Patent Grant
10322417
1. Field of the Invention
This invention relates to a method for isolating and purifying metal-containing solutions, and more specifically the invention relates to a method for enhancing demulsification and phase disengagement in metal extraction systems using magnets.
2. Background of the Invention
Selectively obtaining a compound or element from a mixture, liquid, solid, or gas, can be done in innumerable ways. One way is through solvent extraction. In solvent extraction, the chemical mixture containing a desired moiety is dissolved in a first solvent. The solution containing the moiety is then mixed with an immiscible second solvent that has a higher affinity for the desired moiety than the first solvent. After a thorough mixing of the immiscible solvents, the mixture settles, and the solvents separate over time. During the mixing and settling phases of a solvent extraction, the desired moiety will migrate between solvents because of the moiety's greater affinity for one of the solvents. Typically, the desired moiety should reside mostly or entirely in the second solvent after separation.
Frequently, a mixture containing a desired moiety is dissolved into an aqueous solution. The aqueous solution is then mixed with an organic solvent that is immiscible with water. Typically, the organic solvent will have a higher affinity for the desired moiety than the original aqueous solution. After the original aqueous solution and immiscible organic solvent are thoroughly mixed and then allowed to settle, the two solvents return to separate aqueous and organic phases based on differences in density of the aqueous and organic phases. After the desired moiety transfers to the organic phase, the organic phase is then called the “loaded organic phase.”
Many commercial applications of solvent extraction reuse the organic solvent. These commercial applications strip the loaded organic phase of the desired moiety, using a clean aqueous phase devoid of undesired impurities. The stripped organic phase is then recycled for use in later extractions.
Solvent extraction, sometimes called liquid-liquid extraction, is commonly used in a wide array of applications, from the small scale (e.g., use of a single separatory funnel in a laboratory) to the large scale (e.g., separation of crude oil). In industry, solvent extraction is commonly used to separate desired metal ions after dissolving ore in mining operations. For example, solvent extraction is commonly used to obtain rare earth metals, platinum group metals, base metals, and nuclear materials. As the world's supply of high grade ores containing these materials decreases, solvent extraction becomes more important because solvent extraction is more effective in retrieving desired materials from low grade ores than other techniques.
In industrial applications of solvent extraction, the efficiency of the entire process is often hindered by demulsification issues, i.e., the slow or incomplete separation of the two immiscible solvents used in the solvent extraction process. In such circumstances, two conventional solutions are utilized: (1) spinning the mixture of emulsified immiscible solvents in a centrifugal contactor and (2) demulsification-aiding additives.
Solvent extractions hindered by slow demulsification often utilize centrifugal contactors to spin the mixture of immiscible solvents in order to separate the solvents based on the difference in the two solvents' densities. These centrifugal contactors are effective in demulsifying extraction mixtures that would otherwise very slowly or never completely demulsify without intervention.
Centrifugal contactors are expensive to incorporate into existing processing schemes and refineries, mechanically complex, and difficult to maintain. Large scale solvent extractions hindered by demulsification inefficiencies require many centrifugal contactors, causing large initial and ongoing costs. Also, centrifugal contactors are less effective when separating phases with similar densities; a common occurrence in solvent extraction systems where the organic phase becomes heavy as it is loaded with metal ions.
Other methods for increasing the efficiency of solvent demulsification include the use of chemical additives. However, chemical additives also have drawbacks. First, purchasing chemical additives on a large scale and on an ongoing basis is expensive. Also, to ultimately obtain a purified desired moiety, any demulsification aids must be removed to obtain that purified final product. Further, chemical additives must be removed downstream from extraction processes in order to recycle solvents and to prevent runoff into the environment. Removing additives downstream from an extraction process therefore requires extra steps and additional costs.
Aside from using chemical additives, physically inert solid phase additives have been employed. Specifically, researchers have added magnetic nanoparticles to emulsifications and then subjected that mixture to magnetic fields in attempts to change the magnetic susceptibility of one component of the emulsion, thereby enhancing its separation tendencies. However, as with the use of chemical additives, these additions recreate secondary waste streams which must be addressed. For example, the magnetic particles need to be removed downstream during final polishing of the target moiety.
Furthermore, the addition of relatively inert aggregate material stymies the fluidity of the mixture, particularly in pumping protocols. Therefore, such magnetic particles, fluidized beds, etc., are contraindicated when continuous, pumpable, all liquid processes are sought.
Thus, a need exists in the art for a method and system of accelerating the demulsification of solvents in solvent extractions that are hindered by slow or indefinite demulsification. Ideally, the method and system would not require modification of the extraction infrastructure or the removal of unwanted impurities downstream (i.e., a secondary waste stream).
An object of the invention is to provide a method for accelerating demulsification and phase disengagement in extractions of paramagnetic metal ions that overcomes many of the disadvantages of the prior art.
Another object of the present invention is to provide a method and system for demulsifying solutions having different magnetic susceptibilities. A feature of the method is simultaneously subjecting different fluids with different concentrations of partitioned metal to magnetic fields. An advantage of the method is that pumping of the fluid throughout the various extracting phases is enabled so as to remove target metal ions, chelated metal moieties, biological compounds comprising coordinated metals and other targeted moieties in an uninterrupted protocol.
Yet another object of the invention is to accelerate demulsification and phase disengagement within emulsions containing paramagnetic metal ions. A feature of the method is subjecting the fluids-only mixtures (e.g. mixtures containing no solids whatsoever) to magnetic fields to create magnetic field gradients within the mixtures. This accelerates the coalescence of liquid emulsion droplets into larger droplets that separate from the continuous solvent. An advantage of the invention is that separation is facilitated by both magnetic and gravitational forces, resulting in expedited separations. No additions to the fluid, such as solid substrates (e.g., magnetic- or metallic- or nonmetallic-particles), demulsifiers, or other chemicals, are necessary to facilitate the phase separation.
Still another object of the invention is to provide a method for enhancing phase separation within emulsions. A feature of the invention is using magnetic fields to accelerate coalescence of emulsion droplets into larger droplets that phase separate through gravity. An advantage of the invention is that empirically determined magnetic field positioning projects a high magnetic field gradient across a three-dimensional space containing a volume of emulsion, thereby inducing accelerated phase disengagement within the sample volume and improved phase clarity compared to situations where only gravity is relied upon to effect separations. Another advantage of the method is that its magnetically induced effects of creating larger emulsion droplets remains after the magnetic field is removed, thereby accelerating gravitational phase separation.
Yet another object of the invention is to provide a process aid in large scale solvent extractions involving paramagnetic metal ions. A feature of the invention is that it aids in the separation of phases of emulsions after an extraction process has transferred the paramagnetic metal ions from a first native phase to a second phase. An advantage of the invention is that it can use inexpensive magnets (e.g. permanent magnets) to aid in the demulsification and phase disengagement of existing extractions without expensive modifications to the existing extraction infrastructures.
Briefly, the invention provides a method for magnetically assisting demulsification of extraction phases, the method comprising the steps of contacting a first solution comprising a first solvent and a solvated paramagnetic metal ion with a second solvent, wherein the second solvent is immiscible with the first solvent; mixing the first and second solutions to create an emulsion having a first phase comprising the first solvent and second phase comprising the second solvent wherein the phases of the emulsion contain different concentrations of said paramagnetic metal ion; and applying a magnetic field gradient to the first and second phases of the emulsion for a time and at a magnetic gradient strength sufficient to accelerate separation of the first phase from the second phase.
Also provided is a system for extracting paramagnetic moieties from solution comprising an elongated reaction chamber defining a lumen (such as conduit, a fluid passage way, a channel, etc) having an interior region, an interior surface, and exterior surface; and a magnetic field gradient present within the interior region. Preferably, the elongated reaction chamber has an ingress port and an egress port so that the system and method can accommodate a continual stream of feedstock, and therefore be run continuously. Said system further comprises at least one pair of magnets fixed to opposing sides of the exterior surface of the lumen at substantially the same point along the lumen's longitudinal axis wherein the magnets are substantially parallel and wherein the magnets face the interior of the lumen with the same magnetic pole.
The invention together with the above and other objects and advantages will be best understood from the following detailed description of the preferred embodiment of the invention shown in the accompanying drawings, wherein:
The foregoing summary, as well as the following detailed description of certain embodiments of the present invention, will be better understood when read in conjunction with the appended drawings.
As used herein, an element or step recited in the singular and preceded with the word “a” or “an” should be understood as not excluding plural said elements or steps, unless such exclusion is explicitly stated. Furthermore, references to “one embodiment” of the present invention are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features. Moreover, unless explicitly stated to the contrary, embodiments “comprising” or “having” an element or a plurality of elements having a particular property may include additional such elements not having that property.
An embodiment of the invention leverages the paramagnetic nature of metal ions residing in one constituent of a multi-phase mixture over another constituent. Magnetic field gradients applied to all constituents of the mixture accelerate phase disengagement (a.k.a. demulsification) compared to allowing the phases to settle through gravity alone by accelerating droplet coalescence within the constituent within which the metal ion is most solvated. “Accelerated phase disengagement and demulsification” means that phase demulsification and phase disengagement occur faster than if gravity alone were acting on a mixture of phases. “Paramagnetic” means that the material has a relative magnetic permeability greater than or equal to 1. Phases of paramagnetic fluids vary in their paramagnetic character, with some phases being more paramagnetic than other phases. The relatively more paramagnetic phases are attracted more strongly by magnetic field gradients than less paramagnetic phases.
Specifically, the inventor has discovered that the application of magnetic field gradients to emulsions created in solvent extractions of paramagnetic metal ions (whereby the ions are solvated by the solvents) accelerates demulsification and phase disengagement. Acceleration of demulsification and phase disengagement occurs when the imposed magnetic field gradient transforms substantially the entire bulk of the emulsified solvent extraction system (e.g., an entire emulsified mixture) into a paramagnetic fluid having varying degrees of magnetism. The effects of the applied magnetic field gradient are permanent such that separation of targeted phases remains after the magnetic field is removed.
Therefore, the magnetic field aids in gravity induced separation of constituent phases. Both the magnetic and gravitational forces can be imposed simultaneously, even though, and as stated supra, the magnetic field can be applied, then removed without losing the effect of its action on the emulsion.
The invention provides accelerated demulsification and phase disengagement in solvent extractions involving solvated paramagnetic metal non-solid moieties, examples of such moieties including metal ions, coordination compounds, metal containing or magnetizable biological molecules, metal ions in various solutions (water, polar organic solvents e.g., alcohols, aldehydes, ketones, glycols, acetates, carboxylic acids, peroxides, ethers, etc.), metal ions coordinated to macromolecules such as polymers and other incarnations where metal ions are solvated within a fluid phase, and combinations thereof. The above-stated moiety types are not solid and not intended to be inasmuch as the non-solid moieties envisioned for isolation and extraction hereby enables the use of a continuous, pumpable protocol to streamline metal recovery.
The invented method and system is easily scalable. This means that it is applicable to a myriad of extraction process modalities, including, but not limited to separatory funnels, metal piping, polymer piping and inside industrial-scale mixer-settlers. Embodiments of the invention which use permanent magnets do not require a power source.
The instant invention generally provides a magnetic field gradient to a mixture of immiscible solvents, containing unequal concentrations of paramagnetic metal ions. Mixing two immiscible solvents creates an emulsion with droplets of one phase dispersed in the other. Application of the magnetic field gradient applies force to the droplets depending on the partitioning of paramagnetic metal ions between the dispersed phase and the dispersion medium. For example, in a solvent extraction system, an aqueous phase is usually mixed with a water-immiscible organic phase (such as an oil). If the volume of water is less than that of the oil, then the water becomes the dispersed phase and oil is the dispersion medium after the phases are mixed into an emulsion. In this case, if the paramagnetic ions reside mainly in the dispersed water droplets, then the droplets will be attracted by a magnet and forced together close to the magnet surface.
Conversely, if the paramagnetic metal ions reside mainly in the oil (i.e. the dispersion medium), then the water droplets will be forced away from the magnet's surface as the metal-laden oil phase is attracted by the magnets. As such, the magnetic fields act on the metal ions collectively within a phase and impose a force on the entire phase. Magnetic forces exerted on the emulsion will depend on the volume ratios of the phases and the chemical partitioning of the paramagnetic metal ions between the phases. In all scenarios, the force exerted by the magnetic field will accelerate demulsification of the emulsion, provided that the phases have different magnetic susceptibilities as imparted by the unequal partitioning of paramagnetic metal ions between phases.
In summary of this point, if a first metal moiety (such as metal ion) is more soluble in organic phase than a second metal moiety, then the first metal moiety will be extracted away from the second metal. The magnetic field acts on this entire metal-oil mixture, and not necessarily on the individual ions or charges that the moiety may carry. The extraction experienced by the metal moieties is the result of their unpaired electrons interacting with complementary electrons of molecules defining the extraction media. The effect of net charge is relatively minor. Indeed, the Brownian motion of any of the metal moieties facilitates their dispersion through the emulsion and more than overcomes any effect of a magnetic field on moiety charge.
In either example described above, the magnetic effect forces the droplets of the dispersed phase together. When droplets of the same phase are forced together, they conglomerate and become a larger drop. As the dispersed droplets get larger and larger, large drops of the dispersed phase then separate from the dispersion medium due to gravity.
The force applied by the magnetic field gradient simultaneous with the ubiquitous force of gravity accelerates droplet coalescence which therefore accelerates the phase disengagement. Acceleration of the coalescence due to the magnetic forces density gradient between the two phases therefore accelerates phase disengagement and demulsification.
Curved arrows in
The instant invention can utilize magnets of any kind, shape, and material. Exemplary kinds of magnets include temporary, electro, and permanent. Exemplary magnet shapes include bars, blocks, horseshoes, rods, and rings. Exemplary materials include Alnico (alloy of aluminum, nickel, and cobalt), Neodymium, Ferrite, and combinations thereof. The instant invention can utilize magnets of any strength. Preferably magnets used in the instant invention have strengths from about 0.1 T to about 1 T, more preferably from about 0.3 T to about 1 T and most preferably from about ½ T to about 1 T.
In the dipolar configuration 10, the magnetic field gradient created by the magnets 12 is applied to a feedstock comprising a mixture of immiscible solvents, with paramagnetic metal ions partitioned between the emulsified phases. Immiscibility of the solvents in the feedstock creates an emulsion in which droplets of one immiscible solvent (the dispersed phase) form in a matrix of the other immiscible solvent (dispersion medium). The solvent creating a matrix (dispersion medium) is a first phase (the second phase 34 of
where χ2 is the magnetic susceptibility of the dispersed droplets (the first phase 31 shown in
Returning to
Paramagnetic ions having any charge are suitable for use with the instant invention. Further, the instant invention is suitable for use to accelerate the demulsification of an extraction emulsion containing more than one paramagnetic ion.
If the concentration of paramagnetic metal ion in the dispersed droplets is greater than the concentration in the dispersion medium, the magnetic field gradient generated by the magnets 12 will apply a force to the dispersed phase droplets in the direction toward the nearest magnet as the magnetic susceptibility, χ2, of the dispersed droplets will be greater than the magnetic susceptibility of the dispersion medium, χ1. Under the influence of the magnetic force, the droplets of the phase containing more paramagnetic metal material accelerate and move toward the nearest magnet and are compressed together near the magnet surface, causing the droplets to coalesce into larger droplets.
If the dispersed droplets do not contain or contain less of the paramagnetic metal ion than the dispersion medium then the droplets will experience force in a direction away from the magnets, as the magnetic susceptibility, χ2, of the dispersed droplets will be less than the magnetic susceptibility of the dispersion medium, χ1. The force on the dispersed droplets in this scenario compresses the droplets into the phase volume between the magnets and causing the droplets to coalesce into larger droplets. Therefore, if the droplets contain a higher concentration of paramagnetic metal ion than the dispersion medium, they will coalesce into large drops near the magnets 12. If the droplets contain a lower concentration of paramagnetic metal ion than the dispersion medium then they will coalesce in between the magnets 12.
Solvent extraction relies on differences in density of the phases to separate the phases as they settle through gravitational forces. The magnetic force applied using the instant invention causes droplets of one phase to coalesce in one position while droplets of the other phase conglomerate in another position. As a result of the conglomeration of drops, droplets of higher volume and mass are formed, causing them to settle due to gravity. The magnetic force of the instant invention accelerates drop coalescence which accelerates the formation of larger droplets of greater mass and volume, which results in accelerated demulsification and phase separation of the solvent mixture feedstock.
In this quadrupolar configuration 20, the first pair of magnets 12a repel each other at the center point 22. The second pair of magnets 12b also repel each other at the center point 22. With two pairs of magnets repelling each other at the center point 22, a stronger magnetic field gradient is generated in the quadrupolar configuration 20 than the dipolar embodiment 10. The direction of the magnetic field in the quadrupolar embodiment is shown using the curved arrows in
Dipolar configurations 10 and quadrupolar configurations 20 are suitable configurations of magnets that can be used with the instant invention. Typically, magnets are provided in pairs to assure symmetry, but odd numbered magnets positioned such that the magnetic gradient is focused on a predetermined region in the mixing chamber are also suitable. As such, the illustrated configurations are provided not to be limiting but to give examples of magnet configurations capable of creating a magnetic field gradient across a sample volume.
Any configuration of magnets capable of generating a magnetic field gradient is suitable for use with the instant invention. Preferably, magnets are spaced from each other wide enough to avoid fluid clogging within the lumen as larger droplets form from the coalescence of originally-present smaller droplets in the emulsion. This will facilitate the “continuous” de-emulsification feature of the invention.
Conversely, the magnets are spaced close enough to each other so that their magnetic fields enhance each other to generate field gradients greater than if only a single magnet were present. Generally, configurations wherein all of the positive poles (or negative poles) are opposed to each other will provide adequate strength field gradients. However, configurations of magnets wherein negative poles oppose positive poles are suitable for use where sufficient magnetic field gradient is generated to project across an entire sample volume.
Also, using a pair or plurality of pairs of magnets, or odd numbered magnets at strategic locations along a mixing chamber produce good results. For example, a plurality of dipolar and quadrupolar configurations can be arranged downstream of a first configuration along a conduit, to assure complete separation. Also, odd numbers of magnets, if symmetrically placed about a conduit, can also be utilized, for example, three magnets triangularly positioned.
In summary of this point, phase disengagement is accelerated by increasing magnetic field gradient (symbolized by ∇B in Equation 1, supra). Different configurations and magnet strengths are applied to empirically determine the adequate separation characteristics desired for particular applications of the invention. A plurality of gradients, serially arranged relative to each other along the longitudinal axis of a mixing chamber, also is suitable.
The process 30 depicted in
In an embodiment, the instant invention can be used to accelerate the demulsification and phase disengagement of extractions targeting metal ions that are not paramagnetic. Where a target metal ion is not paramagnetic, the instant invention accelerates demulsification and phase disengagement of an extraction targeting said metal as long as there are unequal concentrations of paramagnetic metal ions between the two phases. This can be achieved where the targeted metal ion is not paramagnetic, for example, if the undesired metal ions 33 that stay in the first phase 31 are paramagnetic.
Solvents and solvent ratios for use with the instant invention can be selected according to conventional extractions of the target ions. Examples of suitable solvent systems can be found in Metal complexes for hydrometallurgy and extraction, Tasker, P. A.; Plieger, P. G.; West, L. C. Edited by McCleverty, Jon A.; Meyer, Thomas J, Comprehensive Coordination Chemistry II (2004), 9, 759-808, the entirety of which is hereby incorporated by reference.
The two phases are then agitated or mixed creating an emulsion 35, as depicted in
In an embodiment, the second phase 34 of
Force is designated by the dashed arrows of
After the magnetic field gradient created by the magnets 12 is applied to the emulsion, two augmented phases emerge, as depicted in
The solutions are then agitated or mixed creating an emulsion 44 of the two solutions, as depicted in
In an embodiment, the third hybrid phase 43 is present in a larger volume than the first phase 36. Thus, χ2 is the magnetic susceptibility of the first phase 36 and χ1 the magnetic susceptibility of the third phase 42. χ1 will be greater than χ2 as the third hybrid phase 43 contains most or all of the paramagnetic metal ion 32. In this embodiment, looking to the relationship defining force above, the third hybrid phase 43 containing the paramagnetic metal ion 32 will experience force toward the nearest magnet 12 as the force will be positive. Conversely, the first phase 36, will experience force away from the magnets as the force will be negative. Force is designated by the dashed arrows of
As noted above, the forces generated by the magnets 12, will cause conglomeration of large drops of each phase. As the two phases have different densities, the conglomeration of drops caused by the magnets 12 will accelerate the creation of a density gradient. The accelerated formation of a density gradient will accelerate separation of the two phases, thereby accelerating demulsification and phase disengagement based on gravity. of the emulsion 44.
After the magnetic field created by the magnets 12 is applied to the emulsion, two phases reestablish as depicted in
One embodiment applies a magnetic field gradient generated from either the dipolar configuration 10 or the quadrupolar configuration 20 to an extraction in a stationary vessel on a fixed volume of solutions. Other embodiments apply a magnetic field gradient generated from either the dipolar configuration 10 or the quadrupolar configuration 20 to modalities transporting extraction emulsification. In these embodiments, the instant invention applies a magnetic field gradient to a flowing mixture of immiscible solvents, one solvating a paramagnetic metal ion, and applies force to both phases of the mixture of immiscible solvents while they are flowing in a tube or other liquid-carrying modality.
The lumen can comprise any material capable of carrying flowing liquid. Exemplary materials include polymers and metals. Ferrous or magnetic tubing also can be utilized when magnets are placed within the mixing chamber. Additionally, the lumen can be of any shape and dimension depending on the scale of the application of the instant invention. In instances where magnets are positioned external of the mixing chamber, the distance from magnets to the mixing chamber will be determined empirically.
Generally, the magnitude of the gradient will depend on the difference in susceptibility between the two phases of the emulsion. A bench top demonstration determined that approximately a 1.5 cm distance between magnet pole and emulsion was sufficient to enhance phase separation. In either the dipolar or quadrupolar configurations, the magnets can be fixed to the exterior of the lumen 57 in a number of ways. Exemplary methods for permanently or removably attaching magnets to the exterior of the lumen include, but are not limited to, clamps, adhesive, welding, and collars that fit over the magnets and can be tightened to hold the magnets in place. Alternatively, magnets can be similarly positioned within the lumen (the mixing chamber) provided the magnet is coated with an inert material vis the components of the emulsion.
Generally, the feedstock or emulsified mixture flows through the lumen 56 and passes the magnets 12 so as to ultimately be downstream of the magnets. The emulsified mixture resides within the magnetic gradient area for a time sufficient to cause phases to separate from each other. Dwell time and gradient strength required to accelerate demulsification of an extraction emulsion involving paramagnetic metal ions differs based on the difference in magnetic susceptibilities of the phases. For example, in the example 1 below, sufficient dwell time was experimentally determined to be 10 seconds. In example 2 below, sufficient dwell time was determined to be 30 seconds. As such, the system is considered as continuous, with flow pressure and magnet spacing optimized, and fluid viscosity therefore adjusted to allow for optimal dwell times. In an embodiment of the invention, the fluid is constantly moving through the lumen. In other embodiments, the fluid flow is interrupted or slowed sufficiently to maximize de-emulsification, so as to be considered semi-continuous. Flow direction is designated with an arrow in
The first phase 54 comprising the first solvent 51 solvating most or all of the paramagnetic metal ion 53 experiences force toward the magnets 12. The second phase 55 experiences force away from the magnets 12,
The lumen can comprise any material. Exemplary materials include glass, polymers and metals, and may be transparent or opaque. Additionally, the lumen can be of any dimension depending on the scale of the application of the instant invention.
In another embodiment, the quadrupolar configuration 20 of the instant invention can be used on the exterior surface of the lumen 57 to create a stronger magnetic field gradient than that generated by the dipolar configuration 10. With the stronger magnetic field gradient, phase disengagement and demulsification of the two phases is further accelerated.
As discussed, supra, the force from the magnetic gradient from each quadrupolar configuration causes conglomeration of large droplets of each phase of a emulsion of immiscible solvents which in turn causes the phases to separate due to gravity. Additional rows 64 of quadrupolar configurations further accelerate the coalescence of larger droplets and thus further accelerate phase disengagement and demulsification. Generally, the rows of magnets are positioned from each other so that their forces do not interact, and the gradients they produce are not unintentionally affected by adjacently positioned rows.
In operation, a first solution 77 comprising a first solvent containing a paramagnetic metal ion enters the mixer compartment through the ingress means 78. A second solution 79 comprising a second solvent wherein the second solvent has a higher affinity for the paramagnetic metal ion than the first solvent enters the mixer chamber through the second means of ingress 80. The second ingress means is positioned between the agitator and the agitator 72. (While
Each system 60 generally comprises a conduit, passageway or lumen 62 having multiple rows of the quadrupolar or dipolar configuration (shown in
In another embodiment, the extraction systems 60 are in fluid communication with adjacent extraction systems 60 through a secondary lumen 85 allowing flow between the lumens 62 of the adjacent systems 60. The number of extraction systems 60 held in the housing 84 can be any number and can be determined by the scale of the extraction taking place in the Mixer-Settler 70 of
Emulsion 81 flows from the mixer compartment through the lumens 62 of the extraction systems 60 of the separator block 73. Flow is represented using solid arrows in
Reestablishment of phases before exiting the separator block increases the overall efficiency of the underlying extraction, thereby reducing the time required between inputting feedstock and harvesting pure phases. This increase in efficiency is such that the number of mixer-settlers used in extractions that subject the same feedstock solution to multiple mixer-settlers can be reduced or limited to one through use of the instant magnetic separator block. Reducing the number of mixer-settlers required to complete an extraction on a commercial scale makes an underlying extraction more time efficient and reduces cost.
Each row 64 of the quadrupolar 20 configuration creates a magnetic field gradient that applies force as described above to the two phases of the emulsion 81 flowing by, accelerating demulsification and phase disengagement of the emulsion 81. When the feedstock solution reaches the downstream (i.e., distal) end 87 of the extraction system 60, the two phases of the emulsion 81 have begun to reestablish such that effluent leaving the distal end 87 of the extraction system 60 comprises a pure first phase 82, a pure second phase 83, and leftover, unseparated emulsion 81.
Returning to
Magnet Detail
Magnetic field gradients suitable for use in this invention allow droplets of each phase to coalesce without clogging or otherwise narrowing the fluid passageway through which the separated products traverse. Clogging or narrowing of the passageways will be evident if during initial construction, the required fluid flow is not occurring. As discussed supra, magnets must be space apart enough to maintain a predetermined fluid flow, but close enough to enhance each other's magnetic fields to create stronger gradients. Distances between about 1 mm and about 25 mm are suitable.
The stronger the magnet the better, such that an upper limit is not an issue. Depending on the spacing between the magnets, magnets of strength above 0.1 T should be useful provided the separation between magnets is narrow enough to give high gradients (e.g., about 1 mm for 0.1 T magnets). Magnets with a strength above about 0.3 T are preferable. Currently, low cost magnets of 0.5 T are available that give much enhanced phase separation at a spacing of about 1 cm and these are suitable for the invention. As stronger permanent magnets become available and affordable in terms of monetary cost, such magnets will also be suitable.
In configurations wherein all positive poles (or negative poles) are opposed to each other, generating suitable gradients is assured by the distance between the centers of opposing magnets. For instance, where magnets having strength of 0.1 T oppose each other with the same pole, a distance of 1 mm between the centers of the magnets assures a sufficient magnetic field gradient for use in the instant invention.
Where magnets having strength of 0.5 T oppose each other with the same pole, a distance of 2.5 cm between the centers of the magnets assures a sufficient magnetic field gradient for use in the instant invention.
The following examples utilize the above magnet placement parameters. However, other configurations and protocols, empirically determined, can also use these parameters.
Depending on the solvents used and the paramagnetic metal ion being extracted, phase disengagement is accelerated two-fold or more compared to if no magnetic field gradient is imposed.
In an embodiment of the invention, chemical extraction of metal ions is allowed to begin prior to application of a magnetic field gradient. In this embodiment, the use of electromagnets may be suitable so as to cycle on and off the magnetic field gradient and vary the field strength.
In another embodiment of the invention, chemical extraction of metal moieties is initiated in a reaction environment already subjected to a continuous magnetic field. For example, in an always on magnetic field environment, demulsification of an extraction emulsion comprising an aqueous solution of 0.5 M Gd(NO3)3 and 3M LiNO3 and an organic phase of tri-n-butyl phosphate can be completed in about 60 seconds. Demulsification of the same extraction took 150 seconds to complete without the presence of a magnetic field.
In the extraction 90 and control extraction 92, the aqueous solution 94 of 0.5 M Gd(NO3)3 and 3M LiNO3 is emulsified with an aqueous-immiscible organic phase 96 of tri-n-butyl phosphate where the ratio of organic phase to aqueous phase is approximately 4:1. (Ratios of between about 1:1 to 10:1 are suitable.) After the phases are agitated to form an emulsion, the Gd(III) partitions mostly to the organic phase 96. The presence of four times the volume of the organic phase 96 compared to the aqueous phase 94 causes drops of the aqueous phase to disperse into the continuous organic phase 96. As the continuous organic phase 96 has a higher concentration of the paramagnetic Gd(III) ion, and is therefore more paramagnetic than the aqueous phase 94, the organic phase 96 experiences force from the magnetic field gradient generated by the magnets 12 toward the magnets.
In
In this stripping, the organic phase 96 of
In
In summary, the invention provides accelerated demulsification and phase disengagement in extraction mixtures from feedstock material supplied as immiscible mixtures of aqueous solutions, organic solutions, liquids, or combinations thereof. As such, the invention facilitates the demulsification and phase disengagement of extraction mixtures from immiscible, liquid phase feedstocks. An embodiment of the invented method uses no solid materials such as metal particles, magnetic particles or other solid phase substrates. Conversely, metal ions in solution can and are used extensively in various separation methods and systems described herein. In an embodiment, extraction phases are added neat to the modality or vessel where the extraction takes place.
Although exemplary implementations of the invention have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions, and the like can be made without departing from the spirit of the invention and these are therefore considered to be within the scope of the invention as defined in the following claims.
Embodiments of the invention enable acceleration of demulsification and phase disengagement of any solvent extraction system involving the uneven partitioning of paramagnetic metal ions between phases. The vast majority of industrial solvent extraction systems will either target a desired paramagnetic metal ion for extraction, or unwanted paramagnetic metal ions in the feed solution. Examples of paramagnetic metal ions that are frequently encountered in solvent extraction systems used in metal refining are Fe(III), Gd(III), Dy(III), Cu(II), Ir(III), Rh(III), Mn(III), however many more persist. High likelihood of high concentration of paramagnetic metal ions in solvent extraction processes makes the technology universally applicable to the refining of precious metals, base metals and rare earth metals. Still yet another embodiment accelerates phase disengagement of extractions of uranium and transuranic elements from nuclear waste, which contains high concentrations of paramagnetic metal ions such as Pu(III/IV) and other fission products (e.g. Dy(III), Gd(III), etc.).
The instant invention provides a device that can be used in conjunction with standard equipment used in the separation of paramagnetic moieties from solution comprising a mixing chamber; the chamber defined by a floor, a ceiling above the floor, walls disposed between the floor and the ceiling, an agitator attached to one of said floor, ceiling, or walls via an attachment, said attachment allowing for rotation of the said agitator, and two solution inlets within one of said floor, ceiling, or walls, said inlets allowing for entry of liquid-phase feedstock into the mixing chamber; a magnetic separation block in fluid communication with the mixing chamber, wherein the magnetic separation block comprises a housing holding a plurality of lumens; and wherein at least one pair of magnets is fixed to opposing sides of the exterior surface of each lumen at substantially the same point along the lumen and wherein the magnets face the interior of the lumen with the same magnetic pole; and a settling chamber in fluid communication with the magnetic separation block; the settling chamber defined by a floor, a ceiling above the floor, walls disposed between the floor and the ceiling, a first solution outlet within one of said ceiling or walls and a second solution outlet within one of said walls or floor. In said device, the at least one pair of magnets is a plurality of pairs of magnets equally spaced along the length of each lumen; and wherein each pair of magnets is fixed on opposing sides of the exterior surface of each lumen at substantially the same point along the lumen; and wherein each pair of magnets faces the interior of the lumen with the same magnetic pole. Said device further comprises at least one second pair of magnets on opposing sides of the exterior surface of each lumen 90 degrees from the opposing sides having the at least one first pair of magnets wherein the at least one second pair of magnets are both positioned at substantially the same point lumen's longitudinal axis as the at least one first pair of magnets and wherein the at least one second pair of magnets are substantially perpendicular to the at least one first pair of magnets, and face the interior of the lumen with the magnetic pole opposite to the magnetic pole of the at least one first pair of magnets facing the interior of the lumen. In said device, the at least one first pair of magnets and at least one second pair of magnets is a plurality of first and second pairs of magnets equally spaced along the length of each lumen's longitudinal axis.
It is to be understood that the above description is intended to be illustrative, and not restrictive. For example, the above-described embodiments (and/or aspects thereof) may be used in combination with each other. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. While the dimensions and types of materials described herein are intended to define the parameters of the invention, they are by no means limiting, but are instead exemplary embodiments. Many other embodiments will be apparent to those of skill in the art upon reviewing the above description. The scope of the invention should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. In the appended claims, the terms “including” and “in which” are used as the plain-English equivalents of the terms “comprising” and “wherein.” Moreover, in the following claims, the terms “first,” “second,” and “third,” are used merely as labels, and are not intended to impose numerical requirements on their objects. Further, the limitations of the following claims are not written in means-plus-function format and are not intended to be interpreted based on 35 U.S.C. § 112, sixth paragraph, unless and until such claim limitations expressly use the phrase “means for” followed by a statement of function void of further structure.
The present methods can involve any or all of the steps or conditions discussed above in various combinations, as desired. Accordingly, it will be readily apparent to the skilled artisan that in some of the disclosed methods certain steps can be deleted or additional steps performed without affecting the viability of the methods.
As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” “more than” and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. In the same manner, all ratios disclosed herein also include all subratios falling within the broader ratio.
One skilled in the art will also readily recognize that where members are grouped together in a common manner, such as in a Markush group, the present invention encompasses not only the entire group listed as a whole, but each member of the group individually and all possible subgroups of the main group. Accordingly, for all purposes, the present invention encompasses not only the main group, but also the main group absent one or more of the group members. The present invention also envisages the explicit exclusion of one or more of any of the group members in the claimed invention.
The U.S. Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the U.S. Department of Energy and UChicago Argonne, LLC, representing Argonne National Laboratory.
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| Number | Date | Country | |
|---|---|---|---|
| 20170001128 A1 | Jan 2017 | US |
