Honeycomb crystallizer, system and method for accelerated evaporation, and method for lithium extraction

Abstract

A method of accelerating water evaporation comprises immersing a portion of a crystallizer into a reservoir of water containing salts to be extracted. The crystallizer comprises a porous body containing, in one embodiment, an array of open channels bounded by porous cell walls. While immersed, the porous body wicks the water via capillary forces. During and / or after the immersion, the water wicked by the porous body evaporates at a rate at least ten times higher than a rate of water evaporation from a surface of the reservoir, and as the water evaporates from the porous body, at least some of the salts from the water accumulate on and / or in the crystallizer.

Description

Attorney Docket No.: SP24-282PCTHONEYCOMB CRYSTALLIZER, SYSTEM AND METHOD FOR ACCELERATED EVAPORATION, AND METHOD FOR LITHIUM EXTRACTIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application No. 63 / 725,123 filed November 26, 2024, the content of which is incorporated herein by reference in its entirety.TECHNICAL FIELD

[0002] The present disclosure relates generally to methods of water evaporation and more particularly to a crystallizer, system and method that can accelerate water evaporation and facilitate salt collection and / or separation.BACKGROUND

[0003] Due to the growth of the electric vehicle industry, the demand for lithium, a critical component of rechargeable (lithium-ion) batteries is on the rise. The gap between lithium supply and lithium demand is expected to increase drastically over the next few years. Currently, lithium is produced mainly by extraction from brine using a large multistage pond evaporation process. The evaporation typically takes about 15-18 months to remove -60% of the water. During the evaporation, a portion of the dissolved salts (e.g., NaCl and KC1) are crystallized. The obtained liquor undergoes further Mg, Ca, SO2', etc. removal, and is ultimately used for precipitation of Li2COs, the final Li product. In Chile, for example, there are about 32.3 square kilometers of such evaporation ponds. It would be advantageous to be able to accelerate the lengthy evaporation process.SUMMARY

[0004] A crystallizer, system and method for accelerating evaporation are described in thisAttorney Docket No.: SP24-282PCT disclosure, along with a method of lithium extraction.

[0005] The crystallizer comprises a porous body comprising, in one embodiment, an array of open channels bounded by porous cell walls, where the porous cell walls have a porosity in a range from 40% to 95%. In another embodiment, the porous body of the crystallizer comprises an array of porous rods extending from a porous support, where the porous rods and the porous support have the porosity in the range from 40% to 95%.

[0006] The system for accelerating evaporation includes: a crystallizer comprising a porous body having a porosity in a range from 40% to 95%; and a source of water containing salts to be extracted. A portion of the crystallizer is immersed in the water.

[0007] The method of accelerating water evaporation comprises immersing a portion of a crystallizer into a reservoir of water containing salts to be extracted. The crystallizer comprises a porous body having a porosity in a range from 40% to 95%. While the portion of the extruded body remains immersed in the reservoir of water, the porous body wicks the water via capillary forces. During and / or after the immersion, the water wicked by the porous body evaporates at a rate at least ten times higher than a rate of water evaporation from a surface of the reservoir. As the water evaporates from the porous body, at least some of the salts from the water accumulate on and / or in the crystallizer.

[0008] The method of lithium extraction comprises immersing a portion of a crystallizer into a reservoir of water containing salts to be extracted. The crystallizer comprises a porous body having a porosity in a range from 40% to 95%. While the portion of the porous body remains immersed in the reservoir of water, the porous body wicks the water via capillary forces. During and / or after the immersion, the water wicked by the porous body evaporates and at least some of the salts from the water accumulate on and / or in the crystallizer. Accumulated salts from the crystallizer are redissolved into the reservoir of water. After achieving a desired concentration of the lithium salt in the water, the water from the reservoir is transported to one or more additional locations for further processing. After transporting the water to a final location, a precipitation agent is added to the water to precipitate a lithium compound, thereby achieving lithium extraction.Attorney Docket No.: SP24-282PCTBRIEF DESCRIPTION OF THE DRAWINGS

[0009] The embodiments may be better understood with reference to the following drawing(s) and description. The components in the figures are not necessarily to scale. Moreover, in the figures, like-referenced numerals designate corresponding parts throughout the different views.

[0010] FIG. 1A is a schematic of an exemplary crystallizer comprising an array of open channels bounded by porous cell walls.

[0011] FIG. IB is a schematic of the exemplary crystallizer of FIG. 1 A positioned in a reservoir of water such that the open channels are oriented along a vertical direction (normal to the surface of the water).

[0012] FIG. 1C is a schematic of the exemplary crystallizer of FIG. 1A positioned in the water such that the open channels are oriented along a horizontal direction (parallel to the surface of the water).

[0013] FIG. 2 is a schematic of four exemplary crystallizers, each having a multi-level structure, positioned in a reservoir of water.

[0014] FIG. 3 is a flow chart of the evaporation process.

[0015] FIG. 4 is a schematic of use of the crystallizer for evaporation in brine obtained from hydraulic fracturing.

[0016] FIG. 5A is a flow chart showing possible steps during a lithium extraction process, where the crystallizer is used only in the first evaporation stage.

[0017] FIG. 5B is a flow chart showing possible steps during a lithium extraction process, where the crystallizer is used in both the first evaporation stage and a second dissolution stage.

[0018] FIG. 6 shows the salt distribution along the height of the 1 in x 1 in bar (crystallizer “HC1”) used in brine water for 2 days and 4 days.

[0019] FIG. 7 shows the Li / Na selectivity at different heights of HC1 used in brine water for 2 days and 4 days.

[0020] FIG. 8 A shows the salt distribution along the height of HC1, inside and outside, after use in brine water for 2 days and 4 days, and in diluted brine water for 10 days.

[0021] FIG. 8B shows Li / Na selectivity vs height of HC1 after use in brine water for 2 days and 4 days, and in diluted brine water for 10 days.Attorney Docket No.: SP24-282PCT

[0022] FIG. 9 is a photograph of HC1, showing that salt is precipitated on the external surface; however, no salt crystals can be observed inside the honeycomb channels.

[0023] FIG. 10 shows Li / Na selectivity for salt collected at different heights inside the honeycombs, where each point is an average of 13-16 cm length of the bars. The three curves are from HC2 used in briny water (brine for 6 days (6D)); HC1 used in briny water for 4 days (4D); and HC1 used in diluted briny water for 10 days (10D).

[0024] FIG. 11 shows calculated water wicking heights versus honeycomb porosity for a D50 pore size of 11 pm and 13 pm to mimic HC1 and HC2 (1 in x 1 in bars, 300 cpsi / 8 mil).

[0025] FIG. 12A-12C shows calculated water wicking heights vs. the channel or cell density (cpsi, cell number per square inch), channel wall thickness and material water contact angle of the honeycomb crystallizers, which take the form of 1 in x 1 in bars.

[0026] FIG. 13 shows Li / Na selectivity difference by different salt dissolving methods, including rinsing a small amount of water through the channels by pouring the same water through the channels three times (open circles), and soaking (solid circles) the honeycombs with the rest of salt in water to dissolve out the remaining salt; the curve (triangles) shows calculated total selectivity from the orange and blue data.

[0027] FIG. 14 shows area specific evaporation rates from five different honeycomb crystallizers that were inserted into a bath of water and compared to evaporation of deionized (DI) water without a crystallizer. The five different honeycombs are (from left to right): (1) Honeycomb 1 (HC1) 1 in x 1 in bar with vertical channels; (2) HC1, 1 in x 1 in bar with horizontal channels; (3) HC1, 4.5 in diameter column with vertical channels; (4) HC2, 2 in diameter bar with vertical channels; (5) HC2, 1 in x 1 in bar with vertical channels.

[0028] FIG. 15 shows crystallizer temperature (measured by IR thermometer) at different heights during water wicking and at different humidities.

[0029] FIG. 16 shows that water evaporation rate (ER) increases by using a crystallizer and / or with wind, where the surface velocity of the wind in the experiment is 200 ft / min, the crystallizers are 18 in x 1 in x 1 in, and the four crystallizers are placed about 1 in apart from each other.

[0030] FIG. 17 shows a crystallizer having a “brush-like” or inverse structure to the honeycomb crystallizer that includes extruded protrusions instead of channels.Attorney Docket No.: SP24-282PCT

[0031] FIG. 18 shows a schematic of a honeycomb crystallizer and geometric design parameters considered in a water wi eking model.

[0032] FIGS. 19A-19D show the impact of crystallizer width, cellular geometry, crystallizer pore size, and crystallizer porosity, respectively, on wi eking height and evaporation rate as determined by computer modeling.

[0033] FIG. 20 shows the impact of contact angle on wicking height and evaporation rate as determined by computer modeling.

[0034] FIG. 21 A-21C show the impact of temperature, relative humidity and mass transfer coefficient on the wicking height and evaporation rate, respectively, as determined by computer modeling.DETAILED DESCRIPTION

[0035] Described in this disclosure is a honeycomb crystallizer that can be used to accelerate water evaporation during the treatment process for lithium extraction from saline waters, as well as during wastewater treatment, salt manufacturing, and other processes. The water evaporation rate can be over ten times higher than that obtained without using a crystallizer. The honeycomb crystallizer can also provide a lithium separation effect, which allows lithium salts to be concentrated inside and especially at an upper portion of the crystallizer. The crystallizers and a system and method for accelerating water evaporation are described in this disclosure.

[0036] The crystallizer 102 comprises a porous body 104 containing, in one embodiment, an array of open channels 106 bounded by porous cell walls 108, as shown for example in FIG. 1 A. The cell walls 108, which may alternatively be referred to as channel walls, have a porosity in a range from 40% to 95%. In some examples, the porosity may be at least 50%, at least 60%, or at least 70%, and / or the porosity may be as high as 85%, or as high as 95%. Pores in the cell walls 108 may have a linear size (e.g., a width or diameter, in a range from 1 micron to 20 microns. The cell walls 108 may have a thickness in a range from 0.05 mm to 1 mm. When a portion of the crystallizer 102 is immersed in a reservoir 114 of water 112, the porosity inherent to the cell walls 108 provides the capillary forces necessary to absorb or wick the water 112, leading to a significant increase in water surface area (compared to, for example, the flat surfaceAttorney Docket No.: SP24-282PCT of the reservoir 114 of water 112) which promotes fast evaporation. Notably, the crystallizer 102 may be positioned in the water 112 such that the open channels 106 of the porous body 104 are oriented along the vertical direction with respect to gravity (normal to the surface 114a of the water 112, as shown in FIG. IB), along the horizontal direction with respect to gravity (parallel to the surface 114a of the water 112, as shown in FIG. 1C), or along a direction in between. The open channels 106 are typically positioned parallel to each other. As long as (only) a portion (e.g., an end or a side) of the crystallizer 102 is positioned in the reservoir 114 of water 112, the desired wicking of water 112 can occur. Accordingly, a system 100 for accelerating evaporation includes the crystallizer 102 described in this disclosure positioned such that a portion of the crystallizer 102 is immersed in a reservoir 114 of water 112 containing salts to be extracted, which may alternatively be referred to as briny water or brine.

[0037] Exposure to solar energy and / or air flow (e.g., ambient air, wind, and / or forced air) through the open channels 106 may promote evaporation. The driving force for air flow may be, for example, a temperature difference between the top and bottom of the crystallizer 102, an air density difference between ambient dry air (molecular weight = ~29 g / mole) to moist channel air (molecular weight=29 g / mole) - vapor (molecular weight 18 g / mol) mixture, or a pressure gradient due to wind or forced air flow through the channels. For example, the crystallizer 102 may have, at one or both ends of the porous body 104, a gas inlet or outlet in fluid communication with the open channels 106. The gas inlet or outlet may be configured for connection to a pump or blower to force air or another gas through the open channels 106.

[0038] In some examples, the crystallizer 102 may have a multi-level structure 110 including two or more of the porous bodies 104 in a vertical stack, as illustrated in FIG. 2. As discussed below, the multi-level structure 110 may facilitate selective harvesting of particular salts after evaporation has occurred. The two or more porous bodies 104 may be aligned such that the open channels 106 are in fluid communication along a length of the crystallizer 102. In such an example, the open channels 106 of each porous body 104 may be aligned along the vertical direction. Alternatively, if the open channels 106 of the porous bodies 104 in the vertical stack are aligned along the horizontal direction or another non-vertical direction, then the open channels 106 may not be in fluid communication with each other over the length of the crystallizer 102, but they may provide some other advantage. For example, the openAttorney Docket No.: SP24-282PCT channels 106 may be beter positioned for air flow therethrough.

[0039] The open channels 106 may extend in parallel along an extrusion or axial direction of the porous body 104. Typically, the open channels 106 have a cell or channel density, which is defined over a transverse cross-section of the porous body 104, in a range from 50 cells per square inch to 1600 cells per square inch. A perimeter of the transverse cross-section of the porous body 104 may define a polygon, such as a rectangle or square, as shown in FIG. 1 A, or a closed curve, such as a circle or an oval. Each of the open channels 106 may have a rectangular, square, triangular, pentagonal, hexagonal, polygonal, circular, oval, elliptical, and / or irregular shape when viewed along the transverse cross-section. Typically, the open channels 106 are arranged in a regular array. Advantageously, a length or height of the porous body 104 (in a direction normal to the reservoir 114 of water 112) may be longer than a wicking height of the porous cell walls 108.

[0040] The porous body 104 and its cell walls 108 may comprise a ceramic, a polymer, or a ceramic-polymer composite. Thus, the extruded body 104 may be referred to as an a porous ceramic body, a porous polymer body, or a porous composite body. The ceramic may comprise cordierite, alumina, mullite, zirconia, silica, glass, silicon carbide, silicon nitrite, and / or aluminum titanate. The polymer may be a thermoplastic polymer comprising polyester, cellulose, and / or polyvinyl alcohol. The ceramic-polymer composite may comprise ceramic particles embedded in a polymer matrix, and may utilize any of the ceramics or polymers referred to above, or others. The crystallizer 102 may be produced by extrusion or another method, such as casting, molding, or 3D printing, In the example of extrusion, the porous body 104 may alternatively be referred to as an extruded body. Fabrication of the crystallizer 102 by extrusion may entail preparation of a precursor paste (e.g., in the case of a ceramic or ceramic composite) or molten polymer mixture (e.g., in the case of thermoplastic polymer). The paste or mixture may include pore forming agents that are removed following extrusion to ensure a desired porosity in the extruded body. During extrusion, the precursor paste or molten polymer mixture may be forced through a die having a geometry determined by the intended extruded product. To produce an extruded body 104 containing the array of channels 106 as described above, the die may include inlets (for the precursor paste / molten mixture) on an inlet side of the die in fluid communication with outlets (for the green extrudate) on an outlet side of theAttorney Docket No.: SP24-282PCT die, where the outlets are shaped to extrude honeycomb cell walls 108. To produce extruded bodies having other desired shapes, e.g., pellets, rods, etc., the outlets of the die may have another suitable geometry. A hydraulic or screw-driven ram may be employed for extrusion. Extrusion may be followed by cooling, drying and / or firing to produce the ceramic, polymer or composite extruded body.

[0041] Referring to the flow chart of FIG. 3, a method of evaporating water includes inserting a portion of the crystallizer 102, which may have any or all of the features described in this disclosure, into a reservoir 114 of water 112 containing salts to be extracted, whereby the porous body 104 absorbs or wicks the water 112 via capillary forces. More specifically, while the portion of the crystallizer 102 remains immersed in the reservoir 114, the water 112 travels through and over the porous cell walls 108 in a direction away from the reservoir 114 to a maximum height on the crystallizer 102, which is referred to the wi eking height. While the crystallizer 102 is exposed to ambient air or optionally to a controlled environment during or after the immersion, the water 112 wicked by the porous body 104 evaporates. Advantageously, evaporation of the water 112 from the crystallizer 102 occurs at a rate at least ten times higher than the rate of evaporation from the surface 114a of the reservoir 114. As the water 112 evaporates, at least some of the salts from the water 112 accumulate on and / or in the porous cells walls 108 of the porous body 104. That is, the salts dissolved in the water 112 precipitate or crystallize during the evaporation process, such that they accumulate or deposit on the porous cell walls 108 as the crystallizer 102 dries.

[0042] The salts that accumulate on and / or in the porous body 104 may have different salt compositions, where each salt has a different solubility in the water 112. For example, the salts may include a first salt, such as NaCl, and a second salt, such as LiCl, where the second salt has a higher solubility in the water than the first salt. The wicking direction is from the bottom to the top of the crystallizer 102, and the evaporation or drying front generally moves from the outside to the inside of the crystallizer 102. Accordingly, the first salt may preferentially accumulate at lower portions of the crystallizer 102 and / or on an external surface of the crystallizer 102, while the second salt may preferentially accumulate at an upper portion of the crystallizer 102 and / or inside the crystallizer 102 (that is, inside the porous cell walls 108). In other words, the first salt may make up a significantly larger fraction of the salts accumulatedAttorney Docket No.: SP24-282PCT on the lower portion and / or the external surface of the crystallizer 102 than in the original briny water 112, and, similarly, the second salt may make up a significantly larger fraction of the salts accumulated on the upper portion and / or the interior of (inside) the crystallizer 102 than in the original briny water 112. When the second salt is a lithium salt such as LiCl and the first salt is NaCl, use of the crystallizer for evaporation and the above-described preferential accumulation of allows for a first separation of lithium from sodium. This process may take about 1 week or less. As discussed below in the examples, after evaporation of the absorbed water 112 and concomitant drying of the crystallizer 102, the open channels 106 may be substantially free of crystallized salts. In contrast, the external surface of the crystallizer 102 may contain a deposit of crystallized salts.

[0043] The method may further include removing the salts from the inside and / or the external surface of the crystallizer 102 after reaching a desired amount of salt accumulation. For example, the crystallizer 102 may be withdrawn from the reservoir 114 of water 112, and some or all of the salts accumulated on the external surface may be removed, e.g., by scraping or brushing. Accordingly, the first salt (e.g., NaCl) may be preferentially removed and / or collected.

[0044] After removing the salts from the external surface, some or all of the salts accumulated inside the porous cell walls 108 may be removed and optionally collected by dissolution in water. For example, a controlled amount of water may be flowed through the open channels 106 to dissolve and remove at least a portion of the salts accumulated inside the porous body 104. The water flowed through the open channels 106 for dissolution may comprise fresh water or briny water (e.g., water from the original reservoir of water or NaCl- saturated wastewater obtained following lithium extraction). This may be described as a rinsing step. Because of the relatively short time duration of the rinse, the more soluble salt(s) may be selectively removed and collected during this process.

[0045] In addition, the rinsing may be selectively applied to particular height sections of the crystallizer 102, such as the upper portion of the crystallizer 102 which preferentially accumulates the second salt (e.g., a lithium salt). When the crystallizer 102 has a multi-level structure including a stack of porous bodies 104, as illustrated in FIG. 2, the rinsing may be applied selectively to one or more of the porous bodies 104 in the stack, such as the upper-mostAttorney Docket No.: SP24-282PCT porous body.

[0046] When the first salt is NaCl and the second salt is a lithium salt such as LiCl, this dissolution rinsing may allow for a second separation of lithium from sodium. The water used for the rinsing may then, if desired, undergo further conventional steps in a lithium extraction process, such as removal of selected cations and anions (e.g., Mg, Ca and / or SO42), and ultimately, addition of sodium carbonate (ISfeCCh) to precipitate out Li2COs. Meanwhile, the crystallizer 102 may optionally be soaked in a bath of water to dissolve out any remaining salts. Accordingly, the crystallizer 102 may be returned to its initial salt-free state and reused. Alternatively, regeneration of the crystallizer 102 may not be needed, and the crystallizer 102 may be reused directly without removal of all accumulated salts.

[0047] When the evaporation is employed as part of a lithium extraction process, the water evaporation from the crystallizer 102 is accompanied by precipitation of the salts from the brine on and / or in the crystallizer 102. Salts accumulated in and / or on the crystallizer 102 may be redissolved into the water from time to time during evaporation. Typically, the goal of evaporation is to increase the lithium salt concentration in the water from <1 wt.% to at least about 6 wt.%. Accordingly, different brines with different initial salt concentrations may require evaporation of different amounts of water. Evaporation may be aided by solar energy and / or wind energy, or another source of air flow, as discussed above. After achieving enough evaporation and reaching the desired lithium salt concentration, the water may be transported (e.g., pumped) to one or more additional locations for further processing, such as further evaporation, precipitation of additional salts (e.g., NaCl, KC1), and / or removal of selected cations and anions (e.g., Mg, Ca and / or SO42) from the water. After transporting the water to a final location, a precipitation agent such as sodium carbonate (Na2COs) may be added to the water to precipitate a lithium compound (e.g., Li2CC>3), thereby achieving lithium extraction.

[0048] It is noted that the briny water 112 in the reservoir 114 may be obtained from any of a number of sources, such as brine deposits beneath salt flats, recycled brine from geothermal power plants, or wastewater from oil / gas drilling (e.g., hydraulic fracturing or “fracking”). The schematic of FIG. 4 illustrates use of the crystallizer(s) 102 in part of an exemplary lithium extraction process where the briny water 112 is obtained from fracking. The schematic shows a drill rig 440 and a borehole 442 to a fracture location 444, where a water mixture is pumpedAttorney Docket No.: SP24-282PCT at high pressure to produce fractures in rock containing oil and / or gas deposits. Wastewater 112 from the process, which may be referred to as “produced water,” returns to the surface through the borehole 442 and can be collected in a reservoir 114 containing the crystallizer(s) 102, as illustrated. There, the evaporation process described above may be carried out. In some examples, after the evaporation step, the crystallizer(s) 102 may be moved from the reservoir 114 to a separation location 446 for salt removal / dissolution as described above to selectively remove sodium and lithium salts from the crystallizer. The accumulated salts, in particular the lithium salt, may be redissolved into the produced water for further processing.

[0049] To summarize, the process of utilizing the honeycomb crystallizer 102 for accelerated evaporation during a lithium extraction may follow process 1 or process 2, as illustrated in FIGS. 5A and 5B, respectively. For process 1, crystallizers may be used in the first evaporation stage, and only for accelerating the water evaporation. With the water evaporation, the accumulated salts on the crystallizer may be dissolved into the water from time to time. When enough water is evaporated, the process may be moved to the next stage, as discussed above.

[0050] For crystallizer modified process 2, the crystallizers are used in the first stage for accelerating water evaporation. After loading or accumulating enough salt and achieving the desired Li / Na separation ratio, which may take two to seven days, the crystallizers may be moved to the second stage for separation. In this stage, the salt collected on the outside of the crystallizers is first removed. Then a controlled amount of water may be flowed through the open channels to dissolve out the salt accumulated inside the porous cell walls over all or part of the crystallizer. For example, a controlled amount of water may be flowed through the open channels of each porous body in the stack separately in the case of a multi-level crystallizer. If the dissolving time is short, Li+and other high water-soluble ions, such as Mg, Ca, SO2', may be preferentially dissolved out over Na and K. This dissolving process can realize the second Li selection. The remaining stages may be the same as the conventional processes, e.g., Mg, Ca, SO2' removal, and Li extraction. The water used for redissolving here can be fresh water, the original briny water or the NaCl saturated wastewater that was generated after Li extraction.

[0051] EXAMPLES

[0052] Example 1. Honeycomb crystallizersAttorney Docket No.: SP24-282PCT

[0053] Two honeycomb crystallizers were used in the experiments. They are 1 in x 1 in square bars, with 300 / 8 cpsi cell geometry. Table 1 lists their pore structures measured by mercury (Hg) porosimetry.Table 1. Honeycomb crystallizer pore and wall structures

[0054] Example 2. Salt crystallization by honeycomb crystallizer and Li / Na separation

[0055] Synthetic saline water 1 (brine) having the concentration shown in Table 2 was used in this experiment. The saline water is held in a container with 266 cm2of open surface area. In an experiment, one honeycomb bar is inserted into the water. Water wicking immediately starts. For brine water, the water wicking height on Honeycomb 1 is 69 cm and on Honeycomb 2 is 85 cm.Table 2. Saline waters employed in experiments

[0056] 2-day and 4-day crystallization experiments with brine water 1 were carried out on Honeycomb 1 (“HC1”). The water wicking height for brine water 1 is 52.6 and 54.3 cm for the 2 and 4 days of experiments, respectively. A total of 42 g and 112 g of salt were collected by the honeycomb (HC1) for the 2-day and 4-day experiments, respectively, including salts accumulated both outside and inside the HC1 structure.

[0057] The salt precipitated at the outside of the honeycomb can be easily scraped off. The salt at different heights of the honeycomb was collected and was further dried and thenAttorney Docket No.: SP24-282PCT weighed. The salts inside the honeycomb at different heights were dissolved in DI water separately and then dried and weighed. FIG. 6 shows the collected salt weight at different locations of HC1. Each data was an average of an approximately 14 cm-long section of the honeycomb.

[0058] The experiments reveal that with the increase of the experiment duration, the amount of salt precipitated on the outside of the honeycombs increased significantly, and the amount of salt precipitated on the inside the honeycomb also increased but not as significantly.

[0059] The collected salts were analyzed by ion chromatography (IC) for Li+and Na+concentrations, as shown in Table 3. The Li and Na concentrations of the brine water used in the experiments were also measured. The Li / Na selectivity can be calculated by

[0060] Li / Na selectivity

[10061] Jwhere the CTLi .,TI and C N.a,i . are from the brine water, ’ and the CTLi .,f „ and C N.a,f „ are from each part of the collected salts.Table 3. Salt analysis by ion chromatographyAttorney Docket No.: SP24-282PCT* Collected salts were in solid form. They were re-dissolved in a certain amount of water for IC measurement to obtain the Li / Na concentration ratios.

[0062] FIG. 7 shows the Li / Na selectivity at different parts of the honeycomb for the collected salts. Salts precipitated on the outside of the honeycombs have lower Li / Na ratios than the brine water (Li / Na selectivity < 1). Salts accumulated inside the honeycombs have higher Li / Na ratios than the brine water (Li / Na selectivity > 1). In addition, the Li / Na selectivity increases with height. After 4 days of crystallization, the highest selectivity reaches 2.7.

[0063] A similar experiment was conducted with diluted brine water 2 (11% salt, Table 2) for 10 days. FIGS. 8 A and 8B show the comparison of salt collection and selectivity with the above experiment. Again, more salts were collected from outside of the honeycombs, but the inside salts seem to have reached a saturation level. FIG. 9 shows that while salts (in particular NaCl) precipitated on the exterior wall of the honeycomb, no salt precipitation on the channel / cell walls is observed. All these phenomena suggest that salts inside the honeycombs are accumulated within the porous structure. FIG. 8B shows the Li / Na selectivity comparison. When the honeycomb HC1 is used in diluted brine (11% salt), the water wicking height is higher (69 cm) compared to use in the more concentrated brine (20% salt, 54 cm). This difference leads to a Li / Na selectivity of 7.2 for the diluted brine.

[0064] A similar experiment was conducted using honeycomb 2 (HC2; Table 1) that has higher porosity (81%). FIG. 10 shows the Li / Na selectivity of the salts collected from inside HC2 in comparison with data from HC1. HC2 water wicking height reached 85 cm, which is higher than that obtained in the experiments with HC1. The highest Li / Na selectivity reached 34. The experiments shown in FIGS. 8B and 10 indicate that high water wicking height can lead to higher Li / Na selectivity. In addition, higher porosity samples have a higher wicking height.

[0065] Peclet number is assumed to reflect the crystallizer’s Li / Na selectivity. It is found that crystallizers having a higher Peclet number also have a higher Li / Na selectivity. PecletAttorney Docket No.: SP24-282PCT number is calculated by the following equation:

[0066] Pe =jH2 / (pRD)

[0067] Where, j is the evaporation rate (ER), p is the solution density, R is the radius of the crystallizer, D is the effective diffusion coefficient of the salt in the porous material, H is wicking height. Since j is also proportional to H, Pe is determined by the cube of H. Therefore, wicking height plays an important role in Li / Na selectivity. The above experiment result is consistent with this Pe number analysis, which shows that a higher porosity honeycomb has a higher wicking height and a higher Li / Na selectivity.

[0068] Modeling results on water wicking height also provide a consistent result. FIGS. 12A-12C show calculated results for honeycombs having a D50 pore size of 13 pm and 11 pm D50. Notably, the wicking heights change with porosity. The modeled HC1 and HC2 are labeled. This result also indicates that higher porosity honeycombs may have a higher wicking height. These calculations are based on a ID model (see Example 4). In the calculation, the honeycomb wall structure is 300 cpsi / 8 mil, and the honeycomb cross-section is 1 in x 1 in. Based on this model, an increase of cell density (cpsi) and / or wall thickness of the honeycomb may also increase the water wicking height (FIG. 12).

[0069] Example 3. Method to dissolve out salt accumulated inside the honeycomb to achieve higher Li / Na selectivity

[0070] In a separate experiment, a cover was put on the brine container to prevent precipitated NaCl from falling into the container. With this cover, the first ~10 cm of the honeycomb did not contribute to the water evaporation and salt precipitation. After 7 days of crystallization, the salt accumulated on the inside of the honeycomb was collected in two steps after drying. (1) Water was streamed through different sections of the honeycombs at different heights to rinse out the salt. (2) The honeycombs (outside salt was removed) were then soaked in DI water to dissolve out the remaining salt in the honeycomb. FIG. 13 shows the Li / Na selectivity at different heights of the honeycomb. The first rinse dissolved more Li vs. Na than that contained inside the honeycomb, with which the selectivity was further improved. This example proves that by dissolving the salt collected in the honeycomb, a second Li / Na separation can be realized.

[0071] Example 4. Water evaporation from different honeycombsAttorney Docket No.: SP24-282PCT

[0072] DI water was used in this experiment. A container with 266 cm2open surface area was used to hold the water. The water evaporation rate was measured by recording the weight loss with the water evaporation. The slope of the weight change is the evaporation rate (ER). The area specific evaporation rate (ASER) is obtained by ER / surface area (SA). The SA for flat water is 266 cm2. The ASER of a honeycomb (ASERh) is obtained by the relation:

[0073] ASERh=(ERh-ASERw*(266-CSAh)) / CSAh

[0074] where ERh is the measured total evaporation rate of one honeycomb in the water bath. It includes both evaporation from the flat water and from the honeycomb. ASERWis the area specific evaporation rate of flat water. It is measured without the honeycomb in the water. CSAh is the cross-sectional area of the honeycomb. Different area specific evaporation rates can be compared directly. FIG. 14 shows the ASER of five different honeycombs compared with that of flat water (or a reservoir of water). The times numbers are the magnitudes that the honeycombs improved the water evaporation rate compared to flat water. The experiment indicates that (1) honeycombs with horizontal channels have higher water evaporation rate; (2) smaller cross-sectional area honeycombs have higher water evaporation rate; and (3) higher porosity honeycombs have higher evaporation rate. The result (3) is consistent with modeling results (FIG. 11).

[0075] Example 5. Honeycomb temperature during water wi eking and evaporation

[0076] FIG. 15 shows honeycomb temperatures at different heights during water wi eking and evaporation at different humidity conditions. The ambient temperature is 21.2 °C (70.2 °F). The results indicate that:

[0077] (1) The evaporation leads to a temperature decrease on the honeycomb. Since the ambient temperature is higher than the temperature of the honeycomb, it is apparent that ambient heat was used to promote evaporation. This makes the process more energy efficient.

[0078] (2) The lower the humidity, the lower the honeycomb temperature, indicating faster evaporation. When the humidity increases to 40%, the honeycomb temperature is close to room temperature, indicating much slower evaporation. The evaporation and salt separation experiment above were done at humidity values in a range of 15%-35%.

[0079] Example 6. Wind impact on water evaporation

[0080] FIG. 16 shows a water evaporation experiment with and without four 18-in long 1Attorney Docket No.: SP24-282PCT in x 1 in honeycomb bars (crystallizers) inserted in a bath of DI water, and with and without wind blowing. The wind generated air surface velocity is 200 ft / min, measured with a Shortridge air velocity meter. The obtained evaporation rates indicate:

[0081] (1) Although water wicking height on the honeycombs is higher than 18 inches, with four such bars in the water bath, the water evaporation rate can be increased by a factor of 15.2.

[0082] (2) Wind can increase the evaporation rate both with and without the crystallizers.

[0083] (3) With wind blowing, the water evaporation rate can further increase by a factor of 2.8.

[0084] Example 7. Brush-like monolith for fast evaporation

[0085] The experiments showed the large impact of convection to evaporation rate. With that in mind, different configurations are proposed that are expected to improve evaporation rate. One of the configurations is illustrated in FIG. 17. This embodiment of the crystallizer 102 includes a monolithic porous body 104 comprising an array of porous rods 118 extending from a porous support 120, where the porous rods 118 and support 120 have a porosity in a range from 40% to 95%. Pores in the rods 118 and support 120 may have a linear size (e.g., a width or diameter), in a range from 1 micron to 20 microns. The porous rods 118 may have a width or diameter in a range from 0.05 mm to 10 mm. The porous rods 118 and the porous support 120 may comprise a ceramic, a polymer, or a ceramic-polymer composite, as discussed above. When a portion of the crystallizer is immersed in a reservoir of water, the porosity inherent to the porous rods provides the capillary forces necessary to absorb or wick the water, leading to a significant increase in water surface area (compared to, for example, the flat surface of the reservoir of water) which promotes fast evaporation. The crystallizer 102 may be positioned in the water such that the porous rods 118 of the porous body 104 are oriented along a vertical direction. Alternatively, the crystallizer 102 may be positioned in the water such that the porous rods 118 are oriented along a non-vertical direction; for example, the porous rods 118 may be oriented along a horizontal direction.

[0086] Example 8. Water wicking ID model for liquid wicking height and evaporation rate

[0087] A one-dimensional physics-based model was developed to investigate the impact of crystallizer macro- and micro- design features on final wicking height and evaporation rate.Attorney Docket No.: SP24-282PCTFor example, the crystallizer can incorporate various macro specifications such as width and cell geometry. More specifically, cell geometry may encompass the number of cells-per-square inch and wall thickness. Within the porous walls, the microstructure can be characterized by its porosity and a representative pore size, which are used to determine capillary pressure and permeability. Leveraging simple mass conservation laws, the final wicking height of the water and evaporation rate may be determined. This may be accomplished by balancing wicking flow through capillary action, an evaporative drying mechanism and gravity body forces. This model adheres to the following assumptions: (1) square cross section crystallizer; (2) uniform temperature with constant properties; (3) vertically oriented channels (4); uniform drying rate on four sides; and (5) combined vapor diffusive transport and evaporative drying on top.

[0088] Referring to FIG. 18: Once the dry crystallizer is in contact with the liquid reservoir, water instantly rises in the channels to height y. This can be determined by balancing surface tension forces with the body force acting upon the fluid column,

[0089] where a is the surface tension, 6 the contact angle, / ? the cellular channel width, pwthe water density and g gravity. Beyond height y, the fluid continues to rise due to capillary action. As it rises, evaporative drying occurs at a wi eking height h where the two are in balance. A form of Darcy’s law, Equation (2) describes the flow rate near the bottom of the crystallizer at the reservoir end beyond y which can be attributed to wi eking action,

[0090] Where k is the flow conductivity or permeability, p the fluid viscosity, A the crystallizer planform wetted cross section, Patmatmospheric pressure and Pcapthe capillary pressure. Since capillary pressure is negative and atmospheric pressure is taken as 0, the pressure differential is positive, driving flow up into the crystallizer. Again, pw■ g ■ h accounts for a gravity body term counteracting wicking flow. Since the crystallizer is exposed to ambient conditions, an evaporative drying mechanism accounts for liquid to vapor phase change at exposed wetted surfaces (3).Attorney Docket No.: SP24-282PCT

[0091] Equation (3) describes the drying rate at the exposed side wetted surfaces, where keis a mass transfer coefficient, w the side width of the crystallizer, psatis the saturation vapor density and RH the ambient relative humidity. At the top surface, a circuit analog is used to calculate the drying rate which accounts for diffusion of vapor through the dry section with length hdryand surface evaporation.

[0092] where Daxiaiis the effective axial diffusion coefficient. Effective diffusivity is dependent on temperature, open-frontal-area of the cellular geometry and porosity of the pore structure. To derive the final form of the equation to determine wicking height h, the rates of wi eking and drying are balanced, equation (5):Qwick Qdry,side T Qdry,top

[0093] After substituting (2), (3), and (4) into (5),

[0094] Multiply each term by h,

[0095] Collect terms to yield resultant quadratic equation to directly solve for the wicking height h and total height ht= h + y

[0096] Table 4 below provides a summary of the model inputs, model results and material properties, which are dependent on temperature. Permeability is dependent on porosity and representative pore size.Attorney Docket No.: SP24-282PCTTable 4. Model inputs, results* and material properties**

[0097] Application, Examples of Macro Design Features

[0098] Base model input values were chosen and are provided in Table 4. Each parameter was explored one at a time to investigate its impact on final wicking height and evaporation rate. This was accomplished by sweeping over a range of parameter values while keeping all other values constant. Final wicking height is plotted in inches and evaporation rate normalized to the crystallizer planform area in units of grams-per-hour-per-square-centimeter.

[0099] Consider macro-scale geometric design parameters width and open-frontal area and their impact, FIGS. 19A and 19B, respectively. As width increases, exposed evaporative drying surface area to wicking volume ratio decreases. This reduces the impact of drying while enhancing the wicking impact, resulting in higher wicking heights and lower drying rates with increasing crystallizer width. Cellular geometry is characterized by the number of cells-per- square-inch (CPSI) and the thickness of walls (c), both of which define the fraction of open frontal area or OF A. OFA increases with decreasing CPSI and / or web thickness c, and vice versa. As OFA is decreased, the final wicking height and drying rates increase. This suggests that with increasing CPSI or c, again the final wicking height and drying rates will trend higher.Attorney Docket No.: SP24-282PCT

[0100] Application, Examples of Micro Design Features

[0101] Additional design features relating to microstructure within the porous walls can be considered, namely porosity and representative pore size. Representative pore size impacts both the capillary pressure driving wicking flow and permeability or flow conductance. Capillary pressure in the pore structure at the liquid-vapor front is assumed to be determined by the Washburn equation (9).

[0103] Where a is the fluid surface tension, 6 is the contact angle and dpa representative pore size of the wall microstructure. For this model, it is assumed the permeability k is proportional to the product of porosity E and square of pore size and dp, where C is a coefficient.

[0104] k = C ■ E ■ dp2(10)

[0105] As pore size increase, both wicking height and evaporation rate are reduced, as shown in FIG. 19C. An increasing flow conductance is offset by a more dramatic decreasing of capillary pressure with increasing pore size.

[0106] Not surprisingly, the wicking height increases with increasing porosity, as shown in FIG. 19D. Permeability is linearly increasing with porosity and therefore a fixed capillary pressure has the ability to pull the liquid front higher up into the crystallizer. Correspondingly, the evaporation rate increases with porosity due to the increase in wicking height and exposed wetted surface area. FIG. 20 depicts the impact of contact angle. This is not necessarily a micro design parameter but is materials-fluid specific, dictated by adhesive-cohesive interacting forces at fluid-solid interfaces. It is included here for completeness. Capillary pressure is directly proportional to the cosine of the contact angle, thus wicking pressures are highest at low contact angles while achieving both higher wicking heights and evaporation rates.

[0107] Application, Examples of External Environment

[0108] Beyond crystallizer macro- and micro design considerations, the external environment plays a role in determining the achievable wicking height and evaporation rate. The impact of environment is captured through temperature T, relative humidity RH and massAttorney Docket No.: SP24-282PCT transfer coefficient ke. Temperature impacts the effective diffusivity thought the dry portion of the crystallizer and the saturation vapor pressure of the surrounding ambient air. Teten’s equation can be used to determine saturation vapor pressure as a function of Celsius temperature T.17.27 TP(kPa) = 0.61078e r+237.3 (11)

[0109] Relative humidity is the fraction of partial pressure of moisture content in the air with respect to the saturation vapor pressure. The diffusivity of water vapor in air is a strong function of temperature, and is based on molecular interaction theory of Lennard-Jones potentials and is in units of cm2 / s.12.73 + 20.13 (12)

[0110] The diffusivity of water vapor in the porous wall is dependent on the open pore space void fraction and geometry of the pore space,

[0111] E the porosity and T the tortuosity which is currently unknown and can be seen as a tuning parameter. Effective honeycomb diffusivity is weighted with vapor diffusivity in the channels and webs using OF A. Upon inspection of FIG. 21 A, as temperature rises evaporation rate increase due to increasing diffusivity and increasing partial pressure of water vapor, leading to suppressed wicking heights. Regarding the impact of relative humidity, as humidity increases from dry conditions R.H.=0 to fully humid R.H.= 1, evaporation rates decrease from a maximum to zero, with the wicking front attaining the maximum height at saturated conditions as the drying mechanism is absent (see FIG. 2 IB). As mass transfer coefficient increases, the evaporation rate increases and again, wicking height is suppressed (FIG. 21C). A low mass transfer coefficient is analogous to stagnant air and a high coefficient to surrounding airflow, allowing for convection of vapor away from the boundary of the crystallizer to be replenished with dryer ambient air while enhancing drying rates.Attorney Docket No.: SP24-282PCT

[0112] Example 9. Rinsing inside salt to realize the second Li / Na selection

[0113] After a brine water wi eking experiment, a 13.5 cm long section from the wicking top of a long bar (crystallizer) was used for inside salt rinsing experiment. This short bar was first dried, and then rinsed by 15 g of DI water. The rinsing water was poured through the honeycomb from one end. The flow out solution was collected from the other end. The collected solution was poured back through the honeycomb. Such rinsing was repeated 10 times. Three rounds of such rinsing were done on this same part. For each round, a fresh 15 g of DI water was used. In the second round of rinsing, the part was dried again before rinsing. In the third round of rinsing, the part was not dried, but changed to a fresh 15 g DI water after the 10 rinses from the second round. After the three rounds rinsing experiments, the part was soaked in water to extract all salts in the honeycomb. All the collected solutions were measured LiCl and NaCl concentration by ionic chromatography. Table 5 summarizes the experimental results.Table 5. Summary of Experimental Results

[0114] This experiment demonstrated that the second Li / Na selection (process 2) can be realized by rinsing out the salt from inside of the honeycomb. In this experiment the Li / Na selectivity is increased from 3.8 to 4.9-7.5 by rinsing the salt out. With the rinsing, the LiCl concentration is increased to as high as 4.42%. If using the original brine water, which contain 0.9% of LiCl, the final collected LiCl concentration can be further increased.Attorney Docket No.: SP24-282PCT

[0115] To clarify the use of and to hereby provide notice to the public, the phrases "at least one of , , . . . and <N>" or "at least one of , , . . . <N>, or combinations thereof or ", , . . . and / or <N>" are defined by the Applicant in the broadest sense, superseding any other implied definitions hereinbefore or hereinafter unless expressly asserted by the Applicant to the contrary, to mean one or more elements selected from the group comprising A, B, ... and N. In other words, the phrases mean any combination of one or more of the elements A, B, ... or N including any one element alone or the one element in combination with one or more of the other elements which may also include, in combination, additional elements not listed. Unless otherwise indicated or the context suggests otherwise, as used herein, "a" or "an" means "at least one" or "one or more."

[0116] While various embodiments have been described, it will be apparent to those of ordinary skill in the art that many more embodiments and implementations are possible. Accordingly, the embodiments described herein are examples, not the only possible embodiments and implementations.

Claims

Attorney Docket No.: SP24-282PCTCLAIMSWhat is claimed is:1 A crystallizer for accelerating evaporation, the crystallizer comprising: a porous body having a porosity in a range from 40% to 95%.2 The crystallizer of claim 1, wherein the porous body contains an array of open channels bounded by porous cell walls, and wherein the porous cell walls have the porosity in the range from 40% to 95%.3 The crystallizer of claim 2, wherein the porous cell walls comprise a pore size in a range from 1 micron to 20 microns.4 The crystallizer of claim 2 or 3, wherein the porous cell walls comprise a thickness in a range from 0.05 mm to 1 mm.5 The crystallizer of any of claims 2-4, wherein the porous cell walls comprise a ceramic, a polymer, or a ceramic-polymer composite.6 The crystallizer of any of claims 2-5, wherein, over a transverse cross-section of the porous body, the open channels have a cell density in a range from 50 cells per square inch to 1600 cells per square inch.7 The crystallizer of claim 1, wherein the porous body comprises an array of porous rods extending from a porous support, and wherein the porous rods and the porous support have the porosity in the range from 40% to 95%.Attorney Docket No.: SP24-282PCT8 The crystallizer of claim 7, wherein the porous rods and the porous support comprise a pore size in a range from 1 micron to 20 microns.9 The crystallizer of claim 7 or 8, wherein the porous rods comprise a width or diameter in a range from 0.05 mm to 10 mm.10 The crystallizer of any of claims 7-9, wherein the porous rods and the porous support comprise a ceramic, a polymer, or a ceramic-polymer composite.11 The crystallizer of any preceding claim, wherein the porous body is an extruded body.12 The crystallizer of any preceding claim, wherein the porosity is at least 50%, at least 60%, or at least 70%, and / or wherein the porosity is as high as 85%.13 A system for accelerating evaporation, the system comprising: a crystallizer comprising a porous body having a porosity in a range from 40% to 95%; and a source of water containing salts to be extracted, wherein a portion of the crystallizer is immersed in the water.14 The system of claim 13, wherein the porous body contains an array of open channels bounded by porous cell walls, and wherein the porous cell walls have the porosity in the range from 40% to 95%.15 The system of claim 14, wherein the porous cell walls comprise a ceramic, a polymer, or a ceramic-polymer composite.Attorney Docket No.: SP24-282PCT16 The system of claim 14 or 15, wherein the porous cell walls comprise a pore size in a range from 1 micron to 20 microns.17 The system of any of claims 14-16, wherein the porous cell walls comprise a thickness in a range from 0.05 mm to 1 mm.18 The system of any of claims 14-17, wherein, over a transverse cross-section of the porous body, the open channels have a cell density in a range from 50 cells per square inch to 1600 cells per square inch.19 The system of any of claims 14-18, wherein the crystallizer is positioned in the water such that the open channels of the porous body are oriented along a vertical direction.20 The system of any of claims 14-18, wherein the crystallizer is positioned in the water such that the open channels are oriented along a non-vertical direction.21 The system of claim 20, wherein the open channels are oriented along a horizontal direction.22 The system of any of claims 14-21, further comprising a gas inlet or outlet in fluid communication with the open channels at one or both ends of the porous body, the gas inlet or outlet being configured for connection to a pump or blower to force a gas through the open channels.23 The system of any preceding claim, wherein the crystallizer has a multi-level structure including two or more of the porous bodies in a vertical stack.24 The system of claim 13, wherein the porous body comprises an array of porous rods extending from a porous support, andAttorney Docket No.: SP24-282PCT wherein the porous rods and the porous support have the porosity in the range from 40% to 95%.25 The system of claim 24, wherein the porous rods and the porous support comprise a pore size in a range from 1 micron to 20 microns.26 The system of claim 24 or 25, wherein the porous rods and the porous support comprise a width or diameter in a range from 0.05 mm to 10 mm.27 The system of any of claims 24-26, wherein the porous rods and the porous support comprise a ceramic, a polymer, or a ceramic-polymer composite.28 The system of any of claims 24-27, wherein the crystallizer is positioned in the water such that the porous rods of the porous body are oriented along a vertical direction.29 The system of any of claims 24-27, wherein the crystallizer is positioned in the water such that the porous rods are oriented along a non-vertical direction.30 The system of claim 29, wherein the porous rods are oriented along a horizontal direction.31 The system of any preceding claim, wherein the porous body is an extruded body.32 The system of any preceding claim, wherein the porosity is at least 50%, at least 60%, or at least 70%, and / or wherein the porosity is as high as 85%,33 A method of accelerating water evaporation, the method comprising:Attorney Docket No.: SP24-282PCT immersing a portion of a crystallizer into a reservoir of water containing salts to be extracted, the crystallizer comprising a porous body having a porosity in a range from 40% to 95%, whereby the porous body wicks the water via capillary forces, and wherein, during and / or after the immersion, the water wicked by the porous body evaporates at a rate at least ten times higher than a rate of water evaporation from a surface of the reservoir, and as the water evaporates from the porous body, at least some of the salts from the water accumulate on and / or in the crystallizer.34 The method of claim 33, wherein the porous body comprises an array of porous rods extending from a porous support, and wherein the porous rods and the porous support have the porosity in the range from 40% to 95%.35 The method of claim 33, wherein the porous body contains an array of open channels bounded by porous cell walls, and wherein the porous cell walls have the porosity in the range from 40% to 95%.36 The method of any preceding claim, wherein the water in the reservoir is obtained from brine deposits beneath salt flats, recycled brine from geothermal power plants, wastewater from oil / gas drilling, or sea water.37 The method of any preceding claim, wherein the salts include a first salt and a second salt, the first salt having a lower solubility in the water than the second salt, and wherein the first salt preferentially accumulates at lower portions of the crystallizer and / or on an external surface of the crystallizer, and wherein the second salt preferentially accumulates at upper portions of the crystallizer and / or inside the crystallizer.38 The method of claim 37, further comprising:Attorney Docket No.: SP24-282PCT after achieving a desired accumulation level of the salts on and / or in the crystallizer, withdrawing the crystallizer from the reservoir of water; removing some or all of the salts accumulated on the external surface of the crystallizer, thereby preferentially collecting the first salt; and flowing a controlled amount of water through the open channels to dissolve some or all of the salts accumulated inside the crystallizer into the water, thereby preferentially collecting the second salt.39 The method of claim 38, wherein the flowing of the controlled amount of water through the open channels is selectively applied to one or more height sections of the crystallizer.40 The method of any preceding claim, wherein the salts include a second salt comprising lithium, and further comprising: redissolving accumulated salts from the crystallizer into the reservoir of water; after achieving a desired concentration of the second salt in the water, transporting the water from the reservoir to one or more additional locations for further processing; and after transporting the water to a final location, adding a precipitation agent to the water to precipitate a lithium compound, thereby achieving lithium extraction.41 The method of any preceding claim, wherein the porous body is an extruded body.42 The method of any preceding claim, wherein the porosity is at least 50%, at least 60%, or at least 70%, and / or wherein the porosity is as high as 85%.43 A method of lithium extraction, the method comprising: immersing a portion of a crystallizer into a reservoir of water containing salts to be extracted, the crystallizer comprising a porous body having a porosity in a range from 40% toAttorney Docket No.: SP24-282PCT95%, whereby the porous body wicks the water via capillary forces, and, during and / or after the immersion, the water wicked by the porous body evaporates and at least some of the salts from the water accumulate on and / or in the crystallizer; redissolving accumulated salts from the crystallizer into the reservoir of water; after achieving a desired concentration of lithium salt in the water, transporting the water from the reservoir to one or more additional locations for further processing; and after transporting the water to a final location, adding a precipitation agent to the water to precipitate a lithium compound, thereby achieving lithium extraction.44 The method of claim 43, wherein the water in the reservoir is obtained from brine deposits beneath salt flats, recycled brine from geothermal power plants, wastewater from oil / gas drilling, or sea water.45 The method of claim 43 or 44, wherein the water wicked by the porous body evaporates at a rate at least ten times higher than a rate of water evaporation from a surface of the reservoir.46 The method of any of claims 43-45, wherein the salts include a sodium salt and a lithium salt, the sodium salt having a lower solubility in the water than the lithium salt, and wherein the sodium salt preferentially accumulates at lower portions of the crystallizer and / or on an external surface of the crystallizer, and wherein the lithium salt preferentially accumulates at upper portions of the crystallizer and / or inside the crystallizer.47 The method of any of claims 43-46, wherein the porous body comprises an array of porous rods extending from a porous support, and wherein the porous rods and the porous support have the porosity in the range from40% to 95%.Attorney Docket No.: SP24-282PCT48 The method of any of claims 43-46, wherein the porous body contains an array of open channels bounded by porous cell walls, and wherein the porous cell walls have the porosity in the range from 40% to 95%.49 The method of claim 48, wherein redissolving the accumulated salts from the crystallizer into the reservoir comprises: withdrawing the crystallizer from the reservoir of water; removing some or all of the salts accumulated on the external surface of the crystallizer; and flowing a controlled amount of water through the open channels to dissolve some or all of the salts accumulated inside the crystallizer into the controlled amount of water, thereby preferentially collecting the lithium salt; and incorporating the lithium salt collected from the crystallizer into the reservoir.50 The method of claim 49, wherein the flowing of the controlled amount of water through the open channels is selectively applied to one or more height sections of the crystallizer.51 The method of any of claims 43-50, wherein the further processing includes further evaporation, precipitation of additional salts, and / or removal of selected cations and anions from the water.52 The method of any of claims 43-51, wherein the porous body is an extruded body.53 The method of any of claims 43-52, wherein the porosity is at least 50%, at least 60%, or at least 70%, and / or wherein the porosity is as high as 85%,

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