Method for separation of chemically pure Os from metal mixtures
10087503 ยท 2018-10-02
Assignee
Inventors
- Hendrik P. Engelbrecht (Columbia, MO, US)
- Cathy S. Cutler (Columbia, MO)
- Leonard Manson (Columbia, MO, US)
- Stacy Lynn Wilder (Columbia, MO, US)
Cpc classification
C22B61/00
CHEMISTRY; METALLURGY
C22B11/042
CHEMISTRY; METALLURGY
Y02P10/20
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C22B7/009
CHEMISTRY; METALLURGY
C01G55/00
CHEMISTRY; METALLURGY
C25C1/06
CHEMISTRY; METALLURGY
C01G55/001
CHEMISTRY; METALLURGY
International classification
C22B7/00
CHEMISTRY; METALLURGY
G21G1/00
PHYSICS
C01G55/00
CHEMISTRY; METALLURGY
C22B3/00
CHEMISTRY; METALLURGY
C22B61/00
CHEMISTRY; METALLURGY
Abstract
A method for separating an amount of osmium from a mixture containing the osmium and at least one other additional metal is provided. In particular, method for forming and trapping OsO.sub.4 to separate the osmium from a mixture containing the osmium and at least one other additional metal is provided.
Claims
1. A method of producing an amount of chemically pure Re-186 isotope, comprising: irradiating a metal target comprising an amount of isotopically enriched osmium isotope consisting of Os-189, Os-192, or a combination thereof in a thermal proton flux to form a mixture comprising at least one osmium isotope and at least one additional metal comprising the Re-186 isotope; contacting the mixture with an oxidizing solution to form a volatile OsO.sub.4 vapor comprising the at least one osmium isotope; distilling the OsO.sub.4 vapor from the oxidizing solution to form a second solution comprising the Re-186 isotope dissolved in the oxidizing solution; and separating the Re-186 isotope from the second solution.
2. The method of claim 1, wherein the Re-186 isotope is separated from the second solution using a method selected from the group consisting of contacting the second solution with a reducing agent, contacting the second solution with a chromatographic column, and electroplating the at least one metal from the second solution.
3. The method of claim 2, wherein the Re-186 isotope is separated from the second solution by contacting the second solution with an alumina chromatographic column and eluting the Re-186 with a saline solution.
Description
DESCRIPTION OF FIGURES
(1) The following figures illustrate various aspects of the embodiments.
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(8) Corresponding reference characters and labels indicate corresponding elements among the views of the drawings. The headings used in the figures should not be interpreted to limit the scope of the claims.
DETAILED DESCRIPTION
(9) I. Overview of Method
(10) Various aspects provide methods of separating osmium from a mixture of metals including the osmium as well as at least one other metal. These methods may be used to produce chemically pure osmium or to remove osmium impurities from a mixture that includes the osmium and at least one other metal. In an aspect, the chemically pure osmium may be a radioisotope. In another aspect, the chemically pure osmium may be used as an isotopically-enriched osmium target to produce radioisotopes by irradiation of the osmium target in an irradiation source including, but not limited to, a thermal neutron flux, a cyclotron, or a linear accelerator. The osmium target may be irradiated by any known type of irradiation, including, but not limited to: proton irradiation, neutron irradiation, deuteron irradiation, alpha particle irradiation, and any other known type of irradiation.
(11) A flowchart describing an aspect of a method 100 is provided in
(12) The mixture may include a variety of radioactive and non-radioactive isotopes. Non-limiting examples of metals that may be included in the mixture include lanthanide metals, transition metals, alkali metals, and metals from the platinum family. Non-limiting examples of specific metal elements that may be included with osmium in a mixture include Rh, Pd, Ir, Pt, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ag, Cd, La, Hf, Ta, W, Re, Au, Hg, Ac, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr, and any combination thereof. In an aspect, the mixture may result from the irradiation of an enriched Os-190 target by a thermal neutron stream and may include Os-191, Os-191.sup.m, Ir-191.sup.m, Ir-191, Ir-192.sup.m, Ir-192, Ir-193, Ir-194, Pt-192, Pt-194, and combinations thereof. In another aspect, enriched Os-190 may be irradiated in a cyclotron to produce a mixture that may include Pt-188, Pt-189, Pt-191, Pt-193m, Pt-195m, and combinations thereof. In an additional aspect, enriched Os-190 may be irradiated in a cyclotron to produce a mixture that may include Re-186, an isotope with at least several potential applications including but not limited to nuclear imaging methods and therapeutic compositions.
(13) In other aspects, the mixture may result from the irradiation of any enriched Os isotope target without limitation. Non-limiting examples of Os isotopes suitable for inclusion in an enriched Os isotope target include Os-184, Os-186, Os-187, Os-188, Os-189, Os-190, and Os-192. In one aspect, the mixture may result from the proton irradiation of an enriched Os-189 and/or Os-192 target to produce a mixture that may include Re-186.
(14) Other aspects of methods of separating osmium from a mixture of metals are described in detail below.
(15) II. Oxidation of Osmium
(16) In various aspects, the osmium within a mixture may be separated from a mixture that includes the osmium and at least one other metal by contacting the mixture with an oxidizing agent to form a volatile OsO.sub.4 vapor. In an aspect, the oxidizing agent may be any compound capable of oxidizing the osmium into OsO.sub.4 in aqueous solution. In another aspect, a relatively strong oxidizing agent may be selected to reduce the overall time to separate the osmium from the mixture and to provide the capability to oxidize the osmium from mixtures in any form including, but not limited to: finely divided powders, shavings, pellets, slugs, and any combination thereof.
(17) Non-limiting examples of suitable oxidizing agents include NaClO, LiClO, KClO, NalO.sub.4, Na.sub.2S.sub.4O.sub.8, XeO.sub.3, NaClO.sub.2, NaClO.sub.3, NaClO.sub.4, NaOH in contact with Cl.sub.2 gas, other alkali salts of ClO, ClO.sub.2, ClO.sub.3 and ClO.sub.4, and combinations thereof. The concentration of the oxidizing agent in an aqueous solution may range from about 5% to about 30% available chlorine. The concentration of oxidizing agent may be selected based on any one or more of at least several factors including, but not limited to: the composition of the mixture, the availability of the oxidizing agent, the safety and ease of use of the oxidizing agent, the temperature and other reaction conditions of the mixture and the oxidizing agent, and the solubility of the oxidizing agent.
(18) The temperature at which the mixture is contacted with the oxidizing agent may range from about 20 C. to about 95 C. The temperature may be selected to result in a relatively rapid but controlled reaction rate without causing the aqueous solution containing the oxidizing agent to boil. In an aspect, the oxidizing agent is NaClO in aqueous solution at a concentration of about 12% available chlorine, and the NaClO solution is contacted with the mixture at a temperature of about 40 C.
(19) In another aspect, the oxidizing solution may be maintained at a temperature of about 40 C. until the mixture containing the osmium and other metals is completely dissolved, and the oxidizing solution may be maintained at a temperature of about 90 C. for the remainder of the reaction. As the mixture containing the osmium and other metals dissolves within the oxidizing solution, the solution may take on a yellowish colored appearance as the osmium is oxidized within the oxidizing solution. As the dissolved OsO.sub.4 is distilled out of the oxidizing solution, the oxidizing solution takes on a transparent white appearance. In an aspect, a colored oxidizing solution containing the dissolved mixture of metals may be maintained at a temperature of about 90 C. until the oxidizing solution again takes on a transparent appearance, indicating that essentially all osmium in the solution has been oxidized and distilled away.
(20) In various aspects, the mixture is contacted with the oxidizing agent in an impinger, shown schematically in
(21) As the oxidizing solution 204 contacts the mixture 216, the osmium within the mixture may be converted into OsO.sub.4 vapor. This OsO.sub.4 vapor may form into bubbles 206 that may float to the surface 210 of the oxidizing solution 204, where the OsO.sub.4 vapor is released into the headspace 212 of the impinger 200. Driven by the building pressure of the gases introduced into the impinger 200, the gases within the headspace 212, which may include OsO.sub.4 vapor, exit the impinger 200 via the impinger exit 214.
(22) The gas that is introduced into the impinger 200 may be any gas that does not interfere with the reaction between the mixture and the oxidizing solution including, but not limited to: air, oxygen, nitrogen, noble gases, and combinations thereof. In an aspect, the gas is selected to be a non-toxic gas capable of being vented to the environment after the OsO.sub.4 has been extracted as described herein below. Non-limiting examples of gases suitable for introduction into the impinger 200 include nitrogen, argon, helium, oxygen, and combinations thereof. In another aspect, the gas introduced into the impinger 200 is nitrogen.
(23) The gas may be introduced at any suitable rate that results in the vigorous mixing of the mixture and the oxidizing solution, so long as the rate does force the venting of any oxidizing solution through the impinger exit 214. The source of the gas may be the atmosphere outside of the impinger 200, or the gas source may be a pressurized tank or any other existing gas source. In other aspects, the rate of introduction of the gas into the impinger 200 may be limited by the design and performance capabilities of the impinger 200, as well as the design and performance capability of other components downstream of the impinger 200, such as the trapping vessel, described in detail herein below.
(24) III. Capture of OsO.sub.4 in Trapping Solution
(25) In various embodiments, the OsO.sub.4 vapor may be bubbled through a KOH trapping solution to form an amount of K.sub.2[OsO.sub.4(OH).sub.2] dissolved within the trapping solution. In an aspect, the KOH trapping solution comprises an aqueous solution of KOH at a concentration ranging from about 10% to about 50% w/v. The concentration of the KOH may be selected based on any one or more of at least several factors including, but not limited to: the rate and concentration at which the OsO.sub.4 vapor is bubbled through the KOH trapping solution, the reaction conditions such as temperature of the KOH trapping solution, and the solubility of the KOH in the aqueous solvent. In an aspect, the KOH trapping solution is an aqueous solution of KOH at a concentration of about 25% w/v at a temperature of less than about 5 C.
(26) In another embodiment, a trap vessel containing the KOH trapping solution is situated within an ice bath. Without being bound to any particular theory, the reduction of the OsO.sub.4 vapor within the KOH trapping solution is an exothermic reaction. Cooling the KOH trapping solution to a lower temperature using an ice bath maintains the KOH trapping solution at a higher solubility for the OsO.sub.4 vapor.
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(28) The concentration of OsO.sub.4 vapor exiting the trap vessel 300 through the trap exit 314 may be less than about 20% of the concentration of the OsO.sub.4 vapor entering the vessel 300 through the trap inlet 308. The degree of reduction of OsO.sub.4 vapor concentration may be governed by the effectiveness the reaction between the OsO.sub.4 and the KOH in the trapping solution 312. The effectiveness of the reaction may depend on any one or more of at least several factors including, but not limited, to: the concentration of KOH in the trapping solution 304, the reaction conditions such as temperature and pressure within the trap vessel 300, the rate of gas introduction into the trap vessel 300, and the design of the trap vessel 300. In other aspects, the concentration of OsO.sub.4 vapor exiting the trap vessel 300 through the trap exit 314 may be less than about 10%, less than about 5%, less than about 1%, or less than about 0.1% of the concentration of the OsO.sub.4 vapor entering the vessel 300 through the trap inlet 308.
(29) In another aspect, the trap vessel 300 may include a two-in-one pipette 400, shown schematically in
(30) Without being tied to any particular theory, the introduction of the gas through the two-in-one pipette 400 imparts more intimate and sustained contact between the bubbles 414 and the trapping solution 304. The bubbles 414 may be distorted into larger surface areas, shaped by capillary forces imparted by the outer surface of the inner pipette 402 and the inner surface of the outer pipette 404. Further, these capillary forces may impede the free movement of the bubbles to the surface of the trapping solution 304, resulting in a sustained time of contact between the gas bubbles 414 and the trapping solution 304. This combination of factors may result in more efficient and extensive conversion of the OsO.sub.4 vapor into K.sub.2[OsO.sub.4(OH).sub.2] within the trapping solution 304. The two-in-one pipette 400 may be immersed in a liquid 408 to facilitate heat transfer from the pipette 400 to a heat sink such as an ice bath (not shown). The bubbles 414 may be released into the headspace 416 of the outer pipette 404 and may exit the two-in-one pipette 400 via a vapor outlet 412.
(31) The rate at which gas from the impinger 200 is introduced into the trapping vessel 300 may depend on any one or more of at least several factors including, but not limited to: the rate at which gases exit the impinger 200, as well as the sizing and design of the trap vessel 300. The rate at which gases exit the impinger 200 may be governed by the rate at which gas is introduced into the impinger 200 as well as the rate of production of OsO.sub.4 vapor within the oxidizing solution 204. The trap vessel 300 may be designed to have a volume that is larger relative to the impinger 200 in order to impart a lower flow velocity through the trap vessel 300. Alternatively, the gases exiting the impinger 200 may be directed into two or more trap vessels 300 attached in parallel, resulting in a larger overall trap vessel volume relative to the impinger 200.
(32) In another aspect, in order to trap a higher proportion of the OsO.sub.4 vapor released by the impinger 200, two or more trap vessels may be connected in series to the impinger exit 214.
(33) IV. Precipitation/Encapsulation of Osmium from Trapping Solution
(34) In various embodiments, the osmium trapped within the dissolved K.sub.2[OsO.sub.4(OH).sub.2] in the KOH trapping solution may be precipitated and/or encapsulated into a usable form by contacting the dissolved K.sub.2[OsO.sub.4(OH).sub.2] with a reducing agent to form an Os precipitate. The particular Os precipitate formed depends upon the species of reducing agent contacted with the dissolved K.sub.2[OsO.sub.4(OH).sub.2]. Non-limiting examples of Os precipitates include Os metal, OsS.sub.2, OsO.sub.2, and K.sub.2[OsO.sub.2(OH).sub.4]. Non-limiting examples of suitable species of reducing agents include absolute ethanol, Zn shavings, Al shavings, Mg shavings, NaBH.sub.4 and other alkali salts of BH.sub.4, NaHS, H.sub.2S gas, Na.sub.2S.sub.2O.sub.3, UV light, phosphine ligands, hydrazine, hydroquinone, hydrophosphorous acid, formaldehyde, hydroxylamine, citrate, ascorbic acid, and hydrogen gas.
(35) In one aspect, the Os is recovered from the KOH trapping solution by reducing the dissolved K.sub.2[OsO.sub.4(OH).sub.2] to K.sub.2[OsO.sub.2(OH).sub.4] crystals by adding an amount of absolute ethanol to the KOH trapping solution. In this embodiment, the concentration of the absolute ethanol added may range from about 1% to about 20% v/v. In another aspect, ethanol is added at a concentration of about 5% v/v. The K.sub.2[OsO.sub.2(OH).sub.4] crystals may then be harvested for encapsulation.
(36) In another aspect, Zn, Mg, or Al metal shavings may be added to the KOH trapping solution, and concentrated HCl may be added to the solution to lower the pH of the solution, resulting in the formation of Os metal. After removal of the shavings, the precipitate may be centrifuged and washed with water to isolate the Os metal.
(37) In an additional aspect, Zn and Al shavings may be added to the basic KOH trapping solution to form a precipitate that may include Os metal, OsO.sub.2, and combinations thereof. In another additional aspect, NaBH.sub.4 may be added to the KOH trapping solution to form an Os metal precipitate or other reduced species of Os such as OsO.sub.2. The precipitate may be centrifuged and washed with water to isolate the Os metal.
(38) In yet another aspect, NaHS may be added to the KOH trapping solution in order to form an OsS.sub.2 precipitate. The OsS.sub.2 precipitate may also be formed by bubbling H.sub.2S gas through the KOH trapping solution. In addition, Na.sub.2S.sub.2O.sub.3 may be added to either the basic or acidified KOH trapping solution to form an OsS.sub.2 precipitate. The OsS.sub.2 precipitate may be centrifuged and washed with water to isolate the OsS.sub.2 precipitate.
(39) In still yet another aspect, the osmium may be encapsulated by drawing an amount of the KOH trapping solution containing the K.sub.2[OsO.sub.4(OH).sub.2] into a thin vial, followed by dipping the thin vial into an aqueous solution containing NaHS to form an encapsulated OsS.sub.2 precipitate within the thin vial.
(40) V. System for Separating Osmium from Mixtures of Other Metals
(41) Various embodiments provide a system for the separation of osmium from a mixture including the osmium and at least one other metal.
(42) In use, a mixture 508 that includes an amount of osmium and at least one other metal may be placed into the impinger 200A along with an amount of oxidizing solution 506. The oxidizing solution 506 may be maintained at about 40 C., and a moderate flow of nitrogen may be introduced into the impinger inlet 504, causing the agitation of the oxidizing solution 506 as well as the fluids within the downstream trap vessels 300A-300C. As the mixture 508 dissolves into the oxidizing solution 506, the oxidizing solution 506 may take on a colored appearance. Once the mixture has completely dissolved within the oxidizing solution 506, the temperature of the oxidizing solution 506 solution may be maintained at about 90 C. until all of the osmium in the oxidizing solution 506 has been oxidized into OsO.sub.4 vapor. In an aspect, the color of the oxidizing solution 506 may change from colored to clear to indicate the oxidation of all dissolved osmium in the oxidizing solution 506.
(43) The OsO.sub.4 vapor formed in the impinger 200A may be carried along with the introduced nitrogen into the first trap vessel 300A. In an embodiment, the first trap vessel 300A includes a two-in-one pipette 516 containing an amount of KOH trapping solution 514. An amount of OsO.sub.4 vapor bubbling through the KOH trapping solution 514 may contact the dissolved KOH, forming dissolved K.sub.2[OsO.sub.4(OH).sub.2]. The introduced nitrogen, along with any untrapped OsO.sub.4 vapor may pass into the second trap vessel 300B, where an amount of OsO.sub.4 may be captured within the second KOH trapping solution 524. Similarly, the introduced nitrogen, along with any further untrapped OsO.sub.4 vapor, may pass into the third trap vessel 300C, where an amount of OsO.sub.4 may be captured within the third KOH trapping solution 530. Any residual OsO.sub.4 vapor leaving the third trap vessel 300C may be captured within the activated charcoal filter 534, and essentially osmium-free nitrogen may exit the filter exit 536 to the atmosphere.
(44) Once essentially all of the dissolved osmium within the oxidizing solution 506 has been oxidized into OsO.sub.4 vapor and bubbled through the trap vessels 300A-300C, the flow of nitrogen gas may be stopped and the dissolved K.sub.2[OsO.sub.4(OH).sub.2] within the KOH trapping solution 514 may be precipitated into a useable form using any of the methods described herein previously. In an aspect, only dissolved K.sub.2[OsO.sub.4(OH).sub.2] within the KOH trapping solution 514 from the first trap vessel 300A is precipitated. In another aspect, the trapping solutions 514, 524, and 530 may be combined and the dissolved K.sub.2[OsO.sub.4(OH).sub.2] within the combined KOH trapping solutions may be precipitated.
(45) In an aspect, the dissolved K.sub.2[OsO.sub.4(OH).sub.2] within the combined KOH trapping solutions may be transferred into a centrifuge tube and combined with an amount of NaHS to form a black OsS.sub.2 precipitate. The OsS.sub.2 precipitate may be further treated after the addition of the NaHS, or the centrifuge tube may be left as long as about 6 hours to about 24 hours to ensure that the K.sub.2[OsO.sub.4(OH).sub.2] has completely reacted with the NaHS. The OsS.sub.2 precipitate in the centrifuge may be agitated with water, centrifuged, and the water supernate may be discarded. This washing process may be repeated two or more times to ensure that any remaining impurities are rinsed from the OsS.sub.2 precipitate.
(46) The water-rinsed OsS.sub.2 precipitate may be additionally rinsed with a solvent such as acetone and dried at room temperature for about 1 hour.
(47) Other Applications of Method
(48) The osmium separation methods of various aspects may be applied in a variety of different contexts. As described herein above, one aspect of the method may be used to separate osmium isotopes or radioisotopes from a mixture including the osmium and at least one other metal. The resulting chemically pure osmium may be an enriched osmium target used for the production of radioisotopes, or the chemically pure osmium may be Os-191 or other Os radioisotopes used in a variety of applications including, but not limited to: a radiotracer composition, a radiotracer source, or as an ingredient in a therapeutic composition.
(49) In another aspect, the osmium separation method may be used to separate an osmium impurity from a mixture including the osmium impurity and at least one other metal. A flowchart of this method 600 is illustrated in
(50) In this aspect, the mixture that includes at least one other metal remains dissolved in the oxidizing solution in the impinger. In an aspect, the at least one other metal may be precipitated out of the oxidizing solution by contacting the oxidizing solution with a reducing agent at step 608 to produce an osmium-free mixture. The selection of reducing agent may depend on one or more of at least several factors including, but not limited to, the particular species of dissolved metal within the oxidizing solution.
(51) In another aspect, if the oxidizing solution contains an amount of Re-186, the Re-186 may be separated from the oxidizing solution by contacting the oxidizing solution with an alumina chromatographic column, and eluting the Re-186 using a saline solution. In another aspect, a dissolved metal may be isolated from the oxidizing solution using electroplating methods.
(52) Having described the invention in detail, it will be apparent that modifications and variations are possible. Those of skill in the art should, in light of the present disclosure, appreciate that many changes could be made in the specific embodiments that are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention, therefore all matter set forth is to be interpreted as illustrative and not in a limiting sense.