PROCESS FOR EXTRACTING METAL PARTICLES BY LIQUID-LIQUID REACTION EXTRACTION AND EQUIPMENT FOR PERFORMING THIS EXTRACTION PROCESS

Abstract

The invention relates to a process for extracting metal particles from aqueous solutions by liquid-liquid reaction extraction and an apparatus for performing such extraction.

Description

[0001] Process for the extraction of a metal species by liquid-liquid reaction extraction

[0002] The present invention relates to a process for extracting a metal species from an aqueous solution by liquid-liquid reactive extraction.

[0003] Extraction generally refers to any separation process in which one or more components are extracted from a mixture of substances using an extractant. In liquid-liquid extraction, a dissolved substance is extracted from a liquid using a liquid extractant, exploiting the different solubilities of the components to be separated in two immiscible solvents. The immiscible solvents are typically a hydrophilic phase such as water and a hydrophobic organic solvent. One application of liquid-liquid extraction is the selective separation of metal ions, which is becoming increasingly important in the context of electromobility and the recycling of used batteries.

[0004] In general, the principle of reactive extraction is based on so-called extraction isotherms, which describe the distribution of a metal species between an aqueous phase (AP) and an organic phase (OP) at a corresponding pH value. The degree of extraction E indicates the proportion of metal species M in the organic phase relative to the total amount of metal species in both phases, where E can theoretically assume any value between 0 and 1, or 0% and 100%:

[0005] Especially in the field of battery recycling, the separation of cobalt, nickel, manganese, and lithium from aqueous solutions is of great importance. The state of the art describes a number of approaches for optimizing this separation.

[0006] The extraction of metals is based on a special form of extraction, so-called reactive extraction. In this form of solvent extraction, the compound to be extracted is transferred to the other phase by reacting with a substance dissolved in the extraction agent. The following equation shows the underlying chemical reaction and the distribution of the various species between the aqueous and organic phases, as is usually indicated by an overline. where M is the metal ion, R is an acid residue and K is the equilibrium constant.

[0007] As can be seen from the formulation of the equilibrium constants, these equilibria are pH-dependent. Metals with high affinity, represented by high values ​​of the equilibrium constant K, are extracted even at low pH values, i.e., from aqueous media with high acidity, while metals with low affinity can only be extracted from the aqueous phase at higher pH values. The pH can be adjusted, for example, by adding alkaline compounds such as NaOH, which capture the protons produced during the reaction.

[0008] Reactive extraction for the separation of metal ions is well known. For example, in their article "Synergistic effect of Cyanex 272 and Cyanex 302 on separation of cobalt and nickel by D2EHPA," published in Hydrometallurgy 77 (2005) 227-238, D. Darvishi et al. describe the advantages achieved by activating the complexing agent D2EHPA with Cyanex 272 and Cyanex 302 in the separation of cobalt and nickel.

[0009] PK Parhi et al. report on the separation of nickel and cobalt in an ammoniacal sulfate solution using Cyanex 272. Their results are published in "Separation of cobalt and nickel from ammoniacal sulfate solution using Cyanex 272", Separation and Purification Technology 59 (2008), 310-317.

[0010] In "Extraction / Separation of Cobalt by Solvent Extraction: A Review", Appl. Chem. Eng. Vol. 26, No. 6, 2015, 631-639, B. Swain et al. summarize various methods for the separation of cobalt.

[0011] In their publication "New Cationic exchangers for the recovery of cobalt(I), nickel(I) and manganese(I) from acidic chloride solutions: Modelling of extraction curves", published in Hydrometallurgy 180 (2018) 96-103, K. Omelchuk et al. describe novel extraction agents for the separation of the mentioned metal species.

[0012] NB Devi et al describe the separation of cobalt(II) and nickel(II) using the sodium salts of D2EHPA, PC 88A and Cyanex 272 in "Separation and recovery of cobalt(II) and nickel(II) from sulphate solutions using sodium salt of D2EHPA, PC 88A and Cyanex 272", Hydrometallurgy 49 (1998) 47-61.

[0013] EP 2 614 868 discloses the use of a liquid-liquid extraction unit to contact an aqueous phase with an organic phase, to separate them and to obtain a desired extract from the thus separated aqueous phase and / or organic phase.

[0014] In "Simultaneous recycling of nickel metal hydride, lithium ion and primary lithium batteries: Accomplishments of European Guidelines by optimizing mechanical pre-treatment and solvent extraction operations", published in Journal of Power Sources 212 (2012) 205-211, G. Granata et al. describe the solvent extraction of Co and Mn, whereby the extraction of Co is carried out with Cyanex 272 at a Cyanex / Co ratio of 4 at a pH of 5 and the extraction of Mn is carried out with D2EHPA at a D2EHPA / Mn ratio of 2 at a pH of 5-6.

[0015] In another publication, "Product recovery from Li-ion battery wastes coming from an industrial pre-treatment plant: Lab scale tests and process stimulations", published in Journal of Power Sources 206 (2012) 393-401, G. Granata et al. describe the recovery of Co and Li using Cyanex 272 and D2HEPA partially saponified with NaOH.

[0016] In their article "Separation of cobalt and nickel via solvent extraction with Cyanes-272: Batch experiments and comparison of mixer-settlers an angitated column as contactors for continuous counter-current extraction", in Separation and Purification Technology 296 (2022) 121326, IR Rodrigues et al. deal with the separation of Co and Ni by solvent extraction using Cyanex-272, with a pH value of 6.

[0017] US 3,666,446 discloses a pH-controlled process for the separation of Cu and Co, wherein the pH is controlled by ion exchange reactions. US 4,353,883 describes the separation of Co and Ni from aqueous solution in the presence of an extractant, wherein the extractant is a phosphinic acid having at least 6 carbon atoms.

[0018] From "Resource recovery of critically-rare metals by hydrometallurgical recycling of spent lithium ion batteries" by R. Sattar et al, published in Separation and Purification Technology 209 (2019) 725-733, a two-stage solvent extraction with Cyanex 272 at a pH of 5.0 is known, whereby the Cyanex was saponified to 50%.

[0019] What all approaches have in common is that, despite the uncertainty associated with the significance of the pH value, the separation is carried out based on extraction isotherms at a pH value determined to be "optimal," which often requires laborious adjustment. Another disadvantage of the known methods is that a large excess of extraction agent is usually required.

[0020] The pH value is generally defined as the negative decimal logarithm of the hydrogen ion activity of a given solution: pH = -lg a (H + )

[0021] The described technology for the separation of metal ions uses the pH value as a control variable, which is generally accepted, but in practice the measurement of the pH value is subject to many uncertainties.

[0022] This means in particular that a measured pH value does not indicate the actual H + The pH value therefore represents an unsatisfactory, uncertain, specific control variable in the context of the reactive extraction described here for maintaining stability. This is especially true if the working range covers only a few tenths of a pH unit at most.

[0023] Against this background, there is a need for an improved process for the separation of metal species and their recovery in very pure form from aqueous solutions, which preferably does not require pH as a control variable.

[0024] Within the scope of the present invention, it was surprisingly found that the liquid-liquid reactive extraction of metal species from aqueous solutions with the aid of the activated extractant and by setting a defined stoichiometric ratio between the activated extractant and the metal species to be extracted does not require the pH value as a control variable.

[0025] Therefore, a first object of the present invention is a process for extracting a metal species from an aqueous solution by means of liquid-liquid reactive extraction, the process comprising the steps of: a) providing an aqueous phase comprising at least one metal species to be extracted; b) providing an organic phase comprising an extractant for extracting the metal species to be extracted; c) activating the extractant in the organic phase with an activating agent; d) contacting the aqueous phase and the organic phase from step c); e) separating the aqueous phase and the organic phase comprising at least a portion of the extracted metal species, wherein the activated extractant and the metal species to be extracted are present in a defined stoichiometric ratio to one another, characterized in that no active regulation of the pH takes place.

[0026] Without being bound to a particular theory, it is assumed that the extraction agent promotes the transition of the metal species from the aqueous to the organic phase. For this purpose, the extraction agent is activated according to the invention. By providing a predetermined, stoichiometric supply of activated extraction agent in relation to the metal species to be extracted, adapted to the separation problem, the pH value can be dispensed with as a control variable for the operating point, and the uncertainty associated with determining the pH value can be avoided. The ratio of activated extraction agent to metal species to be extracted represents the ratio of activating agent, for example, Na +, and the amount of metal species to be extracted, which are coordinated according to the invention. During extraction, it is generally important to find an acceptable compromise between the quality and purity of the species to be extracted and the yield. Within the scope of the process according to the invention, it was surprisingly shown that the pH-independent process allowed the species to be extracted to be obtained in high purity and yield.

[0027] In the process according to the invention, the extractant is activated by an activating agent. The activation of the extractant preferably occurs before contacting the aqueous phase and the organic phase. The activating agent is therefore preferably added to the organic phase in the required amount, adjusted to the amount of metal species to be extracted, before contacting with the aqueous phase. This pre-contacting can be carried out either continuously or in a batch process.

[0028] The process according to the invention provides that the activated extractant is provided in a defined ratio to the metal species to be extracted. It has surprisingly been found that by adjusting this ratio, the separation efficiency and selectivity of the extraction can be controlled, and the process can thus preferably be carried out independently of active pH control. Therefore, in a preferred embodiment, the process according to the invention further comprises a step in which the stoichiometric ratio of activated extractant to the metal species to be extracted is adjusted according to a predefined ratio.

[0029] The defined stoichiometric ratio can be adjusted, for example, based on the concentration of the metal species to be extracted. Therefore, an embodiment of the process according to the invention is preferred in which the concentration of at least the metal species to be extracted in the aqueous phase is determined in a preceding step.

[0030] The extractant is preferably selected from the group of complexing agents and liquid ion exchangers and is accordingly capable of forming a complex with the metal species to be extracted. In a particularly preferred embodiment, the extractant is selected from the group of organophosphinic acids, organophosphonic acids, and organophosphoric acids. Very particularly preferred extractants are those selected from the group consisting of (bis-2-(ethylhexyl)phosphoric acid (D2EHPA), bis(l,3-dibutoxypropan-2-yl)phosphoric acid (Bidiopp), bis(l,3-diisobutoxypropan-2-yl)phosphoric acid (IPA), bis(5,8,12,15-tetraoxanonadecan-10-yl)phosphoric acid (TPA), bis(undecan-6-yl)phosphoric acid (UPA), bis(l,3-dioctyloxypropan-2-yl)phosphoric acid (OPA), bis(l,3-di-2-ethylhexyloxypropan-2-yl)phosphoric acid (EHPA) and bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272).The use of mixtures of the extractants just listed, as well as a mixture of branched monocarboxylic acids and other organic acids, has also proven particularly advantageous, and is therefore preferably used in the context of the present invention. Corresponding products are commercially available, for example, under the name Versatic™ Acid.

[0031] The activating agent activates the extractant, for example, by deprotonating it. Accordingly, the activating agent is preferably matched to the extractant. The activating agent can, for example, be selected from the group of alkali hydroxides and / or ammonia. In particular, the activating agent is sodium hydroxide or lithium hydroxide. In this case, the activation of the extractant and the subsequent extraction of the valuable metal can be formulated according to the following two equations, with the amount of activated extractant being matched to the amount of metal species being extracted.

[0032] Activation: (RHh + 2NaOH = 2RNa + 2H2O

[0033] Extraction: = MR2+ 2 Na +

[0034] For this process, it was surprisingly found that when the extractant is activated with sodium hydroxide solution, it can be completely absorbed by the organic phase. The use of sodium hydroxide solution in a concentration of at least 40 wt% or more has proven particularly advantageous. Good results were achieved using just 20 wt% D2EPAH in Escaid™, such as that available from Exxon Mobil, with diluted sodium hydroxide solution of 20 wt% at 50 °C. Furthermore, activation with 40 wt% sodium hydroxide solution surprisingly led to a single phase that remained stable even after cooling to room temperature. This behavior significantly simplifies the technical implementation. Phase separation is eliminated, and the activation stoichiometry can be precisely defined using exact mass flows, without relying on pH or other control variables.The desired activation content of the extractant can be adjusted directly or after activation by adding non-activated organic phase.

[0035] The process according to the invention aims at the separation of metal species, with particular preference being given to transition metals and rare earth metals. The metal species are preferably selected from the group consisting of cobalt, nickel, manganese, iron, copper, magnesium, aluminum, and lithium. In particular, the metal species are cobalt, nickel, manganese, and aluminum.

[0036] The organic phase is immiscible with the aqueous phase. Therefore, aliphatic and aromatic hydrocarbons, as well as mixtures thereof, are preferably used as the organic phase in the process according to the invention. Kerosene or Escaid™ 120, as commercially available from Exxon Mobile, have proven particularly suitable.

[0037] The process according to the invention is primarily designed for large-scale industrial use and is preferably carried out as a continuous process in multi-stage countercurrent. In an alternative preferred embodiment, the process according to the invention is carried out in batch mode.

[0038] The process according to the invention not only allows the extraction of a metal species from an aqueous solution, but can also be used for the selective separation of several metal species from one another. Therefore, an embodiment is preferred in which the aqueous phase comprises at least one additional metal species, which remains at least partially in the aqueous phase. By setting an appropriate stoichiometric ratio, not only can the separation efficiency be increased, but also the amount of additional metal species transferred into the organic phase can be determined, so that a desired ratio of the metal species in the organic phase is achieved.To ensure the purity of the main component, the extraction can be followed by a washing step, particularly preferably in the form of a booster extraction, in which the loaded organic phase is contacted, for example, with a pure solution of the main component and / or mineral acids, especially sulfuric acid, thereby forcing the secondary components out of the organic phase, such as in the separation of transition metals in the sulfate system. Accordingly, the process according to the invention further comprises a washing step following the extraction.

[0039] The process according to the invention represents an improvement over conventional separation processes that rely on pH as a control variable. Accordingly, an embodiment in which the process is not subject to pH-dependent control is preferred. Although the pH can be measured as an indicator within the scope of the process according to the invention, the required amount of activating agent is preferably added at the desired points via precise gravimetric metering devices, preferably Coriolis mass flow meters. Especially when using extraction columns, the approach with activated extractant and defined stoichiometric ratios is preferable.

[0040] The process according to the invention can be carried out in mixer-settler batteries or in extraction columns, with extraction columns being preferred. Suitable extraction columns are known to those skilled in the art and preferably have mass transfer elements to increase the contact area and mixing between the organic and aqueous phases.

[0041] A further subject of the present invention is a device for carrying out the process according to the invention, wherein the device comprises a reactor for contacting an aqueous phase with an organic phase and wherein the reactor has at least one outlet for removing the aqueous and / or the organic phase.

[0042] Suitable reactors in the device according to the invention are, in particular, mixer-settler batteries and extraction columns, with extraction columns being preferred. The use of an extraction column allows the space requirement to be significantly reduced, and the circulating amounts of organic and aqueous phase can be kept low. Furthermore, the use of extraction columns ensures continuity of the countercurrent, with only a single phase boundary at the top or bottom of the column needing to be regulated. The io

[0043] Construction costs for a column are significantly lower than for large mixer-settler batteries.

[0044] In a further preferred embodiment, the device according to the invention further comprises a module for pre-contacting the organic phase with the activating agent.

[0045] The present invention is explained in more detail with reference to the following examples and drawings, which are in no way to be understood as a limitation of the inventive concept.

[0046] Figures

[0047] Figure 1 schematically shows an example of the degree of extraction in the separation of Mn, Cu, Co, and Ni ions. E = 0 indicates that the corresponding metal species remains completely in the aqueous phase, and E = 1 indicates complete transition into the organic phase. Depending on the acidity of the solution, for example, an organic phase can be obtained that contains a large portion of the Cu and Mn ions, as well as an aqueous raffinate in which the majority of the Co and Ni ions remain. Depending on the prevailing acidity, the separation of the different metal species from one another can be controlled in a targeted manner.

[0048] Figures 2 and 3 show experimentally determined extraction isotherms for cobalt and nickel. Figure 2 shows the individually recorded isotherms, while Figure 3 shows the extraction isotherms of an aqueous solution containing both metals at the same concentration. A competition for the scarcely available extractant according to the inventive process is clearly observable. Due to its higher affinity for the extractant, the cobalt suppresses the co-extraction of nickel, and the isotherms diverge dramatically. The organic phase, thus loaded with the two metals, can subsequently be freed from the unwanted nickel components by contact with a wash solution containing only cobalt or by washing with a mineral acid such as sulfuric acid. It should be noted that a single extraction step is shown here.By using countercurrent operation for both the extraction and washing processes, high yields and high purity can be achieved. Mixer-settlers and columns are suitable devices. Examples.

[0049] The process according to the invention was tested in a first batch approach.

[0050] 600 ml of an equimolar Co- and Ni-containing solution containing 40 g / L Co and 39.88 g / L Ni were prepared from the respective chloride salts and contacted, while stirring, with 1576 ml of an organic solution containing 20 mol% bis-2-(ethylhexyl)phosphoric acid (DEHPA) as the extractant. A 50% NaOH solution was used as the activating agent at 40 °C. Table 1 shows the stoichiometric ratio of extractant, sodium hydroxide solution, and the Co to be extracted. After phase separation, the Co and Ni contents were determined in the organic and aqueous phases, respectively. Table 2 summarizes the results of the analysis.

[0051] Table 1 :

[0052] Table 2:

[0053] * Partition coefficient: D = MOP / MAP with M = Co, Ni; OP: organic phase; AP: aqueous phase

[0054] As can be seen from the table, the process according to the invention achieves efficient separation of Co and Ni by reactive extraction of Co from the aqueous phase. The distribution coefficients D determined on the basis of the measured concentrations result in a separation factor (co = DCO / DNI) of 79. Comparable experiments at a pH of 3.5 with the same extractant and under the same extraction conditions suggest a separation factor of 3. Thus, a significant increase in selectivity can be achieved by the process according to the invention. The process according to the invention thus represents a simple and efficient alternative to pH-controlled extraction, since only the amount of metal species to be extracted needs to be known.

[0055] The separation efficiency could be further increased by operating the process continuously. The experiment described above was therefore repeated in a continuously operated mixer-settler system. The experiment was conducted with six mixer-settler units, each with a volume of 350 ml, and the organic phase was pre-contacted with a 200 g / L NaOH solution.

[0056] After a test duration of 16 hours, distribution coefficients of D(Co) = 20.77 and D(Ni) = 0.011 were calculated based on the Co and Ni concentrations measured in Table 3. Based on this, a separation factor (co = DCO / DNI) of 1888 was obtained.

[0057] Table 3:

Claims

Patent claims:

1. A method for extracting a metal species from an aqueous solution by means of liquid-liquid reactive extraction, the method comprising the steps of: a) providing an aqueous phase comprising a metal species to be extracted; b) providing an organic phase comprising an extractant for extracting the metal species to be extracted; c) activating the extractant in the organic phase with an activating agent; d) contacting the aqueous phase and the organic phase from step c); e) separating the aqueous phase and the organic phase comprising at least a portion of the extracted metal species, wherein the activated extractant and the metal species to be extracted are present in a defined stoichiometric ratio to one another, characterized in that no active regulation of the pH takes place.

2. Process according to claim 1, characterized in that the activation of the extractant takes place before contacting the aqueous and organic phases.

3. The method according to at least one of the preceding claims, characterized in that the method further comprises a step in which the stoichiometric ratio of activated extractant to the metal species to be extracted is adjusted.

4. Method according to at least one of the preceding claims, characterized in that in a preceding step the concentration of at least the metal species to be extracted in the aqueous phase is determined.

5. Process according to at least one of the preceding claims, characterized in that the extractant is selected from the group of complexing agents and liquid ion exchangers.

6. The process according to at least one of the preceding claims, characterized in that the process further comprises a washing step of the separated organic phase.

7. The process according to at least one of the preceding claims, characterized in that the extractant is selected from the group of organophosphinic acids, organophosphonic acids and organophosphoric acids, in particular from the group consisting of (bis-2-(ethyl-hexyl)-phosphoric acid (D2EHPA), bis(l,3-dibutoxypropan-2-yl)-phosphoric acid (Bidiopp), bis(l,3-diisobutoxypropan-2-yl)-phosphoric acid (IPA), bis(5,8,12,15-tetraoxanonadecan-10-yl)-phosphoric acid (TPA), bis(undecan-6-yl)-phosphoric acid (UPA), bis(l,3-dioctyloxypropan-2-yl)-phosphoric acid (OPA), bis(l,3-di-2-ethylhexyloxypropan-2-yl)-phosphoric acid (EHPA), Bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272); mixtures of the above-mentioned extractants as well as mixtures of branched monocarboxylic acids and other organic acids.

8. Process according to at least one of the preceding claims, characterized in that the activating agent is selected from the group of alkali hydroxides and in particular sodium hydroxide or lithium hydroxide.

9. The method according to at least one of the preceding claims, characterized in that the metal species are selected from the group of transition metals and rare earth metals, in particular from the group consisting of cobalt, nickel, manganese, iron, copper, magnesium, aluminum, and lithium, in particular the metal species is cobalt, nickel, manganese and aluminum.

10. Process according to at least one of the preceding claims, characterized in that the organic phase is selected from the group of aliphatic and aromatic hydrocarbons and mixtures thereof.

11. Process according to at least one of the preceding claims, characterized in that the process is carried out as a batch process or a continuous process.

12. The process according to at least one of the preceding claims, characterized in that the aqueous phase comprises at least one further metal species, said further metal species remaining at least partially in the aqueous phase.

13. Method according to at least one of the preceding claims, characterized in that the method is not subject to any pH-dependent control, in particular characterized in that no measurement of the pH value takes place.

14. Process according to at least one of the preceding claims, characterized in that the process is carried out in an extraction column.

15. Apparatus for carrying out the process according to the invention, wherein the apparatus comprises a reactor for contacting an aqueous phase with an organic phase and wherein the reactor has at least one outlet for removing the aqueous and / or the organic phase.

16. Device according to claim 15, characterized in that the reactor is an extraction column and / or the device further comprises a module for pre-contacting the organic phase with the activating agent.

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