Method for extracting elements from solution

Abstract

Nickel(II) / Lithium(I) (Ni 2+ / Li + The present invention provides a process for extracting nickel and lithium from a solution containing a quantity of lithium and a quantity of nickel. 2+ / Li + Providing a solution and Ni 2+ / Li + The solution was treated with an alkaline agent to remove Ni 2+ / Li + The pH of the solution is adjusted to about 1.0 to about 10.0, and Ni 2+ / Li + The solution was then diluted with Ni at that pH. 2+ / Li + Treating the solution with a nickel-selective extractant suitable for extracting nickel from the solution, thereby obtaining a solution containing less than 10 parts per million of Ni. 2+ Li with + and producing a solution. Upon completion, the process provides recoverable nickel and / or lithium that can be recycled into batteries or sold for other uses.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 62 / 754,739, filed November 2, 2018, the entire contents of which are incorporated herein by reference.

[0002] The present disclosure relates to methods for recovering elements from solution. More specifically, the present disclosure relates to methods for recovering lithium and nickel, as optionally produced from waste streams following delithiation of lithium nickel oxide (e.g., LiNiO2) materials. [Background technology]

[0003] Lithium-ion batteries are increasingly being used in critical applications such as powering electric vehicles, mobile phones, and cameras. The increasing use of such batteries in a wide range of technology fields has created an increasing need to extract valuable elements such as nickel and lithium, which are generated as waste streams from the manufacture of these materials or from used lithiated batteries, in a manner that is both cost and time efficient. The materials extracted from these waste streams can be recycled back into the manufacturing process or sold and implemented in other related processes. As such, the recovery of nickel and lithium allows for an economically viable process for the extraction of lithiated nickel oxide active materials.

[0004] According to typical extraction methods currently used in the field, used lithium-ion batteries are mechanically separated. The mechanical separation process includes opening, dismantling, and shredding the batteries to be recycled. Such a process can be time-consuming and environmentally unfriendly if the waste is not properly collected. Once shredded, valuable metals such as nickel and lithium can be leached out of the batteries by an acid leaching process. The components are then separated so that precipitates can be formed from the individual acid leached metals. The Ni- and Li-rich extracts, generated as waste products of the delithiation of materials during the manufacture of battery cathodes, can be directly recycled or disposed of as waste.

[0005] Unfortunately, current extraction or recycling methods often use various oxidizing agents that generate large amounts of waste that must be treated, thereby requiring cleanup time and costs. Furthermore, these methods may not provide effective separation of the extracted components, thereby making individual recovery of the materials impossible. Such deficiencies reduce the amount of material that can be recovered, and also increase both the amount of waste generated and the costs associated with the extraction of battery materials.

[0006] Multi-stage co-extraction has been attempted to recover multiple materials simultaneously, such as both nickel and lithium. Although these methods can produce individually extracted materials, four co-extraction stages and a total of six steps are required to produce individually extracted materials. Therefore, the current co-extraction process is very time-consuming, as each step must be performed separately. Furthermore, the amount of solvent required during the co-extraction process is financially expensive, as different solvents are required during each step.

[0007] Therefore, new methods are needed to improve the efficiency and power of extracting materials such as nickel and lithium from battery waste streams. Summary of the Invention

[0008] The following summary is provided to facilitate understanding of some of the innovative features unique to the present disclosure and is not intended to be a complete description, with the entire specification, claims, drawings, and abstract taken as a whole to provide a full understanding of the various aspects of the present disclosure.

[0009] Nickel(II) / lithium(I) (Ni 2+ / Li + A process for extracting lithium and nickel from a solution is provided. 2+ / Li + The solution may also contain some levels of Ni(III) and Ni(IV). It has been found that certain looping processes allow for substantially complete recovery of nickel and lithium individually in a time-efficient and cost-effective manner. 2+ / Li + The process for extracting nickel and lithium from a solution optionally comprises extracting a Ni 2+ / Li + Providing a solution and Ni 2+ / Li + The solution is treated with an alkaline agent to remove Ni 2+ / Li + and adjusting the pH of the solution to about 1.0 to about 10.0. 2+ / Li + The solution was then diluted with Ni 2+ / Li + and treating with a nickel-selective extractant suitable for extracting nickel from the solution, thereby optionally obtaining less than 1000 parts per million of Ni. 2+ Li with + and producing a solution (a nickel-poor solution).

[0010] In some embodiments, the Ni after combination with the alkaline agent 2+ / Li +The pH of the solution is greater than 3.0. The alkaline agent is optionally selected from the group consisting of sodium hydroxide, potassium hydroxide, aqueous ammonia, and a combination of at least two of the foregoing.

[0011] In some embodiments, the nickel-selective extractant is an oxime or a carboxylic acid. The oxime is optionally selected from the group consisting of 5-nonylsalicylaldoxime, 5-dodecylsalicylaldoxime, 5-nonyl-2-hydroxyacetophenone oxime, and a combination of at least two of the foregoing. The carboxylic acid is optionally a tertiary carboxylic acid, and optionally neodecanoic acid.

[0012] Optionally, the nickel-selective extractant further comprises a hydrocarbon, optionally selected from the group consisting of kerosene, paraffin, naphthene, and combinations of at least two of the foregoing. Optionally, the nickel-selective extractant and the hydrocarbon are present in a volume ratio of 10:90 to 30:70.

[0013] In some embodiments, the nickel-selective extractant 2+ / Li + Ni when processing the solution 2+ / Li + The pH of the solution is 3.0 to 8.0. 2+ / Li + The step of treating the solution is optionally carried out at a pH of about 7.0, which optionally results from combination with an alkali.

[0014] Li obtained from nickel extraction + The Ni in the solution is optionally less than 1000 parts per million, optionally less than 100 parts per million, optionally less than 10 parts per million.

[0015] In some embodiments, the process comprises reacting Li with a carbonation agent to produce a lithium salt. +The method further includes treating the solution. The carbonation agent is optionally selected from the group consisting of carbon dioxide (CO2), ammonium, sodium carbonate, ammonium carbonate, bicarbonate, and combinations of at least two of the foregoing. Optionally, the lithium carbonate is filtered and washed.

[0016] In some embodiments, the process comprises extracting Li with a lithium-selective extractant. + The method further comprises treating the solution to produce a concentrated lithium salt solution. The lithium-selective extractant is optionally 2-ethylhexylphosphonic acid, mono-2-ethylhexyl ester, neodecanoic acid, or a combination of at least two of the foregoing. Optionally, the lithium-selective extractant further comprises a hydrocarbon. The hydrocarbon is optionally kerosene, paraffin, naphthene, or a combination of at least two of the foregoing. [Brief description of the drawings]

[0017] The aspects of the disclosure set forth in the drawings are illustrative and exemplary in nature and are not intended to be limiting of the subject matter defined by the claims. The following detailed description of illustrative aspects of the disclosure can be understood when read in conjunction with the following drawings. [Figure 1] FIG. 1 is an example schematic diagram of a process according to some embodiments illustrating the optional continuous extraction of materials from an example waste or other material. [Diagram 2] FIG. 1 illustrates a flow diagram of the process provided herein showing various stages of extraction (E), washing (W), and stripping (S) with multiple extraction stages and multiple strip stages, and illustrates the organic stage flow, the input Ni2+ / Li2+ solution flow, and the flow of a tank collecting the output of the nickel extraction step of the process provided herein illustrated in a process where the strip steps are in parallel (A) or in series (B). [Diagram 3] 1 is a schematic diagram of an exemplary process provided herein, in accordance with some aspects. [Figure 4]1 is a schematic diagram of an exemplary process provided herein, in accordance with some aspects. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Provided herein is a process for separating nickel and optionally lithium from an input stream, which is optionally a waste stream following delithiation of LiNiO2 material. The process can, for the first time, efficiently and reliably recover nickel and optionally lithium from these streams, such that the resulting isolated nickel and lithium can be used for subsequent processing or for the formation of additional electrochemically active materials. The process provided herein according to some embodiments of the present disclosure utilizes one or more continuous loop systems of countercurrent organic and aqueous phases to allow efficient separation and extraction of nickel, lithium, or both from the input stream. A schematic diagram of the overall process according to some embodiments is shown in FIG. 1.

[0019] In some embodiments, the process uses sequential and optionally multi-step extraction, whereby each extraction does not have to be performed in isolation from the other steps, providing a much more robust overall extraction process that optionally operates in less time and produces less waste than conventional processes. Generally, waste materials are provided by the processes provided herein as a source of Ni and optionally Li for extraction or isolation. As used herein, the term "waste" refers to Ni, Li, Li-, or Li-based materials having either or both in a concentration suitable for extraction. 2+ and Li +The term "waste" is defined as a liquid or solid composition containing both Ni and Li. The term "waste" does not necessarily have to be a spent product of another conventional process, but can be the result of an upstream process, such as the leaching of Ni or Li from a conventional processing step of a desired material. Optionally, waste as used herein is a waste stream from the continuous or discontinuous leaching of Ni and Li produced during the delithiation of lithium nickel oxide, optionally used for the formation of a cathode in a primary or secondary electrochemical cell.

[0020] Ni 2+ / Li + The waste material in the form of a solution is optionally subjected to a continuous multi-step extraction process that can optionally include one or more extraction steps, one or more stripping steps, and one or more washing steps, any or all of the foregoing assembled into a continuous circuit. Optionally, the circuit design includes one or more washing steps. Optionally, the design includes two or more washing steps. The number of washing steps is according to the desires of the user and is not necessarily limited, although in some embodiments, only a single washing step is used.

[0021] The fluid circuit includes one or more extraction stages. The number of extraction stages is optionally 1-10, or any value or range therebetween. Optionally, the number of extraction stages is 2-10, 2-8, 2-6, 3-10, 3-8, 3-6. Optionally, the number of extraction stages is 2, 3, 4, 5, 6, 7, or more. Optionally, the number of extraction stages is 6 or less, optionally 5 or less. The number of extraction stages in the circuit allows for efficient extraction of Ni (or Li) at each stage and the production of a single Ni-rich extractant that can be subjected to further processing to obtain isolated Ni suitable for use in a subsequent production process. The resulting nickel-lean solution (Li + solution) may also be subjected to subsequent isolation of Li.

[0022] Each extraction stage may then be housed in a mixer-settler that can introduce an alkaline agent, a Ni-selective extractant, or both. In an example where there are five extraction stages, the five mixer-settlers are fluidly connected so that the product from one extraction stage can be passed to the subsequent mixer-settler, and as a waste stream, an organic extractant (containing one or more nickel-selective extractants) passed in the opposite direction in series to facilitate the extraction of Ni is transferred from one extraction stage to the subsequent extraction stage. An exemplary generalized process is illustrated in Figures 2A and 2B, with the difference that Figure 2A illustrates strip stages (S1 and S2) used in parallel, and Figure 2B illustrates strip stages (S1 and S2) used in series. As illustrated in Figures 2A and 2B, a waste material containing Ni and Li is included (Tank 1) and used as a feed through the system. The waste material is fed from the extraction stage E1 in the first mixer-settler and is combined with the nickel-selective extractant moving in the opposite direction in series. Thus, the waste material is first contacted with the nickel-selective extractant in stage E1 and transferred from E1 to E5, with the Ni-selective extractant first entering the extraction stage at E5 and transferred from E5 to E1. After reaction in stage E1, the aqueous phase from which Ni has been removed is transferred to E2 and subsequently to E3, E4 and E5, so that Ni is continuously removed and concentrated in the organic phase moving in the opposite direction. The Ni-enriched organic phase may then be optionally scrubbed in a washing stage (W) and transferred directly to the stripping stage(s).

[0023] The Ni-rich organic phase is optionally washed and then transferred to stripping stages S2 and S1, optionally in that order, to strip Ni from the Ni-selective extractant solution (organic), each of which is housed in a separate mixer-settler. Optionally, the number of stripping stages is one or more, optionally two or more. The number of stripping stages is optionally four or less, optionally three or less, optionally two or less. Similar to the extraction stages above, the stripping stage includes a countercurrent flow of an aqueous stripping solution (e.g., acid) to strip Ni from the Ni-rich organic phase and produce Ni salts.

[0024] Within each stripping stage, the Ni-rich organic phase is exposed to a stripping solution containing acid to exchange Ni with hydrogen, and the purified and concentrated nickel is passed to the stripping aqueous phase to produce Ni salts. The Ni salts can be used as input materials for subsequent manufacturing processes themselves, or for subsequent isolation of further elements (e.g., by electrodeposition processes or precipitation) of Ni for subsequent use. The Ni-poor organic phase can then be optionally scrubbed in a washing stage, returned to a storage tank, and / or transferred directly to a Ni extraction stage for subsequent extraction of Ni from the waste material.

[0025] The nickel-poor material obtained as a result of the extraction step (Li + The Li solution is then either transferred to a holding tank (Tank 2) for subsequent recovery of Li or transferred directly to the Li extraction process. + The solution may be subjected to ion exchange. The Li extraction process may optionally include + Either direct precipitation of Li from solution (Figure 3) or transferred to a Li extraction process that is essentially physically set up as above, but using a Li-selective extractant in the extraction step(s) (Figure 4). + The result of the extraction or precipitation is a Li salt that can also serve as a recycled material for the production of additional goods.

[0026] More specifically, in some embodiments of the present disclosure, nickel(II) / lithium(I) (Ni 2+ / Li + ) A process for extracting nickel and optionally lithium from waste materials, comprising: 2+ / Li + solution, and optionally providing waste materials. 2+ / Li + The lithium present in the solution may be derived from any suitable lithium-containing and any suitable nickel-containing compound. Illustratively, Ni 2+ / Li+ The solution may be a waste stream resulting from the delithiation of electrochemically active materials used in electrochemical cells and produced according to art-recognized delithiation methods, such as, for example, LiNiO2 materials, NCM materials, etc. Optionally, Ni 2+ / Li + The solution results from the delithiation of LiNiO2 material, or LiNiMO2, where M is any one of many metals, such as Mn, Mg, Al, Co, and / or most any other transition metal. Other examples include LiNiCoAlO2, LiNiCoAlMO2, where M is optionally a transition metal, or Mg, etc. The transition metal can be any transition metal suitable for use in an electrochemical cell. Illustrative examples of transition metals include, but are not limited to, Ni, Co, Mn, Al, Mg, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, B, or other transition metals.

[0027] Generation of electrochemically active materials or Ni 2+ / Li + Another generation of the solution can be by combination of a lithium compound with a nickel compound. Optionally, the lithium compound is lithium hydroxide, lithium oxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium acetate, lithium peroxide, lithium bicarbonate, or lithium halide, or any combination thereof.

[0028] According to some embodiments, Ni 2+ / Li + The amount of lithium present in the solution can range from about 5 g / L to about 250 g / L, optionally from about 20 g / L to about 150 g / L. 2+ / Li + The amount of lithium present in the solution is from about 10 g / L to about 200 g / L, from about 15 g / L to about 175 g / L, from about 20 g / L to about 150 g / L, from about 25 g / L to about 125 g / L, from about 30 g / L to about 100 g / L, from about 40 g / L to about 75 g / L, or from about 50 g / L to about 60 g / L.

[0029] In some embodiments of the present disclosure, Ni 2+ / Li + The nickel present in the solution may be derived from any suitable nickel-containing compound, such as a hydroxide, oxide, oxyhydroxide, carbonate, or nitrate of Ni.

[0030] According to some embodiments, Ni 2+ / Li + The amount of nickel present in the solution can range from about 5 g / L to about 400 g / L, optionally from about 20 g / L to about 200 g / L. 2+ / Li + The amount of lithium present in the solution is from about 10 g / L to about 300 g / L, from about 15 g / L to about 250 g / L, from about 20 g / L to about 200 g / L, from about 25 g / L to about 150 g / L, from about 30 g / L to about 100 g / L, from about 40 g / L to about 75 g / L, or from about 50 g / L to about 60 g / L.

[0031] The LiNiO2 material may be substantially delithiated by art-recognized processes, illustratively by the process described in U.S. Patent No. 8,298,706, such as by exposing the LiNiO2 material to aqueous 6M H2SO4 at the desired delithiation temperature. Optionally, the LiNiO2 may be delithiated by Li + and Ni 2+ can be delithiated to produce a sulfate matrix having Li +およびNi2+ can then be isolated using the processes described herein. Additionally, the supernatant removed from the wash solution can be separated into the waste stream Ni 2+ / Li + It may be used as a solution.

[0032] Ni 2+ / Li + The process for extracting nickel and / or lithium from solution comprises, in one or more extraction stages, 2+ / Li + The solution is treated with an alkaline agent to remove Ni 2+ / Li+ and adjusting the pH of the solution to about 1.0 to about 10.0. Suitable alkaline agents can include calcium oxide, sodium hydroxide, potassium hydroxide, aqueous ammonia, or combinations thereof. The alkaline agents optionally exclude those that introduce cations into the system that interfere with the recovery of one or more metals from the desired solution. Optionally, the alkaline agents exclude sodium salts. Optionally, the alkaline agents exclude potassium salts. Optionally, the alkaline agents exclude calcium salts.

[0033] Optionally, the alkaline agent is Ni 2+ In one or more extraction steps, Ni 2+ / Li + It is provided in an amount and concentration that adjusts the pH of the solution to between about 1.0 and about 10.0. Optionally, after contact with the alkaline agent, Ni 2+ / Li + The pH of the solution is about 1.5 to about 9.5, about 2.0 to about 9.0, about 2.5 to about 8.5, about 3.0 to about 8.0, about 3.5 to about 7.5, about 4.0 to about 7.0, about 4.5 to about 6.5, about 5.0 to about 6.0, or about 6.0 to about 7.5. Optionally, an alkaline agent is introduced in one or more extraction stages to adjust the pH of the solution to about 3.0 or more, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, or about 8.0 or more. Optionally, the pH is adjusted in one or more extraction stages by contact with an alkaline agent to bring or maintain the pH of the extraction solution to about 6.0 to about 7.0.

[0034] In some embodiments of the present disclosure, Ni 2+ / Li + The process for extracting nickel and lithium from solution is 2+ / Li + The method further comprises treating the solution with a nickel-selective extractant, the nickel-selective extractant being capable of extracting nickel at a desired pH. 2+ / Li + Extracting nickel from the solution, thereby 2+ / Li +Li with less Ni than solution + It is suitable for producing a solution.

[0035] In some embodiments, the nickel-selective extractant is an oxime. Examples of oximes include aldoximes and ketoximes. Such oximes are illustratively described by the following formula I: [ka] In formula I, R is an alkyl group having 1 to 25 carbon atoms, an ethylenically unsaturated aliphatic group containing 3 to 25 carbon atoms, or -OR 1 where R 1 is an alkyl group or an ethylenically unsaturated aliphatic group as defined above, and c is 1, 2, 3, or 4; R 2 is H, an alkyl group containing 1 to 25 carbon atoms, an ethylenically unsaturated aliphatic group containing 3 to 25 carbon atoms, or [ka] n is 0 or 1, R 3 is an alkyl group having 1 to 25 carbon atoms, an ethylenically unsaturated aliphatic group containing 3 to 25 carbon atoms, or -OR 1 and R 1 is an alkyl group or an ethylenically unsaturated aliphatic group as defined above, and optionally R and R 3 The total number of carbon atoms in the group is from 3 to 25. Such oximes are described in U.S. Patents 6,261,526 and 8,986,633.

[0036] Suitable exemplary specific oximes may include aldoximes such as 5-nonylsalicylaldoxime, 5-dodecylsalicylaldoxime, or ketoximes such as 5-nonyl-2-hydroxyacetophenone oxime. Optionally, two or more oximes or oxime types are combined.

[0037] Optionally, the nickel-selective extractant is a carboxylic acid. Optionally, the carboxylic acid nickel-selective extractant is a tertiary carboxylic acid, optionally a branched tertiary carboxylic acid. Optionally, the carboxylic acid includes one or more alkyl radicals bonded to the carboxylic acid group. The alkyl radicals are optionally C1-C10 alkyl radicals, optionally C1-C9. Optionally, three alkyl radicals are connected to a central carbon that is connected to the carboxylic acid group. Each of the three alkyl radicals is independently, optionally, a C1-C10 alkyl. Optionally, the first alkyl radical is methyl. Optionally, the second alkyl is a C1-C10 alkyl. Optionally, the third alkyl is a C1-C5 alkyl. Each alkyl can be linear or branched. Optionally, the carboxylic acid nickel-selective extractant is neodecanoic acid.

[0038] Nickel-selective extractants are those that selectively extract Ni in one or more extraction steps. 2+ / Li + About 5 volume percent to about 50 volume percent of Ni, based on the total volume of the solution. 2+ / Li + Other suitable ranges of nickel-selective extractants include Ni 2+ / Li + Based on the total volume of the solution, the amount can be about 10 volume percent to about 45 volume percent, about 15 volume percent to about 40 volume percent, or about 20 volume percent to about 30 volume percent.

[0039] In a further embodiment of the present disclosure, the nickel-selective extractant further comprises a hydrocarbon as a diluent. Suitable hydrocarbons can include kerosene, paraffin, naphthene, or a combination thereof. The nickel-selective extractant and the hydrocarbon can be present together in various ratios. Optionally, the ratio of the nickel-selective extractant to the hydrocarbon can range from about 1:99 to about 99:1 on a volumetric basis. Optionally, the ratio of the nickel-selective extractant to the hydrocarbon is from about 50:50 to about 20:80 on a volumetric basis. Optionally, the ratio of nickel-selective extractant to hydrocarbon is from about 2:98 volume percent to about 45:55 by volume, from about 3:97 by volume to about 40:60 by volume, from about 5:95 by volume to about 40:60 by volume, from about 7:93 by volume to about 35:65 by volume, or from about 10:90 by volume to about 30:70 by volume, each of the nickel-selective extractant and the hydrocarbon being from a substantially isolated or saturated solution of the nickel-selective extractant or the hydrocarbon, respectively.

[0040] The processes provided herein optionally include one or more extraction stages, in series or parallel. Optionally, nickel-selective extractants, pH adjustments, or other steps may be used to extract Ni. 2+ / Li + The number of extraction stages contacted with the solution may be 1, 2, 3, 4, 5, 6, 7, or more stages. 2+ / Li + It provides rapid and robust extraction of nickel from solution. The result of one or more extraction steps is a nickel-rich solution and a lithium (e.g., Li + A nickel-poor solution (or the result of nickel extraction) is optionally a nickel-poor solution containing less than 1000 ppm Ni. 2+ , 500ppm or less of Ni 2+ , 100ppm or less of Ni 2+ , 10ppm or less of Ni 2+ , 9ppm or less Ni 2+ , 8ppm or less of Ni 2+ , 7ppm or less Ni 2+ , 6ppm or less of Ni 2+ , 5ppm or less Ni2+ , 4ppm or less of Ni 2+ , 3ppm or less of Ni 2+ , Ni below 2ppm 2+ or less than 1 ppm Ni 2+ The nickel-lean solution is optionally subsequently treated to extract lithium from the nickel-lean solution.

[0041] For nickel-poor solutions, optionally add Ni 2+ / Li + The amount of Ni in the solution is less than 10 percent by weight. Optionally, the nickel-poor solution is optionally 2+ / Li + The amount of Ni in solution is less than 1 percent by weight, optionally less than 0.1 percent, optionally less than 0.01 percent, optionally less than 0.001 percent, optionally less than 0.0001 percent.

[0042] The nickel-rich solution resulting from the extraction step is optionally subjected to one or more stripping steps to obtain an isolated Ni product, optionally in the form of a Ni salt. In one or more stripping steps, the pH of the nickel-rich solution is lowered by a combination with an acid such as H2SO4 or other suitable acid. An acid is optionally added to lower the pH from that of the extraction solution(s), optionally to about 3.0 or less, optionally to 2.0 or less, thereby stripping the Ni from the Ni-rich solution and transferring it to the aqueous phase as a Ni salt or for subsequent separation or use. The resulting solution(s) from one or more stripping stages can be passed to a collection tank for direct use, washing, or scrubbing, or the nickel can be precipitated so that it can be collected and, optionally, used for one or more downstream processes or for the formation of other materials.

[0043] The provided process according to some embodiments of the present disclosure comprises a nickel-poor solution (Li +The extraction of Li may optionally be carried out in a continuous manner by adding one or more subsequent extraction stages, either continuously or discontinuously, to extract lithium from the solution. 2+ / Li + This involves the formation of a nickel-lean solution formed as a result of prior Ni extraction from the solution. The nickel-lean solution is optionally subjected to direct precipitation of Li, such as by direct precipitation with a carbonation agent or the like, or to one or more Li extraction steps in which the nickel-lean solution is contacted with one or more lithium-selective extractants, or a combination thereof. The number of Li extraction steps may be the same as or different from the number of Ni extraction steps, and may include Li-selective extractants (organic) and Li-selective extractants similar to those described for Ni extraction. + A countercurrent process of the solution can be used.

[0044] In some embodiments, Li can be converted to Li by contact with a carbonation agent, as shown in FIG. + The carbonation agent is precipitated directly from the solution. Examples of carbonation agents include carbon dioxide and ammonia, carbon dioxide, sodium carbonate, ammonium carbonate, or combinations thereof. The carbonation agent is added to the chamber with Li + The lithium carbonate salt can be formed by contacting the lithium carbonate solution with the lithium carbonate and incubating for a desired time and at a desired temperature, optionally between −5° C. and 120° C. The lithium carbonate can be further washed or otherwise processed, or can be used directly in the manufacture of a cathode electrochemically active material for use in primary or secondary batteries.

[0045] After precipitation, the resulting Li product can then be filtered from the supernatant and washed to form lithium carbonate, which can be utilized for the production of subsequent materials, optionally directly for the production of electrochemically active materials for lithiated cathodes.

[0046] The aqueous supernatant is optionally subjected to nanofiltration or other processes to separate residual sulfate remaining from the prior Ni stripping step and to recover purified water, which can then be used for subsequent stripping in the Ni isolation process.

[0047] In some embodiments, Li + The solution is subjected to an extraction process as shown in FIG. + The solution is passed through one or more extraction stages similar to the Ni extraction discussed above. + The solution may optionally contain an alkaline agent to adjust the pH to a desired level for improved extraction, and Li + The solution is contacted with a lithium-selective extractant suitable for extracting lithium from the solution and transferring it to an organic phase containing the lithium-selective extractant.

[0048] In some embodiments of the present disclosure, the process for the extraction of Li + The solution is contacted with an alkaline agent to form Li + and adjusting the pH of the solution to about 1.0 to about 10.0. Suitable alkaline agents can include calcium oxide, sodium hydroxide, potassium hydroxide, aqueous ammonia, or combinations thereof. Optionally, the alkaline agent excludes sodium salts. Optionally, the alkaline agent excludes potassium salts. Optionally, the alkaline agent excludes calcium salts.

[0049] Optionally, the alkaline agent is Li + In one or more extraction steps, Li + It is provided in an amount and concentration that adjusts the pH of the solution to between about 1.0 and about 10.0. Optionally, Li after contact with the alkaline agent is +The pH of the solution is about 1.5 to about 9.5, about 2.0 to about 9.0, about 2.5 to about 8.5, about 3.0 to about 8.0, about 3.5 to about 7.5, about 4.0 to about 7.0, about 4.5 to about 6.5, about 5.0 to about 6.0, or about 6.0 to about 7.5. Optionally, an alkaline agent is introduced in one or more extraction stages to adjust the pH of the solution to about 3.0 or more, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, or about 8.0 or more. Optionally, the pH is adjusted in one or more extraction stages by contact with an alkaline agent to bring or maintain the pH of the extraction solution to about 6.0 to about 7.0.

[0050] Following or simultaneously with contact with an alkaline agent, Li + The solution is contacted with one or more lithium-selective extractants. Optionally, the lithium-selective extractant is added up to 10%-40% v / v, optionally 10%-30% v / v, optionally 15%-25% v / v. Optionally, the lithium-selective extractant is added at a volume percentage of 10%, 15%, 20%, 25%, or 30%. The solution of lithium-selective extractant is optionally added up to the aforementioned volume percentages from a substantially purified or saturated solution of lithium-selective extractant.

[0051] Examples of such lithium-selective extractants include 2-hydroxy-5-nonylacetophenone oxime (LIX 84-I), LIX 54-100, LIX 55 (BASF), CYANEX 936 (SOLVAY) and CYANEX 923 (SOLVAY), which is a mixture of four trialkylphosphine oxides R3P(O), R2R'P(O), RR'2(O), and R'3P(O), where R is a linear C8-alkyl radical and R' is a linear C6-alkyl radical, or any blend of these reagents. In some embodiments, the lithium-selective extractant is an acid. Suitable acids can include 2-ethylhexylphosphonic acid, mono-2-ethylhexyl ester, neodecanoic acid, or combinations thereof.

[0052] In some embodiments, the lithium-selective extractant further comprises a hydrocarbon as a diluent. Suitable hydrocarbons can include kerosene, paraffin, naphthene, or a combination thereof. The lithium-selective extractant and the hydrocarbon can be present together in various ratios. Optionally, the ratio of the lithium-selective extractant to the hydrocarbon can range from about 1:99 to about 99:1 on a volumetric basis. Optionally, the ratio of the lithium-selective extractant to the hydrocarbon is from about 50:50 to about 20:80 on a volumetric basis. Optionally, the ratio of lithium-selective extractant to hydrocarbon is from about 2:98 volume percent to about 45:55 by volume, from about 3:97 by volume to about 40:60 by volume, from about 5:95 by volume to about 40:60 by volume, from about 7:93 by volume to about 35:65 by volume, or from about 10:90 by volume to about 30:70 by volume, and each of the lithium-selective extractant and hydrocarbon is derived from a substantially isolated or saturated solution of the lithium-selective extractant or hydrocarbon, respectively.

[0053] The processes including Li extraction provided herein optionally include one or more extraction stages, in series or parallel. Optionally, a lithium-selective extractant, pH adjustment, or other may be used to extract Li. + The number of extraction stages contacting the solution may be 1, 2, 3, 4, 5, 6, 7 or more stages. The result of one or more extraction stages is a Li-rich solution and a Li-poor solution. The Li-poor solution (or the result of lithium extraction) optionally contains 1000 ppm Li or less. + , 500ppm or less of Li + , 100ppm or less of Li + , 10ppm or less of Li + , less than 9 ppm Li + , less than 8 ppm Li + , 7ppm or less Li + , 6ppm or less Li + , less than 5 ppm Li + , less than 4ppm Li + , less than 3 ppm Li + , less than 2 ppm Li + or less than 1 ppm Li + It is.

[0054] For lithium-poor solutions, optionally add Li + The amount of Li in the solution is less than 10 percent by weight. Optionally, in the lithium-poor solution, optionally, Li + The amount of Li in the solution is less than 1 percent, optionally less than 0.1 percent, optionally less than 0.01 percent, optionally less than 0.001 percent, and optionally less than 0.0001 percent by weight.

[0055] The lithium-rich solution resulting from the extraction step is optionally subjected to one or more stripping steps to obtain an isolated Li product, optionally in the form of a Li salt. In one or more stripping steps, the pH of the lithium-rich solution is lowered by a combination with an acid such as H2SO4, HCl or other suitable acid. An acid is optionally added to lower the pH from that of the extraction solution(s), optionally to about 3.0 or less, optionally to 2.0 or less, thereby stripping the Li from the Li-rich solution and transferring it to the aqueous phase as a Li salt or for subsequent separation or use. The resulting solution(s) from one or more stripping stages can be passed to a collection tank for direct use, washing, or scrubbing, or the lithium can be precipitated so that it can be collected and, optionally, used for one or more downstream processes or for the formation of other materials.

[0056] The extracted nickel, lithium, or both, are optionally washed, the liquid material is filtered, and the product is suitable for use in one or more downstream processes.

[0057] The process, and the lithium and / or nickel produced thereby, provides an extraction method that produces excellent recovery yields, resulting in materials that can be recycled or sold for use in lithium-ion batteries.

[0058] Various aspects of the present disclosure are illustrated by the following non-limiting examples. The examples are for illustrative purposes and are not intended to limit the practice of the present disclosure. It will be understood that variations and modifications can be made without departing from the spirit and scope of the present disclosure. Reagents and materials shown herein are obtained from commercial sources unless otherwise specified.

[0059] experiment The extraction circuit was set up substantially as shown in Figure 2 so as to be a continuous loop system allowing for consistent extraction of Ni or Li from the initial solution. This example illustrates the extraction of nickel from an aqueous pregnant leach solution (PLS) formed at Ni: 31.03 g / L, Li: 8.06 g / L, pH: 1.94.

[0060] The PLS was prepared in the laboratory from NiSO4·6H2O, Li2SO4, and H2SO4 and was intended to resemble the standard process solution after delithiation of LiNiO2 electrochemically active material. The PLS was diluted 1:1 v / v with water before entering the primary mixing box of the E1 stage (Figure 2). The organic phase used for Ni extraction consisted of a 29.16 v / v% solution of LIX84-IC (water-insoluble 2-hydroxy-5-nonylacetophenone oxime; BASF) in Orform SX-12 (CAS 64742-47-8; Chevron Phillips). The strip solution was 120 g / L H2SO4. Deionized water was used in the wash stage.

[0061] The circuit design from top to bottom (Figure 2) consisted of five extraction stages (E1-E5), one wash stage (W1), and two strip stages (S1, S2). The Ni-rich organic phase was subjected to a series of wash stages upstream of the strip stage. The extraction stages were designed to flow in series. The organic and aqueous solutions were designed to flow countercurrent to each other. Two strip stage configurations were tested: in parallel (Figure 2A) and in series (Figure 2B).

[0062] The organic phase flowed serially from bottom to top across the circuit as shown, from a loaded surge tank, through the extraction stage, through the wash stage, through the strip stage, and back to the loaded surge tank.

[0063] PLS was fed to the furthest extraction stage at the top, E1, as shown in Figures 2A and B. Within each stage, PLS traveled through a primary and secondary mixing box to a settler. The primary mixing box introduced the alkaline agent, and the secondary mixing box introduced the Ni-selective extractant in the organic phase. However, the overall PLS flow was from top to bottom through the circuit, as shown in Figures 2A and 2B.

[0064] When the strip stages were configured in series, the aqueous phase flowed from top to bottom across the circuit, countercurrent to the organic phase.

[0065] A pH dosing pump was used in each extraction stage to maintain the pH in each primary mix box at 7. Each dosing unit pumped a 9:1 diluted 29% ammonium hydroxide solution (reagent:water). Base was added to the primary mix boxes in stages E1 and E2 and to the premix boxes in stages E3-E5 to allow mixing with the PLS prior to contact with the organics in the primary mix boxes.

[0066] Aqueous and organic samples were taken from each settler and analyzed for Ni and Li amounts. The results of Ni extraction are shown in Table 1. [Table 1]

[0067] As shown in Table 1, the amount of Ni in the aqueous phase decreases rapidly as it passes through extraction stages E1 to E5, with virtually no Ni remaining (below the detection limit) by E3. Following the strip stage, Ni is effectively isolated and available for further processing, while the organic phase is renewed, washed if necessary, and can be used for subsequent Ni extraction.

[0068] Various modifications of the present disclosure in addition to those shown and described herein will be apparent to those skilled in the art. Such modifications are also intended to fall within the scope of the appended claims.

[0069] Unless otherwise specified, it is understood that all reagents are available from sources known in the art.

[0070] This description of the specific embodiment(s) is merely exemplary in nature and is in no way intended to limit the scope of the disclosure, its application, or use, which may of course vary. Materials and processes are described in conjunction with non-limiting definitions and terminology contained herein. These definitions and terminology are not designed to serve as limitations on the scope or implementation of the disclosure, but are presented for illustrative and explanatory purposes only. Although a process or composition is described as a sequence of individual steps or using specific materials, the steps or materials may be interchangeable, such that the description of the disclosure may include multiple parts or steps arranged in many ways that are readily understood by those skilled in the art.

[0071] It will be understood that terms such as first, second, third, etc. may be used herein to describe various elements, components, regions, layers, and / or sections, but these elements, components, regions, layers, and / or sections should not be limited by these terms. These terms are used only to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a "first element," "component," "region," "layer," or "section" discussed below could be referred to as a second (or other) element, component, region, layer, or section without departing from the teachings of this specification.

[0072] The terminology used herein is for the purpose of describing only certain aspects of the disclosure and is not intended to be limiting. As used herein, the singular forms "a", "an" and "the" are intended to include the plural, including "at least one", unless the content clearly dictates otherwise. "Or" means "and / or". As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. As used herein, the terms "comprises" and / or "comprising", or "includes" and / or "including" specify the presence of the stated features, regions, integers, steps, operations, elements, and / or components, but are further understood not to preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and / or groups thereof. The term "or combinations thereof" refers to combinations including at least one of the aforementioned elements.

[0073] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure belongs. Terms as defined in commonly used dictionaries should be interpreted to have a meaning consistent with their meaning in the context of the relevant art and this disclosure, and will not be interpreted in an ideal or overly formal sense unless expressly defined herein.

[0074] The patents, publications, and applications mentioned in this specification are indicative of the level of those skilled in the art to which this disclosure pertains. These patents, publications, and applications are herein incorporated by reference to the same extent as if each individual patent, publication, or application was specifically and individually incorporated by reference.

[0075] The foregoing description illustrates certain aspects of the disclosure but is not meant to limit their practice.

Claims

1. Nickel(II) / Lithium(I) (Ni ２＋ / Li ＋ 2.) A process for extracting nickel, lithium, or both from a solution, comprising the steps of: (A) Ni, containing a certain amount of lithium and a certain amount of nickel. ２＋ / Li ＋ Providing a solution; (B) The Ni ２＋ / Li ＋ The solution is treated with an alkaline agent to ２＋ / Li ＋ adjusting the pH of the solution to 1.0 to 10.0; (C) Said Ni ２＋ / Li ＋ The solution is treated with the Ni ２＋ / Li ＋ Treating the solution with a nickel-selective extractant to extract nickel from the solution, thereby ２＋ / Li ＋ Less Ni than solution ２＋ Li having ＋ generating a solution; and The Ni provided in step (A) ２＋ / Li ＋ the solution is a solution of a waste stream following delithiation of a lithium nickel oxide material; and Steps (B) and (C) are repeated alternately between the nickel-selective extractant and the alkaline agent; and The nickel-selective extractant is an oxime or a carboxylic acid; The waste stream after delithiation of the lithium nickel oxide material comprises: LiNiO2, LiNiMO2, where M is Mn, Mg, Al and / or Co; LiNiCoAlO2, or LiNiCoAlM'O2 (wherein M' is Mn, Al, Mg, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si and / or B). a waste stream after delithiation of an electrochemically active material selected from the pH of the Ni 2+ / Li + solution in step (B) is 6.0 to 8.0; the Li+ solution of step (C) contains less than 1000 parts per million of Ni2+; and The process further comprises treating the Li+ solution with a carbonation agent to produce a lithium salt, or the process further comprises treating the Li+ solution with a lithium-selective extractant to produce a concentrated lithium salt solution.

2. The waste stream after delithiation of the lithium nickel oxide material is LiNiO ２ 10. The process of claim 1, which is a waste stream after delithiation of a material.

3. 3. The process of claim 1 or 2, further comprising isolating the lithium salt.

4. The Li ＋ The lithium salt is isolated by treating the solution with a carbonation agent to produce a lithium salt, the carbonation agent being carbon dioxide (CO ２ 4. The process of claim 3, wherein the inorganic salt is selected from the group consisting of sodium carbonate, ammonium carbonate, bicarbonate, and combinations of at least two of the foregoing.

5. 4. The process of claim 3, wherein the lithium salt is filtered and washed.

6. 6. The process of any one of claims 1 to 5, wherein the alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, and combinations of at least two of the foregoing.

7. 6. The process of claim 1, wherein the nickel-selective extractant is an oxime.

8. 8. The process of claim 7, wherein the oxime is selected from the group consisting of 5-nonylsalicylaldoxime, 5-dodecylsalicylaldoxime, 5-nonyl-2-hydroxyacetophenone oxime, and combinations of at least two of the foregoing.

9. 6. The process of claim 1, wherein the nickel-selective extractant further comprises a hydrocarbon.

10. 10. The process of claim 9, wherein the hydrocarbon is selected from the group consisting of kerosene, paraffin, naphthene, and combinations of at least two of the foregoing.

11. 10. The process of claim 9, wherein the nickel-selective extractant and hydrocarbon are present in an amount of from 10:90 volume percent to 30:70 volume percent.

12. The process of any one of claims 1 to 5, wherein step (C) is carried out at a pH of 7.

0.

13. 2. The process of claim 1, wherein the lithium-selective extractant is 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, neodecanoic acid, or a combination of at least two of the foregoing.

14. 10. The process of claim 1, wherein the lithium-selective extractant further comprises a hydrocarbon.

15. 15. The process of claim 14, wherein the hydrocarbons are selected from the group consisting of kerosene, paraffins, naphthenes, or combinations of at least two of the foregoing.

16. Prior to step (A), the process further comprises the steps of: ２ The process of any one of claims 1 to 5, further comprising delithiating the compound.

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