A neodecyl oxyacetyl oxime extractant, its preparation method and application

Abstract

This invention provides a neodecyl azo oxime extractant, its preparation method, and its application, belonging to the field of hydrometallurgical extractant technology. The preparation method involves the reaction of neodecyl chloride under a metal catalyst to generate neodecyl azo, which further reacts with hydroxylamine under alkaline conditions to generate neodecyl azo monooxime or neodecyl azo dioxime extractant. The neodecyl azo oxime extractant prepared by this invention can be applied to the recovery of various metals such as copper, cobalt, nickel, manganese, and rare earth elements. It replaces the aluminum trichloride catalyst used in traditional ketoxime synthesis processes with a manganese-iron alloy, reducing catalyst usage, lowering production costs, and simultaneously reducing the discharge of metal-containing wastewater. The neodecyl azo oxime extractant provided by this invention has advantages such as high metal extraction efficiency, easy back-extraction, and low dosage. Furthermore, the preparation method of the extractant provided by this invention has advantages such as simple operation, low cost, and environmental friendliness.

Description

Technical Field

[0001] This invention belongs to the field of hydrometallurgical extractant technology, and specifically relates to a neodecyl oxycloyl oxime extractant, its preparation method and application. Background Technology

[0002] Solvent extraction is a method that utilizes the difference in solubility of a solute in immiscible solvents to extract the solute from a solution composed of two solvents using one solvent. This separation method has the advantages of continuous operation, high speed, short production cycle, and wide application range, and is an important step in the separation and recovery of different metal ions after mineral leaching.

[0003] Extractants are the core and key component of extraction technology. Ketooxime compounds have excellent extraction performance for metal ions and are widely used in hydrometallurgy. Currently, the main copper extractants used in industrial applications include Lix64 (2-hydroxy-5-dodecylbenzene oxime), Lix65N (2-hydroxy-5-nonylbenzene oxime), Lix70 (2-hydroxy-3-chloro-5-nonylbenzene oxime), Lix841 (2-hydroxy-5-nonylacetophenone oxime), Lix860 (2-hydroxy-5-dodecylsalicylic acid oxime), and N530 (2-hydroxy-4-sec-octylbenzene oxime), etc. In industrial production, copper, cobalt, nickel, etc. are extracted and separated using extractants such as Lix841 (2-hydroxy-5-nonylacetophenone oxime), M5640 (2-hydroxy-5-nonylsalicylic acid oxime), and Lix984N (a 1:1 mixture of 5-nonylsalicylic acid oxime and 2-hydroxy-5-nonylacetophenone oxime).

[0004] Traditional preparation processes for ketoxime extractants require large amounts of aluminum trichloride catalysts, and the reaction necessitates water treatment, inevitably generating significant amounts of aluminum-containing wastewater that pollutes the environment. For example, Chinese patent CN102796027A discloses a process for synthesizing the copper extractant 2-hydroxy-5-nonylacetophenone oxime using 4-nonylphenol, acetyl chloride, and hydroxylamine as raw materials; CN110590598A discloses a method for preparing ketoximes using ketones, ammonia, and hydrogen peroxide as raw materials in an internal spiral reactor under the catalysis of titanium-silicon molecular sieves; and CN112250597A discloses a method using 4-nonylphenol and acetic acid as raw materials. A method for synthesizing ketoxime involves preparing nonylphenol ethyl ester, which then undergoes a rearrangement reaction under microwave treatment to generate 2-hydroxy-5-nonylacetophenone. This ketoxime is then synthesized via oximation, avoiding the extensive use of aluminum trichloride in existing processes. International patent WO2013007054A1 discloses a method for preparing ketoximes using ketones, ammonia, water, and hydrogen peroxide as raw materials under the catalysis of titanium silicate molecular sieves. Japanese patent JP2017149686A discloses a method for generating ketoximes using ketones and ethyl acetylhydroxamic acid as raw materials under the catalysis of scandium trifluoromethanesulfonate, without the need for hydroxylamine and under mild reaction conditions. While these ketoxime synthesis methods effectively reduce environmental pollution by using catalysts such as metal salts of trifluoromethanesulfonate and titanium silicate molecular sieves, and microwave assistance, they also present challenges such as complex operation and increased production costs of ketoxime extractants. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention proposes a neodecyl aliphatic oxime extractant, its preparation method, and its application. This extractant offers strong extraction capability, good selectivity, and ease of back-extraction. It is prepared by reacting neodecyl chloride with metal powder to generate neodecyl aliphatic oxime, which is then reacted with hydroxylamine. This method enables the extraction and recovery of various metals, including copper, cobalt, nickel, manganese, and rare earth elements. It boasts advantages such as wide availability of raw materials, low cost, simple operation, and environmental friendliness.

[0006] To achieve the above objectives, the present invention first proposes a neodecyl azo oxime extractant, characterized in that the extractant is a neodecyl azo monooxime as shown in Formula 1 or a neodecyl azo dioxime as shown in Formula 2:

[0007]

[0008] Among them, R 1 R 2 R 3 R 4 Selected from -H, -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 -C6H 13 -C7H 15 One of them, R 1 and R2 The total number of carbon atoms is 7, R 3 and R 4 The total number of carbon atoms is 7.

[0009] Based on a general inventive concept, this invention also provides a method for preparing a neodecyl oxytocin extractant, comprising the following steps:

[0010] S1. Preparation of neodecyl aloyl: Neodecyl chloride, metal powder, and reaction solvent are heated and reacted under a nitrogen atmosphere. The resulting mixture is distilled under reduced pressure, then an acid solution is added, and finally an organic solvent is added for extraction. After extraction and separation, an organic phase rich in neodecyl aloyl is obtained, which is then dried and evaporated to obtain the neodecyl aloyl compound. The metal powder is one or more of zinc powder, magnesium powder, iron powder, aluminum powder, manganese powder, ferromanganese alloy powder, and stainless steel powder.

[0011] S2. Preparation of decyl oxytocilime extractant: The neodecyl oxytocilime compound obtained in S1, hydroxylamine, and base are dissolved in a methanol aqueous solution. The mixture obtained by heating the reaction is adjusted to pH 6-7 with an acid solution and then distilled under reduced pressure. Then, an organic solvent is added for extraction. After extraction and separation, an organic phase rich in neodecyl oxytocilime compound is obtained. The extractant is then dried and evaporated to obtain the neodecyl oxytocilime extractant.

[0012] In step S1, the molar ratio of neodecanoyl chloride, metal powder, and reaction solvent is 1:0.5-2:0.5-5; the reaction solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylpropionamide.

[0013] Preferably, in step S1, the heating temperature is 60–150°C, the reaction time is 1–12 h, and the temperature for vacuum distillation is 85–150°C.

[0014] Preferably, in step S2, the molar ratio of neodecylazine, hydroxylamine, and base is 1:1.05–1.2:2.1–2.4 or 1:2.1–2.5:4.2–5; the hydroxylamine is one or more of hydroxylamine hydrochloride, hydroxylamine sulfate, and hydroxylamine phosphate; the base is one or more of sodium hydroxide, potassium hydroxide, and sodium methoxide; and the volume ratio of methanol to water in the methanol aqueous solution is 0.5–5:1.

[0015] Preferably, in step S2, the heating temperature is 40–80°C, the reaction time is 3–7 h, and the vacuum distillation temperature is 35–50°C.

[0016] Preferably, the acid solution is one or more of hydrochloric acid, sulfuric acid, and nitric acid, and the organic solvent is one or more of ethyl acetate, dichloromethane, chloroform, acetonitrile, petroleum ether, n-hexane, and cyclohexane.

[0017] Based on a general inventive concept, this solution also provides an application of neodecyl azo oxime extractant in the extraction and recovery of various metals such as copper, cobalt, nickel, manganese, and rare earth elements, including the following steps:

[0018] S1. Extraction: Dissolve neodecyl azo oxime in a diluent to form an organic phase, add it to the aqueous phase, or saponify the organic phase and add it to the aqueous phase containing manganese ions. After extraction, allow it to stand to obtain a loaded organic phase containing the target metal ions.

[0019] S2, Back-extraction: The loaded organic phase is mixed with the back-extraction solution to obtain a back-extraction solution rich in target metal ions. The regenerated organic phase after back-extraction is returned to the extraction process for recycling.

[0020] Preferably, the aqueous phase in step S1 comprises one or more of copper, cobalt, nickel, manganese, zinc, calcium, magnesium, lithium, lanthanum, cerium, praseodymium, and samarium.

[0021] Preferably, in step S1, the organic phase contains 10-60 wt.% neodecyl azo oxime extractant, the diluent is one or more of chloroform, carbon tetrachloride, benzene, toluene, kerosene, aviation kerosene, and sulfonated kerosene, the saponified organic phase is neodecyl azo oxime and the diluent; the volume ratio of the organic phase to the aqueous phase solution is 0.5-5:1, the extraction time is 5-60 min, and the standing time is 5-60 min.

[0022] Preferably, the reagent used for saponification in step S1 is one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, potassium carbonate solution, ammonium carbonate solution, and ammonia water, and the acid solution is one or more of sulfuric acid, nitric acid, and hydrochloric acid.

[0023] Preferably, the saponification rate of the organic phase is 0-50%.

[0024] Preferably, the concentration of the sulfuric acid solution is 0.1–4 mol / L.

[0025] Preferably, the volume ratio of the loaded organic phase to the back-extraction liquid in step S2 is 0.5 to 7:1.

[0026] The extraction principle of the neodecyl oxytocilime extractant of the present invention is as follows:

[0027] The neodecyl group in the neodecyl azo oxime compound of the present invention is as follows: Figure 1 As shown in A, Figure 1 A in R 1 R 2 -H, -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 -C6H 13 -C7H15 R 1 and R 2 The total number of carbon atoms is 7. The neodecyl group with an umbrella-like structure makes neodecyl azo oxime easy to disperse in the organic phase, which improves its solubility in common diluents such as sulfonated kerosene and increases its chance of interacting with metal ions, thereby improving the extraction ability of neodecyl azo oxime.

[0028] The novel decyl azodioxime binding model with metal ions in this invention is as follows: Figure 1 As shown in Figure B, R and R0 represent neodecyl groups, and M represents a metal ion. The neodecyl azodioxime molecule contains two adjacent oxime groups. The carbon-nitrogen double bond on the oxime group gives the nitrogen atom a strong electronegativity, allowing the nitrogen atom on the deprotonated oxime group to form a covalent interaction with the metal ion, while the nitrogen atom on the undeprotonated oxime group forms a coordination interaction with the metal ion, thus forming a stable five-membered ring structure. Simultaneously, the oxygen atom on the deprotonated oxime group forms a hydrogen bond with the hydroxyl group on the undeprotonated oxime group of the other neodecyl azodioxime molecule, strengthening the binding ability of neodecyl azodioxime to the metal ion. The coordination ratio of neodecyl azodioxime to nickel ions is 2. The linear slope method for extracting nickel ions from neodecyl azodioxime yields the extraction equation as 2RH + Ni. 2+ →NiR2+2H + After the interaction of neodecyl azodioxime with nickel ions, the infrared characteristic peaks attributed to OH, C=N, and NO changed, indicating that these groups in neodecyl azodioxime participated in the interaction. Furthermore, the infrared characteristic peak attributed to C=N split into two, suggesting that the two adjacent oxime groups in the neodecyl azodioxime molecule interact with nickel ions in different ways. The optimal model for the interaction of neodecyl azodioxime with nickel ions is as follows: Figure 2 As shown in Figure A.

[0029] The binding model of the neodecyl azo oxime with metal ions in this invention is as follows: Figure 1 As shown in Figure C, where R and R0 are neodecyl groups and M is a metal ion, the carbonyl and oxime groups in the neodecyl azoyl oxime molecule are adjacent. The oxygen atom on the deprotonated oxime group forms a covalent interaction with the metal ion, and the carbonyl group forms a coordination interaction with the metal ion, thus forming a stable six-membered ring structure. Therefore, neodecyl azoyl oxime has a strong metal extraction ability. The coordination ratio of neodecyl azoyl oxime to manganese ions is 2. The linear slope method for the extraction of manganese ions by neodecyl azoyl oxime yields the extraction equation as 2RNa + Mn. 2+ →MnR2+2Na + After the reaction of neodecyl azo oxime with manganese ions, the infrared characteristic peaks attributed to OH, C=O, C=N, and NO changed, indicating that these groups in neodecyl azo oxime participated in the reaction. The optimal model for the reaction of neodecyl azo oxime with manganese ions can be obtained through Gaussian 16 calculations, as shown below. Figure 2 As shown in B.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The neodecyl oxytoximate extractant provided by the present invention is prepared by reacting neodecyl chloride and metal powder to generate neodecyl oxytoximate, and then reacting it with hydroxylamine. By changing the molar amounts of neodecyl oxytoximate, hydroxylamine and base, neodecyl oxytoximate monooxime and neodecyl oxytoximate dioxime can be obtained. The prepared neodecyl oxytoximate monooxime can be reacted with hydroxylamine to prepare neodecyl oxytoximate dioxime. Therefore, the preparation schemes of the two neodecyl oxytoximates can be flexibly adjusted according to actual needs to realize the flexible manufacturing of neodecyl oxytoximate extractant.

[0032] (2) The method for preparing the new decyl azo oxime extractant provided by the present invention uses a manganese-iron alloy to replace the aluminum trichloride catalyst used in the traditional ketoxime synthesis process, thereby reducing the amount of catalyst used, reducing production costs, and reducing the discharge of metal-containing wastewater.

[0033] (3) The neodecyl azo oxime extractant provided by this invention can be applied to the extraction and recovery of various metals such as copper, cobalt, nickel, manganese and rare earth. The extraction process is carried out at room temperature, with good phase separation performance, short phase separation time and clear oil-water interface, which can achieve efficient recovery of copper, cobalt, nickel, manganese and rare earth metals. Compared with the traditional ketoxime extractant Lix841 (2-hydroxy-5-nonylacetophenone oxime), neodecyl azo oxime is easier to back-extract when used as a copper extractant, which reduces the amount of waste acid produced in the hydrometallurgical copper process and makes the extraction process more environmentally friendly. Neodecyl azo dioxime has a stronger binding ability with metal ions, and less amount of target metal ions are used to extract, which effectively reduces the cost of the extraction process. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1 This serves as a model for the binding of neodecyl azo oxime compounds to metal ions. Figure 1 A represents the neodecyl group in the neodecyl azo oxime compound. Figure 1 B represents the model for the binding of neodecyl azodioxime to metal ions. Figure 1 C represents the binding model of neodecyl azoyl oxime with metal ions;

[0036] Figure 2 Calculate the optimal model for the binding of neodecyl azo oxime compounds with metal ions for Gaussian 16. Figure 2A represents the optimal model for the interaction of neodecyl azodioxime with nickel ions. Figure 2 B is the optimal model for the interaction of neodecyl azo oxime with manganese ions;

[0037] Figure 3 This is a synthetic route diagram for preparing the neodecyl azo oxime extractant in Example 4;

[0038] Figure 4 For example, the neodecyl azo oxime in Example 4 1 H NMR spectrum;

[0039] Figure 5 For example, the neodecyl azo oxime in Example 4 13 C NMR spectrum;

[0040] Figure 6 The infrared spectrum of neodecyl azo oxime in Example 4;

[0041] Figure 7 This is the mass spectrum of neodecyl azo oxime in Example 4;

[0042] Figure 8 For example, the neodecyl azodioxime in Example 6 1 H nuclear magnetic resonance spectrum;

[0043] Figure 9 For example, the neodecyl azodioxime in Example 6 13 C NMR spectrum;

[0044] Figure 10 The infrared spectrum of neodecyl azodioxime in Example 6;

[0045] Figure 11 The mass spectrum of neodecyl azodioxime in Example 6;

[0046] Figure 12 The infrared spectrum of the interaction between neodecyl azodioxime and nickel ions in Experimental Example 3;

[0047] Figure 13 The infrared spectrum of the reaction between neodecyl azo oxime and manganese ions in Experiment Example 4;

[0048] Figure 14 This is a flowchart of the extraction and recycling process of valuable metals from waste battery materials in Experiment Example 5. Detailed Implementation

[0049] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments.

[0050] The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the invention. Any modifications or substitutions made to the methods, steps, or conditions of the present invention without departing from the spirit and essence of the invention are within the scope of the invention.

[0051] Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art; unless otherwise specified, the reagents used in the embodiments are all commercially available.

[0052] Example 1

[0053] Preparation of neodecyl azoyl

[0054] 10.00 parts of neodecanoyl chloride (97% purity), 2.10 parts of zinc powder (95% purity), and 9.48 parts of N,N-dimethylformamide (98% purity) were placed in a reaction flask and reacted at 80°C for 6 hours under a nitrogen atmosphere. The resulting mixture was then subjected to vacuum distillation at 95°C to remove the remaining N,N-dimethylformamide. While stirring, 1 mol / L hydrochloric acid solution was added until the remaining zinc powder dissolved. 13.25 parts of dichloromethane were added in three portions for extraction. After oil-water separation, the organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled under vacuum at 45°C to obtain 8.01 parts of a pale yellow oily liquid containing neodecanoyl chloride. The product purity was 90.13%, and the yield based on neodecanoyl chloride was 91.43%.

[0055] Example 2

[0056] Preparation of neodecyl azoyl

[0057] 10.00 parts of neodecanoyl chloride (97% purity), 5.21 parts of magnesium powder (95% purity), and 18.59 parts of N,N-dimethylformamide (98% purity) were placed in a reaction flask and reacted at 90°C for 6 hours under a nitrogen atmosphere. The resulting mixture was then subjected to vacuum distillation at 95°C to remove the remaining N,N-dimethylformamide. While stirring, 1 mol / L nitric acid solution was added until the remaining magnesium powder dissolved. 14.55 parts of acetonitrile were added in three portions for extraction. After oil-water separation, the organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled under vacuum at 50°C to obtain 7.95 parts of a pale yellow oily liquid containing neodecanoyl chloride. The product purity was 89.27%, and the yield based on neodecanoyl chloride was 89.87%.

[0058] Example 3

[0059] Preparation of neodecyl azoyl

[0060] 20.00 parts of neodecanoyl chloride (97% purity), 3.73 parts of ferromanganese alloy powder, and 17.62 parts of N,N-dimethylacetamide (98% purity) were placed in a reaction flask and reacted at 100℃ for 10 h under a nitrogen atmosphere. The mixture was then subjected to vacuum distillation at 105℃ to remove the remaining N,N-dimethylacetamide. While stirring, 1 mol / L hydrochloric acid solution was added until the remaining ferromanganese alloy powder was dissolved. Ethyl acetate was added in three portions for extraction. After oil-water separation, the organic phase was dried over anhydrous sodium sulfate, filtered, and distilled under vacuum at 45℃ to obtain 15.73 parts of a pale yellow oily liquid of neodecanoyl chloride. The product purity was 89.72%, and the yield based on neodecanoyl chloride was 89.36%. The purity of the ferromanganese alloy powder is shown in Table 1 below.

[0061] Table 1. Elemental and purity analysis of ferromanganese alloy powder in Example 3.

[0062] element Mn Fe Si Pb P other purity(%) 82.38 14.96 1.68 0.362 0.125 0.493

[0063] Example 4

[0064] Preparation of neodecyl oxy-oxime

[0065] 3.00 parts of neodecyloxyl (purity 90.13%), 0.80 parts of hydroxylamine sulfate (purity 98%), and 0.80 parts of sodium hydroxide (purity 96%) prepared in Example 1 were dissolved in 12.49 parts of methanol-water solution (methanol to water volume ratio 4:1). The mixture was heated under reflux at 60°C for 2 hours. The pH of the resulting mixture was adjusted to 6.0 by adding 1 mol / L hydrochloric acid solution. The methanol in the mixture was removed under reduced pressure at 40°C. 19.88 parts of dichloromethane were added in three portions for extraction. After oil-water separation, the organic phase was dried with anhydrous sodium sulfate, filtered, and distilled under reduced pressure at 45°C to obtain 3.09 parts of neodecyloxyl-oxime, a pale yellow oily liquid with a product purity of 80.36% and a product yield of 87.60% based on neodecyloxyl. The neodecyloxyl-oxime was purified by column chromatography using ethyl acetate-petroleum ether as the mobile phase and then characterized.

[0066] The synthetic route of neodecyl azo oxime extractant is as follows: Figure 3 As shown;

[0067] The NMR spectrum of neodecyl azodioxime is as follows: Figure 4-5 As shown;

[0068] The infrared spectrum of neodecyl azodioxime is as follows: Figure 6 As shown;

[0069] The mass spectrum of neodecyl azoyl oxime is shown below. Figure 7 As shown:

[0070] The spectral characterization analysis of neodecyl azoyl oxime is shown in Table 2 below:

[0071] Table 2. Characterization methods and results of neodecyl azo oxime

[0072]

[0073] Example 5

[0074] Preparation of neodecyl oxy-oxime

[0075] 5.00 parts of neodecyloxyl (89.72% purity), 1.12 parts of hydroxylamine hydrochloride (98.5% purity), and 1.33 parts of sodium hydroxide (96% purity) prepared in Example 3 were dissolved in 24.98 parts of an aqueous methanol solution (methanol to water volume ratio of 4:1). The mixture was heated under reflux at 60°C for 2 hours. The pH of the resulting mixture was adjusted to 7.0 by adding 1 mol / L hydrochloric acid solution. The methanol was removed from the mixture under reduced pressure at 40°C. 27.06 parts of ethyl acetate were added in three portions for extraction. After oil-water separation, the organic phase was dried with anhydrous sodium sulfate, filtered, and distilled under reduced pressure at 45°C to obtain 4.98 parts of neodecyloxyl-oxime, a pale yellow oily liquid with a product purity of 79.16% and a product yield based on neodecyloxyl of 83.82%.

[0076] Example 6

[0077] Preparation of neodecyl azodioxime

[0078] 3.00 parts of neodecyl aliphatic acyl (89.27% ​​purity), 1.60 parts of hydroxylamine sulfate (98% purity), and 1.60 parts of sodium hydroxide (96% purity) prepared in Example 2 were dissolved in 16.66 parts of methanol-water solution (methanol to water volume ratio 4:1). The mixture was heated under reflux at 60°C for 4 hours. The pH of the resulting mixture was adjusted to 6.0 by adding 1 mol / L hydrochloric acid solution. The methanol was removed from the mixture under reduced pressure at 40°C. 19.88 parts of dichloromethane were added in three portions for extraction. After oil-water separation, the organic phase was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure at 45°C to obtain 3.19 parts of neodecyl aliphatic acyl dioxime, a pale yellow oily liquid with a product purity of 81.79% and a product yield based on neodecyl aliphatic acyl of 88.83%. The neodecyl aliphatic acyl dioxime was purified by column chromatography using ethyl acetate-petroleum ether as the mobile phase and then characterized.

[0079] The NMR spectrum of neodecyl azodioxime is as follows: Figure 8-9 As shown;

[0080] The infrared spectrum of neodecyl azodioxime is as follows: Figure 10 As shown;

[0081] The mass spectrum of neodecyl azodioxime is shown below. Figure 11 As shown;

[0082] The spectral characterization analysis of neodecyl azodioxime is shown in Table 3 below:

[0083] Table 3. Characterization methods and results of neodecyl azodioxime

[0084]

[0085]

[0086] Example 7

[0087] Preparation of neodecyl azodioxime

[0088] 5.00 parts of neodecyl aliphatic acyl (89.72% purity), 2.24 parts of hydroxylamine hydrochloride (98% purity), and 2.65 parts of sodium hydroxide (96% purity) prepared in Example 3 were dissolved in 24.98 parts of methanol-water solution (methanol to water volume ratio 4:1). The mixture was heated under reflux at 60°C for 4 hours. The pH of the resulting mixture was adjusted to 7.0 by adding 1 mol / L hydrochloric acid solution. The methanol was removed from the mixture under reduced pressure at 40°C. 23.4 parts of cyclohexane were added in three portions for extraction. After oil-water separation, the organic phase was dried with anhydrous magnesium sulfate, filtered, and distilled under reduced pressure at 45°C to obtain 5.06 parts of neodecyl aliphatic acyl dioxime, a pale yellow oily liquid with a product purity of 77.56% and a product yield based on neodecyl aliphatic acyl of 79.77%.

[0089] Example 8

[0090] Preparation of neodecyl azodioxime

[0091] 3.00 parts of neodecyl azodioxime (79.16% purity), 0.57 parts of hydroxylamine hydrochloride (98.5% purity), and 0.99 parts of sodium hydroxide (96% purity) prepared in Example 5 were dissolved in 8.33 parts of an aqueous methanol solution (methanol to water volume ratio of 4:1). The mixture was heated under reflux at 60°C for 2 hours. The pH of the resulting mixture was adjusted to 6.0 by adding 1 mol / L hydrochloric acid solution. The methanol was removed from the mixture under reduced pressure at 40°C. 9.02 parts of ethyl acetate were added in three portions for extraction. After oil-water separation, the organic phase was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure at 45°C to obtain 2.99 parts of neodecyl azodioxime, a pale yellow oily liquid with a product purity of 80.27% and a product yield of 95.13% based on neodecyl azodioxime.

[0092] Experimental Example 1

[0093] The extraction performance of neodecyl azo oxime for copper was investigated.

[0094] Cu in copper ion solution 2+The concentration was 0.64 g / L, the pH was 4.58, and the extractants were neodecyl azotoxin monooxime prepared in Example 4, neodecyl azotoxin dioxime prepared in Example 6, and commercially available Lix841 (2-hydroxy-5-nonylacetophenone oxime). The diluent was commercially available sulfonated kerosene. The extractants and diluents were mixed to prepare an organic phase, with the concentrations of neodecyl azotoxin monooxime and Lix841 both at 30 wt.%, and the concentration of neodecyl azotoxin dioxime at 25 wt.%. The organic phase and Cu... 2+ The solutions were mixed at a ratio of O / A = 1:1, with an extraction time of 15 min and a settling time of 15 min. After primary extraction, the supported organic phase was mixed with sulfuric acid aqueous solution at a volume ratio of 1:1 for back-extraction to obtain back-extract and regenerated organic phase. The neodecyl azodioxime and neodecyl azodioxime supported organic phases were back-extracted using 0.1 mol / L sulfuric acid aqueous solution, while the Lix841 supported organic phase was back-extracted using 2 mol / L sulfuric acid aqueous solution.

[0095] Three extraction systems for Cu in copper ion solution 2+ The extraction and back-extraction rates are shown in Table 4 below. The extraction performance of neodecyl azodioxime, neodecyl azodioxime, and Lix841 for copper ions is similar. Neodecyl azodioxime requires a smaller amount of material. Furthermore, neodecyl azodioxime and neodecyl azodioxime can achieve back-extraction of copper ions using a lower concentration of sulfuric acid (0.1 mol / L), while Lix841 is more difficult to back-extract copper ions and requires a higher concentration of sulfuric acid (2 mol / L) to achieve back-extraction.

[0096] Table 4. Extraction and back-extraction results of copper in copper ion solution using different extractants.

[0097]

[0098] Experimental Example 2

[0099] The separation performance of neodecyl azo oxime for copper was investigated.

[0100] Cu in copper ion solution 2+ The concentration of the organic ion was 0.64 g / L, and the concentrations of other metal ions were all 0.60 g / L. The extractants were neodecyl azotoxin monooxime prepared in Example 4 and neodecyl azotoxin dioxime prepared in Example 6. The diluent was commercially available sulfonated kerosene. The extractants and solvents were mixed to prepare an organic phase with a concentration of 30 wt.% for neodecyl azotoxin monooxime and 25 wt.% for neodecyl azotoxin dioxime. The organic phase and the metal ion solution were mixed at a ratio of O / A = 1:1, the extraction time was 15 min, and the settling time was 15 min. After the first-stage extraction, the loaded organic phase was mixed with 0.1 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 for back-extraction to obtain the back-extract and the regenerated organic phase.

[0101] Two extraction systems for Cu in metal ion solutions 2+ The separation performance of neodecyl azodioxime for Cu in solutions of different metal ions is shown in Table 5 below. 2+ Its separation performance is superior to that of neodecyl azo oxime.

[0102] Table 5. Extraction and separation results of copper ions in different separation systems by neodecyl azo oxime.

[0103]

[0104]

[0105] Experimental Example 3

[0106] The extraction and separation performance of neodecyl azo oxime for cobalt and nickel was investigated.

[0107] Cobalt and nickel ion solutions contain either cobalt or nickel, and one of manganese and lithium, wherein Co 2+ and Ni 2+ The concentrations were all 0.59 g / L, Mn 2+ The concentration was 0.55 g / L, Li + The concentration of the extractant was 0.10 g / L. The extractants were neodecyl azotoxin monooxime prepared in Example 4 and neodecyl azotoxin dioxime prepared in Example 6. The diluent was commercially available sulfonated kerosene. The extractant and solvent were mixed to prepare an organic phase with a concentration of 30 wt.% for neodecyl azotoxin monooxime and 25 wt.% for neodecyl azotoxin dioxime. The organic phase was mixed with the metal ion solution at a ratio of O / A = 1:1, the extraction time was 15 min, and the settling time was 15 min. After the first-stage extraction, the loaded organic phase was mixed with 0.1 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 for back-extraction to obtain the back-extract and the regenerated organic phase.

[0108] The infrared spectrum of neodecyl azodioxime reacting with nickel ions is shown below. Figure 12 As shown in Table 6 below, where a is the infrared spectrum of neodecyl azodioxime and b is the infrared spectrum of neodecyl azodioxime after interaction with nickel ions, the results show that after interaction with nickel ions, the infrared characteristic peaks attributed to OH, C=N and NO changed, indicating that these groups in neodecyl azodioxime participated in the interaction. Moreover, the infrared characteristic peak attributed to C=N was divided into two, indicating that the two adjacent oxime groups in the neodecyl azodioxime molecule interact with nickel ions in different ways.

[0109] Table 6. Changes in infrared characteristic peaks before and after the interaction of neodecyl azo oxime with metal ions.

[0110]

[0111]

[0112] The separation performance of the two extraction systems for Co / Mn, Ni / Mn, Co / Li and Ni / Li in metal ion solutions is shown in Table 7 below. Among them, the separation performance of neodecyl azodioxime for Co / Mn, Ni / Mn, Co / Li and Ni / Li is better than that of neodecyl azodioxime.

[0113] Table 7. Extraction and separation results of neodecyl azodicarbonamide for cobalt manganese, nickel manganese, cobalt lithium, and nickel lithium.

[0114]

[0115] Experiment Example 4

[0116] The extraction and separation performance of neodecyl azo oxime for manganese was investigated.

[0117] The manganese ion-containing solution contains manganese, and one of magnesium and lithium, wherein Mn 2+ The concentration was 5.49 g / L, Mg 2+ The concentration was 2.43 g / L, Li + The concentration of the extractant was 0.69 g / L. The extractant was neodecyl azo oxime prepared in Example 5, and the diluent was commercially available sulfonated kerosene. The extractant and solvent were mixed to prepare an organic phase with a concentration of 30 wt.%. The organic phase was saponified using a 30% sodium hydroxide aqueous solution with a saponification rate of 30%. The organic phase and the metal ion solution were mixed at a ratio of O / A = 1:1, the extraction time was 15 min, and the settling time was 15 min. After the first-stage extraction, the loaded organic phase was mixed with a 1 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 for back-extraction to obtain the back-extract and the regenerated organic phase.

[0118] The infrared spectrum of neodecyl azo oxime reacting with manganese ions is shown below. Figure 13 As shown in Table 8, where a is the infrared spectrum of neodecyl azo oxime and b is the infrared spectrum of neodecyl azo oxime after interaction with manganese ions, the results show that after the interaction of neodecyl azo oxime with manganese ions, the infrared characteristic peaks attributed to OH, C=O, C=N and NO changed, indicating that these groups in neodecyl azo oxime participated in the interaction.

[0119] Table 8. Changes in infrared characteristic peaks before and after the interaction of neodecyl azo oxime with metal ions.

[0120] Characteristic Infrared characterization results Neodecyl azoyl oxime 3257(OH),1669(C=O),1630(C=N),1374(NO) <![CDATA[Neodecanoyl monoxime + Mn 2+ > 1695 (C=O), 1375 (NO)

[0121] The extraction and separation performance of neodecyl azo oxime for Mn / Mg and Mn / Li in metal ion solutions is shown in Table 9 below. Neodecyl azo oxime can achieve the extraction and separation of Mn / Mg and Mn / Li.

[0122] Table 9. Extraction and separation results of neodecyl azo oxime for manganese magnesium and manganese lithium.

[0123]

[0124] Experimental Example 5

[0125] Investigation of the application of neodecyl azo oxime in the treatment of leachate from spent lithium batteries

[0126] After dismantling and crushing waste lithium-ion batteries, acid leaching yields a solution containing copper, cobalt, nickel, manganese, and lithium ions, with a pH of 3.0. The metal ion concentrations are shown in Table 10 below. The extraction and recovery process for copper, cobalt, nickel, and manganese is as follows. Figure 14 As shown, copper in the leachate was first extracted and recovered using neodecyl azodioxime, then co-extracted with neodecyl azodioxime to obtain cobalt and nickel, and finally extracted and recovered manganese using saponified neodecyl azodioxime. Extraction and separation of copper in the leachate: The extractant was neodecyl azodioxime prepared in Example 7, and the diluent was commercially available sulfonated kerosene. The extractant and solvent were mixed to prepare an organic phase with a neodecyl azodioxime concentration of 25 wt.%. The organic phase was mixed with the leachate from the waste lithium-ion battery at an O / A ratio of 2:1, with an extraction time of 15 min and a settling time of 15 min.

[0127] After primary extraction, the extraction rates were 53.19% for copper, 0.33% for cobalt, 0.1% for nickel, 0.07% for manganese, and 0.11% for lithium. Secondary countercurrent extraction yielded a loaded organic phase and raffinate. ICP analysis showed that the concentrations of copper ions in the raffinate were 0.19 g / L, cobalt ions 30.21 g / L, nickel ions 2.51 g / L, manganese ions 3.88 g / L, and lithium ions 4.3 g / L, resulting in a copper ion extraction rate of 98.56%. The loaded organic phase was then back-extracted with a 1 mol / L sulfuric acid aqueous solution at a 1:1 volume ratio to obtain a back-extract and a regenerated organic phase. After primary back-extraction, the copper ion concentration in the back-extract was 3.49 g / L, resulting in a copper back-extraction rate of 99.26%.

[0128] Extraction and separation of cobalt and nickel in the leachate: The extractant was neodecyl azodioxime prepared in Example 7, and the diluent was commercially available sulfonated kerosene. The extractant and solvent were mixed to prepare an organic phase with a neodecyl azodioxime concentration of 25 wt.%. The organic phase was mixed with the leachate after copper removal in the previous step, with an O / A ratio of 3:1. The extraction time was 15 min, and the settling time was 15 min. After the first-stage extraction, the extraction rates of cobalt, nickel, manganese, and lithium were 55.49%, 46.26%, 0.13%, and 0.17%, respectively. After a second-stage countercurrent extraction, the loaded organic phase and raffinate were obtained and analyzed by IC50. The concentrations of cobalt ions, nickel ions, manganese ions, and lithium ions in the raffinate were determined by the P method to be 0.36 g / L, 0.11 g / L, 3.86 g / L, and 4.28 g / L, respectively. The calculated extraction rates for cobalt ions were 98.8% and for nickel ions were 95.62%. The supported organic phase was mixed with a 1 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 for back-extraction, yielding a back-extraction solution and a regenerated organic phase. After one-stage back-extraction, the concentrations of cobalt ions and nickel ions in the back-extraction solution were 5.51 g / L and 0.38 g / L, respectively, with back-extraction rates of 98.61% and 98.18%, respectively.

[0129] Extraction and separation of manganese in the leachate: The extractant was neodecyl azo oxime prepared in Example 5, and the diluent was sulfonated kerosene. The extractant and solvent were mixed to prepare an organic phase with a neodecyl azo oxime concentration of 30 wt.%. The organic phase was saponified with a 30% sodium hydroxide aqueous solution, and the saponification rate was 30%. The organic phase was mixed with the leachate after removing cobalt and nickel in the previous step, with a ratio of O / A = 1:1. The extraction time was 15 min, and the settling time was 15 min. After the first-stage extraction, the extraction rate of manganese was 97.56%, and the extraction rate of lithium was 0.92%. The loaded organic phase was mixed with a 1 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 for back-extraction to obtain a back-extraction solution and a regenerated organic phase. After the first-stage back-extraction, the concentration of manganese ions in the back-extraction solution was 3.71 g / L, and the manganese back-extraction rate was 98.52%.

[0130] Table 10 Concentration of Main Metal Ions in Leachate from Waste Lithium-ion Batteries

[0131] Metal elements Cu Co Ni Mn Li Concentration (g / L) 13.22 30.73 2.55 3.89 4.33

[0132] Experimental Example 6

[0133] Investigation of the application of neodecyl azo oxime in the treatment of electrolytic manganese anolyte

[0134] Mn in the anolyte of an electrolytic manganese plant 2+ The concentration was 14.41 g / L, Mg 2+The concentration was 26.30 g / L, and the pH was 4.34. The extractant was neodecyl azo oxime prepared in Example 5, and the solvent was commercially available sulfonated kerosene. The extractant and solvent were mixed to prepare an organic phase. Extraction operations were performed on the electrolytic manganese anolyte using extractants of different concentrations.

[0135] The concentration of neodecyl azo oxime was 30 wt.%, and the organic phase was saponified using a 30% sodium hydroxide aqueous solution, with a saponification rate of 30%. The organic phase was mixed with the electrolytic manganese anolyte at an O / A ratio of 3:1, with an extraction time of 15 min and a settling time of 15 min. After the first-stage extraction, the extraction rate of manganese was 78.19%, and the extraction rate of magnesium was 6.47%, with a manganese-magnesium removal ratio of 12.09, achieving effective separation of manganese and magnesium. A second-stage countercurrent extraction was performed to obtain the loaded organic phase and raffinate. The raffinate was analyzed by ICP. The concentration of manganese ions in the residual liquid was 0.13 g / L, and the concentration of magnesium ions was 21.42 g / L. The extraction rates of manganese ions were calculated to be 99.13% and magnesium ions 18.56%. The supported organic phase was mixed with 1 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 for back-extraction to obtain back-extraction solution and regenerated organic phase. After one-stage back-extraction, the concentration of manganese in the back-extraction solution was 3.15 g / L, and the concentration of magnesium was 0.56 g / L. The back-extraction rate of manganese was 83.82%, and the back-extraction rate of magnesium was 98.56%.

[0136] The concentration of neodecyl azo oxime was 50 wt.%. The organic phase was saponified using a 30% sodium hydroxide aqueous solution, with a saponification rate of 30%. The organic phase was mixed with the electrolytic manganese anolyte at an O / A ratio of 2:1. The extraction time was 15 min, followed by a settling time of 15 min. After the first-stage extraction, the extraction rate of manganese was 93.58%, and the extraction rate of magnesium was 10.69%, with a manganese-magnesium removal ratio of 8.76, achieving effective separation of manganese and magnesium. A second-stage countercurrent extraction was performed to obtain the loaded organic phase and raffinate. ICP analysis was used to determine the extraction... The concentration of manganese ions in the residual liquid was 0.04 g / L, and the concentration of magnesium ions was 17.12 g / L. The calculated extraction rates of manganese ions were 99.69% and magnesium ions were 34.91%. The supported organic phase was mixed with 1 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 for back-extraction to obtain back-extraction solution and regenerated organic phase. After one-stage back-extraction, the concentration of manganese in the back-extraction solution was 5.73 g / L, and the concentration of magnesium was 1.09 g / L. The back-extraction rate of manganese was 84.98%, and the back-extraction rate of magnesium was 77.26%.

[0137] Experimental Example 7

[0138] Investigation of the application of neodecyl azo oxime in the treatment of qualified electrolytic manganese solution

[0139] A qualified electrolytic manganese solution stock solution Mn 2+ The concentration was 32.64 g / L, Mg2+ The concentration was 25.22 g / L, and the pH was 3.61. The extractant was neodecyl azo oxime prepared in Example 5, and the solvent was commercially available sulfonated kerosene. The extractant and solvent were mixed to prepare an organic phase. The extractant concentration was 50 wt.%, and the organic phase was saponified using a 30% sodium hydroxide aqueous solution, with a saponification rate of 30%. Extraction applications were performed on qualified electrolytic manganese solutions under different ratios.

[0140] The saponified organic phase and the qualified electrolytic manganese solution were mixed at an O / A ratio of 3:1, with an extraction time of 15 min and a settling time of 15 min. After the first-stage extraction, the extraction rate of manganese was 76.10%, and the extraction rate of magnesium was 4.26%, with a manganese-magnesium removal ratio of 17.85, achieving effective separation of manganese and magnesium. After a second-stage countercurrent extraction, the loaded organic phase and raffinate were obtained. ICP analysis showed that the concentration of manganese ions in the raffinate was 0.13 g / L, and the concentration of magnesium ions was 16.35 g / L, resulting in a calculated extraction rate of 99.60% for manganese ions and 35.18% for magnesium ions. The loaded organic phase was then back-extracted with a 1 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 to obtain a back-extract and a regenerated organic phase. After a first-stage back-extraction, the concentration of manganese in the back-extract was 7.54 g / L, and the concentration of magnesium was 0.33 g / L, with a back-extraction rate of 91.08% for manganese and 92.09% for magnesium.

[0141] The saponified organic phase and the qualified electrolytic manganese solution were mixed at an O / A ratio of 2:1, with an extraction time of 15 min and a settling time of 15 min. After the first-stage extraction, the extraction rate of manganese was 49.39%, and the extraction rate of magnesium was 2.02%, with a manganese-magnesium removal ratio of 24.42, achieving effective separation of manganese and magnesium. After a second-stage countercurrent extraction, the loaded organic phase and raffinate were obtained. ICP analysis showed that the concentration of manganese ions in the raffinate was 1.51 g / L and the concentration of magnesium ions was 22.77 g / L, resulting in a calculated extraction rate of 95.75% for manganese ions and 15.51% for magnesium ions. The loaded organic phase was then back-extracted with a 1 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 to obtain a back-extract and a regenerated organic phase. After a first-stage back-extraction, the concentration of manganese in the back-extract was 8.75 g / L and the concentration of magnesium was 0.26 g / L, with a back-extraction rate of 99.40% for manganese and 95.41% for magnesium.

[0142] Experimental Example 8

[0143] The extraction performance of neodecyl azo oxime for rare earth elements was investigated.

[0144] La in rare earth ion solutions 3+ Ce 3+ Pr 3+ The concentrations were all 1.40 g / L, Sm3+ The concentration of the extractant was 1.50 g / L. The extractants were neodecyl azotoxin monooxime prepared in Example 5 and neodecyl azotoxin dioxime prepared in Example 8. The diluent was commercially available sulfonated kerosene. The extractant and diluent were mixed to prepare an organic phase with a concentration of 30 wt.% for neodecyl azotoxin monooxime and 25 wt.% for neodecyl azotoxin dioxime. The organic phase was mixed with the metal ion solution at a ratio of O / A = 1:1, the extraction time was 15 min, and the settling time was 15 min. After the first-stage extraction, the loaded organic phase was mixed with 0.5 mol / L sulfuric acid aqueous solution at a volume ratio of 1:1 for back-extraction to obtain the back-extract and the regenerated organic phase.

[0145] Two extraction systems for La in rare earth element solutions 3+ Ce 3+ Pr 3+ 、Sm 3+ The extraction and back-extraction rates are shown in Table 11 below. Neodecyl azo oxime exhibits emulsification during the extraction of rare earth elements, while neodecyl azo dioxime shows better extraction and back-extraction performance for rare earth elements lanthanum, cerium, praseodymium, and samarium.

[0146] Table 11 Extraction and back-extraction results of neodecyl azo oxime for lanthanum, cerium, praseodymium, and samarium.

[0147]

[0148] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A neodecyl oxyacetyl oxime extractant, characterized in that, The extractant is a neodecyl azodioxime as shown in Formula 1 or a neodecyl azodioxime as shown in Formula 2. ， ， Among them, R 1 R 2 R 3 R 4 Selected from -H, -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 -C6H 13 -C7H 15 One of them, R 1 and R 2 The total number of carbon atoms is 7, R 3 and R 4 The total number of carbon atoms is 7.

2. A method for preparing the neodecyl oxycloyl oxime extractant as described in claim 1, characterized in that, Includes the following steps: S1. Preparation of neodecyl aloyl: Neodecyl chloride, metal powder, and reaction solvent are heated and reacted under a nitrogen atmosphere. The resulting mixture is distilled under reduced pressure, then an acid solution is added, and finally an organic solvent is added for extraction. After extraction and separation, an organic phase rich in neodecyl aloyl is obtained, which is then dried and evaporated to obtain the neodecyl aloyl compound. The metal powder is one or more of zinc powder, magnesium powder, iron powder, aluminum powder, manganese powder, ferromanganese alloy powder, and stainless steel powder. S2. Preparation of decyl oxytocilime extractant: The neodecyl oxytocilime compound obtained in S1, hydroxylamine, and base are dissolved in a methanol aqueous solution. The mixture obtained by heating the reaction is adjusted to pH 6-7 with an acid solution and then distilled under reduced pressure. Then, an organic solvent is added for extraction. After extraction and separation, an organic phase rich in neodecyl oxytocilime compound is obtained. The extractant is then dried and evaporated to obtain the neodecyl oxytocilime extractant.

3. The preparation method according to claim 2, characterized in that, In step S1, the molar ratio of neodecanoyl chloride, metal powder, and reaction solvent is 1:0.5-2:0.5-5; the reaction solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylpropionamide.

4. The preparation method according to claim 2, characterized in that, In step S1, the heating temperature is 60~150℃, the reaction time is 1~12 h, and the temperature for vacuum distillation is 85~150℃.

5. The preparation method according to claim 2, characterized in that, In step S2, the molar ratio of neodecyl alkyl acyl, hydroxylamine, and base is 1:1.05~1.2:2.1~2.4 or 1:2.1~2.5:4.2~5; the hydroxylamine is one or more of hydroxylamine hydrochloride, hydroxylamine sulfate, and hydroxylamine phosphate; the base is one or more of sodium hydroxide, potassium hydroxide, and sodium methoxide; and the volume ratio of methanol to water in the methanol aqueous solution is 0.5~5:

1.

6. The preparation method according to claim 2, characterized in that, In step S2, the heating temperature is 40~80℃, the reaction time is 3~7 h, and the temperature for vacuum distillation is 35~50℃.

7. The preparation method according to claim 2, characterized in that, The acid solution is one or more of hydrochloric acid, sulfuric acid, and nitric acid, and the organic solvent is one or more of ethyl acetate, dichloromethane, chloroform, acetonitrile, petroleum ether, n-hexane, and cyclohexane.

8. The application of a neodecyl oxytocilime extractant as described in claim 1 or a neodecyl oxytocilime extractant prepared by any one of claims 2-7 in the extraction and recovery of at least one metal, including copper, cobalt, nickel, and manganese, characterized in that... Includes the following steps: S1. Extraction: Dissolve neodecyl azo oxime in a diluent to form an organic phase, add it to an aqueous phase containing the metal ions to be recovered, or saponify the organic phase and add it to the aqueous phase containing the metal ions to be recovered. After extraction, allow it to stand to obtain a loaded organic phase containing the target metal ions; the metal ions to be recovered include one or more of copper ions, cobalt ions, nickel ions and manganese ions. S2, Back-extraction: After back-extraction of the loaded organic phase with acid solution, a back-extraction solution rich in target metal ions is obtained. The regenerated organic phase after back-extraction is returned to the extraction process for recycling.

9. The application of the neodecyl azodioxime extractant of Formula 2 as described in claim 1 in the extraction and recovery of at least one metal, including lanthanum, cerium, praseodymium, and samarium, characterized in that... Includes the following steps: S1. Extraction: Neodecyl azo oxime is dissolved in a diluent to form an organic phase, which is then added to an aqueous phase containing the metal ions to be recovered. After extraction, the phase is allowed to stand to obtain a supported organic phase containing the target metal ions. The metal ions to be recovered include one or more of lanthanum ions, cerium ions, praseodymium ions, and samarium ions. S2, Back-extraction: After back-extraction of the loaded organic phase with acid solution, a back-extraction solution rich in target metal ions is obtained. The regenerated organic phase after back-extraction is returned to the extraction process for recycling.

10. The application according to claim 8, characterized in that, In step S1, the organic phase contains 10-60 wt.% neodecyl azo oxime extractant, and the diluent is one or more of chloroform, carbon tetrachloride, benzene, toluene, kerosene, aviation kerosene, and sulfonated kerosene. The saponified organic phase is neodecyl azo oxime and the diluent. The volume ratio of the organic phase to the aqueous phase solution is 0.5-5:1, the extraction time is 5-60 min, and the standing time is 5-60 min.

11. The application according to any one of claims 8 to 9, characterized in that, In step S2, the volume ratio of the loaded organic phase to the back-extraction liquid is 0.5 to 7:1.

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