Single and multiple-step electrochemical processes are useable to reduce metal-oxides to their corresponding metallic (unoxidized) state. Such processes are conventionally used to recover high purity metal, metals from an impure feed, and/or extract metals from their metal-oxide ores.
Multiple-step processes conventionally dissolve metal or ore into an electrolyte followed by an electrolytic decomposition or selective electro-transport step to recover unoxidized metal. For example, in the extraction of uranium from spent nuclear oxide fuels, a chemical reduction of the uranium oxide is performed at 650° C., using a reductant such as Li dissolved in molten LiCl, so as to produce uranium and Li2O. The solution is then subjected to electro-winning, where dissolved Li2O in the molten LiCl is electrolytically decomposed to regenerate Li. The uranium metal is prepared for further use, such as nuclear fuel in commercial nuclear reactors.
Single-step processes generally immerse a metal oxide in molten electrolyte, chosen to be compatible with the metal oxide, together with a cathode and anode. The cathode electrically contacts the metal oxide and, by charging the anode and cathode (and the metal oxide via the cathode), the metal oxide is reduced through electrolytic conversion and ion exchange through the molten electrolyte.
Single-step processes generally use fewer components and/or steps in handling and transfer of molten salts and metals, limit amounts of free-floating or excess reductant metal, have improved process control, and are compatible with a variety of metal oxides in various starting states/mixtures with higher-purity results compared to multi-step processes.
Example embodiments include power distribution systems useable in electrolytic reduction systems. Example embodiments may include several cathode and anode assembly electrical contacts that permit flexible modular assembly numbers and placement by using a standardized connection configuration. Cathode and anode assembly electrical contacts may be consecutively or alternately arranged. Example anode and cathode assembly electrical contacts may have an insulated fork shape to mechanically receive a knife-edge electrical contact from modular assemblies. Anode and cathode assembly contacts may include a seating assembly fixing the contacts into a larger reduction system at desired positions, with electrical power being provided via power cables attached to the assemblies.
Cathode and anode assembly electrical contacts in example systems may provide electrical power at any desired levels, including pairs of anode and cathode assembly electrical contacts providing equal and opposite electrical power. Similarly, different cathode assembly electrical contacts may provide different levels of electrical power, even if connected to a same modular cathode assembly. Example systems may include a bus bar providing a common electrical power to anode or cathode assembly contacts. Example methods may include providing any desired level of electrical power through the cathode and anode assembly electrical contacts so as to provide power to an electrolytic reduction system.
Example embodiment electrical systems may be used in combination with an electrolyte container holding an electrolyte into which the modular cathode and anode assemblies extend and are supported above, with the modular cathode and anode assemblies mechanically and electrically connecting to the respective contacts of example electrical systems. Modular anode assemblies may include an anode block into which an anode rod seats, a bus that electrically connects to the anode assembly electrical contacts, and a slip joint electrically coupling the anode block to the bus. The slip joint includes a plurality of lateral members that may expand under high temperatures while maintaining electrical contact with the anode block and bus.
Hereinafter, example embodiments will be described in detail with reference to the attached drawings. However, specific structural and functional details disclosed herein are merely representative for purposes of describing example embodiments. The example embodiments may be embodied in many alternate forms and should not be construed as limited to only example embodiments set forth herein.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of example embodiments. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
It will be understood that when an element is referred to as being “connected,” “coupled,” “mated,” “attached,” or “fixed” to another element, it can be directly connected or coupled to the other element or intervening elements may be present. In contrast, when an element is referred to as being “directly connected” or “directly coupled” to another element, there are no intervening elements present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., “between” versus “directly between”, “adjacent” versus “directly adjacent”, etc.).
As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the language explicitly indicates otherwise. It will be further understood that the terms “comprises”, “comprising,”, “includes” and/or “including”, when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It should also be noted that in some alternative implementations, the functions/acts noted may occur out of the order noted in the figures or described in the specification. For example, two figures or steps shown in succession may in fact be executed in series and concurrently or may sometimes be executed in the reverse order or repetitively, depending upon the functionality/acts involved.
The inventors have recognized a problem in existing single-step electrolytic reduction processes that the known processes cannot generate large amounts of reduced, metallic products on a commercial or flexible scale, at least in part because of limited, static cathode size and configuration. Single step electrolytic reduction processes may further lack flexibility in configuration, such as part regularity and replaceability, and in operating parameters, such as power level, operating temperature, working electrolyte, etc. Example systems and methods described below uniquely address these and other problems, discussed below or not.
Example Embodiment Electrolytic Oxide Reduction Systems
The disclosures of the above-listed co-pending applications are incorporated by reference herein in their entirety.
As shown in
EORS 1000 may include several supporting and structural members to contain, frame, and otherwise support and structure other components. For example, one or more lateral supports 1104 may extend up to and support a top plate 1108, which may include an opening (not shown) above electrolyte container 1050 so as to permit access to the same. Top plate 1108 may be further supported and/or isolated by a glove box (not shown) connecting to and around top plate 1108. Several standardized electrical contacts 1480 (
In
As shown in
The cathode assembly 1300 and anode assembly 1200 are connected to power sources so as to provide opposite charges or polarities, and a current-controlled electrochemical process occurs such that a desired electrochemically-generated reducing potential is established at the cathode by reductant electrons flowing into the metal oxide at the cathode. Because of the generated reducing potential, oxygen in the oxide material within the cathode assemblies 1300 is released and dissolves into the liquid electrolyte as an oxide ion. The reduced metal in the oxide material remains in the cathode assembly 1300. The electrolytic reaction at the cathode assemblies may be represented by equation (1):
(Metal Oxide)+2e−→(reduced Metal)+O2− (1)
where the 2e− is the current supplied by the cathode assembly 1300.
At the anode assembly 1200, negative oxygen ions dissolved in the electrolyte may transfer their negative charge to the anode assembly 1200 and convert to oxygen gas. The electrolysis reaction at the anode assemblies may be represented by equation (2):
2O2−→O2+4e− (2)
where the 4e− is the current passing into the anode assembly 1200.
If, for example, a molten Li-based salt is used as the electrolyte, cathode reactions above may be restated by equation (3):
(Metal Oxide)+2e−+2Li+→(Metal Oxide)+2Li→(reduced Metal)+2Li++O2− (3)
However, this specific reaction sequence may not occur, and intermediate electrode reactions are possible, such as if cathode assembly 1300 is maintained at a less negative potential than the one at which lithium deposition will occur. Potential intermediate electrode reactions include those represented by equations (4) and (5):
(Metal Oxide)+xe−+2Li+→Lix(Metal Oxide) (4)
Lix(Metal Oxide)+(2−x)e−+(2−x)Li+→(reduced Metal)+2Li++O2− (5)
Incorporation of lithium into the metal oxide crystal structure in the intermediate reactions shown in (4) and (5) may improve conductivity of the metal oxide, favoring reduction.
Reference electrodes and other chemical and electrical monitors may be used to control the electrode potentials and rate of reduction, and thus risk of anode or cathode damage/corrosion/overheating/etc. For example, reference electrodes may be placed near a cathode surface to monitor electrode potential and adjust voltage to anode assemblies 1200 and cathode assemblies 1300. Providing a steady potential sufficient only for desired reduction reactions may avoid anode reactions such as chlorine evolution and cathode reactions such as free-floating droplets of electrolyte metal such as lithium or calcium.
Efficient transport of dissolved oxide-ion species in a liquid electrolyte, e.g. Li2O in molten LiCl used as an electrolyte, may improve reduction rate and unoxidized metal production in example embodiment EORS 1000. Alternating anode assemblies 1200 and cathode assemblies 1300 may improve dissolved oxide-ion saturation and evenness throughout the electrolyte, while increasing anode and cathode surface area for larger-scale production. Example embodiment EORS 1000 may further include a stirrer, mixer, vibrator, or the like to enhance diffusional transport of the dissolved oxide-ion species.
Chemical and/or electrical monitoring may indicate that the above-described reducing process has run to completion, such as when a voltage potential between anode assemblies 1200 and cathode assemblies 1300 increases or an amount of dissolved oxide ion decreases. Upon a desired degree of completion, the reduced metal created in the above-discussed reducing process may be harvested from cathode assemblies 1300, by lifting cathode assemblies 1300 containing the retained, reduced metal out of the electrolyte in container 1050. Oxygen gas collected at the anode assemblies 1200 during the process may be periodically or continually swept away by the assemblies and discharged or collected for further use.
Although the structure and operation of example embodiment EORS 1000 has been shown and described above, it is understood that several different components described in the incorporated documents and elsewhere are useable with example embodiments and may describe, in further detail, specific operations and features of EORS 1000. Similarly, components and functionality of example embodiment EORS 1000 is not limited to the specific details given above or in the incorporated documents, but may be varied according to the needs and limitations of those skilled in the art.
Example Embodiment Power Distribution Systems
As shown in
Cathode assembly contacts 485a and 485b may provide different levels of electrical power, voltage, and/or current from each other. For example, contact 485b may provide higher power, matching the levels provided through anode contacts 480 (
Each cathode assembly contact 485a and 485b may be parallel and aligned with other contacts on an opposite side of reduction systems, so as to provide a planar, thin-profile electrical contact area for modular cathode assemblies connecting thereto. Alternately, cathode assembly contacts 485a and 485b may be staggered or placed in alternate positions to match different cathode assembly electrical connector configurations. By repetitive, flexible positioning, variable electrical supply, and standardized design, cathode assembly contacts 485a and 485b permit modular and commercial scaling in modular cathode assembly use. In this way, example embodiment power distribution system 400 permits selective addition, removal, repositioning, and powering of cathode assemblies in electrolytic reduction systems.
As shown in
Power cables 410, 420a, and 420b may be connected to electrical connectors 415 so as to provide desired electrical power to seating assemblies 450 and contacts 480, 485a, and 485b, respectively. Power cables 410, 420a, and 420b may be any type or capacity of line based on the level of power desired to deliver to electrical contacts 480, 485a, 485b, respectively, in example embodiment power distribution system 400. Power cables 410, 420a, and 420b may connect to any shared or independent power source for operating reducing systems. For example, power cables 420a and 420b may connect to adjustable power sources providing variable electrical characteristics to power cables 420a and 420b, while power lines 410 may each connect to a shared bus bar 425 providing an equal current and/or voltage to power cables 410. For example, bus bar 425 may connect to a single power source and each power cable 410 on a given side of EORS 1000. One or more trays 405 on an external portion of reducing devices may separate and/or organize individual power cables 410, 420a, and 420b.
Because individual electrical contacts 480, 485a, 485b may have electrical power provided from individual sources in example embodiment power delivery system 400, it is possible to operate reducing systems including example embodiment power delivery system 400 with different electrical characteristics between each modular anode and cathode assembly. For example, cables 410 and 420b, delivering power to anode contact 480 and cathode contact 485b, respectively, may be operated at equal and opposite higher power/polarity. Modular cathode assemblies 1300 and anode assemblies 1200 connected to their respective contacts 485b and 480 may thus operate at equal power levels and provide a balanced reducing potential. That is, a circuit may be completed between modular cathode and anode assemblies such that substantially equal current flows into 420b and out of 410 (depending on electrical current perspective). Electricity to power cables 420a may be provided at a secondary power level (2.3 V and 225 A, for example), while power cables 410 or 420b may be provided with primary level power (2.4 V and 950 A, for example) at opposite polarities. The polarity of power provided to power cables 420a may be the same as that provided to power cables 410 and opposite that provided to 420b. In this way, cathode assembly contacts 485a and 485b may provide different or opposite power levels to modular cathode assemblies connected thereto, for components of modular cathode assemblies that may use different electrical power levels. Matching or varied electrical systems on an opposite side of electrolytic reducing systems may be operated in similar or different manners to provide electrical power to modular assemblies having multiple electrical contacts. Table 1 below shows examples of power supplies for each contact and power line thereto, with the understanding that any of contacts 480, 485a, and 485b may provide different individualized power levels and/or opposite polarities.
Because individual electrical contacts 480, 485a, 485b may have electrical power provided from individual sources in example embodiment power delivery system 400, it is possible to operate reducing systems including example embodiment power delivery system 400 with different electrical characteristics between each modular anode and basket assembly. For example, cables 420a and 420b, delivering power to cathode assembly contact 485a and cathode assembly contact 485b, respectively, may be operated at opposite polarities and act as a secondary circuit within a cathode assembly 1300, to condition the electrolyte. Similarly, contacts 485a and 485b may be reversed, such that contact 485b provides a secondary anode power level to a cathode basket and contact 485a provides a primary cathode power level to a cathode plate. Modular cathode assemblies 1300 and anode assemblies 1200 may be provided primary power levels through respective contacts 485a or 485b and 480 sufficient to reduce material contained in the cathode assembly 1300. Matching or varied electrical systems on an opposite side of electrolytic reducing systems may be operated in similar or different manner to provide electrical power to modular assemblies having multiple electrical contacts.
Slip connection 285 permits thermal expansion of anode block 286 and/or bus 280 without movement of anode rod 210 or resulting damage. That is, anode block 286 and/or bus 280 may expand and/or contract transversely past each other in slip connection 285, while still remaining in lateral electrical contact. Each component of the example electrical system is fabricated of electrically-conductive material, such as copper or iron alloys and the like. Any number of components may repeat within the electrical system, for example, several anode blocks 286 may be positioned to connect to several corresponding anode rods 210 while still each connecting to plural busses 280 at either end of example embodiment modular anode assembly 200, which may connect to corresponding synchronized voltage sources in the form of anode contacts 480 (
An electrical system insulated from channel frame 201 and anode guard (not shown) may be nonetheless connected to an external electrical source 480 (
A desired power level, measured in either current or voltage, is applied to anode assemblies through an electrical system in the assemblies so as to charge anode rods therein in example methods. This charging, while the anode rods are contacted with an electrolyte, reduces a metal oxide in nearby cathodes or in contact with the same in the electrolyte, while oxidizing oxide ions dissolved into the electrolyte. Example methods may further swap modular parts of assemblies or entire assemblies within reduction systems based on repair or system configuration needs, providing a flexible system that can produce variable amounts of reduced metal and/or be operated at desired power levels, electrolyte temperatures, and/or any other system parameter based on modular configuration. Following reduction, the reduced metal may be removed and used in a variety of chemical processes based on the identity of the reduced metal. For example, reduced uranium metal may be reprocessed into nuclear fuel.
Example embodiments thus being described, it will be appreciated by one skilled in the art that example embodiments may be varied through routine experimentation and without further inventive activity. For example, although electrical contacts are illustrated in example embodiments at one side of an example reducing system, it is of course understood that other numbers and configurations of electrical contacts may be used based on expected cathode and anode assembly placement, power level, necessary anodizing potential, etc. Variations are not to be regarded as departure from the spirit and scope of the example embodiments, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
This invention was made with Government support under contract number DE-AC02-06CH11357, awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
Number | Name | Date | Kind |
---|---|---|---|
422139 | Maxon | Feb 1890 | A |
2089738 | Elmer | Aug 1935 | A |
2800219 | Carroll | Jul 1957 | A |
3562131 | Jasberg | Feb 1971 | A |
3697404 | Paige | Oct 1972 | A |
4013329 | Hugin | Mar 1977 | A |
4039403 | Astley et al. | Aug 1977 | A |
4073703 | Kinosz et al. | Feb 1978 | A |
4203531 | Reichel et al. | May 1980 | A |
4492621 | Stubb | Jan 1985 | A |
4668353 | Smith et al. | May 1987 | A |
4851098 | Kimura et al. | Jul 1989 | A |
4863580 | Epner | Sep 1989 | A |
4880506 | Ackerman et al. | Nov 1989 | A |
5415742 | La Camera et al. | May 1995 | A |
5454914 | Gay | Oct 1995 | A |
5531868 | Miller et al. | Jul 1996 | A |
5582706 | Grantham et al. | Dec 1996 | A |
5689538 | Bonhomme | Nov 1997 | A |
5770034 | Jansen et al. | Jun 1998 | A |
5935394 | Sivilotti et al. | Aug 1999 | A |
6540902 | Redey et al. | Apr 2003 | B1 |
6689260 | Ahluwalia et al. | Feb 2004 | B1 |
6821405 | Marttila | Nov 2004 | B1 |
6866768 | Bradford et al. | Mar 2005 | B2 |
7090760 | Seo et al. | Aug 2006 | B2 |
7638026 | Willit et al. | Dec 2009 | B1 |
7799185 | Willit | Sep 2010 | B1 |
20040007466 | Seo et al. | Jan 2004 | A1 |
20040134785 | Gay et al. | Jul 2004 | A1 |
20040168932 | Wang | Sep 2004 | A1 |
20050067291 | Haiki et al. | Mar 2005 | A1 |
20050205428 | Dees et al. | Sep 2005 | A1 |
20050233634 | Kollmann | Oct 2005 | A1 |
20070082551 | Oesterhaus | Apr 2007 | A1 |
20070295601 | Bayer | Dec 2007 | A1 |
20080128270 | Hiraiwa et al. | Jun 2008 | A1 |
20080152270 | Engesser et al. | Jun 2008 | A1 |
20090050483 | Li | Feb 2009 | A1 |
20090152124 | Ashford et al. | Jun 2009 | A1 |
20100276259 | Phalen | Nov 2010 | A1 |
20110180409 | Willit et al. | Jul 2011 | A1 |
Number | Date | Country |
---|---|---|
622994 | Apr 1992 | AU |
1 142 123 | Mar 1983 | CA |
26 00 344 | Jul 1977 | DE |
3837572 | May 1989 | DE |
19845258 | Mar 2000 | DE |
0 286 092 | Oct 1988 | EP |
0 736 929 | Oct 1996 | EP |
2224542 | Sep 2010 | EP |
284678 | Nov 1928 | GB |
506590 | May 1939 | GB |
516775 | Jan 1940 | GB |
H05279887 | Oct 1993 | JP |
H0972991 | Mar 1997 | JP |
2006-308442 | Nov 2006 | JP |
WO 02066709 | Aug 2002 | WO |
WO 2004018737 | Mar 2004 | WO |
2004031453 | Apr 2004 | WO |
WO 2005035404 | Apr 2005 | WO |
WO 2006007863 | Jan 2006 | WO |
WO 2009062005 | May 2009 | WO |
2010080761 | Jul 2010 | WO |
Entry |
---|
“Proceedings of GLOBAL 2005”, Tsukuba, Japan, Oct. 9-13, 2005, Paper No. 488. |
Jeong, et al., “Electrolytic production of metallic Uranium from U3O8 in a 20-kg batch scale reactor”, Journal of Radioanalytical and Nuclear Chemistry, vol. 268, No. 2, pp. 349-356 (2006). |
International Search Report dated Jan. 30, 2012 issued in PCT/US2011/053878. |
International Search Report dated Feb. 6, 2012 issued in PCT/US2011/053872. |
International Search Report dated Jan. 20, 2012 issued in PCT/US2011/053589. |
Steven D. Herrman, et al., “Electrolytic Reduction of Spent Oxide Fuel—Bench-Scale Test Results”, Global 2005, INL/CON-05-00304, Paper No. 488, Oct. 2005. |
International Search Report issued in connection with PCT/US2011/05387, May 11, 2012. |
International Search Report and Written Opinion issued in International Patent Application No. PCT/US2012/058664, mailed Jul. 8, 2013. |
International Search Report and Written Opinion issued in International Patent Application No. PCT/US2012/058659, mailed Jul. 5, 2013. |
International Search Report and Written Opinion issued in International Patent Application No. PCT/US2012/058661, mailed Jul. 25, 2013. |
Figueroa, J. et al., “GTRI Progress in Developing Pyrochemical Processes for Recovery of Fabrication Scrap and Reprocessing of Monolithic U-MO Fuel”, RERTR 2011—International Meeting on Reduced Enrichment for Research and Test Reactors, Oct. 23, 2011, XP055071122. |
International Search Report and Written Opinion issued in International Patent Application No. PCT/US2012/058663, issued Aug. 12, 2013. |
International Search Report and Written Opinion issued in International Patent Application No. PCT/US2012/058531, issued Aug. 2, 2013. |
European Search Report issued in European Patent Application No. 13163951.0, issued Aug. 29, 2013. |
Number | Date | Country | |
---|---|---|---|
20120160703 A1 | Jun 2012 | US |