This specification relates to systems and methods for treating aqueous lithium solutions, for example lithium containing groundwater or brine, and to ion exchange.
Demand for lithium around the world has increased due to its varied uses across a number of industries including for example, use in ceramics, batteries, chemical additives, and in nuclear applications. Lithium ion batteries are in particularly high demand and represent the greatest consumer of lithium. Some techniques have been investigated for extracting high purity lithium from crude sources such as lithium containing ores, clays, and brines in order to keep up with the increasing demand.
Conventionally, lithium is extracted from crude sources via evaporation and precipitation techniques. For example, brines extracted from underground reservoirs (salar brines) containing lithium are pumped into evaporation ponds and undergo solar evaporation over a number of months or years. Lithium chloride concentrated in the ponds after evaporation is sent to a recovery plant for pretreatment to remove contaminants (such as boron or magnesium) for example via a solvent extraction process and filtration. The remainder is then treated with a reagent such as sodium carbonate (soda ash) or sodium hydroxide in order to precipitate a saleable lithium product such as lithium carbonate or lithium hydroxide. The conversion rates of LiCl to Li2CO3 using these conventional methods may be around 78-88%. The resultant products may contain undesirable amounts of Cl− or SO4= contaminants.
Other methods of treating lithium-containing brines include using mechanical vapor recompression (MVR) evaporators and/or multi-effect steam powered distillation processes in place of evaporation ponds. In other options, the evaporation process is sped up by reverse osmosis used to concentrate the lithium brine.
The following paragraphs are not intended to limit or define the invention. The invention relates to systems and/or methods for treating lithium-containing solutions, for example salar brines or other natural sources of water containing lithium. The systems and methods use ion exchange to avoid the direct addition of sodium carbonate, sodium hydroxide or a similar reagent to filtered solutions. Lithium ions are loaded into an ion exchange resin and then eluted while recharging the resin. Although sodium hydroxide or sodium bicarbonate may be used to recharge the resin, they are not directly mixed with the lithium-containing feed solutions. This may reduce the potential for contamination in the final product, including for example contamination by sodium chloride or sodium sulfate, in the final product. The system or method optionally includes processing an eluate stream to recover one or more compounds for re-use in regenerating the resin bed. In some cases, the conversion rate may also be increased, the energy consumption may be reduced and/or the production of waste products may be reduced, relative to a process with direct addition of the reagent. In some cases, a separate solvent extraction step to remove one or more contaminants, for example boron, is not required.
In some examples, a method is used for treating a softened aqueous feed solution containing monovalent cations, chiefly lithium (for example a feed solution wherein at least 50% of the cations are lithium on a molar basis) but optionally also other ions including chloride, borate and sulfate. The method includes passing the feed solution through an ion exchange resin, for example a strong acid ion exchange resin bed, loaded with monovalent cations other than lithium (optionally called a “counterion” herein), typically sodium. Lithium ions in the feed stream are exchanged with the counterions (i.e. sodium) in the resin creating a raffinate stream comprising the counterions (i.e. sodium) is withdrawn from the ion exchange resin bed. To recharge the ion exchange resin bed, an eluent stream comprising monovalent cations, including a desired counterion, is passed through the ion exchange resin bed to exchange the Li+ ions of the resin with monovalent cations other than lithium (i.e. sodium) of the eluent stream. The eluent stream may contain, for example, sodium carbonate and/or sodium bicarbonate, or sodium hydroxide. An eluate stream comprising lithium hydroxide or lithium carbonate and/or lithium bicarbonate is produced as the eluent stream passes through the ion exchange resin. Optionally, the method may be performed at elevated temperatures up to the maximum operating temperature of the resin (typically 300 F).
The eluate stream may be treated further. In some examples, water is removed from an eluate stream containing lithium hydroxide, for example by evaporation and/or electrodialysis, to produce a lithium hydroxide or lithium hydroxide hydrate crystal. Optionally, a residual liquid remaining after separating the precipitate may be used to at least partially regenerate the ion exchange resin bed. In some examples, an eluate containing sodium bicarbonate is heated to remove water and convert bicarbonate ions to carbonate ions. Lithium carbonate may be precipitated from the eluate. Carbon dioxide released from the eluate due to the decomposition of bicarbonate may be used to convert a sodium carbonate solution to a sodium bicarbonate solution for use in regenerating the anion exchange bed.
In some examples, a system for treating a lithium solution has an ion exchange resin bed. The system may also have a source of a sodium hydroxide, sodium carbonate or sodium bicarbonate solution. Optionally, the system may have one or more brine-concentrating units, for example an evaporator or electrodialysis device. Optionally, a source of sodium bicarbonate may include a source of sodium carbonate and a scrubber tower in communication with an evaporator.
In a prior art process shown in
2LiCl(a)+Na2CO3(a)→Li2CO3(s)+2NaCl(a)
The products are passed through a solid-liquid separation step 110 and distilled water 112 is added to produce a washed Li2CO3 product 114. In practice, the conventional system results in Na+ and SO4= contaminating the Li2CO3 lattice. This limits purity of the product. To remedy this, the conventional system includes a bleeding precipitation circuit 116, which bleeds Na and SO4= to control product purity. However, this limits Li+ conversion and yield.
A system and process for treating lithium solutions described herein may be used in place of the direct addition of sodium carbonate as described above. The lithium solution is preferably pre-treated, for example by way of solar evaporation to concentrate the solution and softening to remove magnesium and calcium. Preferably, 50% or more or 60% or more or 70% or more of the cations, by mol, in the pre-treated solution are lithium. The system and process use one or more ion exchange resin beds to capture lithium ions from the feed solution. When the resin bed is recharged, an eluate stream is produced with different lithium salts in solution. Although it is not a conventional use of the term, the system may be called a metathesis system since it results, in a sense, in (a) the feed solution and (b) a resin bed recharging solution (eluent) exchanging ions and, with further processing of the eluate, in precipitation of a lithium product. Similarly, a process described herein may be called a metathesis process.
The metathesis system has a loading configuration and an elution configuration. The loading configuration has a feed stream comprising monovalent cations, preferably lithium ions, an ion exchange resin having a counterion form, preferably having a sodium ion form (Na+ form), and a raffinate stream. The elution configuration comprises an eluent stream, the same ion exchange resin used in the loading configuration but in a form representing the original cations of the feed stream, and an eluate stream.
In one embodiment, as shown in
The eluent stream in the elution configuration 212 of the system is an aqueous solution comprising sodium ions, for example sodium hydroxide (NaOH), sodium bicarbonate (NaHCO3), sodium carbonate, or NaHCO3 mixed with sodium carbonate (Na2CO3). In other examples, the eluent stream may be an aqueous solution comprising potassium ions. Optionally, the aqueous solution is a strong base. The eluent stream may provide for indirect addition of soda ash using the ion exchange resin. The eluent stream is used to regenerate the ion exchange resin back to the sodium form (or K+ form) and elutes an eluate stream 214. The eluate stream contains Li+ ions combined with the anions of the eluent stream, for example carbonate anions, bicarbonate anions or hydroxide anions. The eluate may be essentially free of chloride or sulfate.
In an exemplary method of lithium metathesis, a feed stream comprising lithium ions is passed through a resin bed in a loading configuration, and the Li+ ions of the feed stream are exchanged for the counterions loaded on the resin bed. The counterions may be Na+ or K+ ions, or alternatively other suitable monovalent cations, possibly H+. A raffinate stream is eluted from the resin bed leaving behind an ion exchange resin in Li+ form. Optionally, the resin bed is rinsed with a low conductivity rinse, for example distilled water, to finish production of the raffinate stream. Then an eluent is passed through the resin bed in Li+ form and an eluate stream is extracted. Optionally, the resin bed is again rinsed with distilled water or other low conductivity rinse, to complete the production of the eluate. The eluate may then be crystallized. The resin bed is preferably in the form of a column or a series of columns. The eluent is preferably added column-wise, i.e. through a series of columns in a specified order. Optionally all fluids are added column-wise.
In another embodiment, a lithium cation bearing aqueous stream with other monovalent cations is passed through a strong acid cation resin bed loaded with Na+ ions. The Li+ ions and other monovalent cations of the solution replace the Na+ ions in the resin bed and the Na+ ions are removed from the resin bed with the anions (for example chloride or sulfate) in a raffinate stream. The raffinate stream also comprises any other non-ionic species that may have been introduced by the feed stream, such as boron. This results in a resin bed loaded with Li+ ions. The Li+ form of the resin bed is eluted with a sodium bicarbonate or sodium carbonate solution, optionally a mixed sodium bicarbonate and sodium carbonate solution. The Na+ ions replace the Li+ ions in the resin bed and Li+ ions, and optionally other monovalent cations, are extracted from the resin bed as lithium carbonate or bicarbonate or monovalent cation carbonate or bicarbonate.
In other examples, the Li+ form of the resin bed is eluted with a sodium or potassium hydroxide solution. The Na+/K+ ions replace the Li+ ions in the resin bed. The monovalent cations, including the Li+ ions, are extracted from the resin bed as lithium hydroxide or monovalent cation hydroxide. In another example, the Li+ form of the resin bed may be eluted with a hydrogen hydroxide (water reacting as a base) solution.
The resin bed used in the invention may be obtained, for example, from any suitable water softener supply reseller or other resin supply manufacturers. The resin is preferably a strong acid cation exchange resin, gel, or macroporous charged with sodium ions for softening applications. In other embodiments, the resin may be charged with K+ions. Optionally, weak acid or chelating resin may be used but the reaction is likely to be slower and require more resin. In another option, an anion exchange resin in the carbonate, bicarbonate or hydroxide form may be used, in which case the Li does not become part of the resin (the Li is optionally collected from the raffinate rather than the eluate) and the eluent may still be a NaOH or NaHCO3 and/or Na2CO3 solution. The resin may be comprised of microbeads, for example gel resin beads. In other examples, the resin may be a sheet-like mesh resin, and a process may be powered by simple diffusion (dialysis) and/or by an electric field as in electrodialysis (i.e. four compartment electrodialysis with streams for the reagent (eluent), raffinate, eluate and feed). The resin bead particle size distribution may be for example between 50 to 3000 microns, or between 50 to 500 microns or between 50 to 150 microns, in diameter. The resin is preferably installed in columns, for example in reinforced plastic pipes or vessels, optionally having a length at least 3 times or at least 5 times their diameter. The system may use one column or multiple columns arranged in series.
The columns of resin in series are preferably operated only in a down flow mode but in a reverse order of columns when the system is operating in an elution configuration compared to a feed configuration. A reversed down flow mode in a three column configuration for eluting Li off resin with NaOH, for example as shown in
In another embodiment, a simulated moving bed system (SMB) comprising many (i.e. 10 or more) columns in series is used, for example as described in U.S. Pat. No. 2,985,589, which is incorporated herein by reference. The columns are connected in series and form a loop but a rotary valve (or multiple ordinary valves) changes the position of the feed to each column periodically, for example such that the last column receiving the feed process becomes the first column to receive the eluent. The SMB may be loaded with for example 50-300 micron resin beads. In an alternative example, a reciprocating flow ion exchange (RFIX) system (as in a reciprocating short bed ion exchange system but without necessarily using short beds) may be used, for example with 50-300 micron, i.e. 50-100 micron, resin beads may be used.
As shown in
In some examples, the resin in the elution configuration is eluted with a solution comprising NaHCO3 and Na2CO3 (soda ash) in order to avoid gas pockets forming in the resin bed, which may induce channeling. By mixing soda ash with the bicarbonate solution, the pH of the solution is raised to around 10 thereby reducing the likelihood of formation of CO2 gas pockets.
In another example, as shown in
In some examples, the eluate aqueous solution achieved from the metathesis process is further converted into a solid lithium rich cake, for example by crystallization. The crystallization conversion reaction may be described by, for example:
2LiHCO3(a)+H2O(g)→Li2CO3(s)+CO2(g)+H2O(g+a)
In some examples, where aLiHCO3/Li2CO3 solution is produced, the eluate may further be crystallized using an evaporative crystallizer or other precipitation means using direct steam or via boiling by indirect heat. The resulting lithium carbonate slurry is filtered, washed and separated from the liquid fraction to produce a washed lithium carbonate cake for use. Carbon dioxide released during the crystallization step is recycled to a re-carbonation step where it is used to convert soda ash into sodium bicarbonate for reuse in the metathesis system.
Where LiOH eluate is achieved from the metathesis process, evaporation or electrodialysis techniques may be used to produce a LiOH*H2O or LiOH crystalline product. Residual liquid after extraction of the crystalline product may be returned to the metathesis process (after partial or full recarbonation prior to use) as a preliminary eluent of the resin.
In another example, where recrystallization is desired, Li2CO3 is added to the re-carbonation stage in place of Na2CO3.
Returning to
In another example where the eluate comprises an aqueous LiOH solution, the eluate may be subject to removal of water by evaporation or electrodialysis to the saturation point of LiOH. Further water is removed by evaporation to crystallize a LiOH*H2O or LiOH crystalline product. The residual liquid phase after crystallization, which is concentrated in other monovalent cations of hydroxide, relative to Li+, is used as a preliminary regeneration of the lithium bearing cation resin before final regeneration with pure NaOH solution. This improves lithium recovery and reduces NaOH usage.
Optionally, the system as shown in
A lithium bearing feed solution was prepared with technical grade chemicals as shown in column 1 of Table 1 below. A series of 3 ion exchange columns are filled with strong acid cation resin (ordinary softener resin), each with a bed height of 975 mm and a diameter of 32.4 mm for a total resin volume of approximately 2400 ml. The bed was conditioned with 10 wt % solution technical grade sodium chloride at 25 ml/min followed by rinsing with distilled water to a conductivity of 7 uMohs. The series of resin bed were fed with 2000 ml of feed with the composition indicated in Table 1 below, at a rate of 27 ml/min. Conductivity was monitored and plotted in
A test demonstrating the conversion of aqueous LiCl in to aqueous LiOH using the metathesis system of the present invention was conducted. The test converted 1 Kg LiCl (dry basis) to a 3% solution of LiOH. Yield loss of Li was approximately 7%. In this test, resin was obtained from a water softener supply reseller. The resin was of gel type with particle size distribution estimated to be between 300 to 1200 microns in diameter. Crosslinking was estimated to be 8 w/w % divinylbenzene. The ion exchange capacity of resin was estimated to be 2.2 meq/l. The resin was installed in 3 clear PVC columns with internal diameter of 1.375″ and a length of 42″. The columns were completely filled with no provision for bed expansion. Each column held approximately 800 ml of resin, for a total of 2400 ml. In view of the estimated ion exchange capacity of 2.2 meq/l, the total column ion exchange capacity was approximated to 5.3 meq. The reagent usage for the test is shown in Table 3 below.
The resin was conditioned with a double regenerant of HCl and rinsed to a conductivity of 25 ppm. The resin used was in H+ form for the initial cycle. The initial cycle, shown as cycle 0 in Table 4 below, loaded 3840 g of LiCl solution (4.5 moles) onto the column, followed by a rinse. First elution of LiOH solution was conducted with 3.0 moles of NaOH. A total of 7 cycles were conducted and a composite of each eluate and raffinate was sampled. Flowrates of reagents and rinses were measured and found to vary from 32 g/min to 45 g/min. A conductivity meter was located at the discharge of the final column for measurements. Each charge of LiCl or NaOH was followed by a charge of rinse water with conductivity less than 125 ppm, adequate to bring the conductivity of the discharge below 250 ppm. The following actions were conducted based on the measured conductivity:
The experimental yield is shown in Table 6 below and indicates that 11.7 g of lithium were lost in the NaCl raffinate which represents a yield loss of 7.4% of lithium. This excess of lithium in the raffinate is due primarily to diffusion limitations for the time frame of each cycle. The total loading/unloading cycle was approximately 2 hours, not including rinses. As such, the experiment may result in lower lost yield of lithium by using slower cycle times. The experiment may be further ameliorated with larger stoichiometric excess of resin over the Li charge for each cycle or by using smaller or more uniform resin beads. Lower crosslinking of beads is another option that will improve kinetics but may reduce volumetric capacity of the resin bed. Natural kinetics may be improved by increasing the temperature of the operation to 65 degree C., which may increase diffusion 16 fold (doubling of diffusion is expected with every 10 degree C. increase in temperature). A commercial unit operating at a higher temperature within the operating range of resin, for example at 65 degrees C., may reduce capital cost and increase yield.
In this experiment, the resin was eluted in a two-step fashion, for example as shown in
A cycle according to Experiment 3 consisted of loading Li on the resin by adding 116 g of feed to a first end, and eluting 136.6 g of raffinate from a second end. The flow was then reversed by adding recycled rinse water followed by 23 g of fresh rinse to the second end. Li was then eluted on resin by adding 22 g of primary eluent to the second end. Following the primary eluent, 98g of secondary eluent was added and 142.8 g of eluate was collected from the first end of the resin. Flow was reversed again by adding recycled rinse water followed by 23 g of fresh rinse to the first end of the resin and the cycle was repeated.
The experiment was operated at approximately 20 C. Each complete cycle had a duration of 62 minutes. In this experiment the above cycle was repeated 12 times to allow the resin and the recycled rinse waters to come to equilibrium. On the 12th cycle, samples of eluate and raffinate were analyzed and the results are shown in Table 7, below.
Based on the above results, lithium loss to raffinate was 0.3% of feed. Stoichiometric requirement for secondary eluent was 101% of lithium value in feed. Chloride and boron contamination of eluate was less than 0.1% of feed value.
This application claims the benefit of U.S. patent application Ser. No. 62/962,595, filed Jan. 17, 2020, which is incorporated by reference.
Filing Document | Filing Date | Country | Kind |
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PCT/US2021/013430 | 1/14/2021 | WO |
Number | Date | Country | |
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62962595 | Jan 2020 | US |