WO2022110821A1 - Carboxylic acid compound, preparation method therefor and use thereof - Google Patents

Abstract

Disclosed are a carboxylic acid compound as represented by formula I, a preparation method therefor and the use thereof. When the carboxylic acid compound is used as an extraction agent for the extraction and separation of metal ions, the carboxylic acid compound has a good ion selectivity, a low reverse extraction acidity and a high saturation capacity and reverse extraction rate.

Description

A kind of carboxylic acid compound and its preparation method and application technical field

The present application relates to a carboxylic acid compound and its preparation method and application.

Background technique

Cobalt is mostly associated with nickel, and most of them appear at the same time in minerals, such as in nickel laterite. In many industries, waste residues containing valuable metals such as nickel and cobalt are generated, such as waste power battery materials, nickel-cobalt-containing waste residues, waste catalysts, etc. Most of these waste residues also contain high manganese at the same time, which has a high recovery value. They can be recycled for the preparation of cathode material precursors for nickel-cobalt-manganese ternary lithium-ion batteries.

Solvent extraction technology is an effective technology for separating and extracting various metals from solution. It has the advantages of high separation efficiency, simple process and equipment, continuous operation, and easy automatic control. With the urgency of environmental protection and resource recycling, higher requirements are also placed on the energy consumption, acid consumption, sewage and production capacity of the extraction system. Therefore, it is necessary to improve the extraction efficiency, separation effect and stability of the extraction agent. and other properties to meet environmental and economic requirements.

Commonly used cation exchange extractants such as acidic phosphoric acid extractants P204, P507, C272 have been widely used in the separation and purification of metal elements. Patent CN109449523A discloses a comprehensive recovery method for waste lithium-ion batteries, which firstly adjusts the pH of the feed liquid to 4.2-4.5, uses P204 to extract the feed liquid, obtains P204 raffinate and a loaded organic phase, and uses sulfuric acid to back extract the loaded organic phase Obtain manganese sulfate; adjust the pH of the P204 raffinate = 4.5 to 5, use C272 to extract the P204 raffinate to obtain a C272 raffinate and a loaded organic phase, and use sulfuric acid to reverse the C272 loaded organic phase. The cobalt sulfate solution is extracted; the pH of the C272 raffinate is adjusted to be 5-5.5, the Ni is extracted from the raffinate with P507, and the P507-loaded organic phase is back extracted with sulfuric acid to obtain a nickel sulfate solution. However, these extractants also have obvious shortcomings in the separation process: P507/P204 is used for the separation of nickel and cobalt, but in terms of recycling cathode materials of lithium ion batteries, nickel, cobalt and manganese cannot be extracted simultaneously, and the cost of recovering nickel, cobalt and manganese separately is high. In addition, the back extraction acidity is high and the pollution is serious; C272 preferentially extracts calcium and magnesium before extracting nickel elements, the operation process is complicated, and the cost of impurity removal is high.

SUMMARY OF THE INVENTION

The present application provides a carboxylic acid compound and a preparation method and application thereof. The carboxylic acid compound is used as an extractant, has good selectivity to ions (especially nickel, cobalt, and manganese ions), low back extraction acidity, and has the advantages of low water solubility, high stability, and low cost.

The present application solves the above technical problems through the following technical solutions.

The application provides a carboxylic acid compound or its salt as shown in formula I:

Wherein, R ₁ and R ₂ are independently C ₃ -C ₁₂ straight-chain or branched-chain alkyl groups.

Wherein, optionally, R ₁ is a C ₄ -C ₉ linear or branched chain alkyl; optionally, R ₁ is a C ₄ -C ₉ linear alkyl group, such as n-butyl, n-pentyl, n-hexyl or n-octyl.

Wherein, optionally, R ₂ is a C ₃ -C ₁₀ straight chain or branched chain alkyl group; optionally, R ₂ is a C ₆ -C ₉ straight chain or branched chain alkyl group; for example, n-nonyl, n-octyl or isooctyl (eg

).

Wherein, optionally, the total carbon number n of R ₁ and R ₂ is 10-20, for example, n is 12, 13, 14 or 15.

Wherein, optionally, the carboxylic acid compound shown in formula I is selected from any of the following compounds:

Wherein, the salt of the carboxylic acid compound shown in formula I is generally prepared by reacting the carboxylic acid compound shown in formula I with a base, for example, the carboxylic acid compound shown in formula I is prepared by reacting The compound and the base are prepared by reacting with a molar ratio of 1:1. The alkali can be a conventional alkali in the art, such as alkali metal hydroxide or ammonia water, or sodium hydroxide, potassium hydroxide or ammonia water, whereby the salt of the carboxylic acid compound can be sodium salt, potassium salt or Ammonium salt.

Wherein, the conditions of the preparation method of the salt of the carboxylic acid compound shown in formula I can be the conventional conditions of the acid-base salt formation reaction conventional in the art.

Wherein, the carboxylic acid compound shown in formula I can be extracted from nature or synthesized by conventional methods, and the extractant can be one of the carboxylic acid compounds shown in formula I when used for extraction or a mixture thereof (eg, two or more).

The present application also provides a method for preparing the carboxylic acid compound shown in formula I, which comprises: in a solvent, under the action of a base, carrying out the reaction between the compound shown in formula II and the compound shown in formula III reaction, you can;

wherein X is halogen, and R ₁ and R ₂ are as defined above.

In the preparation method, optionally, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine or bromine, and another example is bromine.

In the preparation method, the solvent may be a solvent commonly used in this type of reaction in the art, such as an ether-based solvent, and the ether-based solvent is, for example, tetrahydrofuran.

In the preparation method, the amount of the solvent can be the conventional amount of this type of reaction in the art, as long as it does not affect the reaction. For example, the volume-to-mass ratio of the solvent to the compound represented by formula III is used in an amount ranging from 1 to 8 mL/g, for example, 2.96, 3.5, 3.7 or 4.6 mL/g;

In the preparation method, the base can be a base commonly used in such reactions in the art, such as an alkali metal or an alkali metal hydride, such as sodium, such as sodium hydride.

In the preparation method, the amount of the base can be the conventional amount used for this type of reaction in the art, for example, the molar ratio of the base to the compound represented by formula II is (1-1.5): 1, for example 1.1:1, 1.2:1 or 1.35:1.

In the preparation method, the molar ratio of the compound represented by the formula II to the compound represented by the formula III can be a conventional ratio of this type of reaction in the field, and can be optionally 1:(1-1.5), For example 1:1.1 or 1:1.2.

In the preparation method, the temperature of the reaction may be a conventional temperature in this type of reaction in the art, and in this application, it is optionally 60-70°C.

In the preparation method, the progress of the reaction can be detected by conventional monitoring methods in the art (such as TLC, HPLC or NMR), generally when the compound shown in formula II disappears or no longer reacts as the reaction end point. The reaction time can be 6 to 12 hours, for example, 10 hours.

The present application also provides the use of the carboxylic acid compound represented by formula I or its salt as an extractant.

In the application, the extractant may be one of the carboxylic acid compounds shown in formula I or a mixture thereof (for example, two or more), for example, any one of the following compounds or a mixture thereof (e.g. two or more):

In the application, the carboxylic acid compound represented by formula I or its salt is used as an extractant for extraction and separation of metal ions. Optionally, the metal ion is one of Ni ²⁺ , Co ²⁺ and Mn ²⁺ or a mixture thereof (for example, two or more), and the metal ion may also include, for example, Fe ³⁺ , Al ³⁺ , One of Cu ²⁺ , Zn ²⁺ , Cd ²⁺ and Ca ²⁺ or a mixture thereof (eg, two or more), the metal ions may further include other ions such as Mg ²⁺ , Li ⁺ and the like. For example, the metal ions are "at least one of Ni ²⁺ , Co ²⁺ and Mn ²⁺ " and "Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Ca ²⁺ , At least one of ^Mg2+ and Li ⁺ " mix. For another example, the metal ions are Ni ²⁺ , Co ²⁺ , Mn ²⁺ , Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Ca ²⁺ , Mg ²⁺ and Li ⁺ the mix of. Optionally, the metal ions can be derived from waste lithium-ion battery cathode materials, nickel laterite or nickel-cobalt-containing waste residues. Therefore, in an optional solution of the present application, the carboxylic acid compound shown in Formula I or its salt is used as an extractant for extracting and separating waste lithium ion battery cathode materials, nickel laterite or nickel-cobalt-containing waste residues. Metal ion.

The present application also provides an extraction composition comprising an extractant and a diluent, the extractant comprising the above-mentioned carboxylic acid compound shown in formula I and/or the above-mentioned carboxylic acid compound shown in formula I Salt.

In the extraction composition, optionally, the molar ratio of the carboxylic acid compound shown in formula I and the salt of the carboxylic acid compound shown in formula I is (0.4-9): 1 ( For example 1:1).

In the extraction composition, optionally, the extraction agent includes the carboxylic acid compound shown in formula I and the salt of the carboxylic acid compound shown in formula I, and the extraction agent is shown in formula I. The molar ratio of the shown carboxylic acid compound to the salt of the carboxylic acid compound shown in formula I is (0.4-9):1.

In the extraction composition, the diluent can be a diluent commonly used in the art, optionally, the diluent is a solvent oil (for example, No. 200 solvent oil or No. 260 solvent oil), kerosene, Escaid 110, ethyl acetate One of alkane, heptane and dodecane (such as n-dodecane) or a mixture thereof (such as two or more); Alane (eg n-dodecane) and Escaid 110 or a mixture thereof (eg, two or more).

In the extraction composition, the amount of the diluent is not particularly limited, as long as it does not affect the extraction and back-extraction performance of the extraction composition. The volume ratio is 0.1mol/L～1.5mol/L, optionally 0.16mol/L～0.85mol/L, such as 0.16mol/L, 0.33mol/L or 0.6mol/L.

The present application also provides an extraction method, which includes the steps of: extracting an organic phase containing an extractant from an aqueous phase containing metal ions to obtain an organic phase containing metal ions;

In the organic phase containing the extractant, the extractant comprises the above-mentioned carboxylic acid compound shown in formula I and/or the salt of the above-mentioned carboxylic acid compound shown in formula I;

In the water phase containing metal ions, the metal ions include Ni ²⁺ , Co ²⁺ , Mn ²⁺ , Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ and Ca ²⁺ One or a mixture thereof (eg, two or more).

In the water phase containing metal ions, the metal ions may further include other ions such as Mg ²⁺ , Li ⁺ and the like. Optionally, the metal ions can be derived from waste lithium-ion battery cathode materials, nickel laterite or nickel-cobalt-containing waste residues. Optionally, the metal ions are "at least one of Ni ²⁺ , Co ²⁺ and Mn ²⁺ " and "Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Ca ^{2 +} , Mg ²⁺ and Li ⁺ at least one "mixture. For example, the metal ions are Ni ²⁺ , Co ²⁺ , Mn ²⁺ , Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Ca ²⁺ , Mg ²⁺ and Li ⁺ mix.

In the organic phase containing the extractant, optionally, the molar ratio of the carboxylic acid compound shown in formula I and the salt of the carboxylic acid compound shown in formula I is (0.4-9) :1 (eg 1:1).

In the organic phase containing the extractant, optionally, the extractant includes the carboxylic acid compound shown in formula I and the salt of the carboxylic acid compound shown in formula I, such as The molar ratio of the carboxylic acid compound represented by formula I and the salt of the carboxylic acid compound represented by formula I is (0.4-9):1.

In the extraction method, optionally, the organic phase containing the extractant further includes a diluent. The diluent can be a diluent commonly used in the art, optionally, the diluent is mineral spirits (such as No. 200 mineral spirits or No. 260 mineral spirits), kerosene, Escaid 110, hexane, heptane and dodecane Alane (such as n-dodecane) or a mixture thereof (such as two or more); optionally, the diluent is mineral spirits (such as No. 260 mineral spirits), dodecane (such as n-dodecane) ) and Escaid 110 or a mixture thereof (eg, two or more). The amount of the diluent may not be specifically limited, as long as it does not affect the extraction and back-extraction performance of the organic phase containing the extractant. Optionally, in the organic phase containing the extractant, the extractant and The molar volume ratio of the diluent is 0.1 mol/L to 1.5 mol/L, optionally 0.16 mol/L to 0.85 mol/L, such as 0.16 mol/L, 0.33 mol/L or 0.6 mol/L.

In the extraction method, the volume ratio of the extractant-containing organic phase and the metal ion-containing water phase can be the ratio used for conventional extraction in the field; optionally, the extractant-containing organic phase and the The volume ratio of the metal ion-containing water phase is 1:(1-10), optionally 1:(1-5), such as 1:1, 1:2 or 1:4.

In the extraction method, optionally, mass transfer is performed by shaking.

In the extraction method, optionally, the extraction temperature may be conventionally used for such extraction in the art, optionally 10°C to 50°C, optionally 25°C to 40°C. The extraction time can be a time conventional in the art, optionally 5 to 60 minutes, such as 15 minutes or 30 minutes.

The present application also provides a back extraction method, which includes the following steps: mixing the organic phase containing metal ions obtained by the above extraction method with an aqueous acid solution.

In the stripping method, the metal ions supported in the metal ion-containing organic phase are transferred into the aqueous phase to obtain a metal ion-rich aqueous phase and a regenerated organic phase.

In the back extraction method, the molar concentration of the acid aqueous solution can be the molar concentration commonly used in this type of back extraction in the field, optionally 0.5mol/L～5mol/L, optionally 1～3mol/L , such as 1 mol/L or 2 mol/L, the molar concentration refers to the ratio of the amount of the acid substance to the total volume of the acid aqueous solution.

In the stripping method, the acid in the acid aqueous solution may be a conventional acid in the art, optionally an inorganic acid. The inorganic acid is optionally one or more of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, optionally sulfuric acid.

In the stripping method, the volume ratio of the metal ion-containing organic phase to the acid aqueous solution can be a conventional ratio in the field, optionally (1～50):1, optionally (10). ~20):1, such as 10:1 or 15:1.

In the present application, the shaking is required for mass transfer, so that the organic phase and the aqueous phase are mixed uniformly, and other conventional operations in the art, such as stirring and other operations, can also be used instead.

On the basis of not violating common knowledge in the art, the above optional conditions can be combined arbitrarily to obtain optional examples of the present application.

The reagents and raw materials used in this application are all commercially available.

The positive and progressive effects of this application are:

(1) When the carboxylic acid compound of the present application is used as an extractant for the extraction and separation of metal ions, it has good ion selectivity, low back extraction acidity, high saturation capacity (saturated capacity for Ni ²⁺ ≥ 17g/L), and reverse extraction. High extraction rate (one-time stripping rate>99.5%);

(2) The carboxylic acid compound of the present application has high stability and low water solubility (the extracted oil content is less than or equal to 73 mg/L when the equilibrium pH of the extraction system is 7.20), so that the extraction process is stable, and environmental pollution and costs can be reduced;

(3) The carboxylic acid compound of the present application has low cost and great application prospects, and can be used in various systems such as ternary battery recovery and battery-grade nickel sulfate preparation.

Description of drawings

Fig. 1 is the extraction rate E%-pH curve of compound BC196 for each ion.

Detailed ways

The present application is further described below by way of examples, but the present application is not limited to the scope of the described embodiments. The scope of protection of the present application is defined by the claims. The experimental methods that do not specify specific conditions in the following examples are selected according to conventional methods and conditions, or according to the product description.

The following example experiments are used to refer to the source information:

The organic phase refers to an organic phase comprising an extractant and a diluent, wherein the extractant includes the carboxylic acid compound shown in formula I and/or the salt of the carboxylic acid compound shown in formula I.

The water phase refers to the water phase containing metal ions, wherein, the water phase containing metal ions can be prepared by conventional methods, for example, including the following steps: dissolving a certain quality of salt in deionized water, and diluting to the desired concentration. .

The phase ratio (O:A) represents the volume ratio of the organic phase to the aqueous phase.

"Saponification" refers to the conversion of hydrogen ions in the extractant into alkali metal ions and/or NH ₄ ⁺ (the converted alkali metal ions and/or NH ₄ ⁺ are exchanged with the extracted metal ions in the aqueous phase to achieve The function of extraction), and the step of saponification is as follows: the organic phase is mixed with the aqueous alkali solution. Optionally, the aqueous alkali solution used in the saponification may be an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide or an aqueous ammonia solution.

The ratio of saponification refers to the ratio of alkali metal and/or NH ₄ ⁺ to the original hydrogen ion in the extractant, that is, η=(V _base ×C _base )/(V _has ×C _has ) (1)

In formula (1), V _alkali is the volume of the aqueous solution of the alkali added, C _alkali is the concentration of the alkali in the aqueous solution of the alkali added, V _is the volume of the organic phase, and C is the concentration of the _extractant in the organic phase.

In the examples of the present application, the content of metal ions in the aqueous phase is determined by inductively coupled plasma optical emission spectrometry (ICP-OES), and then the content of metal ions in the organic phase is obtained by subtraction.

Potentiometric titration of acid content, according to literature: Yuan Chengye, Hu Shuisheng; Research on organophosphorus compounds XVI: σ ^p constant and group connectivity of long carbon-chain alkyl groups and alkoxy groups of phosphorus compounds [J]. Chinese Journal of Chemistry, 1986 , 44, 590-596, carried out; Potentiometric titrator: Metrohm 907Titrando. The examples of this application use the acid content to represent the purity of the extractant.

The distribution ratio D is the metal ion content in the equilibrium organic phase and the metal ion content in the equilibrium aqueous phase after one extraction is completed (the metal ion content in the equilibrium aqueous phase is detected by inductively coupled plasma optical emission spectrometry (ICP-OES), and then the difference The ratio of the metal ion content in the equilibrium organic phase) is obtained by subtraction, namely

D=C _org /C _aq =(C' _aq -C _aq )/C _aq (2)

In formula (2), C _org represents the metal ion concentration in the equilibrium organic phase after one extraction; C _aq represents the metal ion concentration in the equilibrium aqueous phase after one extraction; C' _aq represents the metal ion concentration in the aqueous phase before one extraction.

The extraction rate E is the percentage of the amount of the extracted substance transferred from the aqueous phase into the organic phase in the extraction process to the total amount of the extracted substance in the original aqueous phase, namely:

E=100%×(C' _aq -C _aq )/C' _aq (3)

In formula (3), C _aq represents the concentration of metal ions in the equilibrium aqueous phase after one extraction is completed; C' _aq represents the concentration of metal ions in the aqueous phase before one extraction.

The separation coefficient β refers to the ratio of the distribution ratio of the two substances to be separated between the two phases during extraction and separation under certain conditions, also known as the extraction separation factor.

The raw materials that do not provide preparation methods in the following examples are all commercially available.

Example 1

Add 84.6g isooctylphenol, 250mL tetrahydrofuran (THF), 8.8g sodium particles to the three-necked flask, react at 60-70℃ for 6h, a large amount of white solids are formed, and a small amount of sodium particles remain; at 60℃, dropwise add 40mL containing 8mol/L THF solution of 2-bromooctanoic acid and continue to react at 60°C for 4h; after cooling, after rotary evaporation to remove THF, add 200mL of water and 200mL of ethyl acetate (EA) to the concentrated solution, shake the layers, and take the water layer; water; The layer was acidified with hydrochloric acid to pH ≈ 1, extracted with ethyl acetate, the organic phase was washed twice with water, and spin-dried to obtain 86 g of a light yellow product, namely compound BC195. ¹ H NMR (400 MHz, CDCl ₃ ) δ 10.20 (1H, br.); 7.32 (2H, t); 6.68 (2H, d); 4.84-4.81 (1H, m); 2.6 (2H, m); 2.20 -2.08(2H,m); 1.66-1.56(5H,m); 1.46-1.38(12H,m); 0.99(3H,t,J=7.3,CH3);0.93(3H,t,J=7.3,CH3) _The ^_ 31.8, 27.5, 22.3, 14.2, 14.1, 13.9; MS[MH] ^- :347.

Example 2

Add 48.4g isooctylphenol, 225mL tetrahydrofuran (THF), 8.8g 60% sodium hydride (dispersed in mineral oil) into the three-necked flask, react at 60～70℃ for 6h, a large amount of white solids are formed, and a small amount of sodium particles remain ; Add 20mL 10mol/L THF solution of 2-bromohexanoic acid dropwise at 60°C and continue to react at 60°C for 4h; after cooling, after rotary evaporation of THF, add 200mL water and 200mL ethyl acetate (EA) to the concentrate , stratify by shaking, and take the water layer; the water layer is acidified with hydrochloric acid to pH ≈ 1, extracted with ethyl acetate, the organic phase is washed twice with water, and spin-dried to obtain 52 g of light yellow product, namely compound BC196. ¹ H NMR (400 MHz, CDCl ₃ ) δ 10.10 (1H, br.); 7.30 (2H, t); 6.66 (2H, d); 4.83-4.81 (1H, m); 2.57 (2H, m); 2.17 -2.04(2H,m); 1.62-1.53(3H,m); 1.42-1.34(10H,m); 0.99(3H,t,J=7.3,CH3); 0.93(3H,t,J=7.3,CH3) _The ^_ 31.8, 14.2, 14.1, 13.9; MS[MH] ^- :319.2

Example 3

Add 54.2g of n-nonylphenol, 200mL of tetrahydrofuran (THF), 5.7g of sodium particles to the three-necked flask, react at 60-70℃ for 6h, a large amount of white solids will be formed, and a small amount of sodium particles will remain; at 60℃, add 20mL dropwise respectively The THF solution of 10mol/L 2-bromohexanoic acid was continued to react at 60°C for 4h; after cooling, after the THF was removed by rotary evaporation, 200mL of water and 200mL of ethyl acetate (EA) were added to the concentrated solution, the layers were shaken, and the water layer was taken; The aqueous layer was acidified with hydrochloric acid to pH≈1, extracted with ethyl acetate, the organic phase was washed twice with water, and spin-dried to obtain the target compound, namely compound BC191.

Compound BC191 ¹ H NMR (400 MHz, CDCl ₃ ) δ 9.20 (1H, br.); 7.31 (2H, t); 6.67 (2H, d); 4.83 (1H, m); 2.5 (2H, m); 2.21 (2H, m); 1.63 (4H, m); 1.46-1.38 (14H, m); 0.93 (3H, t, J=7.3, CH3); 0.90 (3H, t, J=7.3, CH3); MS[ MH] ^- :334.

Example 4

Add 54.2g of n-nonylphenol to the three-necked flask, add 200mL of tetrahydrofuran (THF), 5.7g of sodium particles, react at 60-70℃ for 6h, a large amount of white solids are formed, and a small amount of sodium particles remain; at 60℃, dropwise addition The THF solution of 22mL 10mol/L 2-bromooctanoic acid was continued to react at 60°C for 4h; after cooling, after the THF was removed by rotary evaporation, 200mL of water and 200mL of ethyl acetate (EA) were added to the concentrated solution, the layers were shaken, and the water layer was taken; The aqueous layer was acidified with hydrochloric acid to pH≈1, extracted with ethyl acetate, the organic phase was washed twice with water, and spin-dried to obtain the target compound, namely compound BC192.

Compound BC192 ¹ H NMR (400 MHz, CDCl ₃ ) δ 9.9 (1H, br.); 7.30 (2H, t); 6.67 (2H, d); 4.82 (1H, m); 2.61 (2H, m); 2.19 (2H,m); 1.66-1.46(22H,m); 0.92(3H,t,J=7.3,CH3);0.89(3H,t,J=7.3,CH3); MS[MH] ^- :361.2

Example 5

Add 56.5g n-octylphenol to the three-necked flask, add 200mL tetrahydrofuran (THF), 6.4g sodium particles, react at 60-70℃ for 6h, a large amount of white solids are formed, and a small amount of sodium particles remain; dropwise at 60℃ Add 20mL THF solution of 10mol/L 2-bromohexanoic acid and continue to react at 60°C for 4h; after cooling, after rotary evaporation to remove THF, add 200mL water and 200mL ethyl acetate (EA) to the concentrated solution, shake the layers, take water The aqueous layer was acidified with hydrochloric acid to pH≈1, extracted with ethyl acetate, the organic phase was washed twice with water, and spin-dried to obtain the target compound, namely compound BC193.

Compound BC193 ¹ H NMR (400 MHz, CDCl ₃ ) δ 9.20 (1H, br.); 7.31 (2H, t); 6.67 (2H, d); 4.83 (1H, m); 2.5 (2H, m); 2.21 (2H, m); 1.63 (4H, m); 1.46-1.38 (12H, m); 0.93 (3H, t, J=7.3, CH3); 0.90 (3H, t, J=7.3, CH3); MS[ MH] ^- :319.2.

Example 6

Add 56.5g of n-octylphenol to the three-necked flask, add 200mL of tetrahydrofuran (THF), 6.4g of sodium particles, react at 60-70℃ for 6h, a large amount of white solids are formed, and a small amount of sodium particles remain; at 60℃, dropwise addition The THF solution of 22mL 10mol/L 2-bromooctanoic acid was continued to react at 60°C for 4h; after cooling, after the THF was removed by rotary evaporation, 200mL of water and 200mL of ethyl acetate (EA) were added to the concentrated solution, the layers were shaken, and the water layer was taken; The aqueous layer was acidified with hydrochloric acid to pH ≈ 1, extracted with ethyl acetate, the organic phase was washed twice with water, and spin-dried to obtain the target compound, namely compound BC194.

Compound BC194 1H NMR (400MHz, CDCl3) δ 9.9 (1H, br.); 7.30 (2H, t); 6.67 (2H, d); 4.82 (1H, m); 2.61 (2H, m); 2.19 (2H) , m); 1.66-1.46 (20H, m); 0.92 (3H, t, J=7.3, CH3); 0.89 (3H, t, J=7.3, CH3); MS[M-H]-: 347.2

Effect Example 1 Extraction performance of compound BC196

The structure of compound BC196 is:

(acid content 98%) (acid content refers to extractant purity).

Compound BC196 was dissolved in diluent, namely No. 260 solvent oil, and prepared into 0.6mol/L organic phase, which contained 0.02mol/L Cu ²⁺ , Zn ²⁺ , Fe ³⁺ , Al ³⁺ , Cd ²⁺ , Ni ²⁺ A mixed sulfate solution of , Co ²⁺ , Mn ²⁺ , Ca ²⁺ , Mg ²⁺ and Li ⁺ was used as the aqueous phase. First, the organic phase was saponified with 11 mol/L aqueous sodium hydroxide solution, the saponification rate was 0% to 70%, the initial pH of the water phase remained unchanged at 2.09, and the volume ratio of the organic phase to the water phase after different degrees of saponification was 1:1: The aqueous phase was extracted under the conditions of 1, the equilibration time was 15 min, and the temperature was 25 °C.

After extraction, the extraction rate and equilibrium pH were plotted to obtain the extraction rate E%-pH curve of compound BC196 for each ion. The results are shown in Figure 1 and Table 1. The separation coefficient of compound BC196 for each ion is shown in Table 2. shown.

Table 1: Extraction rate E% of each ion by compound BC196

Table 2: Separation coefficients between compounds BC196 for each ion

It can be seen from Figure 1 that the extraction of nickel, cobalt and manganese by compound BC196 is before magnesium ions, and the extraction sequence of compound BC196 for each ion is Fe ³⁺ , Cu ²⁺ , Ca ²⁺ , Al ³⁺ , Cd ²⁺ , Zn ^{2 +} , Ni ²⁺ , Co ²⁺ , Mn ²⁺ , Mg ²⁺ , Li ⁺ . When the equilibrium pH value of the water phase is 4.6, the extraction rate of compound BC196 for Zn is about 45%, the extraction rate for Ni, Co, Mn is between 5.9% and 17.4%, and the extraction rate for Mg is almost no extraction rate is only 0.5%, at this equilibrium pH, the separation coefficients of Zn from Ni, Co, and Mn are 3.8, 6.1, and 12.9, respectively, and the separation coefficients of Ni, Co, Mn, and Mg are 105.4, 66.8, and 31.3, respectively (Table 1 and Table 2). ), which shows that the separation degree of nickel-cobalt-manganese from impurity metal ions such as magnesium and zinc is high. The above results show that compared with the reported extractants P204, P507 and C272, the compound BC196 has better selectivity for ions, can realize the simultaneous recovery of nickel, cobalt and manganese, and has good separation effect from impurity ions. The recycling of cathode materials has feasible application value.

Effect comparison example 1

The difference from Effect Example 1 is that the compound BC196 was replaced with the extractant CA12 (commercially available, acid content 98%), and the results are shown in Table 3.

Table 3: Separation coefficients of compounds BC196 and CA12 for each ion

It can be seen from Table 3 that under the same experimental conditions, compared with CA12, the separation coefficient of compound BC196 for each ion is higher, about 10-30% higher. At a pH value of about 4.6, the separation coefficients of compound BC196 for Ni/Mg and Zn/Ni are 105.4 and 3.8, respectively, while the separation coefficients of CA12 for Ni/Mg and Zn/Ni are 81.9 and 2.7, respectively. Compound BC196 has better separation effect on ions than CA12.

Effect Example 2 Stripping performance of compound BC196 after loading metal ions

Compound BC196 is dissolved in dodecane and is formulated into 0.62mol/L organic phase, and the water phase is the Ni ²⁺ sulfate solution containing 0.05mol/L as feed liquid, and the organic phase is saponified with 9mol/L ammonia water, and the ratio of saponification is 50%, the saponified organic phase is extracted with a ratio of 1:3 to the feed liquid, the equilibration time is 15min, and the temperature is 25°C. A Ni-loaded organic phase was obtained, and the Ni content in the Ni-loaded organic phase was 0.15 mol/L.

The Ni-loaded organic phase was back-extracted with 1 mol/L sulfuric acid aqueous solution. During back-extraction, the ratio was 10:1, and the back-extraction rate was >99.5%.

However, the organic phase of P507 loaded with Ni is generally back-extracted with 2 mol/L sulfuric acid, and the one-time back-extraction rate is about 85%. The above results show that when the carboxylic acid compound of the present application is used to extract metal ions, a higher stripping rate can be obtained under the premise of lower stripping acidity.

Effect Example 3 Compound BC194 to Ni ²⁺ Saturation Capacity Test

Experimental method: Compound BC194 was dissolved in dodecane to prepare a 0.6 mol/L organic phase. A 50 g/L NiSO ₄ aqueous solution was prepared as the water phase.

Take a 50mL separatory funnel, add 15mL organic phase, and use 10mol/L NaOH aqueous solution for saponification. The saponification ratio is 60%. The organic phase after saponification does not need to be phase-separated, directly add 15mL of water phase, and shake and mix for 15min; The aqueous phase was discharged, and fresh 50 g/L NiSO ₄ aqueous solution (15 mL) was added, and the mixture was shaken and mixed for 15 min; the aforementioned operations were repeated until the ion concentration in the aqueous phase did not change, and the metal concentration in the organic phase was the saturated capacity of the extractant. The saturated capacity of compound BC194 for Ni ²⁺ was 17g/L after stripping the organic phase.

Effect Example 4 Stripping performance of compound BC195 after loading metal ions

The structure of compound BC195 is:

(acid content 95%).

Compound BC195 was dissolved in Escaid 110, prepared into 0.16mol/L organic phase, prepared 0.02mol/L Ni ²⁺ sulfate solution as feed liquid, and saponified the organic phase with 10mol/L NaOH aqueous solution, and the saponification ratio was 50% , the organic phase after saponification is extracted with a ratio of 1:2 to the feed liquid, the equilibrium time is 15min, and the temperature is 25°C. A Ni-loaded organic phase was obtained, and the Ni content in the Ni-loaded organic phase was 0.04 mol/L.

The Ni-loaded organic phase was back-extracted with 1 mol/L sulfuric acid aqueous solution. During back-extraction, the ratio was 15:1, and the back-extraction rate was >99.5%.

However, the organic phase of P507 loaded with Ni is generally back-extracted with 2 mol/L sulfuric acid, and the one-time back-extraction rate is about 85%. The above results show that when the carboxylic acid compound of the present application is used to extract metal ions, a higher stripping rate can be obtained under the premise of lower stripping acidity.

Effect Example 5 Solubility test of extractant BC199 and extractant CA12 in extraction system

Extractant BC199 is obtained by mixing the following compounds in a molar ratio of 1:1:1:1:

(acid content 99%).

Extraction: The extractant BC199 and the diluent Escaid 110 were prepared into a 0.6mol/L solution as the organic phase, the concentration of each compound in the organic phase was 0.15mol/L, and the aqueous phase was a 0.2mol/L _NiSO4 aqueous solution, take a 250mL solution Separation funnel, add 100mL organic phase, add 10mol/L sodium hydroxide aqueous solution for saponification, saponification ratio is 24%, add 100mL water phase after saponification, extract equilibrium 30min, temperature is 25 ℃.

Oil content test: Take 50mL of the above-equilibrated water phase and add it to a 100mL separatory funnel, then add an appropriate amount of HCl to make the pH value of the water phase less than or equal to 2. Use a pipette to accurately measure 25mL of tetrafluoroethylene into the separatory funnel After shaking for 10min, let it stand, put the tetrachloroethylene at the bottom of the separatory funnel into the conical flask, add about 1g/L anhydrous sodium sulfate to the conical flask, shake, and observe that the sodium sulfate does not agglomerate to ensure that the tetrachloroethylene does not agglomerate. The moisture can be removed cleanly. With tetrachloroethylene as the blank group, the oil content in the samples was determined by infrared oil measuring instrument.

Effect comparison example 2

The difference from Effect Example 5 is that the extractant BC199 was replaced by the extractant CA12 (commercially available, with an acid content of 98%), and the solubility of the extractant CA12 in the extraction system was tested.

The test results of Effect Example 5 and Effect Comparative Example 2 are shown in Table 4.

Table 4: Solubility of extractants BC199 and CA12 in extraction system

	CA12	Extraction agent BC199	Diluent Blank
System equilibrium pH	8.09	8.10	-
Organic dissolved amount mg/L	6000	115	45

It can be seen from the above experiments that the diluent blank (that is, no extraction agent is added, and other operation steps are the same as those of Effect Example 5) and the water phase are equilibrated with an oil content of 45 mg/L, and the equilibrium pH of the extraction agent BC199 in the extraction system is 8.10 The extracted oil content was about 115 mg/L, while the extracted oil content of CA12 was about 6000 mg/L when the equilibrium pH of the extraction system was 8.09. The results show that the dissolution loss of CA12 in the extraction system is very large, which is easy to cause unstable process operation. When the extractant BC199 is used for the extraction and separation of metal ions, it solves the problem of high solubility of the extractant in the water phase and greatly reduces the process cost. And the process can run stably.

Effect Example 6

Compound BC196 and diluent Escaid110 were prepared into a 0.62mol/L solution, the aqueous phase was a high magnesium nickel chloride feed solution containing 1.33g/L Ni and 4g/L Mg, a 250mL separating funnel was taken, and 100mL organic phase was added, Add 10 mol/L sodium hydroxide aqueous solution for saponification, the saponification ratio is 24%, add 100 mL of aqueous phase after saponification, extract equilibrium for 30 min, and the temperature is 25 °C.

Oil content test: separate the water phase and add H ₂ SO ₄ . At this time, the [H ⁺ ] concentration of the water phase solution is about 1 mol/L. Extracted with CH ₂ Cl ₂ (30 mL×3), collected the CH ₂ Cl ₂ layer, dried with 1 g of anhydrous Na ₂ SO ₄ to remove the water in CH ₂ Cl ₂ , filtered, and the filtrate was rotary evaporated, and then dried with an oil pump for 30 min. The oil content extracted by CH ₂ Cl ₂ in the system was obtained by weighing the flasks before and after rotary evaporation.

Effect comparison example 3

The difference from Effect Example 6 is that the compound BC196 was replaced by the extractant CA12 (commercially available, acid content 98%).

The test results of Effect Example 6 and Effect Comparative Example 3 are shown in Table 5.

Table 5: Solubility of Compound BC196 and Compound CA12 in Extraction System

	CA12	Compound BC196	Diluent blank
Equilibrate pH	7.15	7.20	-

Organic dissolved amount (mg/L)

4180

73

45

It can be seen from the above experiments that the content of the extracted oil after the diluent blank (no extraction agent is added, and other operation steps are the same as those in Effect Example 6) and the water phase are equilibrated, and the content of the extracted oil is 45 mg/L, and the equilibrium pH of the compound BC196 in the extraction system is about 7.2. The content of the extracted oil is about 73mg/L, while the content of CA12 oil is about 4180mg/L. The dissolution loss of CA12 in the extraction system is very large. When the compound BC196 is used for the extraction and separation of metal ions, it solves the problem that the extractant has a large solubility in the water phase, the process is stable, and the operation cost is reduced.

Claims (17)

1. A carboxylic acid compound or its salt as shown in formula I:

   

   Wherein, R ₁ and R ₂ are independently C ₃ -C ₁₂ straight-chain or branched-chain alkyl groups.
2. The carboxylic acid compound represented by formula I or a salt thereof according to claim 1, wherein R ₁ is a C ₄ -C ₉ straight-chain or branched-chain alkyl group.
3. The carboxylic acid compound represented by formula I or a salt thereof according to claim 1 or 2, wherein R ₂ is a C ₃ -C ₁₀ linear or branched alkyl group.
4. The carboxylic acid compound represented by formula I or a salt thereof according to any one of claims 1 to 3, wherein the salt of the carboxylic acid compound represented by formula I is obtained by adding the compound represented by formula I The carboxylic acid compound shown in the formula is prepared by reacting with the base in a molar ratio of 1:1.
5. The carboxylic acid compound represented by formula I or its salt according to any one of claims 2-4, wherein R ₁ is a C ₄ -C ₉ straight-chain alkyl group, such as n-butyl, n-pentyl, n-hexyl or n-octyl;

   And/or, R ₂ is C ₆ -C ₉ straight or branched chain alkyl; such as n-nonyl, n-octyl or isooctyl (eg

   

   );

   And/or, the sum of the carbon numbers of R ₁ and R ₂ is 10 to 20, for example, n is 12, 13, 14 or 15.
6. The carboxylic acid compound represented by formula I as claimed in claim 1 or a salt thereof, wherein the carboxylic acid compound represented by formula I is selected from any of the following compounds:

   
7. The method for preparing a carboxylic acid compound represented by formula I according to any one of claims 1 to 6, comprising: in a solvent, under the action of a base, mixing the compound represented by formula II with formula III The compounds shown are reacted;

   

   Wherein, X is halogen, and the definitions of R ₁ and R ₂ are as described in any one of claims 1-6.
8. The preparation method of the carboxylic acid compound shown in formula I as claimed in claim 7, wherein, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine or bromine, such as bromine;

   And/or, the solvent is an ether solvent, and the ether solvent is, for example, tetrahydrofuran;

   And/or, the dosage range of the volume-to-mass ratio of the solvent to the compound represented by formula III is 1-8 mL/g, for example, 2.96, 3.5, 3.7 or 4.6 mL/g;

   and/or, the base is an alkali metal or an alkali metal hydride, such as sodium, such as sodium hydride;

   And/or, the molar ratio of the base to the compound represented by formula II is (1-1.5):1, for example, 1.1:1, 1.2:1 or 1.35:1;

   And/or, the molar ratio of the compound represented by the formula II to the compound represented by the formula III is 1:(1-1.5), for example, 1:1.1 or 1:1.2;

   And/or, the temperature of the reaction is 60～70℃;

   And/or, the reaction time is 6-12 hours, for example, 10 hours.
9. Application of the carboxylic acid compound represented by formula I or its salt as an extractant according to any one of claims 1 to 6.
10. The application of the carboxylic acid compound represented by formula I or its salt as an extractant according to claim 9, wherein the extractant is one of the carboxylic acid compounds represented by formula I or a variety of combinations;

    Optionally, the carboxylic acid compound shown in formula I or its salt is used as an extractant for extraction and separation of metal ions; optionally, the metal ions are in Ni ²⁺ , Co ²⁺ and Mn ²⁺ one or a mixture thereof, the metal ion may further comprise one or a mixture of Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ and Ca ²⁺ , the metal ion also Mg ²⁺ and/or Li ⁺ may be further included.
11. As claimed in claim 10, the application of the carboxylic acid compound shown in formula I or its salt as an extractant, the extractant is selected from any one of the following compounds or a mixture thereof:

    

    

    And/or, when the carboxylic acid compound shown in formula I or its salt is used as an extractant for extraction and separation of metal ions, the metal ion is at least one of Ni ²⁺ , Co ²⁺ and Mn ²⁺ A mixture of at least one of Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Ca ²⁺ , Mg ²⁺ and Li ⁺ ; optionally, the metal ion is Ni ² Mixture of ⁺ , Co ²⁺ , Mn ²⁺ , Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Ca ²⁺ , Mg ²⁺ and Li ⁺ .
12. An extraction composition comprising an extractant and a diluent, the extractant comprising the carboxylic acid compound shown in formula I as claimed in any one of claims 1 to 6 and/or as claimed in claims 1 to 6 Any one of the salts of the carboxylic acid compounds represented by formula I.
13. The extraction composition according to claim 12, wherein the molar ratio of the carboxylic acid compound represented by formula I and the salt of the carboxylic acid compound represented by formula I is (0.4-9): 1, for example, 1:1; optionally, the extractant includes the carboxylic acid compound shown in formula I and the salt of the carboxylic acid compound shown in formula I, optionally, the The molar ratio of the carboxylic acid compound represented by formula I and the salt of the carboxylic acid compound represented by formula I is (0.4-9):1;

    And/or, the diluent is one of mineral spirits (such as No. 200 mineral spirits or No. 260 mineral spirits), kerosene, Escaid 110, hexane, heptane and dodecane (such as n-dodecane) or its mixture; alternatively, the diluent is one of mineral spirits (such as No. 260 mineral spirits), dodecane (such as n-dodecane) and Escaid 110 or a mixture thereof;

    And/or, the molar volume ratio of the extractant and the diluent is 0.1mol/L～1.5mol/L, optional 0.16mol/L～0.85mol/L, such as 0.16mol/L, 0.33mol/L or 0.6mol/L.
14. An extraction method, comprising the steps of: extracting an organic phase containing an extractant relative to an aqueous phase containing metal ions to obtain an organic phase containing metal ions;

    In the organic phase containing the extractant, the extractant includes the carboxylic acid compound shown in any one of claims 1 to 6 and/or the carboxylic acid compound shown in any one of claims 1 to 6. The described salt of the carboxylic acid compound shown in formula I;

    In the water phase containing metal ions, the metal ions include Ni ²⁺ , Co ²⁺ , Mn ²⁺ , Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ and Ca ²⁺ one or a mixture thereof.
15. The extraction method according to claim 14, wherein the metal ion is at least one of Ni ²⁺ , Co ²⁺ and Mn ²⁺ and Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd A mixture of at least one of ²⁺ , Ca ²⁺ , Mg ²⁺ and Li ⁺ ; optionally, the metal ions are Ni ²⁺ , Co ²⁺ , Mn ²⁺ , Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Ca ²⁺ , Mg ²⁺ and Li ⁺ mixture;

    And/or, in the organic phase containing the extractant, the molar ratio of the carboxylic acid compound shown in formula I to the salt of the carboxylic acid compound shown in formula I is (0.4-9) : 1, for example 1: 1; optionally, the extractant includes the carboxylic acid compound shown in formula I and the salt of the carboxylic acid compound shown in formula I; The molar ratio of the carboxylic acid compound represented by formula I and the salt of the carboxylic acid compound represented by formula I is (0.4-9):1;

    And/or, the organic phase containing the extractant further comprises a diluent, and the diluent is mineral spirits (such as No. 200 mineral spirits or No. 260 mineral spirits), kerosene, Escaid 110, hexane, heptane and dodecane One or a mixture of alkanes (such as n-dodecane); alternatively, the diluent is mineral spirits (such as No. 260 mineral spirits), dodecane (such as n-dodecane) and Escaid 110 one or a mixture thereof;

    The molar volume ratio of the extractant and the diluent is 0.1mol/L～1.5mol/L, optional 0.16mol/L～0.85mol/L, such as 0.16mol/L, 0.33mol/L or 0.6mol/L L;

    And/or, the volume ratio of the extractant-containing organic phase and the metal ion-containing aqueous phase is 1:(1-10), optionally 1:(1-5), for example 1:1, 1:2 or 1:4;

    And/or, in the extraction method, mass transfer by shaking;

    And/or, the temperature of the extraction is 10°C to 50°C, optionally 25°C to 40°C;

    And/or, the extraction time is 5-60 minutes, such as 15 minutes or 30 minutes.
16. A stripping method comprising the steps of: mixing an organic phase containing metal ions obtained by the extraction method as claimed in claim 14 or 15 with an aqueous acid solution.
17. The stripping method according to claim 16, wherein the molar concentration of the acid aqueous solution is 0.5mol/L～5mol/L, optionally 1～3mol/L, such as 1mol/L or 2mol/L;

    And/or, the acid in the aqueous solution of the acid is an inorganic acid, and the inorganic acid is optionally one or more of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, optionally sulfuric acid;

    And/or, the volume ratio of the metal ion-containing organic phase to the acid aqueous solution is (1-50):1, optionally (10-20):1, such as 10:1 or 15:1 1.

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