SYSTEMS AND PROCESSES FOR RECOVERY OF HIGH-GRADE RARE EARTH CONCENTRATE FROM ACID MINE DRAINAGE
In one aspect, the disclosure relates to a continuous process for treating acid mine drainage while simultaneously recovering a high-grade rare earth preconcentrate suitable for extraction of commercially valuable rare earth oxides. In a further aspect, the preconcentrate is from about 0.1% to 5% rare earth elements on a dry weight basis. In another aspect, the disclosure relates to a method for processing the preconcentrate to generate a pregnant leach solution that does not form gels or emulsions and is suitable for processing via solvent extraction. In another aspect, the disclosure relates to a system and plant for carrying out the disclosed process. In still another aspect, the disclosure relates to a composition containing rare earth elements produced by the process disclosed herein. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.
This application claims the benefit of U.S. Provisional Application No. 62/875,502, filed on Jul. 17, 2019, and U.S. Utility application Ser. No. 16/795,471, filed Feb. 19, 2020, each of which is incorporated herein by reference in its entirety.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENTThis invention was made with U.S. Government support under grant number DE-FE0031524 awarded by the U.S. Department of Energy. The U.S. government has certain rights in the invention.
BACKGROUNDRare earth elements (REEs) are useful and necessary for the manufacture of batteries that power hybrid and electric vehicles, catalytic converters, computer memory, fluorescent lighting and lasers, smartphones and tablet computers, cameras including electronic components and lenses, e-readers, magnets, night-vision goggles, GPS and communications equipment, military applications including precision-guided weapons and vehicle armor, aircraft engines, personal protective equipment, and in other applications including defense applications. Some REEs can be used in air pollution control mechanisms, oil refineries, in medical diagnostic equipment such as, for example, X-ray and MRI machines, as phosphors, as catalysts, as components of ceramics and paints, and/or as polishing compounds. Although REEs and critical minerals (CM) can be extracted from many waste products and ores, few such resources are economically attractive. Due to current and possibly continuing export controls for REEs from China, it would be desirable to develop domestic sources of REEs.
Acid mine drainage (AMD) is a pollutant generated by coal and other mines and must be treated in compliance with federal and state clean water regulations to adjust pH and remove metal ions including iron, aluminum, and manganese. There are vast instances of acid mine drainage (AMD) in the northern, central, and southern Appalachian basins, as well as the Illinois coal basin and elsewhere in the U.S. Across the northern and central Appalachian Coal Basins, water pollution caused by AMD is the single greatest cause of stream impairment. Processes for treating AMD for regulatory compliance have been the subject of massive research and infrastructure investments since the early 1970s. It is estimated that, in the Appalachian states alone, more than 50 new, large AMD treatment plants will be installed in the next 10 years, in an effort to address increasing stream pollution. Although trace amounts of REEs are known to exist in AMD, a reliable method of concentrating and extracting them has not yet been developed.
Despite advances in the treatment of acid mine drainage, there is still a scarcity of methods that are able to recover REEs from AMD and that are environmentally sound, inexpensive, scalable, and able to be retrofitted to existing plants. Ideally, the method would produce insignificant amounts of naturally-occurring radioactive material and/or other noxious wastes as well as reducing stream pollution. Additionally, it would be desirable if the method could be adapted to extract REEs from other sources. It would also be advantageous for the process to operate continuously and without forming insoluble material such as, for example, aluminosilicate gels. It would further be desirable to have a domestic source of REEs. These needs and other needs are satisfied by the present disclosure.
SUMMARYIn accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to a continuous process for treating acid mine drainage to comply with Clean Water Act requirements while simultaneously recovering a high-grade rare earth concentrate suitable for extraction of commercially valuable rare earth oxides. In a further aspect, the high-grade rare earth preconcentrate is from about 0.1% to about 5% total REE on a dry weight basis. Also disclosed herein is a method for processing the rare earth preconcentrate to generate a pregnant leach solution that does not form gels or emulsions and that is suitable for processing via solvent extraction. In another aspect, disclosed herein is a system that includes a plant capable of carrying out the method disclosed herein. In yet another aspect, disclosed herein is a composition containing the REEs prepared by the disclosed process.
Other systems, methods, features, and advantages of the present disclosure will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. In addition, all optional and preferred features and modifications of the described embodiments are usable in all aspects of the disclosure taught herein. Furthermore, the individual features of the dependent claims, as well as all optional and preferred features and modifications of the described embodiments are combinable and interchangeable with one another.
Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
DETAILED DESCRIPTIONMany modifications and other embodiments disclosed herein will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein.
Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure.
Any recited method can be carried out in the order of events recited or in any other order that is logically possible. That is, unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.
All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation.
While aspects of the present disclosure can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present disclosure can be described and claimed in any statutory class.
It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.
Prior to describing the various aspects of the present disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in the present disclosure.
DefinitionsAs used herein, “comprising” is to be interpreted as specifying the presence of the stated features, integers, steps, or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Moreover, each of the terms “by”, “comprising,” “comprises”, “comprised of,” “including,” “includes,” “included,” “involving,” “involves,” “involved,” and “such as” are used in their open, non-limiting sense and may be used interchangeably. Further, the term “comprising” is intended to include examples and aspects encompassed by the terms “consisting essentially of” and “consisting of.” Similarly, the term “consisting essentially of” is intended to include examples encompassed by the term “consisting of.
As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a rare earth element” includes, but is not limited to, mixtures of two or more such rare earth elements, and the like.
It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. For example, if the value “about 10” is disclosed, then “10” is also disclosed.
When a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’. The range can also be expressed as an upper limit, e.g. ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘less than x’, less than y′, and ‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y′, and ‘greater than z’. In addition, the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”.
It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1% to 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range.
As used herein, the terms “about,” “approximate,” “at or about,” and “substantially” mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In such cases, it is generally understood, as used herein, that “about” and “at or about” mean the nominal value indicated ±10% variation unless otherwise indicated or inferred. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about,” “approximate,” or “at or about” whether or not expressly stated to be such. It is understood that where “about,” “approximate,” or “at or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
As used herein, the term “effective amount” refers to an amount that is sufficient to achieve the desired modification of a physical property of the composition or material. For example, an “effective amount” of a buffer refers to an amount that is sufficient to achieve the desired improvement in the property modulated by the formulation component, e.g. achieving and maintaining a desired solution pH. The specific level in terms of wt % in a composition required as an effective amount will depend upon a variety of factors including the amount and type of buffer, size of processing plant (i.e., bench top, mobile, or commercial scale), amount and type of feedstock being treated, and end use of the REEs recovered during the process.
As used herein, the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
As used herein, the term “rare earth element” (REE) is refers to a composition comprising one or more rare earth elements, including one or more of a lanthanide chemical element, i.e., lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium. and can sometimes also include the elements scandium and yttrium. The elements scandium and yttrium often occur in the same ore deposits as lanthanides and also have some similar chemical properties. Rare earth elements are useful in a variety of applications in the electronics, defense, and medical industries, as well as in other applications. An oxide of a rare earth element is a “rare earth oxide” and can be used for analytical purposes or may be useful as a component of ceramics, catalysts, and/or coatings, among other uses. It is to be understood that when referencing rare earth elements that any of the elements can be present in a zero valence or elemental state, or in an ionized or valence state associated in the art with the individual element, and all forms are understood to be collectively included within the meaning of “rare earth elements”. Moreover, it is to be understood that reference to any individual rare earth element, i.e., any one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, including scandium and yttrium, can be present in a zero valence or elemental state, or in an ionized or valence state associated in the art with the given element, and all forms are understood to be collectively included within the meaning of reference to said element. For example, reference to “lanthanum”, “an element such as lanthanum”, “a composition comprising lanthanum”, and the like, it is understood that the reference inclusive any or all forms of lanthanum such as La0, La+1, La+2, and La+3. It is further understood that a reference to any given rare earth element is inclusive of all isotopic forms of the element.
As used herein, the terms “heavy rare earth elements” and “HREE” can be used interchangeably and refer to yttrium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. It is to be understood that yttrium can be classified as a heavy rare earth element due to chemical properties and co-location with other HREEs in ores, but can also be yttrium is classified as a light rare earth element due to its lower atomic weight.
As used herein, the terms “light rare earth elements” and “LREE” can be used interchangeably and refer to scandium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium. In some aspects, these designations may differ slightly but are generally based on atomic weight.
As used herein, the term “total rare earth elements” and “TREE” can be used interchangeably and refer the total REE present in a disclosed composition or product of a disclosed process, method, or device, wherein the REE comprises
“Critical minerals” (CM) as used herein include minerals important to national security and the economy. REEs are considered critical minerals due to their numerous industrial uses. Other critical minerals may also be purified and concentrated using the disclosed process including, but not limited to, cobalt, gallium, germanium, hafnium, indium, niobium, rhenium, rubidium, tantalum, and tellurium.
As used herein, “gangue” metals and other materials are undesired materials that surround or are co-located with the REEs being isolated and concentrated by the disclosed process. In one aspect, in the present process, gangue material can include, but is not limited to, aluminum, calcium, magnesium, manganese, silicon, chloride, and the like. In some aspects, gangue materials may have little or no economic value. In other aspects, gangue materials may have industrial uses but their presence alongside more valuable REEs can complicate the recovery of the REEs.
“Acid mine drainage” (AMD) as used herein refers to acidic water that outflows from mines such as, for example, metal mines or coal mines. In one aspect, AMD intensifies in scale and scope when construction, mining, and other activities that disturb the earth occur in and around rocks containing sulfide minerals. AMD can have high concentrations of metal ions that can cause detrimental effects to aquatic environments, especially in combination with low pH. AMD from coal mines and other sources often contains trace amounts of REEs, as well.
“AMD precipitate” (AMDp) as used herein refers to a byproduct of AMD treatment. In one aspect, AMDp contains REEs but may also contain gangue metals such as, for example, iron and aluminum. In one aspect, AMDp contains from about 0.06% to about 0.1% REE. As used herein, “enriched AMD precipitate” (eAMDp) refers to an AMD product having from about 0.1% to about 5% REE on a dry weight basis. In another aspect, eAMDp has a lower gangue metal content then AMDp.
A “feedstock” as used herein is a raw material processed to recover REEs and other valuable components (e.g., CMs). A feedstock may be too toxic to release into the natural environment and, in one aspect, the disclosed process can remove commercially valuable components from the feedstock while simultaneously rendering the feedstock suitable for environmental release.
As used herein, “pregnant leach solution” (PLS) is water with an acidic pH and a high metal content. In one aspect, PLS can be processed using several purification technologies including, but not limited to, solvent extraction, ion exchange resins, selective precipitation, and fractional crystallization to remove and/or concentrate the metals. In some aspects, PLS may have a high solids content and may require filtration prior to further processing.
“Raffinate,” meanwhile, refers to a product of chemical separation, wherein one or more components have been removed. In one aspect, following solvent extraction as disclosed herein, raffinate is the aqueous component depleted in REE content. In another aspect, raffinate can include undesired gangue material.
As used herein, “GEOTUBE®” refers to a dewatering device made from a polypropylene fabric that can be produced according to the needs of a particular project or industry. In one aspect, sludge or other material to be separated is pumped into a GEOTUBE® container and a fabric liner keeps solids trapped inside while filtrate water escapes and can be directed to a treatment facility.
Unless otherwise specified, temperatures referred to herein are based on atmospheric pressure (i.e. one atmosphere).
Pregnant Leach Solution (PLS) Composition.In various aspects, the present disclosure pertains to a pregnant leach solution (“PLS”) composition, e.g., a PLS composition, obtained from an acid mine discharge (“AMD”) feedstock material using the disclosed processes, methods, and systems. In a further aspect, the disclosed PLS composition is enriched in one or more REE material compared to the AMD feedstock material used. The disclosed PLS composition can be used in further steps, as disclosed herein, to further enrich or purify one or more REE material.
In a further aspect, the PLS composition can vary depending on the composition of the AMD feedstock used. Representative average values that were experimentally determined for multiple PLS compositions prepared using the disclosed processes, methods, and devices are shown in Tables 1.1 below.
Further representative average values that were experimentally determined for multiple PLS compositions prepared using the disclosed processes, methods, and devices are shown in Table 2 below.
In a further aspect, the PLS composition comprises TREE present at a concentration of at least about 10 mg/L, about 11 mg/L, about 12 mg/L, about 13 mg/L, about 14 mg/L, about 15 mg/L, about 16 mg/L, about 17 mg/L, about 18 mg/L, about 19 mg/L, about 20 mg/L, about 21 mg/L, about 22 mg/L, about 23 mg/L, about 24 mg/L, about 25 mg/L, about 26 mg/L, about 27 mg/L, about 28 mg/L, about 29 mg/L, about 30 mg/L, about 31 mg/L, about 32 mg/L, about 33 mg/L, about 34 mg/L, about 35 mg/L, about 36 mg/L, about 37 mg/L, about 38 mg/L, about 39 mg/L, about 40 mg/L, about 41 mg/L, about 42 mg/L, about 43 mg/L, about 44 mg/L, about 45 mg/L, about 46 mg/L, about 47 mg/L, about 48 mg/L, about 49 mg/L, about 50 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values; wherein it is understood that the TREE comprises at least three of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of at least about 10 mg/L, about 11 mg/L, about 12 mg/L, about 13 mg/L, about 14 mg/L, about 15 mg/L, about 16 mg/L, about 17 mg/L, about 18 mg/L, about 19 mg/L, about 20 mg/L, about 21 mg/L, about 22 mg/L, about 23 mg/L, about 24 mg/L, about 25 mg/L, about 26 mg/L, about 27 mg/L, about 28 mg/L, about 29 mg/L, about 30 mg/L, about 31 mg/L, about 32 mg/L, about 33 mg/L, about 34 mg/L, about 35 mg/L, about 36 mg/L, about 37 mg/L, about 38 mg/L, about 39 mg/L, about 40 mg/L, about 41 mg/L, about 42 mg/L, about 43 mg/L, about 44 mg/L, about 45 mg/L, about 46 mg/L, about 47 mg/L, about 48 mg/L, about 49 mg/L, about 50 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values; wherein it is understood that the TREE comprises at least four of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of at least about 10 mg/L, about 11 mg/L, about 12 mg/L, about 13 mg/L, about 14 mg/L, about 15 mg/L, about 16 mg/L, about 17 mg/L, about 18 mg/L, about 19 mg/L, about 20 mg/L, about 21 mg/L, about 22 mg/L, about 23 mg/L, about 24 mg/L, about 25 mg/L, about 26 mg/L, about 27 mg/L, about 28 mg/L, about 29 mg/L, about 30 mg/L, about 31 mg/L, about 32 mg/L, about 33 mg/L, about 34 mg/L, about 35 mg/L, about 36 mg/L, about 37 mg/L, about 38 mg/L, about 39 mg/L, about 40 mg/L, about 41 mg/L, about 42 mg/L, about 43 mg/L, about 44 mg/L, about 45 mg/L, about 46 mg/L, about 47 mg/L, about 48 mg/L, about 49 mg/L, about 50 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values; wherein it is understood that the TREE comprises at least five of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of at least about 10 mg/L, about 11 mg/L, about 12 mg/L, about 13 mg/L, about 14 mg/L, about 15 mg/L, about 16 mg/L, about 17 mg/L, about 18 mg/L, about 19 mg/L, about 20 mg/L, about 21 mg/L, about 22 mg/L, about 23 mg/L, about 24 mg/L, about 25 mg/L, about 26 mg/L, about 27 mg/L, about 28 mg/L, about 29 mg/L, about 30 mg/L, about 31 mg/L, about 32 mg/L, about 33 mg/L, about 34 mg/L, about 35 mg/L, about 36 mg/L, about 37 mg/L, about 38 mg/L, about 39 mg/L, about 40 mg/L, about 41 mg/L, about 42 mg/L, about 43 mg/L, about 44 mg/L, about 45 mg/L, about 46 mg/L, about 47 mg/L, about 48 mg/L, about 49 mg/L, about 50 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values; wherein it is understood that the TREE comprises at least six of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of at least about 10 mg/L, about 11 mg/L, about 12 mg/L, about 13 mg/L, about 14 mg/L, about 15 mg/L, about 16 mg/L, about 17 mg/L, about 18 mg/L, about 19 mg/L, about 20 mg/L, about 21 mg/L, about 22 mg/L, about 23 mg/L, about 24 mg/L, about 25 mg/L, about 26 mg/L, about 27 mg/L, about 28 mg/L, about 29 mg/L, about 30 mg/L, about 31 mg/L, about 32 mg/L, about 33 mg/L, about 34 mg/L, about 35 mg/L, about 36 mg/L, about 37 mg/L, about 38 mg/L, about 39 mg/L, about 40 mg/L, about 41 mg/L, about 42 mg/L, about 43 mg/L, about 44 mg/L, about 45 mg/L, about 46 mg/L, about 47 mg/L, about 48 mg/L, about 49 mg/L, about 50 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values; wherein it is understood that the TREE comprises at least seven of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of at least about 10 mg/L, about 11 mg/L, about 12 mg/L, about 13 mg/L, about 14 mg/L, about 15 mg/L, about 16 mg/L, about 17 mg/L, about 18 mg/L, about 19 mg/L, about 20 mg/L, about 21 mg/L, about 22 mg/L, about 23 mg/L, about 24 mg/L, about 25 mg/L, about 26 mg/L, about 27 mg/L, about 28 mg/L, about 29 mg/L, about 30 mg/L, about 31 mg/L, about 32 mg/L, about 33 mg/L, about 34 mg/L, about 35 mg/L, about 36 mg/L, about 37 mg/L, about 38 mg/L, about 39 mg/L, about 40 mg/L, about 41 mg/L, about 42 mg/L, about 43 mg/L, about 44 mg/L, about 45 mg/L, about 46 mg/L, about 47 mg/L, about 48 mg/L, about 49 mg/L, about 50 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values; wherein it is understood that the TREE comprises at least eight of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of at least about 10 mg/L, about 11 mg/L, about 12 mg/L, about 13 mg/L, about 14 mg/L, about 15 mg/L, about 16 mg/L, about 17 mg/L, about 18 mg/L, about 19 mg/L, about 20 mg/L, about 21 mg/L, about 22 mg/L, about 23 mg/L, about 24 mg/L, about 25 mg/L, about 26 mg/L, about 27 mg/L, about 28 mg/L, about 29 mg/L, about 30 mg/L, about 31 mg/L, about 32 mg/L, about 33 mg/L, about 34 mg/L, about 35 mg/L, about 36 mg/L, about 37 mg/L, about 38 mg/L, about 39 mg/L, about 40 mg/L, about 41 mg/L, about 42 mg/L, about 43 mg/L, about 44 mg/L, about 45 mg/L, about 46 mg/L, about 47 mg/L, about 48 mg/L, about 49 mg/L, about 50 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values; wherein it is understood that the TREE comprises at least nine of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of at least about 10 mg/L, about 11 mg/L, about 12 mg/L, about 13 mg/L, about 14 mg/L, about 15 mg/L, about 16 mg/L, about 17 mg/L, about 18 mg/L, about 19 mg/L, about 20 mg/L, about 21 mg/L, about 22 mg/L, about 23 mg/L, about 24 mg/L, about 25 mg/L, about 26 mg/L, about 27 mg/L, about 28 mg/L, about 29 mg/L, about 30 mg/L, about 31 mg/L, about 32 mg/L, about 33 mg/L, about 34 mg/L, about 35 mg/L, about 36 mg/L, about 37 mg/L, about 38 mg/L, about 39 mg/L, about 40 mg/L, about 41 mg/L, about 42 mg/L, about 43 mg/L, about 44 mg/L, about 45 mg/L, about 46 mg/L, about 47 mg/L, about 48 mg/L, about 49 mg/L, about 50 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values; wherein it is understood that the TREE comprises at least ten of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of at least about 10 mg/L, about 11 mg/L, about 12 mg/L, about 13 mg/L, about 14 mg/L, about 15 mg/L, about 16 mg/L, about 17 mg/L, about 18 mg/L, about 19 mg/L, about 20 mg/L, about 21 mg/L, about 22 mg/L, about 23 mg/L, about 24 mg/L, about 25 mg/L, about 26 mg/L, about 27 mg/L, about 28 mg/L, about 29 mg/L, about 30 mg/L, about 31 mg/L, about 32 mg/L, about 33 mg/L, about 34 mg/L, about 35 mg/L, about 36 mg/L, about 37 mg/L, about 38 mg/L, about 39 mg/L, about 40 mg/L, about 41 mg/L, about 42 mg/L, about 43 mg/L, about 44 mg/L, about 45 mg/L, about 46 mg/L, about 47 mg/L, about 48 mg/L, about 49 mg/L, about 50 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values; wherein it is understood that the TREE comprises lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises three or more of the following materials in the indicated amounts: Sc present at a concentration of from about 0.05 mg/L to about 1 mg/L; Y present at a concentration of from about 0.5 mg/L to about 10 mg/L; La present at a concentration of from about 0.05 mg/L to about 5 mg/L; Ce present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; Pr present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; Nd present at a concentration of from about 0.5 mg/L to about 10 mg/L; Sm present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; Eu present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Gd present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tb present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Dy present at a concentration of from about 0.1 mg/L to about 5 mg/L; Ho present at a concentration of from about 0.05 mg/L to about 2 mg/L; Er present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tm present at a concentration of from about 0.05 mg/L to about 2 mg/L; Yb present at a concentration of from about 0.05 mg/L to about 5 mg/L; and Lu present at a concentration of from about 0.01 mg/L to about 1 mg/L; or a sub-range within any of the foregoing ranges; or one or more discrete values within any of the foregoing ranges.
In a further aspect, the PLS composition comprises TREE present at a concentration of about 5 mg/L to 100 mg/L, 5 mg/L to 95 mg/L, 5 mg/L to 85 mg/L, 5 mg/L to 80 mg/L, 5 mg/L to 75 mg/L, 5 mg/L to 70 mg/L, 5 mg/L to 65 mg/L, 5 mg/L to 60 mg/L, 5 mg/L to 55 mg/L, 5 mg/L to 50 mg/L, 5 mg/L to 45 mg/L, 5 mg/L to 40 mg/L; or a sub-range within any of the foregoing ranges; or any set of the values with the foregoing ranges; wherein it is understood that the TREE comprises at least three of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of about 5 mg/L to 100 mg/L, 5 mg/L to 95 mg/L, 5 mg/L to 85 mg/L, 5 mg/L to 80 mg/L, 5 mg/L to 75 mg/L, 5 mg/L to 70 mg/L, 5 mg/L to 65 mg/L, 5 mg/L to 60 mg/L, 5 mg/L to 55 mg/L, 5 mg/L to 50 mg/L, 5 mg/L to 45 mg/L, 5 mg/L to 40 mg/L; or a sub-range within any of the foregoing ranges; or any set of the values with the foregoing ranges; wherein it is understood that the TREE comprises at least four of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of about 5 mg/L to 100 mg/L, 5 mg/L to 95 mg/L, 5 mg/L to 85 mg/L, 5 mg/L to 80 mg/L, 5 mg/L to 75 mg/L, 5 mg/L to 70 mg/L, 5 mg/L to 65 mg/L, 5 mg/L to 60 mg/L, 5 mg/L to 55 mg/L, 5 mg/L to 50 mg/L, 5 mg/L to 45 mg/L, 5 mg/L to 40 mg/L; or a sub-range within any of the foregoing ranges; or any set of the values with the foregoing ranges; wherein it is understood that the TREE comprises at least five of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of about 5 mg/L to 100 mg/L, 5 mg/L to 95 mg/L, 5 mg/L to 85 mg/L, 5 mg/L to 80 mg/L, 5 mg/L to 75 mg/L, 5 mg/L to 70 mg/L, 5 mg/L to 65 mg/L, 5 mg/L to 60 mg/L, 5 mg/L to 55 mg/L, 5 mg/L to 50 mg/L, 5 mg/L to 45 mg/L, 5 mg/L to 40 mg/L; or a sub-range within any of the foregoing ranges; or any set of the values with the foregoing ranges; wherein it is understood that the TREE comprises at least six of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of about 5 mg/L to 100 mg/L, 5 mg/L to 95 mg/L, 5 mg/L to 85 mg/L, 5 mg/L to 80 mg/L, 5 mg/L to 75 mg/L, 5 mg/L to 70 mg/L, 5 mg/L to 65 mg/L, 5 mg/L to 60 mg/L, 5 mg/L to 55 mg/L, 5 mg/L to 50 mg/L, 5 mg/L to 45 mg/L, 5 mg/L to 40 mg/L; or a sub-range within any of the foregoing ranges; or any set of the values with the foregoing ranges; wherein it is understood that the TREE comprises at least seven of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of about 5 mg/L to 100 mg/L, 5 mg/L to 95 mg/L, 5 mg/L to 85 mg/L, 5 mg/L to 80 mg/L, 5 mg/L to 75 mg/L, 5 mg/L to 70 mg/L, 5 mg/L to 65 mg/L, 5 mg/L to 60 mg/L, 5 mg/L to 55 mg/L, 5 mg/L to 50 mg/L, 5 mg/L to 45 mg/L, 5 mg/L to 40 mg/L; or a sub-range within any of the foregoing ranges; or any set of the values with the foregoing ranges; wherein it is understood that the TREE comprises at least eight of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of about 5 mg/L to 100 mg/L, 5 mg/L to 95 mg/L, 5 mg/L to 85 mg/L, 5 mg/L to 80 mg/L, 5 mg/L to 75 mg/L, 5 mg/L to 70 mg/L, 5 mg/L to 65 mg/L, 5 mg/L to 60 mg/L, 5 mg/L to 55 mg/L, 5 mg/L to 50 mg/L, 5 mg/L to 45 mg/L, 5 mg/L to 40 mg/L; or a sub-range within any of the foregoing ranges; or any set of the values with the foregoing ranges; wherein it is understood that the TREE comprises at least nine of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of about 5 mg/L to 100 mg/L, 5 mg/L to 95 mg/L, 5 mg/L to 85 mg/L, 5 mg/L to 80 mg/L, 5 mg/L to 75 mg/L, 5 mg/L to 70 mg/L, 5 mg/L to 65 mg/L, 5 mg/L to 60 mg/L, 5 mg/L to 55 mg/L, 5 mg/L to 50 mg/L, 5 mg/L to 45 mg/L, 5 mg/L to 40 mg/L; or a sub-range within any of the foregoing ranges; or any set of the values with the foregoing ranges; wherein it is understood that the TREE comprises at least ten of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises TREE present at a concentration of about 5 mg/L to 100 mg/L, 5 mg/L to 95 mg/L, 5 mg/L to 85 mg/L, 5 mg/L to 80 mg/L, 5 mg/L to 75 mg/L, 5 mg/L to 70 mg/L, 5 mg/L to 65 mg/L, 5 mg/L to 60 mg/L, 5 mg/L to 55 mg/L, 5 mg/L to 50 mg/L, 5 mg/L to 45 mg/L, 5 mg/L to 40 mg/L; or a sub-range within any of the foregoing ranges; or any set of the values with the foregoing ranges; wherein it is understood that the TREE comprises lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In a further aspect, the PLS composition comprises four or more of the following materials in the indicated amounts: Sc present at a concentration of from about 0.05 mg/L to about 1 mg/L; Y present at a concentration of from about 0.5 mg/L to about 10 mg/L; La present at a concentration of from about 0.05 mg/L to about 5 mg/L; Ce present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; Pr present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; Nd present at a concentration of from about 0.5 mg/L to about 10 mg/L; Sm present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; Eu present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Gd present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tb present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Dy present at a concentration of from about 0.1 mg/L to about 5 mg/L; Ho present at a concentration of from about 0.05 mg/L to about 2 mg/L; Er present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tm present at a concentration of from about 0.05 mg/L to about 2 mg/L; Yb present at a concentration of from about 0.05 mg/L to about 5 mg/L; and Lu present at a concentration of from about 0.01 mg/L to about 1 mg/L; or a sub-range within any of the foregoing ranges; or one or more discrete values within any of the foregoing ranges.
In a further aspect, the PLS composition comprises fiver or more of the following materials in the indicated amounts: Sc present at a concentration of from about 0.05 mg/L to about 1 mg/L; Y present at a concentration of from about 0.5 mg/L to about 10 mg/L; La present at a concentration of from about 0.05 mg/L to about 5 mg/L; Ce present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; Pr present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; Nd present at a concentration of from about 0.5 mg/L to about 10 mg/L; Sm present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; Eu present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Gd present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tb present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Dy present at a concentration of from about 0.1 mg/L to about 5 mg/L; Ho present at a concentration of from about 0.05 mg/L to about 2 mg/L; Er present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tm present at a concentration of from about 0.05 mg/L to about 2 mg/L; Yb present at a concentration of from about 0.05 mg/L to about 5 mg/L; and Lu present at a concentration of from about 0.01 mg/L to about 1 mg/L; or a sub-range within any of the foregoing ranges; or one or more discrete values within any of the foregoing ranges.
In a further aspect, the PLS composition comprises six or more of the following materials in the indicated amounts: Sc present at a concentration of from about 0.05 mg/L to about 1 mg/L; Y present at a concentration of from about 0.5 mg/L to about 10 mg/L; La present at a concentration of from about 0.05 mg/L to about 5 mg/L; Ce present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; Pr present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; Nd present at a concentration of from about 0.5 mg/L to about 10 mg/L; Sm present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; Eu present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Gd present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tb present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Dy present at a concentration of from about 0.1 mg/L to about 5 mg/L; Ho present at a concentration of from about 0.05 mg/L to about 2 mg/L; Er present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tm present at a concentration of from about 0.05 mg/L to about 2 mg/L; Yb present at a concentration of from about 0.05 mg/L to about 5 mg/L; and Lu present at a concentration of from about 0.01 mg/L to about 1 mg/L; or a sub-range within any of the foregoing ranges; or one or more discrete values within any of the foregoing ranges.
In a further aspect, the PLS composition comprises seven or more of the following materials in the indicated amounts: Sc present at a concentration of from about 0.05 mg/L to about 1 mg/L; Y present at a concentration of from about 0.5 mg/L to about 10 mg/L; La present at a concentration of from about 0.05 mg/L to about 5 mg/L; Ce present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; Pr present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; Nd present at a concentration of from about 0.5 mg/L to about 10 mg/L; Sm present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; Eu present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Gd present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tb present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Dy present at a concentration of from about 0.1 mg/L to about 5 mg/L; Ho present at a concentration of from about 0.05 mg/L to about 2 mg/L; Er present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tm present at a concentration of from about 0.05 mg/L to about 2 mg/L; Yb present at a concentration of from about 0.05 mg/L to about 5 mg/L; and Lu present at a concentration of from about 0.01 mg/L to about 1 mg/L; or a sub-range within any of the foregoing ranges; or one or more discrete values within any of the foregoing ranges.
In a further aspect, the PLS composition comprises eight or more of the following materials in the indicated amounts: Sc present at a concentration of from about 0.05 mg/L to about 1 mg/L; Y present at a concentration of from about 0.5 mg/L to about 10 mg/L; La present at a concentration of from about 0.05 mg/L to about 5 mg/L; Ce present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; Pr present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; Nd present at a concentration of from about 0.5 mg/L to about 10 mg/L; Sm present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; Eu present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Gd present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tb present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Dy present at a concentration of from about 0.1 mg/L to about 5 mg/L; Ho present at a concentration of from about 0.05 mg/L to about 2 mg/L; Er present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tm present at a concentration of from about 0.05 mg/L to about 2 mg/L; Yb present at a concentration of from about 0.05 mg/L to about 5 mg/L; and Lu present at a concentration of from about 0.01 mg/L to about 1 mg/L; or a sub-range within any of the foregoing ranges; or one or more discrete values within any of the foregoing ranges.
In a further aspect, the PLS composition comprises nine or more of the following materials in the indicated amounts: Sc present at a concentration of from about 0.05 mg/L to about 1 mg/L; Y present at a concentration of from about 0.5 mg/L to about 10 mg/L; La present at a concentration of from about 0.05 mg/L to about 5 mg/L; Ce present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; Pr present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; Nd present at a concentration of from about 0.5 mg/L to about 10 mg/L; Sm present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; Eu present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Gd present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tb present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Dy present at a concentration of from about 0.1 mg/L to about 5 mg/L; Ho present at a concentration of from about 0.05 mg/L to about 2 mg/L; Er present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tm present at a concentration of from about 0.05 mg/L to about 2 mg/L; Yb present at a concentration of from about 0.05 mg/L to about 5 mg/L; and Lu present at a concentration of from about 0.01 mg/L to about 1 mg/L; or a sub-range within any of the foregoing ranges; or one or more discrete values within any of the foregoing ranges.
In a further aspect, the PLS composition comprises ten or more of the following materials in the indicated amounts: Sc present at a concentration of from about 0.05 mg/L to about 1 mg/L; Y present at a concentration of from about 0.5 mg/L to about 10 mg/L; La present at a concentration of from about 0.05 mg/L to about 5 mg/L; Ce present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; Pr present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; Nd present at a concentration of from about 0.5 mg/L to about 10 mg/L; Sm present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; Eu present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Gd present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tb present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Dy present at a concentration of from about 0.1 mg/L to about 5 mg/L; Ho present at a concentration of from about 0.05 mg/L to about 2 mg/L; Er present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tm present at a concentration of from about 0.05 mg/L to about 2 mg/L; Yb present at a concentration of from about 0.05 mg/L to about 5 mg/L; and Lu present at a concentration of from about 0.01 mg/L to about 1 mg/L; or a sub-range within any of the foregoing ranges; or one or more discrete values within any of the foregoing ranges.
In a further aspect, the PLS composition comprises the following materials in the indicated amounts: Sc present at a concentration of from about 0.05 mg/L to about 1 mg/L; Y present at a concentration of from about 0.5 mg/L to about 10 mg/L; La present at a concentration of from about 0.05 mg/L to about 5 mg/L; Ce present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; Pr present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; Nd present at a concentration of from about 0.5 mg/L to about 10 mg/L; Sm present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; Eu present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Gd present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tb present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; Dy present at a concentration of from about 0.1 mg/L to about 5 mg/L; Ho present at a concentration of from about 0.05 mg/L to about 2 mg/L; Er present at a concentration of from about 0.1 mg/L to about 5 mg/L; Tm present at a concentration of from about 0.05 mg/L to about 2 mg/L; Yb present at a concentration of from about 0.05 mg/L to about 5 mg/L; and Lu present at a concentration of from about 0.01 mg/L to about 1 mg/L; or a sub-range within any of the foregoing ranges; or one or more discrete values within any of the foregoing ranges.
In a further aspect, the disclosed PLS composition comprises Fe a lower concentration than present in the AMD feedstock. In a still further aspect, the disclosed PLS composition comprises Fe at a concentration less than about 25 mg/L, about 24 mg/L, about 23 mg/L, about 20 mg/L, about 19 mg/L, about 18 mg/L, about 17 mg/L, about 16 mg/L, about 15 mg/L, about 14 mg/L, about 13 mg/L, about 12 mg/L, about 10 mg/L, about 9 mg/L, about 8 mg/L, about 7 mg/L, about 6 mg/L, about 5 mg/L; or a range having a lower limit of essentially about 0 mg/L to an upper limit that is any of the foregoing values; or a range having a lower limit of essentially about 5 mg/L to an upper limit that is any of the foregoing values; or a range having a lower limit of essentially about 7.5 mg/L to an upper limit that is any of the foregoing values; or any combination of the foregoing values.
In a further aspect, the disclosed PLS composition comprises thorium and uranium present in a total concentration of less than about 10 mg/L, about 9 mg/L, about 8 mg/L, about 7 mg/L, about 6 mg/L, about 5 mg/L, about 4 mg/L, about 3 mg/L, about 2 mg/L, about 1 mg/L, about 0.9 mg/L, about 0.8 mg/L, about 0.7 mg/L, about 0.6 mg/L, about 0.5 mg/L, about 0.4 mg/L, about 0.3 mg/L, about 0.2 mg/L, about 0.1 mg/L; or a range encompassed by any two of the foregoing values; or any set of the foregoing values.
In a further aspect, the disclosed PLS composition comprises cobalt in an amount of about 1 mg/L to about 30 mg/L, about 1 mg/L to about 25 mg/L, about 1 mg/L to about 20 mg/L, about 1 mg/L to about 15 mg/L, about 5 mg/L to about 30 mg/L, about 5 mg/L to about 25 mg/L, about 5 mg/L to about 20 mg/L, about 5 mg/L to about 15 mg/L, about 10 mg/L to about 30 mg/L, about 10 mg/L to about 25 mg/L, about 10 mg/L to about 20 mg/L, about 10 mg/L to about 15 mg/L, about 15 mg/L to about 30 mg/L, about 15 mg/L to about 25 mg/L, about 15 mg/L to about 20 mg/L, about 20 mg/L to about 30 mg/L, about 20 mg/L to about 25 mg/L; or a sub-range within any of the foregoing ranges; or a set of values within any of the foregoing ranges.
In a further aspect, the disclosed PLS composition comprises about 50 wt % to about 80 wt % cobalt, about 55 wt % to about 80 wt % cobalt, about 60 wt % to about 80 wt % cobalt, about 65 wt % to about 80 wt % cobalt, about 70 wt % to about 80 wt % cobalt, about 50 wt % to about 85 wt % cobalt, about 55 wt % to about 85 wt % cobalt, about 60 wt % to about 85 wt % cobalt, about 65 wt % to about 85 wt % cobalt, about 70 wt % to about 85 wt % cobalt, about 50 wt % to about 90 wt % cobalt, about 55 wt % to about 90 wt % cobalt, about 60 wt % to about 90 wt % cobalt, about 65 wt % to about 90 wt % cobalt, about 70 wt % to about 90 wt % cobalt; or any sub-range within the foregoing ranges; or any set of values within the foregoing ranges.
Process for an Enriched Pregnant Leach Solution from Acid Mine Discharge.
In one aspect, the present disclosure relates to processes for providing a pregnant leach solution (“PLS”) enriched in REE materials, in which the feedstock for the process is an acid mine discharge (“AMD”) feedstock. In a further aspect, the PLS can be utilized, as disclosed herein, in a solvent extraction process, or other suitable purification technology, as disclosed herein, and to obtain one or more REE that is further purified or enriched.
In a further aspect, the disclosed processes comprise the following steps: (1) transfer raw AMD feedstock to a separator; (2) aerate feedstock and add an effective amount of at least one base to the separator to raise the resultant mixture pH; (3) optionally add an effective amount of one or more flocculating and/or coagulating agent; (4) separate solid and aqueous phases, and discard solids; (5) optionally, if recovering scandium, transfer the aqueous phase from the preceding step to a separator and add an effective amount of base to raise resultant solution pH, followed by (5)(a) optionally, add an effective amount of coagulating and/or flocculating agents; and then, (5)(b) separate solid and aqueous phases and collect Sc-enriched solid concentrate; (6) transfer the aqueous phase from step (4) or from optional step (5) to a separator; (7) add an effective amount of at least one base to raise resultant mixture pH; (8) optionally add an effective amount of one or more flocculating and/or coagulating agent; (9) discharge effluent and collect REE-enriched pre-concentrate; (10) dewater pre-concentrate and transfer dewatered REE-enriched pre-concentrate to a mixer; (11) add an effective amount of at least one acid to lower resultant solution pH, and optionally add an effective amount of one or more oxidizing agents; (12) optionally add an effective amount of one or more flocculating and/or coagulating agent; (13) transfer resultant solution to from the preceding step a filtration apparatus, filter, and discard residual solids retained by the filter; (14) transfer resultant filtrate solution from the preceding step to a mixer; (15) add an effective amount of at least one base to raise resultant solution pH; (16) transfer resultant solution to a filtration apparatus, filter, and discard residual solids retained by the filter; and (17) the resultant pregnant leach solution (PLS) may be stored. In a further aspect, the PLS may be utilized in a solvent extraction process, or other suitable purification technology, as disclosed herein, and to obtain one or more REE that is further purified or enriched.
In one aspect, feedstock useful in step 1 can include raw AMD. In a further aspect, distribution of REE and major elements in 155 AMD sources in the Northern and Central Appalachian coal basins are provided in Table 2 below.
In a further aspect, feedstocks with the compositional ranges in Table 1 are useful in the process disclosed herein. In one aspect, AMD can be the feedstock for the disclosed process; however, other feedstocks are also contemplated. In one aspect, the feedstocks useful herein do not include high levels of uranium, thorium, or other hazardous components.
In one aspect, the process disclosed can utilize an AMD feedstock with a pH of from less than 2 to less than about 5.5, or of about less than 2, 2.5, 3, 3.5, 4, 4.5, 5, or 5.5. In one aspect, the feedstock pH is less than 3. In another aspect, the feedstock pH is less than 2. A typical distribution of AMD REE concentrations as a function of pH can be seen in
In one aspect, in step 2 as disclosed above, an effective amount of at least one base is an amount sufficient to raise the resultant mixture pH to about 4 to about 4.5, or at least about 4, 4.1, 4.2, 4.3, 4.4, or about 4.5, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In a further aspect, the base can be NaOH, KOH, ammonia or ammonium hydroxide, calcium pellets, quicklime, lime slurry, or a combination thereof. In one aspect, the base is lime slurry.
In a further aspect, in step 4 as disclosed above, the discarded solids can comprise iron or aluminum and/or other gangue metals with similar chemical and physical properties.
In one aspect, if scandium is being recovered and step 5 in the disclosed process is being performed, when base is added, the desired resultant pH can be from about 4.9 to about 5.1, or about 4.9, 5.0, or about 5.1, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In a further aspect, the base can be NaOH, KOH, ammonia or an ammonium compound, calcium pellets, quicklime, lime slurry, or a combination thereof. In one aspect, the base is lime slurry.
In one aspect, in step 7 as disclosed above, an effective amount of at least one base is an amount sufficient to raise the resultant mixture pH to about 8 to about 8.5, or at least about 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, or about 8.7, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In a further aspect, the base can be NaOH, KOH, ammonia or ammonium hydroxide, calcium pellets, quicklime, lime slurry, or a combination thereof. In one aspect, the base is lime slurry. In one aspect, a higher pH from within the disclosed range may aid in recovering additional cobalt.
In one aspect, in step 11 as disclosed above, the desired resultant pH is from about 0.5 to about 3.2, or is about 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, or about 3.2, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In some aspects, pH in this step can be chosen based on economic considerations such as, for example, sales value of product versus cost of acid added in this step. In another aspect, various acids are contemplated in this step including, but not limited to, sulfuric acid, nitric acid, hydrochloric acid, or a combination thereof. In one aspect, the acid is nitric acid. In another aspect, the acid is hydrochloric acid.
In a further aspect, acid contact with the feedstock, raw material, or AMDp/eAMDp preconcentrate occurs in a reactor that is open to the atmosphere. In another aspect, this step can be conducted at room temperature. In a still further aspect, prior to acid addition, the feedstock, raw material, or AMDp/eAMDp preconcentrate can be contacted with water while mixing to create a slurry. In a yet further aspect, the slurry is mixed with acid in step 11 as described above with continuous mixing to dissolve the REEs out of the solid feedstock.
In a further aspect, as noted above, optionally step 11 can further comprise addition of an oxidizing agent. In a still further aspect, the step 11 comprises the addition of an oxidizing agent, such that this aspect is not an optional aspect. In a still further aspect, the oxidizing agent can be hydrogen peroxide. Without wishing to be bound by a particular theory, it is believed that the addition of an oxidizing agent can enhance the efficiency of gangue metal separation from REE in the aqueous phase. It is believed, moreover, without wishing to be bound by theory, the reducing agent may precipitate iron and manganese hydroxides from the PLS. In a further aspect, and without wishing to be bound by theory, filtration at an acidic pH in this step prevents the formation of aluminosilicate gels and/or emulsions. It is believed, in addition, without wishing to be bound by a particular theory, it is believed that gels and emulsions can prevent downstream steps of the process from proceeding to completion and can interfere with pumping and mixing. In an even further aspect, an effective amount of an oxidizing agent can be added to based on the equation:
H2O2=Df(Fe+(2Mn)),
where:
-
- H2O2=hydrogen peroxide (moles)
- Df=design factor
- Fe=total iron (moles)
- Mn=total manganese (moles)
such that Df has a value of about 1.05 to about 1.7, about 1.1 to about 1.6, about 1.2 to about 1.5; or a sub-range within the foregoing ranges; or a value or set of values within any of the foregoing ranges.
In any of the above aspects, mixers in any step that requires a mixer can be connected in sequence to aid in product transfer from one mixer to the next. In some aspects, any of the above processes can be conducted partially (i.e., not to completion) if it is desired to reduce cost.
In a further aspect, in step 12, as disclosed above,
In one aspect, in step 13 as disclosed above, residual solids discarded in this step can include a large portion of silicon. In a further aspect, step 13 removes essentially all silicon from the feedstock. In a further aspect, a filter or other separation mechanism such as, for example, a plate and frame filter press, can be used to separate solids from liquid. In a further aspect, solids are retained in the filter or filter press, which is then cleaned and can be re-used. In some aspects, the filtering component can be made from or lined with polypropylene cloth.
In another aspect, in step 15 as disclosed above, the desired resultant solution pH can be from about 2.8 to about 3, or can be about 2.8, 2.85, 2.9, 2.95, or about 3, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In some aspects, when HCl is used as the acid in step 13, MgO may be a suitable base for use in step 15. In other aspects, other bases can be used including, but not limited to, NaOH, KOH, ammonia or ammonium hydroxide, calcium pellets, quicklime, lime slurry, or a combination thereof. In one aspect, the base is NaOH.
In one aspect, in step 16 as disclosed herein, residual solids discarded typically include iron. In a further aspect, step 13 removes essentially all iron from the feedstock. In a further aspect, a filter or other separation mechanism such as, for example, a filter press or a plate and frame filter press, can be used to separate solids from liquid. In a further aspect, solids are retained in the filter or filter press, which is then cleaned and can be re-used. In some aspects, the filtering component can be made from or lined with polypropylene cloth. In some aspects, an oxidizing agent can optionally be used in step 13 to convert ferrous iron to ferric iron, which, without wishing to be bound by theory, may help with precipitation of iron compounds. In a further aspect, the oxidizing compound can be hydrogen peroxide or another chemical oxidizer. In an alternative aspect, mechanical or electrochemical oxidation can be used.
A flow diagram of the disclosed process can be seen in
Full-Scale Unit Construction. In one aspect, disclosed herein is a full-scale AMD treatment plant with an integrated REE/CM recovery operation. In a further aspect, potential alterations to the treatment plant can include, but are not limited to: (1) staged precipitation using multiple clarifiers/thickeners in series; (2) independent pH control in each clarifier; and (3) additional materials handling and filtration units to recover and dewater the REE-enriched concentrates.
In a further aspect, to augment the traditional AMD treatment system, a state-of-the-art automation and control system to remotely monitor key operating parameters is disclosed herein. In another aspect, this package can provide real-time measurements of pump and mixer motor conditions, pH measurements, select ion concentrations, and other variables. In still another aspect, these values can be logged in an archival data format and used for feedback loop control.
In one aspect, all parts of the process disclosed herein can be conducted while following all pertinent local, state and federal regulations. In another aspect, upon completion of the construction activities a safety analysis/review can be performed prior to equipment startup and shakedown.
Full-Scale Unit Operation. In one aspect, disclosed herein are the following parameters for full-scale operation of an upstream concentrator as disclosed herein: (1) the specific locations of sampling points within the system and expected consistency of those samples (liquid, solid, or slurry); (2) the specific procedures for obtaining, handling, transporting, and storing various sample types; (3) the expected frequency and extent of sample collection for both routine and intensive analysis; (4) the specific protocols for analyzing samples and interpreting the resultant data; and (5) the protocols for retaining and archiving samples.
In one aspect, disclosed herein is a test matrix to gather performance data under different operating conditions while ensuring that the final water discharge meets National Pollutant Discharge Elimination System (NPDES) permit requirements. In a further aspect, the test matrix is based on results from the small-scale unit evaluation and includes expected variations in AMD flow and REE concentration that follow seasonal variations throughout the calendar year. In a further aspect, these natural variations can be tracked over time and used to evaluate the robustness and resiliency of the REE/CM enrichment process.
In a further aspect, after identifying and validating the optimal process operational parameters, the upstream concentrator will be operated continuously at those settings. In one aspect, REE/CM preconcentrates generated during this time will be collected into 55-gallon drums or geotextile super sacks and stored for future testing in the disclosed downstream processing units.
Acid Leaching/Solvent Extraction.System Design. In one aspect, disclosed herein is a system that processes the preconcentrates generated from the large-scale upstream concentration unit. Further in this aspect, the system includes, but is not limited to: (1) a mass-balanced process flowsheet, (2) piping and instrumentation diagrams, (3) a proposed facility layout, (4) a construction cost estimate based on vendor quotes, (5) a daily operational cost estimate, and (6) final engineering drawings of the pilot-scale plant.
In one aspect, the pilot-scale facility is co-located with the upstream concentrator at the host site. Further in this aspect, this location has adequate access to water, power, and other utilities that will be required for the pilot-scale system. In still another aspect, only minimal changes to the facility will be required prior to system commissioning.
System Procurement, Construction, and Installation. In one aspect, site preparation may include clearing unnecessary equipment, reinforcing foundations or structures, and/or adding mechanical and electrical utilities. In a further aspect, these initial preparations ensure that equipment installation and assembly can be completed in a timely manner. In a still further aspect, fabricated components and final equipment can be shipped directly to the host site.
System Shakedown, Training, and Troubleshooting. In one aspect, the primary safety hazard expected herein is the use of strong acids in the leaching and solvent extraction units. At a minimum, acid resistant gloves and gowns and adequate ventilation in the testing area can be used to minimize risk to personnel, as will laboratory safety and chemical hygiene training.
In one aspect, a series of shakedown tests will be conducted to identify and resolve operational issues that may arise during the detailed system testing. In a further aspect, shakedown testing can provide an opportunity to mitigate these issues while providing key operational data that can support a detailed test campaign. In a still further aspect, specific goals of this testing program include, but are not limited to: (1) verify vendor specifications on capacity and power; (2) ensure the sufficiency of various ancillary equipment and utilities; (3) identify the operational limits to be used in detailed system testing. In a still further aspect, shakedown testing can be conducted by operating all unit operations under “water-only” conditions to first ensure the structural integrity of the process units. Further in this aspect, after water-only testing, solids can be slowly incorporated into the test regimen to ensure the adequacy of valves, pumps, and other fittings. In another aspect, strong acids and other chemicals can be added only after the system has been proven in these more benign conditions.
In one aspect, disclosed herein is a state-of-art real time monitoring and control system that can provide real-time measurements of pump and mixer motor conditions, pH measurements, select ion concentrations, and other variables. In a further aspect, these values can be logged in an archival data format and used for feedback loop control. In still another aspect, this task also includes all troubleshooting needed to ensure consistent and safe operation of the pilot-scale system.
System Parametric Testing. In one aspect, using feedstocks produced from previous stages of the process disclosed herein, acid leaching and solvent extraction tests can be conducted over an extended operating period. In another aspect, each experimental condition may require at least 64 hours of continuous testing, and the solvent extraction (SX) operation is anticipated to run continuously for 24 hours per day. In still another aspect, the specific items to be analyzed during this test campaign may include but are not limited to: (1) the influence of SX extractant type and concentration; (2) the influence of SX solvent type and ratio; (3) the influence of extracting and stripping acid type and pH; (4) the number of extracting and stripping stages needed to reach the target purity level. In another aspect, provided herein are pathways to remove non-target impurities and optimize the process with regards to separation efficiency, solvent recycling, and waste minimization. In one aspect, a test matrix can be generated using a statistical design of experiments, and specific conditions can be blocked and repeated to assess experimental error while mitigating the influence of covariates, such as ambient environmental conditions. In yet another aspect, results from this experimental design can be analyzed using a response surface methodology to identify the optimal conditions leading to the highest recovery and selectivity.
Alternative Feedstock Testing.In one aspect, after meeting objectives using the preferred AMD feedstock, other feedstocks can be evaluated in the ALSX pilot plant. In a further aspect, specific examples include, but are not limited to, AMD treatment sludges, coal refuse and under clays, fly ash and gasification char, other REE-enriched coal byproducts, and combinations thereof.
Laboratory Support and Testing.In one aspect, both aqueous and solid samples can be routinely analyzed for REE/CM, major gangue metals, trace gangue metals, and CMs. In a further aspect, REE aqueous concentrations can be determined using inductively coupled plasma-mass spectrometry (ICP-MS). In a still further aspect, solid samples can be digested by sodium peroxide (Na2O2) fusion and re-dissolution in hydrochloric acid and resulting aqueous analysis can then be undertaken using ICP-MS. In one aspect, major ions such as iron (Fe) and aluminum (Al) will be determined by a suitable technique such as, for example, inductively coupled plasma optical emission spectrometry (ICP-OES).
In yet another aspect, a broad scan of feedstocks can be used to identify other CMs and, if economically attractive, ensure that the disclosed ALSX process is modified for their recovery.
Economic Systems Analysis.In one aspect, experimental results from the various testing campaigns as well as model results from the system design optimization can be compiled into a techno-economic analysis (TEA). Further in this aspect, the analysis can report costs and performance at the existing scale and project those costs to the next design scale and/or a commercial implementation using standard scaling factors and itemized costs as appropriate. In one aspect, all analyses will use guidelines and assumptions provided by the National Energy Technology Laboratory (NETL), and results will be presented in accordance with NI 43-101 reporting standards for disclosing mineral projects. In any of these aspects, at a minimum, this analysis will include: a clear statement of the assumptions; cash forecasts on an annual basis; a discussion of potential net present value (NPV) and internal rate of return (IRR); a summary of the tax structure imposed; and a sensitivity analysis with respect to grade, price, and other significant input factors.
Environmental Systems Analysis.In one aspect, an environmental systems analysis can be conducted concurrently with the other project activities and may focus on two specific objectives: materials handling considerations and environmental compliance. In one aspect, the materials handling design will address the dewatering, filtration, and the short- and long-term material storage requirements for the upstream concentration process. In one aspect, specific research tasks to be addressed for the material handling system design include, but are not limited to:
-
- 1. In one aspect, the following elements for the woven geotextile GEOTUBE® bags proposed for the first and second splits have been explored at field scale: engineering strength and permittivity design, GEOTUBE® proportion sizing (length and diameter ratios), GEOTUBE® stacking configurations and techniques to ensure safe and environmentally benign dewatering operations.
- 2. In another aspect process treatment requirements for the GEOTUBE® water filtrate, primary liquid containment, liquid transport design and layout, and geotechnical material characterization consisting of material testing for physical, strength and permeability properties will be determined.
- 3. In another aspect, a series of numerical modeling activities can be performed for mathematical characterization of drainage in the system and the potential improvements. The outcome of the modeling is to compare and contrast with the laboratory testing and field results.
- 4. In still another aspect, increasing process efficiency can be studied to identify and reduce barriers to future technology entry into the REE/CM commercialization. Further in this aspect, one specific area for efficiency improvement is sediment dewatering of the feedstock from splits 2 and 3, and the iron-rich sediment from split 1.
In one aspect, using hydrometallurgical methods in the disclosed process at the bench scale, we produced a concentrate with 80% rare earth oxides from AMD treatment sludge (
In one aspect, we have evaluated extraction of REE/CM from AMD treatment precipitates and from untreated AMD. In one aspect, unprocessed AMD treatment solids can be transported to a central acid leaching/solvent extraction (ALSX) facility for final processing into a high grade mixed rare earth oxide (MREO). In an alternative aspect, a field concentrate can be extracted and dewatered upstream of a conventional AMD treatment plant and transported to the ALSX facility. In a further aspect, the process disclosed herein can accept and produce an REE/CM concentrate from either source.
Now having described the aspects of the present disclosure, in general, the following Examples describe some additional aspects of the present disclosure. While aspects of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intent to limit aspects of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure.
REFERENCESThe following references are cited herein throughout.
- Ref 1. Stumm, W., and Morgan, J. J. 1995. Aquatic Chemistry, Chemical Equilibria and Rates in Natural Waters, 3rd ed. Hoboken, N.J.: John Wiley & Sons, Inc.: 1022 pp.
- Ref 2. Kim, E and Osseo-Asare, K. 2012. “Aqueous stability of thorium and rare earth metals in monazite hydrometallurgy: Eh-pH diagrams for the systems Th—, Ce—, La—, Nd—(PO4)-(SO4)-H2O at 25° C.,” Hydrometallurgy, 113-114:67-78.
- Ref 3. Pourbaix, M., 1966. Atlas of electrochemical equilibrium in aqueous solution. New York, N.Y.:Pergamon.
- Ref 4. Bourricaudy, Ernesto et al. 2016. “Commissioning of a Mini SX Pilot Plant at SGS Minerals—Lakefield Site”. In: IMPC 2016: XXVIII International Mineral Processing Congress Proceedings. Quebec, Canada: pp. 1-16.
- Ref 5. Chiarizia, Renato and Alexandra Briand, 2007. “Third phase formation in the extraction of inorganic acids by TBP in n-Octane,” Solvent Extraction and Ion Exchange, 25:351-371.
- Ref 6. Kedari, C S et al., 2006. “Third Phase Formation in the Solvent Extraction System Ir (IV)— Cyanex 923,” Solvent Extraction and Ion Exchange, 23:545-559.
- Ref 7. Koermer, Scott and Aaron Noble (2018). “Unpublished Solvent Extraction Research”. PhD thesis. Virginia Polytechnic University.
- Ref 8. Ren, Panpan, 2019. “Recovery of Rare Earth Elements (REEs) from Coal Mine Drainage Sludge Leachate,” PhD thesis. West Virginia University.
- Ref 9. Ritcey, G. M., 1980. “Crud in solvent extraction processing—a review of causes and treatment,” Hydrometallurgy, 5:97-107.
- Ref 10. Ritcey, G. M. and A. W. Ashbrook, 1979. Solvent Extraction Principles and Applications to Process Metallurgy Part II. Volume 1. Amsterdam: Elsevier Scientific Publishing.
- Ref 11. Ritcey, G. M. and A. W. Ashbrook, 1984. Solvent extraction Principles and Applications to Process Metallurgy Part I. Volume 1. Amsterdam: Elsevier Scientific Publishing.
- Ref 12. Takeno, Naoto, 2005. “Atlas of Eh-pH diagrams—Intercomparison of thermodynamic databases” Geological Survey of Japan, Tech. Rep. 419:1-287.
- Ref 13. Wang, Weiwei, Yoko Pranolo, and Chu Yong Cheng, 2013. “Recovery of scandium from synthetic red mud leach solutions by solvent extraction with D2EHPA,” Separation and Purification Technology, 108: 96-102.
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in ° C. or is at ambient temperature, and pressure is at or near atmospheric.
Example 1: Analytical MethodsICP-MS was conducted using a Nexlon 2000-P instrument from Perkin Elmer equipped with an external Auto-diluter S400V from Elemental Scientific. Syngistic 2.4 software was used to collect and analyze data according to the EPA 200.8 Rev. 5.4 method (1994).
ICP-OES was conducted on an ICP-OES 720 instrument from Agilent Technologies using Expert II software according to method EPA 200.7 Rev. 4.4 (1994).
A Gallery Discrete Analyzer System (CPQ-00096605 from Thermo Fisher Scientific) was used for some measurements including pH. Data was collected and analyzed using Gallery software 6.0.1 according to method SM 4500-E 2011.
Thermogravimetric was conducted using a TGA 801 instrument from LECO with software package cornerstone version 2.8.8. The method used to determine moisture levels was developed inhouse with sample being brought from room temperature to 105° C. and held to constant weight.
Acid digestion was a manual technique using a 1:1 ratio of nitric acid to sample. Additional data analysis for all techniques was conducted using Microsoft Excel.
Example 2: Laboratory-Scale Experiments and Process ConsiderationsLaboratory experiments were performed prior to scaling up the disclosed process. Preliminary results produced solid feedstock with REE/CM averaging 2.88% in the laboratory (see Table 3) to 0.2% in an initial, continuous field extraction trial. Of that amount, 0.14% were mixed REE oxides (MREO), including the five REEs that are also CM (0.07%) and the critical mineral cobalt (0.06%).
A field trial of a mobile version of the plant disclosed herein (see
The disclosed plant and process feature a staged precipitation/AMD treatment unit that concentrates REEs away from major gangue elements while simultaneously producing clean water for discharge. Significant gains in efficiency and cost can be made by integrating AMD treatment with REE/CM recovery. Standard compliance-based AMD treatment raises the pH of the AMD from the inflow value (typically 2.5 to 3.5) to the final value needed for discharge (7 to 8) in a single stage. This single-step precipitation can significantly concentrate REEs; however, it also captures several problematic gangue metals into the sludge byproduct. Previous work focusing on REE extraction from sludge showed that these gangue metals contribute to high transportation costs, high acid consumption, and challenging separation.
The current process focuses on raw AMD in the early stages of standard treatment and use staged precipitation to isolate the REEs from the other gangue elements. A simplified process schematic for performing this staged precipitation is shown in
Testing shows that the disclosed process can effectively concentrate REE/CMs from raw AMD, with overall enrichment factors ranging from 13,000× to 15,000×. More importantly, the process has proven to be extremely robust, as testing on different water feedstocks representing a variety of geochemical settings has consistently produced similar results with respect to final REE purity. Other testing has evaluated in the influence of raw water characteristics, alkaline material, pH endpoint, redox potential, and the use of flocculant, and the number of process stages. When properly optimized, these procedures have consistently achieved REE/CM recovery >96% and generated products with REE/CM grade consistently between 0.1% to 5% wt %.
Specific testing of the host site will focus on a single AMD source in continuous run mode, as described in the Examples that follow. The upstream concentrator will be evaluated on its ability to manage variations in flow and AMD concentration while satisfying three parameters: NPDES permit compliance, operating costs and ability to supply the ALSX plant with feedstock of adequate grade (˜0.1% to 5% MREO). The ALSX plant will be evaluated based on operating cost and product grade approaching or exceeding 35% to 95%. The added infrastructure includes an additional clarifier in series with the two clarifiers normally required of an AMD plant of this capacity. Also, independent lime dosing and additional materials handling will be needed to isolate the REE preconcentrate. Since the beginning and ending pH points for this process are similar to those of conventional AMD treatment, the process is expected to add only modestly to base consumption. This outcome is particularly favorable given the high consumable costs for many REE concentration strategies.
Table 4 illustrates the data analysis based on laboratory testing to identify pH set points for the AMD/REE preconcentrator, based on laboratory batch testing. Recovery to precipitate indicates the extent to which the major gangue elements are rejected at the early stages of the process while REEs are recovered to the final precipitate to a very high degree (97%). With a grade of 48,015 mg REE/kg or 4.8%.
The incremental lime dosage rates and costs for the Upstream Concentrator and resulting resource, grade and recovery are estimated at each pH set point (Table 5). Based on two samples from an initial testing site, this type of analysis can be used to quickly identify the most efficient pH set points based on operating cost, grade and recovery. This type of testing protocol and knowledge gained while processing upstream concentrate samples through our ALSX plant will minimize scaling risk as the AMD/REE is designed, installed and operated.
The disclosed processes involves an acid leaching/solvent extraction process that can further enrich the REE preconcentrates to commercially attractive purity levels. A bench-scale solvent extraction system to extract REEs from AMD precipitates and concentrate them into a final REO product has been designed. The Rare Earth Extraction Facility (REEF) on the West Virginia University (WVU) campus contains an acid leaching circuit, 100 mixer-settler units, and downstream precipitation vessels. The system has also integrated state-of-the-art sensors and controls provided by Rockwell Automation (
Bench-scale testing has allowed problems to be addressed prior to full site scale-up. Given the distribution and concentration of metals in typical AMD-based leachates, crud formation has proven to be a major nuisance in SX operation. Gangue element concentration was carefully monitored during testing and leaching conditions were adjusted as necessary.
Data collected from this test facility has proven the technical feasibility of concentrating REEs from AMD-based feedstocks. Prior testing campaigns have investigated the influence of several operational variables, including leaching pH, extractant concentration, organic to aqueous ratios, stripping acid type and concentration, precipitation conditions, and system feed flow rates. From this testing, optimal operating conditions have been identified and the process has been validated using three sources of run-of-mine AMD treatment solids. Sources include the Omega, DLM and Royal Scott AMD treatment plants operated by West Virginia Department of Environmental Protection (WVDEP). Resulting MREO concentrations ranged from 62 to 80%.
The preconcentrate from the upstream concentrator can be transported to an adjacent pilot-scale ALSX plant for final concentration to the high-grade MREO product. This approach includes several key changes from existing ALSX facilities. First, these efforts represent an increase in project scale. The existing plant has a maximum production rate of 3 g/hr and the pilot-scale plant is expected to yield about 15.5 g MREO/hr. Second, the solid feedstock to the ALSX system will be modified with the pilot scale ALSX being fed by a preconcentrated feedstock from which most of the gangue metals have been removed. This modification has improved overall ALSX performance; prior laboratory-scale testing on preconcentrates from the staged precipitation process have shown that a 54% MREO product can be generated from a single stage of solvent extraction (
The disclosed AMD/REE process facility can be based on two critical process technologies: 1) upstream concentration and 2) acid leaching/solvent extraction. A block flow diagram showing the individual steps associated with each process is shown in
The upstream concentration unit has been matured to a technology readiness level (TRL) of 7 (full-scale system demonstration), while the ALSX has been matured to a TRL of 6 (pilot-scale demonstration). The upstream concentration development has been designed and operated as a scaled-down version of the AMD treatment facility to be deployed at the host site. This scaled unit has further been used to evaluate and optimize operating parameters. The pilot-scale ALSX unit has been designed to be approximately 1/20th the size of a full-scale unit.
The technical criteria defining project success are shown in Table 6. These values represent targets necessary for a commercial installation. To be competitive with other commercial REE resources (not including scandium or other CMs), overall production costs must be on the order of $50 to $75/kg of REE produced. The target performance requirements defined in this table represent a combination that is expected to achieve this cost target.
A flow diagram of the constructed upstream mobile concentration plant is shown in
A mobile plant as shown in
Elemental analysis of the products of the upstream concentration unit are shown in Table 7.
An ALSX plant was constructed to recover REEs from AMD precipitates. The plant design was based on extensive acid leaching and solvent extraction laboratory-scale studies. An initial system closely resembled the proposed design and shakedown testing was performed on each module of the plant to identify any construction or design oversights ranging from minor leaks to improper component specification. Following testing, modifications to the overall process were instituted to overcome any observed obstacles.
After shakedown testing and plant modification, the ALSX plant was placed into operation by implementing a decoupled, semi-batch process. The bench-scale system includes three operating units: an acid leaching and filtration module, a solvent extraction module, and a precipitation module. Initially, small batches (˜60 L) of AMD precipitate (AMDp) were converted to pregnant leach solution (PLS) using the acid leaching portion of the plant. As the acid leaching technique was refined, larger batches were produced that could supply feedstock to the solvent extraction (SX) module for week-long runs. The SX process was scheduled to operate in eight hour shifts for five days per week until the PLS was exhausted.
Upon completion of the SX plant run, the stripped aqueous product was processed using the precipitation module to convert the REE cations to oxalates. Next, the REE oxalate solids were calcined to transform the oxalates to oxides. After calcination, multiple washing stages were required to separate the REEs from gangue elements; therefore, increasing the grade of the final product. As a result of these procedures, a 62% mixed rare earth oxide material was acquired from the ALSX plant.
Feedstock Acquisition and Material HandlingAMDp was collected from the proposed feedstock sites for processing in the ALSX bench-scale plant. Ten 55-gallon drums of AMDp were collected from each of the three AMD sites evaluated for this research. A small excavator was used to remove the AMDp from on-site storage ponds. Plastic drum liners were used to isolate the AMDp from the inside of the steel drums. Upon delivery to the facility, the drums were stored in a controlled environment until the material was required for leaching tests. Drums were placed on pallets at the time of loading. Once at the ALSX facility, a pallet jack was employed to maneuver the drums into the storage area. When required for leaching, the drums were maneuvered using an overhead crane and tilting drum-lifting mechanism. This configuration was utilized to hoist the drums to the acid leaching module where the AMDp was removed from the lined drum and placed into five-gallon buckets. Each of the buckets was individually weighed to record the mass of AMDp before it was used in the acid leaching process.
Acid Leaching ModuleThe acid leaching module is located adjacent to the solvent extraction system.
During the shakedown testing of the ALSX system, several operational difficulties were encountered when using the ALSX system as it was initially designed. As a result, modifications to the acid leaching flow diagram were required to address these issues. The major operational challenges encountered and the flow diagram modifications implemented to overcome the unforeseen complications are presented below.
Gel Formation of PLSDuring initial shakedown testing, several batches of PLS would form into a gelatinous mixture when the pH was raised above the leaching pH set-point. This issue was observed in feedstock from all three AMD sites.
In order to alleviate this issue, several lab-scale experiments were conducted to address the issue of gel formation. During testing, it was discovered that the PLS did not form a gel when an additional filtration step was added to the procedure.
This extra filtration step was introduced directly after the PLS was lowered to the leaching pH value of 0.7. When tested on the acid leaching module, the additional filtration step prevented the congealing of the PLS at pH values less than 4.0. As a result, this additional filtration step was implemented into the operating procedure.
FiltrationEven in the absence of PLS gel formation, the vacuum pan filter was unable to filter the PLS as it did not have a sufficient filtering area for the amount of solid material remaining after acid leaching. This condition was not addressed in the design phase because the small-scale testing apparatus used did not allow for a proper evaluation of the filtration. For example, leaching tests were conducted using vacuum filtration with a Buchner funnel and filter paper. This operating condition did not produce a significant amount of precipitate to evaluate the bed depth and therefore the necessary filtration area required to perform an efficient solid-liquid separation.
To mitigate this issue, a bench-scale plate and frame filter press were employed to efficiently filter the PLS. Multiple batches of PLS were created using the three different feedstocks. Testing indicated that the filter press was capable of filtering the PLS solutions from all of the feedstocks at multiple pH values. Results from this experiment indicated a 2 cubic-foot filter press was of sufficient capacity to properly filter PLS from a 75-gallon agitated leach tank and create a clarified PLS.
Full-scale testing with the 2 ft3 filter press was successful with all three feedstocks as a direct result of the increased filtration area. Originally, the pan filter had a usable filtration area of 25 ft2. The new filtration unit increased the filtration area by a factor of almost 1.75 to 43 ft2.
A Sandpiper S07 air diaphragm pump with a maximum capacity of 23 gpm was used to feed the filter press. The pump was supplied with polyvinylidene fluoride (PVDF) internal components to resist the corrosion when pumping acidic liquids. The filter cake obtained from the filter press achieved moisture values of approximately 60%, which was substantially better than previous filter cakes acquired using vacuum filtration.
After modifying the acid leaching process and equipment, an updated process flow diagram was created as shown in
After filtration, the clean PLS was pumped into a leaching vessel. Next, the pH of the PLS was adjusted upward with 50% sodium hydroxide, to a pH value of 3.0, to remove gangue metals. Once again, this process was preformed step-wise over several hours until equilibrium was realized at the desired pH set-point. Finally, the PLS was again filtered to remove any solids that precipitated during the upward pH adjustment. The filtrate from this process was sampled then transferred to the SX module as feed for the liquid-liquid extraction.
Table 8 shows the reagents and conditions implemented to create the Royal Scot PLS. Combined, the two batches created a total of 282 liters of PLS for the subsequent SX process. The total acid consumption of the leaching procedure was 1.24 g acid/g feed. While the acid consumption of this batch process is high, other processes could be employed to reduce this metric. For example, countercurrent leaching could be employed to obtain a more efficient use of the leaching acid.
Analytical testing was performed on the feed, concentrate, and tailings of the comprehensive leaching process. These samples were analyzed using ICP-MS and ICP-OES methods to determine the REE concentrations and major ion concentrations, respectively. Tables 9A and 9B show the results of the analytical tests as well as the mass balance for both leaching batches.
The analytical results revealed several significant outcomes resulting from the leaching process. Both leaching batches yielded PLS with generally similar concentrations of elements. Overall, approximately 51% of the REEs were recovered into the PLS solution, while only 27% of the other major ions were recovered, indicating a significant rejection of gangue material. More noteworthy, the pH adjustment procedure resulted in the rejection of almost all of the Fe from the PLS. This is significant as Fe can interfere with the subsequent SX process. Other gangue material was also rejected from the PLS including Al (40%), Ca (65%), Mg (50%), Mn (49%), and Si (3%).
Additionally, in regard to the REEs, the individual recoveries generally decrease as the atomic number of the REE increases. Once exception to this observation is Sc, which possesses a much lower average recovery of 16%. The low recovery is not readily explained by standard thermodynamic considerations (e.g. Eh-pH diagrams) which indicate that Sc should remain in solution at pH values less than 6. Additionally, Sc is also readily leached from other feedstocks using mineral acids. As a result, the current interpretation of these results is that other constituents within the PLS were causing interference with the Sc, resulting in either precipitation at the pH value of less than 3.0 or preventing the Sc from transferring to an aqueous phase with the acid digestion.
The overall mass balance of the acid leaching process indicated a large variation between the balance and initial elemental masses of approximately 27% for the major ions and 37% for the rare earths. This discrepancy is quite large and indicative of analytical errors resulting from the sampling process or deficiencies existed in the measurement and recording procedures. Furthermore, these types of mass balance errors have been consistent throughout his research when using a saturated AMDp feedstock. Previous research using thermogravimetric analysis to explore the residual moisture in AMDp material after desiccation has indicated that some residual moisture may be left in the solid after traditional dehydration methods. Given the high moisture contents of the feedstock, even a small change in moisture values could have a significant impact on the overall mass balance of the system.
Solvent Extraction ModuleA bench-scale solvent extraction system with 100 individual mixer-settlers was acquired for this research.
Multiple shakedown tests were performed on this system to empirically obtain a minimum set of operational parameters. Initially, a hydrostatic test was completed to identify any leaks in the system. Additionally, each unit's operation was evaluated during shakedown testing using multiple parameters to establish the key operating set-points required to perform the necessary process. This was accomplished by using PLS from each feedstock to test the extraction, scrubbing, stripping, and saponification circuits in a batch-wise fashion until analytical testing showed the circuit was preforming in a satisfactory manner. After the most promising parameters were identified, each feedstock was then processed using the SX bench-scale plant in a continuous fashion to develop a baseline result from which parametric testing could identify the effect of changing individual SX parameters on the overall performance of the plant.
Solvent Extraction Shakedown TestingThroughout shakedown testing, several issues were noted that inhibited the operation of the bench-scale system. As each issue was discovered, changes were implemented to the as-designed system to alleviate the deficiencies. Each operational challenge that was observed during this testing regime is described below.
Third-Phase Crud FormationDuring initial shakedown tests, two of the feedstocks (DLM and Omega) caused considerable third-phase formation as seen in
Before a continuous SX process flow diagram is finalized, a thorough investigation of third phase formation is necessary. Issues encountered during the initial testing runs included difficulties in obtaining mass balances, organic loss to aqueous streams, and complete blockages of tubing connecting the mixer-settlers. Unfortunately, the generation of large amounts of crud renders parametric testing with these feedstocks difficult, if not impossible, to complete.
Multiple exploratory tests were conducted in an attempt to prevent the formation of crud in the mixing chamber. These tests included dilution of the PLS, use of the modifier tributyl phosphate, varying extractant concentrations, and changing the extractant organic:aqueous (O:A) ratio. It was found that crud was caused by the gradual oxidation of ferrous ion to the ferric form during solvent extraction. It was also found that addition of the oxidization agent hydrogen peroxide on a roughly 1:1 molar basis with ferrous ion concentration in PLS allowed precipitation of all iron as ferric hydroxide during PLS preparation. This eliminated crud formation during solvent extraction.
When the PLS of the three feedstocks was compared, as shown in Table 10, it was evident that the Fe and Ca content in the Royal Scot PLS was considerably lower than in the other two feedstocks. The current hypothesis is that Fe or Ca will reach a limiting organic concentration (LOC) where the metal ions will start to precipitate and create a nucleus that allows for crud formation. As a result, the Royal Scott PLS was used to demonstrate this technology while DLM and Omega feedstocks were subjected to further leaching tests to remove the excess gangue metals.
Another operational difficulty encountered in the operation of the SX plant involved maintaining a consistent O:A ratio in the mixing chamber. This issue was not observed in the SX unit operations that had an advance ratio of 1:1. Conversely, unit operations that required high or low O:A ratios often presented challenges in regard to maintaining a consistent mixing O:A ratio. Two potential causes were identified.
First, overtime, the Tygon tubing used to recycle the aqueous phase in the settler back to the mixer can become hardened and prevent operation of the roller-clamp that restricts flow in the recycle line. The second issue is inherent to the roller clamp design. Often the roller-clamps could not provide the fine adjustment required to properly maintain the preferred mixing O:A range of 1.5:1 to 1:1.5 as recommended by the SX plant manufacturer. To alleviate this issue, in-line valves were installed into the recycle lines of the SX processes that require advance ratios greater than the recommended mixing range.
Organic Loss During SaponificationDuring initial shakedown testing, four unit operations were utilized (extraction, scrubbing, stripping, and saponification). During these tests, a large fraction of the organic phase was reporting to the saponification raffinate and not recycling back to the organic tank. Further research indicated that an additional stage was needed to separate the organic and aqueous phases. As a result, the Megon Rare Earth Circuit was referenced and an additional circuit (acid wash) was implemented directly after the saponification stage. This additional stage greatly improved the recovery of organic to the organic recycle tank.
While the addition of the acid wash circuit improved the recovery of the organic to a level that was acceptable for the operation of the bench-scale plant, further modification may be necessary as the scale of the plant increases. Organic loss constitutes a significant cost for industrial-scale SX operations. As a result, the addition of a coalescence device or other chemical modifier should be evaluated as the technological readiness level (TRL) of this process increases.
SX Procedure and ResultsIn order to develop a baseline test prior to parametric testing, a batch of PLS was processed in the SX system with an initial set of operating parameters. Table 11 shows the parameters used in establishing this baseline test. The extractant, Elixore 205, is a highly-refined aliphatic diluent, similar to kerosene, with a high flash point, low viscosity, and ultra-low aromatic content. This diluent was chosen for three reasons. First, standard kerosene was used in some initial shakedown testing; however, a strong odor was emitted by the kerosene that permeated the enclosed area. Second, the use of a diluent specifically designed for use in solvent extraction was necessary to minimize further scale-up issues as the TRL of the project increased. Third, previous phase separation tests showed a slight advantage in phase separation times with Elixore 205 versus othertotal diluents.
Next, di-(2-ethylhexyl)phosphoric acid (D2EHPA) was chosen as the primary extractant based on the wide industrial acceptance. Initial shakedown testing indicated third-phase crud formation occurred in the extraction, scrubbing, and stripping circuits. In order to address this issue, tributyl phosphate (TBP) was added as a modifier.
The extraction and scrubbing advance O:A ratios were both set at 1:1 to provide equal transfer of the REEs and gangue metals to the organic phase and scrubbing raffinate, respectively. For the stripping circuit, an O:A ratio of 10:1 was utilized to concentrate the REEs into the stripped raffinate, while minimizing the volume of the raffinate. This was advantageous for the next process, as smaller volumes required less material handling. Finally, the saponification and acid wash O:A ratios were of 5:1 and 1:1, respectively, based on previous shakedown testing results. Mixer speeds were 856 rpm for every mixer in the SX plant. Lastly, every SX process was conducted using five mixer-settlers, with the exception of the acid-wash stage where only three mixer-settlers were utilized. This quantity is in excess of the number of stages identified in exploratory testing; however, using additional stages reduces the effects of other system inefficiencies that may occur during testing. During parametric testing unit-by-unit sampling will later identify the critical number of stages required.
The plant was operated over a period of eight days with a total operating time of 58 hours. This equates to roughly 7.2 operating hours per day or 90% operational availability. During this time, 281 liters of the PLS feedstock was processed through the system and concentrated into 28.3 liters of stripped raffinate. Additionally, the organic phase was constantly recycled back to the extraction stage. This demonstrated the ability of the process to run continuously, while showing that no metal ions remained attached to the extractant; therefore, reducing the extraction rate in the first circuit. An aqueous sample was obtained at the end of each operating day to evaluate the performance of the system.
In the extraction stage, the PLS and organic phases mix and settle, transferring REEs into the organic phase. Next, scrubbing removes unwanted elements from the organic while leaving the REEs in the organic phase using water or a mild acid. In the stripping stage, 6M HCl was used to remove the REEs from the organic phase. In this stage a high advance ratio was used to concentrate the REEs into the aqueous strip raffinate. Furthermore, the strip raffinate contained the valuable product from this operation that was used in the next plant module to recover the REEs. The last two stages, saponification and acid wash were used to regenerate the extractant, cleaning the cation exchange sites on each D2EHPA molecule.
Tables 12A and 12B below show the results of the daily analytical testing preformed on the PLS raffinate. While there was not a major change in the concentrations of the gangue material over the length of the test, it did take several days for the system to achieve steady state in regard to consistent extraction of the REEs. During the first three days, several of the LREEs were not fully extracted. This could be a function of the pH within the mixing cell not reaching equilibrium. Conversely, the HREEs approached steady-state extraction at day 2.
Additionally, the daily analytical testing results for the scrubbing raffinate are shown in Tables 13A and 13B below. This data indicated that there was some variation in the removal of chloride and sodium ions from the extractant using water as a scrubbing medium. Additionally, the scrubbing stage did not reach a steady-state condition until after day 4.
The precipitation module used to recover the REEs from the stripped raffinate is shown in
After all of the PLS was processed through the solvent extraction plant, the stripping raffinate was collected for processing in the precipitation module.
Once the target pH was achieved, the solution was allowed to decant overnight until three quarters of the supernatant was left in the decanting vessel and the remaining quarter was separated using a pressure filter with Whatman Grade 40 ashless filter paper with a nominal particle retention of 8 μm. Next, the precipitate was dried in a Yamato DX602C oven at 105° Celsius. A sample was taken from the precipitate and assayed to determine the REE content, as shown in Table 14.
The oxalic acid precipitation process resulted in 190 g of precipitate containing 11.1 g of REEs. The represents a TREE recovery of 97%. The majority of the measured major analytes were rejected during the precipitation with the exception of Ca, which entirely co-precipitated with the REEs.
The REE oxalate precipitate was then calcined in a Lindberg muffle furnace at a temperature of 750° Celsius for a duration of four hours. A sample of this material indicated the calcination procedure resulted in almost doubling of the concentration of the REO product from 5.8% to 11% as shown in Table 15. Additionally, 22% of the dried product consisted of Ca. In order to further concentrate the REO product a series water and acid washing steps were implements.
The washing procedure consisted of multiple washing cycles. After decanting and filtering, the REO product was agitated in 1 L of deionized water for thirty minutes. This procedure was repeated until the conductivity of the supernatant was below 50 μS/cm. In all, ten washing cycles were completed. Following washing, analysis of a sample of the REO product indicated that only small portions of the gangue material Ca (2 g) and CI (0.7 g) were removed. As a result, a more intense washing procedure was implemented, where the pH of the wash water was lowered to a pH of 3.5 to remove the remaining Ca.
Next, the REO product was subjected to an acid wash. This was conducted by placing the REO product in 1 L of deionized water and the pH was lowered using 3M nitric acid until a pH value of 3.5 was obtained. During this procedure, a notable effervesces occurred as the pH lowered. After washing and drying of the residual solid material, a noticeable loss of mass was observed as the sample was reduced from 68. g to 13.8 g. ICP-MS analysis confirmed the majority of the Ca was removed.
The nominal AMD feed rate of the disclosed plant is 500 gpm with a maximum capacity of 1,000 gpm. Ideal REE production is projected to be 1,000 kg MREO/year or 110 g MREO/hr. The plant treats all of the approximately 456 tons of acid load in the AMD stream per year with an estimated lime consumption cost of $65,000/year. At a contained value of $237/kg MREO, the annual yield can generate annual revenue of about $237,000, which is more than enough to cover the cost of AMD treatment. The plant is configured so that its AMD treatment train can operate independently and without performance degradation regardless of whether the REE recovery process is operating on a given day. In one aspect, the disclosed processes allow the plant's operator to maintain its Clean Water Act compliance obligations independently of REE recovery.
In addition to treating AMD and generating a preconcentrate, the disclosed plant includes a continuous acid leaching/solvent extraction train at its downstream end that can produce a MREO grade exceeding 90%. Production capacity is estimated to equal 15.5 g MREO/hour (Table 16).
In some cases, the REE resource at individual AMD treatment sites and individual AMD sludge ponds may be limited. Results from a regional survey showed that the REE flux from an average AMD outfall is only 400 kg/year, while the average sludge pond contains less than 10,000 kg REE in total. In some aspects, neither of these values are large enough to justify a commercial-scale REE concentration and refining plant at a single AMD treatment site. However, in some cases, a dispersed network of on-site handling operations can be integrated to feed a centralized ALSX system. In a feasibility study, we showed that a 2,100 TPD ALSX facility processing raw AMD sludge has the potential to produce an IRR of 37% and a net present value of $80 million over a 20-year operating period. The total capital cost for this plant is $46 million and the operating cost is $141/kg.
A detailed techno-economic analysis showed that these favorable results are sensitive to sludge acid consumption and sludge feed moisture. For example,
Traditional compliance-based treatment of AMD tends to push both the sludge acid consumption and the sludge moisture to unfavorable values. Many AMD treatment operators tend to overdose lime addition to avoid non-compliant discharges. This practice leaves large quantities of unreacted lime in the final precipitate, and this base must be fully consumed during the acid leaching step of treatment processes at a significant cost to the REE producer. Moreover, traditional sludge drying cells are ineffective at reducing sludge moisture, and many of the sludge samples evaluated in our prior studies have values exceeding 80-90%. Both of these issues are problematic for commercialization as they reduce the number of viable sludge sites that meet thresholds for economic viability. Sludge samples that do not meet the economic thresholds are considered stranded resources and are not considered relevant to a regional production scenario. When taken together these results indicate that the hypothetical 2,100 tons per day (TPD) ALSX plant described herein may have difficulty identifying a sufficient quantity of raw sludge feedstock that meet these criteria. A reduction in total plant throughput will inevitably lead to a proportional reduction in economic outcomes.
However, the upstream concentration process described herein offers a comprehensive solution to these issues. Most significantly, the upstream concentrator will increase the grade of the ALSX feed by rejecting iron and aluminum during the standard water treatment process.
This techno-economic analysis (TEA) has used standard economic guidelines provided by NETL and incorporates the most recent process knowledge regarding the disclosed ALSX process. Since the upstream concentrator can be easily integrated into existing AMD treatment technologies, the capital and operating costs for this process are assumed to be external to the REE producing entity and are not included in the analysis; however, an additional $50/t feedstock acquisition cost is included to account for any additional reagent addition, capitalization expenses, or handling needed to deliver the pre-concentrate to the ALSX plant. The results of this analysis are shown in Table 17 for a nominal 175 TPD plant.
The results confirm the economic gains inherent to the upstream concentration prior to ALSX. Compared to the prior scenario, which treated raw sludge, the current model output shows that a similar NPV ($80 million) can be achieved at a much smaller overall plant size (175 TPD vs. 2,100 TPD). The smaller plant also entails a much lower capital cost and a lower operating cost, $20 million and $54/kg REE respectively. While both scenarios have been shown to be economically favorable, the pre-concentrated route is much more viable from a commercial perspective, owing to the smaller feedstock requirement and reduced capital cost. Both of these items reduce overall project risk and are thus more favorable for investment. In addition,
Other matters pertaining to commercialization include permitting and regulatory factors, downstream refining capacity, and REE pricing factors. Wastes from the disclosed processes can be easily integrated into the existing infrastructure without the need for new permits. This outcome is also desirable for commercialization, as it minimizes the startup time needed to initiate new projects. With regard to refining capacity, the US currently has no domestic facilities that can produce refined REE products from mixed REOs. In one aspect, disclosed herein is the generation of REO concentrates, which can be used in downstream refining studies. With regard to pricing, all of the economic results in Table 17 have been determined using a price discount of 50% relative to the standard oxide prices provided by NETL. This price discount accounts for charges from downstream refining and also indicates that the process can still be profitable despite price volatility.
Example 6: Removal of Gangue ElementsRemoval of gangue elements in an AMD feedstock during preparation of a disclosed PLS using the foregoing methods is further illustrated in Table 18 below. The data therein shows that at the first pH step 712, aluminum and iron are significantly removed, and at the second pH step 718, REE and cobalt are removed from the aqueous phase, i.e., the effluent 724, and are recovered in the REE-enriched pre-concentrate.
The disclosed process results in removal of gangue elements at the first pH step 712, e.g., aluminum, iron, and silicon; while concentrating REE and cobalt in the pre-concentrate after the second pH step 718.
It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.
Claims
1. A pregnant leach solution composition comprising:
- lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium;
- wherein a total rare earth element concentration is a sum of each concentrations of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium;
- wherein thorium and uranium are present in an aggregate concentration of less than 1 mg/L;
- wherein cobalt is present in an amount less than about 20 mg/L; and
- wherein the total rare earth concentration is about 5 mg/L to about 50 mg/L.
2. The pregnant leach solution composition of claim 1, wherein scandium is present at a concentration of from about 0.05 mg/L to about 1 mg/L; yttrium is present at a concentration of from about 0.5 mg/L to about 10 mg/L; lanthanum is present at a concentration of from about 0.05 mg/L to about 5 mg/L; cerium is present at a concentration of from about 0.5 mg/L to about 7.5 mg/L; praseodymium is present at a concentration of from about 0.05 mg/L to about 2.5 mg/L; neodymium is present at a concentration of from about 0.5 mg/L to about 10 mg/L; samarium is present at a concentration of from about 0.1 mg/L to about 2.5 mg/L; europium present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; gadolinium is present at a concentration of from about 0.1 mg/L to about 5 mg/L; terbium is present at a concentration of from about 0.05 mg/L to about 1.5 mg/L; dysprosium present at a concentration of from about 0.1 mg/L to about 5 mg/L; holmium is present at a concentration of from about 0.05 mg/L to about 2 mg/L; erbium is present at a concentration of from about 0.1 mg/L to about 5 mg/L; thulium is present at a concentration of from about 0.05 mg/L to about 2 mg/L; ytterbium is present at a concentration of from about 0.05 mg/L to about 5 mg/L; and lutetium is present at a concentration of from about 0.01 mg/L to about 1 mg/L.
3. The pregnant leach solution composition of claim 1, wherein iron is present at a concentration less than or equal to about 25 mg/L.
4.-5. (canceled)
6. The pregnant leach solution composition of claim 1, wherein the pregnant leach solution has a pH of from about 2.8 to about 3.0.
7.-28. (canceled)
29. The pregnant leach solution composition of claim 1, wherein scandium is present at a concentration of from about 0.05 mg/L to about 1 mg/L.
30. The pregnant leach solution composition of claim 1, wherein yttrium is present at a concentration of from about 0.5 mg/L to about 10 mg/L
31. The pregnant leach solution composition of claim 1, wherein lanthanum is present at a concentration of from about 0.05 mg/L to about 5 mg/L.
32. The pregnant leach solution composition of claim 1, wherein cerium is present at a concentration of from about 0.5 mg/L to about 7.5 mg/L.
33. The pregnant leach solution composition of claim 1, wherein praseodymium is present at a concentration of from about 0.05 mg/L to about 2.5 mg/L
34. The pregnant leach solution composition of claim 1, wherein neodymium is present at a concentration of from about 0.5 mg/L to about 10 mg/L.
35. The pregnant leach solution composition of claim 1, wherein samarium is present at a concentration of from about 0.1 mg/L to about 2.5 mg/L.
36. The pregnant leach solution composition of claim 1, wherein europium present at a concentration of from about 0.05 mg/L to about 1.5 mg/L.
37. The pregnant leach solution composition of claim 1, wherein gadolinium is present at a concentration of from about 0.1 mg/L to about 5 mg/L
38. The pregnant leach solution composition of claim 1, wherein terbium is present at a concentration of from about 0.05 mg/L to about 1.5 mg/L
39. The pregnant leach solution composition of claim 1, wherein dysprosium present at a concentration of from about 0.1 mg/L to about 5 mg/L
40. The pregnant leach solution composition of claim 1, wherein holmium is present at a concentration of from about 0.05 mg/L to about 2 mg/L
41. The pregnant leach solution composition of claim 1, wherein erbium is present at a concentration of from about 0.1 mg/L to about 5 mg/L
42. The pregnant leach solution composition of claim 1, wherein thulium is present at a concentration of from about 0.05 mg/L to about 2 mg/L
43. The pregnant leach solution composition of claim 1, wherein ytterbium is present at a concentration of from about 0.05 mg/L to about 5 mg/L
44. The pregnant leach solution composition of claim 1, wherein lutetium is present at a concentration of from about 0.01 mg/L to about 1 mg/L.
Type: Application
Filed: Jul 17, 2020
Publication Date: Aug 18, 2022
Inventors: Paul ZIEMKIEWICZ (Morgantown, WV), Aaron NOBLE (Blacksburg, WV), Chris VASS (Rainelle, WV)
Application Number: 17/627,484
