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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Major element composition controls rare earth element solubility during leaching of coal fly ash and coal by-products

Coal combustion ash and pre-combustion coal refuse are currently under consideration as potential sources of rare earth elements. One of the early steps in recovering REEs from coal by-products is often acid leaching, which can result in low pH leachates with complex aqueous chemistry. The aim of this work was to understand the connection between REE solubility, pH, and major elemental components of leachates for coal by-products. To accomplish this, we investigated the effects of solids concentration (i.e., pulp density) and pH adjustment on REE solubility in acid leachates of coal fly ashes from the Powder River Basin (PRB) and Appalachian Basin in the United States, and a coal processing refuse from the Southwestern U.S. For PRB ashes, the concentrations of soluble REEs generally increased with increasing pulp density; however, at pulp density values above 80–100 g/L, the soluble REE concentrations in the leachates were markedly lower. Similarly, the soluble concentrations of other major solutes (Fe, Al, Si) that leached from PRB fly ashes were also non-linear with pulp density. These major elements tended to reach maximum concentration values at 60–70 g/L pulp density. In contrast, for the Appalachian fly ashes and the coal by-product, soluble concentrations of REE and major elements in leachates increased linearly with pulp density. Chemical equilibria calculations of mineral saturation indices indicated that trends in soluble REE concentrations could be explained by saturation conditions for Fe and Al-(hydr)oxides and possibly sulfate minerals, but not lanthanide hydroxides. Furthermore, pH adjustment of the acid leachates showed that REEs and many major solutes were removed from solution at pH values above 4.5, also consistent with Fe- and Al-(hydr)oxide precipitation. These results highlight the importance of understanding the chemical composition of leachates when designing REE recovery processes for low-grade geologic feedstocks and that precipitation of hydr(oxide) or sulfate minerals of major elements rather than discreet formation of REE mineral phases could be used for process optimization.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Liberation and release of rare earth minerals from Middle Kittanning, Fire Clay, and West Kentucky No. 13 coal sources

Here, 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.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2017

Process evaluation and flowsheet development for the recovery of rare earth elements from coal and associated byproducts

Coal and coal byproducts produced annually contain enough rare earth elements (REEs) to meet current U.S. demand. Here, the REEs exist in the form of minerals, ion-exchanged elements associated with clays and chemically bonded elements within the organic coal matrix. Researchers at three universities have collaborated to evaluate the effectiveness of existing physical and chemical concentration processes for the recovery of the REEs. The efforts have found that physical separation processes can increase the total REE content in the thickener underflow material collected from a Central Appalachian coal cleaning facility from around 300 ppm to values greater than 17,500 ppm on an ash basis. Leaching followed by solvent extraction was found to be the most effective to recover the REEs from coarse middlings materials collected from multiple coal basins as indicated by recovery values exceeding 80%. Based on material characterization data and process evaluations conducted for several potential feed coal sources, economic recovery of the REEs will require byproduct production of both clean coal and REE concentrate using a process flowsheet that is unique for each source.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Concentrating Rare Earth Elements in Coal mine drainage Using Coal Combustion Products through Abandoned Mine Land Reclamation

Rare earth elements (REEs) (including scandium, yttrium and a group of 15 lanthanides) are often considered to be critical components in the productions of renewable energy hardware, electric vehicles, health care and military equipment, and consumer electronic products. The demand of REEs has been projected to be growing at an annual rate of 5-9% in the next 25 years. In 2011, the global demand of total rare earth oxides (REOs) was estimated to be approximately 105,000 tons, which is expected to grow to 210,000 tons by 2025. China overwhelmingly dominates the current worldwide rare earth productions but has strategically restricted its exports, causing significant instability for the global market. In response to the increasing demand for REEs and the supply dominance of China, identifying alternative sources of REEs has become a critical issue for the United States and other countries. Coal, coal ash, and coal mine drainage (CMD) are considered to be the alternative sources of REEs. In the U.S., high REE concentrations have been reported to be closely associated with coal deposits, including the Appalachian Basins. When surface and/or groundwater come in contact with geologic strata containing sulfide minerals exposed by coal mining, the accelerated oxidation of sulfide minerals in the presence of ferric iron and/or oxygen can produce sulfuric acid. The process promotes the weathering of REE-bearing rocks and minerals in the host geologic strata. Compared to average river water and seawater, the concentrations of REEs can be orders of magnitude higher in CMD. In this study, we demonstrated a trap-extract-precipitate (TEP) process that can effectively recover REEs from CMD. The three-stage TEP process uses alkaline industrial by-products to capture REEs from CMD and then applies an extraction/precipitation procedure to produce a feedstock that can be economically processed to produce marketable rare earth oxides. The alkaline industrial by-products tested in this study include the residual from a water softening process (DRWP sludge) and two types of stabilized flue gas desulfurization materials (sFGDs). sFGD material is a mixture of lime (CaO) and two coal combustion by-products, calcium sulfite FGD by-product and fly ash. The objectives of this study are to (1) validate the effectiveness and feasibility; (2) determine mechanisms controlling the rare earth recovery, (3) quantify the associated economic and environmental benefits, and (4) evaluate the full-scale application. To achieve these objectives, tasks to be carried out in this proposed project are organized into three phases. In the first phase, the research team collaborated with Ohio Department of Natural Resources, American Electric Power, The Wilds (a nonprofit wildlife conservation organization), and a private landowner to carry out field investigations aimed to screen and evaluate the seasonal changes of rare earths in the CMD discharges that have high recovery potentials. Next, the recovery of REEs from CMD was tested using a series of lab-scale column and batch tests under, respectively, percolation and completely mixed conditions. Results obtained from these lab-scale studies show that all three tested solids are very effective in retaining REEs. Over 98% of the CMD REEs that contacted the solids were captured before the solids exhausted their neutralization capacities. We also determined an extraction process using a non-acid, organic ligand extraction solution that can effectively remobilize the retained REEs from the spent solids (over 90%). The REE concentrate (>7.5 wt. % of total REEs) is then formed in an aeration process. The TEP process uses environmentally benign industrial by-products and a naturally-occurring organic ligand to mitigate CMD and recover REEs. Techno-economic analysis (TEA) and life-cycle assessment (LCA) was carried out in the third phase. The engineering-economic costs and net energy, net CO2 emissions, and water and other requirements were investigated to understand the economic and environmental implications of this process. This work uses mass and energy balances from laboratory-scale experiments to estimate the economic costs and environmental impacts. The results suggest that passive treatment systems that use DRWP sludge are preferred over those that use sFGD material, because of lower economic costs ($89,300/yr with a unit cost of $86/gT-REE vs. $89,800/yr, or $278/gT-REE) and improved environmental performance across all indicators from two different impact assessment methods. These differences are largely attributable to the larger capacity of DRWP sludge in the passive treatment application. We envision this TEP process can be integrated with abandoned mine land (AML) reclamation to create an approach that can add economic incentives for AML reclamation, remediate CMD discharge, and eliminate public safety hazards and threats to local environment and ecological systems posed by AMLs. It can restore lands and communities that are adversely impacted by legacy mining.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2019

Conversion of Coal in a Fluidized Bed Chemical Looping Combustion Reactor with and without Oxygen Uncoupling

Chemical looping combustion (CLC) is a carbon capture technology that involves circulating metal-based oxygen carrier particles between two reactors, where the metal is alternately oxidized by air and then reduced by fuel as the fuel combusts. In the variant of CLC known as chemical looping with oxygen uncoupling (CLOU), the oxygen carrier releases gaseous O 2 in the fuel reactor, allowing for a rapid reaction with solid fuels. This study focuses on improving the understanding of mechanisms responsible for carbon conversion of coal and coal char in a bench-scale fluidized bed reactor using oxygen carriers with and without oxygen uncoupling properties. Effects of coal particle size and temperature on the rate of carbon conversion are evaluated in order to quantify performance and to aid in design and modeling of large-scale fully circulating chemical looping systems. The data confirms that conversion with a copper-based CLOU carrier is faster and results in lower CO and CH 4 concentrations than the natural ore ilmenite, which does not have CLOU properties. Furthermore, with coal as fuel, the increase in the rate of char carbon conversion with CLOU is lower than that previously reported because of competition for oxygen by volatiles. Conversion is also faster with smaller particles but results in higher CO concentrations as small particles gasify and release volatiles more quickly.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2015

Influence of additives on the increase of the heating value of Bayah’s coal with upgrading brown coal (UBC) method

UBC (upgrading brown coal) is a method of improving the quality of coal by using oil as an additive. Through processing in the oil media, not just the calories that increase, but there is also water repellent properties and a decrease in the tendency of spontaneous combustion of coal products produced. The results showed a decrease in the water levels of natural coal bayah reached 69%, increase in calorific value reached 21.2%. Increased caloric value and reduced water content caused by the water molecules on replacing seal the pores of coal by oil and atoms C on the oil that is bound to increase the percentage of coal carbon. As a result of this experiment is, the produced coal has better calorific value, the increasing of this new calorific value up to 23.8% with the additive waste lubricant, and the moisture content reduced up to 69.45%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Production of Salable Rare Earths Products from Coal and Coal Byproducts in the U.S. Using Advanced Separation Processes (Final Technical Report)

The entirety of the report that follows this brief Executive Summary Chapter is the product of a Funding Announcement by the US Department of Energy (DOE), Office of Fossil Energy, originally issued 09/28/2016, otherwise known as Funding Opportunity Number: DE-FOA-0001627, under the title of “Production of Rare Earth Elements from Domestic U.S. Coal and Coal By-Products” The solicitation was subsequently amended several times ending in amendment 000005. Ultimately a consortium designated “Minerals Refining and Rare Earth Consortium” (to which many of the remaining participants recited in this report joined) filed a proposal on December 8, 2016. On June 9, 2017, the contracting office of the US DOE, National Energy Technology Laboratory (NETL), alerted Dr. Keim, the Authorized Representative of the December 08, 2016, proposal, that the consortium proposal had been selected. In summary, this report presents the results of the efforts in meeting the stated project objectives as outlined in DE-FOA-0001627 to wit: “The main objective of the proposed work is to design and construct a demonstration plant that can extract rare earth elements (REEs) from domestic U.S. coal and coal by-products. The plant will produce salable rare earth elements and intermediates, including at a minimum three individual REEs (preferably heavy rare earths) at 90-99% purities, with output capacities in excess of 10 pounds per day of composite rare earth products (reported as oxides). In addition, the plant will produce high value premium solid fuels, magnetite and other materials to increase the economic viability of the plant and to create jobs. If successful, the proposed work will help develop a domestic supply chain of the critical materials that are essential for the development of renewable energy resources, high-tech industries and a strong national defense.” The principal investigators immediately launched the tasks outlined in the Statement of Project Objectives (SOPO) in accordance to its Project Management Plan (PMP) based on their collective knowledge of the subject matter and the expectations generated by preliminary laboratory results. Events and circumstances related in part to the vagaries of the coal mining, processing, and marketing industry triggered a series of carefully deliberated step-wise transitions from the original Lower Kittanning coal source in West Virginia to an ultimate stopping point with the Fire Clay Seam (Hazard No. 4) rejects from Blue Diamond Coal Company in Kentucky (Operated by Blackhawk Mining LLC). These transitional steps are discussed in substantial detail in the body of this report. Notably, substantial data of potential future significance, both in terms of sample collection, processing, and testing, were collected in the process. Unfortunately, as reported in the Techno-Economic Chapter of this report, none of these efforts resulted in an anticipated economically viable venture. Thus, the principals associated with this project elected not to transition into a “Pilot Plant” operation. A proposal for funding that pilot plant was therefore not requested. The outcome of this initiative under DE-FOA-0001627 notwithstanding, the following portions of this Executive Summary outline the activities of the investigators. That said, the reader is encouraged to examine the main body of this report in which each chapter is assembled as a free-standing product, complete with Table of Contents, for practical and easy reference purposes.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

A survey study on arsenic speciation in coal fly ash and insights into the role of coal combustion conditions

Coal fly ashes (CFAs) are the low-density byproducts of the coal combustion process. Improper or uncontrolled CFA disposal poses significant environmental and health concerns due to the potential leaching of toxic heavy metals such as arsenic (As). Previous studies have investigated the content and speciation of As in different CFA samples, yet systematic information on As speciation in CFA with representative coal source and combustion conditions is still missing. Based on a recent survey study on the typical coal sources and combustion conditions across the U.S., this study selected 19 representative CFA samples to systematically investigate As speciation and potential correlations with these parameters. The composition, morphology, mineralogy, and As speciation of these CFA samples were characterized by complementary analytical, microscopic, and spectroscopic techniques. Synchrotron X-ray spectroscopy and microscopy analyses revealed the dominant As oxidation state to be As(V) and with strong associations to Ca, with the exception of 3 samples that had 19–51% As(III), likely due to the use of selective catalytic reduction (SCR) process. Principal component analysis was conducted to identify potential correlations of As concentration and oxidation state with parameters such as major element content, loss on ignition (LOI), average particle size, coal source, and combustion condition. Al 2 O 3 and FeO content were found to capture a majority of the variability. Further, results from this study provide fundamental basis for understanding the correlations between coal source, combustion conditions, CFA characteristics, and As speciation, and providing insights for downstream beneficial utilization or disposal management.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2017

Collaborative simulations and experiments for a novel yield model of coal devolatilization in oxy-coal combustion conditions

Oxy-coal combustion is an emerging low-cost “clean coal” technology for emissions reduction and Carbon Capture and Sequestration (CCS). The use of Computational Fluid Dynamics (CFD) tools is crucial for the development of cost-effective oxy-fuel technologies and the minimization of environmental concerns at industrial scale. The coupling of detailed chemistry models and CFD simulations is still challenging, especially for large-scale plants, because of the high computational efforts required. The development of scale-bridging models is therefore necessary, to find a good compromise between computational efforts and the physical-chemical modeling precision. This paper presents a procedure for scale-bridging modeling of coal devolatilization, in the presence of experimental error, that puts emphasis on the thermodynamic aspect of devolatilization, namely the final volatile yield of coal, rather than kinetics. The procedure consists of an engineering approach based on dataset consistency and Bayesian methodology including Gaussian-Process Regression (GPR). Experimental data from devolatilization tests carried out in an oxy-coal entrained flow reactor were considered and CFD simulations of the reactor were performed. Jointly evaluating experiments and simulations, a novel yield model was validated against the data via consistency analysis. In parallel, a Gaussian-Process Regression was performed, to improve the understanding of the uncertainty associated to the devolatilization, based on the experimental measurements. Potential model forms that could predict yield during devolatilization were obtained. The set of model forms obtained via GPR includes the yield model that was proven to be consistent with the data. Finally, the overall procedure has resulted in a novel yield model for coal devolatilization and in a valuable evaluation of uncertainty in the data, in the model form, and in the model parameters.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Upgraded Coal and Coal Waste to Graphite for Lithium-Ion Battery Applications

Presentation to the Fortieth Annual International Pittsburgh Coal Conference, Istanbul, Turkiye, October 4–6, 2023. To assist in meeting the global graphite supply limitations, this study aims to investigate efficient ways to synthesize high-quality graphite from abundant coal and coal waste resources that exist in many areas around the world. A recently developed upgraded coal-to-products (UCP) process has shown great promise in the ability to reduce coal-borne impurities and produce a graphitizable product that yields good quality graphite for LIB applications. Preliminary results show that the quality of coal-derived graphite obtained by the UCP process is similar to that of commercial LIB-grade graphite. Available results are presented and discussed as well as maturation plans and flexibility of the UCP technology.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2016

Constitution of Drop-Tube-Generated Coal Chars from Vitrinite- and Inertinite-Rich South African Coals

The structural transformations of coal and the resultant char morphologies are strongly dependent on the initial structure and degree of thermoplasticity achieved during coal-to-char transition. These are a function of petrographic composition, rank, particle size, and heating rate and strongly affect combustion behavior. This study compares the devolatilization and subsequent combustion behavior of an inertinite-rich (87.7% dmmf) and a vitrinite-rich (91.8% dmmf) South African coal, wet-screened to a narrow particle size distribution of 200 x 400 mesh. Pyrolysis chars were generated under rapid-heating conditions (104-105 °C/s) in a drop-tube reactor to closely resemble chars generated in pulverized combustion conditions. The inertinite-rich coal took ~ 400 ms to devolatilize in the drop-tube, compared to only ~ 240 ms for the vitrinite-rich sample. The chemical and physical structure (the constitution) of the chars were investigated through a range of chemical, physical, and optical characteristics including the maceral differences, and high ash yields. To evaluate the combustion reactivity non-isothermal burn-out profiles were obtained through thermogravimetrical analyses (TGA) in air. The vitrinite-rich char had on average 20% higher reaction rates than the inertinite-rich char under the various combustion conditions. The char samples were de-ashed with HCl and HF acid which resulted in an increase in combustion reactivity. The maximum reaction rate of the high-ash (36% ash yield) inertinite-rich char increased with 80% after de-ashing. While the vitrinite-rich char with an ash yield of 15%, had a 20% increase in reactivity after de-ashing. The ash acted as a barrier, and the removal of ash most likely increased the access to reactive surface area. The chemical and physical structures of the chars were characterized through a range of different analytical techniques to quantify the factors contributing to reactivity differences. The morphologies of the chars were characterized with SEM and optical microscopy, while quantitative information on the ordered nature of chars was obtained through XRD on de-ashed chars. The inertinite-rich coal experienced limited fluidity during heat-treatment, resulting in slower devolatilization, limited growth in crystallite height (11.8 to 12.6Å), only rounding of particle edges, and producing > 40% of mixed-dense type chars. The vitrinite-char showed more significant structural transformations; producing mostly (80%) extensively swollen crassisphere, tenuisphere, and network-type chars, and XRD showed a large increase in crystallite height (4.3 to 11.7Å). Nitrogen adsorption and small-angle X-ray scattering (SAXS) were utilized to compare the nitrogen surface areas and pore size distributions. Both chars were mostly mesoporous but the inertinite-rich char had double the average pore size, which also resulted in a larger nitrogen surface area since nitrogen can only access surface areas in larger pores. The BET surface area was 3.9 and 2.7 m2/g for the inertinite- and vitrinite-rich chars respectively. SAXS data showed that the vitrinite-rich char had 60% higher frequencies of pores in the micropore range. Helium porosimetry indicated that the inertinite-rich coal and resultant char had higher densities than the vitrinite coal and char; 1.6 and 2.0 g/cm3, compared to 1.3 and 1.9 g/cm3 (dry basis). Non-isothermal TGA burnout profiles showed the inertinite-rich char had a burnout temperature of 680°C, slightly higher than the vitrinite-rich char’s 650 °C. This, along with the peak shape and position in the burnout profiles indicate that the vitrinite-rich char has a higher reactivity. The higher reactivity is due to a combination of factors likely including less organization, grater porosity and access to the reactive site, less ash blocking, and char morphology differences.

Combustion↗
NASA NTRS1978

Remote sensing of strippable coal reserves and mine inventory in part of the Warrior Coal Field in Alabama

Methods by which estimates of the remaining reserves of strippable coal in Alabama could be made were developed. Information acquired from NASA's Earth Resources Office was used to analyze and map existing surface mines in a four-quadrangle area in west central Alabama. Using this information and traditional methods for mapping coal reserves, an estimate of remaining strippable reserves was derived. Techniques for the computer analysis of remotely sensed data and other types of available coal data were developed to produce an estimate of strippable coal reserves for a second four-quadrangle area. Both areas lie in the Warrior coal field, the most prolific and active of Alabama's coal fields. They were chosen because of the amount and type of coal mining in the area, their location relative to urban areas, and the amount and availability of base data necessary for this type of study.

Joiner, T. J.↗
DOE OSTI2025

Sustainable recovery of Rare Earth Elements (REEs) from coal and coal ash through urban mining: A Nature Based Solution (NBS) for circular economy

The demand for rare earth elements (REEs) has surged in recent years, driven by their crucial role in various industrial applications and their uneven geological distribution. As a result, urban mining from secondary resources, particularly coal and coal ash, has gained traction as a sustainable solution within a circular economy framework. This study highlights the significant presence of REEs in coal and coal ash, revealing that certain samples contain REE concentrations that rival traditional ores. Notably, coal ash has the potential to yield approximately 312,000 tons of REEs annually, far exceeding global demand. The research delves into advanced techniques for analyzing REEs, including elemental, isotopic, and mineralogical studies. Additionally, it explores innovative extraction methods such as the use of green solvents, nature-based solutions, and bioleaching and biosorption. By leveraging coal and its byproducts as secondary resources, this study underscores the opportunity to reduce dependence on conventional mining, enhancing the sustainability of REE recovery. Here, a comprehensive literature review was conducted to highlight technological advancements and emerging opportunities that can address current challenges in this field.

Circular economy↗
DOE OSTI2023

Using National-Scale Data to Inform Coal Power Plant Redevelopment and Coal Community Revitalization Planning

In the United States, individual coal plants have high variation in their construction and operation. Coal plants commonly have multiple units, with different commissioning ages, operational position, and maintenance conditions – even multiple fuels. These units may be in changing states of utilization, with variation in productivity depending on economic contexts. Coal plants themselves may be temporarily offline, mothballed, retired, or decommissioned due to owner/operator portfolios or market conditions, and the current posture of the plant may be difficult to ascertain without local news sources (Tarekegne et al. 2021). Anticipated dates of plant closures are prospectively represented to regulators and to the Energy Information Administration (EIA), but may also experience uncertainty due to the engineering, environmental, economic and social complexity of closing a very large power plant. As noted in this report, closure of the first unit to the last within a single plant may span more than 20 years. Yet tracking and predicting the position of our nation’s coal fleets on a national scale is deeply important. In developing a case for federal datasets and an approach to building and curating these data, this report identified that data must have high fidelity at the plant-level to be meaningful in aggregate. Plant-scale detail is also a match for its application: national priorities in federal investment range from economic revitalization for coal plant communities to maintaining reliable electric grid operations. This document is organized into a statistical review of coal plant retirements, past and prospective, in the United States; trends in the relationship between closures and existing federal investment programs for community revitalization; and potential methods for accelerating site redevelopment through advanced geospatial analysis based on federal data.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2017

A Diaminopropane-Appended Metal–Organic Framework Enabling Efficient CO 2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism

Here, a new diamine-functionalized metal-organic framework comprised of 2,2-dimethyl-1,3-diaminopropane (dmpn) appended to the Mg 2+ sites lining the channels of Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) is characterized for the removal of CO 2 from the flue gas emissions of coal-fired power plants. Unique to members of this promising class of adsorbents, dmpn-Mg2(dobpdc) displays facile step-shaped adsorption of CO 2 from coal flue gas at 40 °C and near complete CO 2 desorption upon heating to 100 °C, enabling a high CO 2 working capacity (2.42 mmol/g, 9.1 wt %) with a modest 60 °C temperature swing. Evaluation of the thermodynamic parameters of adsorption for dmpn-Mg 2 (dobpdc) suggests that the narrow temperature swing of its CO 2 adsorption steps is due to the high magnitude of its differential enthalpy of adsorption (Δh ads = -73 ± 1 kJ/mol), with a larger than expected entropic penalty for CO 2 adsorption (Δs ads = -204 ± 4 J/mol·K) positioning the step in the optimal range for carbon capture from coal flue gas. In addition, thermogravimetric analysis and breakthrough experiments indicate that, in contrast to many adsorbents, dmpn-Mg 2 (dobpdc) captures CO 2 effectively in the presence of water and can be subjected to 1000 humid adsorption/desorption cycles with minimal degradation. Solid-state 13 C NMR spectra and single-crystal X-ray diffraction structures of the Zn analogue reveal that this material adsorbs CO 2 via formation of both ammonium carbamates and carbamic acid pairs, the latter of which are crystallographically verified for the first time in a porous material. Taken together, these properties render dmpn-Mg 2 (dobpdc) one of the most promising adsorbents for carbon capture applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Economical and Environmentally Benign Extraction of Rare Earth Elements (REES) from Coal & Coal Byproducts

This final report provides a complete summary of the activities, results, analytical discussion, and overall evaluation of the project titled “Economical and Environmentally Benign Extraction of Rare Earth Elements (REES) from Coal & Coal Byproducts” under DOE Award Number DE-FE-0027155 that started in March 2016 and ended December 2017. Fly ash was selected as the coal-byproduct source material due to fact that it is readily available with no need for extensive methods to obtain the material, it is produced in large quantities (>50 million tons per year) and had REE concentrations similar to other coal-byproducts. The selected fly ash used throughout this project was from the Mill Creek power generating facility operated by Louisville Gas and Electric located in Louisville, KY and was subjected to a variety of physical and chemical characterization tests. Results from fusion extractions showed that the selected fly-ash had a TREE+Y concentration of 480 ppm with critical REEs concentration of 200 ppm. The fly ash had an outlook ratio of 1.25 and an estimated value of $16-$18 worth of salable REEs per 1-tonne of fly ash. Additional characterizations by optical evaluation, QEMSCAN, XRD, size fractionation, and SEM analysis showed the fly ash consisted of small glassy spherules with a size range between 1 to 110 µm (ave. diam. of 13 um), was heterogeneous in chemical composition (main crystalline phases: aluminum oxides and iron oxides) and was primarily an amorphous material (75 to 80%). A simple stepped approach was completed to estimate the total REE resource quantity. The approach included REE characterization of the representative samples, evaluation of fly-ash availability, and final determination estimated resource availability with regards to REE grade on a regional and national scale. This data represents the best available information and is based upon the assumptions that the power generating facility where the fly-ash was obtained will use the same coal sources (actual mines were identified), the coal materials will have relatively consistent REE concentrations, and the REE extraction process developed during this project can achieve 42% REE recovery (validated and confirmed). Calculations indicated that the estimated REE resource is approximately 175,000 tonnes with a current estimated value of $3,330MM. The proposed REE extraction and production process developed during this project used four fundamental steps; 1) fly-ash pretreatment to enhance REE extraction, 2) REE extraction by acid digestion, 3) REE separation/concentration by carbon adsorption and column chromatography, and 4) REE oxide production. Secondary processing steps to manage process residuals and additional processing techniques to produce value-added products were incorporated into the process during the project. These secondary steps were not only necessary to manage residuals, but also provided additional revenue streams that offset operational and capital expenditures. The process produces one value product stream (production of zeolite Na-P1), a solids waste stream, and one liquid stream that met RCRA discharge requirements. Based upon final design criteria and operational parameters, the proposed system could produce approximately 200 grams of REOs from 1-tonne of fly-ash, thereby representing a TREE+Y recovery of 42% (project target of > 25%). A detailed economic model was developed to evaluate both CAPEX and OPEX estimates for systems with varying capacities between 100 kg to 200 tonnes of fly ash processed per day. Using a standard system capacity of 10 tonne/day system, capital costs were estimated at $88/kg fly ash while operating costs were estimated at approximately $450/kg fly ash. This operating cost estimate includes a revenue of $495/tonne of fly ash processed from the value-added product produced from the system (zeolite Na-P1). Although operating cost savings due to zeolite production were significant, the capital + operating cost for a 10 tonne system was more expensive than the total dollar value of REEs present in the fly ash material. Specifically, the estimated cost per 1-tonne of fly ash treated is approximately $540 while the estimated value of REEs in the fly ash is $18-$20/tonne. This is an excessive difference showing that the proposed process is not economically feasible strictly on the basis of REE revenue compared to extraction costs. Although the current proposed system does not produce sufficient quantities of REEs or additional revenue sources to offset operational and capital costs, supplementary factors including US strategic concerns, commercial demands, and defense department requirements must be factored. At this time, the process developed during this project provides foundational information for future development of simple processes that require low capital investment and one that will extract a valuable quality and quantity of REE oxides from industrial waste.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2019

A Field Survey of Rare Earth Element Concentrations in Process Streams Produced by Coal Preparation Plants in the Eastern USA

I this work, 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).

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2016

CFD-aided benchmark assessment of coal devolatilization one-step models in oxy-coal combustion conditions

Coal devolatilization, as first step in thermochemical processes involving solid fuels, has been targeted in plenty of CFD investigations: despite the variety of models that were developed to define the rate of the process and the amount of volatile matter released, not all of them are suitable for CFD simulations of large-scale coal combustors. Empirical models ensure both simplicity and feasibility, but not full reliability for all coal types and operating conditions. CFD modeling results for coal conversion during devolatilization in an entrained flow reactor and oxy-conditions are presented and compared to experimental data. A benchmark assessment of one-step models on the accuracy of the volatile yield prediction is then performed. It is shown that the heating rate strongly influences the devolatilization process and its modeling, not only in terms of rate but also in terms of yield, which differs significantly from the proximate analysis value. Furthermore, this indicates the need for a model able to predict the variation of coal volatile yield with temperature and heating rate, in addition to the kinetic model.

01 COAL, LIGNITE, AND PEAT↗