Method for preparing high purity nickel sulfate solution

Abstract

The present invention provides a method for preparing a high purity nickel sulfate solution comprising the steps of: i. providing an aqueous feed solution comprising nickel, cobalt, calcium and magnesium; ii. extracting cobalt, calcium and partially magnesium from said aqueous feed solution using a first solvent comprising a first alkyl phosphorus based acidic extractant, thereby obtaining an aqueous raffinate comprising nickel and magnesium; iii. extracting magnesium from said aqueous raffinate comprising nickel and magnesium using a second solvent comprising a second alkyl phosphorus based acidic extractant, thereby obtaining a high purity aqueous nickel sulfate solution comprising nickel and magnesium; and iv. stripping the first entraining solvent comprising cobalt, calcium and magnesium with an aqueous solution comprising a mineral acid.

Description

[Technical field]

[0001] The present invention relates to a novel method for producing a high purity aqueous nickel sulfate solution, which can be further processed in a crystallization unit to produce high purity nickel sulfate crystals having sufficient purity for use in electroless plating of nickel metal layers or in the production of battery materials. [Background technology]

[0002] The development of lithium-ion batteries, especially the use of nickel-manganese-cobalt and nickel-cobalt-aluminum cathode materials, has led to an increased demand for high-purity nickel sulfate, either as a solid or in solution. Indeed, impurities in the cathode material strongly affect the performance of the battery. Therefore, significant efforts have been devoted to the production of high-purity nickel sulfate in an industrially relevant manner.

[0003] In this regard, US2014 / 322109 provides a method for obtaining high purity nickel sulfate with low levels of impurities, specifically low levels of magnesium and chloride, by employing a selective nickel sulfide precipitation step and redissolution of nickel sulfide in a nickel sulfate solution. This solution is further purified by solvent extraction to remove cobalt and magnesium impurities, adjusting the concentration and pH of the acidic organic extractant or the acid concentration during processing. For concentrated nickel sulfate solutions, the described processing strategy is cumbersome, since it requires intermediate precipitation and redissolution of the nickel bulk, followed by solvent extraction to remove the impurities cobalt and magnesium. In particular, the nickel sulfide step is hazardous due to the risk of hydrogen sulfide generation. In addition, unrefined nickel crude typically contains much more impurities, while solvent extraction is only used to remove cobalt and magnesium.

[0004] CN107162067 relates to the field of solid waste recycling, and specifically discloses a method for recycling high-purity nickel sulfate from nickel-containing waste batteries. The method includes the steps of dismantling nickel-containing waste batteries into battery powder, dissolving the battery powder with acid to obtain a metal-containing solution, adding alkali metal sulfate, removing iron by oxidation precipitation method, further removing impurities by solvent extraction method to obtain magnesium-containing nickel liquid, passing the magnesium-containing nickel liquid through a chelating resin exchange column to selectively adsorb nickel ions and flowing out the magnesium-rich solution for treatment, desorbing nickel ions to obtain nickel sulfate solution, evaporating, cooling, crystallizing, filtering, and finally drying the nickel sulfate solution to obtain a purified nickel sulfate product. This lengthy and complicated process ensures that the recycled nickel sulfate is a high-purity product with a nickel content of up to 99.5% or more, while the impurity, i.e., magnesium, has a content of less than 0.005%. However, three different solvent extraction units are proposed to remove copper, manganese and cobalt in separate steps. Apart from the high investment costs, other impurities such as calcium and magnesium do not even appear to be removed. Finally, nickel is recovered by adsorption onto a resin, requiring a fourth separation step and a consumption of neutralizing agent equal to the amount of metal ions adsorbed. Overall, the described method is considered to be neither simple nor efficient.

[0005] EP1252345 describes a method for extracting cobalt from a cobalt-nickel solution with a nickel-added solvent to obtain a purified nickel sulfate stream. However, it does not teach how to remove impurities such as calcium and magnesium to very low levels, thereby producing a purified nickel sulfate solution for electroless nickel or battery applications. It seems likely that a solvent extraction method will be developed in which the formation of insoluble ammonium / nickel double sulfates can be avoided.

[0006] EP2784166 describes a method for producing a pure nickel sulfate solution in a number of process steps including sulfiding, redissolving, purification by precipitation and solvent extraction. In particular, the sulfiding and redissolving steps are costly operations that use sulfiding agents and produce nickel sulfide intermediates, both products being toxic and that can result in high toxicity and gaseous hydrogen sulfide generation upon contact and reaction with mineral acids. At the final stage, the purified nickel sulfate solution still contains 50 mg / L of magnesium impurity, which is too much for battery grade nickel sulfate, demonstrating the lack of selectivity of the proposed process.

[0007] EP 3733884 describes a solvent extraction process allowing the selective separation of magnesium from an acidic aqueous solution of sulfuric acid. The solvent extraction process involves the selective extraction of magnesium into an organic solvent by contacting an acidic aqueous solution of sulfuric acid containing nickel, cobalt and magnesium with an organic solvent under very specific extraction conditions, where magnesium is extracted either at a fairly low pH=1.5-2, i.e. with a concentrated solvent containing 40-60% alkylphosphonic acid as extractant, or at a higher pH=2.0-2.5 with a lower extractant concentration, i.e. with a solvent containing 20-50% alkylphosphonic acid. The process aims only at the removal of magnesium and does not separate cobalt from the nickel solution. Surprisingly, under the same extraction conditions, up to 46% of magnesium was removed from the nickel sulfate solution, with already about 9% of co-extracted nickel. Under such conditions, Mg / Ni separation factors of only 8-23 are obtained. When the extractant concentration in the solvent used was reduced below 40 vol.%, higher Mg / Ni separation factors of up to 35 were obtained, but with significantly lower magnesium removal, i.e., less than 28%.

[0008] EP3222735 discloses a method for separating cobalt and magnesium from a nickel-containing feed solution by liquid-liquid extraction, where the organic solvent used contains an alkylphosphinic acid as the extracting agent. Both cobalt and magnesium are extracted together with some nickel. First, the nickel is washed out of the loading solvent with an acidic solution. The resulting nickel solution may contain some cobalt and is returned to the feed solution. After this, the magnesium is washed out of the solvent with an acidic solution. The resulting magnesium solution may contain some cobalt and is treated elsewhere. The cobalt is stripped from the solvent with a dilute aqueous solution of acid to form a cobalt strip solution. Besides cobalt and magnesium, this patent does not address the removal of other metal contaminants in the nickel sulfate solution, such as calcium, zinc, cadmium, copper, manganese and iron. The patent also does not detail how to reach the desired pH for the extraction of cobalt and magnesium from the nickel sulfate solution, which considers the release of acidic protons during extraction with an acidic extractant.

[0009] When EHEHPA, also known as PC88A, is used as the extractant, the extraction behavior for magnesium or calcium is similar to that for nickel. JP10-310437 discloses an example of the separation of nickel and cobalt by extraction of cobalt together with other impurities such as calcium, copper, zinc, iron and magnesium by solvent extraction using PC88A as the extractant. When a solution containing nickel in high concentration is subjected to solvent extraction, the problem arises that the extraction efficiency of magnesium or calcium is reduced. Difficulties are mentioned for removing magnesium from nickel sulfate solutions. The final impurity output concentrations in the purified nickel sulfate solution were still 3-26 mg / L cobalt, 2-7 mg / L calcium and 10-27 mg / L magnesium when it contained 90-117 g / L nickel. The present invention solves the problem of insufficient calcium extraction by the selection of operating conditions that favor calcium extraction but at the same time reduce magnesium extraction. This is offset by carrying out an additional separate solvent extraction of magnesium using a more favorable extractant and more favorable operating conditions.

[0010] In JP2021 / 031729, the treatment of a crude nickel sulfate solution in one solvent extraction process is shown, in which it is attempted to simultaneously remove all cobalt, magnesium and calcium from the nickel sulfate solution. The ratio of the amount of nickel added to the solvent to the concentration of cobalt in the nickel sulfate solution must vary depending on the desired removal of impurities. However, from the examples it can be seen that it is not possible to remove all the impurities, since the purified nickel sulfate solution still contains 1-60 mg / L cobalt, 1-20 mg / L magnesium and 1-15 mg / L calcium. Moreover, the removal of magnesium seems to be slight, since the input concentration of magnesium in the crude nickel sulfate solution is very low, only 19-31 mg / L magnesium, compared to the very high cobalt concentration of 8-12 g / L cobalt. This principle of co-extracting even trace amounts of magnesium together with large amounts of cobalt, even if incomplete, is evidence that a large amount of nickel is necessarily used in the solvent. It merely asserts that increasing the amount of nickel added to the solvent, relative to the concentration of cobalt in the crude nickel sulfate solution, will result in better magnesium removal. A similar patent, JP2021 / 031730, asserts that the amount of magnesium reported for the cobalt eluate from coextraction into the solvent can be influenced by the selected amount of nickel in the solvent, relative to the concentration of cobalt present in the crude nickel sulfate solution. It is the same example as JP2021 / 031729. The purified nickel sulfate solution may still contain impurities as high as 1-60 mg / L cobalt, 1-20 mg / L magnesium, and 1-15 mg / L calcium. It should be noted that the reported amount of magnesium coextracted into the cobalt eluate may vary appreciably.

[0011] In US6,149,885, a method is described in which impurities such as cobalt, calcium, copper and zinc are removed from a crude nickel sulfate solution by solvent extraction. A method is disclosed on how nickel is added to a solvent that can be used later to remove impurities from the crude nickel sulfate solution. However, magnesium is only sparingly removed. In one example, 34 mg / L of magnesium still remains in the purified nickel sulfate solution, which is usually considered too impure for battery grade nickel sulfate quality. In another example, as much as 354 ppm of magnesium for 100% nickel remains in the purified nickel sulfate solution. Removal of other metals such as cadmium and manganese from the crude nickel sulfate solution is not even considered.

[0012] JP2021 / 105206 discloses a solvent extraction method that can improve the separability between nickel and cobalt in the nickel recovery stage. The presented solvent extraction method includes a nickel recovery stage, in which an acidic extraction agent carrying nickel and cobalt and an acid are contacted to obtain a nickel recovery solution for nickel back extraction. The extraction temperature in the nickel recovery stage is set at 47-60°C. Since the extraction temperature in the nickel recovery stage is set at 47°C or higher, the distribution ratio of cobalt to the organic solvent can be increased while a low distribution ratio of nickel to the organic solvent is maintained, so that the separability between nickel and cobalt can be improved. While JP2021 / 105206 shows that the amount of magnesium and calcium in the nickel solution is influenced by the extraction method for separating nickel from cobalt, it does not teach how to optimally reduce the amount of magnesium and calcium impurities in the nickel solution.

[0013] US2008 / 0003154 describes a two-stage solvent extraction circuit for selectively removing zinc and cobalt metal impurities from the valuable metal nickel. In order to selectively extract zinc, there must be sufficient separation between zinc and cobalt in the Cyanex 272 system. Similarly for cobalt and nickel, the separation factor must be large enough to obtain a pure nickel product. The process for solvent extraction of metal impurities is operated at a temperature of 80°C to 100°C. It is recognized that cobalt can be selectively extracted from nickel, and that any iron, copper, zinc, manganese and magnesium are completely co-extracted with the cobalt. Further removal of impurities from the nickel is not advised, and therefore the impurities are considered to be present at very low levels. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] US2014 / 322109 [Patent Document 2] CN107162067 [Patent Document 3] EP1252345 [Patent Document 4] EP2784166 [Patent Document 5] EP3733884 [Patent Document 6] EP3222735 [Patent Document 7] JP10-310437 [Patent Document 8] JP2021 / 031729 [Patent Document 9] JP2021 / 031730 [Patent Document 10] US6,149,885 [Patent Document 11] JP2021 / 105206 [Patent Document 12] US2008 / 0003154 Summary of the Invention [Problem to be solved by the invention]

[0015] In conclusion, there is a need for a simple and practical method, which achieves high purity nickel sulfate with low levels of cobalt, calcium, magnesium and other impurities, resulting in nickel sulfate that can be used in applications requiring high purity, such as electroless plating of nickel metal layers or precursors for battery cathode materials. It is an object of the present invention to provide a novel method for producing a high purity nickel sulfate solution from an aqueous nickel solution containing impurities such as cobalt, magnesium and calcium, and optionally iron, zinc, copper, cadmium and manganese. Moreover, it is an object of the present invention that nickel sulfate with stable quality can be produced simply. Finally, it is an object of the present invention to provide a method capable of producing a cobalt-rich aqueous solution suitable for further processing from nickel crude. [Means for solving the problem]

[0016] The current invention provides a solution to at least one of the aforementioned problems by providing a method for preparing a high purity nickel sulfate solution as claimed in claim 1.

[0017] The present invention has the advantage that the elements cobalt, zinc, manganese, cadmium, aluminum, copper, calcium, as well as magnesium, if any, are completely separated from nickel. The present invention consists of a two-stage solvent extraction process in which the mentioned impurities are completely removed in a first step, all except magnesium, and in a second step the residual magnesium is removed.

[0018] The overall process described in the present invention is efficient in the sense that it provides a high purity nickel solution, i.e. at least 99.8 at.% nickel with respect to the metal content of said solution, while avoiding material losses due to minimal co-extraction of the matrix element nickel, and by this means avoiding the formation of complex nickel-containing mixtures. The process described in the present invention is therefore environmentally friendly. The processing strategy is such that it avoids the presence in the final solution of undesired ions such as calcium from the calcium base, sodium from the sodium base and chloride from the hydrochloric acid, originating from the reagents used during the nickel purification process in the nickel sulfate final solution. Thus, the nickel sulfate solution obtained from the presented process can be easily further processed by crystallization or spray drying to form nickel sulfate crystals or granules, respectively, which can be easily transported. Advantageously, the present invention can also produce a cobalt-rich eluate, which can be further processed separately to produce high purity cobalt salts, for example as cobalt chloride, cobalt sulfate or others. The process of the present invention is simple, environmentally friendly and provides high purity nickel sulfate.

[0019] As a further guide, figures are included to better understand the teachings of the present invention. The figures are intended to aid in the explanation of the present invention and are not intended to limit the invention disclosed herein. The figures and symbols contained herein have meanings commonly understood by those skilled in the art to which the present invention pertains. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 shows a schematic diagram of a method according to a first embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Unless otherwise defined, all terms used in disclosing the present invention, including technical and scientific terms, have the meanings commonly understood by one of ordinary skill in the art to which this invention belongs. As a further guide, definitions of terms are included to better understand the teachings of the present invention.

[0022] As used herein, the following terms have the following meanings:

[0023] As used herein, "a," "an," and "the" refer to both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a compartment" refers to one or more than one compartment.

[0024] As used herein, "about" refers to measurable values ​​such as parameters, amounts, durations, and the like, and is meant to encompass variations of the particular value and variations from the particular value of + / -20% or less, preferably + / -10% or less, more preferably + / -5% or less, even more preferably + / -1% or less, and even more preferably + / -0.1% or less, insofar as such variations are appropriate to play a role in the disclosed invention. However, values ​​to which the modifier "about" refers are themselves to be understood as specifically disclosed.

[0025] As used herein, "comprise," "comprising," and "comprises," as well as "comprised of," are synonymous with "include," "including," "includes," or "contain," "containing," or "contains," and are inclusive or open-ended terms that at least specify the presence of what follows, but do not exclude or preclude the presence of additional, unrecited components, properties, elements, materials, or steps that are known in the art or disclosed herein.

[0026] The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range, as well as the recited endpoints. Unless otherwise defined or a different meaning is apparent to one of ordinary skill in the art from its usage and the context in which it is used, all percentages are to be understood as mass percentages, abbreviated as "wt.%," or volume percentages, abbreviated as "vol.%," or atomic percentages, abbreviated as "at.%."

[0027] With respect to the organic phase, the following terms are used to identify its components or in totality: i. An "extractant" or extracting agent is an active component in the organic phase that extracts metal species into the organic phase by chemically bonding with the active component and forming a metal-extractant complex that is better soluble in the organic phase than in the aqueous phase. ii. "Diluent" is an organic molecule or a mixture of different organic molecules that is usually added to the organic phase to dilute the extractant and to allow dissolution of the metal complexes, improve the physical properties of the organic phase (especially the phase separation phenomenon) and reduce its cost, considering that the diluent is usually cheaper than the extractant. The diluent is often a kerosene fraction and can be an aliphatic or aromatic hydrocarbon, naphthene, etc., or a mixture of these. iii. The organic phase may contain "modifiers". Modifiers are sometimes added to improve the solubility of metal complexes in the organic phase, to change the physical properties of the solvent, and to avoid crud formation or the formation of a third phase, which are undesirable during solvent extraction. Modifiers can be added to prevent chemical decomposition of the extractant or diluent. However, modifiers may impair the selectivity of the organic phase, since they may participate in the complexation of metals with the extractant. iv. "Organic Phase" is another term used to identify a "solvent" or "solvent mixture" and includes a mixture of extractants, diluents, and optionally modifiers.

[0028] The "selectivity" S of an extractant for one metal over another can be expressed as the ratio of the distribution coefficients D for both metals. SMg / Ni =D Mg / D Ni

[0029] The "partition coefficient" of a metal is understood to be the ratio of the equilibrium concentrations of that metal in the organic phase and the same metal in the aqueous phase, respectively; D M =[M] O / [M] A where M is a metal such as nickel or magnesium, O refers to the organic phase, and A refers to the aqueous phase.

[0030] In the context of the present invention, the term "solvent extraction circuit" should be understood as a synonym of the terms "solvent extraction", "solvent extraction method", "solvent circuit", "solvent loop" or "solvent extraction loop" and refers to a series of one or more solvent extraction sections, each consisting of one or more solvent extraction stages. Although each extraction section can proceed with a different set of process parameters such as temperature, pH profile and solvent-water ratio, a solvent extraction circuit utilizes only one organic phase. The organic phase composition of a solvent extraction circuit is fixed, since it is characterized by a single set of parameters such as extractant type, diluent type and extractant-diluent ratio.

[0031] In a first aspect, the present invention provides a method for preparing a high purity nickel sulfate solution, comprising the steps of: i. providing an aqueous feed solution comprising nickel, cobalt, calcium and magnesium, and, if present, zinc, manganese, cadmium, and / or copper; ii. extracting cobalt, calcium and at least some magnesium from said aqueous feed solution using a first organic phase comprising a first alkyl phosphorus based extractant (I) and a first diluent, thereby obtaining an aqueous raffinate solution (A1) containing nickel and residual magnesium content, and a cobalt-rich organic phase (O1), the organic phase typically containing calcium, magnesium and nickel, and, if present, zinc, copper, cadmium and manganese; iii. extracting magnesium from said aqueous raffinate solution (A1) using a second alkylphosphorus based extractant (II) and a second organic phase (O2) comprising a second diluent, thereby obtaining a magnesium-depleted aqueous high-purity nickel sulfate solution (A2) and a magnesium-enriched organic phase; The present invention provides a method comprising:

[0032] The invention has the advantage that the elements cobalt, magnesium, calcium and, if present, further zinc, manganese, cadmium, iron, aluminum and copper are completely separated from nickel in a single process. By this process, a high purity aqueous nickel sulfate solution (A2) is obtained, which contains nickel with a concentration of 40-200 g / L and magnesium with a concentration of at most 10 mg / L, two added organic phases, namely a cobalt-rich organic phase (O1) containing calcium, magnesium and nickel and, if present, zinc, copper, cadmium and manganese, and a magnesium-enriched organic phase (O2) containing nickel and magnesium. Preferably, said high purity aqueous nickel sulfate solution contains at most 5 mg / L magnesium, and even more preferably at most 1 mg / L. The first and second organic phases may contain modifiers.

[0033] The aqueous raffinate solution A1 contains magnesium at a concentration of 20 mg / L to 20 g / L, preferably 20 mg / L to 2 g / L, and more preferably 20 mg / L to 500 mg / L, together with nickel sulfate.

[0034] Generally, the residual magnesium content in the resulting aqueous raffinate solution (A1) is too concentrated for high purity applications and is therefore subjected to a second solvent extraction step.

[0035] The solvent extraction steps ii and iii can be carried out in any suitable apparatus, without any particular limitation. The solvent extraction equipment generally comprises at least one or more apparatuses consisting of mixer settlers, column contactors, centrifugal contactors or any other type of contactor. Preferably, the extraction is carried out in a countercurrent configuration.

[0036] Preferably, the present invention further provides a method according to the first aspect of the present invention, further comprising a step iv, in which the cobalt-rich organic phase (O1), containing calcium, magnesium and nickel, and, if present, zinc, copper, cadmium and manganese, is stripped with an aqueous solution containing a mineral acid, thereby effectively resulting in the elution of cobalt, calcium, magnesium and, if present, zinc, copper, cadmium and manganese from the first solvent. Preferably, the mineral acid is one or more selected from the group comprising hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, boric acid and perchloric acid. More preferably, the mineral acid is one or more selected from the group comprising hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid and perchloric acid. In another embodiment, the mineral acid is sulfuric acid. Most preferably, the mineral acid is hydrochloric acid. This allows a concentrated eluate containing cobalt, calcium, magnesium and, if present, zinc, copper, cadmium and manganese to be obtained from the first solvent.

[0037] The stripping step can be carried out in any suitable device, and is not particularly limited.The stripping equipment generally includes at least one or more devices consisting of a mixer settler, a column contactor, a centrifugal contactor, or any other type of contactor.Preferably, the stripping step is carried out in a countercurrent configuration.

[0038] In a preferred embodiment, the present invention provides a method according to the first aspect of the invention, wherein said aqueous feed solution comprising nickel, cobalt, calcium, magnesium and optionally zinc, copper, cadmium and manganese is obtained by a step of removing iron and / or aluminium from a pregnant leach solution comprising nickel, cobalt, calcium, magnesium and iron and / or aluminium, and optionally calcium, zinc, copper, cadmium and manganese. The iron and / or aluminium may advantageously be removed by adding a basic reagent such as a hydroxide or other to said aqueous solution, thereby forming an iron and / or aluminium hydroxide precipitate. Potentially, for example the addition of an oxidising agent such as oxygen or hydrogen peroxide may be included in the iron and / or aluminium removal step.

[0039] In a preferred embodiment, the iron and / or aluminum is removed by precipitation using a calcium base such as calcium hydroxide, calcium oxide, calcium carbonate, calcium bicarbonate, or any other calcium-containing basic reagent. The use of a calcium base is advantageous because calcium forms calcium sulfate, also called gypsum, which has low water solubility in this step of the process. Therefore, the use of an excess of calcium base is not detrimental to the purity of the resulting nickel sulfate solution. Only a limited amount of calcium will remain in the nickel solution sent to the solvent extraction step ii. The latter process is designed to allow complete removal of calcium from the nickel solution. The formation of calcium sulfate during the precipitation of iron and / or aluminum enhances the filterability of the iron and / or aluminum precipitate. Therefore, it may be preferred that a calcium base is used in a stoichiometric excess with respect to the amount of iron and / or aluminum impurities present in the feed aqueous solution containing nickel, cobalt, magnesium, and iron and / or aluminum.

[0040] In another preferred embodiment, the base used may be nickel hydroxide or carbonate or any other nickel-containing basic reagent, thereby introducing beneficial nickel ions into the nickel sulfate solution. Other preferred nickel bases are nickel bicarbonate and nickel hydroxysulfate.

[0041] In yet another preferred embodiment, the base used may be magnesium hydroxide or carbonate or any other magnesium-containing basic reagent since magnesium is efficiently and effectively removed in subsequent steps of the process of the present invention. Other preferred magnesium bases are magnesium bicarbonate and magnesium hydroxysulphate.

[0042] In yet another preferred embodiment, impurities such as iron and / or aluminum may be separated by precipitation using a combination of two or more precipitating agents selected from calcium bases, magnesium bases and nickel bases.

[0043] Moreover, impurities such as iron and / or aluminum may be removed by precipitation in two or more precipitation steps, where a different precipitant can be used in each precipitation step. In a preferred embodiment, a nickel base is used in the first precipitation step and a calcium base is used in the subsequent precipitation step.

[0044] Alternatively, impurities such as iron and / or aluminum can be separated by other methods such as neutralization, however, the use of an alkaline base such as sodium hydroxide or potassium hydroxide introduces metal impurities into the aqueous feed solution that cannot be extracted by subsequent solvent extraction methods, and therefore may complicate potential crystallization or granulation processes at the end of the flowsheet.

[0045] In another embodiment, calcium is already present in the nickel feed solution involved in solvent extraction step ii, either because it was introduced previously with the feedstock or by using a calcium-containing reagent such as a calcium base, calcium hydroxide, calcium oxide, calcium carbonate, calcium bicarbonate, or another Ca-containing basic reagent prior to participating in solvent extraction step ii.

[0046] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the aqueous feed solution provided in step i comprises nickel in an amount of at least 60 at.% relative to the total metal content of the aqueous feed solution and cobalt in an amount of at most 40 at.% relative to the total metal content of the aqueous feed solution. Preferably, the aqueous feed solution comprises nickel in an amount of at least 70 at.% and cobalt in an amount of at most 30 at.%, more preferably the aqueous feed solution comprises nickel in an amount of at least 80 at.% and cobalt in an amount of at most 20 at.%, and most preferably the aqueous feed solution comprises nickel in an amount of at least 90 at.% and cobalt in an amount of at most 10 at.%.

[0047] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the aqueous feed solution provided in step i further comprises calcium, magnesium, zinc, copper, cadmium and manganese in a total amount of up to 25 at.% relative to the total metal content of the aqueous feed solution. Preferably, the aqueous feed solution further comprises calcium, magnesium, zinc, copper, cadmium and manganese in a total amount of up to 10 at.%, even more preferably in an amount of up to 5 at.%.

[0048] Thereby, the aqueous feed solution can come from all kinds of sources, such as mixed hydroxide precipitate, crude nickel sulfate or any other kind of suitable source, suitable as such or processed into a suitable feed solution, as required. The process can include filtration, selective filtration, dissolution, precipitation steps and / or any other kind of pre-treatment steps. Combinations of these are also possible. For example, a pre-treated battery recycle material containing nickel, cobalt, manganese and lithium can be processed in this flowsheet to produce a pure nickel sulfate solution, if the pre-treatment includes at least filtration and finally prior lithium removal. Alternatively, lithium is removed in the final stage of step iii, for example using a lithium ion exchange column.

[0049] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the extractant used in steps ii and iii comprises an alkyl phosphorus acid. Suitable alkyl phosphorus acids include bis(2-ethylhexyl)phosphoric acid (D2EHPA), (2-ethylhexyl)phosphonic acid mono(2-ethylhexyl)ester (EHEHPA, PC88A), bis-(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272 or IONQUEST 290), and diisooctylphosphinic acid (DOPA). Alkyl phosphorus acids function as chelating extractants due to the presence of coordinated phosphorus and oxygen atoms in these molecules. Compared with elements in aqueous solutions that are less likely to form chelates, elements that form corresponding chelates with higher stability are more likely to promote extraction efficiency.

[0050] When EHEHPA (PC88A) is used as an extractant, the extraction behavior of magnesium and calcium is similar to that of nickel. Therefore, when a solution containing nickel in high concentration is subjected to solvent extraction, the problem of reduced extraction efficiency of magnesium and calcium arises. The present invention solves the problem of insufficient calcium extraction by selecting operating conditions that favor calcium extraction but at the same time reduce magnesium extraction. The latter is offset by carrying out an additional separate solvent extraction of magnesium with a more favorable second extractant and operating conditions more favorable for the extraction of magnesium.

[0051] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the second extractant (II) has a higher magnesium selectivity than the first extractant (I). In other words, the second extractant (II) has a higher affinity for magnesium than the affinity of the first extractant (I). In addition, the second extractant (II) has a higher selectivity for magnesium over nickel. Most preferably, the second extractant (II) comprises an alkylphosphinic acid such as IONQUEST 290.

[0052] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the first extractant (I) has a higher selectivity for calcium over nickel than the second extractant (II). In other words, the first extractant (I) has a higher affinity for calcium over nickel than the affinity for calcium over nickel of the second extractant (II). In addition, the first extractant (I) has a higher selectivity for calcium over nickel. Most preferably, the first extractant (I) comprises an alkylphosphonic acid such as PC88A. Preferably, the first alkylphosphoric extractant (I) comprises an alkylphosphonic acid and / or a nickel salt thereof, and the second alkylphosphoric extractant (II) comprises an alkylphosphinic acid and / or a nickel salt thereof.

[0053] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the first and second diluents are hydrocarbons. More generally, any water-immiscible organic solvent capable of dissolving the extractant may be used. Thus, the diluent is not particularly limited. As examples of diluents, kerosene-based compounds may be used, which may be aliphatic, naphthenic, aromatic or even mixtures thereof.

[0054] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the first organic phase used in step ii comprises the first extractant (I) in an amount of 5-50 vol.% relative to the total volume of the first organic phase, and the first diluent in an amount of 50-95 vol.% relative to the total volume of the first organic phase. More preferably, the first organic phase comprises the first extractant (I) in an amount of 30-40 vol.% and the first diluent in an amount of 60-70 vol.%.

[0055] In a preferred embodiment, the present invention provides a process according to the first aspect of the present invention, wherein the second organic phase used in step iii comprises the second extractant (II) in an amount of 5-50 vol.% relative to the total volume of the second organic phase, and the second diluent in an amount of 50-95 vol.% relative to the total volume of the second organic phase. More preferably, the second organic phase comprises the second extractant (II) in an amount of 10-25 vol.% and the diluent in an amount of 75-90 vol.%. It has been found that the extractant concentration in the organic phase allows optimal extraction of magnesium without losing the processability of the solvent.

[0056] In a preferred embodiment, the extractant used in steps ii and iii is neutralized with an alkali metal hydroxide and preloaded with nickel at high pH, ​​before contacting the organic phase used for extraction in steps ii and iii, preloaded with nickel, with the aqueous feed solution containing impurities. In such a case, on the one hand, an exchange reaction occurs in which elements more likely to be extracted than nickel are transferred to the solvent, and on the other hand, nickel in the organic phase is transferred to the aqueous phase. As a result, impurities are removed from the aqueous feed solution, while increasing the nickel concentration in the resulting raffinate solution, thus largely avoiding the introduction of alkali metals from the neutralizing agent into the main process (raffinate) stream. As alkali metal hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide or the like may be used. Furthermore, preferably, sodium hydroxide is used as the alkali metal hydroxide.

[0057] It has been found that pre-loading the extractant used in steps ii and iii with nickel allows an optimum and improved extraction without losing the processability of the extractant. During this pre-loading step, the partially neutralized extractant, i.e. the alkali metal is in a converted form, exchanges the alkali metal of the extractant, typically sodium, with nickel from the aqueous nickel sulfate solution. Preferably, the residual amount of alkali metal in the pre-loading solvent is as low as possible, in order to limit the transfer of residual alkali metal from the pre-loading solvent to the aqueous feed solution when extracting impurities from this solution.

[0058] A portion of the nickel can be replaced by another harmless metal that will exchange with the impurities to be extracted from the aqueous nickel sulfate solution to be purified. This can be an alkali metal, such as sodium or potassium, or a similar species, such as ammonium. However, these other metals can cause extraction of such metals present in the aqueous nickel sulfate solution to be purified, or even contaminate the nickel sulfate solution by exchange with the impurities to be extracted.

[0059] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, in which prior to extraction, the extractant is converted into their nickel salts corresponding to the appropriate conversion of the extractant, thus containing nickel in an amount of 20-70% of the available extractant volume and residual sodium occupying up to a concentration of 2 g / L, preferably up to a concentration of 0.5 g / L, more preferably up to a concentration of 0.1 g / L. Preferably, nickel is pre-added in an amount of 25-60% of the available extractant volume, preferably more than 30% of the available extractant volume, and residual sodium occupying up to a concentration of 0.5 g / L. More preferably, nickel is pre-added in an amount of 30-50% of the available extractant volume and residual sodium occupying up to a concentration of 0.1 g / L.

[0060] The preferred nickel concentration of the pre-loading solvent is therefore based on the extractant concentration and the degree of conversion, both of which are determined by the target pH of the aqueous feed solution and are therefore a function of the total amount of impurities to be removed. On the one hand, a higher degree of conversion of the extractant leads to a higher pH during extraction, allowing for a greater extraction of impurities (and nickel) from the nickel-containing feed solution, and on the other hand, a lower degree of conversion of the extractant leads to a lower pH during extraction, allowing for a better selectivity of impurities relative to nickel.

[0061] In a preferred embodiment, the pre-loaded solvent containing nickel and possibly some other metals such as sodium, potassium or other metals, or other cations such as ammonium, may be contacted again with a pure nickel-containing solution such as a nickel sulfate or nickel chloride solution, thereby further exchanging the metallic sodium, potassium, ammonium or other metals of the solvent with nickel from the pure nickel-containing solution. The nickel pre-loading operation can be carried out in two or more stages, preferably in countercurrent operation, with at least a pure nickel sulfate solution, so as to possibly scrub the alkali metals co-extracted from the base used from the solvent. As a result, a nickel pre-loaded solvent containing significantly less other metals is obtained, which can be used in the extraction steps ii and iii, by which means contamination of the aqueous nickel solution with undesired metals is avoided to the greatest extent possible.

[0062] In a preferred embodiment, the present invention provides a process according to the first aspect of the present invention, wherein the aqueous feed solution involved in step ii has a pH between 1.0 and 6.0 prior to contacting with the solvent comprising extractant I, more preferably at a pH between 2.0 and 5.5, most preferably at a pH between 3.0 and 5.0 to generate chemical equilibrium between the aqueous nickel solution and the solvent.

[0063] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein said extraction in step ii is carried out at a temperature between 25 and 70°C, preferably between 30 and 60°C, more preferably between 30 and 55°C, or even between 30 and 50°C. More preferably, said extraction in step ii is carried out at a temperature between 35 and 45°C. The inventors have found that the extraction of calcium from the nickel solution is improved at lower temperatures. Thus, the extraction temperature in step ii is preferably below 50°C, preferably below 45°C. However, at lower temperatures the efficiency of cobalt extraction is reduced. Therefore, it is preferred that an extraction temperature above 25°C, preferably above 30°C, more preferably above 35°C is used. Therefore, most preferably, the extraction temperature in step ii is higher than 25°C and lower than 45°C, preferably higher than 30°C and lower than 45°C, more preferably higher than 35°C and lower than 45°C. In particular, said extraction temperature is 36°C, 38°C, 40°C, 42°C or 44°C, or any temperature in between.

[0064] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the aqueous raffinate solution obtained from step ii and involved in step iii has a pH of 2.0-7.0 prior to contacting with a second solvent comprising said extractant II, more preferably at a pH of 3.0-6.5, most preferably at a pH of 4.0-6.0 to generate chemical equilibrium between the aqueous nickel solution and the second solvent.

[0065] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein said extraction in step iii is carried out at a temperature of at least 25°C, at least 30°C, preferably at least 35°C, and at most 80°C. Preferably, said extraction in step iii is carried out at a temperature of 40-70°C, or even 45°C-65°C. More preferably, said extraction in step iii is carried out at a temperature of 50-60°C. The inventors have found that the extraction of magnesium from nickel solutions is improved by higher extraction temperatures. Nevertheless, it is preferred that the extraction temperature is limited to less than 80°C, less than 70°C or less than 65°C due to the processability of the organic solvent and the safety aspects of the organic solvent.

[0066] In a preferred embodiment, the present invention provides a method according to the first aspect of the invention, wherein said extraction in step iii is carried out at a temperature higher than the temperature of said extraction in step ii. Preferably, the temperature in step iii is at least 5°C higher than the temperature in step ii, more preferably at least 10°C higher, more preferably 10°C to 20°C higher, most preferably about 15°C higher.

[0067] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the high purity aqueous nickel sulfate solution obtained after step iii is subjected to crystallization or granulation. Preferably, the nickel sulfate in the nickel sulfate solution is crystallized, whereby an additional purification step can be performed. In case of granulation, any granulation technique known to the person skilled in the art is suitable, such as, for example, spray drying.

[0068] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, in which nickel is scrubbed from the cobalt-rich organic phase and / or from the magnesium-enriched organic phase. Nickel is first selectively scrubbed from these solvents by washing with an acidic solution, such as aqueous sulfuric acid, in order to recover this co-extracted nickel from the added organic phase before proceeding to the impurity stripping step. Nickel is selectively scrubbed by applying optimal conditions of pH, and in particular the acidity of the final scrubbing solution, and the amount of acid added is adapted to reach the required pH.

[0069] In a preferred embodiment, the present invention provides a method according to the first aspect of the present invention, wherein the stripping step in step iv is carried out with hydrochloric acid. The stripping step allows nickel to be eluted from the first loading solvent (O1) together with cobalt, calcium, magnesium and, if present, zinc, copper, cadmium and manganese. Thus, the extractant is regenerated to produce a metal-free solvent that can be reused for extraction or preloading. Considering the presence of calcium in the resulting stripping solution, the use of hydrochloric acid is preferred. The stripping step with hydrochloric acid leads to the formation of calcium chloride, which is readily soluble in water. In this way, the metal content can be concentrated from the solvent into the aqueous solution. Considering the low solubility of calcium sulfate, the use of sulfuric acid may induce the formation of solid precipitates that interfere with the solvent extraction process.

[0070] In a preferred embodiment, the hydrochloric acid solution has a concentration of at least 50 g / L, more preferably between 100 g / L and 300 g / L.

[0071] In a preferred embodiment, said stripping step in step iv is carried out at a temperature between 40°C and 55°C, preferably between 40°C and 50°C, more preferably at a temperature of about 45°C.

[0072] In a preferred embodiment, the present invention provides a post-treatment step according to the first aspect of the present invention, wherein said magnesium-depleted high purity nickel sulfate aqueous solution comprises nickel in a concentration of 40-180 g / L and magnesium in a concentration of at most 5 mg / L, preferably at most 1 mg / L. Preferably, said high purity nickel sulfate aqueous solution has a calcium, cobalt, iron, aluminum, zinc, manganese and / or cadmium content, each individually in an amount of at most 15 mg / L, preferably at most 10 mg / L, or even at most 5 mg / L.

[0073] In a preferred embodiment, the present invention provides a work-up step according to the first aspect of the present invention, in which the cobalt-enriched organic phase is additionally washed with sulfuric acid after the step of stripping with hydrochloric acid in step iv. Preferably, the solvent is washed with sulfuric acid in an aqueous solution having a concentration of 10-200 g / L. Washing with sulfuric acid allows the chloride ions and possibly residual metals such as iron or aluminum to be removed from the solvent. Thus, the solvent can be regenerated after pre-addition and reused for extraction.

[0074] In a preferred embodiment, the invention provides a step of stripping the second solvent containing magnesium and nickel with sulfuric acid. Preferably, the solvent is washed with sulfuric acid in an aqueous solution having a concentration of 10-200 g / L. In some cases, washing with sulfuric acid can also remove residual metals such as iron or aluminum from the solvent. Therefore, the solvent can be regenerated after pre-addition and reused for extraction. EXAMPLES

[0075] For each process step, examples are provided to further clarify the invention, but these examples are based on empirically derived data and are not intended to limit the scope of the invention.

[0076] Preparation of Feed Solutions The leaching solution was treated with NiSO 4 The leachate is obtained from the filtration of the crude material. The leachate is used as the Ni(OH) 2followed by Ca(OH) 2 The nickel sulfate aqueous solution is subjected to a de-ironization operation by neutralization with 2-methyl-2,4-diphenyl-1,1-tetrahydrofuran (1,2,3,4-tetramethylphenyl) ...

[0077] [Table 1]

[0078] Preparation of extractant I preloaded with nickel A first solvent is prepared by combining (2-ethylhexyl)phosphonic acid mono(2-ethylhexyl)ester (PC88A) and a hydrocarbon diluent, Escaid 110 (ExxonMobil). The first solvent is composed of 36 vol.% PC88A and 64 vol.% hydrocarbon diluent. In two successive steps, the solvent is contacted with an aqueous high-purity nickel sulfate solution containing 125 g / L nickel and 1.0 g / L sodium. A 125 g / L NaOH solution is added in the mixer settler in a volume such as to target a pre-loaded solvent containing 11 g / L nickel. This corresponds to a degree of conversion of 36% of the total extractant volume. After one pre-loading step, the solvent contains 10.4 g / L nickel and 0.82 g / L sodium. After the second pre-loading step, a solvent containing 10.8 g / L nickel and a residual sodium concentration of 0.12 g / L is obtained.

[0079] Extraction of cobalt, calcium and other impurities The aqueous feed solution is mixed in stages with a first solvent containing PC88A, preloaded with 9.1 g / L of nickel to extract cobalt, calcium, zinc, copper, manganese and some magnesium at a temperature of 40° C. The extraction section consists of four successive mixer settlers. A first loading solvent (O1) containing nickel, cobalt, calcium, magnesium, copper, zinc, manganese and cadmium and an aqueous raffinate solution (A1) containing significant residual amounts of magnesium together with nickel sulfate are obtained by adding sodium with a concentration of less than 1 g / L. The composition of the feed solution and the raffinate are presented in the table below. The increase in the nickel concentration in the aqueous raffinate compared to the nickel concentration in the aqueous feed solution is due to the nickel of the preloading solvent being stoichiometrically exchanged with impurities from the feed solution during the extraction.

[0080] [Table 2]

[0081] Stripping of Extractant I with Hydrochloric Acid After extraction, the first loading solvent containing sodium, nickel, cobalt, calcium, magnesium, zinc, cadmium and manganese is treated with an aqueous solution composed of hydrochloric acid having a concentration of 200 g / L at a temperature of 43° C. The elution section consists of a multi-stage mixer-settler setup. The solvent is regenerated, producing an aqueous eluate with a residual hydrochloric acid of 35 g / L. The composition of the loading and stripped solvent is presented in the table below.

[0082] [Table 3]

[0083] First solvent wash with sulfuric acid After the elution section, the first solvent may be washed with an aqueous solution composed of sulfuric acid. The most important goal of this post-treatment of the stripped solvent is to remove the hydrochloric acid entrained from the previous elution section. For this purpose, the stripped solvent is contacted with a sulfuric acid (33 g / L) solution. As a result, all residual impurities are removed from the stripped solvent, with Ni, Co, Ca, Mg, Zn, Mn, Cd, Na and Cl all being <1 mg / L. This solvent can therefore be regenerated for the next cycle.

[0084] Scrubbing of Extractant I with Sulfuric Acid After extraction, an additional scrubbing step, preceding the stripping step, may be determined to avoid nickel losses in the eluate. A first additive solvent containing sodium, nickel, cobalt, calcium, magnesium, zinc and manganese is combined with an aqueous solution composed of sulfuric acid with a concentration of 500 g / L. The experiment is carried out at a temperature of 40° C. The scrubbing section consists of three successive mixer settlers. The composition of the solvent before and after scrubbing is presented in the table below. A high selectivity is obtained, on the one hand, nickel is scrubbed with a yield of 91% and Mg with 13%, and on the other hand, all other impurities remain in the solvent.

[0085] [Table 4]

[0086] Preparation of nickel preloaded extractant II The second solvent is prepared by combining bis-(2,4,4-trimethylpentyl)phosphinic acid (IONQUEST 290) and the hydrocarbon diluent Escaid 110 (ExxonMobil). The second solvent is composed of 15 vol.% IONQUEST 290 and 85 vol.% Escaid 110. In two successive steps in a countercurrent configuration, the solvent is contacted with an aqueous high-purity nickel sulfate solution containing 130 g / L nickel and 0.90 g / L sodium. A 125 g / L NaOH solution is used, thereby obtaining a pre-loaded solvent containing approximately 5.0 g / L nickel. This corresponds to a conversion degree of 38% of the total extractant volume. After one pre-loading step, the solvent contains 2.2 g / L nickel and 79 mg / L sodium. After the second pre-loading step, a solvent containing 4.6 g / L nickel and a residual sodium concentration of 67 mg / L is obtained. In effect, the amount of nickel or residual sodium in the pre-added solvent may depend on the exact conditions.

[0087] In another example, a higher extractant concentration was applied. The second solvent containing IONQUEST 290 and Escaid 110 is contacted in one step with a high purity aqueous nickel sulfate solution containing 97 g / L nickel, 40 mg / L magnesium and 27 mg / L sodium at a temperature of 55° C. The pH is kept constant at a value of 6.0 with a 125 g / L NaOH solution. The amount of nickel added to the solvent is displayed in the table below as a function of the extractant concentration.

[0088] [Table 5]

[0089] Extraction of magnesium to produce high purity nickel sulfate solutions. The aqueous raffinate (A1) obtained after the first solvent extraction contains 127 g / L nickel and 690 mg / L magnesium and is mixed with a second solvent containing IONQUEST 290, preloaded with 6.0 g / L nickel, and the remaining part of magnesium is extracted at a temperature of 55° C. The extraction section consists of five mixer settlers in a countercurrent configuration. What remains in the solvent extraction unit are (i) the second loading solvent (O2) containing nickel and magnesium, and (II) a high-purity aqueous nickel sulfate solution (A2) containing only 1.0 mg / L magnesium, and can therefore proceed to a crystallization or granulation operation to obtain a high-purity nickel sulfate product. The nickel concentration in the aqueous raffinate increases to 138 g / L because the nickel of the preloading solvent is stoichiometrically exchanged with impurities from the feed solution during the extraction.

[0090] Scrubbing of Extractant II with Sulfuric Acid After extraction and prior to elution, an additional scrubbing step may be determined to avoid nickel losses in the eluate. A second additive solvent containing 1.10 g / L nickel and 1.30 g / L magnesium is combined with an aqueous solution composed of sulfuric acid with a concentration of 70 g / L. The experiment is carried out at a temperature of 40° C. The scrubbing section consists of three successive mixer settlers. A scrubbing yield of 99.7% is obtained, with a nickel concentration reduction in the scrubbed solvent to 0.003 g / L nickel. During this scrubbing operation, no magnesium is co-scrubbed, producing a scrubbed solvent with 1.30 g / L magnesium.

[0091] Effect of temperature on the extraction rate of different impurities In this example, the effect of temperature on the extraction rates of calcium, cobalt and magnesium is shown. A first solvent containing 35 vol.% PC88A and 65 vol.% Escaid 110, pre-doped with 17 g / L nickel, is contacted in two successive steps with an aqueous feed solution containing 118 g / L nickel, 9 mg / L calcium, 68 mg / L cobalt and 124 mg / L magnesium. The extraction percentages at 25° C. and 65° C. for different impurities are shown in the table below. On the one hand, low temperatures favor the extraction of calcium, and on the other hand, high temperatures favor the extraction of cobalt and magnesium.

[0092] [Table 6]

[0093] Therefore, the experimental results show that the extraction rate of calcium from nickel solution is improved at a lower extraction temperature. Therefore, it is preferred that the extraction temperature in this process is less than 50°C, preferably less than 45°C. However, at lower extraction temperatures, the efficiency of cobalt extraction is also reduced. Therefore, it is preferred to use an extraction temperature above 25°C, preferably above 30°C, more preferably above 35°C. Most preferably, the extraction temperature is higher than 25°C and lower than 45°C, preferably higher than 30°C and lower than 45°C, more preferably higher than 35°C and lower than 45°C.

[0094] In another example, the effect of temperature on the extraction rate of magnesium is shown. A second solvent containing 15 vol% IONQUEST 290 and 85 vol% Escaid 110 is contacted in one step with a feed aqueous solution containing 127 g / L nickel and 180 mg / L magnesium. The pH is controlled at pH=5.0. The table below shows that on the one hand, the extraction rate percentage of magnesium increases from 25°C to over 44°C up to 65°C, while on the other hand, the extraction rate of nickel remains low. As a result, the selectivity of magnesium over nickel increases at higher temperatures.

[0095] [Table 7]

[0096] From the experimental results in the above table it is clear that the extraction of magnesium from nickel solutions is improved by higher extraction temperatures, i.e. at least 25° C., preferably at least 30° C., or even at least 35° C. More preferably, said extraction temperature is higher than 40° C., higher than 50° C., higher than 55° C., or even higher than 60° C. Nevertheless, due to the processability of organic solvents, safety aspects of organic solvents and avoiding the need for high energy inputs, it is preferred that the extraction temperature is limited to less than 80° C., less than 70° C., or less than 65° C.

Claims

1. 1. A method for preparing a high purity nickel sulfate solution, comprising the steps of: i. providing an aqueous feed solution comprising nickel, cobalt, calcium and magnesium; ii. extracting cobalt, calcium and at least some of the magnesium, and, if present, zinc, copper, cadmium and manganese, from said aqueous feed solution using a first solvent extraction circuit comprising a first alkyl phosphorus-based extractant (I) and a first organic phase comprising a first diluent, thereby obtaining an aqueous raffinate solution containing nickel and residual magnesium contents, and a calcium-containing organic phase rich in cobalt; iii. extracting magnesium from the aqueous raffinate solution using a second organic phase comprising a second alkylphosphorus-based extractant (II) and a second diluent in a second solvent extraction circuit, thereby obtaining a magnesium-depleted aqueous high-purity nickel sulfate solution and a magnesium-enriched organic phase; iv. stripping the cobalt-rich organic phase obtained in step ii with an aqueous solution containing a mineral acid; A method comprising:

2. 2. The method of claim 1, wherein the first solvent extraction circuit and the second solvent extraction circuit operate at different temperatures and / or with different extractants.

3. 3. The method according to claim 1 or 2, wherein the mineral acid is hydrochloric acid.

4. 4. The method of claim 1, wherein the aqueous feed solution further comprises zinc, copper, cadmium, and / or manganese.

5. 5. The method according to claim 1, wherein nickel is scrubbed from the cobalt-rich organic phase and / or from the magnesium-enriched organic phase.

6. 6. A method according to any one of claims 1 to 5, wherein the aqueous feed solution is obtained from an aqueous feed solution comprising nickel, cobalt, calcium, magnesium and, if present, zinc, copper, cadmium and / or manganese, and further comprising iron and / or aluminium, respectively, by a step of removing iron and / or aluminium.

7. 7. The method of claim 6, wherein the iron and / or aluminum is removed by precipitation using a precipitating agent, the precipitating agent comprising a calcium base.

8. 8. The method of claim 6 or 7, wherein the iron and / or aluminium is removed by precipitation using a precipitating agent, the precipitating agent comprising a magnesium base.

9. 9. A method according to any one of claims 6 to 8, wherein the iron and / or aluminium is removed by precipitation using a precipitating agent, the precipitating agent comprising a nickel base.

10. 10. The method according to any one of claims 6 to 9, wherein the iron and / or aluminium are removed by precipitation in two or more precipitation steps, and different precipitating agents or combinations of precipitating agents may be used in each precipitation step.

11. 11. The method according to claim 1, wherein the first and second alkylphosphorus-based extractants comprise an alkylphosphorus-based acid and / or a nickel salt thereof.

12. 12. The method according to claim 1, wherein the second extractant (II) has a higher magnesium selectivity than the first extractant (I).

13. 13. The method according to claim 1, wherein the first alkylphosphorus-based extractant (I) comprises an alkylphosphonic acid and / or a nickel salt thereof, and the second alkylphosphorus-based extractant (II) comprises an alkylphosphinic acid and / or a nickel salt thereof.

14. 14. The method of any one of claims 1 to 13, wherein the first and second extractants are converted to their nickel salts and contain nickel having a concentration of at least 20% of the available extractant volume.

15. 15. The method of claim 14, wherein the first and second extractants are converted to nickel salts and the first and second organic phases contain less than 2 g / L of sodium.

16. 16. The method according to any one of claims 1 to 15, wherein the first and second organic phases provided in steps ii and iii respectively comprise the first and second extractants in an amount of 5 to 50 vol.% relative to the total volume of the solvent, and the diluent in an amount of 50 to 95 vol.% relative to the total volume of the solvent.

17. 17. The method according to any one of claims 1 to 16, wherein the extraction in step ii is carried out at a temperature of from 25 to 55°C.

18. 18. The method according to any one of claims 1 to 17, wherein the extraction in step iii is carried out at a temperature of 40 to 70°C.

19. 19. The process according to any one of claims 1 to 18, wherein the stripping step iv is carried out at a temperature of from 40°C to 50°C.

20. 20. The method according to any one of claims 1 to 19, wherein the magnesium-depleted aqueous high purity nickel sulfate solution contains nickel in a concentration of 40 to 180 g / L and magnesium in a concentration of up to 5 mg / L.

21. 21. The method according to any one of claims 1 to 20, wherein the aqueous feed solution provided in step i comprises nickel in an amount of at least 60 at.%, relative to the total metal content of the aqueous feed solution, and wherein the aqueous feed solution provided in step i comprises cobalt, calcium, magnesium and, optionally, zinc, copper, cadmium and manganese in an amount of up to 40 at.%, relative to the total metal content of the aqueous feed solution.

22. 22. The method according to any one of the preceding claims, wherein the high purity aqueous nickel sulphate solution obtained after removal of residual magnesium in step iii is subjected to crystallization or granulation.

23. 23. The method according to any one of claims 1 to 22, wherein the first organic phase is washed with sulfuric acid after the step of stripping with mineral acid.

24. 24. The method according to claim 1 , wherein the first and / or second organic phase, after a step of washing or stripping with sulfuric acid, is doped with nickel using an alkali hydroxide and a nickel salt containing solution such as a nickel sulfate solution or a nickel chloride solution, and is subsequently recycled in step ii and / or step iii, thereby completing the process loop.

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