This document relates generally to power generation from coal-based materials and to the enhanced recovery of valuable elements, such as rare earth elements, from the combustion by-products of that power generation.
It is increasingly important to recover valuable elements from alternative and secondary resources. Toward this end, this document relates to an apparatus and method for (a) combusting coal-based material to generate heat used in the generation of electrical power and (b) enhanced recovering of valuable elements from the resulting combustion by-products. For purposes of this document, “valuable elements” include rare earth elements (REEs), cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), holmium (Ho), lanthanum (La), lutetium (Lu), neodymium (Nd), praseodynium (Pr), promethium (Pm), samarium (Sm), scandium (Sc), terbium (Tb), thulium (Tm), ytterbium (Yb) and yttrium (Y), as well as other elements including cobalt (Co), gallium (Ga), indium (In), tellurium (Te), lithium (Li), germanium (Ge) and vanadium (V).
More specifically, when coal-based materials are used for power generation, the valuable elements are enriched in the ash by-products (fly ash and bottom ash) due to the removal of the carbon and volatile matter. However, combustion temperatures exceeding 1200° C. are used in most conventional coal-fired power plants. At these high temperatures, significant mineralogical changes of the original mineral matter occur. For example, instead of occurring as individual minerals, it has been reported that most REEs are homogeneously distributed in a glassy amorphous matrix. As such, strong acidic and/or basic solution is required to dissolve the REEs from the fly ash material. In addition to the high costs of the lixiviants, the dissolution of the fly ash material needed to achieve a high REE recovery results in an excessive amount of contaminate ions in solution which hinders the ability to achieve high grade REE concentrates from downstream processes.
It has now been found that when coal-based material is combusted at lower temperatures of between 500-900° C. and, more particularly, between 600-750° C., such as commonly employed in fluidized bed combustors for power generation, the combustion by-products tend to be enriched with valuable elements, such as REEs, that are more easily dissolved in mild acid solutions. As a consequence, the combustion by-products are ideal for achieving relatively high recovery of these valuable elements from leaching processes.
Further, where the coal combustion is completed in the absence of alkaline additives, such as lime, used to capture sulfur, it is possible to produce sulfuric acid from the exhaust gases of the combustor. That sulfuric acid may then be used for the leaching of the REEs from the combustion by-product.
It is believed that the proposed apparatus and method set forth in this document are the first to achieve efficient power production from coal-based materials while simultaneously allowing for more enhanced recovery of valuable elements, including REEs, from the combustion products including fly ash and bottom ash. Thus, the apparatus and method disclosed herein represent a significant advance in the art.
In accordance with the purposes and benefits described herein, a new and improved apparatus is provided that allows for efficient energy production from the combustion of coal-based materials while also allowing for enhanced recovery of valuable elements from the combustion by-products. Advantageously, this can all be done at one location in a single facility using the apparatus and its related method.
The apparatus comprises; (a) a combustor operating at a temperature of 500-900° C., (b) at least one leach tank downstream from the combustor and (c) a valuable element recovery apparatus downstream from the leach tank. The leach tank (a) receives combustion by-product from the combustor, (b) extracts valuable elements from the combustion by-product and (c) produces a valuable element solution. The valuable element recovery apparatus is configured to recover the valuable elements from the valuable element solution.
Without being limited to one method, the valuable element recovery apparatus may include at least one of a thickener and a filter press adapted to remove residual solids from the valuable element solution and thereby generate a pregnant leach solution. In addition, the recovery apparatus may include a solvent extraction and precipitation apparatus, downstream from the thickener and/or filter press, adapted to concentrate valuable elements, such as REEs, in the pregnant leach solution and then selectively precipitate the concentrated valuable elements. Still further, the recovery apparatus may also include a roaster downstream from the solvent extraction and recovery apparatus. That roaster is adapted to produce a pure valuable element oxide mix from which it is possible to recover pure valuable elements with further processing in accordance with processing steps known in the art.
In one or more of the many possible embodiments of the apparatus, the combustor is operated at a temperature of 550-850° C., 550-800° C. or 600-750° C. In one or more of the many possible embodiments, the combustor is a fluidized bed combustor (FBC).
In at least one of the many possible embodiments, the combustor is operated in the absence of alkaline additives, such as lime, commonly employed in the coal powered generation industry to capture sulfur and prevent that sulfur from being exhausted in the exhaust or flue gas of the combustor. In such an embodiment, the apparatus also includes a sulfuric acid plant adapted to produce sulfuric acid from the sulfur in the exhaust gases of the combustor in a manner known in the art. That sulfuric acid is then delivered to the leach tank for use in leaching the valuable elements from the combustion by-products.
In accordance with yet another aspect, a new and improved method is provided for power generation and valuable element recovery from coal-based materials. That method comprises the steps of: (a) combusting the coal-based materials to generate heat at a temperature of 500-900° C., 550-850° C., 550-800° C. or, more specifically, 600-750° C., (b) using the heat generated to produce steam and generate electric power, (c) leaching valuable elements from the combustion by-products of the coal-based materials into a valuable element solution and (d) recovering the valuable elements from the valuable element solution.
The recovering step may include steps of: (a) concentrating the valuable elements into a pregnant leach solution, (b) precipitating the valuable elements from the pregnant leach solution and (c) roasting the valuable elements to produce a pure valuable element oxide mixture.
More particularly, the method may include the optional steps of: (a) combusting the coal-based materials in an absence of alkaline additives used to capture sulfur, (b) producing sulfuric acid from the sulfur in the exhaust gases generated during the combusting of the coal-based material and (c) using the sulfuric acid to leach the valuable elements in the extracting of the valuable elements from the combustion by-products.
In one or more of the many possible embodiments of the method, solvent extraction is used in the concentrating of the valuable elements. In one or more of the many possible embodiments of the method, stage precipitation and/or selective precipitation is used in the precipitating of the valuable elements.
In the following description, there are shown and described several preferred embodiments of the apparatus and method. As it should be realized, the apparatus and method are capable of other, different embodiments and their several details are capable of modification in various, obvious aspects all without departing from the apparatus and method as set forth and described in the following claims. Accordingly, the drawings and descriptions should be regarded as illustrative in nature and not as restrictive.
The accompanying drawing figures incorporated herein and forming a part of the patent specification, illustrate several aspects of the apparatus and method and together with the description serve to explain certain principles thereof.
Reference is now made in detail to multiple possible embodiments of the apparatus and method as illustrated in the accompanying drawing figures.
Reference is now made to
As illustrated in
The combustor 12 is particularly adapted for operating at a temperature of between 500-900° C. In some embodiments of the apparatus 10, the operating temperature is 550-850° C., in others 550-800° C. and in still others 600-750° C. Operating temperatures above the indicated ranges tend to reduce valuable element/REE recovery and should be avoided in order to improve recovery efficiencies. A cyclone 14, connected to the flue gas exhaust port 16 of the combustor 12, recovers particulates from the flue gas exhausted from the combustor 12.
The apparatus 10 includes at least one leach tank 18 downstream from the combustor 12. The leach tank 18 is adapted to receive combustion by-product, including fly ash and bottom ash, from the combustor 12 and ash particulates recovered from the flue gas by the cyclone 14. Delivery of the combustion by-product to the leach tank 18 may be by conveyor or other appropriate means. The leach tank 18 is also adapted for the extraction of valuable elements from the combustion by-product into a solution using an acid reagent such as sulfuric acid, nitric acid or hydrochloric acid. More particularly, a valuable element solution is produced in the leach tank 18 in a manner known in the art. That valuable element solution is then processed in a valuable recovery apparatus 20 configured to recover valuable elements from the valuable element solution.
In the illustrated embodiment, the recovery apparatus 20 includes a thickener 22 and a filter press 24 downstream from the leach tank 14. More specifically, in the illustrated embodiment, the thickener 22 is immediately downstream from the leach tank 18 and the filter press 24 is downstream from the thickener. A filter feed tank 26 is provided between the thickener 22 and the filter press 24 to ensure that solution is fed into the filter press at the desired rate for most efficient processing. In other possible embodiments, the apparatus 20 only includes the thickener 22 or only includes the filter press 24. Those skilled in the art recognize that any number of methods may be utilized to achieve solid/liquid separation.
The thickener 22 and/or the filter press 24 function to separate residual solids from the valuable element solution and recover a valuable element enriched, pregnant leach solution. More particularly, in the illustrated embodiment shown in
In the illustrated embodiment, the solvent extraction and precipitation apparatus 28 is adapted to receive the pregnant leach solution from the thickener 22, further concentrate the valuable elements and recover those valuable elements by staged precipitation or selective precipitation. One solvent extraction and precipitation apparatus 28 useful for this purpose is disclosed and described in detail in copending U.S. patent application Ser. No. 16/534,738, filed on Aug. 7, 2019 entitled “CONTINUOUS SOLVENT EXTRACTION PROCESS FOR GENERATION OF HIGH GRADE RARE EARTH OXIDES FROM LEACHATES GENERATED FROM COAL SOURCES”, the full disclosure of which is incorporated herein by reference.
As illustrated in
In the
The apparatus 10 shown and described in
The recovering step may include the steps of concentrating the valuable elements into a pregnant leach solution, precipitating the valuable elements from the pregnant leach solution and roasting the valuable elements to produce a pure valuable element oxide mixture.
Optionally, the method may include: (a) combusting the coal-based materials in an absence of alkaline additives of the type used to capture sulfur, (b) producing sulfuric acid from the exhaust gases generated during combustion and (c) using the produced sulfuric acid for leaching the valuable elements. This is the method of the embodiment illustrated in
The method may also include the steps of: (a) using at least one of a thickener and a filter press to remove residual solids from the valuable element solution and produce the pregnant leach solution, (b) using solvent extraction in the concentrating of the valuable elements in the pregnant leach solution and (c) using staged precipitation, selective precipitation or staged and selective precipitation in the precipitating of the valuable elements. The precipitation of valuable elements is described in further detail in copending U.S. patent application Ser. No. 16/185,120, filed on Nov. 9, 2018 and entitled “LOW-COST SELECTIVE PRECIPITATION CIRCUIT FOR RECOVERY OF RARE EARTH ELEMENTS FROM ACID LEACHATE OF COAL WASTE”, the full disclosure of which is incorporated herein by reference. In some possible embodiments of the invention, the solvent extraction step is eliminated and the pregnant leach solution is only subjected to precipitation of the valuable elements.
In one or more of the many possible embodiments of the method, the combusting of the coal-based materials is at a temperature of 550-850° C. In other possible embodiments, the combusting of the coal-based materials is at a temperature of 550-800° C. In still other embodiments, the combusting of the coal-based materials is at a temperature of 600-750° C.
Experimental
Leaching of FBC Ash Containing Lime
The results were obtained from acid leaching tests performed on FBC ash samples are shown in
The FBC2 unit received feed from the Illinois No. 6 coal seam, and tests conducted on the 1.4 SG float and 1.4-1.8 SG fractions of a sample collected from the same seam revealed that a calcination temperature of 900° C. reduces REE recovery to values approaching 30% (see next section). The leach recovery values achieved for the FBC2 ash materials were around 60% (see
Calcination Tests to Simulate not Adding Lime to FBC Unit
To lower the acid consumption for the recovery of REEs a proposed embodiment will combust coal without the addition of lime. To determine the efficacy of this embodiment acid leaching tests were performed on both the original and calcined coal samples to compare the REE leaching characteristics. As shown in
REEs in low-ash coals can be classified into organic (in forms of organic compounds and/or ionic species in the carbon matrix) and inorganic (ash-forming mineral matter dispersed within the organic matrix) associations. There are two factors that may contribute to the enhanced recovery after calcination: (1) the organically and inorganically associated REEs were liberated after calcination, which might be more leachable (e.g., REEs on the surfaces and entrapped within the inner layer of microdispersed clays), and (2) high-temperature calcination transformed the REEs into ore leachable forms such as rare earth oxides. After calcination at 600° C. or higher for 2 h, the organic matter was completely removed from all the coals as indicated by proximate analysis data. The findings of a previous study reported by Mardon and Hower showed that REEs are relatively non-volatile when coals are burned in boilers (>1000° C.). As such, all the organically associated REEs stayed in the coal ashes, most likely in the form of an oxide. However, in high-rank coals, the organically associated REEs represent a small fraction of the total REEs, that is, less than 10% for LREEs, and thus the enhanced recovery was more likely due to the mineralogy changes caused by calcination. It has been reported that a portion of the REEs is associated with clays in coal. Calcination of clays, especially kaolinite, causes dehydration, which significantly increases their surface area. This effect may provide another explanation for the enhanced recovery and agrees with the XRD characterization findings.
As shown in
The acid leaching kinetics of REEs from the calcined samples was characterized by a quick release within the first 5 min of the leaching process (see
The effects of pretreatment time on REE leaching recovery from the coal sources are critical since the residence time in an FBC unit is limited, varying from several seconds to several minutes. As shown in
The foregoing has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the embodiments to the precise form disclosed. Obvious modifications and variations are possible in light of the above teachings.
For example, the illustrated embodiment includes a single leach tank 18 downstream from the combustor 12. Multiple leach tanks may be provided, arranged in series and/or parallel. Another example, in the illustrated embodiment, the pregnant leach solution (PLS) is subjected to solvent extraction to recover the valuable elements such as REEs. It should be appreciated that processes other than solvent extraction may be used for this purpose. Such alternative processes include, but are not necessarily limited to, the concentration of the valuable elements/REEs by selective precipitation using chemical additives and/or pH adjustments, selective redissolution of the precipitate followed by selective precipitation using oxalic acid and pH control.
All such modifications and variations are within the scope of the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitably entitled.
This application claims priority to U.S. provisional patent application Ser. No. 62/835,105, filed on Apr. 17, 2019, the full disclosure of which is incorporated herein by references.
This invention was made with government support under Grant No. DE-FE0031525 awarded by the Department of Energy. The government has certain rights in the invention.
Number | Date | Country | |
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62835105 | Apr 2019 | US |