materials, including coal, coal refuse, coal mine drainage, and coal combustion byproducts particularly fly ash. The scientific basis and technology development have been supported by coal geologists and extractive metallurgists, and through these efforts, the concept has progressed from feasibility assessment to pilot-scale production over the last five years. Physical beneficiation, acid leaching, ion-exchange leaching, bio-leaching, thermal treatment, alkali treatment, solvent extraction, and other recovery technologies have been evaluated with varying degrees of success depending on the feedstock properties. In general, physical beneficiation can be a suitable low-cost option for preliminary upgrading; however, most studies showed exceedingly low recovery values unless ultrafine grinding was first performed. This finding is largely attributed to the combination of small RE-bearing mineral particle size and complex REE mineralogy in coal-based resources. Alternatively, direct chemical extraction by acid was able to produce moderate recovery values, and the inclusion of leaching additives, alkaline pretreatment, and/or thermal pretreatment considerably improved the process performance. The studies reviewed in this article revealed two major pilot plants where these processes have been successfully deployed along with suitable solution purification technologies to continuously produce high-grade mixed rare earth products (as high as +95%) from coal-based resources. This article presents a systematic review of the recovery methods, testing outcomes, and separation mechanisms that are involved in REE extraction from coal-related materials. The most recent findings regarding the modes of occurrence of REEs in coal-related materials are also included.
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    Correlations between the Mineralogy and Recovery Behavior of Rare Earth Elements (REEs) in Coal Waste
    Ji, Bin (Virginia Tech, 2023-01-12)
    Many literatures have been published recently regarding the recovery of REEs from coal-related materials, such as coal waste, acid mine drainage, and coal combustion ash. The recovery of REEs from coal waste has been investigated by the author in recent years, and it was found that after calcination at 600 ℃ for 2 h, a significant improvement in REE recovery can be achieved. In order to reveal the mechanisms of the enhanced REE recovery after calcination, coal waste samples from two different seams, i.e., Western Kentucky No. 13 and Fire Clay, were selected to investigate the modes of occurrence of REEs. Scanning electron microscopy- and transmission electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS and TEM-EDS) analyses were conducted to investigate the mineralogy of REEs in two coal waste samples. Totally, 49 and 50 REE-bearing particles were found from the SEM specimens of Western Kentucky No. 13 and Fire Clay coal waste samples, respectively. Based on the elemental composition analyses and TEM-EDS characterization, it was found that apatite, monazite, and crandallite-group minerals were the major light REE (LREE) carriers, while the heavy REEs (HREE) primarily occurred in zircon and xenotime in these two coal waste samples. Further analyzing the REE content and number of REE-bearing particles, it was confirmed that monazite, xenotime, and crandallite-group minerals were the dominant contributors to the total REE (TREE) contents in both materials. In addition to the mineralogy of REEs, the morphology of REE-bearing particles was also investigated. The SEM images suggested that the particle size of most REE-bearing particles was less than 5 μm. Moreover, not only completely liberated particles, but particles encapsulated by the host minerals present in the two coal waste samples. To identify the changes of mineralogy of REEs after recovery, the leaching solid residues of the raw and calcined coal waste samples were also characterized by SEM-EDS analysis. After REE recovery, the same REE mineralogical results were observed from the leaching residues of the raw coal waste samples. However, as for the calcined samples, the crandallite-group minerals disappeared. These results suggested that the crandallite-group minerals were decomposed into easy-to-leach forms after calcination at 600 ℃, thus leading to the improved REE recovery. Moreover, the number of REE-bearing particles (N) found from per area of the calcined leaching residue was confirmed to be larger compared to that of the raw ones. A combination analysis of these results indicated that two mechanisms of the enhanced REE recovery after calcination can be confirmed: (1) decomposing the crandallite-group minerals into more soluble species; and (2) promoting the liberation of the REE-bearing particles encapsulated in the host minerals. The thermal decomposition of crandallite-group minerals was mainly responsible for the enhanced REE recovery from coal waste. However, as a result of the complex isomorphic substitutions and association characteristics, it is difficult to collect a pure endmember of crandallite-group mineral for characterization. Therefore, florencite-(Ce) was synthesized in this study. X-ray diffraction (XRD), SEM-EDS, TEM, thermogravimetric and differential thermal analyses (TGA-DTA), and acid leaching tests were conducted on the synthesized product. The results showed that the variation in Ce leaching recovery corresponded to the phase transformation of florencite. The gradual transformation of florencite from a crystalline mineral into an amorphous phase resulted in the increases in the solubility of Ce. In addition, the thermal transformation of florencite was an independent reaction, which was not interfered by the host materials, such as kaolinite and coal waste.
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    Critical Elements Recovery from Acid Mine Drainage
    Li, Qi (Virginia Tech, 2024-02-13)
    The rapid development of advanced technologies has led to an increase in demand for critical elements that are essential in the manufacturing of high-tech products. Among these critical elements, manganese (Mn), cobalt (Co), and nickel (Ni) are used in the production of batteries, electronics, and other advanced applications. The demand for these elements has been growing exponentially in recent years, driven by the rise of electric vehicles, renewable energy, and other emerging technologies. However, the United States is heavily dependent on foreign sources of critical minerals and on foreign supply chains, resulting in the potential for strategic vulnerabilities to both economy and military. To address this problem and reduce the Nation's vulnerability to disruptions in the supply of critical minerals, it is important to develop critical minerals recycling technologies. A systematic study was conducted to develop a process for producing high-purity Mn, Co, and Ni products from an acid mine drainage (AMD). As major contaminants, Fe and Al in the solution were sequentially precipitated and eliminated by elevating the pH. After that, a pre-concentrated slurry containing Mn, Co, Ni, and Zn was obtained by collecting the precipitates formed in the pH range of 6.50 to 10.00. The pre-concentrated slurry was redissolved for further purification. Sodium sulfide was added into the redissolved solution to precipitate Co, Ni, and Zn selectively while retaining Mn in the solution. Almost 100% of Co, Ni, and Zn but only around 15% of Mn were precipitated using a sulfur-to-metal molar ratio of 1 at pH 4.00. The sulfide precipitate was calcined and then completely dissolved. The critical elements existing in the dissolved solution were efficiently separated using a two-stage solvent extraction process. Ultimately, Co and Ni products with almost 94% and 100% purity were obtained by sulfide and alkaline precipitation, respectively. AMD also contains rare earth elements (REEs), which can be recovered through selective chemical precipitation. REE removal improved at pH 4.0 after converting ferrous to ferric ions with H2O2. Aluminum species in the solution hindered REE adsorption on ferric precipitates, and ferrous ions reduced REE adsorption on aluminum precipitates at lower pH, but at higher pH, REE removal increased due to ferrous ion precipitation. Various tests and analyses were conducted to understand the partitioning mechanisms of REE during the precipitation process of AMD. Sulfide precipitation is crucial to separate Mn from other elements, but the presence of contaminants like Fe and Al can affect sulfide precipitation efficiency. The effects of Al3+ iii and Fe2+ on the precipitation characteristics of four valuable metals, including Mn2+, Ni2+, Co2+, and Zn2+, were investigated by conducting solution chemistry calculations, sulfide precipitation tests, and mineralogy characterizations. It was found that the ability of the valuable metals to form sulfide precipitates followed an order of Zn2+ > Ni2+ > Co2+ > Mn2+. The sulfide precipitate of Zn2+ was the most stable and did not re-dissolve under the acidic condition (pH 4.00 ± 0.05). In addition, the sulfide precipitation of Zn2+ was barely affected by the contaminant metal ions. However, in the presence of Al3+, the precipitation recoveries of Mn2+, Ni2+, and Co2+ in a solution containing all the valuable metals were noticeably reduced due to simultaneous hydrolysis and competitive adsorption. The precipitation recoveries of Ni2+ and Co2+ in solutions containing individual valuable metals also reduced when Fe2+ was present, primarily due to competitive precipitation. However, the recovery of Mn2+ was enhanced due to the formation of ferrous sulfide precipitate, providing abundant active adsorption sites for Mn species. In the solution containing all the valuable metals, Fe2+ promoted the recoveries of the valuable metals due to the higher concentration of Na2S and the formation of ferrous sulfide precipitate.
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    Editorial: The Separation and Removal of Inorganic Ions and Organics From Aqueous Solutions
    Bao, Shenxu; Peng, Hong; Rao, Feng; Zhang, Wencai (Frontiers, 2021-11-01)
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    The Effect of Conditioning on the Flotation of Pyrrhotite in the Presence of Chlorite
    Chen, Yanfei; Shi, Qing; Feng, Qiming; Lu, Yiping; Zhang, Wencai (MDPI, 2017-07-20)
    The influence of conditioning on the flotation of pyrrhotite in the presence of chlorite was investigated through flotation tests, sedimentation tests, and X-ray photoelectron spectroscopy (XPS) analysis. The flotation results show that chlorite slimes dramatically impair the flotation of pyrrhotite. Sedimentation and flotation tests reveal that conditioning can effectively remove chlorite slimes from pyrrhotite surfaces, resulting in an enhanced flotation recovery of pyrrhotite. When mixed minerals were conditioned under the natural atmosphere, a faster conditioning speed and longer conditioning time decreased the flotation recovery of pyrrhotite. However, when mixed minerals were conditioned under a nitrogen atmosphere, a more intensive conditioning process provided better flotation results. XPS analyses illustrate that a faster conditioning speed and longer conditioning time under the natural atmosphere accelerates the oxidation of pyrrhotite, leading to a decrease in the flotation recovery of pyrrhotite.
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    Effects of contaminant metal ions on precipitation recovery of rare earth elements using oxalic acid
    Zhang, Wencai; Noble, Aaron; Ji, Bin; Li, Qi (2022-01-01)
    Solution equilibrium calculations were performed in this study to understand the impact of contaminant metal ions on the precipitation efficiency of selected rare earth elements (Ce3+, Nd3+, and Y3+) using oxalic acid as a precipitant. Trivalent metal ions, Al3+ and Fe3+, were found to considerably affect the precipitation efficiency of REEs. When Al3+ and Fe3+ concentrations were increased by 1 × 10−4 mol/L, in order to achieve an acceptable cerium recovery of 93% from solutions containing 1 × 10−4 mol/L Ce3+, oxalate dosage needed to increase by 1.2 × 10−4 and 1.68 × 10−4 mol/L, respectively. Such great impacts on the required oxalate dosage were also observed for Nd3+ and Y3+, which indicates that oxalic acid consumption and cost will be largely increased when the trivalent metal ions exist in REE-concentrated solutions. Effects of the divalent metal ions on the oxalate dosage is minimal. Furthermore, solution equilibrium calculation results showed that the precipitation of Fe3+ and Ca2+ (e.g., hematite and Ca(C2O4)∙H2O(s)) likely occurs during the oxalate precipitation of REEs at relatively high pH (e.g., pH 2.5), which will reduce rare earth oxalate product purity. In addition to the metal ions, anionic species, especially SO42−, were also found to negatively affect the precipitation recovery of REEs. For example, when 0.1 mol/L SO42− occurs in a solution containing 1 × 10−4 mol/L Ce3+ and 4 × 10−4 mol/L oxalate, the pH needed to be elevated from 2.0 to 3.3 to achieve the acceptable recovery. Overall, findings from this study provide guidance for the obtainment of high-purity rare earth products from solutions containing a considerable amount of contaminant metal ions by means of oxalic acid precipitation.
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    Effects of Sodium Alginate on the Flotation Separation of Molybdenite From Chalcopyrite Using Kerosene as Collector
    Zeng, Guangsheng; Ou, Leming; Zhang, Wencai; Zhu, Yuteng (Frontiers, 2020-04-28)
    In this paper, the effect of sodium alginate (SA) on the flotation separation of molybdenite (MoS2) from chalcopyrite using kerosene as collector was systematically investigated. The results of single-mineral micro-flotation tests indicated that SA exhibited strong depression on chalcopyrite flotation while it imposed no impact on the floatability of molybdenite. However, in the chalcopyrite–molybdenite mixed-mineral flotation system, the presence of chalcopyrite significantly increased the depressing effect of SA on molybdenite flotation, leading to a considerable reduction in the flotation selectivity. The negative impact of chalcopyrite on the performance of SA in molybdenite flotation was eliminated by adding a certain dosage of kerosene prior to SA. A concentrate containing 53.43% of molybdenum (Mo) was obtained at 76.90% of recovery using 19 mg/L kerosene and 40 mg/L SA at pH 5.4. Zeta potential measurements indicated that the adsorption of SA on chalcopyrite surfaces was stronger than that on molybdenite surfaces, which agreed with the single-mineral flotation test results. The adsorption of SA on chalcopyrite was further confirmed to be chemisorption by Fourier-transform infrared spectroscopy (FTIR) spectra analyses. When Cu2+ appeared in solution, the flotation of molybdenite was strongly depressed by SA. Mechanism analyses indicated that more active sites were generated on molybdenite surfaces after the addition of Cu2+, thus promoting the adsorption of SA.
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    Engineering Properties, Hydration Kinetics, and Carbon Capture in Sustainable Construction Materials
    Tran, Thien Quoc (Virginia Tech, 2023-12-20)
    Concrete, the second most consumed material on earth after water, is a source of environmental problems due to global urbanization. The production of this construction material requires a large amount of natural resources, and portland cement (PC) is responsible for around 8 % of planet-warming CO2 emissions. Producing 1 ton of PC will release roughly 1 ton of CO2 into the atmosphere. In 2021, around 92 million metric tons of PC were produced in the U.S., and a total of 4.4 billion tons were manufactured worldwide. While there was a yearly increase of around 1.5 % in the direct CO2 intensity of cement production from 2015 to 2021, urgent annual declines of 3 % until 2030 are necessary to be in line with the Net Zero Emissions by 2050 Scenario. This dissertation presents different approaches and technologies to offset the CO2 footprint of the production of cement clinker, concrete, and cementitious materials in general. First, this dissertation investigated the possibility of using end-of-life tire (ELT) rubber powder and its zinc-recovered residual (treated ELT rubber) to partially replace fine aggregates of different construction and infrastructure materials including stabilized soft soil (0 %, 10 %, 30 %, and 50 % ELT rubber added by clay volume), portland cement concrete (0 %, 10 %, 20 %, and 30 % ELT rubber added by sand volume), and asphalt concrete (20 % ELT rubber added by sand volume). This work was discussed through aspects of engineering properties and environmental impacts. The results reveal that the ELT rubber had both negative and positive effects on the engineering properties of the three materials while this waste posed a huge leachability of zinc and total organic carbon (TOC) content when being subjected to aqueous environments. However, the findings indicate that all three materials' matrices could effectively immobilize most leachable zinc from the ELT rubber by more than 90 %. Meanwhile, only stabilized soft soil and asphalt concrete could effectively deal with leachable TOC content from ELT rubber, and portland cement concrete needed the addition of silica fume to reduce TOC concentration in its leachate. Second, while previous studies have shown that steel furnace slag (SFS) can stabilize clay soils, the evidence is not clear if the stabilization mechanism is chemical and/or mechanical. This dissertation used isothermal calorimetry (IC) to quantify the heat of hydration of the mixture to assess the chemical aspects of the stabilization. Specifically, kaolin and bentonite clays were each blended with 40 % SFS by mass at water-to-binder ratios ranging from 1.0 to 1.5. The hydration properties of stabilized mixtures using lime or PC were also tested for comparison at the same experimental conditions. The obtained thermal power and total heat curves of stabilized mixtures confirmed that, for the specific SFS in this study, there is a hydration process taking place in clay stabilized by SFS. Relative to lime and PC, the SFS performed similarly in terms of heat of hydration behavior. When blended into clays, SFS provided a more significant heat of hydration behavior than cement, but that was much milder than lime. X-ray diffraction (XRD) and thermogravimetric analysis (TGA) were also employed to qualitatively analyze the mineralogy of the stabilized mixtures. Finally, this dissertation adopted a Digestion-Titration Method (DTM) for the determination of CO2 content in cementitious materials that has been mineralized in the form of calcium carbonate (CaCO3). This method was modified based on tests that were originally developed in the early 1900s. The method uses hydrochloric acid to digest CaCO3 under vacuum conditions. The CO2 released is captured by a barium hydroxide solution, which is then titrated to quantify the amount of CO2 absorbed. A design of experiments approach was used to optimize the experimental conditions. Samples of known CaCO3 content were first evaluated to establish the baseline test performance, and additional tests were performed on portland cement and various rock samples. The results were also compared to TGA, including a discussion to compare the two test methods. The data suggest that the new test method is feasibly applicable to chemically determine the CO2 captured in cementitious materials, and it can be an alternative method for TGA with lower experimental cost and easier access. Overall, it is evident that cement, concrete, and construction materials are essential to the functionality of civilization. Dealing with CO2 emissions and natural resource depletion induced by the production of these construction materials is urgent for sustainable development. Attempts toward construction materials with lower embodied CO2 by using low-carbon aggregates (e.g., waste aggregates, recycled aggregates) and alternative cementitious binders while controlling the environmental effects of the utilized waste materials are currently viable sustainable approaches. In addition, tools or new test methods that can support measuring the effectiveness of these reduced carbon cementitious materials are necessary. This dissertation investigates the feasibility of the use of ELT rubber waste in construction materials to reduce the exploitation of natural resources considering engineering properties and environmental impacts. It also provides a deeper understanding of the hydration behavior of stabilized soil using SFS which is expected to partially or fully replace PC in the material. Experimentally, it develops a chemical test model as an alternative method for TGA with lower experimental cost, less interference, and easier access to determine the CO2 captured in cementitious materials.
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    Enhanced Bauxite Recovery Using a Flotation Column Packed with Multilayers of Medium
    Zhang, Pengyu; Zhang, Wencai; Ou, Leming; Zhu, Yuteng; Zhu, Zicheng (MDPI, 2020-06-30)
    An innovative self-designed medium was packed in a bench-scale flotation column to study its influence on the flotation recovery of bauxite. Computational fluid dynamics (CFD) simulation was conducted to reveal the impact of the packing medium on the turbulent characteristics of collection zone in the column. Simulation results show that multilayer packing of the medium divides the collection zone into small units having different turbulent intensities, which is more suitable for flotation separation. The packing medium decreases the turbulence kinetic energy (from 1.08 × 10−2 m2/s2 to 2.1 × 10−3 m2/s2), turbulence eddy dissipation (from 3.71 × 10−2 m2/s3 to 9.8 × 10−3 m2/s3) and axial fluid velocity of fluid in the column. With three layers of packing, the recovery of Al2O3 increased by 2.11% and the aluminum to silicon content ratio of the concentrate improved from 5.16 to 9.72.
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    Fine Bauxite Recovery Using a Plate-Packed Flotation Column
    Zhang, Pengyu; Jin, Saizhen; Ou, Leming; Zhang, Wencai; Zhu, Yuteng (MDPI, 2020-09-02)
    In this investigation, the fine-grained bauxite ore flotation was conducted in a plate-packed flotation column. This paper evaluated the effects of packing-plates on recovering fine bauxite particles and revealed the fundamental mechanisms. Bubble coalescence and break-up behaviors in the packed and unpacked flotation columns were characterized by combining Computational Fluid Dynamics (CFD) and Population Balance Model (PBM) techniques. Flotation experiments showed that packing-plates in the collection zone of a column can improve bauxite flotation performance and increase the smaller bauxite particles recovery. Using packing-plates, the recovery of Al2O3 increased by 2.11%, and the grade of Al2O3 increased by 1.85%. The fraction of −20 μm mineral particles in concentrate increased from 47.31% to 54.79%. CFD simulation results indicated that the packing-plates optimized the bubble distribution characteristics and increased the proportion of microbubbles in the flotation column, which contributed to improving the capture probability of fine bauxite particles.
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    Flotation separation of scheelite from calcite using mixed collectors
    Yan, Weiping; Liu, Cheng; Ai, Guanghua; Feng, Qiming; Zhang, Wencai (Elsevier, 2017-12)
    Flotation separation of scheelite from calcite is difficult due to the similarities in their surface properties. In this work, the flotation behavior of scheelite and calcite using oxidized paraffin soap(OPS), benzohydroxamic acid(BHA) and the mixed OPS/BHA collectors was investigated through micro-flotation experiments. The flotation results of single mineral experiments demonstrated a higher selectivity for the flotation of scheelite from calcite at pH 9 than individual OPS and BHA when using water glass as depressant. In order to probe the validity of the findings, mixed binary minerals experiments, contact angle and zeta potential experiments were also carried out successfully.
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    Identification, Characterization, and Speciation of Rare Earth Elements in Coal Refuse
    Russell, Alexandra Dawn (Virginia Tech, 2021-06-24)
    Rare earth elements are the 14 lanthanides on the periodic table, plus yttrium and scandium. These elements play a critical role in modern-day technologies such as liquid-crystal displays, GPS systems, and fiber optic cables. A majority of the mining of these elements is from China; however, due to decreasing reserves a need for alternative processes for extracting and processing rare earth elements (REEs) is becoming increasingly important. Special focus has been placed upon the identification of REEs within coal refuse, but the phase designation and speciation is not fully understood. This investigation focuses on the characterization, speciation, and morphology of REEs within fine and coarse coal refuse. During this study, physical and chemical characterization was conducted on coal refuse samples to understand characteristics, which influence REE phase designation. Experimental methods were chosen to specifically evaluate REE content and speciation across four key characteristics: size distribution, density, seam location, and thermal decomposition. Characterization of the refuse material was conducted in two campaigns: (1) an exploratory campaign, which focused on size distribution, and physical imaging of REEs within fine refuse, and (2) a detailed campaign, which utilized sequential chemical extraction methods alongside calcination to understand the phases in which REEs are present in coarse refuse. The results show that REEs within fine coal refuse are smaller than ten microns and found with phosphorus. In general, as size decreased REE content increased, likely due to increased clay content. Further conclusion could not be drawn from simple microscopic analysis. Consequently, detailed chemical characterization was conducted to fully understand REE speciation. The tests showed that a majority of REEs within coarse refuse were within insoluble species. A calcination treatment was found to greatly increase the recovery of REEs from the metal oxide fraction, thus increasing the overall soluble species contained within the coarse refuse material.
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    Investigating the Effects of Particle Loading and Agglomeration on Respirable Coal Mine Dust Particle Classification by SEM-EDX
    Sweeney, Daniel Joseph (Virginia Tech, 2024-06-03)
    Respirable coal mine dust (RCMD) still poses serious occupational health hazards to coal miners and can lead to incurable lung diseases such as coal workers' pneumoconiosis (CWP, also referred to as "black lung"). Further, CWP can develop into a more severe form known as progressive massive fibrosis (PMF). There has been a resurgence of PMF since the late 1990s. Coal miners are also exposed to crystalline silica, which can lead to a lung disease known as silicosis. While coal mining related disease is on the rise, the historic dust monitoring data does not indicate such a striking resurgence. As a result, there has been an increased interest in research surrounding RCMD to understand exposure as well as prevent health effects. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) is a powerful tool that can analyze RCMD on a particle-level. The images produced by the SEM can size and characterize morphology of micron and submicron-sized particles. In addition, the EDX can determine elemental content, which can be used to infer mineralogy. However, particle classification can be impacted by interferences due to particle loading density (PLD) and agglomeration. PLD refers to the number of particles per unit area of substrate, while agglomeration describes clustered or overlapping particles. This thesis includes two studies aimed at exploring the effects of both PLD and agglomeration on SEM-EDX analysis. Study 1 includes an investigation into the effect of PLD on RCMD classification by SEM-EDX analysis. Dust recovered from the sample parent filters under low and high PLD conditions were used to isolate the effect of PLD. The comparison between the low and high PLD filters was then used to establish modified classification criteria to correct for high PLD. When the modified criteria were then applied to RCMD particles analyzed direct-on-filter, minimal change was observed in the apparent mineralogy distributions for most samples. These results suggest that particle agglomeration may have substantial effects on the particle classification of respirable dust analyzed direct-on-filter. Study 2 includes an investigation into the effect of particle agglomeration on RCMD by SEM-EDX analysis. Automated and manual SEM-EDX analysis was performed on paired filters collected from a parent filter. The manual analysis targeted respirable silica containing agglomerates. Each pair consisted of a filter analyzed directly and a filter that underwent a recovery process to deposit dust particles onto a new filter. The mineralogy distributions from the automated analysis suggest that agglomeration affects sizing and particle classification. Based on the manual analysis, there was an apparent increase in independent silica and a decrease in respirable silica-containing agglomerates after the recovery process. A limited collection of passive samples revealed more agglomerates than on the filters that were collected using a pump and size-selector cyclone. The work in this thesis is relevant to the research efforts aimed at the resurgence of coal mining related lung diseases, as the use of SEM-EDX can characterize RCMD by geographic region, geology, and location within a mine. Future work in this area of study might look at methods to estimate PLD in the field, other dust recovery methods, and a comparison of sampling methods.
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    Leaching recovery of rare earth elements from the calcination product of a coal coarse refuse using organic acids
    Ji, Bin; Li, Qi; Zhang, Wencai (Elsevier, 2022-02-01)
    Due to the increasing criticality of rare earth elements (REEs), it has become essential to recover REEs from alternative resources. In this study, systematic REEs leaching tests were performed on the calcination product of a coal coarse refuse using hydrochloric acid and different types of organic acid as lixiviants. Experimental results show that the recovery of REEs, especially heavy REEs (HREEs) and scandium (Sc), is improved by using selected organic acids. Citric acid and DL-malic acid afford the best leaching performances; whereas, malonic acid, oxalic acid, and DL-tartaric acid are inferior to hydrochloric acid. Results of zeta potential measurements and solution chemical equilibrium calculations show that malonic acid is more likely adsorbed on the surface of the calcined material compared with citric acid and DL-malic acid. The adsorption may reduce the effective concentration of malonic species in solution and/or increase the amount of REEs adsorbed on the surface, thereby impairing the leaching recovery. Compared with light REEs (LREEs), a stronger adsorption of the HREEs on the surface is observed from electro-kinetic test results. This finding explains why organic acids impose a more positive impact on the leaching recovery of HREEs. By complexing with the HREEs, organic acids can keep the metal ions in solution and improve the leaching recovery. The adsorption of Sc3+ on the surface is the lowest compared with other REEs. Therefore, rather than complexing, the organic anionic species likely play a function of solubilizing Sc from the solid, which is similar to that of hydrogen ions.
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    Municipal Solid Waste Incineration (MSWI) Ash Characterization and Physical Concentration
    Escalante Pedraza, Sharon Daiana (Virginia Tech, 2023-05-24)
    Bottom ash (BA), generated from the incineration of municipal solid waste (MSW), contains valuable elements which present a potential economic incentive to attempt recovery. The first study of this thesis investigated the physical, chemical, and mineralogical characterization of MSWI-BA samples through a number of experiments. To develop a proper physical characterization of the BA material, the sample was ground and subjected to particle size distribution, wet magnetic separation, and a float-sink test. As for the chemical and mineralogical characterization, the sample was subjected to XRD, XRF, SEM-EDX, and elemental composition analysis. Additionally, sequential chemical extraction and acid-leaching tests were conducted. The results from this section revealed that carrying out a combination of beneficiation processes using the MSWI-BA sample previously classified into the coarse, middle, and fine-size fractions could lead to better metal concentration yield and recovery optimization. The wet magnetic separation showed outstanding metallurgy indicators towards Fe, with enrichment ratios close to 2.0 and recovery values near to 80%. Metals such as Cu and Co were also enriched by 1.51 and 1.66, respectively, suggesting that the magnetic separation performance and enrichment are a function of the bound of multi-metallic oxides fractions. The 2.95 SG density test reached enrichment ratios higher than 2.0 in Fe, Cu, Co, and Ni in the coarse fraction of the BA fraction, which decreases when reducing the size fraction. When reducing the density cutoff, the results showed that the sink fraction yield increased as the medium density decreased, and the enrichment ratios of the minor elements (Mn, Co, Ni, Sn, and V) were similar across the different size fractions. Complementary information was obtained by the mineralogical characterization of the enriched streams from the physical concentration test, which explains the results obtained. The Cu speciation and mineral phases identified were copper oxide, copper sulfate, and cupric sulfite. While the main Fe-rich constituents existed in chemical forms of iron oxides, such as magnetite, hematite with substituted varieties, spinel group, and metallic inclusions. The enrichment ratios of Mn, Cr, Cu, and Ni obtained through magnetic separation can be explained by the presence of metallic inclusions, where these elements exhibit an affinity for the iron-bearing particles. The acid leaching test revealed that metals such as Fe, Mn, Co, Cu, and Zn can be efficiently leached using 1M HCl within 30 min of the reaction. The second part of this research study constituted the evaluation of the effect of the particle size reduction, which was performed to assess the intraparticle heterogeneity of MSWI BA. The evaluation consisted of particle size reductions by crushing and grinding for different residence times and then subjecting the sample to a sequence of physical concentration tests, such as particle size distribution, froth flotation, and wet magnetic separation. Additionally, the elemental composition after each test was determined through ICP-MS analysis to compare the particle size effect in the recovery and concentration of the valuable elements. The elemental composition results revealed that the comminution process promotes the interaction of Fe, Zn, and Cu, in the fine fraction, by generating more surface area. In contrast, the minor elements were not significantly enriched by reducing the size fraction, suggesting that the comminution process does not impact the mobility and redistribution of the elements in low concentrations. The froth flotation performed in this study showed that when using 0.338 g/ton diesel as a collector, adjusting and controlling the pH between 8.8 to 9.2 throughout the test, the organic matter content can be efficiently reduced in the BA sample from 14.73% to 4.25% when the sample has been previously ground for 30 min. Slight enrichment ratios were observed in the concentrate stream of the froth flotation, suggesting that these elements are associated with the organic matter in the BA sample. In contrast, the wet magnetic separation results revealed significant enrichment ratios of Fe, Mn, Co, and Ni after 10 min of grinding.
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    Notes on the Potential for the Concentration of Rare Earth Elements and Yttrium in Coal Combustion Fly Ash
    Hower, James; Groppo, John; Henke, Kevin; Hood, Madison; Eble, Cortland; Honaker, Rick; Zhang, Wencai; Qian, Dali (MDPI, 2015-06-23)
    Certain Central Appalachian coals, most notably the Fire Clay coal with a REY-enriched volcanic ash fall tonstein, are known to be enriched in rare earth elements. The Fire Clay tonstein has a greater contribution to the total coal + parting REY than would be inferred from its thickness, accounting for about 20%–35% of the REY in the coal + parting sequence. Underground mining, in particular, might include roof and floor rock and the within-seam partings in the mined product. Beneficiation, necessary to meet utility specifications, will remove some of the REY from the delivered product. In at least one previously published example, even though the tonstein was not present in the Fire Clay coal, the coal was enriched in REY. In this case, as well as mines that ship run-of-mine products to the utility, the shipped REY content should be virtually the same as for the mined coal. At the power plant, however, the delivered coal will be pulverized, generally accompanied by the elimination of some of the harder rock, before it is fired into the boiler. Overall, there are a wide range of variables between the geologic sample at the mine and the power plant, any or all of which could impact the concentration of REY or other critical materials in the coal combustion products.
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    Process Development and Techno-Economic Analysis for the Recovery of Rare Earth Elements and Critical Materials from Acid Mine Drainage
    Metivier-Larochelle, Tommee (Virginia Tech, 2023-01-17)
    Rare earth elements (REE) exhibit particular and unique properties that render them essential to technological applications. Of particular interest is their involvement in the transition toward global sustainability and their military applications. The magnetic properties of the rare earth elements is of primordial importance to sustainable development. More specifically, terbium and dysprosium are two elements with no known substitutes in critical applications and with no domestic or allied sourcing available. These elements are currently mined by in-situ leaching of ion-absorbed clays, mostly from illegal operations in Myanmar financed by Chinese companies. The demand from both elements, and for the other magnet rare earths is projected to growth at very high rates through 2035 while the world undergoes a transition toward sustainability, and a drastic reduction in greenhouse gases emissions. Our team has been evaluating the potential of acid mine drainage (AMD) as a source of rare earth elements and critical materials (CM). Acid mine drainage is the result of in-situ generation of sulfuric acid due to the weathering of sulfide ores. It is a significant legacy environmental issue and one of the largest pollutants in many mining districts throughout the world. The objective of the present work is to provides a roadmap for the utilization of AMD as a critical material feedstock to preserve the independence of the United States of America with regards to these materials. To that effect, a fundamental economic assessment of REE/CM recovery from AMD using a network sourcing strategy in addition to a robust, flexible feedstock separations and refining facility was undertaken. A techno-economic analysis of the extraction, refining, separation and reduction to metal is presented along with a sensitivity analysis.The results of this analysis show that, with the exception of the minimum price scenario, all operational configurations have positive economic indicators with rates of return varying from 25% to 32% for the contemporary price scenario. This is primarily due to the very high enrichment in terbium and dysprosium of AMD. The optimal configuration was determined to be production of Co, Mn, and all REEs except for mischmetal, which is not recovered. Sensitivity analysis and Monte Carlo Simulation show that capital cost and HCl consumption are the two major factors influencing rate of return, thus indicating opportunities for future technology development and cost optimization. In order to reduce both the capital and operation cost of the facility, alternative ionic liquids extractants based on conventional acidic extractants where synthesized and investigated. The results show that the ionic liquids varied in performance, with [c101][D2EHP] and [c101][EHEHP] performing poorer than their conventional counterparts and [c101][c572] performing better. The performance of [c101][c572] was 13% superior to Cyanex 572, 20% superior to EHEHPA and 27% superior to D2EHPA the current commercially used extractants. Recommendations for further study on [c101][c572] include stripping tests, continuous pilot testing, and techno-economic analysis. The test work revealed that zinc and to a lesser extent calcium were significant deleterious elements in the solvent extraction circuit, and that selective removal would significantly reduce the acid-base consumption of the separation circuit. A process was developed to selectively remove calcium and zinc from AMD-derived feedstock and from REE products. The ammonium chloride leach process offer many advantages, including the possibility of closing the cycle by using carbon dioxide sequestration as a step to regenerate the ammonium chloride in a zero-discharge process.
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    Rare Earth Element Recovery and Hydrochar Evaluation from Hyperaccumulator by Acid Leaching and Microwave-Assisted Hydrothermal Carbonization
    Li, Shiyu; Ji, Bin; Zhang, Wencai (MDPI, 2024-03-06)
    Phytomining is a sustainable approach that uses hyperaccumulators for critical element extraction from various substrates, such as contaminated soils, mine tailings, and aqueous solutions. In this study, grass seeds were fed with a solution containing Y, La, Ce, and Dy, resulting in around 510 mg/kg (dry basis) of total rare earth elements (TREEs) accumulated in grass leaves. Electron probe microanalyzer (EPMA) analysis showed that rare earth elements (REEs) in the grass leaves (GL) predominantly complexed with phosphorous (P). Around 95% of Y, 93% of La, 92% of Ce, and 93% of Dy were extracted from the GL using 0.5 mol/L H2SO4 at a solid concentration of 5 wt.%. Subsequently, microwave-assisted hydrothermal carbonization (MHTC) was used to convert the leaching residue into hydrochar to achieve a comprehensive utilization of GL biomass. The effect of temperature on the structural properties and chemical composition of the resulting hydrochar was evaluated. Scanning electron microscopy (SEM) analysis revealed that the original structure of GL was destroyed at 180 °C during MHTC, producing numerous microspheres and pores. As the reaction temperature increased, there was a concurrent increase in carbon content, a higher heating value (HHV), and energy densification, coupled with a decrease in the hydrogen and oxygen contents of hydrochar. The evolution of H/C and O/C ratios indicated that dehydration and decarboxylation occurred during MHTC. The results showed that the waste biomass of the GL after REE extraction can be effectively converted into energy-rich solid fuel and low-cost adsorbents via MHTC.
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    Rare Earth Elements (REEs) Recovery and Hydrochar Production from Hyperaccumulators
    Li, Shiyu (Virginia Tech, 2024-11-14)
    Phytomining is a promising method for metal recovery, but rare studies have been devoted to metal recovery from hyperaccumulator biomass. The objective of this study was to propose efficient and sustainable methods for treating REE hyperaccumulators, aimed at enhancing REE recovery and obtaining value-added byproducts. Firstly, grass seeds fed with a solution containing Y, La, Ce, and Dy, were found to have the capacity to accumulate around 510 mg/kg (dry basis) of total rare earth elements (TREEs) in grass leaves. With the use of conventional hydrometallurgy, around 95% of Y, La, Ce, and Dy were extracted from the GL using 0.5 mol/L H2SO4 at a solid concentration of 5 wt.%. Subsequently, microwave-assisted hydrothermal carbonization (MHTC) was used to convert the leaching residue into hydrochar to achieve a comprehensive utilization of GL biomass. Scanning electron microscopy (SEM) analysis revealed that the original structure of GL was destructed at 180 °C during MHTC, producing numerous microspheres and pores. As the reaction temperature increased, there was a concurrent increase in carbon content, HHV, and energy densification, coupled with a decrease in hydrogen and oxygen contents of hydrochar. The results showed that the waste biomass of the GL after REE extraction can be effectively converted into energy-rich solid fuel and low-cost adsorbent via MHTC. In addition to utilizing conventional hydrometallurgy for REE recovery and employing MHTC to convert leaching residue into hydrochar, MHTC was also applied to directly recover REEs and produce hydrochar from the GL as a more efficient approach. The effects of acid type and acid concentration on REE extraction from GL using MHTC were investigated. The utilization of 0.2 mol/L H2SO4 led to the extraction of nearly 100% of REEs from the GL into the resulting biocrudes. Concurrently, the acid-mediated MHTC system also caused the degradation of amorphous hemicellulose and crystalline cellulose present in the GL, thereby enhancing the thermal stability of the resulting hydrochar. The physiochemical properties of the hydrochar were also influenced by acid type and acid concentration. Using 0.2 mol/L H2SO4 as the reaction medium, MHTC resulted in a yield of 28% hydrochar with enhanced high heating value and energy densification. These results suggest that MHTC in the presence of an appropriate concentration of H2SO4 is an effective way to extract REEs and produce hydrochar from the GL. A process that combines solvent extraction and struvite precipitation was developed for the treatment of biocrudes containing REEs and other elements. In the extraction step, 95.6% of REEs were extracted using 0.05 mol/L di(2-ethylhexyl)phosphoric acid (D2EHPA) with an aqueous to organic (A/O) ratio of 1:1 at pH 3.0. However, other impurity metals were co-extracted into the organic phase with the REEs. To solve this issue, a subsequent scrubbing step using deionized water was applied, with the removal of over 98% of these impurities, while incurring negligible loss of REEs. After the scrubbing step, over 97% of REEs were ultimately stripped out from the organic phase as REE oxalates using 0.01 mol/L oxalic acid. Furthermore, phosphorous (P) was found to be retained in the raffinate after the solvent extraction process. 94.4% of the P was recovered by forming struvite precipitate at pH 9.0 and a Mg/P molar ratio of 1.5. In general, high purity and value-added REE products and struvite precipitate were eventually achieved from biocrudes in environmentally friendly and economically viable ways. In summary, this study contributes a sustainable and efficient framework for REE hyperaccumulator treatment that integrates acid leaching, MHTC, solvent extraction, and struvite precipitation. This work supports a circular economy, minimizing waste and promoting resource reuse.