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Coal and coal combustion byproducts are potential candidates for alternative resources of REEs (rare earth elements). The Illinois Basin is a major coal-producing district in the USA, but little work is available on speciation of REEs in the basin’s coals. In this study, a total number of 382 samples from known locations in the Illinois Basin coal beds were acquired, analyzed for their REE contents, and investigated for any spatial trends or chemical correlations. This study includes Springfield, Herrin, and Baker coal beds—the most heavily mined coals in the basin. An average coal ash from the basin contains 320 ppm REE, with Baker being the highest (407 ppm on average). However, the distribution of REEs in the coal beds was laterally and vertically heterogeneous. A number of trends were found in the REE variations. The most important trend was the relationships of the REE concentrations and fractionations with the distance from the syndepositional sandstones. The total REE concentrations were higher in the proximity of the sandstones, likely due to the increased deposition of detrital material. This increase was the most significant in Springfield coal (90%) and least in Baker (6%). Those coal samples from the Springfield and Herrin coal beds distal from the syndepositional sandstones had a heavy to light REE ratio (H/L ratio) of 0.40 on average, whereas in proximal locations, the ratio was dropped to an average of 0.30. This trend was not significant in the Baker coal bed. In general, higher mineral matter in the coals was associated with higher REEs. In coal preparation plants, refuse rocks can have up to 360 ppm REE. However, the ashes of the cleanest coals had higher REE levels. Such ashes also have a higher ratio of heavy to light REEs. The highest REE concentrations were found in the claystones and the shales associated with the coal beds. Since the naturally occurring calcite, quartz, and pyrite samples were depleted in REEs, an association of REEs with the clay minerals can be suggested.

Low-temperature plasma (LTP) oxidation has been widely used to study the mineralogy of the mineral matter existing in coal sources. The current study investigated the potential of LTP oxidation as a pre-treatment method to improve rare earth element (REE) leachability from coal and its by-products. Representative density-fractionated samples of Baker and Fire Clay coarse refuse seam materials were ground to a top size of 180 µm and subjected to low-temperature plasma oxidation. Subsequently, the treated samples were leached at 1% w/v solids concentration and 75 °C for 5 h using (i) de-ionized (DI) water, (ii) 0.1 mol/L of ammonium sulfate, and (iii) 1.2 mol/L of sulfuric acid. It was determined that LTP treatment improved REE leaching characteristics, especially the leaching of heavy REEs (HREE), existing in the lighter density fractions of the Baker seam coarse refuse material. For instance, the HREE recovery for the 1.6 specific gravity (SG) float fraction increased from 8% to 33% using 0.1 mol/L of ammonium sulfate solution after 32 h of LTP treatment. This finding indicated that HREEs associated with the organic matter were released by the LTP treatment and adsorbed onto the surfaces of highly negative charged mineral matter and was exchanged with ammonium to allow their recovery. Similarly, when using 1.2 mol/L of sulfuric acid, the HREE recovery increased from 23% to 53% for the 1.6 SG float fraction. Interestingly, LTP oxidation did not provide significant improvement in REE recovery from the 2.2 sink density fractions, which was likely due to its lower organic content. No significant benefits were observed when treating the Fire Clay coarse refuse material, which was likely due to the lack of organic affinity and the difficult-to-leach REE minerals associated with the coal source such as monazite, xenotime, and zircon. Conversely, high-temperature oxidation within a temperature range of 600–750 °C significantly improved REE leaching characteristics for both coal sources. Improvement in REE recovery was due to decarbonization of the material, clay dehydroxylation and subsequent conversion of liberated REE-bearing minerals into a more leachable form. However, increasing the temperature above 800 °C decreased REE recovery due to the conversion of meta-kaolinite into mullite, which is chemically stable.

In the metallurgical extraction of rare earth elements (REEs), the ratio of contaminant ions to REEs in the leachate dictates the cost and operational efficiency of the downstream processes. The current study investigated the potential iron contamination removal from the feed to the hydrometallurgical process by calcination followed by magnetic separation. The 2.20 specific gravity sink fraction of Baker coal seam coarse refuse was pulverized to finer than 180 μm, calcined at various temperatures, and separated into magnetic and non-magnetic fractions using a wet high-intensity magnetic separator at different field strengths. The untreated feed, calcined products, and their subsequent magnetic and non-magnetic fractions were subjected to acid leaching tests with 1.2 M sulfuric acid at 75 °C and 1% w/v solids concentration. The recovery of light and heavy rare earth elements (LREEs and HREEs, respectively) along with the concentration of common contaminant ions (Al, Ca, and Fe) were measured as output variables. The weight percent of magnetic material was maximized at approximately 29% by calcination at a temperature of 400 °C. Magnetic removal of this fraction using a field strength of 1.15 Tesla resulted in the rejection of 81% of the iron. Leaching of the magnetic fraction provided significantly higher Fe recovery relative to untreated feed material and the non-magnetic fraction. The non-magnetic fraction was subsequently calcined at 600 °C to dehydroxylate the clays and released the REE minerals in the same manner as the treatment of the original coarse refuse material. A comparison of the leachate elemental concentrations resulting from the leaching of both the calcined non-magnetic and original coarse refuse showed only a slight reduction in the iron content from the non-magnetic material. This finding combined with the REE loss in the magnetic fraction resulted in the conclusion that the magnetic removal step was unfavorable.

Recovery of rare earth elements (REE) from coal-related resources has recently received significant interest due to supply concerns and their key roles in critical industries and defense-related technologies. An integrated flowsheet consisting of sorting, crushing/grinding, physical separation, acid leaching, solvent extraction, and selective precipitation was designed to achieve continuous production of rare earth products from various coal-related resources such as coarse refuse and acid mine drainage. A pilot plant was constructed that enabled continuous testing of the circuitry on a range of different coal-based feedstocks. Despite achieving significant success in producing high-grade rare earth oxide products, low REE recovery values and high operational costs necessitated a re-evaluation of the process flowsheet. This article describes the circuitry improvements that were based on both laboratory and pilot plant test results. Roasting as a pre-leach treatment was found to significantly improve the leaching rate and overall REE recovery values. After roasting West Kentucky No. 13 and Fire Clay coal refuse materials at 600 °C, REE recovery increased by 60 and 40 absolute percentage points, respectively. Rare earth concentration in the pregnant leachate solution (PLS) was increased to around 700 ppm prior to solvent extraction using a staged precipitation method. REEs in the precipitate were re-dissolved, purified, and extracted from the PLS using solvent extraction and selective precipitation to values of around 80%. As a result of the improvements, chemical consumption in the acid leaching and solvent extraction processes was significantly reduced. A techno-economical assessment of the improved flowsheet indicated significant commercialization potential.

A field study was undertaken to experimentally measure the concentrations of rare earth elements (REEs) contained in the process streams generated by a group of 20 coal preparation plants located in the eastern USA. For each site, representative samples of clean coal product, coarse refuse, and fine refuse were collected. Each sample was then partitioned into preselected size and density classes by wet screening/sieving and float-sink testing. The resultant products were dried and subjected to laboratory analyses to determine ash contents and rare earth element concentrations including Yttrium and Scandium. A detailed analysis of the database generated by this exercise showed that coal-based products from these preparation plants contained significant quantities of rare earth elements. In particular, the coarse refuse streams currently discarded by the 20 plants examined were found to contain a sufficient tonnage of REEs to satisfy the current domestic demand for these important elements. The data also showed a strong positive correlation between ash content and REE concentration, which suggested that the primary association of REEs in eastern USA bituminous coal sources is likely within fractions containing inorganic impurities. This association was well described using a simple power equation relating ash content and REE concentration. The ratio of heavy-to-light rare earth elements was discovered to be significantly higher in organically rich fractions of clean coal, suggesting that mineral impurities intimately associated with carbonaceous matter have elevated concentrations of heavy rare earth elements. A similar trend was observed for a grouping of rare earth elements (Y, Nd, Eu, Tb, and Dy) that are likely subject to near-term supply shortages. Finally, the database showed that a linear correlation existed between La for many REEs of interest, although there were several notable exceptions for some high-value REEs (Lu, Pr, and Tb).

An environmental concern at coal preparation operations is the release of elements resulting from the oxidation or dissolution of certain minerals contained in the process waste streams. Using a standard conductivity test, the electrical conductivity (EC) of water samples obtained from mixing with various particle size and density fractions of a given plant waste material were measured as an indicator of total dissolved solids. The net neutralization potential (NNP) of the fractions were also measured to predict the pH of the supernatant upon disposal. As a result, the particle size and density fractions contributing to high EC levels were identified with the objective of potentially extracting and isolating these fractions which can significantly reduce the negative environmental impacts. The results showed that the EC generated from coarse refuse streams were significantly higher than the values obtained from fine refuse streams. Based on the NNP values, the coarse refuse stream generates highly acidic pH, while the fine refuse in contact with water produces circumneutral pH. Furthermore, the high specific gravity (>2.68) fractions which comprised less than 10% of the coal waste streams were found to be the primary source of elevated EC levels. The remaining fractions were found to be of minimal environmental concern. Based on the obtained results, modifications to the coal preparation plants were proposed to minimize the environmental concerns of coal waste disposal. Modifications include pyrite removal from the spiral refuse and desulfurization of flotation feed and sieve bend underflow streams using low-cost mineral spiral circuitry. After the segregation, the pyrite (high density) fraction, which encompasses around 1% of the coarse and fine refuse streams, will be isolated/encapsulated and the fine refuse stream dewatered and co-disposed with the coarse refuse stream. The proposed modifications to the processing and disposal practices not only minimize the generation of acid mine drainage thereby reducing the release of trace elements and EC of the discharged water, but also enhances the recovery and quality of the final clean coal product.

The pretreatment of middlings and coarse refuse material collected from a Pocahontas No.3 coal source using calcination was investigated for the potential of improving the leaching recovery of rare earth elements. Calcination at 600 °C significantly and preferentially improved light REE (LREE) recovery to values in the range of 80–90% using 1.2 M HCl. The positive effect was due to the increased pore diameter and volume as well as thermal decomposition of the minerals associated with the LREEs. Heavy REE recovery was not increased after calcination at 600 °C due to the need for higher temperatures to achieve thermal decomposition of HREE minerals. Furthermore, some HREEs were also associated with sulfide minerals (e.g., pyrite) which were transformed into low-solubility oxides (e.g., hematite) after roasting at 600 °C. Based on the leaching characteristics of the major elements (Fe, Al, Ca and Mg) and REEs along with SEM-EDX data, it was concluded that REEs in the two samples mainly occurred as phosphate minerals. In the middlings, some of the minerals were completely encapsulated by kaolinite, which was less apparent in the coarse refuse. In addition, it was found that a portion of the REEs (10–25%) in the samples were associated with the organic matter and micro-dispersed minerals in the organic matrix, was released after calcination and easily recovered using 0.1 M (NH4)2SO4 solution at pH 5. Scandium primarily occurred in mineral forms with minimum amounts associated with ion-adsorbed clays and organic association.

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 pretreating 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 1.2 M HCl at 75 °C 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 °C in an oxidizing environment to study the effect on leaching characteristics. The results showed that pretreatment at 600 °C for 2 h resulted in a significant increase in REE recovery...

The existence of rare earth elements (REEs) in coal sources at elevated concentrations has been the focus of several studies over the past decade. However, limited research has been conducted on methods to recover and refine the REEs. This paper reports the results of a detailed study into the potential of selectively recovering REEs in an Illinois basin coal source by leaching. Leaching characteristics are obtained for several segments obtained from a core sample as well as three different reject materials collected at a coal processing plant. Using a 1.2 mol/L sulfuric acid solution at 75 °C, over 60% REE recovery is achieved from the direct floor and an inner parting material as well as the coal-rich core segments that are pretreated by low-temperature plasma oxidation to obtain access to the micro-dispersed mineral matter. In the leachable parting material, fluorapatite is detected by XRD analysis, which is one of the more soluble phosphate minerals with a documented association with REEs. For the three plant reject samples, the leaching recovery values obtained for the heavy REEs are higher than those obtained for the light REEs under the standard leaching conditions and when 0.1 mol/L (NH4)2SO4 was used to extract REEs by an ion exchange mechanism. Thermal activation by roasting or chemical activation by pretreatment using 8 mol/L NaOH solution increases the total REE recovery with significantly higher gains obtained for the light REEs. Leaching kinetics are relatively fast within the first 2 h and then slow to provide relatively low overall recovery values under the standard test conditions for the coarse and fine reject samples. However, significantly higher recovery values are realized when treating mixed-phase (middling) particles existing within the coarse reject material.

Bastnaesite, monazite and xenotime are rare earth minerals (REMs) that are typical sources for rare earth elements (REEs). To advance the understanding of their leaching and precipitation behavior in different hydrometallurgical processes, Eh-pH diagrams were constructed and modified using the HSC 9.9 software. The aqueous stability of rare earth elements in H2O and acid leaching systems, i.e., the REE-Ligands-H2O systems, were depicted and studied based on the Eh-pH diagrams. This study considers the most relevant lixiviants, their resulting equilibrium states and the importance in the hydrometallurgical recovery of rare earth elements (REMs). A literature review was performed summarizing relevant Eh-pH diagrams and associated thermodynamic data. Shifting stability regions for REEs were discovered with additions of acid ligands and a narrow stability region for soluble REE-(SO4/Cl/NO3) complexes under highly acidic conditions. As such, the recovery of REEs can be enhanced by adjusting pH and Eh values. In addition, the Eh-pH diagrams of the major contaminants (i.e., Fe, Ca and Al) in leaching systems were studied. The resulting Eh-pH diagrams provide possible insights into potential passivation on the particle surfaces due to the formation of an insoluble product layer.

Recovery of rare earth elements (REEs) from coal samples collected from the Fire Clay coal seam using diluted mineral acid solutions was investigated. The initial processing step was coal recovery using conventional froth flotation which concentrated the REEs in tailing material resulting in an upgrade to values around 700 ppm on a dry whole mass basis. Leaching experiments were performed on the flotation tailings material using a 1.2 M sulfuric acid solution adjusted to a temperature of 75 &deg, C to study the extractability of REEs from coal material. The effect of particle size, leaching time, leaching temperature, and solid concentration on REE leaching recovery were evaluated. The kinetic data obtained from leaching over a range of temperatures suggested that the leaching process follows the shrinking core model with possibly a mixed control mechanism that may be a result of several heterogenous materials leaching simultaneously. Leaching recovery increased rapidly at the beginning of the reaction then slowed as the system reached equilibrium. The apparent activation energy determined from test data obtained over a range of temperatures using 1 M sulfuric acid was 36 kJ/mol for the first 20 min of reaction time and 27 kJ/mol for the leaching period between 20 and 120 min. The leaching of light REEs during the initial stage was determined to be driven by a chemical reaction, followed by the formation of a product layer, which required lower activation energy in the later stage of leaching. In regards to the heavy REEs, the major mechanism for leaching is desorption and the product layer formation does not affect the heavy REEs significantly.

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.

Selective depression of calcite in a monazite-calcite flotation system was systematically studied using micro-flotation and electrokinetic tests as well as X-ray photoelectron spectroscopy (XPS) characterization and solution chemistry calculations. Monazite was found to be depressed by both sodium silicate and sodium hexametaphosphate when calcium ions appeared in solution. It was hypothesized that co-adsorption of calcium species (CaHCO3+ and CaCO3(aq)) and Si ( OH ) 4 as well as SiO ( OH ) 3 - via hydrogen bonding formed a compact layer over the monazite surface, thereby reducing octanohydroxamic acid adsorption by steric hindrance. The use of citric acid or EDTA formed soluble chelates (e.g. CaCit− and CaEdta2−) with the calcium ions which negated the flotation suppression effect. An XPS study indicated that both EDTA and citric acid chemically adsorbed on the monazite surface, while the adsorption on the calcite surface was achieved mainly through hydrogen bonding. EDTA was more effective than citric acid due to two reasons: (i) citric acid itself presented stronger depression effects and (ii) citric acid has weaker chelating properties for calcium. Using 2.5 × 10−4 M octanohydroxamic acid, 0.05 g/L sodium silicate and 6 × 10−5 M EDTA, monazite recovery of more than 90% was achieved while recovering only 20% of the calcite.

Recovery of rare earth elements (REEs), especially heavy and critical REEs, from alternative resources such as coal refuse has recently become increasingly important. A natural leachate containing 6.14 ppm of REEs with a pH value of 2.70 was collected from a coal coarse refuse pile and utilized as a feedstock for REE recovery tests. The pH value of the natural leachate was gradually increased in a step-wise manner using a sodium hydroxide solution which produced several precipitates. A precipitate containing about 1.1% total REEs was obtained in the pH range of 4.85–6.11 while recovering >80% of the REEs contained in the original leachate. The leaching and staged precipitation process enriched both the critical and heavy REE fractions. The ratios of heavy-to-light (H/L) and critical-to-uncritical (C/UC) REEs in the precipitate were much higher than the coarse refuse material (H/L: 1.54 vs 0.21, C/UC: 1.51 vs 0.34). Additionally, the precipitate contained 18.4% Al, 1.7% Zn, 1.4% Cu, 1.1% Mn, 0.5% Ni and 0.2% Co. A solution chemistry study indicated that the hydroxide and hydroxysulphate precipitates of Al, Si and Cu produced in the pH range of 4.85–6.11 contributed to the fractionation of the REEs and other metal ions such as Zn, Mn and Co to the precipitate. The iron hydroxide precipitates formed at lower pH values did not contain a significant amount of REEs. An explanation may be the competitive adsorption between Al, which was present at higher solution concentrations, and REEs on the iron hydroxide and/or hydroxysulphate precipitate surfaces as proven by results of precipitation tests conducted on model solutions. A product containing 94% of a rare earth oxide mix was obtained by re-dissolution of the REE enriched precipitates followed by selective precipitation using oxalic acid. The overall results including an economic assessment indicate that leachate solutions generated naturally from coarse coal refuse may be a valuable source of critical and heavy REEs that can be effectively recovered and concentrated using staged precipitation.

The majority of rare earth elements (REEs) existing in the feed to coal preparation plants report to the coarse refuse streams which are transported for permanent storage in contained piles. In this study, an integrated flowsheet was developed based on laboratory test data which combines physical separation, pyrite bio-oxidization, heap leaching, selective precipitation and solvent extraction processes. The test data was obtained from (1) characterization of a number of natural leachate and solid samples collected from different preparation plants which process coals from a number of coal seams and (2) laboratory acid leaching and selective precipitation tests results. The highly-valued critical REEs (i.e., Y, Nd, Eu, Tb and Dy) were selectively leached from the refuse samples in the natural environment due to the acid generated by pyrite oxidization. The leachate samples were evaporated to remove water and obtain residual solids (i.e., dissolved solids in the leachates). The total REE content in the dissolved solids from a given leachate sample was 380 ppm, which was higher than the REE content of the coarse refuse material that generated the leachate (322 ppm). Acid leaching tests recovered as much as 80% of the total REEs from the coarse refuse samples using a 1.2 M sulfuric acid solution. Afterwards, the pH of the leachate was increased in a step-wise fashion which resulted in the production of precipitates containing 0.3–1.1% total REEs. A significant amount of contaminants, such as Fe, Al, and Ca, were eliminated in the sequential precipitation process, which allowed further upgrading using oxalic acid precipitation and/or solvent extraction. In the proposed flowsheet, the coarse refuse is arranged in heap leach pads and the acid needed for REE leaching is primarily produced from pyrite bio-oxidization, which enhances the selectivity of REE recovery and significantly reduces the cost. The successful application of the flowsheet would result in significant benefits to both the coal and rare earth industries.

A laboratory REE release test procedure was designed to better understand the association and liberation characteristics of rare earth elements (REEs) from coal-based material, such as coal middlings and refuse. For this particular study, three samples of mixed-phase, middling material was collected from three coal preparation plants operating in three different coal basins and coal seams, namely Fire Clay, Middle Kittanning, and West Kentucky #13. In these release tests, the mixed-phase material was first ground in a laboratory ball mill for a designated amount of time and subsequently decarbonized using staged flotation. The REE content of the high ash tailings and low ash concentrate was determined, and the process was repeated for various target grind sizes down to the micron range. The results indicate that smaller grind sizes produce increased REE concentrations in the high ash tailings, and this result is predominantly driven by the increased ash content in the decarbonized tailings. The grinding characteristics of the Fire Clay coal source showed that more energy is needed to achieve the desired particle size reduction; however further size reduction of this sample resulted in a significantly higher ash and REE content in the tailings material due to improved liberation. For the Middle Kittanning and West Kentucky #13 sources, the grinding and release data indicates that the mineral matter is liberated at a coarser particle size, and micronizing the coals only produces marginal improvements in rare earth mineral liberation and recovery.

Rare earth element (REE) recovery from coal and coal byproducts using physical and/or chemical methods has been the focus of recent investigations due to concerns over worldwide supply. In the current study, the association characteristics of REEs and the recovery of REEs from the organic and inorganic components were systematically studied for a Fire Clay seam coal source. The coal sample was ground in a stirred ball mill and treated by froth flotation in stages to obtain clean coal concentrates and tailing samples. The clean coal concentrate from the first stage was re-ground to liberate more micro-dispersed mineral matter followed by flotation. After six grinding and recovery stages, the cumulative grinding time was 110 min, which reduced the particle size from 90% passing 84.3 μm to 4.5 μm. Analyses conducted on the tailing samples collected from each stage revealed that the REEs have a strong association with micro-dispersed kaolinite. The REE content in the tailings material increased from around 580 ppm to 1200 ppm on an ash basis. The ratio of heavy-to-light REEs in both the clean coal concentrates and tailing samples increased, which indicated a stronger affinity between the heavy REEs and the finest mineral matter grains in the organic matrix. Based on these findings, REE concentration tests were performed using froth flotation, magnetic separation and acid leaching. A product containing nearly 7000 ppm of REEs was achieved from a feed containing 500 ppm REEs using a batch WHIMS unit. The elemental content indicated that the rare earth mineral in the concentrate was primarily monazite. Leaching the high ash content fractions generated from the sequential grinding and flotation steps using 1 M nitric acid resulted in recovering more than 80% of total REEs with the exception of scandium. A lower recovery value obtained for scandium indicated a unique association with the mineral matter relative to the other REEs.

Leaching recovery of rare earth elements (REEs) from two natural kaolinite samples were investigated in this study. Using standard leach conditions without pretreatment, only 10% and 56% of the total REEs were leached from the raw samples, respectively. However, pretreatment by calcination at temperatures between 500 °C and 900 °C increased the leaching recovery of total REEs to values as high as 93% for both samples. Mineralogical characterization and acid leaching results suggested that the decomposition of the kaolinite structure occurs as a function of calcination temperature. Comparisons between the REEs and the major constituent elements of kaolinite showed that their leaching characteristics contrasted. Moreover, sequential chemical extraction results suggested that the fractions of REEs occurring in an ion-adsorption form were negligible. Therefore, the REEs were primarily associated with REE-bearing minerals of which, a portion was encapsulated in kaolinite aggregates while the remaining existed as liberated particles. These association characteristics were proven through SEM-EDX analysis. Based on the mineralogy characterization, acid leaching, and sequential chemical extraction results, it was concluded that the REEs have complicated modes of occurrence and association characteristics with kaolinite. The positive impacts of calcination on the leaching recovery of REEs are likely due to two mechanisms, i.e., (1) liberation of the encapsulated REE-bearing minerals through expansion of the kaolinite aggregates, and (2) conversion of the REE-bearing minerals into more soluble forms.

The present study concentrated on a novel froth flotation process with the addition of hydrophobic magnetic particles. The effects of the concentration of hydrophobic particles, coal type, and the ...

Rare earth elements (REEs) found in coal are in the form of minerals, ion-adsorbed onto clay surfaces or inner layers, or organically bound. Rare earth minerals such as monazite exist in coal and have grain sizes smaller than 5 µm. In this study, froth flotation was successful in concentrating rare earth minerals existing in a thickener underflow material derived from Fire Clay seam coal that contained around 431 ppm of total rare earth elements (TREE) on a dry ash basis. Conditioning with fatty acid followed by processing using multiple stages of conventional flotation produced a final concentrate containing 2,300 ppm TREE. Using a laboratory flotation column to limit hydraulic entrainment, the TREE content was further enriched to around 4,700 ppm, which equated to an enrichment ratio of 10:1..

The surface charge mechanisms of monazite were studied using electrokinetic tests, solution equilibrium calculations, crystal structure characterization, and electrostatic model predictions. The isoelectric point (IEP) of a natural monazite sample was found to occur at pH 6.0. To allow a theoretical study of the surface charge on monazite, fundamental values associated with cerium monazite (CePO 4 ) were utilized to quantify the isoelectric point (IEP) and point of zero charge (PZC) using solution equilibrium calculations and electrostatic models. The IEP and PZC of the cerium monazite were determined to be equal with a pH value of 7.2. Hydroxyl and hydrogen were found to be potential determining ions and preferential hydrolysis of the lattice ions played a minor role. The findings support the hypothesis that the charge of monazite surfaces in water is a result of protonation/deprotonation reactions. The difference in the IEP values obtained for the natural monazite and cerium monazite along with the wide range of values reported in literature may be partially explained by the amount of carbon dioxide dissolved in solution. When equilibrating with carbon dioxide at 10 –3.5 atm partial pressure, the IEP of the cerium monazite shifted to a solution pH value of 4.5.

The adsorption mechanism of octanohydroxamic acid (OHA) on monazite was studied using kinetic, isotherm, and thermodynamic adsorption tests as well as FTIR, titration, and micro-flotation experiments. The adsorption mechanism was described as a chemisorption/surface precipitation process. At low OHA concentrations, adsorption occurred by chemisorption as a result of the reaction between surface active sites and OHA molecules. With an increase in concentration and interaction time, surface precipitation occurred. For chemisorption, adsorption was an exothermic and entropy driven process and maximum adsorption was achieved at pH 9.0 due to more active sites. In an acidic environment, such as pH 3.0, adsorption was achieved via chemisorption and hydrophobic bonding. However, a strong basic and higher temperature environment contributes to surface precipitation of basic rare earth hydroxamate. FTIR tests showed the movement of CH 2 band position from 2924 cm − 1 to 2920 cm − 1 with increases in pH values from 3.0 to 6.0, 9.0, and 11.0, which corresponds to the status of chemisorbed and surface precipitated OHA, respectively.

A laboratory study was conducted to evaluate and compare the effectiveness of nine different frother types when used in a three-phase, continuously operating froth flotation system. The frothers included several that are commonly used in the industry (e.g., MIBC, 2EH, and F-1) as well as unique frother types (e.g., F-3). The tests were conducted in a 5-cm diameter laboratory flotation column that provided near plug-flow mixing conditions due to a length-to-diameter ratio of around 50:1. Test results indicate that F-1, MIBC, and MPC (in order of decreasing effectiveness) provided the weakest performance in terms of combustible recovery while F-2, MAC, and 2EH were the top three generating the highest separation efficiencies. When processing ultrafine coal, the ash content of the flotation concentrate ranged from 10% to 15% while recovering over 80% of the combustible material. F-3, F-4, and DIBC provided over 80% recovery of combustibles at the expense in the amount of hydraulic entrainment. The flotation performances were also closely examined in accordance with the fundamental properties of the nine tested frothers, and their correlations were addressed in detail.

A study of the mobility of major and potentially hazardous trace elements from coal processing waste materials was conducted using two types of leaching tests. The baseline leaching test simulates stable waste storage under water, whereas the kinetic test models the storage of waste under more variable conditions including intermittent exposure to air and variations in humidity. Coarse and fine refuse materials were obtained from three commercial coal preparation plants that were being used to upgrade US bituminous run-of-mine coal containing low-to-high amounts of pyritic sulfur. X-ray diffraction analyses revealed a large variation in mineralogy between the coarse and fine refuse streams due to the mineral fractionation that occurs in the processing units and plant. The coarse refuse samples contained higher pyrite contents while the fine refuse samples had high clay content and a minor amount of calcite. This variation in mineralogy resulted in relatively large difference in the leaching characteristics of the waste streams. The most acidic pH and highest release of trace elements were observed in the leachate of coarse refuse containing medium-to-high amounts of coal pyrite, while the fine refuse samples released lower amounts of trace elements in their circumneutral leachate. The least amount of trace elements was observed in the leachate of low pyritic refuse streams. The test data suggested that the most effective disposal practice for coal waste material is segregation and isolation of the coal pyrite and co-disposal of the coarse and fine refuse streams.

The dissolution of minerals provides elevated concentrations of alkaline earth metal ions such as calcium (Ca 2+ ) in water which may have a significant influence on flotation performance. The effects of Ca 2+ ions dissolved from calcite surfaces on the flotation performance of a monazite-calcite system have been investigated using micro-flotation tests followed by fundamental collector adsorption studies. The results indicate that specially adsorbed CaOH + via hydrogen bonding competed with hydroxamic acid for the phosphate-oxygen active sites on the monazite surface and decreased its hydrophobicity due to hydration. Electrostatically adsorbed CaOH + on monazite increased the adsorption density of hydroxamic acid through a chelating interaction. At higher dosages of calcium and hydroxamic acid, bulk and surface precipitation of calcium-hydroxamate occurs in the monazite-calcium-hydroxamic acid system.

The effect of hydrophobic and magnetic plastic particles having a contact angle of around 83° on flotation performance was evaluated using coal particles of varying degrees of floatability. The magnetic plastic material were recovered by a low intensity magnetic separator and recycled back to the flotation feed for re-use. Flotation rate tests conducted on coal using a conventional cell proved that combustible recovery and flotation rate were significantly enhanced with the addition of the plastic particles, especially for difficult-to-float coals, which was corroborated by flotation column tests. Carrying capacity and particle size-by-size flotation tests further showed that the magnetic plastic particles preferentially increased the recovery of coarse particles by as much as 35 absolute percentage points due to froth stabilization which reduced the selective detachment of coarse and/or weakly hydrophobic particles. The enhanced flotation recovery was attributed to the influence on liquid drainage rate in the froth zone, froth stability, bubble coalescence and flotation rates.

The surface of subbituminous coal contains a significant amount of oxygen containing functional groups which contribute to a low degree of hydrophobicity. As such, upgrading of the fine fractions is difficult using conventional flotation practices which rely on bubble-coal particle attachment and separation based on density. Alternatively, reverse flotation provides a viable option whereby the mineral matter is made hydrophobic through the addition of a collector while a depressant is added to make the coal particle non-floatable. Bench-scale reverse flotation experiments were conducted using artificial mixtures of subbituminous coal and quartz of varying particle size to assess the flotation performance. The process provided a reduction on the ash content from values around 35% to while recovering nearly 85% of the combustible material. The performance was achieved using mixtures of coarse coal with fine quartz and medium-size coal with fine silica. The performance was significantly better than that achieved by the conventional practice of floating the coal and rejecting the mineral matter to the underflow stream. The separation efficiency obtained when evaluating a mixture of fine coal and quartz particles was not as favorable due to the effect of hydraulic entrainment.

Rock dust consisting of ultrafine calcium carbonate particles is required in underground coal mines to suppress the potential for coal dust explosions. When the dust is applied in a moist mining atmosphere or placed in the mine in wet form, caking of the rock dust particles occurs which negatively effects dispersion of the dust during an event thereby creating the potential for an explosion. An earlier investigation found that sodium oleate was effective in rendering the surfaces of rock dust particles hydrophobic thereby allowing the water to drain, eliminating the caking effect and enhancing their dispersive properties. However, subsequent research has shown that increasing the sodium oleate concentration above a specific value reverses the positive impact on dispersion by inducing particle agglomeration through hydrophobic particle-particle interactions. A detailed investigation found that monolayer adsorption of sodium oleate occurs most likely within the oleate concentration range of 0.1% and 0.15% by weight. A further increase in the oleate concentration resulted in a corresponding rise in the surface contact angle to a maximum of 126°. As a result, the inter-particle interactions become dominated by the attractive hydrophobic interaction force which results in spontaneous particle agglomeration upon contact between the rock dust particles. In addition, precipitated calcium oleate nucleated on top of the hydrophobic dust surface as nanoparticles and tended to agglomerate at high oleate concentrations. As a result, the benefits of hydrophobizing rock dust particles are limited to lower reagent dosages to maintain the desired dispersion characteristics.

An environmental concern at mining operations is the potential leaching of trace elements from overburden and byproduct streams of processing plants. To provide a timely assessment of this concern, electrical conductivity of the leachate emanating from the plant waste streams can be measured as an indicator of the trace element content levels using the USGS Field Leach Test (FLT). However, the research reported in this publication revealed the need to modify the FLT procedure to improve the precision of the test results. The primary issue involved the importance of leachant volume-to-particle surface area ratio in the assessment of the leaching potential for a given source. To determine the key factors impacting leachability of a given material, a statistically-designed parametric study was performed. The experimental program evaluated the effects of particle surface area, the leachant volume-to-surface area ratio, and the amount of oxidant used to expedite the leaching rate during the test. The results revealed that the significant parameters are leachant volume-to-solid surface area ratio and the amount of oxidant. The findings were used to recommend a modification to the conductivity screening test.

The production of superior metallurgical-grade silicon requires the use of ultra-clean coal containing

Coarse and fine samples of a Class F fly ash obtained from commercial combustion of Illinois bituminous coal have been exposed to two long-term leaching tests designed to simulate conditions in waste impoundments. ICP-AES analysis indicated that the coarse and fine fly ash samples contained 135 and 171mg/kg Cr, respectively. Measurements by XAFS spectroscopy showed that the ash samples originally contained 5 and 8% of the chromium, respectively, in the hexavalent oxidation state, Cr(VI). After exposure to water for more than four months, the percentage of chromium as Cr(VI) in the fly-ash decreased significantly for the coarse and fine fly-ash in both tests. Combining the XAFS data with ICP-AES data on the concentration of chromium in the leachates indicated that, after the nineteen-week-long, more aggressive, kinetic test on the coarse fly ash, approximately 60% of the Cr(VI) had been leached, 20% had been reduced to Cr(III) and retained in the ash, and 20% remained as Cr(VI) in the ash. In contrast, during the six-month-long baseline test, very little Cr was actually leached from either the coarse or the fine fly-ash (

Underground coal mine explosions is perhaps the most hazardous danger in the coal mining industries. Efforts have been made to abate the coal dust explosion by applying rock dust either dry or wet. Dry dust has the best lift characteristic which efficiently quenches the flame propagation of a potential explosion. As a trade-off, undesired respirable dust particles are thereby generated imposing a severe health hazard on coal miners. Wet dusting is an alternative to dry dusting which significantly reduces the exposure to respirable dust particles. However, wet dust is subject to adverse caking issues which lead to a drastic reduction in the dispersibility of the particles. The present work summarizes the studies conducted to date regarding the surface modification of rock dust particles for the purpose of eliminating or alleviating the problems accompanying coal mine dusting applications, meanwhile improving the dispersive properties of dust particles and the ability to suppress the coal dust explosion.

The modern air-based density separator achieves density-based separation for particle sizes greater than 6 mm. Parametric studies, conducted with a modified laboratory-scale unit, operating at an optimal feed rate of 200 kg/hr to upgrade low-rank coal, have demonstrated the applicability to clean finer size fractions up to 1 mm. However, there is a lack of fundamental understanding of the separation process that can be provided utilizing numerical modeling techniques. The separation process was numerically modeled using K-Epsilon and RSM turbulence formulations and validated using experimental dataset. The results prove that the effect of fine coal vortices forming around the riffles act as a transport mechanism for higher density particle movement across the table deck resulting in 43% displacement of the high-density particles to the product side. The velocity and vector plots show high local variances of air speeds and pressure near the feed end and an increase in feed rate results in a drop in...

Acid mine leachate (AML) may be a significant source of rare earth and other critical elements needed for the manufacturing of advanced electronics and renewable energy technologies. A systematic study was performed on a natural leachate collected from a coal preparation plant that treated bituminous coal containing elevated amounts of pyrite. The leachate contained 1.96 ppm total REEs, 2.52 ppm Zn, 2.15 ppm Ni, 1.22 ppm Cu, 0.77 ppm Co, and 25 ppm Mn. Sequential precipitation using simple pH control generated a pre-concentrate containing 0.82% total REEs, 1.08% Zn, 0.91% Ni, 0.50% Cu, 0.34% Co, 7.1% Mn. The pre-concentrate was further treated by re-dissolution using a 10 M HNO3 solution, which resulted in a solution pH of 1.5. The addition of oxalic acid to selectively precipitate the REEs followed by roasting of the precipitate generated a product containing >98% rare earth oxides. More than 95% of the Cu and Zn were recovered from the residual liquid using Na2S at pH 2 and 3, respectively. The CuS and ZnS contents in the corresponding concentrates were 60% and 58%, respectively. The majority of the Co and Ni remained in the residual liquid. Based on these findings, a process flowsheet was developed to recover the REEs and critical metals from AML.

Lithium recovery from the density fractions of Baker (namely West Kentucky No. 13) seam coal was investigated in this study. Proximate and elemental analyses showed that lithium contents in the 1.8–2.2 SG and 2.2 SG sink fractions were 185 ppm and 150 ppm, respectively, which are significantly higher than the average content of coal sources (12 ppm) and coal ashes (66 ppm) worldwide. Moreover, due to the high lithium contents and mass distribution, nearly 90% of the lithium present in the Baker coal sample was distributed in the two density fractions. Direct leaching using a HCl solution resulted in less than 10% lithium recovery, which was due to nearly 90% of the lithium being associated with insoluble solids as determined by the results from sequential extraction tests. Calcination of both density fractions under 600 °C for two hours followed by leaching resulted in recovery increases in the range of 70% to 80%. The pyro-metallurgical pretreatment step converted most of the associated lithium minerals to more easy-to-leach forms such as carbonate and metal oxide. Based on mineralogy characterization and leaching test results, it was concluded that the positive effects of calcination on lithium leachability resulted from the dehydration and disintegration of kaolinite as well as dehydroxylation and expansion of muscovite/illite. An analysis of the leaching kinetics revealed that the leaching rate of lithium was controlled by interface transfer and diffusion across the product layer and was negatively impacted when the calcination temperature exceeded 600 °C due to sintering of the kaolinite.

The impacts of calcination on the leaching recovery of rare earth elements (REEs) and other critical metals from a Baker seam coal refuse material were investigated in this study. Acid leaching test results showed that leaching recovery of the REEs, especially the light REEs, was increased significantly from around 24% to 80–90% after calcination under 600–750 °C for two hours. By considering the major element leaching kinetics and the mineralogical changes of the dominant minerals caused by calcination, two mechanisms were proposed for the improved leaching performance: (1) decomposition of difficult-to-dissolve REE-bearing minerals into soluble forms; and (2) liberation of REE-bearing minerals encapsulated in clays after calcination due to the dehydration and disintegration of the layered clay structure. Sequential chemical extraction tests showed that a significant fraction (around 75%) of the REEs in the raw material were present in an insoluble form. After calcination under proper temperatures (600–800 °C), the majority of the insoluble light REEs (LREEs) were converted into soluble forms. Changes in the modes of occurrence of the LREEs and phosphorous based on leaching rate and sequential leaching correlated well as a function of the calcination temperature. This finding in addition to SEM-EDX results tends to indicate the potential that the LREEs occur primarily as rare earth phosphates such as monazite in the untreated coal refuse material. The acid leaching and sequential chemical extraction results show that co-extraction of REEs and other critical metals such as Co, Mn, and Li is possible using a calcination-acid leaching procedure.

Production of silicon for solar cells and semiconductors requires the use of ultra-clean coal as the main reducing agent in the silicon production process. Most coal preparation plants employ magnetite suspensions as the dense medium in coal cleaning processes. Although downstream operations are designed to remove and recover magnetite, the unavoidable presence of residual magnetite in the final coal product dramatically decreases the purity and suitability of the coal for the silicon market. Given that silicates are the main raw materials in the silicon production, a systematic study through laboratory dense-medium cyclone tests was used to evaluate fine silica-based alternative materials as a substitute for magnetite in coal cleaning operations. These alternative silica materials include byproducts generated during the silicon production process. The results indicate that laboratory tests with silica-based materials were able to achieve similar separation performance when compared to plant operations using magnetite. Following the outcomes of the experimental study, a novel flowsheet arrangement was designed using silica-based media rather than magnetite. If properly implemented, this new separation system can eliminate iron contamination and provide coal that can be marketed as a high-quality silicon feedstock.

The separation of carbon from fly ash significantly improves the potential end-us of combustion byproducts. Froth flotation is the most effective separation technique for ultrafine material. Diesel dosages, conditioning time, and impeller rotating speeds' influences on carbon flotation performance were studied. From flotation products, + 25 and − 25 μm fractions were screened out to study their different flotation behaviors. At a given impeller speed, carbon recovery of +25 μm fraction increased significantly from 38.46% to 74.22% over a range of diesel dosage from 0.5 to 4.5 kg/t, while that of -25 μm fraction was relatively constant at 85% over the same diesel dosage range. Morphologies and microstructures of coarse and fine carbon were studied by using scanning electron microscope. Porous structures of coarse carbon were observed. It's difficult for diesel droplets of several microns to penetrate the pores of coarse carbon particles, which increases diesel consumption. Increasing impeller speeds from 1200 to 1600 rpm during conditioning improved the carbon recovery and separation efficiency of + 25 μm fraction by 79% and 110%, respectively, which significantly reduced diesel consumption. Flotation kinetic studies indicate that increasing impeller speeds during conditioning stage can improve the flotation rate constant and maximum carbon recovery for both + 25 and − 25 μm fractions.

Maceral separation is one possible technique to expand coking coal resources, either by increasing the blending ratio of non- or slightly caking coal or rationally utilizing the coking coal according to the different behaviors of macerals in coking. The success of maceral enrichment for a given coal usingfiotation is dependent on the differences in flotation kinetic rate among macerals. This paper presents theflotation rates and zeta potentials of the vitrinite-rich and inertinite- rich maceral concentrates obtained from six coal samples of different ranks — from high-volatile B bituminous coal with mean random vitrinite reflectance (Rrandom) of 0.64 percent to low-volatile bituminous coal with Rrandom of 1.73 percent — using a float-sink procedure. The flotation results show that vitrinite-rich concentrates can be produced in tap water using froth flotation only with frother for the high-volatile B and A bituminous coal samples, but there was no good performance for the high-volatile C bituminous and medium- to low-volatile bituminous coal samples. The zeta potential results show that froth flotation could probably separate the high-volatile C bituminous coal samples well by adjusting pH, but there was no good performance for the higher-rank coal samples.

Previous research indicates that coal and coal by-products are a potential source of critical elements including rare earth elements (REE) with estimated amounts in the range of 50 million metric tons. Despite the proven presence of elevated REE concentrations, commercial extraction and recovery have not been realized. This article provides a review of the abundance, mode of occurrence, and recovery methods of rare earth elements in coal and coal by-products. The feasibility of using established REE extraction and recovery technologies is discussed along with issues associated with their use with coal resources.

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. Published version

Silica minerals are one of the major contaminants in coal. They significantly deteriorate the coal quality and need to be removed before the use of coal. Conventional coal preparation techniques are wet processing methods that require huge quantities of water and chemical reagents, which induce high operation cost and environmental pollution. Therefore, dry separation technique to preconcentrate coal before the wet processing or even substitute the wet processing is required. In this study, the coal–silica mixture was beneficiated using a novel rotary triboelectrostatic separator (RTS). This new type of electrostatic separator is characterized with high particle charging efficiency, good separation environment and high throughput. The experiment result shows the surface charge densities of the coal, and the silica particles are greatly enhanced and the ash rejection of coal–silica mixture is achieved using the RTS. The ideal coal–silica mixture electrostatic separation characteristic using the RTS was determined. The charge density difference between coal and silica particles is distinct after the charging process. Better separation efficiency could be obtained when an industrial size RTS is available to use.

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 ℃. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.