Multidimensional, multimodal chromatographic method for producing high purity, high yield lithium, cobalt, nickel, and manganese salts from waste lithium ion batteries and other feedstocks

Abstract

A versatile and efficient method is described for recovering a high purity material (target) or multiple materials (targets) from a complex mixture in a batch or continuous chromatography system. When a completely selective sorbent for the target is available, a fixed pattern batch capture method in series or series carousel capture method is preferred. When a completely selective sorbent for the target is not available, batch capture, carousel capture, isocratic SMB, non-isocratic SMB, and isotactic displacement methods can be deployed in series or parallel to produce high purity products with high yield and high productivity.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This patent application claims priority to co-pending U.S. Provisional Patent Application Serial No. 63 / 323,755, filed March 27, 2022, which is incorporated by reference in its entirety herein. Technical Field The novel technology of the present invention relates generally to the field of chromatography, and more particularly to a chromatographic method for recovering constituent elements from spent lithium ion batteries (LIBs) and other lithium feedstocks. [Background technology]

[0002] Driven by the need to reduce carbon emissions and pollution associated with traditional fossil fuel-powered vehicles, the market share of electric vehicles (EVs) has increased rapidly in recent years. Lithium (Li), cobalt (Co), nickel (Ni), and manganese (Mn) are the four essential elements in the cathode materials found in lithium-ion batteries (LIBs) required for EV power, energy storage, and powering electronic devices. Demand for batteries is expected to increase eight-fold by 2030. Global reserves of extractable Co, 7.1 million tons, are estimated to be nearly depleted by 2035. Global reserves of extractable Li, 12-14 million tons, are estimated to be more than 50% depleted by 2035. Recycling Li, Co, Ni, and Mn in LIBs is essential for a circular economy and a sustainable clean energy future.

[0003] Current pyrometallurgical processes require high temperatures (>1400°C) to reduce the mixed metal oxides to alloys of Co and Ni. These alloys require further processing to produce the pure metals. Li and Mn cannot be reduced and are collected in the slag and are not recovered. These processes have high capital costs, high energy consumption, and high greenhouse gas (GHG) emissions. Hydrometallurgical methods use organic and / or inorganic acid leaching to convert metal oxides in the cathode material to soluble salts. Metal ions can be purified using sequential selective precipitation or multi-stage solvent extraction. However, selective precipitation methods cannot produce high purity (>99%) salts in high yields (>95%) due to co-precipitation of various salts caused by inaccurate control of local solution pH. Solvent extraction methods require flammable solvents and multiple stages to achieve high purity products, resulting in high chemical, capital, and waste disposal costs. Current pyrometallurgical, hydrometallurgical, and / or sulfidation methods cannot produce high purity (>99.5%) Li, Co, Ni, and Mn in high yields (>99%) from LIB-derived cathode materials. Thus, there remains a need for improved methods to recover Li, Co, Ni, and Mn from waste LIBs. The novel technology of the present invention addresses this need. Summary of the Invention

[0004] New chromatographic methods have been invented to produce high purity (99.5%) lithium, cobalt, nickel, and manganese salts in high yields (99%) from waste lithium-ion batteries and other feedstocks. These new methods require relatively low temperature processing and low GHG emissions. The new methods are based on intrinsic (scale-independent) engineering parameters, which allows the process to be easily scaled from laboratory to pilot to commercial production scale. The new methods are more efficient and therefore more economical than traditional extraction and purification methods. Most of the chemicals can be recycled and little waste is generated. The high purity products enable universal use of essential materials recovered from waste LIBs and other feedstocks. [Brief description of the drawings]

[0005] [Figure 1A-B] Figure 1A illustrates an unsustainable linear pathway for essential materials. Figure 1B illustrates a method to enable a sustainable circular economy of essential materials for lithium-ion batteries. [Figure 2A] Sherwood plot of various metallic elements. [Figure 2B] FIG. 1 illustrates the estimated production costs (best fit correlation thick lines) for producing pure Li or Co from conventional sources (brine and mineral) and waste LIBs. [Diagram 3] FIG. 1 illustrates three different modes of interaction resulting from this novel technology. [Figure 4A] FIG. 1 is a block flow diagram for the application of the novel chromatographic method for producing high purity Li, Co, Ni, and Mn salts. [Figure 4B-C] Figure 4B is a schematic of a model simulation of the reaction and separation kinetics in the present chromatography system, and Figure 4C is a schematic of a four-zone simulated moving bed chromatography system having eight operatively connected columns. [Figure 5A] FIG. 1 is a schematic representation of a batch scale capture process according to one embodiment of the present novel technology. [Figure 5B] FIG. 1 illustrates the concentration dynamic profile in a single-column capture process according to one embodiment of the present novel technology. [Figure 6A] FIG. 1 illustrates the correlation between dimensionless column length and dimensionless intraparticle diffusion rate. [Figure 6B] FIG. 13 is a block diagram showing a constant pattern design method for single column capture. [Figure 7] FIG. 1 is a block diagram showing a process for producing a mixture of Li, Mn, Co, Ni salts from black mass. [Figure 8] FIG. 1 illustrates an in-line capture process for producing high purity individual elements from NMC cathode leachate. [Figure 9A] FIG. 1 illustrates a three-column carousel process according to one embodiment of the present novel technology. [Figure 9B] FIG. 1 illustrates a first cycle of a four-segment carousel process in accordance with one embodiment of the present novel technology. [Figure 9C]13 is a chart showing concentration waves as a function of normalized column position in the first two segments of the carousel. [Figure 10A-B] Figure 10A illustrates the column concentration dynamic profile of displacement chromatography according to one embodiment of the novel technology of the present invention. Figure 10B illustrates displacement chromatography. [Figure 11] FIG. 1 illustrates a displacement chromatography process according to one embodiment of the novel technology of the present invention. [Figure 12] FIG. 1 illustrates the substitution to produce high purity Li, Mn, Co, and Ni from LIB cathodes using Li as a presaturating agent and Ni as a displacing agent according to one embodiment of the present novel technology. [Figure 13] FIG. 13 is a block diagram showing a flowchart of a constant pattern design method when a yield is specified. [Figure 14] FIG. 1 is a block diagram illustrating a flow chart of a constant pattern design methodology for achieving maximum productivity given purity requirements. [Figure 15A] FIG. 1 illustrates a four-zone SMB configuration with four pumps and a Li-selective adsorbent. [Figure 15B] FIG. 1 illustrates an open-loop three-zone SMB configuration with three pumps and a Li-selective adsorbent. [Figure 15C] FIG. 1 illustrates the configuration of a four-zone SMB for splitting a ternary mixture. [Figure 15D] FIG. 1 illustrates a four-zone SMB configuration with four pumps for splitting a four-component mixture. [Figure 15E] FIG. 1 illustrates a four-zone SMB configuration for binary splitting of an N-component mixture into two products. [Figure 15F] FIG. 1 illustrates an 8-zone SMB configuration with 8 pumps. [Figure 15G] FIG. 1 illustrates a six-zone SMB configuration having six pumps. [Figure 15H] FIG. 1 illustrates a simplified 6-zone SMB configuration with four pumps. [Figure 16] FIG. 1 illustrates the simulated elution history of the capture of impurities from a leachate derived from black mass. [Figure 17] FIG. 1 illustrates the simulated elution history of the production of high purity Li from a Mg / Li binary mixture. [Figure 18] FIG. 1 illustrates the capture of Mn from a mixture of Li, Co, Ni, and Mn in a Purolite MTX7010 column. [Figure 19] FIG. 1 illustrates the capture of Co in a Purolite MTX8010 column. [Figure 20] FIG. 1 illustrates the elution history of Ni capture using an IDA column. [Figure 21A] FIG. 13 illustrates the simulated eluate history at the end of the second segment. [Figure 21B] FIG. 1 illustrates the column dynamic concentration profile before supply port switching. [Figure 22A] FIG. 1 illustrates a serial carousel and fractionation chromatography system according to one embodiment of the present novel technology. [Figure 22B] FIG. 1 illustrates a serial carousel and fractionation chromatography system according to another embodiment of the present novel technology. [Diagram 23] FIG. 1 illustrates a simulated elution history for the production of high purity LiOH. [Figure 24] FIG. 1 illustrates experimental and simulated eluate histories for the conversion of LiSO4 to LiOH using anion exchange. [Figure 25A-C] FIG. 1 illustrates the elution history of several substitution examples. [Figure 26] FIG. 1 illustrates the elution history shown in Example 6.1. [Figure 27] FIG. 6 illustrates the elution history of pH and metal ions shown in Example 6.2. [Figure 28] FIG. 1 illustrates the elution history of pH and metal ions shown in Example 6.3. [Figure 29] FIG. 1 is a block diagram showing the process of the pilot test of Li recovery. [Diagram 30] FIG. 1 illustrates the experimental and simulated eluate histories of the Li recovery pilot test. [Fig. 31A-B] FIG. 1 illustrates the concentration of extractables (31A) and raffinates (31B) as a function of time. [Fig. 32A-B] 32A and 32B are diagrams illustrating concentration as a function of normalized column position for a simulated column dynamic profile at a start step and an end step, respectively. [Fig. 33A-F] FIG. 1 illustrates the SMB cycle of Example 9. [Fig. 34A-C] FIG. 13 illustrates the elution history and column profile at steady state for Example 9. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] For the purposes of promoting an understanding of the principles of the present novel technology and setting forth its best currently understood mode of operation, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same, it being understood, however, that no limitation of the scope of the novel technology is thereby intended, and that such changes and further modifications in the illustrated apparatus, and such further applications of the principles of the novel technology illustrated therein, as would normally occur to one skilled in the art to which the novel technology pertains, are contemplated. This multidimensional and multimodal chromatography method invention achieves efficient separation of complex mixtures using (1) various stationary phases with different functional groups and adsorption / desorption mechanisms, (2) various operation modes including batch or continuous capture, displacement, and / or elution, and (3) synergistic combination of various reactions. Specifically, the new methods include (1) a fixed pattern batch capture method, (2) a fixed pattern carousel capture method, (3) a fixed pattern serial capture method for producing multiple pure components from a mixture, (4) a generalized displacement fractionation method for producing multiple pure components from a mixture, and (5) a general simulated moving bed method for continuously producing high purity products from a complex mixture.

[0007] The generic fixed pattern batch capture method allows for easy design of single-column capture processes based on the specific adsorption and mass transfer parameters of the stationary phase and the captured target components, which can be extrapolated from small-scale laboratory-scale embodiments. Using this method, high capture yields and high productivity can be achieved. The fixed pattern carousel capture method ensures the achievement of cycle steady state, 100% resin capacity utilization, high capture yields (>99%), and high productivity of the stationary phase.

[0008] Highly selective adsorbents can be used in a series of columns connected in series to sequentially capture target components from a mixture. The method can also be applied to recover high purity Li, Co, Ni, and Mn from brines or minerals. Below, we use examples of a universal method to show that high-purity (>99.5%) salts of Li, Co, Ni, and Mn can be economically produced in high yields (>99%) from waste LIB cathode materials. The new method requires relatively low-temperature processing, resulting in low GHG emissions. The design method is based on intrinsic (scale-independent) engineering parameters, which allows the process to be easily scaled from laboratory to pilot to commercial production scales. The new method is more efficient and economical than traditional extraction and purification methods. Most of the chemicals can be recycled, and little waste is generated. The high-purity products enable universal use of essential materials recovered from waste LIBs.

[0009] Driven by the need to reduce carbon emissions and pollution associated with traditional fossil fuel-powered vehicles, the market share of electric vehicles (EVs) has increased rapidly in recent years. In the United States, EV sales are expected to exceed 200,000 in 2020 and double in less than five years. In 2021, General Motors announced plans to produce only EVs by 2035. Analysts have predicted that 18% of all new cars globally will be EVs by 2030. A key component of electric vehicles is the lithium-ion battery (LIB). For example, the battery pack of a Tesla Model S has 7,104 LIB cells and generates 85 kWh. Each EV requires approximately 90 kg of Li, Co, Ni, and Mn to make the cathode material of the LIB. LIBs have been widely used in portable electronic devices and electric vehicles over the past decades due to their high energy density, high efficiency, high stability, and long life. The market size of LIBs is nearly $3 billion in the United States and is expected to increase in the future due to the booming EV industry. The demand for batteries is expected to increase eightfold by 2030. The average lifespan of a LIB is 7 to 10 years.

[0010] Lithium (Li) and cobalt (Co) are the two essential elements for LIBs. Approximately 90% of the world's supply of lithium and over 50% of cobalt are used in LIBs. Demand for batteries is expected to increase eight-fold by 2030. The growing EV market has led to increased demand and higher prices for lithium and Co. However, Co production (140,000 tonnes / year) is concentrated in the Democratic Republic of Congo (DRC), which accounts for about 70% of the world's supply in 2020. It is estimated that the world's reserves (or economically extractable supply) of Co, 7.1 million tonnes, will be nearly depleted by 2035. It is estimated that the world's reserves of Li, 12-14 million tonnes, will be more than 50% depleted by 2035. Recycling Li and Co in LIBs is essential for a circular economy and a sustainable clean energy future. Currently, the majority of lithium (87%) is produced from Li-rich brines containing 200-3,000 ppm Li. The brines are concentrated by solar evaporation to 7,000-10,000 ppm Li before further purification. About 13% of lithium is produced from ores containing about 0.5-7% Li by mass. To produce one tonne of lithium, up to 200 tonnes of ore or up to 3,000 tonnes of Li-rich brine would be required, consuming 1,900 tonnes of water in the extraction process. However, only 28 tonnes of waste LIBs are needed to produce the same amount of Li material.

[0011] Less than 10% Co is produced as the primary product, with over 90% produced as copper or nickel by-products. Approximately 70% of the Co supply comes from DRC. The ore is first crushed and ground, followed by a high-pressure acid leaching process. Copper in the leachate can be recovered using electrowinning, and cobalt is separated and precipitated as hydroxide. The cobalt hydroxide is then redissolved and used to produce the metal product by electrolysis. Over 50% of the world's cobalt supply is used in LIBs for electronics and electric vehicles. Recovering Li and Co from LIBs reduces supply risks, mitigates the environmental impacts associated with mining, and helps achieve a sustainable circular use of limited minerals (see Figure 1). In addition, producing essential materials from waste LIBs can be more economical and energy efficient than producing them from minerals or brine, as explained below.

[0012] Waste LIBs are better feedstocks for producing Li and / or Co than ores or brines. A crude assessment of the economic feasibility of producing target minerals from new feedstocks is performed as follows. This crude analysis is based on the general trend that the price of the product is related to the concentration of the target product in the feedstock. The lower the concentration of the target in the feedstock, the higher the cost of producing high purity target products from the feedstock. The current prices of nine pure metals (Au, Ag, Pt, Cu, Zn, Ni, Mg, U, W) are plotted in a log-log plot against the mass fraction of the metal in the feedstock. A best fit line can be obtained with a correlation coefficient of 0.98 and a small standard deviation of 0.04 (see Figure 2A). Because the price of the feedstock is usually low compared to the price of the pure metals, the market price of the pure metals is usually in the same order of magnitude as their production costs.

[0013] This best-fit line for predicting the market price for producing Li from Li-rich brines is verifiable. For clarity, the metal points from Figure 2A are not shown in Figure 2B. Because this best-fit line represents a crude estimate of the production costs of the metals, we add two dashed lines to Figure 2B to indicate the uncertainty of the crude estimate and to take into account the price differences between the metals and metal salts. Currently, Li-rich brine is first concentrated to >0.7% Li by evaporating the water using solar energy, and then further purified. The cost of the brine and the cost of producing the Li concentrate are negligible, so the concentrate containing 0.7% Li can be considered as a feedstock. The processing cost to produce pure Li metal from this feedstock is about $30 / kg according to best case scenario, which is in the same order of magnitude as the current market price of Li2CO3 of $40 / kg. In contrast, the cost of producing Li as the primary product from Li-rich brines containing 200 ppm Li, estimated from a best fit line, is over $700 per kg of Li metal, indicating that low-concentration brines are not a competitive feedstock for Li concentrates containing >0.7% Li. Similar analyses indicate that production of Li from ore would require ores containing 0.7% Li or more to be competitive with current production from Li concentrates.

[0014] A best-fit line can be applied to estimate the cost of producing Li from waste LIBs, a non-conventional feedstock. Typical black mass (cathode and anode active materials) from LIBs contains 4-7 wt% Li, which is much higher than Li-rich brines, brine concentrates, and most Li ores. This analysis shows that high-purity Li salts can be produced from waste LIB batteries at a lower cost than from brine or ores. In addition to Li, black mass from waste LIBs also contains 5-20% Co by mass, which is much higher than the 0.01%-1.5% in typical Co minerals. The estimated cost to produce Co salts from waste LIBs as the primary product is lower than the market price of Co salts, indicating the profit potential. This is significantly lower than the cost from minerals (see Figure 2B), indicating that waste LIBs may be a higher-grade "ore" for both Li and Co. If both Li and Co are produced from waste LIBs, the overall profit potential is even higher than producing Li or Co from traditional sources. Furthermore, if Ni or Mn (approximately 8% of black mass from waste LIBs) are also produced as by-products from waste LIBs, the profit potential is even higher.

[0015] This analysis also shows that in a linear economy of essential materials, as high-grade minerals or brines are depleted, production of essential materials from lower-grade feedstocks will require higher production costs, and therefore higher prices, than the essential materials. Recycling Li, Co, Ni, and Mn from waste LIBs could prevent price increases for essential materials and slow the depletion of the main feedstocks for essential materials. LIBs are traditionally recycled through two routes: direct recycling and chemical recycling. The direct recycling process involves disassembling the electrodes, reconditioning, and reusing the materials in remanufacturing LIBs. This method has low energy and chemical consumption, but is highly dependent on the condition of the waste batteries. This method also has low flexibility in handling various electrode compositions or in controlling the composition of the recycled electrodes. The quality of the remanufactured LIBs cannot be guaranteed. Direct recycling has a relatively high yield of total materials and low waste generation, but the method is complex, requires pre-sorting, and has high production costs. In addition, the materials recovered from a certain type of cathode are not easy to modify to produce different types of cathode materials.

[0016] Chemical recycling routes use either pyrometallurgical or hydrometallurgical methods. In pyrometallurgical methods, high temperatures (>1,400 °C) are required to reduce the mixed metal oxides to an alloy consisting of Co and Ni, while Li and Mn cannot be reduced and are collected in the slag. Pyrometallurgical processes are popular in industry due to their simplicity and high productivity. Several companies have already commercialized the process. The process has high capital costs and high energy consumption. The material recovered is an alloy of Ni and Co, while Li and Mn are not recovered. Hydrometallurgical methods can be used to convert metal oxides in LIB cathode materials to soluble salts in high yields (>90%) by using organic or inorganic acid leaching. A reducing agent, e.g., hydrogen peroxide, is usually used in the leaching process to prevent the oxidation of Co(II) to insoluble Co(III) and improve the recovery yield. Metal ions in the leachate can be further purified by (1) selective or sequential precipitation, (2) solvent extraction, (3) electrodeposition, or (4) sulfidation.

[0017] In selective or sequential precipitation processes, metal ions present in the leachate are precipitated by adjusting the pH or by adding a precipitating agent, such as an oxalate or carbonate. Although these methods can achieve relatively high yields, typically greater than 95%, the purity of the product is usually low, typically less than 99% pure, which is unacceptable for the production of LIB cathode materials. Further purification is required before the material can be used in production. Solvent extraction can achieve higher product purity than pyrometallurgy or precipitation methods, but also requires multiple equilibration stages (mixer / settler units) to achieve high product purity (>99%). To produce high purity Mn product, the extractant di-(2-ethylhexyl) phosphoric acid (P204, HDEHP) is commonly used, while Co is separated from Ni using 2-ethylhexyl 2-ethylhexyl phosphonic acid or similar. Lithium ions often remain in the aqueous phase in the solvent extraction process and can be precipitated as lithium carbonate. However, significant losses of Li to the organic phase occur during extraction of Mn, Co, and Ni. Solvent extraction has high capital costs, high initial purchase costs for solvents, and equipment is specific to the feedstock.

[0018] The electrodeposition process uses concentrated chloride salts to form anionic cobalt chloride complexes, while Ni remains as a cationic species. Co and Ni are separated in an electric field with the addition of a polymer electrolyte to adjust the selectivity. However, relatively low purities have been reported, 96.4% for Co and 94.1% for Ni. Both are recovered as mixtures of metals, which must be oxidized and redissolved in strong acid before purification. The sulfurization process uses sulfur and sulfur dioxide to react with the ground cathode material at 1,000 °C to convert the metal oxides to metal sulfides. The reaction products dissociate at high temperature into three immiscible liquids: nickel-rich sulfide, cobalt-rich sulfide, and manganese oxide sulfide. Low recovery yields (<90%) have been reported, and high purity material has not been recovered. Further purification of the products is difficult, as the metal sulfides are insoluble in strong acids (>10 M). [Table 1-1] [Table 1-2] In summary, prior art methods described in the literature are unable to produce high purity (>99.5%) Li, Co, Ni, and Mn in high yields (>99%) from cathode materials for LIBs.

[0019] In contrast, the novel technology described below is based on advanced chromatographic methods, which have a large active surface area per unit volume. The method is more efficient, more productive, and has a smaller footprint compared to solvent extraction methods. High purity (>99.5%) materials can be produced from complex mixtures derived from waste LIBs with high yields (>99%) and high throughput. The first principles and intrinsic parameter-based design methods are versatile and scalable, and can be applied to various feed compositions and production scales. The purification method requires only room temperature, leading to high energy efficiency, low energy costs, and low GHG (greenhouse gas) emissions. In addition, less chemical consumption is required than selective precipitation and extraction methods, almost all chemicals can be recycled and reused, and little waste is generated. The entire process is economical and environmentally friendly.

[0020] When the feedstock containing the essential material of interest is a complex mixture, an effective strategy is to first generate concentrates of the target components. Examples include: (1) low-cost physical separation by differences in particle size, particle density, or magnetic properties; (2) free solar energy for concentration by evaporation of water; (3) H + , O.H. - These include precipitation reactions using carbonates, phosphates, sulfates, oxalates, and / or chelating agents. Concentrates containing essential materials can be purified using the novel chromatographic method. The most valuable components in waste LIBs are the cathode materials containing Li, Co, Ni, and Mn. The novel technology is primarily focused on recovering these materials from the cathode materials of LIBs or from any other concentrates containing Li, Co, Ni, or Mn. The examples discussed herein below are primarily focused on recovering these materials from the cathode materials from waste LIBs.

[0021] The new technology uses a versatile multidimensional, multimodal chromatographic method for the separation and purification of essential materials from spent LIB cathode materials and other complex mixtures. Three "dimensions" or axes are considered and evaluated in the design of the separation of the target solute from the impurities: (1) X-axis: the interaction of the solute with functional groups on the stationary phase, e.g., sulfonic acid, iminodiacetic acid, aminophosphonic acid, phosphate, or trimethylammonium groups; (2) Y-axis: the separation mode, including capture, elution, or displacement modes. For each mode, there are two types of operation to consider: batch separation and continuous separation; (3) Z-axis: the interaction or reaction of the solute with agents in the mobile phase, e.g., soluble organic solvents, ions (hydrogen ions, hydroxyl ions), or chelators (see Figure 4).

[0022] Various separation strategies are designed based on three-dimensional considerations, as shown in FIG. 4. A particular separation strategy will have a unique coordinate in the three-dimensional space. In the first dimension (X-axis), the selectivity of various stationary phases (or adsorbents) for the desired product species should be evaluated first. An ideal adsorbent should have high selectivity (>10) for either the product or the impurities. If the adsorbent has high selectivity (>10) for the product species over the impurities and has a large capacity, the adsorbent can be used in a capture process to capture the product species. A capture process (first separation mode on the Y-axis) is relatively easy to design, has high productivity, high yield, and may have the lowest processing cost. Alternatively, if the adsorbent has high selectivity for the impurities, the adsorbent can be used in a capture process to remove the impurities from the product species. An initial screening and evaluation of various adsorbent candidates is performed to select the adsorbent with the highest selectivity and capacity for the capture target. An example of capturing three impurities (iron, copper, and aluminum ions) from the leachate of a LIB cathode material is discussed in Example 1 below.

[0023] The capture method can also be used to separate Mg from Li in Li-rich brines. As discussed in Example 2 below, a column packed with iminodiacetic acid resin can capture Mg ions, while Li elutes first as a high-purity product. A serial capture method is typically used when multiple products are desired and each of the products has an ideal capture adsorbent. For the recovery of multiple components (Li, Co, Ni, Mn) from a feedstock (the leaching of the cathode material of a LIB), a serial capture process for sequentially recovering Mn, Co, Ni, and Li is discussed in Example 3. An example of recovery of Ni from a mixture of Li and Ni in a continuous carousel capture process is discussed in Example 4.

[0024] The high purity LiCl or LiSO4 salts produced from the in-line capture process can be converted to high purity lithium hydroxide (LiOH) in an anion exchange process. - A column pre-equilibrated with LiOH can be used as a trap column for chloride or sulfate ions. The chloride or sulfate ions in the feed solution exchange with the hydroxyl ions in the resin, resulting in the elution of LiOH from the column. The LiOH in solution can be crystallized to produce LiOH solids. This process is discussed in detail in Example 3 below. In traditional production, lithium chloride or lithium sulfate is first precipitated with sodium carbonate (Na2CO3) to form Li2CO3, which is then reacted with calcium hydroxide (Ca(OH)2) to form LiOH. The final product usually contains small amounts of Li2CO3 or CaCO3. The LiOH produced from the anion exchange process is carbonate-free. This process is discussed in Example 5 below.

[0025] If the desired components have similar structures and properties, fractionation methods (second and third separation modes on the Y-axis), such as elution or displacement methods, can be designed to recover the individual components. An example of displacement separation to recover Li, Co, Ni, and Mn from the leachate of LIB cathode material is discussed in Example 6. A pilot-scale study of Li purification is discussed below in Example 7. This example was a direct 10-fold or greater scale-up from the lab-scale studies, thus demonstrating the scalability of the purification process. A four-zone simulated moving bed for separation of Ni from Li in a binary mixture is discussed in Example 8. A six-zone simulated moving bed for continuous partitioning of Li from Ni, Co, and Mn is discussed in Example 9 below.

[0026] If none of the potential adsorbents (X-axis) have sufficient selectivity for economical capture or fractionation of the product species (Y-axis), a third dimension (Z-axis) is considered. Selective chelating agents or other agents can be added to the mobile phase, elution, or displacement methods designed to achieve separation and recovery. The choice of separation mode (Y-axis) depends on the number and properties of the desired products. If a single product is desired and an ideal sorbent is available, capture chromatography can be used to capture the desired product or capture all impurities. If multiple products are desired and there is an ideal capture sorbent for each of the products, a serial capture method is typically used. If there is an ideal sorbent for only one or a few products, but not all products, capture or serial capture combined with fractionation methods can be considered and designed to recover all desired products. If there is no ideal capture sorbent for any of the desired products, a fractionation process can be considered and adjusted based on the separation factor of the sorbent or interactions or reactions in the mobile phase (Z-axis).

[0027] The general design methodology disclosed herein is applicable to a wide range of feed compositions, process scales, and product requirements (see Figures 5A-5C). The system dimensions and operating conditions can be adapted to any scale for any feed composition. The methodology is robust and can account for variations in composition and operating conditions. A general kinetic model and simulation package has been developed based on detailed kinetic models of multicomponent adsorption and chromatography with reactions in the mobile or stationary phase. The model is capable of simulating reactions and separations in single column, carousel, simulated moving bed, and other continuous chromatographic processes.

[0028] The model is a general simulator that can generate "digital process twins" of a wide range of liquid chromatography systems with reactions, i.e. accurate models of real processes. The simulations so generated are based on first principles and intrinsic parameters (scale independent). The basic mechanisms of convection, axial dispersion, membrane mass transfer, intraparticle diffusion, pore diffusion, and surface diffusion are considered in the mass balance using general rate equations. The solute adsorption / desorption phenomena are considered with various equilibrium or non-equilibrium adsorption rate equations. The various reactions in the mobile or stationary phase are considered with specific reaction rate equations. The intrinsic parameters of these processes can be estimated, for example, by using a few laboratory-scale experiments. Based on the parameters, the rate models, and the specific operation, the model generates dynamic column profiles and elution histories to unravel complex multicomponent adsorption, reaction, and separation phenomena in batch or continuous processes.

[0029] Models are valuable tools for teaching, researching, or developing new theories or new processes. After some validation of the kinetic models and intrinsic parameters using a few laboratory-scale tests, model simulations can minimize the number of actual experiments required, reducing the time and cost of developing new theories or new processes. Dynamic column profiles and elution histories can be simulated in minutes using a personal computer, whereas actual experiments can take days or weeks. After successful testing of the models and parameters at laboratory scale, the models can be used to scale up the laboratory-scale process to pilot scale for further testing, and then the process can be scaled up for commercial production. The models can also be integrated with models of pre-chromatographic or post-chromatographic operations in a plant-wide model for optimization of the entire production process to develop the most economical and environmentally friendly process. The above capture and purification method was also generalized for the design of affinity chromatography (with highly selective ligands on the stationary phase), which is widely used for the recovery of antibodies, enzymes, or other biochemicals. This generalized design method based on analytical solutions and intrinsic parameters was predictive and did not require process simulation or extensive experiments. Once the intrinsic adsorption and diffusion parameters were estimated from a few bench-scale experiments, it was straightforward to design an efficient capture chromatography process that met the yield and throughput requirements.

[0030] Models have been useful in the development of chromatographic theory and methods for systems with selectivity functionalities (chelators) immobilized on the mobile phase and / or on the stationary phase. In this application, model simulations are used to support the validity of new methods. Close agreement between model-simulated chromatograms and experimental chromatograms obtained from the new design methods further supports the validity of the new design methods. Using examples, the following methods for recovering and purifying essential materials from waste LIBs or Li-rich brines are described in detail below: (1) single column (batch) capture method, (2) in-line capture method, (3) anion exchange method, (4) continuous carousel capture, (5) displacement fractionation method, and (6) continuous multi-zone simulated moving bed fractionation.

[0031] Fixed-pattern single-column (batch) capture method Single-column capture methods are simpler to design and implement, and have higher throughput than fractionation methods, such as elution or displacement. For these reasons, capture methods are typically tested and evaluated first before considering elution or displacement methods. Typically, various sorbents are screened for high selectivity (>10) for the desired product and / or impurities. When such affinity sorbents are available, a single-column capture process can be designed, tested, and evaluated. The single-column capture process consists of three steps: (1) capture of the target component from a complex mixture, (2) washing to remove non-adsorbed components, and (3) stripping of the target component (see Figure 6A).

[0032] The concentration profile in a single-column capture process is shown in Figure 6B. The concentration wave spreads due to the effects of diffusion and dispersion. The length of the region where the concentration changes from 95% to 5% of the feed concentration is defined as the length of the mass transfer zone at a cut of 0.05 (θ = 0.05) (Figure 5B). The length of the mass transfer zone increases (t1-t3) as the concentration wave moves through the column. If the column is long enough, the wave spreading is offset by the wave sharpening due to adsorption, and the concentration wave shape and the length of the mass transfer zone remain fixed (t4). This wave is called a constant pattern wave. Advantages of fixed pattern capture. Fixed pattern design methods for batch and continuous capture are described herein. In single column capture (or batch capture), the highest column capacity utilization can be achieved by operating in a fixed pattern. This is beneficial when expensive sorbents are used to capture valuable products. The fixed pattern design method can also guarantee the required capture yield for the target product. The design is also relatively simple, flexible, and robust to variations in feed concentration, linear velocity, and column volume.

[0033] Minimum column length to form a consistent pattern. If a consistent pattern wave forms before exiting the column, it will travel the remainder of the column without changing its shape. The length of the mass transfer zone remains the same. Extra column length will not improve the rate, but will result in longer capture times and therefore lower adsorbent productivity (on a per column volume basis). To maximize productivity, it is advantageous to find the minimum column length to reach a consistent pattern in the capture process. A general correlation for predicting the minimum column length to reach a consistent pattern in a single column capture process is described below. Given a feed composition c f and the supply volume V f For an ideal system (no wave spreading due to diffusion or dispersion effects), the minimum column length to capture all of the desired solute is given the feed concentration c f It depends on the equilibrium column volume at f When equilibrated at a given feed concentration c f Equilibrium column volume q f can be described using the Langmuir isotherm:

[0034]

number

number

number

[0035] The general dimensionless column length φ is L c Against L c,id It can be expressed as a ratio of

number

[0036] In the formula, L f is the loading factor, which is defined as the fraction of the equilibrium capacity used for capture.

number

[0037]

number

number

[0038] In the capture chromatography wave, α e is infinite, and therefore,

number

number

number

number

number

number

[0039] In a diffusion controlled system, equation (5a) becomes:

number

[0040] In a capture system in which equation (3a) is applied, equation (4) becomes:

number

[0041] In a diffusion-controlled capture system, Eq. (6b)

number

number

[0042] In a diffusion-controlled system, φ min is N D is a function of φ, which divides the design space into a transient region of single-column capture and a constant pattern region. min vs. N D A plot of N is shown in Figure 7A.D At φ = 1, min is approximately 1.9, which means that the minimum column length to reach a constant pattern for capture is the corresponding ideal system column length L c,id This means that the ratio is about 1.9 times that of the original value.

[0043] The derivation of the general correlation makes the following assumptions: (1) the adsorption isotherm is highly nonlinear; (2) the amount of solute remaining in the intraparticle voids is negligible compared to the amount adsorbed; (3) the system is diffusion controlled; and (4) the feed concentration (c f The value of the column volumetric capacity (q f ), which is much lower than that of trapping chromatography. The same assumptions should be met when applying the general correlation to trapping chromatography. The minimum column length estimated from this general correlation is conservative because the correlation is based on a cutoff of 0.0001 of the mass transfer zone length. Combining equation (3b) and equation (6d), we get

number

[0044] Equation (7) can be rearranged to obtain the minimum column length at a given feed volume to reach a constant pattern trapped front wave.

number

number

[0045] Combining the column length equation (8) with equation (9a),

number

number

number

[0046] Equation (9c) reveals that productivity is a function of linear velocity at a given feed volume. The higher the linear velocity, the higher the productivity. However, the linear velocity is limited by the maximum pressure drop of the system. The pressure drop across the column can be calculated using the Kozeny-Karman equation as shown below:

[0047]

number

[0048] The capture targets can be either the desired product components or the undesired impurities. If the adsorbent has high selectivity (separation factor >10) for a single desired product component, the capture process is designed to capture the desired product in high yield (>99%), while weakly adsorbing or non-adsorbing impurities are displaced by strongly adsorbing components and collected in the column eluate during the loading and washing steps. A breakthrough cut of 0.05 or less can be used to achieve high yields (>99%) of the captured components. The adsorbed components are then stripped as high purity products. If the adsorbent has high affinity for multiple desired product components in the feedstock, the capture process is tailored to capture all the desired components in high yield. After washing to remove impurities, the desired product components can be stripped as a mixture or concentrate of desired products, which can be further separated or purified by other methods.

[0049] If the adsorbent has a high affinity for all impurities, the capture process is tuned to capture all impurities. Weakly adsorbing or non-adsorbing product components are collected during the loading and washing steps. The collected mixture of desired products can be further separated or purified by using fractionation methods. The capture column is then regenerated by stripping the adsorbed impurities. When both product trapping and impurity trapping adsorbents are available at similar cost, and the cost of stripping chemicals is also similar, an adsorbent with a higher trapping capacity for minor components is typically selected for the trapping process to reduce the required column volume and the amount of stripping chemicals required.

[0050] Serial constant pattern acquisition method Impurity capture. Black mass originates from waste lithium-ion batteries. It can be used as a feedstock for producing high purity salts of metal oxides, e.g., Li, Mn, Co, and Ni, for producing metal oxides for NMC cathode materials. Black mass includes carbon black, graphite, and metal oxides, and also has small or trace amounts of various impurities. A calcination step is first used to remove the organic binder in the black mass, followed by a sieving step to remove large particles (e.g., particles with dimensions greater than 106 μm), which are mainly iron, copper, and aluminum. Carbon black and graphite can then be separated from the cathode material (metal oxides) using flotation or density separation methods based on density and / or particle size differences. However, the metal ion impurities Fe 3+ , Cu 2+ , and Al 3+ may be present along with the metal oxides from the black mass. Some chelating resins, such as iminodiacetic acid and aminophosphonic acid resins, have a high affinity for such impurities. Trapping processes have been designed to trap the impurities. The desired essential material (Li + , Mn 2+ , Co 2+ , and Ni 2+ ) and impurities (Fe 3+ , Cu 2+ , and Al 3+ The leachate containing the desired ions is fed to a trap column where the impurities are adsorbed and the desired ions are eluted ahead of the impurities. A mixture containing only Li, Mn, Co, and Ni salts is produced and can be used for the manufacture of NMC cathodes or as a feedstock for further purification to produce high purity individual elements. An overview of this process is shown in Figure 8.

[0051] Mn 2+ , Co 2+ , and Ni 2+In-series capture of. If selective adsorbents are available for capturing each individual component from a complex mixture, the capture method can be applied in series to produce high purity Li, Co, Ni, and Mn salts as an alternative to single column fractionation methods. After impurity capture, the leachate contains only Li, Mn, Co, and Ni ions. Highly impure Mn, Co, Ni, and Li salts can be produced by a three-step in-series capture process (see Figure 9A). At pH 2.5, Mn in the leachate 2+ was selectively captured by the HDEHP-impregnated resin, while other components in the leachate were not adsorbed. The captured Mn was either stripped using dilute acid and precipitated by adjusting the pH of the solution to 9 to produce high-purity Mn hydroxide, or crystallized as high-purity Mn sulfate. The pH of the Mn-free eluate containing Li, Co, and Ni from the Mn trapping column was adjusted to pH 4.5 and then loaded onto a Cyanex272 impregnated resin column, where Co was selectively trapped at pH 4.5, but Li and Ni were not adsorbed. After dilute acid stripping, a high purity Co salt solution fraction was produced from this column and precipitated as hydroxide by adding base to adjust the pH of the solution to 6. The Co fraction can also be crystallized to form Co salt crystals. The early eluate from this column contained only Li and Ni.

[0052] A chelating resin with iminodiacetic acid functional groups has a much higher affinity for Ni than for Li (separation factor >10) and was used to capture Ni from a binary mixture of Li and Ni. The early eluting Li was collected in the eluate as a high-purity fraction, which was precipitated as the carbonate salt. The Ni captured on the column was stripped off using acid. The Ni in the acid solution could be precipitated as high-purity Ni hydroxide (by using base) or crystallized as high-purity Ni salt.

[0053] Anion Exchange The Li product produced from the purification step is typically either the chloride or sulfate salt, however, synthesis of cathode active materials for lithium-ion batteries will require either Li2CO3 or LiOH. Conventional methods for producing high-purity Li2CO3 require the addition of a precipitant, such as Na2CO3, at high temperature and washing the precipitated Li2CO3 with hot water. The product from one-step precipitation usually cannot meet the purity requirements of cathode active material synthesis. Therefore, in the known art, multiple steps of re-dissolution and re-precipitation are required to increase the purity. The conventional method for producing high purity LiOH from these salts involves the following steps: (1) precipitation of Li using Na2CO3, (2) filtration and drying of the Li2CO3 solid, (3) reaction of Li2CO3 with lime to form LiOH and CaCO3, (4) leaching of LiOH, and (5) evaporation and crystallization of LiOH. This conventional method is lengthy and carries a high risk of Ca or carbonate contamination of the final product.

[0054] Alternatively, in this new technology, an anion exchange capture process is produced based on the fixed pattern capture technology disclosed herein. Type I anion exchange resin has a higher affinity for sulfate and chloride than hydroxide. High purity LiCl or Li2SO4 solution collected from the in-line capture process can be used as the feedstock. When the Li salt solution is loaded onto the column saturated with hydroxide ions, chloride and / or sulfate ions can displace the hydroxide ions and be captured on the column. The eluent is high purity (>99.9%) LiOH. If Li2CO3 is required as a product, carbon dioxide gas can be used to convert the high purity LiOH to Li2CO3 without introducing other impurities. This new method has fewer steps and is substantially free of contamination compared to the conventional method.

[0055] Fixed pattern carousel capture Single-column trapping methods typically have limited column volume utilization as the flow rate for trapping increases. Wave broadening due to mass transfer resistance increases with increasing flow rate. To maintain high trapping yields of >99%, the breakthrough cut is typically kept below 0.05. As a result, a large portion of the column is required to contain the broadened concentration wave, resulting in low utilization of the adsorbent volume.

[0056] When the adsorbent is virtually completely selective for the target solute, high product yield, high throughput, and high column utilization can be achieved by designing the carousel capture process. A carousel process for capture usually has three or more segments. When the feed has no unadsorbed impurities, a three-segment carousel can work to recover the target solute, as shown in Figure 9A. In step 1, segments A and B are connected, the first segment A is used as a "saturation" column, segment B is used to trap the concentration wave, and the third segment is a reserve segment. At the end of step 1, segment A is fully saturated. In step 2, the feed port is switched from the inlet of A to the inlet of B, and the outlet of B is connected to the inlet of C to continue the capture process, while segment A is stripped to recover the target solute. In step 3, both the feed and stripping ports move to the next segment. Now segments C and A are connected to continue the capture process, while segment B is stripped to regenerate.

[0057] If the feed contains non-adsorbed impurities, a washing step can be added before the stripping step to remove non-adsorbed impurities from the voids or particle pores of the bed. This washing step can prevent non-adsorbed impurities from contaminating the product. Alternatively, a four-segment carousel process can be implemented with a washing zone before stripping, as shown in Figure 9B. In step 1, segments A and B are connected, the first segment A is used as a "saturation" column, segment B is used to trap the concentration wave, and the third segment is a reserve segment. Non-adsorbed or weakly adsorbed impurities are collected as waste in the eluate of B. At the end of step 1, segment A is fully saturated. In step 2, the feed port is switched from the inlet of A to the inlet of B, and the outlet of B is connected to the inlet of C to continue the capture process. During the loading of B and C in step 2, a washing solvent is used to remove non-adsorbed impurities in the voids or pores of the adsorbent bed of segment A, and the eluate from segment A is collected as waste.

[0058] In step 3, both the feed and wash ports move to the next segment. Segments C and D are now connected to continue the capture process while segment B is washed. Segment A is stripped and regenerated. The captured product is collected in the eluate of segment A. In the last step of the first cycle, all ports move to the next segment. Segment D is connected to segment A, cleaned in step 3, to continue capturing product from the feed while segment C is washed and segment B is stripped and regenerated. After three cycles, the carousel process typically reaches a cycle steady state. In this new technology, the length of the column segments is designed to reach a fixed pattern state for trapping a single component. The adsorption isotherm in most high affinity systems follows the Langmuir (convex) isotherm. If the column is long enough, a fixed pattern mass transfer wave will eventually develop within the column in the Langmuir system. The column capacity in the mass transfer zone is not fully utilized. The segment lengths and flow rates in the carousel process are designed to reach a fixed pattern concentration wave as described in the single column trapping process.

[0059] One simple design method is to make the first segment completely saturated with product and the second segment just contain the fixed pattern mass transfer zone (Figure 9C). In this design, the combined length of the two segments is the minimum column length in the fixed pattern design method for single column capture. Assuming that the wave spreading in the second segment is symmetric, the loading factor should be 0.75. The total column length can be calculated from equation (3a) by setting the loading factor to 0.75.

number

number

[0060] The linear velocity required to reach a constant pattern is given by L c It can be calculated from equation (8) using This constant pattern design can ensure the highest productivity with the desired yield of captured product. The carousel process can be implemented not only for the capture of impurities from the black mass, but also for each capture process of the serial capture process to produce individual elements with high purity.

[0061] Substitution fraction Displacement fractionation uses only one adsorbent and a minimum amount of solvents and chemicals, potentially minimizing separation costs. Displacement chromatography uses the displacer with the highest affinity to the adsorbent to displace, separate, and concentrate the adsorbed solutes (see Figure 10). During loading, the high affinity solute displaces the low affinity solute, resulting in the appearance of a band of the low affinity solute. Partial separation occurs during loading (t1). After loading (t2), a strongly adsorbing displacing agent is introduced into the column. The displacing agent has the highest affinity for the stationary phase, so it displaces the high affinity solute component, which in turn displaces the low affinity solute component. The mixing region between the low affinity solute band and the high affinity solute band narrows (t3) as the displacing agent displaces the two solutes in the column, and is finally removed (t4). This is called the "self-sharpening effect" in displacement systems. The low affinity solute and the high affinity solute form trapezoidal bands with sharp boundaries. These two bands move through the column at the same speed as the displacing agent front (t4-t6). This is called the formation of an "isotachic train" in displacement chromatography.

[0062] Specifically, resins with iminodiacetic acid functional groups can be used to separate metal ions in LIB cathode leachates because they are Ni 2+ It is highest for 2+ , followed by Mn 2+ , and Li + The selectivity between adjacent elements is quite high (typically greater than 4). Convenient presaturants are species that exhibit lower selectivity than the divalent metal of interest. For example, Na - or NH4 +It is possible to start with an IDA column presaturated with H (see Figure 11). During feed loading, partial separation occurs as Ni displaces Co, which in turn displaces Mn. The weakly adsorbed Li elutes early. Feed loading is followed by a wash step to further remove weakly adsorbed Li and ensure adsorption of the feed components in the voids. The IDA resin is H + Since dilute acid (0.5M) has the highest affinity for , a displacement band will appear on the column, and a high-purity salt will be produced. After displacement, the column is washed with H + and is regenerated by a NaOH (or NH4OH) wash followed by a water wash.

[0063] Alternatively, in conventional substitution, Na is used as a presaturant. + or NH4 + , and H as a substitute + Instead of using species such as Li, the component with the lowest affinity in the complex mixture to be separated, can be used as the presaturating agent, and Ni, the component with the highest affinity, as the displacing agent (see FIG. 12). In this case, the column is pre-equilibrated with Li. When the feed mixture is loaded onto the column, partial separation occurs in the loading zone, while Li elutes early. As with conventional displacement, a washing step may also be required to wash out the non-adsorbed solutes and ensure adsorption of the solutes in the voids of the loading zone. A Ni salt solution is used as the displacing agent to induce isotactic train in the column. After displacement, the column is saturated with Ni ions, which can be quickly stripped off using dilute acid. The column can then be washed and regenerated with LiOH and water.

[0064] H as the replacement species + Instead of Ni 2-When using Na, higher displacement agent concentrations can be used because it is less corrosive to the equipment and adsorbent. This results in higher displacement band concentrations, higher product concentrations, and higher adsorbent productivity. The use of Li as a presaturant eliminates an additional Li purification step by producing pure Li directly from the column. + or NH4 + When species such as are used as presaturants, they show similar selectivity and therefore co-elute with Li.

[0065] Using the fixed pattern design method in non-ideal displacement chromatography, the operating conditions (feed volume V) to achieve a particular yield or purity requirement for a given feed mixture and a given column are determined. f and linear velocity u0) can be obtained. A general correlation, equation (4), was developed to predict the minimum column length required to form a constant pattern isotactic train in a nonideal displacement system.

[0066] The component (Y i The yield of

number

number

number

number

[0067] The purity of the components can be correlated with the yield and the breakthrough cut.

number

number

number

number

number

number

number

[0068] If a target yield is not specified, a range of linear velocities can be scanned to find the maximum productivity. For each linear velocity, the Peclet number, the dimensionless membrane mass transfer coefficient, and the dimensionless pore phase diffusion coefficient are calculated. The specific dimensionless overall mass transfer coefficient

number

number

[0069] The constant pattern design method does not rely on experimental trial and error or simulation. By operating the system with a general constant pattern correlation, the formation of a constant pattern isotactic train is guaranteed, where the length of the mass transfer zone can be calculated using shock layer theory and intrinsic parameters. The length of the mass transfer zone and the mass balance equations can be used to predict yield and productivity. By solving algebraic equations including the yield equation (Eq. 12), the purity correlation (Eq. 14), and the mass transfer correlation, the operating parameters including the loading volume and flow rate are determined. This design method allows for easy and fast optimization of displacement chromatographic separations.

[0070] Several assumptions are made for the development of the design method: (1) the amount of solute remaining in the voids within the particles is negligible compared to the amount of solute adsorbed, and (2) the value of the nonlinear distribution coefficient is

number

[0071] In the novel technology of the present invention, several modifications are made to accommodate specific displacement separation configurations where (a) the nonlinear distribution coefficient is not much greater than 1 (see Examples 6 and 7), (b) presaturants or displacing agents are components in the feed mixture (Examples 6.2 and 6.3), and (c) high linear velocities are applied for the feed loading and washing steps to reduce the overall cycle time and increase the adsorbent productivity (Example 7). A detailed description of the novel features is provided below.

[0072] In configuration (a), the capacity of the adsorbent, q d is the concentration of the displacing agent c d When the order of magnitude of the nonlinear distribution coefficient is the same as that of the nonlinear distribution coefficient, the nonlinear distribution coefficient is not much larger than 1.

number

number

[0073] In configuration (c), the linear velocity during loading can be increased to reduce cycle time. Because adsorbents have different selectivities for different solutes, the original design method for displacement fractionation considers partial separation of components during loading. If high linear velocities are applied for the loading and washing steps, mass transfer resistance will significantly impair partial separation. This results in the formation of a nearly uniform mixed band near the inlet of the column. As the displacing agent is introduced into the column, a displacement train begins to form. Instead of the design method for displacement chromatography, the design method previously developed for ligand-assisted displacement chromatography can be used.

[0074] Sequential fractionation in multi-zone, multi-mode SMB Simulated moving bed (SMB) is a specific type of continuous chromatography. A typical SMB has eight columns connected in a loop with two inlet ports (for the addition of desorbent and feed) and two outlet ports (for the withdrawal of extract and raffinate products) (Figure 4C). The ports move periodically along the mobile phase flow direction to follow the solute bands moving in the loop. The movement of the ports simulates the movement of a countercurrent bed in the loop. High purity, slow moving solutes are withdrawn from the extract port, while high purity, fast moving solutes are withdrawn from the raffinate port. The feed is introduced in the band overlap region. Unlike batch chromatography, SMB produces pure products in high yields without the need for complete separation of the two solute bands in the loop. In SMB, the product is not diluted and a significantly larger portion of the stationary phase is utilized. For these reasons, SMB can produce concentrated pure products in 99% yield, with adsorbent productivity and solvent efficiency about 10 times higher than batch chromatography.

[0075] One conventional design method, called the "trigonometric method," was based on the assumption of an "ideal system" where diffusion or dispersion effects were negligible. This assumption is only valid for systems with micron-sized adsorbent particles, which are costly and require the use of high-pressure equipment (>1,000 psi). The trigonometric method cannot guarantee product purity or yield in economical low-pressure SMB systems with large adsorbent particles.9 Extensive exploration using simulations or experiments in the design parameter space is required.

[0076] A concentration standing wave design method was developed based on the concept of confining specific concentration waves to specific flow zones in a multi-zone SMB to control product purity and yield. The key idea is to match the target concentration wave velocity with the average port velocity in an ideal system. In a non-ideal system, the flow rate is adjusted from that of the ideal system based on theoretical and intrinsic adsorption parameters, dispersion coefficients, intraparticle diffusion coefficients, and zone lengths. After the intrinsic adsorption and mass transfer parameters are estimated and verified using small column tests, the operating parameters are solved directly from the simultaneous algebraic equations. This method was extended to non-linear adsorption systems and non-isocratic systems with thermal or pH gradients. A fast design and optimization method, called the "Speedy Standing Wave Design" (SSWD) method, was also developed based on the dimensionless group. Fourteen decision variables can be optimized to achieve either maximum productivity, minimum solvent usage, or lowest separation cost. This method was extended to non-linear adsorption systems and non-isocratic systems with thermal or pH gradients. A fast design and optimization method based on dimensionless groups, called the "Speedy Standing Wave Design" (SSWD) method, has also been developed. Fourteen decision variables can be optimized to achieve either maximum productivity, minimum solvent usage, or lowest separation costs. The optimization calculations can be performed in a few seconds using a laptop. In contrast, the literature method requires millions of kinetic model simulations to search in a nine-parameter space. Each simulation requires solving multiple simultaneous partial differential equations, and the optimization problem can take days on a fast computer, with no guarantee that a global optimum will be found.

[0077] In the present novel technology, a general standing wave design methodology is developed for splitting an N-component mixture to produce two or more products in a multi-zone SMB, as described below. A new multizone, multimodal SMB fractionation of complex mixtures. The adsorbents in conventional SMB methods were based on functional groups in the stationary phase. Binary or ternary mixtures were split into two products, raffinate or extract, in an SMB with three or four zones. The desorbent was the same solution or solvent for the feed components. The separation mechanism was based on elution separation with a desorbent of constant composition, temperature, pH, ionic strength, or solvent strength.

[0078] In this new technology, the functional groups can be present in the mobile or stationary phase. Two or more desorbents can be used to split the mixture into three fractions with high purity and high yield. In addition to the desorbent in the separation zone of the elution separation, a second desorbent (or stripping agent) can be used in a separate zone to strip out the strongly adsorbed products or impurities in the stripping zone. The adsorbent can be regenerated, washed, and re-equilibrated in separate zones. A multi-zone SMB can have more than four zones consisting of stripping, washing, regeneration, and re-equilibration zones in addition to the elution or displacement separation zone. Two or more SMBs based on different adsorbents can be designed in series for fractionation of complex mixtures. Herein we define a new multi-zone, multi-mode SMB (abbreviated as mSMB).

[0079] A new general design method for determining the operating zone and port velocities of mSMB is developed and described below. The general method is based on intrinsic adsorption and mass transfer parameters and instrumental parameters and applies to various functional groups on the stationary phase or in the mobile phase. Separation mechanisms include size exclusion, hydrogen bonding, ion exchange, chelation, affinity, or a combination of various mechanisms. The operating parameters that enable high purity products to be produced in high yields in mSMB can be found without empirical exploration in a multidimensional design parameter space. The new design method is verified using VERSE simulations or experimental data in the examples. A column pre-packing strategy is also developed to shorten the start-up period of SMB to a few steps, whereas traditional SMB start-up (with clean columns) requires more than three cycles to reach cycle steady state. Standing wave design methods in mSMB. Some newer adsorbents are selective for Li based on functional groups with high affinity for Li or special adsorbent structures that favor the adsorption of Li to the exclusion of larger divalent ions. Examples include lithium-aluminum layered double hydroxide chloride, titanium zirconium phosphate, etc. However, these adsorbents are either costly or not currently available in large quantities. Most available commercial adsorbents show high selectivity for divalent ions such as Ni, Co, and Mn rather than Li. Examples of such adsorbents include metal oxides, zirconium phosphates, zeolites, and adsorbents with chelating functional groups such as aminopolycarboxylic acid, citric acid, and bispicolylamine, and combinations thereof.

[0080] A mixture of Li, Ni, Co, Mn (LiNMC for short) can be split into two groups in a three-zone or four-zone SMB. An example of splitting a binary mixture of Li and Ni into two products to produce high-purity Li in the raffinate and high-purity Ni in the extract is shown in Figure 15A. If there is no need to recycle or reuse the desorbent in a particular application, a three-zone open-loop SMB is simpler to design and operate than a four-zone SMB (see Figure 15B). A ternary mixture of Ni, Co, and Li split into two products to produce Ni and Co in the extract and Li in the raffinate is shown in Figure 15C.

[0081] mSMB Method: 4 Zone SMB A four-zone SMB based on size exclusion sorbents, inorganic sorbents, or chelating agents in the mobile phase, which results in a slower rate of Ni migration in the column than Li migration, can be designed for the separation of Li and Ni in a closed-loop four-zone SMB or a three-zone open-loop SMB where the desorbent is not recycled. In a particular application, if there is no need to recycle or reuse the desorbent, the three-zone open-loop SMB is simpler to design and operate than the four-zone SMB.

[0082] In a continuous moving bed, when wave spreading is negligible (defined as an ideal system), e.g., in a system with adsorbent particles of a few μm, the port velocity can be simply matched to the travel velocity of the important wave in each zone. The important waves are (1) the desorption wave of the slow moving solute Ni in zone I, (2) the desorption wave of the fast moving solute Li in zone II, (3) the adsorption wave of the slow solute Ni in zone III, and (4) the adsorption wave of the fast solute Li in zone IV. In a linear system with constant wave travel velocity, e.g., a size exclusion system or a system with a linear adsorption isotherm, the wave velocity of component i in zone j is

[0083]

number

number

number

number

number

[0084] Retention Factor

number

number

number

number

number

number

number

number

number

[0085] In an ideal system, there are six unknowns (four zone speeds, port speed, and feed rate) and five equations to solve. To obtain a unique solution, one parameter must be fixed. If the feed rate is fixed, the five SMB operating parameters, u0, can be solved using the five equations in (15a-d) and (16). I , u0 II , u0 III, u0 IV , and v can be solved. If the port speed is fixed, five equations can be solved for the feed speed and the four zone speeds.

[0086] Non-ideal standing wave design method for separation of binary mixtures in a four-zone SMB. In non-ideal systems with significant wave spreading, the gap velocities in Zones I and II can be adjusted so that the critical wave velocities in these two zones are greater than the port velocity, while the critical wave velocities in Zones III and IV are less than the port velocity. The difference between the wave velocities and the port velocity can focus the critical waves in each zone so that they remain confined to their respective zones at the cycle steady state. The adjustment of the gap flow velocity in each zone is derived previously for linear non-ideal systems as follows:

[0087]

number

number

[0088]

number

number

number

number

number

[0089] If there is no need for desorbent recycle, zone IV in Figure 15A can be omitted as shown in Figure 15B. In this case, only three pumps are required, and therefore the design equations for the four-zone SMB can be adapted for a three-zone SMB.

[0090] A non-ideal standing wave design method for separating a multicomponent mixture into two products in a four-zone SMB. An example of partitioning a ternary mixture of Ni, Co, and Li into two products to produce high purity Li in the raffinate and a mixture of Ni and Co in the extract is shown in FIG. 15C. To ensure high purity and high yield separation, the Ni desorption wave can be confined to zone I, the Li desorption wave to zone II, the Co adsorption wave to zone III, and the Li adsorption wave to zone IV. Note that in this method, the Co adsorption wave in zone I, which moves faster than the Ni adsorption wave, automatically focuses or "sandwiches" toward the boundary between zone I and zone II. Similarly, the Ni adsorption wave in zone III, which moves slower than the Co adsorption wave in zone III, is "sandwiched" in the region between zone II and zone III. The stationary component of the SWD equation, equation (17), can be modified accordingly. The operating parameters solved from the SWD equation can ensure high purity and high yield of both the raffinate and the extract.

[0091] Partitioning of a quaternary mixture of Ni, Co, Mn, and Li into two products, Ni and Co in the extract and Mn and Li in the raffinate, is shown in FIG. 15D. To ensure high purity and high yield partitioning, the Ni desorption wave is confined to zone I, the Mn desorption wave to zone II, the Co adsorption wave to zone III, and the Li adsorption wave to zone IV. Note that the Co desorption wave, which moves faster than Ni, is pinched toward the boundary between zone I and zone II; the Li desorption wave, which moves faster than Mn, is pinched toward the boundary between zone II and zone III; the Ni adsorption wave, which moves slower than Co, is pinched toward the boundary between zone II and zone III; and the Mn adsorption wave, which moves slower than Li, is pinched toward the boundary between zone III and zone IV. In this way, Ni and Co are recovered in the extract and Mn and Li are recovered in the raffinate with high yields.

[0092] This design strategy can be generalized to the separation of a mixture of N components into an extract product containing components 1-j and a raffinate product containing components k-N, as shown in FIG. 15E. To ensure high purity and high yield separation, the desorption wave of component 1 is confined to zone I, the desorption wave of component k is confined to zone II, the adsorption wave of component j is confined to zone III, and the adsorption wave of component N is confined to zone IV. Note that the desorption waves of components 2-j, which move faster than component 1, are pinched toward the boundary between zones I and II; the desorption waves of components k+1-N, which move faster than component k, are pinched toward the boundary between zones II and III; the adsorption waves of 1-j-1, which move slower than component j, are pinched toward the boundary between zones II and III; and the adsorption waves of components k-N-1, which move slower than component N, are pinched toward the boundary between zones III and IV. The standing and pinched waves in FIG. 15A-15E are shown in Table 2A.

[0093] The SWD equations for a non-ideal system that splits an N-component mixture are given below.

number

[0094] [Table 2] SWD method for the partitioning of N-component mixtures in a multizone SMB (mSMB) with a separation zone coupled to a stripping zone and a re-equilibration zone The desorbent in the 4-zone SMB is the same as the solvent for dissolving the feed mixture. The components are separated into two products by isocratic elution in the 4-zone SMB. The faster moving solutes are recovered in the raffinate and the slower moving solutes are recovered in the extract. If the feed contains impurities and the adsorbent has a much higher affinity for the impurities than Ni, Co, Mn, and Li, the impurity removal and column regeneration process can be coupled with the fractionation process in the 4-zone SMB in a series of 8-zone SMBs, as shown in Figure 15F.

[0095] Li is separated from NMC in zones I to IV. The column with strongly adsorbed impurities is then transferred to stripping zone BII. A stripping agent is used to strip the strongly adsorbed impurities, and then the column is transferred to water wash zone BI. Presaturant is then loaded in zone AII, and the column is washed with water in zone AI to remove unadsorbed presaturant. The pre-equilibrated column is then transferred from zone AI to zone IV. The four-zone SMB section for the binary split of Li and NMC can be designed as previously described. The stripping and regeneration zones can be designed to have the same step times as those of the four-zone SMB. This mSMB with eight zones requires eight pumps and 16 columns, with two columns in each zone.

[0096] Adsorbents with chelating functional groups, such as bispicolylamine, iminodiacetic acid, or other aminopolycarboxylic acid functional groups, are much more selective for Ni, Co, and Mn than Li. If an isocratic elution four-zone SMB based on a chelating adsorbent is designed to separate Li from NMC, the NMC in the extract will be diluted many times and the productivity of the adsorbent will be low (see Example 8). A 6-zone SMB based on IDA-functionalized resin is shown in Figure 15G. In this new design, the strongly adsorbed solute NMC is stripped in zone BII. Zone I, loaded with the feed, is washed with water (or a weak desorbent) in zone I to confine the Li desorption wave to zone I so that there is no loss of Li to the stripping zone. Zone II is not required because the slow moving solute NMC is recovered in stripping zone BII. The feed is added between zone I and zone III. The Mn adsorption wave is confined to zone III, so the Co and Ni adsorption waves are sandwiched between zone I and zone III, and there is no loss of NMC to the raffinate. Zone IV is omitted because there is no desorbent recycle. When the port velocity is fixed, the feed rate and the velocities of zone I and zone III are determined from the standing wave equation to achieve high yields of high purity products.

[0097] This 6-zone design in Figure 15G requires 6 pumps and the column has 6 inlet options, but most lab-scale SMBs only have 4 pumps and 4 inlet / outlet options. The design in Figure 15G can be further simplified to 4 zones with 4 pumps as shown in Figure 15H. To reduce the number of pumps, zones BI and BII are combined to share one pump. Zones AI and AII are combined to share one pump. The design in Figure 15H was tested in a lab-scale SMB and detailed results are reported in Example 9. The standing and pinching waves in Figures 15F-15H are shown in Table 2B. [Table 3] EXAMPLES

[0098] Example 1 Capture of impurities from LIB black mass derived leachate The black mass comes from waste LIBs and contains graphite, carbon black, cathode active material, and trace amounts of other metal oxide impurities. Graphite and carbon black can be separated from metal oxides using physical separation methods based on different density and / or particle size. Metal oxides can be converted to soluble salts by an acid leaching step. The leachate is a mixture of the target products Li, Mn, Co, and Ni with trace amounts of impurities such as Fe, Cu, Al. Removal of these impurities is useful. These impurities have a higher affinity to HDEHP impregnated resin, iminodiacetic acid (IDA) resin, or aminomethylphosphonic acid (AMP) resin than the target elements. A fixed pattern capture design method is applied to capture the impurities from the leachate.

[0099] A leachate containing 0.29N Li, 0.09N Mn, 0.18N Co, 0.27N Ni, and 0.05N Fe (as a synthetic leachate containing Fe as a representative impurity) was prepared. A laboratory-scale batch process for impurity capture was designed following the fixed pattern design detailed above. A 50 cm column made of glass with a diameter of 1.5 cm was packed with HDEHP impregnated resin. Li, Mn, Co, and Ni do not adsorb, whereas Fe is strongly adsorbed. The feed was loaded onto the column at a flow rate of 1.5 mL / min (2.43 cm / min). The impurities were captured by the column. The simulated eluate history from the capture column is shown in Figure 16. The eluate history is a mirror image of the column profile. Impurities with the highest affinity for the resin were trapped and concentrated in the column. A wash step was used after loading to ensure that impurities were trapped in the column voids and that non-adsorbed components were washed away. Dilute acid was used to strip impurities from the column and regenerate the column. As shown in the eluate history of this capture process (see Figure 16), the non-adsorbed components Li, Mn, Co, and Ni started to break through at the void volume (0.5 CV). The mixed product of Li, Mn, Co, and Ni without impurities was collected at 0.5-9 CV. All the captured Fe was stripped off in the acid stripping step. The column was then washed with water and reused in the capture process.

[0100] Example 2 Mg from binary Mg / Li mixtures to produce high purity Li products 2+ Capture of In Li recovery from Li-rich brines, Na and K, which are less soluble than Mg and Li and are the majority of impurities, precipitate during solar evaporation. The supernatant containing Mg and Li is collected for further purification.

[0101] A binary Mg / Li solution with a composition similar to that of a brine obtained in Clayton Valley, USA, was used as the feedstock, containing 0.144N Li and 0.041N Mg. A glass column was packed with Purolite MTS9320 (IDA) resin with a selectivity of Mg over Li of 10, a uniform particle diameter of 620 μm, and a capacity of 1.5 meq. / mL (PUROLITE is a registered trademark (Registration No. 4313122, January 15, 2013) of Purolite Corporation, DELAWARE, 2201 Renaissance Blvd., Suite 400 King of Prussia PENNSYLVANIA 19406). A 50 cm column with a diameter of 1.5 cm was packed with the resin pre-equilibrated with Li. The feed was loaded onto the column at a flow rate of 1.5 mL / min (2.43 cm / min). Mg ions were captured by the column. High purity Li salt was produced from the eluate (0.5 CV - 10 CV). The simulated eluate history is shown in Figure 17. After 10 CV of loading, the captured Mg was stripped off using weak acid. The column was washed with water to remove residual acid and reused in the batch capture process. Alternatively, a continuous carousel capture process (see Example 4) may be designed according to the detailed method.

[0102] Example 3 In-line capture for recovery of high purity Li, Mn, Co, and Ni from black mass derived from waste LIBs Capture of Mn. A leachate was obtained from a waste LIB cathode material. It contained 0.2N Li, 0.14N Mn, 0.15N Co, and 0.135N Ni. The pH of the leachate was adjusted to 2.5. A column (length 17.5 cm and diameter 1.16 cm) was packed with Purolite MTX7010 resin (macroporous polystyrene divinylbenzene impregnated with HDEHP). The leachate was loaded onto the column at a superficial velocity of 0.946 cm / min until it was fully saturated. The column was then washed using 1.5 CV of DI water and then stripped with 0.5M HCl. The eluate was collected in fractions and analyzed using ICP. The eluate history is shown in Figure 18. Only Mn was adsorbed onto the column. High purity Mn product was collected during the acid stripping step. If the capture column is long enough, Mn-free fractions can be collected during the loading and washing steps.

[0103] Co capture. A simulated mixture of Mn-free chloride salts of Li, Ni, and Co (Li: 0.1N, Ni: 0.054N, Co: 0.08N) was prepared with a solution pH of around 3.5. The solution pH was titrated to 4.5 using NaOH solution. The solution was continuously stirred and the pH was stable at 4.5 for 20 minutes. This mixture was used as the feed to the column to estimate the Co capacity. The feed was loaded to the column at a superficial velocity of 0.946 cm / min until fully saturated. The column was then washed with 1.5 CV of DI water and then stripped with 0.5 M HCl. The eluate was collected in fractions and analyzed using ICP. The eluate history is shown in Figure 19. Only Co was adsorbed on the column. High purity Co product was collected during the acid stripping step. If the capture column is long enough, Co-free fractions can be collected during the loading and washing steps.

[0104] Ni capture. A Co-free simulant was prepared containing only Li and Ni. The column was packed with Purolite MTS9300 (IDA resin). The feed was loaded onto the column at a superficial velocity of 0.946 cm / min. The eluate was collected in fractions and analyzed using ICP. The eluate history is shown in Figure 20. Only Ni was captured on the column, with the high purity Li product collected in the early eluting fractions, 1.8-4.0 CV.

[0105] Example 4 Carousel trapping for recovery of high purity metal salts from complex mixtures Example 4.1 Carousel capture for recovery of high purity Li from Li / Ni binary mixtures A three-segment carousel was designed to continuously capture Ni from a binary Ni / Li mixture (0.25N Li, 0.15N Ni) with a composition similar to that of the feed solution in the last step of Example 3. Each segment has a column length of 51 cm and a diameter of 5 cm. The total column length is 153 cm. The column was packed with AmberSep IRC748 resin (IDA, 575 μm) (AMBERSEP is a registered trademark (Registration No. 1186259, January 19, 1982) of Delaware's Rohm and Haas Company CORPORATION, 100 Independence Mall W., Philadelphia, PENNSYLVANIA, 191052399).

[0106] The carousel design ensures the formation of a constant pattern concentration wave of Ni in the two segments. To ensure high purity Li product (>99.9%), the feed port can be switched when the Ni concentration reaches 0.5% of the feed concentration at the outlet of the second segment. The eluate history at the outlet of the second segment is shown in Figure 21A. The second segment can always contain a constant mass transfer zone after the cycle steady state because a constant pattern is formed. The column dynamic concentration profile before the feed port switching is shown in Figure 21B. The third segment was used for regeneration. The saturated segment was quickly stripped using dilute acid (0.5 M HCl). High purity Li product was collected at the outlet of the second segment in each cycle, and high purity Ni product was collected during the stripping of the saturated segment.

[0107] Example 4.2: In-line carousel capture and fractionation for recovery of high purity metal salts from spent lithium ion battery leachate As shown in Figures 22A and 22B, two series carousel capture and fractionation processes are designed to recover individual high purity metal salts from spent lithium ion battery leachate.

[0108] The first in-line carousel capture and fractionation process (FIG. 22A) is designed based on the single column in-line capture process of Example 3. The first carousel of this process using MTX7010 as the adsorbent can effectively capture Mn from the leachate adjusted to pH 3. Mn is recovered as high purity salt after stripping from the saturated segment using dilute acid (pH 1). Unadsorbed Li, Co, and Ni will be collected during the loading and washing steps. The collected ternary solution is adjusted to pH 5 and then fed to the second carousel, which uses MTX8010 for effective Co capture. Co can be stripped from the saturated segment as a high purity product. Unadsorbed Li and Ni are collected during the loading and washing steps and separated in the third carousel, which captures Ni using IDA resin. A second example of the tandem carousel capture and fractionation process (FIG. 22B) uses M4195 and MTX7010 resins. M4195 is a chelating resin with bis-picolylamine functional groups. Metal ion adsorption is strongly dependent on the pH of the solution. At pH 1, M4195 resin adsorbs Ni ions but not other metal ions such as Li, Mn, and Co. At pH 2, Co is strongly adsorbed but Li and Mn are not adsorbed. The first two carousels of this tandem carousel design take advantage of this pH-dependent adsorption. The pH 1 leachate is used as the feed to carousel 1, where Ni is captured and stripped as a high purity salt. The ternary mixture of Li, Mn, and Co from carousel 1 is introduced into the second carousel (carousel 2) after adjusting the pH to 2. Co is captured and recovered from this ternary mixture as a high purity product. The final carousel (Carousel 3) will use the MTX7010 to separate Li and Mn into two high purity salts. If desorption of the captured solute is required followed by washing or pre-equilibration prior to loading, more segments can be added to the carousel system.Compared to serial capture processes using a single column and batchwise operation, serial capture processes can continuously produce high purity product and greatly improve column capacity utilization and productivity.

[0109] Example 5 Exchange of hydroxide ions for chloride or sulfate ions to produce high purity LiOH product Type I anion exchange resins (trimethylammonium functional group) have the lowest affinity for OH ions. If a high purity lithium sulfide or chloride salt is loaded onto an anion exchange column pre-equilibrated with OH ions, the sulfate or chloride ions will be retained on the column, and the OH - The ion is replaced by the cation Li + Coeluting with LiOH of high purity was produced.

[0110] Example 5.1 Exchange of chloride and hydroxide ions to produce LiOH In this example, AmberLite HPR9000 OH ion exchange resin was used. The sorbent was a macroporous type I anion exchange resin with a uniform particle diameter of 650 μm and a capacity of 0.8 meq. / mL. The sorbent was packed into a 50 cm column with a diameter of 1.5 cm. The feed 0.5 N LiCl solution was loaded onto the column at a flow rate of 1 mL / min (1.62 cm / min). High purity (99.5%) LiOH was produced. The simulated eluate history is shown in FIG. 23.

[0111] Example 5.2 Formation of Li2CO3 from a mixture of Li2SO4 and (NH4)2SO4 In this example, three Omnifit columns with an internal diameter of 2.5 cm were packed with Amberlite HPR9200 resin (640 μm, macroporous, type I anion exchange) and converted to the OH form (AMBERLITE is a registered trademark of DDP SPECIALTY ELECTRONIC MATERIALS US 8, LLC, LIMITED LIABILITY COMPANY of DELAWARE, 974 CENTRE ROAD, WILMINGTON, DELAWARE, 19805, registration number 0257757, February 23, 1989; OMNIFIT is a registered trademark of DIBA INDUSTRIES LIMITED CORPORATION, Cambridge, England, CAMBRIDGESHIRE, UNITED KINGDOM, CB1 3 HD, registration number 1167022, September 1, 1981). The final lengths of the three columns were 38 cm, 41 cm, and 41 cm, respectively, and a mixture of Li2SO4 and (NH4)2SO4 was used as the feed to the anion exchange column. The feed was 1.29N Li - , 0.71N NH4 + , and 2.0N SO4 2- The feed solution contained 100 mL of the column at a flow rate of 2.5 mL / min. The column was then washed with 600 mL (1 C.V.) of water. The eluate was collected in 10 mL fractions and each fraction was analyzed using ICP-OES to determine the amount of Li + and SO4 2-The concentration of Li was determined. The elution history is shown in Figure 24. The simulation parameters are shown in Table 3. All Li was dissolved in SO4 2- The LiOH was collected without contamination, indicating complete conversion of sulfate to hydroxide. The Li-containing fraction was collected in a beaker and the solution was boiled using a hot plate for 1 hour to remove NH4OH. Excess CO2 gas (10 scfh, 6 hours) was bubbled into the solution to convert LiOH to Li2CO3. The resulting solution was placed on a hot plate and all the water was evaporated to produce the solid Li2CO3 product. A 0.5 g sample of the solid product was collected and dissolved in 50 mL of 2% nitric acid. When this solution was analyzed using ICP-OES, no other cations or sulfates were detected in the solution, indicating high purity Li2CO3 product.

[0112] [Table 4]

[0113] Example 6 Substitution method for separation and purification of Li, Co, Ni, and Mn from waste LIBs This section includes three different examples that demonstrate the displacement fractionation of metal ions from a complex mixture derived from spent lithium-ion batteries. Different adsorbents, presaturants, feed compositions, displacement agents, and operating conditions were used and are summarized in Tables 4 and 5. A summary of the eluate histories of the three displacement examples is shown in FIG. 25. Simulation parameters are shown in Table 6 and a summary of yields and productivity can be found in Table 7. Each example is described in detail below.

[0114] Example 6.1 In this example, AmberSep IRC 748 UPS (IDA functional group) was used as the adsorbent, and ammonium ions were the presaturating agent. Dilute acid (0.5N H2SO4) was used as the displacing agent. The fractionation process was designed based on the constant pattern displacement design method (Section V5). For the design parameters, pulse tests were used to estimate porosity, single component frontal tests were used to estimate adsorbent capacity and diffusivity, and binary mixture frontal tests were used to estimate selectivity. The composition of the feed solution was analyzed using ICP-OES. The eluate was collected in fractions and each fraction was analyzed using ICP-OES to determine the concentrations of Li, Mn, Co, and Ni. The concentrations of Co and Ni in the eluate were also monitored with an online photodiode array (PDA) detector. The concentration profiles from the ICP-OES analysis are plotted as discrete points in Figure 26. The PDA trace is shown as the dashed curve. The experimental eluate history is in close agreement with the simulation results, validating the design methodology and the intrinsic parameters used in the design. The eluate was also monitored with an online pH sensor. The pH profile of the eluate is plotted along with the concentration profile in Figure 26. Iminodiacetic acid is a weak acid with a pKa value of 1.83. When the IDA resin is presaturated with ammonium ions, the IDA functional groups tend to hydrolyze and adsorb hydrogen ions from the water, resulting in a high pH of the eluate (~9) after the resin is converted to the ammonium form and washed prior to feed loading.

[0115] When a feed containing divalent metal ions (pH 3.0) was introduced to the column, the IDA functional groups chelated the divalent metal ions, reducing the effects of hydrolysis. At the end of the feed loading, the pH was reduced from 9 to 7. One-half CV of DI water (pH 5.5) was used to wash the column and adsorb the unbound ions in the feed into the column void volume. As the displacing agent, 0.5N H2SO4 (pH 0.3), is loaded onto the column, the adsorbed metal ions are transported to the H +ions. This displacing agent displaces Ni, which in turn displaces Co, Mn, and Li. Eventually, a patterned isotactic train forms and elutes from the column. As the displacement bands of Mn, Co, and Ni exit the column, the eluate shows the pH of the metal sulfate solution, and the pH of the eluate further decreases from 7 to less than 4. Although the nominal displacement agent concentration was 0.5 N, the plateau concentration of the displacement band that formed was only 0.37 N. This decrease was due to the increased H of the adsorbent compared to the divalent metal ions. + This may be due to the higher capacity of the ions.

[0116] Example 6.2 In this example, Purolite Chromalite MIDA / C (IDA functional group, particle diameter 200 μm) was used as the adsorbent, lithium ions were the presaturating agent, and dilute acid (0.5N H2SO4) was used as the displacing agent. When the presaturant is Li ions, the Li ions in the feed can be considered as a non-adsorbing solute. When the feed was introduced to the column, the presaturated Li ions were displaced by the higher valence Mn, Co, and Ni ions, which eluted in the void volume along with the Li ions in the feed (Figure 27). A total concentration of 0.9N was observed in the eluate, which is consistent with the total concentration in the feed. When the displacing agent was introduced to the column, it displaced Ni, which in turn displaced Co, Mn, and the remaining Li. Eventually, a fixed pattern isotactic train was formed. The experimental eluate history closely matches the simulation. Similar to Example 6.1, due to the higher capacity of H ions, the displacement band concentration was 0.37 N when the nominal displacer concentration was 0.5 N. The pH eluate history followed the same trend as that obtained in Example 6.1. When Li ions are the presaturant, a high purity Li sulfate product is collected in the eluate. + Or Na + ) is not required to separate Li sulfate further.

[0117] Example 6.3 In this Example 6.3, Purolite Chromalite MIDA / C (IDA functional group, particle diameter 200 μm) was used as the adsorbent, Na ions were the presaturating agent, and nickel chloride solution (0.5 N) was used as the displacing agent instead of dilute acid. After feed loading, a large volume (1.7 CV) of DI water was used in the wash step, and most of the Li was eluted during this wash step, as shown in Figure 28. Because the increased water wash promoted the elution of Li, a lower apparent selectivity for Li was used in the simulation.

[0118] In Examples 6.1 and 6.2, H + ions are the displacers, and the displacement band concentration is H + This is clearly lower than the displacing agent concentration, + This is because the capacity of the adsorbent for ions is higher than that of the displaced divalent ions. In contrast, when nickel solution was used as the displacer in this example, the obtained displacement band concentration was the same as the displacement agent concentration of 0.5N, because the capacity of the displaced ions and the displacer were the same. Nickel solution as the displacer (Example 6.3) is less corrosive than the acid solution, and can achieve higher displacement band concentration, higher product concentration, and higher adsorbent productivity (Table 7). Examples 6.2 and 6.3 reached much higher adsorbent productivity than Example 6.1, because the particle size of the adsorbent used in Examples 6.2 and 6.3 was 200 μm, which is much smaller than that of the adsorbent used in Example 6.1, 575 μm.

[0119] [Table 5] [Table 6] [Table 7]

[0120] [Table 8]

[0121] Example 7 Pilot-scale testing of lithium purification from lithium-ion battery black mass pregnant leaching solution Seven gallons of pregnant leachate from black mass of lithium-ion batteries were first mixed to obtain a mixture. The mixture had high total metal ion concentration and high acidity (>1M acid). The pH of the mixed solution was adjusted to about 2 by adding ammonium hydroxide solution (30%) to prevent corrosion of the stainless steel tubing and damage to the resin. A grey-green solid formed during the pH adjustment step. The resulting slurry was filtered and the resulting filtrate was used as the feed to the column. A pilot-scale chromatography unit was used for the purification test. Three columns (each column 1 m long and 7.62 cm in diameter) were packed with IDA-functionalized resin, AmberSep IRC748 UPS resin, which is the same resin tested in Example 6.1. The feed was loaded onto the columns at a high linear gap velocity of 16.87 cm / min. Any feed remaining in the tube was flushed through the columns using minimal water. A slow linear velocity (2.42 cm / min) was then employed in the acid exchange step to collect the high purity Li product, and after all the Li was eluted, a fast linear velocity (12.26 cm / min) was used to strip out other metal ions. The process overview is shown in Figure 29. The eluate history is shown in Figure 30. The simulation parameters are shown in Table 8.

[0122] The yield of Li product with a purity of 99.9% was 88%. The productivity was 6.81 kg / m based on Li metal ion. 3 / day, and 36.2 kg / m2 on a Li carbonate basis 3 / day was achieved. The collected Li fraction can produce up to 170 g of Li carbonate. The collected NMC fraction can be further separated into high purity metal salts.

[0123] [Table 9]

[0124] Example 8 Isocratic 4-zone SMB for Li and Ni separation In this example, AmberSep M4195 resin is used as the adsorbent. The bis-picolylamine functional groups in the stationary phase can strongly chelate divalent metal ions, such as Cu and Ni, even at low pH (<2), while Li ions remain as non-adsorbed species. The adsorbed metal ions can be eluted using dilute sulfuric acid. An isocratic four-zone SMB based on AmberSep M4195 for the separation of Li and Ni is developed as described below. The feed composition is shown in Table 9.

[0125] [Table 10] The system parameters are shown in Table 10. The isotherm parameters were estimated from the literature and resin product data sheets and are shown in Table 11. [Table 11]

[0126] [Table 12]

[0127] In this nonlinear adsorption isotherm system, the effective retention coefficients of stationary components in the four zones are

number

[0128] The standing wave design equations for each wave speed in the four zones are:

number

[0129] Supply flow volume:

number

number

[0130] Switching Time:

number

[0131]

number

number

number

number

number

[0132] Note that in Zone III, the wave velocity is set to be the port velocity and is not corrected by the mass transfer coefficient. This is because in a highly nonlinear system, the self-sharpening effect can balance with the mass transfer effect and eventually form a constant pattern front wave as long as the column length is long enough. The column length in the design is selected so that the length of Zone III can include the mass transfer length of the Ni adsorption wave. Iterative calculations yielded the operating parameters for the non-ideal designs shown in Table 12.

[0133] [Table 13]

[0134] The simulated eluate history is shown in Figure 31, and the column dynamic profiles at the start and end of the step after cycle steady state is reached are shown in Figures 32A and 32B, respectively. Purity and yields of >99% were achieved for both Li and Ni. Li productivity was 14.1 kg / m 3 / day (metal basis), or 74.9 kg / m 3 / day (based on Li carbonate).

[0135] In a virtually ideal design, applied to a system with no substantial wave broadening, a large desorbent flow rate is required to match the Ni desorption wave velocity in zone I with the fast Li adsorption wave velocity in zone III. As a result, the Ni concentration in the extract is diluted to about 46% of that in the feed. In a non-ideal design based on AmberSep M4195 particle diameter of 400 μm, the Ni desorption wave in zone I (Figure 32) is significantly broadened due to intraparticle and axial dispersion at high desorbent flow rates. Since the zone length is fixed at 120 cm for both ideal and non-ideal designs, an increased desorbent flow rate is required to confine the Ni desorption wave to zone I. As a result, the Ni concentration in the extract is only 5.5% of that in the feed (Table 12). This example shows that for highly selective adsorbents with high Langmuir "a" values, the extract product is significantly diluted (5.5% of the Ni concentration in the feed in Example 8) when the slower moving components have a much higher effective retention factor than the faster moving solutes. This problem can be solved by designing a multi-zone SMB where the slower moving solutes are desorbed in a separate stripping zone by using a stronger stripping agent, as shown in Example 9.

[0136] Example 9 Multizone simulated moving bed for continuous partitioning of Li from nickel, cobalt, and manganese In this example, a high purity Li product is continuously recovered from a complex mixture containing Li, Mn, Co, and Ni. A continuous chromatography system was used with four pumps and eight operably connected columns. Each column had four inlet and four outlet ports. In this example, a four-zone SMB configuration was established (see Figures 15G and 33). Six columns packed with AmberSep IRC748 UPS (IDA) resin were connected in a continuous chromatography system and were all converted to the ammonium form (presaturant) prior to the experiment.

[0137] The feed solution was a mimic with a similar composition to the leachate of black mass from spent lithium ion batteries in Example 7. Before the first step of the SMB operation, two columns in zone III were preloaded with the feed solution to reduce the number of steps required to achieve cycle steady state. Water was used as a desorbent for Li and introduced into zone I, which allowed weakly adsorbed Li to migrate quickly to zone III and be collected in the eluate (raffinate) in zone III, while strongly adsorbed divalent Ni, Co, and Mn ions were retained in zone I. Adsorbed Ni, Co, and Mn ions were stripped using dilute acid in zone B. After complete stripping of the metal ions, water was used to flush the acid in zone B. In zone A, the column was regenerated to the ammonium form and washed with water. Complete regeneration and washing took 60 min, which established the average port velocity (0.5 cm / min) and step time of 60 min. Frontal simulations were performed to establish the minimum flow rate required to completely wash the Li in the bulk from Zone I for a given step time. The feed flow rate was then calculated using a standing wave design method. Ideal and non-ideal designs, as well as detailed system and operating conditions, are shown in Tables 13-16.

[0138] Six steps were performed to verify the operation of the SMB. ICP-OES was used to analyze the eluate from the raffinate port (Zone III outlet) and Zone B outlet (stripped divalent metals). The close agreement between experimental and simulated eluate histories validated the mSMB design methodology for selecting the operating and intrinsic parameters estimated from laboratory-scale tests. The novel preloading strategy resulted in reaching a cycle steady state within six steps. In SMB tests, a yield of 97% could be achieved with high purity Li (purity >99.9%). Productivity was 16 kg Li ions / m 3 / day or 85kg Li2CO3 / m 3 / day. Mn, Co, and Ni were recovered as mixed sulfates in >70% yield and 99.9% purity. This mixture of Mn, Co, and Ni from the mSMB can be further separated using a second and third mSMB in series, or using other novel fractionation methods, as described in Examples 1-8 of the previous examples.

[0139] [Table 14]

[0140] [Table 15] [Table 16]

[0141] [Table 17]

[0142] Summary and Conclusion As shown in the above examples, versatile and efficient multidimensional and multimodal chromatographic methods (Figure 3) can be utilized to recover single or multiple products in high purity and yield from multicomponent mixtures. A brief summary of potential applications of the new methods is provided below.

[0143] Case 1: If only one target component needs to be recovered from a complex mixture (from saltwater, ore, or waste LIBs), the following cases should be considered. Case 1A. A completely selective adsorbent should be found for use in the capture process, either adsorbing only the target or with very high selectivity (>20) for the target. A single column (or batch) fixed pattern capture process (Figure 5A and Examples 1, 2, and 5) can be utilized to produce high purity (99%) product in high yield. The target component will be recovered in a stripping or desorption zone. If a very high yield (>99%) of product is desired, high adsorbent utilization is not achieved (<75%) in the batch capture method. To achieve high target yield (>99%), 100% adsorbent utilization, and higher adsorbent productivity than the batch capture process, a fixed pattern continuous carousel capture process (Figure 9B, Example 4.1) should be utilized. Case 1B: An adsorbent that has very high selectivity over all other components (impurities) in the feed mixture, but does not adsorb the target component, can be utilized in a batch capture process (as in Example 1) or a continuous carousel capture process (as in Example 4.1) to produce a high purity target in the flow-through stream and the impurities are removed in a stripping zone.

[0144] Case 1C: If no highly selective adsorbent for the target or highly selective adsorbent for the impurities is available, a moderately selective adsorbent (>3) for either the target or the impurities can be utilized, and a continuous isocratic four-zone SMB (Figure 4C) can be utilized to recover the highly pure target in high yield either in the extract or raffinate (Figure 15A). If the target is a slow-moving component with a relatively high retention factor (>3), a non-isocratic four-zone SMB should be utilized to recover the concentrated pure target in the stripping zone to reduce the amount of desorbent required for the separation. In this case, an additional stripping zone is added to the separation zone, and a stripping agent is used to quickly remove the strongly adsorbed solutes in the stripping zone. The stripping agent can be used to reduce the retention time of the strongly adsorbed solutes by changing the pH, solvent strength, ionic strength, or temperature of the mobile phase, thereby increasing the productivity of the adsorbent and the product concentration. Case 1D. The isotactic displacement method can be used to recover the target in high purity (Example 7). To achieve high yields of the target, it may be necessary to recycle the two mixed bands.

[0145] Case 2: If two pure targets (e.g. Ni and Li) need to be produced from a binary mixture of two, the following options should be considered: Case 2A: If an adsorbent is available that is highly selective for one of the two targets (e.g., Ni over Li) with a selectivity greater than 10, a batch capture process (Figure 5A) or a carousel capture process (Figure 9B) can be used to produce two high purity products. Case 2B: If highly selective adsorbents for the two targets are not available, an isocratic four-zone SMB with moderate selectivity (>2) can be used to produce both products in high purity (99%) and high yield (99%). If the retention factor of the slower moving components is relatively high (>3), a four-zone non-isocratic SMB (Figure 15H, Example 9) can be used to recover the concentrated extract product, with both products having high purity and high yield.

[0146] Case 3. If three targets (e.g., Li, Ni, Co) need to be produced in high purity and high yield from a ternary mixture of the three, the following case should be considered. Case 3A: If highly selective adsorbents for each target are available, a fixed pattern in-line capture process (Figure 8, Example 3) or a fixed pattern in-line carousel process (Figure 22) can be used to produce high purity products with high yields and high adsorbent productivity. Case 3B. If a completely selective adsorbent for the three targets is not available, but an adsorbent with good selectivity (>2) for all three targets is available, a four-zone isocratic SMB (Figure 15C) can be used to produce the two highly selective targets in the extract and the less selective target in the raffinate. A second four-zone SMB can be used in series to produce the most selective target in the extract and the second most selective target in the raffinate (similar to Figure 15B). If the adsorbent for the second SMB has a high retention factor (>3), a non-isocratic four-zone SMB (Figure 15H, Example 9) can be used to produce a high purity product. Case 3C. A four-zone non-isocratic SMB can be used to recover the least selective target (e.g., Li) in the raffinate and the more selective targets (e.g., Ni and Co) in the extract (Example 9). The extract (binary mixture) can be further separated in a batch capture process based on a sorbent that is highly selective for one of the two targets (Figure 5A) or a carousel capture process based on the same sorbent (Figure 9B). Case 3D. An isotactic displacement process can be utilized to produce three high purity products (eg, Ni, Co, and Li) in high purity and yield, similar to Example 6.

[0147] Case 4: If four targets (eg, Li, Ni, Co, and Mn) need to be produced from a mixture of the four, the following case should be considered. Case 4A. When perfectly selective adsorbents are available for each target or for three of the four targets, the fixed pattern in-line capture method (Example 3) or the fixed pattern in-line carousel capture method (Figure 22) are preferred. Case 4B. If a completely selective adsorbent for a target is not available, a four-zone isocratic SMB can be utilized to recover the least selective target (e.g., Li) in the raffinate and a mixture of the other three targets (e.g., Ni, Co, and Mn) in the extract (similar to Example 8). The ternary mixture of the three targets can be further separated to produce high purity products as described in Case 3.

[0148] Case 4C. A four-zone isocratic SMB can be used as the first step to split the four targets into two fractions (e.g., Ni and Co in the extract and Mn and Li in the raffinate, FIG. 15D). A second isocratic four-zone SMB can be used to separate the raffinate mixture (e.g., Mn and Li) from the first SMB to produce pure products (similar to FIG. 15A). In parallel, a third isocratic four-zone SMB can be used to separate the extract (e.g., Ni and Co) from the first SMB to produce pure products. Alternatively, instead of the third isocratic four-zone SMB, a non-isocratic four-zone SMB (similar to FIG. 15H or Example 9) can be used to recover the most selective target (e.g., Ni) in the stripping zone and the other target (e.g., Co) in the raffinate.

[0149] Case 4D. A four-zone non-isocratic four-zone SMB can be used first to recover the least selective target (e.g., Li) in the raffinate and the other three targets (e.g., Ni, Co, and Mn) as a mixture in the stripping zone (Example 9). The ternary mixture can be further fractionated as discussed in Case 3. Case 4E. As shown in Example 6, an isotactic displacement process can be used to produce four high purity products (eg, Li, Ni, Co, and Mn) from a four-component mixture. Case 4F. As described in Example 7, Figure 30, an isotactic displacement method can be utilized to produce a high purity product (e.g., Li in the early eluting fraction) and a mixture of three other targets (e.g., Ni, Co, and Mn) in the late eluting fraction. The mixture of three targets (Ni, Co, and Mn) can be further separated as discussed in Case 3.

[0150] Case 5. Four pure products (e.g., Li, Ni, Co, and Mn) are mixed with four components and impurities (e.g., Fe +3 ), the following cases are discussed below: Case 5A. Impurity (Fe +3 If a completely selective adsorbent for Fe was available, it could be used in a patterned batch capture process (FIG. 5A, similar to Example 1) or a carousel capture process (FIG. 9B, similar to Example 4) to remove impurities (Fe) from the feed mixture. +3 ) can be removed. The quaternary mixture (e.g., Li, Ni, Co, and Mn) can be further purified as described in Case 4. Case 5B.Fe +3 In the absence of any adsorbents available that are completely selective for Fe +3 Adsorbents with good selectivity (>5) for Fe were utilized in a nonisocratic eight-zone SMB (Figure 15F) to remove Fe in the stripping zone. +3 The least selective target (e.g. Li) can be recovered from the raffinate and a mixture of other targets (e.g. Ni, Co, and Mn) in the extract. The extract (ternary mixture) can be further separated as described in Case 3. If an 8-zone SMB apparatus is not available, a non-isocratic 4-zone SMB (Figure 15H, similar to Example 9) can be utilized to remove impurities.

[0151] In conclusion, when only one product needs to be purified from a complex mixture, a fixed pattern batch capture method or a carousel capture method is preferred. When a highly selective adsorbent for target capture is not available, an isocratic or non-isocratic SMB method or an isotatic displacement method can be utilized. When more than one product needs to be produced from a complex mixture, a capture or fractionation method, a four-zone SMB or a multi-zone SMB is required. In general, versatile and efficient capture methods (single column or carousel capture), serial capture, serial carousel capture, isocratic SMB, isocratic serial SMB, and non-isocratic four-zone SMB or multi-zone SMB methods can be utilized in series or parallel to produce high purity products with high yield and high productivity.

[0152] Advantages of the new approach All these new methods can achieve high yields (>99%) of high purity (>99.5%) products (either all four elements as a group or the four elements individually) from complex mixtures. Impurities were effectively removed down to ppm levels before further purification or direct precipitation, crystallization, or electrowinning. Compared to state-of-the-art purification methods, these methods have small processing volumes, small footprints, and high productivity. The new purification methods use only safe and mild chemicals at ambient temperature and low pressure equipment, which results in lower capital and energy costs and also improves safety. The process produces only Na or ammonium salts, which can be recycled back into acids and bases. The methods are applicable to N component mixtures and the products can be mixtures of individual elements or any combination of Li, Mn, Co, and Ni. The methods are highly efficient and flexible for processing feedstocks with different compositions and different production scales.

[0153] While the present invention has been illustrated and described in detail in the drawings and the foregoing description, these are to be considered as illustrative and not restrictive in character. It is understood that the embodiments have been shown and described in the foregoing specification to satisfy the best mode and enabling requirements. It is understood that those skilled in the art can easily make an almost infinite number of very slight modifications and alterations to the above-described embodiments, and it would be impractical to attempt to describe all such variations of the embodiments herein. It is therefore understood that it is desired to protect all modifications and alterations that come within the spirit of the present invention.

Claims

1. 1. A method for continuously recovering high purity materials from a complex mixture, comprising: a) preparing a complex mixture containing metal elements Q, X, Y, and Z; b) introducing the complex mixture into a chromatography system having four pumps and at least four operatively connected columns, each column having multiple inlet ports and multiple outlet ports; c) establishing a four-zone simulated moving bed configuration, with each of the six columns defining zones A, B, I, and III packed with resin and the two columns defining zone III preloaded with the feed solution; d) introducing a feeding solution or mimetic; e) introducing a desorbent for Q into zone I to promote migration of weakly adsorbed Q to zone III where it is recovered in the eluate of zone III; f) retaining strongly adsorbed X, Y, and Z ions in zone I; g) stripping the adsorbed X, Y, and Z ions with dilute acid in zone B; h) washing out the acid in zone B after complete stripping of metal ions; and i) regenerating the columns defining zone A The method includes:

2. 10. The method of claim 1, wherein the chromatography system comprises four pumps and eight operably connected columns, each column having at least four inlet ports and at least four outlet ports.

3. j) extracting the eluate from the outlet port of zone III; and k) verifying that the Q extracted from the outlet port of zone III is greater than 99% pure. The method of claim 1 further comprising:

4. The method of claim 1 , further comprising repeating steps ai until a steady state is reached.

5. 5. The method of claim 4, wherein a steady state is achieved in six repetitions of steps ai.

6. 2. The method of claim 1, wherein Q is lithium, X is cobalt, Y is nickel, and Z is manganese.

7. 2. The method of claim 1, wherein the chromatography system has six pumps and twelve columns operably connected, each column having at least four inlet ports and at least four outlet ports, establishing a six-zone simulated moving bed configuration.

8. A method for separating the target elements Li, Co, Ni, and Mn in a mixture derived from waste LIB or other feedstock, comprising the steps of: a) physically separating the carbon black and graphite in the black mass from the metal oxides; b) acid leaching the metal oxides to produce metal salts in a feed solution; c) passing the feed solution through a series of operatively connected columns, including a first column containing an adsorbent having high selectivity for impurities and a second column containing an adsorbent having high selectivity for separation of a selected element, the second column being pre-saturated with ions selected from the group consisting of lithium ions and non-lithium ions having a low affinity for the adsorbent; d) trapping at least one impurity in a first column; e) replacing lithium with manganese in a second column; f) replacing manganese with cobalt in a second column; g) replacing the cobalt with nickel in a second column; and h) replacing the nickel in a second column with a displacing agent having high selectivity for the adsorbent. The method includes:

9. 9. The method of claim 8, wherein the at least one impurity is selected from the group consisting of aluminum, iron, and copper ions.

10. A single column method for capturing target lithium ion battery elemental or impurities from waste lithium ion batteries or other feedstocks, comprising: a) providing a chromatography column having a first predetermined diameter and a second predetermined length; b) placing a resin for capturing metal ions in a chromatography column, the resin being selected from the group consisting of a resin having high selectivity for one of the lithium ion battery component metal ions and a resin having high selectivity for one of the lithium ion battery impurity metal ions; c) pre-saturating the chromatographic column with weakly adsorbing species; d) passing the solution of metal salts leached from the waste lithium ion batteries through a chromatography column; and e) establishing a consistent pattern of captured targets in the chromatography column; wherein the predetermined column length is sufficient to allow for the formation of a consistent pattern of the target elements.

11. f) removing the captured target elements from the column using a stripping agent; g) passing the eluate from the first column through a second column packed with a resin having high selectivity for the second target element, and repeating steps a) to f). The method of claim 10 further comprising:

12. 1. A method of using a carousel to capture a target element from a mixture of lithium ion battery elements and impurities or other feedstock, comprising: a) providing a first, second, and third chromatography column; b) disposing in each chromatography column a resin for capturing a metal ion of interest; c) passing the solution of metal salts leached from the waste lithium ion batteries through the first chromatography column into the second chromatography column; d) when the concentration of a predetermined metal ion in the solution of metal salts exiting the first chromatography column reaches a predetermined limit, flowing the solution of metal salts through the second column to the third column while isolating the first column from the second and third columns and stripping it with dilute acid; e) when the concentration of a predetermined metal ion in the solution of metal salts exiting the second chromatography column reaches a predetermined limit, flowing the solution of metal salts through a third column to the first column while isolating the second column from the first and third columns and stripping it with dilute acid; f) when the concentration of a predetermined metal ion in the solution of metal salts exiting the third chromatography column reaches a predetermined limit, flowing the solution of metal salts through the first column to the second column while isolating the third column from the first and second columns and stripping it with dilute acid; and g) repeating steps d) to f) until the solution of metal salt is depleted. The method includes:

13. 1. A serial capture method for sequentially recovering multiple target components from waste LIB or other feedstock, comprising: a) providing first, second, and third chromatography column assemblies; b) disposing a first resin for capturing a first predetermined metal ion component in a first chromatography column assembly; c) disposing a second resin in a second chromatography column assembly for capturing a second predetermined component; d) disposing a third resin in a third chromatography column assembly for capturing a third predetermined component; e) flowing a solution of metal salts leached from spent lithium ion batteries or other feedstock through a first chromatography column assembly to capture a first predetermined target component; f) flowing the eluate from the first chromatography column assembly through a second chromatography column assembly to capture a second predetermined target component; g) flowing the eluate from the second chromatography column assembly through a third chromatography column assembly to capture a third predetermined target component; and h) extracting remaining components from the eluate exiting the third column assembly. The method includes:

14. The method of claim 13 , wherein each column assembly defines a respective carousel system that defines a plurality of columns.

15. The method of claim 13 , wherein each of the at least one column assemblies defines a respective carousel system that defines a plurality of columns.

16. 1. An anion exchange process for producing high purity LiOH, comprising: a) containing an anion exchange resin and - providing a chromatography column pre-equilibrated with b) running a high purity lithium salt solution through a chromatography column; and c) flushing the high purity LiOH eluate from the chromatography column. The method includes:

17. The method of claim 16 , wherein the single column defines a carousel system.

18. 1. A method for recovering metal ions from waste materials, comprising: a) identifying a chromatography assembly having three operatively connected columns, each column filled with resin; b) identifying a quantity of pregnant leach solution from lithium ion battery black mass defining a mixture, the mixture defining a total metal ion concentration and a high acidity of greater than 1 M; c) adjusting the pH of the mixture to about 2 to prevent degradation of the device; d) forming solids during the pH adjustment to define a slurry; e) filtering the slurry to recover a filtrate; f) using the filtrate as column feed; g) loading the column feed into each column at a first linear velocity; h) displacing the column feed with acid at a second, slower linear velocity to collect the high purity Li product; i) after dissolving lithium, stripping other metal ions at a third faster linear velocity that is faster than the second linear velocity; wherein the other metal ion is selected from the group comprising nickel, manganese, and cobalt.

19. j) collecting other metal ions; and k) separating the nickel, manganese, and cobalt from each other.

20. The method for recovering metal ions from waste materials as set forth in claim 18, further comprising:

Images