Process for the separation of rare earth elements from phosphogypsum

Abstract

Systems and methods are provided for separation / extraction of rare earth elements (REE) and / or yttrium from phosphogypsum. Gypsum can be extracted from the phosphogypsum by dissolution with an aqueous medium that can optionally include salinity, followed by leaching with acidic aqueous media. The gypsum can be largely or completely removed from the phosphogypsum through selective dissolution. The remaining residue can contain the REE and / or yttrium at an order of magnitude higher concentration than in the initial phosphogypsum.

Description

[0001] DESCRIPTION

[0002] PROCESS FOR THE SEPARATION OF RARE EARTH ELEMENTS FROM PHOSPHOGYPSUM

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 639,808, filed April 29, 2024, and U.S. Provisional Application Serial No. 63 / 680,413, filed August 7, 2024, the disclosures of which are hereby incorporated by reference in their entireties, including all figures, tables, and drawings.

[0005] BACKGROUND

[0006] Demand for rare earth elements has been on the rise, driven by the transition to renewable energy technologies (e.g., electric motors, generators in wind turbines). The industrial extraction of phosphate for fertilizer from phosphate ores creates phosphogypsum waste, which includes most of the rare earth elements and yttrium (REY) contained in the original phosphate ore. There is currently no significant commercial rare earth element and / or yttrium extraction process from phosphogypsum, due at least in part to the cost of recovering diluted REY from large quantities of waste.

[0007] BRIEF SUMMARY

[0008] Embodiments of the subject invention provide novel and advantageous systems and methods for separation / extraction of rare earth elements (REE) and / or yttrium from phosphogypsum. Gypsum can be extracted from the phosphogypsum by dissolution with an aqueous medium that can optionally include salinity (e.g., at a concentration in a range of from 0.01 molar (M) to 6 M), followed by leaching with acidic (e.g., 0.01 M to 3M) aqueous media. The gypsum can be largely (e.g., 98% or more) or completely removed from the phosphogypsum through selective dissolution (see also Figure 2 and step 1 in Figures 1 and 3). The remaining residue can contain the REE and / or yttrium (collectively, REY) at an order of magnitude (or more; i.e., 10 times or more) higher concentration than in the initial phosphogypsum.

[0009] In an embodiment, a method for extraction of REE from phosphogypsum can comprise: i) dissolving the phosphogypsum in a first aqueous medium to give a first solution;

[0010] J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke ii) precipitating gypsum from the first solution to give extracted gypsum and a first residue; iii) treating the first residue with a second aqueous medium that is acidic to give an intermediate liquor and a second residue, wherein the intermediate liquor comprises the REE; and iv) filtering the intermediate liquor to obtain the REE. Step i), step iii), and / or step iv) can be performed at ambient temperature. A ratio of the mass of the REE obtained in step iv) to the mass of the REE present in the phosphogypsum can be at least 80% (e.g., at least 85%, at least 90% at least 95%, or in a range of from 80% to 100% (or any value, about any value, or any subrange contained therein)). The phosphogypsum can comprise yttrium, the intermediate liquor can further comprise the yttrium, and step iv) can comprise filtering the intermediate liquor to obtain the yttrium. The second aqueous medium can comprise at least one mineral acid. A concentration of the at least one mineral acid can be in a range of, for example, from 0.01 M to 3 M (or any value, about any value, or any subrange contained therein. The at least one mineral acid can comprise at least one of nitric acid, hydrochloric acid, and sulfuric acid, though embodiments are not limited thereto. The first aqueous medium can comprise at least one salt. A concentration of the at least one salt can be in a range of, for example, from 0.01 M to 6 M. The at least one salt can comprise, for example, a chloride salt, a nitrate salt, a sodium salt, and / or an ammonium salt (and can comprise no salt of calcium or magnesium). The extracted gypsum can have a concentration of radium that is lower than that of the phosphogypsum (e.g., at least 50% less than that of the phosphogypsum, such as at least 75% less than that of the phosphogypsum). The precipitating of the gypsum from the first solution can comprise using fractional crystallization of the first solution, partial evaporation of the first solution, or both. The precipitating of the gypsum from the first solution can comprise heating to the first solution (e.g., by adding steam to the first solution). The method can further comprise adding a solvent (e.g., ammonium hydroxide) to the intermediate liquor before step iv). Step iv) can comprise neutralizing the intermediate liquor and precipitating the REE as, for example, REE carbonate, REE oxalate, or both. Steps i) and ii) can be performed in a first tank, and the first tank can optionally be stirred. The first tank can be a first sedimentation tank. Step iii) can be performed in a second tank, and the second tank can optionally be stirred. The second tank can be a second sedimentation tank. The first tank can be the same as, or different from, the second tank. The extracted gypsum can have a radium activity of, for example, 15 picocuries per gram (pCi / g) or less (e.g., 10 pCi / g or less, about 5 pCi / g or less, or 5 pCi / g or less).

[0011] J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke BRIEF DESCRIPTION OF DRAWINGS

[0012] Figure 1 shows a schematic view of a process for extracting rare earth elements and / or yttrium from phosphogypsum, according to an embodiment of the subject invention.

[0013] Figure 2 shows a schematic view, with images, of part of a process for extracting rare earth elements and / or yttrium from phosphogypsum, according to an embodiment of the subject invention.

[0014] Figure 3 shows a bar chart of percentage of gypsum extracted (in %) for different stacks and locations. The bars are mostly made of (beige) portions represented by Step 1 (i.e., the rinse step shown in Figure 1). The small bars at the top of some of the stacks or locations represent step 2 (orange), step 3 (gray), and residue (green). Figure 3 shows that greater than 98% of gypsum was extracted in Step 1 for all stacks and locations.

[0015] Figure 4 shows a bar chart of percentage of rare earth elements and yttrium (REY) extracted (in %) for different stacks and locations. The bars are mostly made of (orange) portions represented by Step 2 (i.e., the adding of the dilute acid shown in Figure 1). Figure 4 shows that greater than 78% of REY was extracted in Step 2 for all stacks and locations, with many stacks and locations showing greater than 90% extraction of REY in Step 2.

[0016] DETAILED DESCRIPTION

[0017] Embodiments of the subject invention provide novel and advantageous systems and methods for separation / extraction of rare earth elements and / or yttrium from phosphogypsum. Gypsum can be extracted from the phosphogypsum by dissolution with an aqueous medium that can optionally include salinity (e.g., at a concentration in a range of from 0.01 molar (M) to 6 M), followed by leaching with acidic (e.g., 0.01 M to 3M) aqueous media. The gypsum can be largely (e.g., 98% or more) or completely removed from the phosphogypsum through selective dissolution (see also Figure 2 and step 1 in Figures 1 and 3). The remaining residue can contain the rare earth elements and / or yttrium (collectively, REY) at an order of magnitude (or more; i.e., 10 times or more) higher concentration than in the initial phosphogypsum.

[0018] Rare earth elements (REE) can be extracted in bulk from phosphogypsum residue by selective leaching with dilute mineral acids (e.g., nitric, hydrochloric, sulfuric, etc.; at, e.g., 0.01 M to 3 M) at ambient temperature leaving a final residue, which can contain most (e.g., 90+%) or all of the radium that the initial phosphogypsum contained. High yields of the REE can be obtained, such as 80% or more of the REE present in the initial phosphogypsum. The

[0019] J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke extracted REE can be subsequently precipitated from solution, for example as carbonates, oxalates, and / or hydroxides.

[0020] The high demand for REE (and yttrium) makes the extraction of REY from non- traditional sources such as mine wastes (including phosphogypsum) have economic motivation. Due to dilution by gypsum and sand, the REY content of phosphogypsum seems too low to exploit,. However, embodiments of the subject enables the extraction of valuable rare earths from phosphogypsum after gypsum is removed, thus improving the economics of REY extraction.

[0021] There are nearly two billion tons of phosphogypsum stacked globally, with more than a billion tons stacked in Florida alone, and the global phosphogypsum contains nearly half a million tons (or more) of REY. This amount of REY is equivalent to a half-century supply at the current rate of United States rare earth consumption. REE extracted using embodiments of the subject invention can be used to form the input for a rare earth separation supply chain, yielding materials from which permanent magnets (e.g., Nd-Fe-B, Sm-Co) are developed for use in electric vehicle (EV) traction motors, wind turbine generators, and other applications, including in military applications (e.g., the F-35 fighter program). REY can be used in the production of yttrium-barium copper oxide (YBCO) and rare earth-barium copper oxide (REBCO) tapes for producing high temperature superconductor magnets employed in the fusion energy industry and magnetic resonance imaging (MRI) instruments. The REY derived from phosphogypsum are rich in terbium, dysprosium, and yttrium, in contrast to the most abundant rare earth ores associated with hard rock deposits (e.g., bastnesite, REE-carbonate) that lack commercially extractable quantities of such heavy rare earths. While supplies of Nd may be derived from either type of ore, there is a dearth of ores that can supply the heavy REE (Tb, Dy) needed to provide resistance to demagnetization at operating temperatures of permanent magnets. Likewise, bastnesite ores do not yield significant quantities of yttrium for manufacture of YBCO tape, while phosphorite ores and their phosphogypsum waste can be important sources of yttrium.

[0022] Figure 1 shows a schematic view of a process for extracting rare earth elements and / or yttrium from phosphogypsum, according to an embodiment of the subject invention. Referring to Figure 1, the gypsum can be removed through selective dissolution (see also Figure 2 and step 1 in Figure 3) where the residue can contain the REY minerals at a concentration that is an order of magnitude higher than in the initial phosphogypsum. In addition or alternatively, the REE-bearing minerals can be physically separated from the

[0023] J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke phosphogypsum by flotation and / or density separation. The first step can include extraction of gypsum from the phosphogypsum by dissolution with an aqueous medium that can optionally include salinity (e.g., at a concentration in a range of from 0.01 M to 6 M). This first step can optionally include adding heat (e.g., via steam) during gypsum extracti on / precipitati on .

[0024] After a residue is formed by the selective leaching of gypsum (step 1), acidic aqueous media can be applied to the residue to give an intermediate liquor, which can be referred to as a REE-bearing liquor or REY-bearing liquor. The acidic aqueous media can include one or more dilute mineral acid (e.g., at concentration in a range of from 0.01 M to 3 M), and such mineral acid can include, for example, nitric acid, hydrochloric acid, or sulfuric acid, though embodiments are not limited thereto. The rare earth-bearing liquor can then be physically separated from the leached residue (see Figure 4 (step 2)). An additional leaching step (see also Figure 4 (step 3)) can be applied using a stronger mineral acid (not including hydrofluoric acid), in which a small amount (e.g., less than 10% additional) REY can be extracted. This additional leaching step can be performed to determine / confirm whether the reaction was completed in step 2. The residue produced after the additional leaching step (i.e., step 3, if performed) can have a solvent added to it (e.g., ammonium hydroxide (NFUOH)) to produce a solution, and the solution can be filtered (step 4) to give REE or REY. The remaining residue after step 2 (or after step 3, if performed) can contain a variety of mineral material, much of it sand and / or clay that may contain 10-20% of REY in zircons, clays, and / or other phases that cannot be easily accessed by the leaching media, but can be confirmed by aggressive acidic (e.g., HF and / or HNO3) dissolution of the post-step 3 residue (see also Figure 4). The intermediate liquor can then be neutralized, and the REY can be precipitated using existing technologies to yield a bulk rare earth carbonate and / or oxalate. Any or all steps can be performed at ambient temperature (e.g., in a range of from 20 °C to 30 °C, such as 25 °C or about 25 °C). In some embodiments, all steps other than adding heat (if performed) during the gypsum precipitation can be performed at ambient temperature.

[0025] Embodiments of the subject invention efficiently extract REE and / or yttrium (REY) from phosphogypsum in a two-step process involving the extraction of gypsum by selective leaching (referred to herein as step 1) to give a residue, followed by leaching of the residue with acidic, aqueous media of dilute mineral acids (e.g., nitric, hydrochloric, sulfuric, etc.) at 0-3 M at ambient temperature (Step 2).

[0026] J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke While related art methods that attempt to extract REE from phosphogypsum return the impure gypsum residue to the stacks after extraction of rare earths, embodiments of the subject invention utilize phosphogypsum that has begun to undergo valorization that in some embodiments involves a chemical or physical separation from gypsum, the majority phase, while leaving REY minerals intact. The REY mineral residues are more easily leachable than related art methods, needing only dilute acid at ambient temperatures to liberate REY. The REY-bearing liquor can then be neutralized and precipitated into rare earth solids, including but not limited to rare earth carbonates and / or oxalates. The efficiency, energy requirements, and acid disposal needs make processes of embodiments of the subject invention more cost- effective and safer than related art processes. Because the REY extraction is performed in series with gypsum extraction, an additional benefit is the eventual demolition of the stack.

[0027] In some embodiments, percolation of an acidic medium through phosphogypsum can be employed to cost-effectively extract REY, leaving gypsum as a residue. This process minimizes the use of water and energy involved in the extraction. The extractant phases can be acidic, aqueous media of dilute (e.g., 0-3 M) mineral acids (e.g., nitric, sulfuric, hydrochloric, etc.) at ambient temperature that, in some embodiments, include chelating agents.

[0028] In some embodiments, dilute mineral acids (e.g., < 1 M) at room temperature (e.g., less than 30 °C, such as 25 °C or about 25 °C) can include crushing of phosphogypsum to liberate mineral inclusions for high recoveries of rare earths at variable liquid to solid (L:S) ratios (such as L:S ratio in a range of from 1 to 50, or any value, subrange, or about any value therewithin). This process is more economical and environmentally friendly than related art methods due to the reduction in volume of leachate (water) and the lower concentration of acidic media needed for leaching.

[0029] In some embodiments, a process can involve the extraction of the rare earths and / or yttrium from phosphogypsum by leaching with mildly acidic (e.g., < 1 N or < 1 M) aqueous media at a L:S ratio in a range of from 1 to 50 at ambient temperature. In some embodiments, comminution of the phosphogypsum can be applied to liberate mineral inclusions that improves efficiency of rare earth extraction. For example, phosphogypsum can be treated with 0.1 N (or 0.1 M) nitric acid at a L:S ratio of 1 at ambient temperature of 25 °C. The rare earth-bearing liquor can then be physically separated from the leached residue. In order to determine whether the reaction was completed, and to reduce the phosphate content of the phosphogypsum, an additional leaching step can be applied using 2 N (or 2 M) nitric acid.

[0030] J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke The remaining residue after these steps can hold most of the gypsum and sand, containing 10% to 20 % of REY in sand grains that cannot be profitably accessed by related art rare earth extraction technologies. The extracted acidic media can then be neutralized and the REY precipitated (e.g., using existing technologies) to yield a bulk rare earth carbonate or oxalate.

[0031] In some embodiments, only dilute acid at ambient temperatures is used to liberate REY, thereby requiring less acid, no thermal energy for dissolution, and including fracturing of the gypsum compared with related art methods that attempt to extract rare earths from phosphogypsum. The REY-bearing liquor can then be neutralized and precipitated into rare earth solids, including but not limited to rare earth carbonates and oxalates. The efficiency, energy requirements, and acid disposal needs make this process more cost-effective and safer than related art processes.

[0032] In some embodiments, percolative acid leaching can be used to selectively extract REY (and radium) from solid phosphogypsum at low fluid to solid ratios. In some embodiments, the REY are extracted separately from barium (Ba) and radium (Ra) in milder acid, followed by stronger acid leaching to remove the barium and radium. In other embodiments, the REY-Ba-Ra are extracted together and the resulting solution is subsequently group-separated in sulfuric acid to yield dissolved REY and Ba-Ra precipitate. The process allows the addition of element-specific chelators to increase the yields of Ba and Ra. In some embodiments, the use of stronger acid leaching steps enables the extraction of arsenic. The resulting residue is gypsum that has desirable properties being low in phosphate, arsenic, and radioactivity, which can be safely used as construction aggregate or soil supplements.

[0033] When ranges are used herein, combinations and subcombinations of ranges (e.g., any subrange within the disclosed range) and specific embodiments therein are intended to be explicitly included. When the term “about” is used herein, in conjunction with a numerical value, it is understood that the value can be in a range of 95% of the value to 105% of the value, i.e. the value can be + / - 5% of the stated value. For example, “about 1 kg” means from 0.95 kg to 1.05 kg.

[0034] A greater understanding of the embodiments of the subject invention and of their many advantages may be had from the following examples, given by way of illustration. The following examples are illustrative of some of the methods, applications, embodiments, and variants of the present invention. They are, of course, not to be considered as limiting the

[0035] J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke invention. Numerous changes and modifications can be made with respect to embodiments of the invention.

[0036] EXAMPLE 1

[0037] The extraction methods disclosed herein were performed on five different phosphogypsum stacks - referred to as “old gypsum stack”, “south stack”, “east cap pond”, west cap pond 1”, and “west cap pond 2”. In particular, the residue after step 1 was treated with 0.1 nitric acid at an L:S ratio (liquid:solid ratio) of 10 at ambient temperature of 25 °C. The REY-bearing liquor was then physically separated from the leached residue (labeled as step 2 in Figure 4). Figure 3 shows the percentage of gypsum extracted for the different stacks in each step, and Figure 4 shows the percentage of REY extracted for the different stacks in each step. Referring to Figure 4, the yields of REY obtained were greater than 80% for all 24 representative samples obtained from four drill cores through the Piney Point phosphogypsum stack (in Florida, United States of America). In order to determine whether the reaction was completed, an additional leaching step (referred to as step 3 in Figure 4) was applied using stronger mineral acids (e.g., hydrofluoric acid (HF) and nitric acid (HNO3)), but less than 10% additional REY was extracted. The remaining residue after these steps held a variety of mineral material, much of it sand and / or clay that contained 10-20% of REY in zircons, clays, and / or other phases that cannot be easily accessed by the leaching media, but were determined by aggressive HF-HNO3 dissolution of the post-step 3 residue (Figure 4). The step 2 liquor was then neutralized and the REY were precipitated using existing technologies to yield bulk REE carbonate and / or oxalate.

[0038] It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.

[0039] All patents, patent applications, provisional applications, and publications referred to or cited herein (including those in the References section, if present) are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification.

[0040] J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke REFERENCES

[0041] U.S. Patent Application Publication No. 2012 / 0114538A1 (Abramov et al.).

[0042] Kolyasnikov S.V., Borisov M.M., Kirillov E.V. and Rybina M.L., Extraction Method of Rare- Earth Metals from Phosphogypsum, RU Patents RU2487834C1, 20 July 2013.

[0043] Li S., Malik M. and Azimi G. (2022) Extraction of rare earth elements from phosphogypsum using mineral acids: process development and mechanistic investigation. Industrial and Engineering Chemistry Research 61, 102-114, https: / / doi.org / 10.1021 / acs.iecr. lc03576.

[0044] Liang H., Zhang P., Jin Z. and DePaoli D. (2017) Rare earths recovery and gypsum upgrade from Florida phosphogypsum. Minerals & Metallurgical Processing 34, 201-206.

[0045] Rychkov V.N., Kirillov E.V., Smirnov, A.L., Jazev V.A. and Ivanko V.A. (2014) Method of Extracting Rare-Earth Elements from Phosphogypsum. Russian patents: RU2509726C2, 20 March 2014.

[0046] Xie G., Guan Q., Zhou F., Yu W., Yin Z., Tang H., Zhang Z. and Chi R. (2023) A critical review of the enhanced recovery of rare earth elements from phosphogypsum. Molecules 28, 20 pp., https: / / doi.org / 10.3390 / molecules28176284

[0047] J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke

Claims

CLAIMSWhat is claimed is:

1. A method for extraction of rare earth elements (REE) from phosphogypsum, the method comprising: i) dissolving the phosphogypsum in a first aqueous medium to give a first solution; ii) precipitating gypsum from the first solution to give extracted gypsum and a first residue; iii) treating the first residue with a second aqueous medium that is acidic to give an intermediate liquor and a second residue, wherein the intermediate liquor comprises the REE; and iv) filtering the intermediate liquor to obtain the REE.

2. The method according to claim 1, wherein step i), step iii), and step iv) are performed at ambient temperature.

3. The method according to any of claims 1-2, wherein a ratio of the mass of the REE obtained in step iv) to the mass of the REE present in the phosphogypsum is at least 80%.

4. The method according to any of claims 1-3, wherein the phosphogypsum comprises yttrium, wherein the intermediate liquor further comprises the yttrium, and wherein step iv) comprises filtering the intermediate liquor to obtain the yttrium.

5. The method according to any of claims 1-4, wherein the second aqueous medium comprises at least one mineral acid.

6. The method according to claim 5, wherein a concentration of the at least one mineral acid is in a range of from 0.01 molar (M) to 3 M.J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke7. The method according to any of claims 5-6, wherein the at least one mineral acid comprises at least one of nitric acid, hydrochloric acid, and sulfuric acid.

8. The method according to any of claims 1-7, wherein the first aqueous medium comprises at least one salt.

9. The method according to claim 8, wherein a concentration of the at least one salt is in a range of from 0.01 molar (M) to 6 M.

10. The method according to any of claims 8-9, wherein the at least one salt comprises a chloride salt.

11. The method according to any of claims 8-10, wherein the at least one salt comprises a nitrate salt.

12. The method according to any of claims 8-11, wherein the at least one salt comprises a sodium salt.

13. The method according to any of claims 8-12, wherein the at least one salt comprises an ammonium salt.

14. The method according to an;Tof claims 8-13, wherein the first aqueous medium does not comprise any salt of calciun or magnesium.

15. The method according to any of claims 1-14, wherein the extracted gypsum has a concentration of radium that is lower than that of the phosphogypsum.

16. The method according to any of claims 1-15, wherein the concentration of radium in the extracted gypsum is at least 50% less than that of the phosphogypsum.

17. The method according to any of claims 1-16, wherein the concentration of radium in the extracted gypsum is at least 75% less than that of the phosphogypsum.J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke18. The method according to any of claims 1-17, wherein the precipitating of the gypsum from the first solution comprises using fractional crystallization of the first solution and / or partial evaporation of the first solution.

19. The method according to any of claims 1-18, wherein the precipitating of the gypsum from the first solution comprises heating to the first solution.

20. The method according to claim 19, wherein the heating of the first solution comprises adding steam to the first solution.

21. The method according to any of claims 1-20, further comprising adding a solvent to the intermediate liquor before step iv).

22. The method according to claim 21, wherein the solvent is ammonium hydroxide.

23. The method according to any of claims 1-22, wherein step iv) comprises neutralizing the intermediate liquor and precipitating the REE as REE carbonate, REE oxalate, or both.

24. The method according to any of claims 1-23, wherein steps i) and ii) are performed in a first tank, and wherein the first tank is optionally stirred.

25. The method according to claim 24, wherein the first tank is a first sedimentation tank.

26. The method according to any of claims 1-25, wherein step iii) is performed in a second tank, and wherein the second tank is optionally stirred.

27. The method according to claim 26, wherein the second tank is a second sedimentation tank.J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke28. The method according to any of claims 26-27, wherein the first tank is the same as the second tank.

29. The method according to any of claims 26-27, wherein the first tank is different from the second tank.

30. The method according to any of claims 1-29, wherein the extracted gypsum has a radium activity of 10 picocuries per gram (pCi / g) or less.

31. The method according to any of claims 1-30, wherein the extracted gypsum has a radium activity of 5 pCi / g or less.J:\FSU\151CXPCT (24-033PRCWO)\Application\Application-asfiled.docx / ke

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