Evaluation Of Rare Earth Element Extraction From North Dakota Coal-Related Feed Stocks

The rare earth elements consist of the lanthanide series of elements with atomic numbers from 57-71 and also include yttrium and scandium. Due to their unique properties, rare earth elements are crucial materials in an incredible array of consumer goods, energy system components and military defense applications. However, the global production and entire value chain for rare earth elements is dominated by China, with the U.S. currently 100% import reliant for these critical materials. Traditional mineral ores including previously mined deposits in the U.S., however, have several challenges. Chief among these is that the content of the most critical and valuable of the rare earths are deficient, making mining uneconomical. Further, the supply of these most critical rare earths is nearly 100% produced in China from a single resource that is only projected to last another 10 to 20 years. The U.S. currently considers the rare earths market an issue of national security. It is imperative that alternative domestic sources of rare earths be identified and methods developed to produce them. Recently, coal and coal byproducts have been identified as one of these promising alternative resources. This dissertation details a study on evaluation of the technical and economic feasibility of rare earth element recovery from North Dakota lignite coal and lignite-related feedstocks. There were four major goals of this study: i) identify lignite or lignite-related feedstocks with total rare earth element content above 300 parts per million, a threshold dictated by the agency who funded this research as the minimum for economic viability, ii) determine the geochemistry of the feedstocks and understand the forms and modes of occurrence of the rare earth elements, information necessary to inform the development of extraction and concentration methods, iii) identify processing methods to concentrate the rare earth elements from the feedstocks to a target of two weight percent, a value that would be sufficient to leverage existing separation and refining methods developed for the traditional mineral ore industry, and iv) develop a process that is economically viable and environmentally benign. To achieve these overall goals, and to prove or disprove the research hypotheses, the research scope was broken down into three main efforts: i) sampling and characterization of potential feedstocks, ii) laboratory-scale development and testing of rare earth element extraction and concentration methods, and iii) process design and technical and economic feasibility evaluation. In total, 174 unique samples were collected, and several locations were identified that exceeded the 300 ppm total rare earth elements target. The results showed that on a whole sample basis, the rare earths are most concentrated in the clay-rich sediments associated with the coal seams, but on an ash basis in certain locations within certain coal seams the content is significantly higher, an unexpected finding given prior research. At Falkirk Mine near Underwood, North Dakota three coal seams were found to have elevated levels of rare earths, ranging from about 300 to 600 ppm on an ash basis. Additionally, exceptionally high rare earths content was found in samples collected from an outcropping of the Harmon-Hansen coal zone in southwestern North Dakota that contained 2300 ppm on an ash basis. The results dictated that extraction and concentration methods be developed for these rare earth element-rich coals, instead of the mineral-rich sediments. This effort also found that that at a commercial-scale, due to non-uniformity of the rare earths content stratigraphically in the coal seams, selective mining practices will be needed to target specific locations within the seams. The bulk mining and blending practices as Falkirk Mine result in a relatively low total rare earths content in the feed coal entering the Coal Creek Power Station adjacent to the mine. Characterization of the coal samples identified that the predominant modes of rare earths occurrence in the lignite coals are associations with the organic matter, primarily as coordination complexes and a lesser amount as ion-exchangeable cations on oxygen functional groups. Overall it appears that about 80-95% of rare earths content in North Dakota lignite is organically associated, and not present in mineral forms, which due to the weak organic bonding, presented a unique opportunity for extraction. The process developed for extraction of rare earths was applied to the raw lignite coals instead of fly ash or other byproducts being investigated extensively in the literature. Rather, the process uses a dilute acid leaching process to strip the organically associated rare earths from the lignite with very high efficiency of about 70-90% at equilibrium contact times. Although the extraction kinetics are quite fast given commercial leaching operations, there is some tradeoff between extraction efficiency and contact time. However, at shorter contact time there is improved rare earths selectivity that results in a more concentrated product due to limiting extraction of unwanted impurities. There is also a significant difference in the extraction kinetics for the more valuable heavier molecular weight rare earths, which are much faster than the light rare earths. The testing showed that in a one-step process consisting of leaching for two hours with 0.5M sulfuric acid at 40°C, a rare earth concentrate of about 1.4 weight percent rare earths could be achieved with about 70% total rare earths extraction, while also producing a residual coal byproduct that has superior qualities to the feed coal, such as reduced ash content. This represents a concentration factor of 24 over the feed coal. The target of two weight percent rare earths could be achieved by a number of secondary processing methods, such as pH modification or forced air oxidation to selectively precipitate impurities from the rare earths-containing solution. The process developed in this study is simple, highly effective, low cost and novel, with several differentiating benefits compared to methods being developed in the literature. These are made possible by the unique properties of North Dakota lignite coals and the weakly-bonded organic association of the rare earth elements. Key differentiators include the use of the raw coal as the feedstock, the ability to use a mild leaching process, and not needing extensive physical beneficiation processes prior to rare earths extraction. The process is environmentally benign and was demonstrated to be economically viable at the current market conditions. Due to the use of the raw coal as the feedstock, the process can be advantageously integrated with any number of coal utilization processes to augment economics, lower costs and maximize efficiency and synergies. This study evaluated a configuration of rare earths extraction combined with activated carbon production co-located at a combined heat and power facility, and was shown to have highly attractive economics even at small scales representing a first-of-a-kind demonstration system

Leaching Behavior of Rare Earth Elements in Fort Union Lignite Coals of North America

Fort Union lignite coal samples were subjected to a series of aqueous leaching experiments to understand the extraction behavior of the rare earth elements (REE). This testing was aimed at understanding the modes of occurrence of the REE in the lignite coals, as well as to provide foundational data for development of rare earth extraction processes. In a first series of tests, a sequential leaching process was used to investigate modes of occurrence of the REE of select lignite coals. The tests involved sequential exposure to solvents consisting of water, ammonium acetate and dilute hydrochloric acid (HCl). The results indicated that water and ammonium acetate extracted very little of the REE, indicating the REE are not present as water soluble or ion-exchangeable forms. However, the data shows that a large percentage of the REE were extracted with the hydrochloric acid (80-95wt%), suggesting presence in HCl-soluble mineral forms such as carbonates, and/or presence as organic complexes. A second series of tests was performed involving single-step leaching with dilute acids and various operating parameters, including acid type, acid concentration, acid/coal contact time and coal particle size. For select samples, additional tests were performed to understand the results of leaching, including float-sink density separations and humic acid extraction. The results have shown that the majority of REE in Fort Union lignites appear to be associated weakly with the organic matrix of the coals, most likely as coordination complexes of carboxylic acid groups. The light REE and heavy REE exhibit different behaviors, however. The extractable light REE appear to have association both in acid-soluble mineral forms and as organic complexes, whereas the extractable heavy REE appear to be almost solely associated with the organics. Scandium behavior was notably different than yttrium and the lanthanides, and the data suggests the extractable content is primarily associated as acid-soluble mineral forms