Adsorbents comprising highly hydrated lithium-containing aluminum hydroxide compositions

Abstract

The present disclosure relates to sorbents for selective metal extraction from solutions, and more specifically, to highly hydrated lithium-incorporated aluminum-hydroxide (HHA) configured for lithium extraction. 2 The present disclosure relates to compositions comprising 2 The H-LIAH compositions of the present disclosure are distinguished from conventional LIAH compositions at least in part by their crystallization-hydrate to lithium molar ratio, which is readily detectable by analytical characterization. 2 The LIAH compositions of the present disclosure can be readily: (i) prepared by the manufacturing methods described herein; (ii) incorporated into an apparatus for recovering lithium from saltwater described herein; and / or (iii) deployed in a method for recovering lithium from saltwater described herein. 2 The -LIAH composition was developed after discovering a surprising pH effect that induces the unexpected formation of a gel-like material during manufacturing. The gel-like material is a H that has unconventional properties as described herein. 2 -Can be tailored to the LIAH composition.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority under applicable law to U.S. Provisional Patent Application No. 63 / 339,170, filed May 6, 2022, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] FIELD OF THEINVENTION The present disclosure relates generally to sorbents for selective metal extraction from solutions, and more specifically to lithium-incorporated-aluminum-hydroxide (LIAH) compositions configured for lithium extraction. [Background technology]

[0003] Lithium-containing aluminum hydroxide (LIAH) compositions are a promising class of inorganic sorbents for direct lithium extraction (DLE). DLE is an alternative to traditional lithium recovery approaches, such as open-cut mining and evaporation in large ponds, both of which can result in land destruction, potential pollution, and / or high water consumption. DLE utilizes selective sorbents to extract lithium from saltwater, potentially mitigating these effects.

[0004] Although LIAH compositions can be effective sorbents for the extraction of lithium from a variety of brine types, their preparation and / or use tend to require fewer chemical inputs than alternative inorganic sorbent categories. Unfortunately, however, conventional methods for preparing LIAH sorbent compositions are limited by synthetic constraints that provide little room for tailoring the final composition toward desirable properties such as high hardness, high selectivity for lithium, high lithium uptake capacity, and narrow particle size distribution. These properties are likely central to the widespread application of DLEs.

[0005] Impregnation of gibbsite is a conventional approach for preparing LIAH compositions. This process can be complicated by long preparation times, for example, due to the slow dissolution of gibbsite. Furthermore, adsorbents produced by impregnation of gibbsite tend to have low lithium uptake capacities.

[0006] In situ precipitation of LIAH compositions has been explored as a method for producing lithium adsorbents, however, the reported processes tend to result in products with broad particle size distributions, low crystallinity, and / or low lithium uptake capacities.

[0007] Hydrothermal processes have also been explored for the preparation of LIAH compositions. Unfortunately, there are many limitations to the adsorbents they produce, and the processes themselves can introduce undesirable costs and / or complications with respect to their high pressure and / or high temperature parameters.

[0008] There is an unmet need for new LIAH compositions suitable for extracting lithium from saltwater. There is also an unmet need for (i) methods of manufacture that allow the new LIAH compositions to be tailored toward desired properties; (ii) apparatus for recovering lithium from saltwater that utilize the new LIAH compositions; and (iii) methods for recovering lithium from saltwater that use the new LIAH compositions. Summary of the Invention

[0009] The present disclosure relates to a highly hydrated lithium-containing aluminum hydroxide (H 2 The present disclosure reports adsorbents containing the H-LIAH composition and methods for their manufacture. 2The -LIAH composition was developed after extensive research into alternative methods for lithium adsorbent preparation revealed a surprising pH effect during manufacture. As described in this disclosure, the pH effect can be exploited to induce the unexpected formation of a gel-like material, which can then be processed into a LIAH composition with desired properties. Analytical characterization indicates that the gel formation is exothermic and that the resulting material is characterized by a lattice structure that incorporates extensive crystallization-hydrates. Without being bound to any particular theory, the H of this disclosure is believed to be a promising candidate for the preparation of a LIAH composition. 2 The incorporation of crystallization-hydrates into the -LIAH composition may affect d-spacing and / or lattice formation during crystallization, which may explain why the gel-like material formed during fabrication is amenable to tuning towards desirable properties (e.g., high lithium capacity, high hardness, high physical durability under operating conditions, high chemical durability under operating conditions, large average particle size, and / or narrow particle size distribution) by selecting and implementing appropriate hardening protocols (e.g., aging, rinsing, drying, and sieving).

[0010] In the context of this disclosure, the terms "crystallization-hydrate" (singular and plural) are used interchangeably and refer to a material having an endothermic transition detectable by differential scanning calorimetry (DSC) at about 270°C to about 350°C. Thus, the presence, absence, and / or degree of crystallization-hydrate incorporation in a material can be readily determined by one of ordinary skill in the art. This disclosure provides teachings on determining the molar ratio of crystallization-hydrate to lithium from DSC data in combination with supplemental characterization including inductively-coupled plasma optical emission spectrometry (ICP-OES), thermogravimetric analysis (TGA), and / or X-ray diffraction (XRD). H of this disclosure 2The LIAH compositions are distinguished from conventional LIAH compositions at least in part by their crystallization-hydrate to lithium molar ratios, as described in the appended claims. 2 The LIAH compositions can be readily (i) prepared by the manufacturing methods described herein, (ii) incorporated into an apparatus for recovering lithium from saltwater, and / or (iii) deployed in a process for recovering lithium from saltwater.

[0011] One aspect of the present disclosure is an adsorbent for recovering lithium from a lithium-containing solution, comprising a H2O2 solution having a molar ratio of crystallized hydrate to lithium of at least about 2.1:1.0. 2 - A sorbent comprising a LIAH composition.

[0012] In one embodiment of the present disclosure, H 2 - The molar ratio of crystallization hydrate to lithium of the LIAH composition is from about 2.1:1.0 to about 4.3:1.0.

[0013] In one embodiment of the present disclosure, H 2 - The molar ratio of crystallization hydrate to lithium in the LIAH composition is from about 2.1:1.0 to about 2.9:1.0.

[0014] In one embodiment of the present disclosure, H 2 - The LIAH composition has a crystallization-hydrate to lithium molar ratio of about 2.9:1.0 to about 4.0:1.0.

[0015] In one embodiment of the present disclosure, H 2 - Crystallization of the LIAH composition - The molar ratio of hydrate to lithium is determined from DSC, ICP-OES, TGA, or a combination thereof.

[0016] In one embodiment of the present disclosure, H 2 The -LIAH composition has an XRD pattern with 2θ reflectivity peaks at about 11.5° 2θ, 23.1° 2θ, 35.0° 2θ, 35.7° 2θ, or combinations thereof.

[0017] In one embodiment of the present disclosure, H 2 The -LIAH composition has an XRD pattern that is absent a 2θ reflectance peak at 18.2° 2θ.

[0018] In one embodiment of the present disclosure, H 2 The LIAH composition has a molar ratio of aluminum to lithium of at least about 1.9:1.0.

[0019] In one embodiment of the present disclosure, H 2 The -LIAH composition has a molar ratio of aluminum to lithium of about 2.0:1.0 to about 3.0:1.0.

[0020] In one embodiment of the present disclosure, H 2 The -LIAH composition has a molar ratio of aluminum to lithium of about 2.4:1.0 to about 2.6:1.0.

[0021] In one embodiment of the present disclosure, H 2 - The LIAH composition has the formula 1: Li a X mAl(OH)3 nH2O cr formula 1 (In the formula, a is about 1; X is a monovalent anion; m is from about 1.9 to about 3.0; n is from about 2.4 to about 4.3; H2O cr is as described in Crystallization--designates hydrate).

[0022] In one embodiment of the present disclosure, H 2 -LIAH compositions are lithium aluminum layered double hydroxide compositions.

[0023] In one embodiment of the present disclosure, the sorbent further comprises a binder, an encapsulating agent, or a combination thereof.

[0024] In one embodiment of the present disclosure, H 2- The LIAH composition has a lithium uptake capacity of at least about 8.0 mg / mL.

[0025] In one embodiment of the present disclosure, H 2 - The lithium uptake capacity of the LIAH composition is at least about 9.0 mg / mL.

[0026] In one embodiment of the present disclosure, H 2 - The lithium uptake capacity of the LIAH composition is from about 9.5 mg / mL to about 12.0 mg / mL.

[0027] In one embodiment of the present disclosure, H 2 - The LIAH composition is processable to provide a particle size distribution in which at least about 40% of the particles are between about 500 μm and about 1,000 μm.

[0028] In one embodiment of the present disclosure, H 2 - The LIAH composition is processable to provide a particle size distribution in which at least about 50% of the particles are between about 500 μm and about 1,000 μm.

[0029] In one embodiment of the present disclosure, H 2 - The LIAH composition is processable to provide a particle size distribution in which at least about 55% of the particles are between about 500 μm and about 1,000 μm.

[0030] In one embodiment of the present disclosure, H 2 - The LIAH composition is suspended in deionized water to provide a solution having a pH of about 7.0 to about 6.2.

[0031] In one embodiment of the present disclosure, H 2 -LIAH compositions are suspended in deionized water to provide turbidity values ​​of less than 10 NTU.

[0032] In one embodiment of the present disclosure, H 2 - The LIAH composition is suspended in deionized water to provide a turbidity value of less than 5 NTU.

[0033] In one embodiment of the present disclosure, H 2 -LIAH compositions are suspended in deionized water to provide turbidity values ​​of about 2.5 NTU to about 5 NTU.

[0034] In one embodiment of the present disclosure, H 2 The LIAH composition has a Mohs hardness of at least about 5.0.

[0035] In one embodiment of the present disclosure, H 2 The LIAH composition has a Mohs hardness of at least about 6.0.

[0036] In one embodiment of the present disclosure, H 2 The LIAH composition has a Mohs hardness of at least about 7.0.

[0037] In one embodiment of the present disclosure, H 2 -LIAH compositions are robust to physical degradation for at least about 500 column cycles.

[0038] In one embodiment of the present disclosure, H 2 -LIAH compositions are robust to physical degradation for at least about 5000 column cycles.

[0039] One aspect of the present disclosure is 2 - a method of producing a LIAH composition, comprising: (i) contacting an initial aliquot of a hydroxide solution with an initial aliquot of a solution comprising a lithium halide and an aluminum halide to form a reaction mixture wherein the hydroxide solution is present in excess and the pH of the reaction mixture is at least about 9.0; (ii) adding an additional aliquot of the solution containing lithium halide and aluminum halide to the reaction mixture to reduce the pH of the reaction mixture to less than about 4.0; (iii) allowing the reaction mixture to form a gel-like material; (iv) adding an additional aliquot of hydroxide solution to the reaction mixture to raise the pH of the reaction mixture to about 6.0 to about 7.5.

[0040] In one embodiment of the present disclosure, in step (i), an initial aliquot of hydroxide solution is added to an initial aliquot of a solution comprising lithium halide and aluminum halide.

[0041] In one embodiment of the present disclosure, in step (i), the pH of the reaction mixture is from about 9.0 to about 11.0.

[0042] In one embodiment of the present disclosure, in step (i), the pH of the reaction mixture is about 10.0.

[0043] In one embodiment of the present disclosure, in step (ii), the pH of the reaction mixture is from about 2.5 to about 4.0.

[0044] In one embodiment of the present disclosure, in step (ii), the pH of the reaction mixture is about 3.0.

[0045] In one embodiment of the present disclosure, in step (i), an initial aliquot of a solution containing lithium halide and aluminum halide is added to an initial aliquot of hydroxide solution.

[0046] In one embodiment of the present disclosure, the initial aliquot of the solution comprising lithium halide and aluminum halide and the further aliquot of the solution comprising lithium halide and aluminum halide are derived from the same stock solution.

[0047] In one embodiment of the present disclosure, the initial aliquot of hydroxide solution and the further aliquot of hydroxide solution are derived from the same stock solution.

[0048] In one embodiment of the present disclosure, the solution containing lithium halide and aluminum halide has a molar ratio of lithium to aluminum of about 1.0:2.0 to about 1.0:3.0.

[0049] In one embodiment of the present disclosure, the hydroxide solution has a concentration of about 6.5M to about 8.0M.

[0050] In one embodiment of the present disclosure, the lithium halide is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, or a combination thereof.

[0051] In one embodiment of the present disclosure, the lithium halide is lithium chloride.

[0052] In one embodiment of the present disclosure, the aluminum halide is aluminum trifluoride, aluminum trichloride, aluminum tribromide, aluminum triiodide, or a combination thereof.

[0053] In one embodiment of the present disclosure, the aluminum halide is aluminum trichloride.

[0054] In one embodiment of the present disclosure, the hydroxide solution is a sodium hydroxide solution, a potassium hydroxide solution, a calcium hydroxide solution, a magnesium hydroxide solution, or a combination thereof.

[0055] In one embodiment of the present disclosure, the hydroxide solution is a sodium hydroxide solution.

[0056] In one embodiment of the present disclosure, the rate of addition of the hydroxide solution in step (i) and / or step (iv) is from about 9.5 mL / min to about 10.5 mL / min.

[0057] In an embodiment of the present disclosure, in step (iii), step (iv), or a combination thereof, the reaction mixture is stirred to adjust the viscosity of the gelled material.

[0058] In one embodiment of the present disclosure, the temperature of the reaction mixture in step (iii), step (iv), or a combination thereof, is controlled to adjust the viscosity of the gel-like material.

[0059] In an embodiment of the present disclosure, the pressure of the reaction mixture in step (iii), step (iv), or a combination thereof, is controlled to adjust the viscosity of the gelled material.

[0060] In one embodiment of the present disclosure, the reaction time in step (iii), step (iv), or a combination thereof, is controlled to adjust the viscosity of the gelled material.

[0061] In one embodiment of the present disclosure, the rate of addition in step (ii), step (iv), or a combination thereof, is controlled to adjust the viscosity of the gel-like material.

[0062] In one embodiment of the present disclosure, the method further comprises: (v) curing the gel material to form a H 2 - The method further comprises the step of forming into a LIAH composition.

[0063] In one embodiment of the present disclosure, step (v) comprises drying at a temperature between about 85°C and about 105°C.

[0064] In one embodiment of the present disclosure, step (v) comprises drying for about 24 hours to about 75 hours.

[0065] In one embodiment of the present disclosure, step (v) includes drying at a pressure of about 76 mmHg to 760 mmHg.

[0066] In one embodiment of the present disclosure, step (v) comprises aging, rinsing, drying, sieving, or a combination thereof.

[0067] One aspect of the present disclosure relates to an adsorbent produced by the process defined herein.

[0068] One aspect of the present disclosure is an apparatus for recovering lithium from a lithium-containing solution, comprising: a vessel having an inlet, an outlet, and a continuous flow path therebetween; and The adsorbent in the vessel has a molar ratio of crystallized hydrate to lithium of about 2.1:1.0 to about 4.3:1.0. 2 - an adsorbent comprising the LIAH composition.

[0069] One aspect of the present disclosure is an apparatus for recovering lithium from a lithium-containing solution, comprising: a vessel having an inlet, an outlet, and a flow path therebetween; and An apparatus comprising a sorbent within a container, the sorbent being as defined herein.

[0070] One aspect of the present disclosure is a method for recovering lithium from a lithium-containing solution comprising: contacting the lithium-containing solution with a sorbent composition to extract lithium from the lithium-containing solution; and leaching lithium from the sorbent composition to form a lithium eluate; The adsorbent composition has a molar ratio of crystallized hydrate to lithium of about 2.1:1.0 to about 4.3:1.0. 2 - A method comprising the LIAH composition.

[0071] One aspect of the present disclosure is a method for recovering lithium from a lithium-containing solution comprising: contacting the lithium-containing solution with a sorbent composition to extract lithium from the lithium-containing solution; and leaching lithium from the sorbent composition to form a lithium eluate; The adsorbent composition comprises H 2 - A method comprising the LIAH composition.

[0072] 1. A method for recovering lithium from a lithium-containing solution comprising: The lithium-containing solution is treated with H 2- extracting lithium from a lithium-containing solution by contacting the lithium-containing solution with an adsorbent comprising a LIAH composition; and e) eluting the lithium from the sorbent to form a lithium eluate. [Brief description of the drawings]

[0073] In the drawings and descriptions provided herein, like reference numbers refer to like components. For simplicity and clarity, not all drawings include references to all components and features, and references to some components and features may appear in only one drawing. Components and features of the present disclosure shown in other drawings can be easily inferred therefrom. [Figure 1] 1 shows a differential scanning calorimetry (DSC) graph 100 illustrating the relative enthalpy change as a function of temperature for a conventional lithium aluminum hydroxide (LIAH) composition and a highly hydrated lithium-containing aluminum hydroxide (H2-LIAH) composition. [Diagram 2] 2 shows a normalized thermogravimetric analysis (TGA) plot 200 illustrating sample weight change (expressed as a relative percentage) as a function of temperature. A series of H2-LIAH compositions of the present disclosure are shown and their major decomposition events are indicated. [Diagram 3] 3 shows an X-ray diffraction (XRD) diffractogram 300 showing the characteristic crystallographic patterns of two H2-LIAH compositions of the present disclosure overlaid with that of a conventional LIAH composition prepared by gibbsite impregnation method. The major characteristic peaks of the H2-LIAH composition of the present disclosure and the conventional LIAH composition are indicated. [Figure 4] 4 shows a Fourier transform infrared (FTIR) spectral overlay 400 of the H2-LIAH composition of the present disclosure before high temperature drying 401 and after high temperature drying 402. The major absorbance bands of the primary aluminum-oxygen bonds are shown. [Diagram 5]1 shows a microscope image of the H2-LIAH composition of the present disclosure, along with standard 1 / 10 rulers for particle size reference (i.e., each division represents 1 mm). [Figure 6] 6 shows an absorbance curve 600 illustrating the relative change in lithium concentration as a function of time for brine and the H2-LIAH sorbent material of the present disclosure during a lithium extraction cycle. [Figure 7] 1 shows a curve depicting lithium concentration as a function of time over multiple lithium extraction cycles for the H2-LIAH adsorption material of the present disclosure. [Figure 8] 8 shows an apparatus 800 for recovering lithium from a lithium-containing solution according to one embodiment of the present disclosure. FIG. 8 also shows a method 850 for recovering lithium from a lithium-containing solution according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0074] The following detailed description and examples are illustrative and should not be construed as further limiting the scope of the present invention. Rather, it is intended that all alternatives, modifications, and equivalents that may be included as described herein may be encompassed. The objects, advantages, and other features of the compositions, methods, and devices will become more apparent and be better understood by those skilled in the art upon reading the following non-limiting description and reference to the accompanying drawings.

[0075] Most conventional methods for preparing LIAH compositions by in situ precipitation use Al(OH)3 instead of AlCl3 as a starting material because the former can be hazardous and difficult to handle safely. Conventional methods using AlCl3 as a starting material tend to employ a single addition step: (i) slow, controlled addition of LiCl / AlCl3 solution to a basic (e.g., hydroxide) solution to lower the pH to 6.5-7.0, but not substantially below this range; or (ii) no pH control is used during the addition of a stoichiometric amount of LiCl / AlCl3 solution to a basic (e.g., hydroxide) solution, so that the final pH of the mixture is often greater than 7, and most likely 8.5-10.

[0076] In contrast, the disclosed manufacturing method utilizes a pH reversal protocol that includes multiple steps. The disclosed pH reversal protocol differs from conventional approaches in that the amounts and order of addition are adjusted and / or selected to cause the pH of the reaction mixture to drop beyond the range described above to an acidic minimum, such as about 3.0, and then slowly return to about 6.5 to about 7.0. In other words, the disclosed pH reversal protocol swings past neutral and then approaches neutral from the acidic side of the pH scale. The disclosed pH reversal protocol induces the formation of a gel-like material at or near the pH minimum. Gel formation is readily detectable as a change in solution viscosity, and it has been determined that the strength of the gel can be adjusted by varying the mixing speed, reagent concentration, reagent addition order (and / or other reaction parameters). The disclosed pH reversal protocol 2 The properties of the LIAH composition are (i) the strength of the gel thus produced, and (ii) the final H 2The artisan having the benefit of the teachings of the present disclosure will appreciate that control and optimization of batch scale-up parameters can affect gel strength (e.g., mixing volume for reaction type, sizing of mixing equipment, and balancing of reaction dilution against drying time constraints), and that the specific curing protocol (e.g., proper homogenization and mixing during the aging process, rinsing to remove salt impurities, drying to remove moisture, and / or sieving for selected particle sizes) can affect gel strength, as well as the ability to produce a LIAH composition tailored to one or more desired qualities as described herein. 2 It will be appreciated that the present invention may be used to produce a -LIAH composition.

[0077] As described above, analytical characterization is 2 - indicates that the LIAH composition is characterized by a lattice structure that incorporates crystallization-hydrates extensively. In the context of this disclosure, the terms "crystallization-hydrate" and "crystallization-hydrates" are used interchangeably and refer to a substance that has an endothermic transition detectable by differential scanning calorimetry (DSC) at about 270°C to about 350°C. Crystallization-hydrates may contain water incorporated within or released from the crystal lattice, partial decomposition products of the crystal lattice, and / or complete decomposition products of the crystal lattice. In the context of this disclosure, crystallization hydrates are distinguished from "surface hydrates", which term refers to a substance that has an endothermic transition detectable by DSC at about 30°C to about 130°C.

[0078] Without being bound to any particular theory, the incorporation of crystallization-hydrates into the LIAH compositions of the present disclosure may affect d-spacing and / or lattice formation during crystallization. This process may explain why the gel-like materials formed during fabrication are amenable to tailoring toward desirable properties (e.g., high lithium capacity, high lithium selectivity, high hardness, high physical durability under operating conditions, high chemical durability under operating conditions, large average particle size, and / or narrow particle size distribution) by selecting and implementing appropriate curing protocols (e.g., aging, rinsing, drying, and sieving).

[0079] These and other teachings, objects, features, embodiments, scope, thresholds, and advantages of the present disclosure are not limited by the appended claims, but are instead illustrated in the following detailed description of the present disclosure with reference to the accompanying drawings. 2 Certain embodiments of the -LIAH compositions, including their incorporation into sorbents for recovering lithium from saltwater, their methods of manufacture, their incorporation into apparatus for recovering lithium from saltwater, and their use in methods for recovering lithium from saltwater, will be apparent to those of skill in the art in light of the following description.

[0080] H 2 - Adsorbent containing LIAH composition H of this disclosure 2 The LIAH compositions were analyzed using a series of analytical techniques to ascertain various characteristics, as described below. With reference to exemplary examples, it will be apparent to those skilled in the art to, for example, determine the crystallization-hydrate to lithium ratio of the LIAH compositions, and more generally, to determine the H of the present disclosure. 2 Specific results are discussed using teachings that allow for the detection of features that distinguish LIAH compositions from conventional LIAH compositions. 2 -Analysis of LIAH compositions need not be limited to the analytical techniques discussed below, and one of skill in the art will appreciate that other characterization techniques may supplement, support, or replace one or more of the foregoing analyses without departing from the scope of the present disclosure.

[0081] H 2The endothermic transition of the LIAH composition can be determined by DSC. Those skilled in the art will understand the details of routine DSC characterization as used in this disclosure. FIG. 1 shows the endothermic transition of the LIAH composition 111 and the H of the present disclosure. 2 1 shows a DSC graph 100 illustrating the relative enthalpy change as a function of temperature for H-LIAH composition 121. 2 In the representative -LIAH composition, a characteristic enthalpy event 122 is observed with a unique and characteristic onset temperature of about 270° C. as compared to the conventional LIAH composition 112, which is observed with an onset temperature of about 200° C. In FIG. 1, surface hydrate loss 105 can be indicated by a broad, low intensity enthalpy event centered at about 80° C. for both materials.

[0082] H 2 The degradation patterns of the -LIAH compositions can be determined by TGA. Those skilled in the art will understand the details of routine TGA characterization as used in the context of this disclosure. Figure 2 shows a series of H-LIAH compositions prepared by various manufacturing methods according to the present disclosure. 2 2 shows a normalized TGA plot 200 illustrating sample weight change (expressed as relative percent) as a function of temperature for the -LIAH composition. Over the series of decomposition events, a major decomposition event 211 can be seen with an onset starting at about 270° C. and an end point ending at about 310° C., complementing the DSC characterization in FIG. 1. Surface hydrate loss is also detectable in FIG. 2, as indicated by reference numeral 212. The series shown in FIG. 2 shows the H-LIAH composition prepared by various manufacturing methods of the present disclosure. 2 - Supports the general reproducibility of pyrolysis parameters for LIAH compositions.

[0083] H 2 The crystalline diffraction patterns of the -LIAH compositions can be determined by XRD. Those skilled in the art will understand the details of routine XRD characterization as used in the context of this disclosure. 2The XRD diffractogram 300 showing the characteristic crystallographic pattern of the LIAH compositions (311 and 321) is overlaid with that of a conventional LIAH composition produced by gibbsite impregnation method 331. 2 The main characteristic peak of the -LIAH composition is at about 11.5° 2θ (312). 2 Additional characteristic peaks for LIAH compositions 313, 314, and 315 are at about 23.1° 2θ, about 35.0° 2θ, and about 35.7° 2θ, respectively. The main characteristic peak for the conventional LIAH composition is at about 18.2° 2θ (332). This peak is consistent with the H 2 -LIAH compositions are notably absent. In one embodiment of the present disclosure, 2 The -LIAH composition has an XRD pattern substantially as shown in Figure 3 (311 and 321).

[0084] The molecular formula outlined by Formula 1 is incorporated herein by reference in the preparation information and subsequent H 2 -LIAH characterization data can be used to determine the exemplary H 2 In accordance with the embodiments provided herein that discuss the -LIAH composition, the specific use of lithium chloride specifies that the integer "a" is 1 and the monovalent anion "X" is chloride. Thus, the partial molecular formula is initially LiCl·mAl(OH)3·nH2O cr It can be determined that:

[0085] Exemplary H of the present disclosure 2 -With respect to the LIAH composition, 2 The elemental composition data of the -LIAH composition can be determined by ICP-OES. Those skilled in the art will understand the details of routine ICP-OES characterization as used in the context of this disclosure. 2 The elemental composition data of the -LIAH composition are summarized in Table 1.

[0086] [Table 1]

[0087] Thus, the exemplary H of this disclosure 2 For the -LIAH composition, the aluminum to lithium ratio, normalized to a lithium molar concentration of 1, is determined to be 2.32:1. After normalizing the ratio to lithium, the aluminum ratio can be entered into Equation 1 as an integer "m", and the partial molecular formula is further refined to LiCl·2.32Al(OH)3·nH2O. cr It can be written as follows.

[0088] In the context of the present disclosure, the crystallization-hydrate to lithium ratio of the LIAH composition may be determined as follows.

[0089] Using the TGA data, it is possible to distinguish the specific heating zones within which surface hydrates and crystallized hydrates are lost, respectively, during the analysis of hydrate-containing LIAH materials. Table 2 shows the typical H 2 -LIAH Composition, summarizes TGA data at two specific time points and describes the temperature range in which crystallization-hydrate can be observed.

[0090] [Table 2]

[0091] In the context of the present disclosure, the relative TGA mass value can be used to determine the crystallization-hydrate specific relative mass loss in percentage terms, as outlined in Equation 2. Relative Loss cry = Relative Mass 120℃ -Relative Mass 350℃ formula 2 (In the formula, Relative Mass 120℃ is the TGA measurement of relative mass at 120°C, Relative Mass 350℃ is the TGA measurement of relative mass at 350°C.)

[0092] Exemplary H of the present disclosure 2For the -LIAH composition and its TGA data in Table 2, the relative mass loss of the crystallization-hydrate was determined to be 20.387%.

[0093] In the context of the present disclosure, the molar ratio of crystallization-hydrate to lithium can be calculated by mass balance from the TGA and ICP-OES data using Equation 3. The ICP-OES data is first evaluated to provide the molar ratio of aluminum to lithium, which is then used in Equation 3. Alternatively, if desired, similar ratios can be determined using mass values ​​obtained from these data. 2 The -LIAH composition was determined to have an aluminum to lithium ratio of about 2.3:1.0 based on the data in Table 1.

[0094]

number

[0095] Exemplary H of the present disclosure 2 For the -LIAH composition and its TGA data, the relative mass loss of the crystallization-hydrate was determined to be 2.5. Thus, specifying the final integer "n", the exemplary H 2 The specific molecular formula of the LIAH composition can be fully expressed. Thus, Formula 1 is determined as follows: LiCl 2.3Al(OH)3 2.5H2O cry

[0096] H of this disclosure 2 -LIAH material compositions were evaluated by a series of analytical techniques to determine the effect of crystallization-hydration loss. Representative experimental results are outlined below.

[0097] FIG. 4 is a schematic diagram of the H 2 4 shows a Fourier transform infrared (FTIR) spectral overlay 400 of the H-LIAH composition before 411 and after 421 high temperature drying. Individual FTIR bands are identified and assigned to their respective materials for purposes of this discussion. For simplicity, the x-axis is truncated by a median cutoff 405. General -OH bond stretching absorbance can be noted for both materials, but only the H-LIAH composition before high temperature drying is shown. 2 For the -LIAH composition 415, a strong relative absorbance was observed, and the H 2 The absorbance of the aluminum bond is reduced for the H-LIAH composition 425 before drying at high temperature. 2 -LIAH compositions are identified by reference numbers 416 and 417. After high temperature drying, H 2 The -LIAH composition shows a clear loss of the Al-O-stretch bands 426 and reduced Al-OH bend bands 427. Without being bound to a particular theory, the observed changes in the Al-O-bond bands suggest a significant loss of crystallinity as a result of high temperature drying. The loss of crystallinity associated with high temperature drying can also be observed in the DSC data above. The endotherm 301 observed in FIG. 1 lacks any indication of a subsequent recrystallization event as observed in the peak shape and graph trends, e.g., symmetry, Gaussian shape, and lack of steepness as a result of the supercooling recrystallization event.

[0098] H of this disclosure 2The hydroxide ion retention was determined for the H-LIAH composition and the conventional LIAH composition. In each case, the pH of the solution obtained by suspending the dried sample in deionized water was measured using a calibrated pH meter. The results are shown in Table 3. 2 The -LIAH compositions have been found to have lower hydroxide retention than conventional LIAH compositions, which may provide improved performance in adsorbents for lithium recovery, especially in applications involving saltwater with non-negligible concentrations of divalent ions that tend to precipitate in the presence of hydroxide ions.

[0099] [Table 3]

[0100] H of this disclosure 2 The structural and chemical robustness of the LIAH composition and the conventional LIAH composition were evaluated via turbidity measurements. 2 The turbidity results for the H-LIAH composition and the conventional LIAH composition are shown in Table 4. The results are consistent with the H-LIAH composition of the present disclosure. 2 The structural and chemical robustness of the -LIAH composition has been shown to be improved compared to conventional LIAHs, which may correlate with improved chemical durability as an adsorbent for lithium recovery from brine.

[0101] [Table 4]

[0102] H of this disclosure 2 The hardness of the H-LIAH composition and the conventional LIAH composition was determined using scratch testing and the Mohs hardness scale. 2 The hardness results for samples related to the LIAH-LIAH composition and the conventional LIAH composition are shown in Table 5. The results are consistent with the H 2 The hardness of the -LIAH composition was shown to be improved compared to conventional LIAH compositions, which may correlate with improved physical durability as an adsorbent for lithium recovery from saltwater.

[0103] [Table 5]

[0104] FIG. 5 is a schematic diagram of the H 2 - shows a microscope image of the LIAH composition and a standard 1 / 10 ruler (i.e., each division represents 1 mm) for particle size reference. The LIAH composition can be processed to provide a particle size distribution such that at least: (i) about 40% of the particles are between about 500 μm and about 1,000 μm; (ii) about 50% of the particles are between about 500 μm and about 1,000 μm; or (iii) at least about 55% of the particles are between about 500 μm and about 1,000 μm.

[0105] Using a bench-scale column apparatus, the H 2 The lithium uptake capacity was determined for the -LIAH composition and the conventional LIAH composition.

[0106] The apparatus featured a laboratory stand and a jacketed glass column with an internal diameter of about 3.2 cm and a height of about 20 cm, with a frit to minimize particle loss. Heating of the column was performed by an external circulating water bath with a set operating temperature. In each case, a pre-weighed mass (between about 50 g and about 70 g) of test composition of a given particle size range was transferred to the column. The height of the packed adsorbent was determined after pumping water or eluent (200 ppm Li solution) through the column using the operating flow path (top-down). To prepare the test composition for adsorption, an initial elution was performed using up to a total of 10 column bed volumes of eluent to remove the entrained lithium. Following this, the adsorption and elution stages were performed at elevated temperatures between 40 °C and 80 °C using the prepared synthetic brine feed and eluent, respectively. The synthetic brine contained the set of species listed in Table 6 at the concentrations listed, as determined by ICP-OES or inductively coupled plasma mass spectrometry (ICP-MS).

[0107] [Table 6]

[0108] The processing volume for the adsorption step was calculated based on the amount of adsorbent weighed and loaded into the column, using a target maximum lithium capacity of 10 mg / g (which correlated to 5-10 bed volumes). The flow rate was adjusted so that the flow rate of fluid through the adsorbent was between 300-400 L / m2 / hr. To determine the performance of the test compositions during the adsorption step, samples were taken from the outlet (bottom of the column) at regular time intervals, and the composition of each sample was determined by ICP-OES.

[0109] FIG. 6 shows a plot 600 of lithium concentration as a function of sampling time, providing a visual depiction of the capacity of the test composition. In FIG. 6, the lithium concentration of the bulk solution is shown at 611, and the lithium concentration at the outlet is shown at 621. This can be described as a sharp decrease in lithium concentration at the outlet relative to the initial brine concentration. The low lithium concentration, characteristic of the sorbent, extends for a period of time and then begins to rise again, thus taking the form of a "bathtub". As the sorbent approaches saturation, the Li concentration at the outlet increases until it reaches the initial Li concentration of the brine feed.

[0110] A more formal determination of capacity was determined by the amount of Li adsorbed, as calculated by Eq. 4. Absorbed Lithium = ([Li] 初期 -[Li] 最終 )×Vol 塩水 formula 4 (In the formula, Lithium absorbed = total lithium absorbed (mg) [Li] 初期 : Initial lithium concentration (mg / L) [Li] 最終 : Final lithium concentration (mg / L) Vol 塩水 : Volume of saltwater tested (L).

[0111] The capacity of the adsorbent is then calculated by Equation 5.

[0112]

number

[0113] As an example of continuous use, FIG. 7 shows the H of the present disclosure deployed in one embodiment of an apparatus for recovering lithium from a lithium-containing solution according to the present disclosure, and in a method for recovering lithium from a lithium-containing solution according to the present disclosure. 2 An excerpt of process monitoring data 700 is shown for the -LIAH composition. For simplicity, the x-axis is truncated by a median cutoff 705. A typical cycle 711 begins with brine being charged to the system, then lithium is added to the H 2 Figure 1 shows the variation of lithium concentration as it is adsorbed onto a -LIAH packed column. The column performance is maintained through successive cycles so that the chemical and / or physical durability can be evaluated. Samples were taken from the outlet (bottom of the column) at regular time intervals and the composition of each sample was determined by ICP-OES.

[0114] In this embodiment, elution was performed using a volume of eluent equal to the brine feed, at a flux rate corresponding to 300-800 L / m2 / h. Sampling was performed similarly to the adsorption stage. For adsorbent evaluation, for comparison, 2-3 adsorption / elution cycles were performed using a synthetic feed before evaluation using real brine samples.

[0115] One aspect of the present disclosure relates to an adsorbent for recovering lithium from a lithium-containing solution, the adsorbent comprising a LIAH composition having a molar ratio of crystallized hydrate to lithium of at least about 2.1:1.0. In the context of the present disclosure, the LIAH composition may comprise a single compound or multiple compounds. In one embodiment of the present disclosure, the LIAH composition may have a molar ratio of crystallized hydrate to lithium of about 2.1:1.0 to about 4.3:1.0. In one embodiment of the present disclosure, the LIAH composition may have a molar ratio of crystallized hydrate to lithium of about 2.4:1.0 to less than about 2.9:1.0. In one embodiment of the present disclosure, the LIAH composition may have a molar ratio of crystallized hydrate to lithium of less than about 4.3:1.0. In one embodiment of the present disclosure, the LIAH composition may have a molar ratio of crystallized hydrate to lithium of about 2.9:1.0 to less than about 4.0:1.0. Those skilled in the art having the benefit of the teachings of the present disclosure will understand how to adjust the manufacturing conditions to provide a LIAH composition within the described ranges. For example, the following parameters can be controlled to induce a higher crystallization-hydrate to lithium molar ratio (reference numbers refer to the manufacturing steps of the methods described herein): - increasing the concentration of the hydroxide solution used in step (i) and / or step (iv); - in step (i), increasing the pH of the reaction mixture to above about 9.0 (e.g., to about 10.0 or to about 11.0); - in step (ii), lowering the pH of the reaction mixture to less than about 4.0 (e.g., to about 3.0 or to about 2.0); - minimizing high shear mixing during step (iii); and / or - Reducing the reaction time of step (iii) and / or step (iv).

[0116] In one embodiment of the present disclosure, the crystallization-hydrate to lithium molar ratio of the LIAH composition can be determined from DSC, ICP-OES, TGA, or a combination thereof. 2The analysis of -LIAH compositions need not be limited to these analytical techniques. Those skilled in the art will appreciate that other characterization techniques may supplement, support, or replace one or more of the aforementioned analyses without departing from the scope of this disclosure. In the context of this disclosure, analysis by DSC may require that the samples be loaded into aluminum moving crucibles prior to analysis. Each crucible may be capped and each cap may be pierced with a sharp point to generate gas throughout the experiment. During the analysis, the samples may be processed to increase the temperature at a constant rate from ambient temperature to 450°C. Experimental data may be provided as enthalpy change during heating. In the context of this disclosure, samples for TGA may be loaded into aluminum moving crucibles. During the analysis, the samples may be processed to increase the temperature at a constant rate from ambient temperature to 450°C. Experimental data may be provided as relative mass loss (%) during heating. In the context of this disclosure, prior to elemental analysis by ICP-OES (or alternatively ICP-MS), samples may be digested in acid in plasticware and diluted with deionized water for analysis. In the context of this disclosure, FTIR samples may be prepared by grinding the material into a powder, which may then be mounted on an FTIR spectrometer equipped with an ATR accessory. Spectra are measured from 4000 to 400 cm. -1 In the context of the present disclosure, samples analyzed by XRD can be de-masked, mounted on an X-ray transparent support (e.g., single crystal silicon), and analyzed using a Bragg-Brentano instrument geometry. In one embodiment of the present disclosure, the LIAH composition can be characterized by 2θ reflectance peaks at about 11.5° 2θ, 23.1° 2θ, 35.0° 2θ, and 35.7° 2θ, or combinations thereof, by XRD. Similarly, the LIAH composition of the present disclosure can be characterized by the absence of a 2θ reflectance peak at 18.2° 2θ by XRD.

[0117] In one embodiment of the present disclosure, the LIAH composition may have a molar ratio of aluminum to lithium of at least about 1.9:1.0. In one embodiment of the present disclosure, the LIAH composition may have a molar ratio of aluminum to lithium of about 2.0:1.0 to about 3.0:1.0. In one embodiment of the present disclosure, the LIAH composition has a molar ratio of aluminum to lithium of about 2.4:1.0 to about 2.6:1.0. One of skill in the art will appreciate that such elemental ratios may be determined by ICP or another suitable analytical technique.

[0118] In one embodiment of the disclosure, the LIAH composition has Formula 1: Li a X mAl(OH)3 nH2O cr formula 1 (In the formula, a is about 1; X is a monovalent anion (e.g., F - , Cl - , Br - and / or I - ) and; m is from about 1.9 to about 3.0; n is from about 2.4 to about 4.3; H2O cr may be as described in Crystallization-Designating a hydrate).

[0119] In one embodiment of the present disclosure, the LIAH composition can be a lithium-aluminum layered double hydroxide composition.

[0120] In one embodiment of the present disclosure, the adsorbent may further include a binder, an encapsulating agent, or a combination thereof. Suitable agents may be organic or inorganic and may include alginates, biochar, biopolymers, carbonaceous ores, clays, polyvinyl alcohol, methacrylates, graphene, metal organic frameworks, nanotubes, polyphenols, synthetic polymers, polysaccharides, silicates, combinations thereof, and the like.

[0121] In one embodiment of the present disclosure, the LIAH composition may have a lithium uptake capacity of at least about 8.0 mg / mL. In one embodiment of the present disclosure, the lithium uptake capacity of the LIAH composition may be at least about 9.0 mg / mL. In one embodiment of the present disclosure, the lithium uptake capacity of the LIAH composition may be from about 9.5 mg / mL to about 12.0 mg / mL. In one embodiment of the present disclosure, the LIAH composition may be processable to provide a particle size distribution in which at least about 40% of the particles are from about 500 μm to about 1,000 μm. In one embodiment of the present disclosure, the LIAH composition may be processable to provide a particle size distribution in which at least about 50% of the particles are from about 500 μm to about 1,000 μm. In one embodiment of the present disclosure, the LIAH composition may be processable to provide a particle size distribution in which at least about 55% of the particles are from about 500 μm to about 1,000 μm. Those skilled in the art having the benefit of the teachings of the present disclosure will understand how to adjust the manufacturing conditions to provide a LIAH composition within the described ranges. For example, the following parameters can be controlled to induce larger particle sizes (reference numbers refer to the manufacturing steps of the methods described herein): - increasing the concentration of the hydroxide solution used in step (i) and / or step (iv); - in step (i), increasing the pH of the reaction mixture to above about 9.0 (e.g., to about 10.0 or to about 11.0); - in step (ii), lowering the pH of the reaction mixture to less than about 4.0 (e.g., to about 3.0 or to about 2.0); - minimizing high shear mixing during step (iii); - reducing the reaction time of step (iii) and / or step (iv); - in step (v), drying the gelled material at a temperature of about 85°C to 120°C; - drying the gel material in step (v) to a thickness of at least about 4 cm; - drying the gel-like material in step (v) for about 24 hours to about 72 hours; and / or - In step (v), drying the gelled material to a mass loss of about 30% to about 60%.

[0122] In one embodiment of the present disclosure, the LIAH composition can be suspended in deionized water to provide a solution having a pH of about 7.0 to about 6.2. 2 The H-LIAH compositions of the present disclosure may retain relatively low concentrations of residual hydroxide ions. 2 The -LIAH composition can be suspended in deionized water to provide a solution having a pH of less than about 5, less than about 6, or from about 6.5 to about 7. This can be beneficial in that formation of insoluble hydroxides can result from exposure to complex saltwater. Without being bound to any particular theory, complex saltwater contains relatively high concentrations of Ca. 2+ and Mg 2+ However, these may precipitate from solutions containing relatively high concentrations of hydroxides. This may manifest as an increased pressure drop in the adsorbent column, which in turn leads to lower operating flow rates and poorer lithium uptake performance. 2 The -LIAH composition may alleviate this problem.

[0123] In one embodiment of the present disclosure, turbidity values ​​of less than 10 NTU can be obtained by suspending the LIAH composition in deionized water. In one embodiment of the present disclosure, turbidity values ​​of less than 5 NTU can be obtained by suspending the LIAH composition in deionized water. In one embodiment of the present disclosure, turbidity values ​​of about 2.5 NTU to about 5 NTU can be obtained by suspending the LIAH composition in deionized water. This can be beneficial to DLE sorbent process engineering in that it can correlate with improved structural integrity in the process flow. In the context of the present disclosure, turbidity measurements can include suspending a unit of material in deionized water and gently mixing to disperse. The suspension can be decanted into another beaker and turbidity measurements can be taken on the decanted solution.

[0124] In one embodiment of the present disclosure, the LIAH composition may have a Mohs hardness of at least about 5.0. In one embodiment of the present disclosure, the Mohs hardness of the LIAH composition may be at least about 6.0. In one embodiment of the present disclosure, the Mohs hardness of the LIAH composition may be at least about 7.0. The hardness of the LIAH composition of the present disclosure may be characterized by the Mohs scale of mineral hardness, which is a qualitative ordinal scale of 1 to 10 that characterizes the scratch resistance of various minerals by which harder materials can scratch softer materials. In the context of the present disclosure, determining the hardness of the sample (prior to manual grinding and sieving) may include scratching with hardness-increasing items (e.g., a fingernail, a copper wire, a piece of glass, and a stainless steel pick) and recording whether the particles broke or generated a large amount of dust. Particle hardness may be measured using a bracketing method. For example, it has been observed that if a sample does not fracture with a fingernail, but does fracture with a copper wire, the batch corresponds to a Mohs hardness of 2-3. Without being bound to any particular theory, the high hardness of the compositions of the present disclosure may be a physical manifestation of high crystallinity. This may be the basis for their performance as adsorbents for DLE.

[0125] In one embodiment of the disclosure, the LIAH composition may be robust with respect to degradation for at least about 500 column cycles. In one embodiment of the disclosure, the LIAH composition is robust with respect to degradation for at least about 5000 column cycles.

[0126] H 2 -Method of manufacture of LIAH composition According to an embodiment of the present disclosure, H 2The -LIAH composition was prepared as follows: Lithium chloride (0.961 kg) was dissolved in a solution of AlCl3 (21.733 kg, 25-30%) and mixed with an overhead stirrer. The Li to Al ratio was about 1:2. With the mixing speed set at about 240 rpm, an aliquot of NaOH solution (2.18 kg, 50%) was mixed with an aliquot of the LiCl / AlCl3 mixture. The pH of the reaction mixture was monitored as it rose to above about 10 and the temperature of the reaction mixture rose to about 90°C to about 97°C. With continued mixing, an additional aliquot of the LiCl / AlCl3 solution was slowly added and the reaction mixture was observed to thicken as the pH decreased to below about 3. A gel-like material formed when the entire amount of the LiCl / AlCl3 solution had been added. The mixing speed was reduced to about 100 rpm to reduce the possibility of over-shearing the material, and a further aliquot of 50% NaOH solution was added until the pH of the gel-like material was about 6.8-7.2. The reaction mixture was weighed, transferred to a drying tray, and placed in a drying oven and aged at about 95°C for about 5 hours. The layering of the slurry was reduced to less than about 4 cm to reduce the generation of fines (e.g., particles less than about 250 μm in size) and maintain a particle size range of about 250 μm to more than about 2000 μm. After this time, the solids formed a wet cake, which was remixed and then drying continued to reduce its mass to 60% of its initial value. After cooling, the solids were desalted by rinsing with deionized water under suction filtration (e.g., to remove NaCl) until the rinse achieved a conductivity of less than about 15 ms / cm. The final gel was returned to the oven and dried at about 95°C for about 16 hours to about 24 hours, followed by drying in H 2 The LIAH composition was obtained as a dry product. 2 - sieving the LIAH composition to obtain a particle fraction having a particle size in the range of about 250 μm to greater than about 2000 μm; 2 -LIAH compositions were characterized as described herein.

[0127] According to an embodiment of the present disclosure, H 2The -LIAH composition was prepared as follows: Lithium chloride (0.961 kg) was mixed with a solution of AlCl3 (17.045 kg, 28-30%) such that the molar ratio of Li to Al was approximately 1:2, respectively. The LiCl / AlCl3 mixture was mixed at 200 rpm to ensure complete dissolution of the salt. Separately, NaOH pellets (110 g) were dissolved in deionized water (380 mL) to form a 7.2 M (or approximately 29% wt / vol) hydroxide solution. The LiCl / AlCl3 mixture was added slowly (at a rate of 2 L / min) with mixing via an overhead mixer to the hydroxide solution, and the pH of the reaction mixture was monitored. The pH of the reaction mixture dropped from greater than about 12 to less than about 3 before the addition of the LiCl / AlCl3 mixture was complete. As the reaction mixture approached the minimum of this pH transition, a noticeable increase in solution viscosity occurred. The mixing speed was then increased to a speed sufficient to maintain a vortex in the gel-like material while avoiding the possibility of excessive shear. Mixing was continued for about 10 minutes after addition of the LiCl / AlCl3 mixture. The mixing speed was then reduced to 100 rpm and an additional aliquot of hydroxide solution was added to adjust the pH of the gel-like material to about 7.0. The gel-like material remained without any noticeable decrease in the viscosity of the reaction mixture. The reaction mixture was transferred to a bank of drying trays, weighed, and each tray was loaded to a minimum thickness of about 4 cm to reduce excess production of fines (e.g., less than 250 μm) and maintain a particle size range of about 250 μm to greater than about 2000 μm. The loaded drying trays were placed in a drying oven where the reaction mixture was aged at about 95° C. for 5 hours. After this time, the solids formed a wet cake which was remixed and then dried until its mass was reduced to about 70% of its initial value. After cooling, the solids were desalted (to remove NaCl) by rinsing with deionized water under suction filtration until the rinse achieved a conductivity of less than about 15 ms / cm. The final gel-like material was placed back in the oven and dried at 95°C for 24 hours. 2 The LIAH composition was obtained as a dry product. 2 - sieving the LIAH composition to obtain a particle fraction having a particle size in the range of about 250 μm to greater than about 2000 μm; 2 -LIAH compositions were characterized as described herein.

[0128] In one embodiment of the present disclosure, as the reaction mixture approaches the minimum of the pH transition associated with the addition of the LiCl / AlCl mixture and a gel-like material forms, the mixing time can be selected to balance: (i) increasing the homogeneity and thereby modulating the strength of the gel; (ii) reducing the formation of carbonates generated from prolonged atmospheric exposure; and / or (iii) reducing impurity formation.

[0129] One aspect of the present disclosure is a method of making a LIAH composition, comprising: (i) combining an initial aliquot of hydroxide solution with an initial aliquot of a solution comprising lithium halide and aluminum halide to form a reaction mixture wherein the hydroxide solution is present in excess and the pH of the reaction mixture is at least about 9.0; (ii) adding an additional aliquot of the solution containing lithium halide and aluminum halide to the reaction mixture to reduce the pH of the reaction mixture to less than about 4.0; (iii) allowing the reaction mixture to form a gel-like material; (iv) adding an additional aliquot of hydroxide solution to the reaction mixture to raise the pH of the reaction mixture to about 6.5 to about 7.5.

[0130] In one embodiment of the present disclosure, in step (i), an initial aliquot of hydroxide solution is added to an initial aliquot of a solution comprising lithium halide and aluminum halide.

[0131] In one embodiment of the present disclosure, in step (i), an initial aliquot of a solution containing lithium halide and aluminum halide is added to an initial aliquot of hydroxide solution.

[0132] In one embodiment of the present disclosure, the initial aliquot of the solution comprising lithium halide and aluminum halide and the further aliquot of the solution comprising lithium halide and aluminum halide are derived from the same stock solution.

[0133] In one embodiment of the present disclosure, the initial aliquot of hydroxide solution and the further aliquot of hydroxide solution are derived from the same stock solution.

[0134] In one embodiment of the present disclosure, the solution containing lithium halide and aluminum halide has a molar ratio of lithium to aluminum of about 1.0:2.0 to about 1.0:3.0.

[0135] In one embodiment of the present disclosure, the hydroxide solution has a concentration of about 6.5M to about 8.0M.

[0136] In one embodiment of the present disclosure, the lithium halide is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, or a combination thereof.

[0137] In one embodiment of the present disclosure, the lithium halide is lithium chloride.

[0138] In one embodiment of the present disclosure, the aluminum halide is aluminum trifluoride, aluminum trichloride, aluminum tribromide, aluminum triiodide, or a combination thereof.

[0139] In one embodiment of the present disclosure, the aluminum halide is aluminum trichloride.

[0140] In one embodiment of the present disclosure, the hydroxide solution is a sodium hydroxide solution, a potassium hydroxide solution, a calcium hydroxide solution, a magnesium hydroxide solution, or a combination thereof.

[0141] In one embodiment of the present disclosure, the hydroxide solution is a sodium hydroxide solution.

[0142] In one embodiment of the present disclosure, the rate of addition of the hydroxide solution is from about 9.5 mL / min to about 10.5 L / min.

[0143] In an embodiment of the present disclosure, in step (iii), step (iv), or a combination thereof, the reaction mixture is stirred to adjust the viscosity of the gelled material.

[0144] In one embodiment of the present disclosure, the temperature of the reaction mixture in step (iii), step (iv), or a combination thereof, is controlled to adjust the viscosity of the gel-like material.

[0145] In one embodiment of the present disclosure, in step (iii), step (iv), or a combination thereof, the pressure of the reaction mixture is controlled to adjust the viscosity of the gelled material.

[0146] In one embodiment of the present disclosure, the reaction time in step (iii), step (iv), or a combination thereof, is controlled to adjust the viscosity of the gelled material.

[0147] In one embodiment of the present disclosure, the rate of addition in step (ii), step (iv), or a combination thereof, is controlled to adjust the viscosity of the gel-like material.

[0148] In one embodiment of the present disclosure, the method further comprises the step of (v) hardening the gel material into a LIAH composition.

[0149] In one embodiment of the present disclosure, step (v) comprises drying at a temperature of about 85°C to about 95°C.

[0150] In one embodiment of the present disclosure, step (v) comprises drying for about 24 hours to about 75 hours.

[0151] In one embodiment of the present disclosure, this includes drying at a pressure of about 76 mmHg to about 760 mmHg.

[0152] In one embodiment of the present disclosure, step (v) comprises aging, rinsing, drying, sieving, or a combination thereof.

[0153] One aspect of the present disclosure relates to an adsorbent produced by the process defined herein.

[0154] Increasing mixing speed, reactant concentration, reagent addition order versus stoichiometric control, and changes in viscosity corresponded to increased gel strength.

[0155] Increased gel strength correlates with higher amounts of crystallized hydrate.

[0156] In contrast to the above-mentioned protocols that utilize a pH reversal protocol, conventional methods of LIAH production (i) use LiCl / AlCl3 addition to a hydroxide solution without dropping the pH substantially below about 6.5; or (ii) do not use pH control during the addition of the stoichiometric amount of LiCl / AlCl3 solution to the hydroxide solution such that the final pH of the mixture exceeds 6.5, do not result in a gel-like material, and are not compatible with the HIAH described herein. 2 - Did not provide LIAH composition.

[0157] H 2 -Apparatus and method for recovering lithium from salt water using LIAH compositions FIG. 8 illustrates an apparatus 800 for recovering lithium from a lithium-containing solution according to one embodiment of the disclosure. FIG. 8 also illustrates a method 850 for recovering lithium from a lithium-containing solution according to an embodiment of the disclosure. The apparatus 800 is configured to perform the method 850 using a lead, guard, elution column configuration. The lead column is shown with cross-hatching, the guard column is shown with horizontal hatching, and the elution column is shown with vertical hatching. In operation, the columns are rotated through an extraction cycle. This process is illustrated in FIG. 8, where the apparatus 800 includes columns 808, 810, and 812, which process the brine according to steps 852, 854, and 856 as follows:

[0158] In step 852, column 808 is absorbing lithium while column 810 acts as a guard column to recover any remaining lithium before the depleted brine is discharged as a raffinate which can be recycled for additional lithium extraction, further processed, stored, or disposed of. Also in step 802, eluent is flowed through column 812 to desorb the lithium absorbed during the previous cycle. This results in a lithium-enriched eluate which can proceed to water recovery techniques.

[0159] In step 854, column 810 is reconfigured from a guard column to a lead column, where column 810 receives the brine and absorbs lithium therefrom, and in step 854, column 812 is reconfigured from an elution column to a guard column and absorbs residual lithium, and in step 854, column 808 is reconfigured from a lead column to an elution column and desorbs the retained lithium from step 852.

[0160] In step 856, column 812 is reconfigured from a guard column to a lead column, which receives the brine and absorbs lithium therefrom. Also in step 856, column 808 is reconfigured from an elution column to a guard column and absorbs residual lithium. Also in step 856, column 810 is reconfigured from a lead column to an elution column and desorbs the retained lithium from step 854.

[0161] Steps 852, 854, and 856 may be cycled by adjusting a valve manifold (or alternative means for fluid control) to direct the flow of salt water, eluent, etc.

[0162] Apparatus and methods for recovering lithium from lithium-containing solutions are generally known to those of skill in the art, so apparatus 800 is one of many configurations that may be suitable for recovering lithium in the context of this disclosure (as well as method 850), as one of skill in the art will appreciate. PCT Patent Publication WO 2020 / 257937(A1), the contents of which are incorporated herein by reference, may disclose apparatus and methods for recovering lithium from saltwater that are suitable in the context of this disclosure. One of skill in the art will understand the science and engineering fundamentals (e.g., equilibrium and mass transfer considerations) associated with using adsorbents in such apparatus and / or methods, as demonstrated by Gableman, A., "Absorption Basics: Part 1," Chemical Engineering Progress, 113(7), pp 48-53 (July 2017). For example, an apparatus for lithium recovery according to the present disclosure can be configured as a continuous flow system (also referred to as a "daisy chain" flow system) configured in parallel, in series, or a combination of parallel and series, flowing in either upflow or downflow mode. Similarly, an apparatus for lithium recovery according to the present disclosure can employ a countercurrent extraction method. In a countercurrent extraction method, the eluent is pumped countercurrent to the adsorbent travel direction, for example, by an indexed multiport valve system and / or a carousel of adsorbent vessels. An apparatus for lithium recovery according to the present disclosure can be configured to operate under a variety of temperature and pressure conditions. For example, an apparatus for lithium recovery according to the present disclosure can operate at temperatures below about 60°C, between about 60°C and about 100°C, and / or above about 100°C.

[0163] In the context of the present disclosure, the lithium-containing solution may be a saltwater, such as that recovered from a naturally occurring terrestrial saltwater deposit. The lithium-containing solution may also be from a fluid saltwater suspension produced from hydromining operations of a geological formation, and / or from saltwater and wastewater produced from oil and gas production activities. The composition of the lithium-containing solution suitable for use with the sorbents, apparatus, and / or methods of the present disclosure may vary widely. For example, lithium-containing solutions having a total dissolved solids (TDS) of about 50 ppm to about 5000 ppm, about 5000 ppm to about 10,000 ppm, about 10,000 ppm to about 100,000 ppm, or about 100,000 to about 250,000 ppm may be suitable. With respect to cation loading, suitable lithium-containing solutions may contain various concentrations of lithium, sodium, potassium, calcium, magnesium, or combinations thereof. For example, the lithium-containing solution may have a total dissolved solids (TDS) of about 5000 ppm. + , about 1000 ppm Na + , about 500 ppm Li + , and about 50 ppm Ca 2+ may include:

[0164] In the context of this disclosure, the term "brine" may refer to natural saltwater, synthetic saltwater, or combinations thereof. In the context of this disclosure, the term "ion" is defined as a metal ion of any valence, including, but not limited to, lithium, potassium, calcium, magnesium, manganese, iron, zinc, cobalt, nickel, titanium, aluminum, tin, gallium, silver, gold, copper, cadmium, or combinations thereof. In the context of this disclosure, the term "lithium" is used broadly to encompass lithium ions in solution, lithium ions absorbed on surfaces, and lithium ions in chemical compositions such as lithium chloride, lithium carbonate, and lithium hydroxide. Those skilled in the art will recognize that lithium ions can take a variety of forms, all of which are within the scope of this disclosure. For example, lithium ions can be hydrated, involved in coordinated ion pairs, held in interstitial sites, suspended in colloidal form, etc.

[0165] One aspect of the present disclosure is an apparatus for recovering lithium from a lithium-containing solution, comprising a vessel having an inlet, an outlet, and a continuous flow path therebetween, and a H2SO4 solution having a molar ratio of crystallized hydrate to lithium of at least 2.1:1.0. 2 and an adsorbent comprising the LIAH composition.

[0166] One aspect of the present disclosure relates to an apparatus for recovering lithium from a lithium-containing solution, the apparatus comprising a vessel having an inlet, an outlet and a continuous flow path therebetween, and a sorbent as defined herein.

[0167] One aspect of the disclosure relates to a method for recovering lithium from a lithium-containing solution, comprising contacting the lithium-containing solution with a sorbent composition to extract lithium from the lithium-containing solution and leaching lithium from the sorbent composition to form a lithium leachate, wherein the sorbent composition comprises a LIAH composition having a molar ratio of crystallized-hydrate to lithium of at least 2.1:1.0.

[0168] One aspect of the present disclosure relates to a method for recovering lithium from a lithium-containing solution, comprising contacting the lithium-containing solution with a sorbent composition to extract lithium from the lithium-containing solution, and eluting lithium from the sorbent composition to form a lithium eluate, wherein the sorbent composition comprises a LIAH composition as defined herein.

[0169] The present invention also relates to a method of recovering lithium from a lithium-containing solution, the method comprising the steps of contacting the lithium-containing solution with an adsorbent comprising a LIAH composition as defined herein to extract lithium from the lithium-containing solution, and eluting the lithium from the adsorbent to form a lithium eluate.

[0170] Further notes While the invention has been described and illustrated with respect to preferred embodiments and its preferred uses, it should not be so limited, since modifications and variations are possible that are within the full intended scope of the invention as will be understood by those skilled in the art.

[0171] While particular aspects of the subject matter described herein have been shown and described, changes and modifications can be made based on the teachings herein without departing from the subject matter described herein and its broader aspects. It will therefore be apparent to those skilled in the art that the appended claims encompass within their scope all such changes and modifications as are within the true spirit and scope of the subject matter described herein.

[0172] It should be noted that in the specification and drawings, the same components may be designated by multiple reference numbers. For example, a feature designated by the numeral 100 in Figure 1 may be designated by the numeral 200 in Figure 2, 300 in Figure 3, etc. Features designated by the same numerals in different figures are equivalent and / or the same features, albeit in different embodiments, and should be considered equivalent and / or the same for purposes of interpreting the specification and / or drawings.

[0173] It will be understood by those skilled in the art that, in general, the terms used in this specification, and particularly the terms used in the appended claims, are generally intended as "open" terms (e.g., the term "comprising" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," the term "has" should be interpreted as "having at least," etc.).

[0174] It will be further understood by those skilled in the art that if a specific number is intended for an introduced claim recitation, such intent will be explicitly stated in the claim, and in the absence of such recitation, no such intent exists. For example, as an aid to understanding, the following appended claims may include the use of the introductory phrases "at least one" and "one or more" to introduce a claim recitation. However, the use of such phrases should not be interpreted to imply that the introduction of a claim recitation with the indefinite article "a" or "an" limits any particular claim that includes a claim recitation so introduced to a claim that includes only one such recitation, even if the same claim includes the introductory phrases "one or more" or "at least one" and an indefinite article such as "a" or "an" (e.g., "a" and / or "an" should typically be interpreted to mean "at least one" or "one or more"). The same is true for the use of definite articles used to introduce claim recitations. In addition, even when a particular number is explicitly recited in an introduced claim recitation, a person of ordinary skill in the art will recognize that such a recitation should typically be interpreted to mean "at least the recited number" (e.g., a recitation of "two or more than two of something," without other modifiers, typically means at least two of something, or more than two of something).

[0175] Furthermore, when conventional language similar to "at least one of A, B, and C, etc." is used, such syntax is generally intended in the sense that one of ordinary skill in the art would understand the conventional language (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, systems having only A, only B, only C, both A and B, both A and C, both B and C, and / or both A, B, and C, etc.). When conventional language similar to "at least one of A, B, or C, etc." is used, such syntax is generally intended in the sense that one of ordinary skill in the art would understand the conventional language (e.g., "a system having at least one of A, B, or C" includes, but is not limited to, systems having only A, only B, only C, both A and B, both A and C, both B and C, and / or both A, B, and C, etc.).

[0176] It will further be appreciated by those skilled in the art that disjunctive words and / or phrases presenting two or more alternative terms, whether in the specification, claims, or drawings, should typically be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms, unless the context indicates otherwise. For example, "A or B" is typically understood to include the possibilities of "A" or "B," or "A and B."

[0177] With respect to the appended claims, those skilled in the art will appreciate that the operations described therein may generally be performed in any order. Also, while various operational flows are presented in sequence(s), it should be understood that various operations may be performed in orders other than those depicted, or may be performed simultaneously. Examples of such alternative orderings may include overlapping, interleaving, interrupting, reordering, incrementing, preparing, supplementing, simultaneous, reversing, or other variant orderings, unless the context indicates otherwise.

[0178] Throughout this application, the terms "in an embodiment," "in one embodiment," "in (multiple) embodiments," "in some embodiments," "in at least one embodiment," and "in various embodiments" may be used. Each of these terms, and all such similar terms, should be interpreted as "in at least one embodiment, and possibly not in all embodiments," unless expressly stated otherwise. Specifically, unless expressly stated otherwise, the intent of phrases such as these is to provide non-exclusive and non-limiting examples of implementations of the subject matter.

[0179] The degree term "substantially" as used herein means a reasonable amount of deviation of the modified term such that the end result does not change significantly. The term "substantially" should be interpreted as including a ±5% deviation of the modified term if this deviation does not negate the meaning of the term it modifies. The degree terms "about" and "approximately" should be interpreted as including a ±20% deviation. For example, when the terms "approximately" or "about" are used in connection with a numerical value, they modify it up or down with a 20% variation compared to the nominal value. This term can also take into account, for example, experimental error of a measuring device or rounding of values. Other degree terms should be interpreted as including a ±5% deviation of the modified term.

[0180] When a range of values ​​is referred to in this application, the lower and upper limits of the range are always included in the definition, unless otherwise indicated. When a range of values ​​is referred to in this application, it is intended that all intermediate ranges and subranges, as well as individual values ​​included in the range, are included.

[0181] The mere statement that one, some, or many embodiments include one or more things or have one or more features does not imply that all embodiments include one or more things or have one or more features, nor does it imply that such embodiments must exist, it is merely an indicator of an example and should not be construed differently unless explicitly stated.

[0182] Those skilled in the art will appreciate that the specific exemplary compositions, apparatus, and / or methods described above are representative of more general processes and / or devices and / or techniques that are taught elsewhere herein, such as in the appended filed claims and / or elsewhere in this disclosure.

Claims

1. An adsorbent for recovering lithium from a lithium-containing solution, comprising highly hydrated lithium-containing aluminum hydroxide (H) having a crystallized-hydrate to lithium ratio of at least about 2.1:1.0 ２ An adsorbent for recovering lithium from a lithium-containing solution, comprising the LIAH composition.

2. The aforementioned H ２ - The adsorbent according to claim 1, wherein the ratio of crystallized LIAH composition to hydrate to lithium is about 2.1:1.0 to about 4.3:1.0, preferably 2.1:1.0 to about 2.9:1.0 or 2.9:1.0 to about 4.0:1.

0.

3. The aforementioned H ２ -Crystallization of the LIAH composition- The ratio of hydrate to lithium is determined by differential scanning calorimetry, inductively coupled plasma atomic emission spectrometry, thermogravimetric analysis, or a combination thereof, as described in claim 1.

4. The aforementioned H ２ - The LIAH composition has at least one of the following properties: The X-ray diffraction pattern has reflectance peaks at 11.5°2θ, 23.1°2θ, 35.0°2θ, 35.7°2θ, or combinations thereof. The aluminum-to-lithium ratio of the H2-LIAH composition is at least about 1.9:1.0, preferably about 2.0:1.0 to about 3.0:1.0 or about 2.4:1.0 to about 2.6:1.

0. The lithium uptake capacity of the H2-LIAH composition is at least about 8.0 mg / mL, preferably at least about 9.0 mg / mL, and more preferably about 9.5 mg / mL to about 12.0 mg / mL. The Mohs hardness of the H2-LIAH composition is at least about 5.0, preferably at least about 6.0, and more preferably at least about 7.

0. The adsorbent according to any one of claims 1 to 3.

5. The aforementioned H ２ - LIAH composition, formula 1: Li ａ X・mAl(OH) ３ •nH ２ O ｃｒ Formula 1 (In the formula, a is approximately 1; X is a monovalent anion; m is approximately 1.9 to approximately 3.0; n is approximately 2.4 to approximately 4.3; H ２ O ｃｒ The adsorbent according to any one of claims 1 to 3, as described in (where crystallized hydrate is specified).

6. The aforementioned H ２ - The adsorbent according to any one of claims 1 to 3, wherein the LIAH composition is a layered double hydroxide composition of lithium-aluminum.

7. The adsorbent according to any one of claims 1 to 3, further comprising a binder, an embedding agent, or a combination thereof.

8. The aforementioned H ２ - The adsorbent according to any one of claims 1 to 3, wherein the LIAH composition can be processed to provide a particle size distribution in which at least about 40%, preferably at least about 50%, and more preferably at least about 55% of the particles have a particle size in the range of about 500 μm to about 1,000 μm.

9. The aforementioned H ２ - The adsorbent according to any one of claims 1 to 3, wherein suspending the LIAH composition in deionized water provides an aqueous suspension having a pH of about 7.0 to about 6.2 and / or a turbidity value of less than 10 NTU, preferably less than 5 NTU, more preferably about 2 NTU to about 5 NTU.

10. The aforementioned H ２ - The LIAH composition is physically durable for at least about 500 cycles, preferably at least about 5000 cycles, and / or under operating conditions. The lithium-containing aluminum hydroxide composition is chemically durable for at least about 500 cycles, preferably at least about 5,000 cycles, under operating conditions, as an adsorbent according to any one of claims 1 to 3.

11. A method for producing a lithium-containing aluminum hydroxide composition: (i) A step of bringing an initial aliquot of the hydroxide solution into contact with an initial aliquot of the solution containing lithium halide and aluminum halide to form a reaction mixture in which an excess of the hydroxide solution is present and the pH of the initial reaction mixture is at least about 9.0; (ii) Adding further aliquots of a solution containing lithium halide and aluminum halide to the reaction mixture to lower the pH of the reaction mixture to less than about 4.0; (iii) The step of forming a gel-like material in the reaction mixture; (iv) A method comprising the step of adding an additional aliquot of the hydroxide solution to the reaction mixture to raise the pH of the reaction mixture to about 6.5 to about 7.

5.

12. The method according to claim 11, wherein the initial aliquot of the solution containing the lithium halide and the aluminum halide and the further aliquot of the solution containing the lithium halide and the aluminum halide are derived from the same stock solution, and / or the initial aliquot of the hydroxide solution and the further aliquot of the hydroxide solution are derived from the same stock solution.

13. The method according to claim 11 or 12, wherein the hydroxide solution has a concentration of about 6.5 M to about 8.0 M.

14. The method according to claim 11 or 12, wherein the lithium halide is lithium chloride and / or the lithium halide is aluminum trichloride and / or the hydroxide solution is a sodium hydroxide solution.

15. The method according to claim 11 or 12, wherein in step (ii), the rate of addition of the hydroxide solution is about 9.8 L / min to about 10.8 L / min.

16. Between step (iii), step (iv), or a combination thereof, the viscosity of the gel-like material changes Stir the reaction mixture. Controlling the temperature of the reaction mixture, Controlling the pressure of the reaction mixture, Controlling reaction time, Controlling the addition rate, The method according to claim 11 or 12, which is adjusted by one or more of the following.

17. (v) The gel-like material is cured and the H ２ - Further comprising the step of making a LIAH composition, step (v) is, Dry at a temperature of approximately 85°C to 105°C. Dry for approximately 24 to 75 hours. Drying at a pressure of approximately 76 mmHg to approximately 760 mmHg. Rinsing, drying, sieving, or a combination thereof, The method according to claim 11 or 12, comprising one or more of the above.

18. A highly hydrated lithium-containing aluminum hydroxide composition produced by the method described in claim 11 or 12.

19. An apparatus for recovering lithium from a lithium-containing solution: A container having an inlet, an outlet, and a flow path between them; and The adsorbent in the container comprises a highly hydrated lithium-containing aluminum hydroxide composition having a molar ratio of crystalline hydrate to lithium of about 2.1:1.0 to about 4.3:1.

0. A device equipped with the following features.

20. A method for recovering lithium from a lithium-containing solution: The steps include: bringing the lithium-containing solution into contact with an adsorbent to extract lithium from the lithium-containing solution; The steps include: eluting lithium from the adsorbent to form a lithium eluate; The method comprises a highly hydrated lithium-containing aluminum hydroxide composition having a molar ratio of crystalline hydrate to lithium of approximately 2.1:1.0 to 4.3:1.0 as the adsorbent.

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