I know the other so called competitor mentioned their ability to use lasers on laser extractions on REE but it seems they are not alone, maybe we could also do this?
https://labpartnering.org/patents/US20230212709Rare Earth Laser-Assisted Metal Production and Separation (US20230212709)Application
AbstractA compound or complex containing a rare earth element is impinged with a pulsed laser that is so controlled as to photochemically reduce and obtain a rare earth metal (REM). A mixture of REM salts can be impinged using laser light tuned to selectively reduce a particular rare earth-containing salt of the mixture to separate out as its respective rare earth metal.
InventorsCajetan Ikenna Nlebedim
Abhishek Sarkar
Pranav Shrotriya
Denis Prodius
Ho-Won Noh
Thomas LograssoAssignees[ "Iowa State University Research Foundation, Inc." ]DetailsThis invention was made with government support under Grant No. DE-AC-02-07CH11358 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
FIELD OF THE INVENTION
The present invention relates to method and apparatus for producing a rare earth metal from a compound or complex containing a rare earth element or from a mixture thereof.
BACKGROUND OF THE INVENTION
Rare earth elements (REEs) are crucial for our modern society, and the resiliency of their supply chains is essential for the nation's technological advancement, energy security, economic prosperity, and defense. Electric vehicles (EVs) can significantly reduce greenhouse gasses and help achieve the transition to a net-zero economy by 2050. Still, such achievement will depend on substantial advancement in rare earth metal (REM) production technologies. Apart from their many other applications, REMs is a key component of EVs, wherein REMs are needed for the drivetrains. In 2019, 80% of REE-containing compounds consumed in the U.S. were imported. Some domestically sourced REEs are shipped and further processed abroad due to lack of domestic processing facilities.
Separation of rare earth elements is an essential step towards their reduction to rare earth metals for practical applications. It is an important purification step, the product of which are typically oxides that are further subjected to reduction processes to obtain the desired metal. The need for separation also arises for recycled rare earth products in which they are typically recovered as mixed salts or oxides which, again, requires subsequent reduction to obtain the desired metals for applications, e.g., permanent magnets development.
The industrial separations process involves leaching, followed by a selective extraction. The leaching processes require strong oxidizing/harsh chemicals for dissolution of rare earth concentrates or recycled products which pose a significant environmental impact towards disposal of acidic waste effluents. Also, operating conditions for the different separation processes vary depending on feedstock type, making them economically taxing.
For metal production, the commercial methods involve metallothermic and electrolytic reduction of REE salts and oxides. For example, calciothermic methods require REE halides or oxides, followed by thermic reduction using Ca in an inert atmosphere. The need for high-temperature results in an energy-intensive process; fluorination is operationally risky due to the typical need for HF and hydrogen evolution. Moreover, achieving high purity and high yield in the process appear to be mutually exclusive. All these make the process costly. Although NdC13 has been proposed as a substitute for NdF3, it is limited by high hygroscopicity, hence low yield and high impurities. Also, molten salt electrolytic reduction processes have poor yield and scalability.
Moreover, the logistics of both REE separation and metal reduction being performed by different companies with different business focuses and technological capabilities, result in increased costs which subsequently impacts the price of the final product. This is exacerbated by the current state-of-the-art separation and reduction processes being energy intensive, environmentally taxing, requiring substantial amounts of hazardous chemicals and producing significant amounts of solid and liquid wastes. There is a need for an improved method to obtain one or more REMs from compounds, complexes, etc., containing one or more REEs. This need is better addressed if metal reduction is a means for separation.
SUMMARY OF THE INVENTION
Certain embodiments of the present invention provide a rare earth laser-assisted metal production and separation (RELAMPS) technology by photochemical selective reduction of various REE-containing compounds and complexes as well as others using a pulsed laser wherein such other compounds and complexes include, but are not limited to La, Ce, Pr, Nd, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
Certain embodiments of the present invention employ a pulsed laser to implement the selective reduction (separation) process at room temperature. The pulsed laser light is impinged and controlled to selectively dissociate molecular bonds in REE oxides, oxalates, halides and other compounds and complexes.
Practice of embodiments of the present invention is advantageous in that an infinitesimally small time-period for bond cleaving and energy transport using a picosecond and femtosecond laser prevents loss of energy makes practice of method embodiments very efficient. Consequently, instead of the typically required high temperatures (>800° C.) heretofore employed, practice of method embodiments can achieve separation of REE-containing compounds and complexes by reduction to REMs (rare earth metals) at ambient temperature conditions and excludes the use of harsh chemicals. Moreover, the versatility of laser irradiation of a REE-containing compound or complex at different frequencies provides a unique advantage in that UV lasers induce large energy to dissociate strong molecular bonds such as REE oxides and halides but have low penetration depth. IR lasers are more suitable for weaker bonds like REE hydroxides and oxalates but have larger penetration depths. Practice of embodiments of the present invention will not only enable improvement in availability of REMs, but also have a reduced energy and carbon footprint, compared to traditional processes.
Certain other embodiments of the present invention involve using RELAMPS technology to separate out certain rare earth metal(s) from a mixture of rare earth element-containing compounds and complexes (e.g. rare earth salts) using tunable pulsed laser light tuned to a wavelength to selectively reduce a certain rare metal compound or compound of the mixture to its respective rare earth metal.
The above objects and advantages of practice of the present invention will become more readily apparent in view of the following detailed description with the following drawings.
DETAILED DESCRIPTION OF THE INVENTION
Certain embodiments of the present invention illustrate use of a controlled pulsed laser light impingement to achieve a selective reduction (separation) process are described in detail below for purposes of illustration and not limitation wherein rare earth element-containing hydroxides, oxides and oxalates such as Nd(OH)3, Nd2(C2O4)3, and (Nd0.75Pr0.25)2(C2O4)3, and Gd2(C2O4)3, and others represented by (Nd1-xPrOx)2(C2O4)3, at room temperature are impinged by pulsed laser light controlled to selectively dissociate the constituents to yield a REM (rare earth metal), which can comprise at least one of La, Ce, Pr, Nd, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. The Examples are offered for purposes of illustration and not limitation since embodiments of the present invention can be practiced with respect to other rare earth element-containing compounds, complexes and other material that contain a rare earth element bonded in a manner that can be dissociated by impingement of the material by properly controlled pulsed laser light to this end.
EXAMPLES
Embodiments of the RELAMPS method have been demonstrated with Nd and Gd salts using the laser processing chamber shown in FIG. 1, in which chamber a cold pressed, powder pellet cube-shaped sample (“Sample”
is positioned on a titanium pedestal below a quartz (fused silica, 1064 nm permeable) window 10 as shown prior to laser conversion. The RELAMPS method has been demonstrated by pulsed laser treatment on pellets of Nd(OH)3, Nd2(C2O4)3, and (Nd0.75Pr0.25)2(C2O4)3, and Gd2(C2O4)3 in the controlled atmosphere laser processing chamber under N2 blanket and at 1 mbar pressure (sub-atmospheric pressure) with inlet 12 for N2 gas entry to the chamber and outlet 14 for chamber evacuation by vacuum pumping. Other alternate blanket gases can be used in lieu of nitrogen such as argon, helium, and others. A 1064 nm, 12 ps Nd-YAG pulsed laser positioned outside the chamber was used with 3W power for the conversion process with its beam scanned through the quartz window 10 across the sample in lines of 15 mm length with a scan speed of 2 mm/s and a line spacing of about 128 μm, which are parameters that can be optimized for specific systems. In the Example, the laser beam did not go through the entire pellet sample only because the available laser system could not achieve full penetration. For example, the pellet samples (10 mm cubes) for laser treatment were 300-400 microns in thickness; yet the available laser beam penetrated to 100-200 microns. A more powerful pulsed laser system can be chosen to overcome this limitation of the Examples.
For the Nd salt samples (i.e. Nd(OH)3), the starting hydroxide pellet powder sample, FIG. 1, was converted into a dark metal powder after laser treatment using the 1064 nm, 12 ps Nd-YAG pulsed laser. To this end, FIG. 2a shows laser-treated and untreated areas of a sample. FIG. 2b (with metallic luster) shows metal sample from the laser treated area which also reveals the laser tracks during the processing. FIG. 2c shows a sample that was exposed to air for 24 hrs. and 72 hrs. and was observed to re-convert to the original hydroxide/oxide form. As a result, the laser-treated sample needs to be kept in inert atmosphere to prevent oxidation. That includes handling, storage and transportation in inert atmosphere chambers. However, this becomes less of a concern if the result REM powder is melted into an ingot.
Similar results using the same pulsed laser parameters, i.e. wavelength 1064 nm, pulse width 12 ps and scan speed 2mm/s, were obtained for the laser-treated samples of Nd2(C2O4)3, and (Nd0.75Pr0.25)2(C2O4)3, and Gd2(C2O4)3 where Nd0 metal and Gd0 metal were obtained at the laser-treated areas.
For the Gd oxalate (Gd2(C2O4)3) samples, since Gd metal has a Curie point near room temperature (293 K), it was possible to use ferromagnetism as a signature of metal production. Coercivity in the magnetic hysteresis loop obtained at 273 K for the Gd metal and increasing magnetic moment with reducing temperature, are both signals of ferromagnetism—typical of Gd metal. Oxides or oxalates are paramagnetic, rather than ferromagnetic.
Furthermore, although the Examples used a picosecond pulsed laser, femtosecond lasers can also be used. The laser frequency is also crucial. IR lasers (as used in the Examples 1064 nm) have larger sample penetration depth but lower energy transmittance (slower conversion). While UV or shorter wavelength lasers typically have lower penetration but better energy transmittance (or faster dissociation). The selection of the laser frequency and parameters therefore depends on sample material, thickness and operational conditions. For purposes and illustration and not limitation, the pulsed laser can include but is not limited to Nd:YAG, Nd:YLF, Nd:YVO4, YLF, LiCAF, LiLuF, LiSAF, etc. as they are relevant laser crystal media for UV to IR range femtosecond pulsed lasers. CO2 lasers that are microsecond/continuous may likely not be applicable.
FIG. 3 is a schematic illustration of production apparatus for practicing RELAMPS method embodiments of the present invention offered for purposes of illustration and not limitation since other apparatus may be used. The apparatus comprises a roll-by-roll conversion mechanism wherein a line beam of the pulsed laser shaped via the point-to-line lens system will continuously convert REE-containing materials on a moving platform under an inert atmospheric condition to a REM.
Additional Examples Certain other embodiments of the present invention involve selective separation of mixtures of rare earth salts (or other compounds and complexes) into a separate rare earth metal or metal alloy via reduction in the manner described above by using an appropriate selectively tuned pulsed laser wavelength to this end.
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