A SYSTEM AND METHOD FOR SEPARATION AND PURIFICATION OF DISSOLVED RARE EARTH/PRECIOUS METALS ELEMENTS/COMPOUNDS
A method for purification and separation of mixed elements, comprising at least a first free flow electrophoresis separation chamber, wherein a solution of the mixed elements is passed through the first separation chamber, an electric field submitted perpendicular to the solution flow and separating mobile ions of the solution based on electrophoretic mobility. A continuous method comprises selecting a complexing ligand, and controlling the temperature and pH of the solution. Also, a system or method for separating components of a multi-component concentrate comprising directing solution to at least a first and second channel each receiving part of the solution; each channel comprising a concentration section comprising a first transverse electric field across the channel, a fractionation section comprising a second electric field in a direction opposite the first electric field thereby distributing ions of the solution across the channel, and a flow splitter at an output of the fractionation section that divides the flow of each channel into subflows concentrated in heavier elements and concentrated in lighter elements.
The present invention relates to a system and a method to separate and refine rare earth/precious metals elements/compounds. More precisely, the present invention relates to a system and method for binary or multicomponent fractional separation and purification of dissolved rare earth/precious metals elements/compounds produced in hydrometallurgical processes while they are dissolved in an acidic or weakly basic medium, without any intermediate precipitation step.
BACKGROUND OF THE INVENTIONRare earth elements (REE) occur together in nature, and any given mineral contains several or most of them. Production of high purity individual rare earth (RE) elements/compounds from their ores generally requires two stages of processing, including mineral processing and hydrometallurgy.
Mineral processing and hydrometallurgy processing of the ore before REE purification is relatively simple and quite achievable though conventional methods. However, producing individual REE from mixed REs compounds is tremendously tedious. RE processing often requires dozens of steps, each resulting in minute improvement in the complex RE streams. Separating and extracting a single REE requires a great deal of time, resources and expertise. Today, an advanced RE refinery facility cost hundreds of millions of dollars to build.
Most REE are currently extracted in liquid phase using a combination of slightly selective solvent extraction dissolution in organic and aqueous strong acids, which involve a number of cycles. High purity RE concentrates are separated into individual REE using solvent-based (mainly) or ion exchange methods. Although there are several techniques to separate RE, most of them suffer from different types of drawbacks. For instance, solvent extraction requires a great number of cycles to achieve high purity of REE. Techniques using ion-exchanger for separation and refinery operate with low REE concentrations in solution, which leads to very large liquid volume quantity, bulky tanks, dehydrators, pumps and etc.
There is still a need in the art for a system and a method for binary or multicomponent fractional separation and purification of dissolved rare earth/precious metals elements/compounds.
SUMMARY OF THE INVENTIONMore specifically, in accordance with the present invention, there is provided a method of purification and separation of mixed elements, using differences between electrophoresis mobility of the elements or coordination complexes thereof in a continuous process, comprising selecting a complexing ligand and forming a solution of the complexing ligand and the mixed elements; controlling the temperature and pH of the solution; and submitting a flow of the solution to an electric field submitted perpendicular to the solution.
There is further provided a system for purification and separation of mixed elements, comprising at least a first free flow electrophoresis separation chamber, wherein a solution of the mixed elements is passed through the first separation chamber, an electric field being submitted perpendicular to the solution flow and separating mobile ions of the solution based on electrophoretic mobility.
There is further provided a multi-channel separation system for purification and separation of elements in a solution, comprising at least a first and a second channels each receiving part of the solution; each channel comprising a concentration section, a fractionation section, and a flow splitter at an output of the fractionation section; the concentration section comprising electrodes that create a first transverse electric field across the channel, and the fractionation section comprising electrodes that create a second electric field in a direction opposite the first electric field across the channel, thereby distributing ions of the solution across the channel; the flow splitter dividing the flow of each channel into a subflow concentrated in heavier elements and a subflow concentrated in lighter elements.
There is further provided a method for separating components of a multi-component concentrate, comprising a) preparing a solution of the multi-component concentrate and a reagent; b) directing the solution to at least a first and a second channel each receiving part of the solution; each channel comprising a concentration section comprising a first transverse electric field across the channel, a fractionation section comprising a second electric field in a direction opposite the first electric field across the channel thereby distributing ions of the solution across the channel, and a flow splitter at an output of the fractionation section that divides the flow of each channel into a subflow concentrated in heavier elements and a subflow concentrated in lighter elements; c) repeating step b) until a target separation of isolated components is achieved; and d) recovering the isolated components.
Other objects, advantages and features of the present invention will become more apparent upon reading of the following non-restrictive description of specific embodiments thereof, given by way of example only with reference to the accompanying drawings
In the appended drawings:
The present method and system use electrophoretic mobility variation of REE or precious metals in an electrical field to separate them, thereby reducing the cost of separation and circumventing intrinsic environmental issues of solvent based methods and systems. At the purification stage, the present method and system remove impurities and separate REE/precious metal elements simultaneously. The present method and system will be hereinafter described in relation to REE.
Free flow electrophoresis (FFE) is used to fractionate REE ions, using a uniform electric field applied perpendicular to a solution flow and separating the mobile ions based on electrophoretic mobility (Ui).
Basically, in a FFE system, the translational flow of ions in a laminar flow regime along a channel is affected by a perpendicular electrophoretic force exerted by a static electric field on each ion. The magnitude of this force and hence the deviation of the ions form straight trajectories along the channel, dependent upon the charge to size ratio of each ion, which is expressed as electrophoretic mobility Ui.
The present method and system provide selecting a combination of separation parameters based on the electrophoretic mobility Ui for the separation of elements/compounds.
In the case of REE, as is the case with other properties of REE, the electrophoretic mobility Ui does not vary significantly from one element to another. Typically, REE's Ui values are quite close, ranging from 72.3×10−5 cm2 V−1 s−1 to 67.0×10−5 cm2 V−1 s−1 for Lanthanum and Lutetium for example. Consequently, purification and separation of single REE may appear inefficient in such perspective.
However, the variation between the electrophoretic mobility Ui of REE can be controlled i.e. increased for example, by controlling the temperature and selecting a complexing ligand. The present method and system therefore use an adequate temperature control with a proper complexing agent to improve the electrophoretic mobility Ui variation significantly, for an effective fractionation and separation of REE.
In a first experiment, three triadic synthetic mixtures of non-neighboring REE La, Eu and Yb (1 gr/L total) were prepared in a dilute nitric acid (2% volume) with different REE compositions. These mixtures were separated in a FFE system, at a temperature of about 23° C. using background electrolyte (BGE) containing 10 mM 4-methyl benzyl amine and 4 mM HIBA acting as complexing ligand. The pH was adjusted to 4.4 using diluted acetic acid. The FFE system was a separation chamber 60 cm long, 10 cm wide with an effective separation width of 7 cm, and a 0.2 mm gap width (see
In a second experiment, several synthetic mixtures (1 gr/L) of neighboring REE were separated in the same FFE system as described hereinabove using similar operating conditions as reported in the first experiment.
For instance,
Based on those separation experiments which were performed in a FFE system, i.e. a single channel reactor, a multi-channel separation system 10 is presented for binary separation of REE, as shown in
In
In each channel 12, 14, 16, 18, 20, 22, a first set of electrodes 24, 26, 28, 30, 32, 34, referred to as the concentration electrodes, develops a first electric field that concentrates REE ions in liquid layers flowing close to the wall of the channel, adjacent to the negative plate. In each channel, a second set of electrodes 36, 38, 40, 42, 44, 46, referred to as the fractionation electrodes, applies a second electric field in the opposite direction relative to the electric field created by the first set of electrodes, thus forcing the REE ions to migrate across the channel toward the opposite electrode and eventually fractionating them based on variations in their respective electrophoretic mobility.
As the second electric field distributes REE ions across the channel, concentration profiles of the elements are not identical across and along the channel due to the different mobilities of the REE ions. A flow splitter 48, 50, 52, 54, 56, 58 at the end of each fractionation section divides the flow into two parts, including an upper part and a lower part which have different concentration of each element, heavier elements being more concentrated in the upper part and lighter elements, which migrate faster, being loaded in the lower part.
An electric field of 75 V/cm was selected for both fields in the examples given herein. In practice, it is easier to use identical intensities, but they could be different.
Thus, turning back to
For multicomponent fractionation, a number of separation units (from A to C in
The nature of the background electrolyte (BGE), the pH value and the temperature at each separation phase are selected for the ionic REE fractionation in order to optimize the number of fractionation steps per separation phase. Also, the number of fractionation steps and of separation phases, i.e. the size of the system, depend, as mentioned hereinabove, on the electric field intensity, the residence time of the ions in the electric field and the REE concentrations.
For instance, a mixture of 1 gr/L REE ions is separated using a BGE comprising 10 mM 4-methyl benzyl amine and 4 mM HIBA, which forms a complexing agent at pH of 4.4, i.e. for example in an acetic acid solution, at a temperature of 23° C., under an electric field of 75 V/cm, in a 4 to 5 minutes residence time.
The flow ratio between the REE mixtures, i.e. the analytes, and the background electrolyte BGE is adjusted depending on the nature of the mixtures and the other operating conditions.
The temperature is generally selected in the range between 5 and 70° C., for example between 15 and 25° C., for a pH between 2 and 10, for example between 3 and 6, and a flow ratio between the REE mixtures, i.e. the analytes, and the background electrolyte BGE in a range between 1/100 and 1/3, for example between 1/10 and 1/3. The ligand or complexing agent concentration, given as molar ratio of total ligands to total metal ions, is selected in a range between 1/1 and 10/1, for example between 2/1 and 5/1.
The electrodes that generate the electric fields within the channels may be conductive plates connected to a DC power supply. The electrodes may be inserted into the walls of the channels in direct contact with the liquid flow. Alternatively, they may be positioned outside of the channels, inducing electrostatic field into the solution flowing inside.
The electric field intensity is selected according to the concentration and mobility differences between the REE which are to be separated at each phase.
The separation channels or chambers can comprise semi-permeable membranes, such as Nafion® for example, which are conductive to protons (H+) and hydroxyl (OH−) and obstruct metallic ions and their complexes, thereby to preventing metal ions to reach the electrodes in case the electrodes are positioned in direct contact with the liquid flow.
The REE separation output is in ionic form. Then, pure REE may be recovered from the solution in any desired solid form (i.e. carbonate, hydroxide, oxide . . . ).
The depleted solutions from the REE precipitation unit 69 (step 74) and from the purification unit 67 (step 75) are then processed in a regeneration unit 76 to be recycled as a recycled reagent 61. Indeed, the complexing agent in FFE separation (i.e. 4-methyl benzyl amine and HIBA in acetic acid solution as described hereinabove) is the reagent in the overall process. This reagent is regenerated and recycled after separation in order to keep the process sustainable and feasible. However, since the regeneration of any reagent is limited to a certain efficiency, a make-up stream of reagent 62 may be needed.
This separation method and system allow replacing most of the multiple, complex chemical transformations usually required to separate and purify REE. They greatly reduce costs, time, and usage of a variety of chemical reagents that could produce environmental and safety problems. Capital costs are greatly reduced compared to the all-chemical methods and systems currently being used.
Although the method and system were described hereinabove for use in separating REE from each other, they may be used in other hydrometallurgical methods for either concentrating or rejecting element/compound. In the latter case, they could be used to remove impurities directly from the solution without the need for filtration and rewashing methods that result in valuable element/compound losses and dilution of streams containing the values sought.
Although the present invention has been described hereinabove by way of embodiments thereof, it may be modified, without departing from the nature and teachings of the subject invention as described.
REFERENCES
- Kasicka, V., 2009, From micro to macro: Conversion of capillary electrophoretic separations of biomolecules and bioparticles to preparative free-flow electrophoresis scale: Electrophoresis, v. 30, p. S40-S52.
- Santoyo, E., R. Garcia, K. A. Galicia-Alanis, S. P. Verma, A. Aparicio, and A. Santoyo-Castelazo, 2007, Separation and quantification of lanthanides in synthetic standards by capillary electrophoresis: A new experimental evidence of the systematic “odd-even” pattern observed in sensitivities and detection limits: Journal of Chromatography A, v. 1149, p. 12-19.
Claims
1. A method of purification and separation of mixed elements, using differences between electrophoresis mobility of the elements or coordination complexes thereof in a continuous process, comprising:
- selecting a complexing ligand and forming a solution of the complexing ligand and the mixed elements;
- controlling the temperature and pH of the solution; and
- submitting a flow of the solution to an electric field submitted perpendicular to the solution.
2. The method of claim 1, wherein said selecting the complexing ligand comprises selecting the complexing ligand with a concentration in a range between 1 μmol/L and 1 mol/L.
3. The method of claim 1, comprising controlling a flow ratio between the mixed elements and the complexing ligand in a range between 1/100 and 1/3.
4. The method of claim 1, comprising controlling a flow ratio between the mixed elements and the complexing ligand in a range between 1/10 and 1/3.
5. The method of claim 1, comprising controlling the concentration of complexing ligand in a range between 1/1 and 10/1.
6. The method of claim 1, comprising controlling the concentration of complexing ligand in a range between 2/1 and 5/1.
7. The method of claim 1, wherein the complexing ligand comprises 10 mM 4-methyl benzyl amine and 4 mM HIBA.
8. The method of claim 1, wherein said controlling the temperature comprises controlling the temperature in a range between 5 and 70° C.
9. The method of claim 1, wherein said controlling the temperature comprises controlling the temperature in a range between 15 and 25° C.
10. The method of claim 1, wherein said controlling the pH comprises controlling the pH in a range between 2 and 10.
11. The method of claim 1, wherein said controlling the pH comprises controlling the pH in a range between 3 and 6.
12. The method of claim 1, wherein the mixed elements are mixed rare earth elements or mixed precious metals.
13. A system for purification and separation of mixed elements, comprising at least a first free flow electrophoresis separation chamber, wherein a solution of the mixed elements is passed through the first separation chamber, an electric field being submitted perpendicular to the solution flow and separating mobile ions of the solution based on electrophoretic mobility.
14. The system of claim 13, comprising at least a second separation chamber, said second separation chamber being in series and/or in parallel with the first separation chamber for fractionation and refinery of metallic ions at the output of the first separation chamber.
15. A multi-channel separation system for purification and separation of elements in a solution, comprising at least a first and a second channels each receiving part of the solution;
- each channel comprising a concentration section, a fractionation section, and a flow splitter at an output of the fractionation section;
- said concentration section comprising electrodes that create a first transverse electric field across the channel, and said fractionation section comprising electrodes that create a second electric field in a direction opposite the first electric field across the channel, thereby distributing ions of the solution across the channel;
- said flow splitter dividing the flow of each channel into a subflow concentrated in heavier elements and a subflow concentrated in lighter elements.
16. The system of claim 15, further comprising a connection merging the subflows concentrated in heavier elements from the first and second channels, and a connection merging the subflows concentrated in lighter elements from the first and second channels.
17. The system of claim 15, further comprising a connection merging the subflows concentrated in heavier elements from the first and second channels, and a connection merging the subflows concentrated in lighter elements from the first and second channels;
- further comprising a third and a fourth channels, the third channel receiving the merged subflows concentrated in lighter elements and said fourth channel receiving the merged subflows concentrated in heavier elements;
- each one of the third and fourth channels comprising a concentration section, a fractionation section, and a flow splitter at an output of the fractionation section;
- said concentration section comprising electrodes that create a first transverse electric field across the channel, and said fractionation section comprising electrodes that create a second electric field in a direction opposite the first electric field across the channel, thereby distributing ions of the solution across the channel;
- said flow splitter dividing the flow of each channel into a subflow concentrated in heavier elements and a subflow concentrated in lighter elements.
18. The system of claim 15, wherein the first electric field concentrates metallic ions or complexes to a first wall of the respective channel along the flow direction, and the second electric field forces the metallic ions or complexes to migrate across the respective channel to an opposite wall of the respective channel.
19. The system of claim 15, wherein each channel comprises semi-permeable membranes preventing ions to reach the electrodes.
20. A method for separating components of a multi-component concentrate, comprising:
- a) preparing a solution of the multi-component concentrate and a reagent;
- b) directing the solution to at least a first and a second channel each receiving part of the solution; each channel comprising a concentration section comprising a first transverse electric field across the channel, a fractionation section comprising a second electric field in a direction opposite the first electric field across the channel thereby distributing ions of the solution across the channel, and a flow splitter at an output of the fractionation section that divides the flow of each channel into a subflow concentrated in heavier elements and a subflow concentrated in lighter elements;
- c) repeating step b) until a target separation of isolated components is achieved; and
- d) recovering the isolated components.
21. The method of claim 20, further comprising diverting a stream of impurities and rejected components to a purification unit.
22. The method of claim 20, further comprising processing a depleted solution from the recovery of the isolated components to a regeneration unit to yield a recycled reagent for use in step a).
23. The method of claim 20, further comprising diverting of impurities and rejected components to a purification unit, and further comprising processing at least one of: i) a depleted solution from the recovery of the isolated components and ii) a depleted solution from the purification unit to a regeneration unit to yield a recycled reagent for use in step a).
Type: Application
Filed: May 28, 2014
Publication Date: May 19, 2016
Inventor: Pouya Hajiani (St-Lambert)
Application Number: 14/653,777