CN112457188B

CN112457188B - Carboxylic acid compound and preparation method and application thereof

Info

Publication number: CN112457188B
Application number: CN202011330314.XA
Authority: CN
Inventors: 王雪
Original assignee: Suzhou Bocui Recycling Technology Co ltd
Current assignee: Suzhou Bocui Recycling Technology Co ltd
Priority date: 2020-11-24
Filing date: 2020-11-24
Publication date: 2022-07-08
Anticipated expiration: 2040-11-24
Also published as: CN112457188A; WO2022110821A1

Abstract

The invention discloses a carboxylic acid compound and a preparation method and application thereof. When the carboxylic acid compound of the present invention is used as an extractant for the extraction and separation of metal ions, the ion selectivity is good, the acidity of back extraction is low, the saturation capacity is high, and the back extraction rate is high. The carboxylic acid compound of the invention has high stability and low water solubility, so that the extraction process is stable, and the environmental pollution and cost can be reduced. The carboxylic acid compound of the invention has low cost and great application prospect, and can be used in various systems such as ternary battery recovery and battery-grade nickel sulfate preparation.

Description

Carboxylic acid compound and preparation method and application thereof

Technical Field

The invention relates to a carboxylic acid compound and a preparation method and application thereof.

Background

Cobalt is mostly associated with nickel and is mostly present in minerals, such as nickel laterites. In many industries, waste residues containing valuable metals such as nickel, cobalt and the like are generated, such as waste power battery materials, waste residues containing nickel and cobalt, waste catalysts and the like, most of the waste residues also contain high manganese, have high recycling value and can be recycled to be used for preparing nickel-cobalt-manganese ternary lithium ion battery anode material precursors.

The solvent extraction technology is an effective technology for separating and extracting various metals from a solution, and has the advantages of high separation efficiency, simple process and equipment, continuous operation, easy realization of automatic control and the like. With the urgent need of environmental protection and resource recycling, higher requirements are also put forward on energy consumption, acid consumption, pollution discharge, capacity and the like of an extraction system, and therefore, the extraction efficiency, separation effect, stability and other performances of the extractant need to be improved to meet the environmental and economic requirements.

Commonly used cation exchange extractants such as acidic phosphoric acid extractants P204, P507 and C272 have been widely used for separating and purifying metal elements. Patent CN109449523A discloses a comprehensive recovery method of waste lithium ion batteries, which comprises the steps of firstly adjusting the pH value of a feed liquid to be 4.2-4.5, extracting the feed liquid by using P204 to obtain P204 raffinate and a loaded organic phase, and back-extracting the loaded organic phase by using sulfuric acid to obtain manganese sulfate; adjusting the pH value of the P204 raffinate to 4.5-5, extracting the P204 raffinate by adopting C272 to obtain C272 raffinate and a loaded organic phase, and performing back extraction on the C272 loaded organic phase by adopting sulfuric acid to obtain a cobalt sulfate solution; adjusting the pH value of C272 raffinate to 5-5.5, extracting Ni from the raffinate by adopting P507, and back-extracting a P507 loaded organic phase by adopting sulfuric acid to obtain a nickel sulfate solution. However, these extractants also have significant disadvantages in the separation process: the P507/P204 is used for separating nickel and cobalt, but in the aspect of recycling the lithium ion battery anode material, nickel, cobalt and manganese cannot be synchronously extracted, the process cost for respectively recycling nickel, cobalt and manganese is high, the back extraction acidity is high, and the pollution is serious; c272, calcium and magnesium are preferentially extracted before nickel element extraction, the operation process is complex, and the impurity removal cost is high.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a carboxylic acid compound and a preparation method and application thereof. The carboxylic acid compound is used as an extracting agent, has good selectivity on ions (particularly nickel-cobalt-manganese ions), is low in reverse extraction acidity, and has the advantages of low water solubility, high stability, low cost and the like.

The invention solves the technical problems through the following technical scheme.

The invention provides a carboxylic acid compound or salt thereof shown as a formula I:

wherein R is₁And R₂Independently is C₃～C₁₂Straight or branched chain alkyl.

Wherein, preferably, R₁Is C₄～C₉A linear or branched alkyl group; more preferably, the first and second liquid crystal display panels are,R₁is C₄～C₉Straight-chain alkyl radicals, for example n-butyl, n-pentyl, n-hexyl or n-octyl.

Wherein, preferably, R₂Is C₃～C₁₀A linear or branched alkyl group; more preferably, R₂Is C₆～C₉A linear or branched alkyl group; such as n-nonyl, n-octyl or isooctyl (e.g. n-nonyl, n-octyl or isooctyl)

)。

Wherein, preferably, R₁And R₂The total number of carbon atoms n is 10 to 20, for example n is 12, 13, 14 or 15.

Wherein, preferably, the carboxylic acid compounds shown in formula I are selected from any one of the following compounds:

the salt of the carboxylic acid compound shown in the formula I is generally prepared by reacting the carboxylic acid compound shown in the formula I with a base, for example, the carboxylic acid compound shown in the formula I and the base are reacted at a molar ratio of 1:1. The base may be a base conventional in the art, such as an alkali metal hydroxide or aqueous ammonia, further such as sodium hydroxide, potassium hydroxide or aqueous ammonia, whereby the salt of the carboxylic acid compound may be a sodium salt, a potassium salt or an ammonium salt.

The preparation method of the salt of the carboxylic acid compound shown in the formula I can be carried out under the conventional conditions of acid-base salt formation reaction in the field.

The carboxylic acid compounds shown in the formula I can be extracted from natural substances or synthesized by a conventional method, and the extracting agent used for extraction can be one or a mixture (for example, more than two) of the carboxylic acid compounds shown in the formula I.

The invention also provides a preparation method of the carboxylic acid compound shown in the formula I, which comprises the following steps: reacting a compound shown as a formula II with a compound shown as a formula III in a solvent under the action of alkali;

wherein X is halogen, R₁And R₂As defined above.

In the preparation method, preferably, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine or bromine, and further such as bromine.

In the preparation method, the solvent may be a solvent commonly used in such reactions in the art, such as an ether-based solvent, for example, tetrahydrofuran.

In the preparation method, the solvent can be used in the conventional amount of the reaction in the field, so as not to influence the reaction. For example, the volume-to-mass ratio of the solvent to the compound represented by formula III is 1 to 8mL/g, for example, 2.96, 3.5, 3.7, or 4.6 mL/g;

in the preparation process, the base may be a base commonly used in such reactions in the art, such as an alkali metal or an alkali metal hydride, such as sodium, e.g. sodium hydride.

In the preparation method, the amount of the base can be the amount conventionally used in such reactions in the field, for example, the molar ratio of the base to the compound represented by the 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 shown in the formula II to the compound shown in the formula III can be the conventional ratio of the reactions in the field, and is preferably 1: (1-1.5), for example 1:1.1 or 1: 1.2.

In the preparation method, the reaction temperature can be the temperature conventional in the reaction in the field, and the temperature is preferably 60-70 ℃ in the invention.

In the preparation method, the progress of the reaction can be detected by a conventional monitoring method in the art (such as TLC, HPLC or NMR), and the end point of the reaction is generally determined by disappearance or no longer reaction of the compound represented by the formula II. The reaction time can be 6-12 hours, such as 10 hours.

The invention also provides application of the carboxylic acid compound shown as the formula I or the salt thereof as an extracting agent.

In the application, the extracting agent may be one or a mixture (for example, two or more) of the carboxylic acid compounds shown in formula I, for example, any one or a mixture (for example, two or more) of the following compounds:

in the application, the carboxylic acid compound shown in the formula I or the salt thereof is used as an extracting agent for extracting and separating metal ions. Preferably, the metal ion is Ni²⁺、Co²⁺And Mn²⁺Or a mixture thereof (e.g., two or more), the metal ions may also include, for example, Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺And Ca²⁺May further comprise, for example, Mg²⁺、Li⁺And other ions. For example, the metal ion is "Ni²⁺、Co²⁺And Mn²⁺At least one kind of "and" Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺、Ca²⁺、Mg²⁺And Li⁺A mixture of at least one of the above. As another example, the metal ion is Ni²⁺、Co²⁺、Mn²⁺、Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺、Ca²⁺、Mg²⁺And Li⁺And (3) mixing. Preferably, the metal ions can be derived from waste lithium ion battery positive electrode materials, nickel laterite ore or waste slag containing nickel and cobalt. Therefore, in a preferred embodiment of the invention, the carboxylic acid compound shown in formula I or the salt thereof is used as an extracting agent for extracting and separating metal ions in the waste lithium ion battery positive electrode material, the nickel laterite ore or the waste residue containing nickel and cobalt.

The invention also provides an extraction composition, which comprises an extraction agent and a diluent, wherein the extraction agent comprises the carboxylic acid compound shown in the formula I and/or the salt of the carboxylic acid compound shown in the formula I.

In the extraction composition, preferably, the molar ratio of the carboxylic acid compound shown in the formula I to the salt of the carboxylic acid compound shown in the formula I is (0.4-9): 1 (e.g., 1: 1).

In the extraction composition, preferably, the extractant includes the carboxylic acid compound shown in formula I and the salt of the carboxylic acid compound shown in formula I, and a 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.

in the extraction composition, the diluent may be a diluent commonly used in the art, preferably, the diluent is one or a mixture (e.g., two or more) of mineral spirit (e.g., mineral spirit No. 200 or mineral spirit No. 260), kerosene, Escaid110, hexane, heptane, and dodecane (e.g., n-dodecane); more preferably, the diluent is one of or a mixture (e.g., two or more) of mineral spirits (e.g., mineral spirits No. 260), dodecane (e.g., n-dodecane), and Escaid 110.

The amount of the diluent used in the extraction composition is not particularly limited as long as the extraction and stripping performance of the extraction composition is not affected, and preferably, the molar volume ratio of the extractant to the diluent is 0.1mol/L to 1.5mol/L, preferably 0.16mol/L to 0.85mol/L, such as 0.16mol/L, 0.33mol/L or 0.6 mol/L.

The invention also provides an extraction method, which comprises the following steps: extracting the organic phase containing the extracting agent from the aqueous phase containing the metal ions to obtain an organic phase containing the metal ions;

in the organic phase containing the extracting agent, the extracting agent comprises the carboxylic acid compound shown as the formula I and/or the salt of the carboxylic acid compound shown as the formula I;

the aqueous phase containing metal ions including Ni²⁺、Co²⁺、Mn²⁺、Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺And Ca²⁺One kind or a mixture thereof (e.g., two or more kinds).

In the aqueous phase containing the metal ions, the metal ions may also comprise, for example, Mg²⁺、Li⁺And other ions. Preferably, the metal ions can be derived from waste lithium ion battery positive electrode materials, nickel laterite ore or waste slag containing nickel and cobalt. Preferably, the metal ion is "Ni²⁺、Co²⁺And Mn²⁺At least one kind of "and" Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺、Ca²⁺、Mg²⁺And Li⁺A mixture of at least one of the above. For example, the metal ion is Ni²⁺、Co²⁺、Mn²⁺、Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺、Ca²⁺、Mg²⁺And Li⁺And (3) mixing.

In the organic phase containing the extracting agent, preferably, the molar ratio of the carboxylic acid compound shown in the formula I to the salt of the carboxylic acid compound shown in the formula I is (0.4-9): 1 (e.g., 1: 1).

In the organic phase containing the extracting agent, preferably, the extracting agent comprises the carboxylic acid compound shown in the formula I and the salt of the carboxylic acid compound shown in the formula I, and the molar ratio of the carboxylic acid compound shown in the formula I to the salt of the carboxylic acid compound shown in the formula I is (0.4-9): 1.

in the extraction method, preferably, the organic phase containing the extracting agent further comprises a diluent. The diluent can be a diluent commonly used in the art, preferably, the diluent is one of or a mixture (e.g., two or more) of mineral spirits (e.g., 200 # mineral spirits or 260 # mineral spirits), kerosene, escoid 110, hexane, heptane, and dodecane (e.g., n-dodecane); more preferably, the diluent is one of or a mixture (e.g., two or more) of mineral spirits (e.g., mineral spirits No. 260), dodecane (e.g., n-dodecane), and Escaid 110. The amount of the diluent used is not particularly limited as long as the extraction and stripping performance of the organic phase containing the extractant is not affected, and preferably, the molar volume ratio of the extractant to the diluent in the organic phase containing the extractant is 0.1mol/L to 1.5mol/L, preferably 0.16mol/L to 0.85mol/L, such as 0.16mol/L, 0.33mol/L or 0.6 mol/L.

In the extraction process, the volume ratio of the extractant-containing organic phase to the metal ion-containing aqueous phase can be in the proportions conventionally used in extraction in the art; preferably, the volume ratio of the organic phase containing the extractant to the aqueous phase containing the metal ions is 1 (1-10), more preferably 1 (1-5), such as 1:1, 1:2 or 1: 4.

In the extraction process, mass transfer is preferably by shaking.

In the extraction method, the temperature of the extraction can be preferably used conventionally in the field for such extraction, and is preferably 10 ℃ to 50 ℃, more preferably 25 ℃ to 40 ℃. The extraction time may be a time conventional in the art, preferably 5 to 60 minutes, for example 15 minutes or 30 minutes.

The invention also provides a back extraction method, which comprises the following steps: mixing the organic phase containing metal ions obtained by the extraction method with an aqueous solution of acid.

In the back extraction method, the metal ions loaded in the organic phase containing the metal ions are transferred into the water phase to obtain the water phase rich in the metal ions and a regenerated organic phase.

In the stripping method, the molar concentration of the aqueous solution of the acid may be a molar concentration commonly used in such stripping in the art, preferably 0.5mol/L to 5mol/L, more preferably 1 to 3mol/L, such as 1mol/L or 2mol/L, and the molar concentration refers to a ratio of the amount of the substance of the acid to the total volume of the aqueous solution of the acid.

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

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

In the present invention, the oscillation is for the mass transfer requirement, so that the organic phase and the water phase are uniformly mixed, and other conventional operations in the field such as stirring and the like can be adopted instead.

The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows:

(1) when the carboxylic acid compound is used as an extractant for extracting and separating metal ions, the carboxylic acid compound has good ion selectivity, low back extraction acidity and high saturation capacity (to Ni)²⁺The saturation capacity is more than or equal to 17g/L), and the back extraction rate is high (primary back extraction rate)>99.5％)；

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

(3) the carboxylic acid compound has low cost and great application prospect, and can be used for various systems such as ternary battery recovery, battery-grade nickel sulfate preparation and the like.

Drawings

FIG. 1 is a plot of the extraction E% -pH of compound BC196 for each ion.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

The following examples are used for experiments involving source information:

the organic phase is an organic phase containing an extracting agent and a diluent, wherein the extracting agent comprises carboxylic acid compounds shown in the formula I and/or salts of the carboxylic acid compounds shown in the formula I.

The aqueous phase refers to an aqueous phase containing metal ions, wherein the aqueous phase containing metal ions can be prepared according to a conventional method, for example, the method comprises the following steps: dissolving a certain mass of salt in deionized water, and diluting to a required concentration.

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

"saponification" means the conversion of hydrogen ions in the extractant to alkali metal ions and/or NH₄ ⁺(alkali metal ion and/or NH after conversion)₄ ⁺Exchange with extracted metal ions in the aqueous phase to achieve the effect of extraction), and the saponification step is as follows: mixing the organic phase with an aqueous alkali solution. Preferably, the aqueous solution of the alkali used for the saponification may be an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide or aqueous ammonia.

The saponification ratio refers to alkali metal and/or NH in the extractant₄ ⁺The ratio of original hydrogen ions, i.e. eta ═ V_Alkali×C_Alkali)/(V_{Is provided with}×C_{Is provided with}) (1)

In the formula (1), V_AlkaliVolume of aqueous solution of base added, C_AlkaliIs the concentration of the base in the aqueous solution of the added base, V_{Is provided with}Volume of organic phase, C_{Is provided with}Is the concentration of the extractant in the organic phase.

In the examples of the present invention, the content of metal ions in the aqueous phase was measured by inductively coupled plasma emission spectrometry (ICP-OES), and then the content of metal ions in the organic phase was determined by the subtraction method.

Potentiometric titration of the acid content, according to the literature: bearing industry, humifuse euphorbia; study of organophosphorus Compounds XVI: sigma of long-carbon chain alkyl and alkoxy of phosphorus compounds^pConstant to group connectivity [ J]Journal of chemistry, 1986, 44, 590-; potentiometric titrators: switzerland wantong 907 Titrando. The acid content is used in the examples of the present invention to indicate the purity of the extractant.

The distribution ratio D is the ratio of the metal ion content in the equilibrium organic phase to the metal ion content in the equilibrium water phase after the primary extraction is finished (the metal ion content in the equilibrium water phase is detected by inductively coupled plasma emission spectrometry (ICP-OES), and then the metal ion content in the equilibrium organic phase is obtained by the subtraction method), namely

D＝C_org/C_aq＝(C’_aq-C_aq)/C_aq (2)

In the formula (2), C_orgShowing the concentration of metal ions in the equilibrium organic phase after the completion of one extraction; c_aqShowing the concentration of metal ions in the equilibrium water phase after the completion of the primary extraction; c'_aqThe concentration of metal ions in the aqueous phase before the first extraction is indicated.

The extraction rate E is the percentage of the amount of extracted substances transferred from the water phase to the organic phase in the extraction process to the total amount of the extracted substances in the raw water phase, namely:

E＝100％×(C’_aq-C_aq)/C’_aq (3)

in formula (3), C_aqShowing the concentration of metal ions in the equilibrium water phase after the completion of the primary extraction; c'_aqThe concentration of metal ions in the aqueous phase before the first extraction is indicated.

The separation coefficient beta is the ratio of the distribution ratio of two substances to be separated between two phases when extraction separation is performed under certain conditions, and is also called as an extraction separation factor.

The starting materials for which the preparation methods are not provided in the following examples are commercially available.

Example 1

Adding 84.6g of isooctylphenol, 250mL of Tetrahydrofuran (THF) and 8.8g of sodium granules into a three-neck flask, and reacting at 60-70 ℃ for 6 hours to obtain a large amount of white solid and a small amount of sodium granules; 40mL of THF solution containing 8 mol/L2-bromooctanoic acid is dripped at the temperature of 60 ℃, and the reaction is continued for 4 hours at the temperature of 60 ℃; cooling, performing rotary evaporation to remove THF, adding 200mL of water and 200mL of Ethyl Acetate (EA) into the concentrated solution, shaking for layering, and taking a water layer; the aqueous layer was acidified with hydrochloric acid to pH 1, extracted with ethyl acetate, and the organic phase was washed with water 2 times and spin-dried to obtain 86g of a pale yellow product, compound BC 195.¹H NMR(400MHz,CDCl₃)δ10.20(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)；0.90(3H,t,J＝7.3,CH3)；¹³C NMR(101MHz,CDCl₃)δ173.0,153.4,131.5,129.6,128.4,114.6,115.6,125.5,125.5,90.0,41.1,32.5,29.3,31.8,27.5,22.3,14.2,14.1,13.9；MS[M-H]^-:347.

Example 2

Adding 48.4g of isooctylphenol, 225mL of Tetrahydrofuran (THF) and 8.8g of 60% sodium hydride (dispersed in mineral oil) into a three-neck flask, and reacting at 60-70 ℃ for 6 hours to obtain a large amount of white solid and a small amount of sodium particles; dripping 20mL of 10mol/L THF solution of 2-bromohexanoic acid at 60 ℃ and continuing to react for 4h at 60 ℃; cooling, performing rotary evaporation to remove THF, adding 200mL of water and 200mL of Ethyl Acetate (EA) into the concentrated solution, shaking for layering, and taking a water layer; the aqueous layer was acidified with hydrochloric acid to pH 1, extracted with ethyl acetate, and the organic phase was washed with water 2 times and spin-dried to obtain 52g of a pale yellow product, compound BC 196.¹H NMR(400MHz,CDCl₃)δ10.10(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)；0.90(3H,t,J＝7.3,CH3)；¹³C NMR(101MHz,CDCl₃)δ173.0,153.4,131.5,129.6,128.4,114.6,115.6,125.5,125.5,90.0,41.1,32.5,29.3,31.8,14.2,14.1,13.9；MS[M-H]^-:319.2

Example 3

Adding 54.2g of n-nonylphenol, 200mL of Tetrahydrofuran (THF) and 5.7g of sodium granules into a three-neck flask, and reacting at 60-70 ℃ for 6 hours to obtain a large amount of white solid and a small amount of sodium granules; respectively dropwise adding 20mL of 10mol/L THF solution of 2-bromohexanoic acid at 60 ℃ and continuously reacting for 4h at 60 ℃; cooling, performing rotary evaporation to remove THF, adding 200mL of water and 200mL of Ethyl Acetate (EA) into the concentrated solution, shaking for layering, and taking a water layer; the water layer is acidified by hydrochloric acid until the pH value is approximately equal to 1, extracted by ethyl acetate, and the organic phase is washed by water for 2 times and is dried by spinning to obtain the target compound, namely the compound BC 191.

Compound BC191¹H NMR(400MHz,CDCl₃)δ9.20(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[M-H]^-:334.

Example 4

Adding 54.2g of n-nonylphenol into a three-neck flask, adding 200mL of Tetrahydrofuran (THF) and 5.7g of sodium granules, reacting at 60-70 ℃ for 6 hours, wherein a large amount of white solid is generated, and a small amount of sodium granules are left; 22mL of 10mol/L THF solution of 2-bromooctanoic acid is respectively dripped at 60 ℃, and the reaction is continued for 4 hours at 60 ℃; cooling, performing rotary evaporation to remove THF, adding 200mL of water and 200mL of Ethyl Acetate (EA) into the concentrated solution, shaking for layering, and taking a water layer; acidifying the water layer with hydrochloric acid until the pH value is approximately equal to 1, extracting with ethyl acetate, washing the organic phase for 2 times, and spin-drying to obtain the target compound, namely the compound BC 192.

Compound BC192¹H NMR(400MHz,CDCl₃)δ9.9(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[M-H]^-:361.2

Example 5

Respectively adding 56.5g of n-octyl phenol, 200mL of Tetrahydrofuran (THF) and 6.4g of sodium granules into a three-neck flask, reacting at 60-70 ℃ for 6 hours to generate a large amount of white solid, and leaving a small amount of sodium granules; respectively dropwise adding 20mL of 10mol/L THF solution of 2-bromohexanoic acid at 60 ℃ and continuously reacting for 4h at 60 ℃; cooling, performing rotary evaporation to remove THF, adding 200mL of water and 200mL of Ethyl Acetate (EA) into the concentrated solution, shaking for layering, and taking a water layer; the water layer is acidified to pH value of about 1 by hydrochloric acid, extracted by ethyl acetate, the organic phase is washed by water for 2 times, and is dried by spinning to obtain the target compound, namely the compound BC 193.

Compound BC193¹H NMR(400MHz,CDCl₃)δ9.20(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[M-H]^-:319.2.

Example 6

Adding 56.5g of n-octyl phenol into a three-neck flask, adding 200mL of Tetrahydrofuran (THF) and 6.4g of sodium granules, reacting at 60-70 ℃ for 6 hours, wherein a large amount of white solid is generated, and a small amount of sodium granules are left; 22mL of 10mol/L THF solution of 2-bromooctanoic acid is respectively dripped at 60 ℃ and the reaction is continued for 4 hours at 60 ℃; cooling, performing rotary evaporation to remove THF, adding 200mL of water and 200mL of Ethyl Acetate (EA) into the concentrated solution, shaking for layering, and taking a water layer; acidifying the water layer with hydrochloric acid until the pH value is approximately equal to 1, extracting with ethyl acetate, washing the organic phase for 2 times, and spin-drying to obtain the target compound, namely the compound BC 194.

Compound BC 1941H 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, CH 3); 0.89(3H, t, J ═ 7.3, CH 3); MS [ M-H ] -:347.2

Effect example 1 extraction Performance of Compound BC196

The structure of compound BC196 is:

(acid content 98%) (acid content means extractant purity).

Dissolving the compound BC196 in a diluent, namely No. 260 solvent oil, preparing into an organic phase with the concentration of 0.6mol/L and preparing into a solution containing 0.02mol/L Cu²⁺、Zn²⁺、Fe³⁺、Al³⁺、Cd²⁺、Ni²⁺、Co²⁺、Mn²⁺、Ca²⁺、Mg²⁺And Li⁺The mixed sulfate solution of (a) as an aqueous phase. Firstly, saponifying an organic phase by adopting 11mol/L sodium hydroxide aqueous solution, wherein the saponification rate is 0-70%, the initial pH of an aqueous phase is kept not to be 2.09, and the volume ratio of the organic phase to the aqueous phase after saponification in different degrees is 1:1, and the aqueous phase is extracted, the equilibrium time is 15min, and the temperature is 25 ℃.

After extraction, the extraction rate was plotted against the equilibrium pH to obtain an extraction rate E% -pH curve of the compound BC196 for each ion, and the results are shown in fig. 1 and table 1, and the separation coefficient of the compound BC196 for each ion is shown in table 2.

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

Table 2: separation coefficient between compound BC196 and each ion

As shown in FIG. 1, the BC196 compound is combined with the Ni, Co and Mn before the Mg ions are extractedThe extraction sequence of each ion by the material BC196 is Fe³⁺、Cu²⁺、Ca²⁺、Al³⁺、Cd²⁺、Zn²⁺、Ni²⁺、Co²⁺、Mn²⁺、Mg²⁺、Li⁺. When the water phase equilibrium pH value is 4.6, the extraction rate of the compound BC196 to Zn is about 45%, the extraction rate to Ni, Co and Mn is between 5.9% and 17.4%, and the extraction rate to Mg is hardly 0.5%, under the equilibrium pH value, the separation coefficients of Zn to Ni, Co and Mn are respectively 3.8, 6.1 and 12.9, and the separation coefficients of Ni, Co, Mn and Mg are respectively 105.4, 66.8 and 31.3 (Table 1 and Table 2), thereby showing that the separation degree of nickel, cobalt and manganese to impurity metal ions such as magnesium and zinc is high. The results are combined to show that compared with the reported extracting agents P204, P507 and C272, the compound BC196 has better selectivity on ions, can realize synchronous recovery of nickel, cobalt and manganese, has good separation effect with impurity ions, and has feasible application value in the aspect of recovery of the lithium ion battery anode material.

Effect comparative example 1

Effect example 1 differs in 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 respective ions

As can be seen from table 3, under the same experimental conditions, the separation coefficient of compound BC196 for each ion was higher than that of CA12 by about 10 to 30%. At a pH of about 4.6, the separation coefficients of compound BC196 for Ni/Mg and Zn/Ni were 105.4 and 3.8, respectively, while the separation coefficients of CA12 for Ni/Mg and Zn/Ni were 81.9 and 2.7, respectively, thus demonstrating the superior separation effect of compound BC196 for ions compared to CA 12.

Effect example 2 stripping Performance after Metal ion Loading of Compound BC196

The compound BC196 is dissolved in dodecane to prepare a 0.62mol/L organic phase, and an aqueous phase contains 0.05mol/L Ni²⁺Sulfuric acidSalt solution is used as feed liquid, 9mol/L ammonia water is used for saponifying the organic phase, the saponification proportion is 50%, and the organic phase after saponification is compared with 1: 3 extracting the feed liquid, wherein the balance time is 15min and the temperature is 25 ℃. Obtaining an organic phase loaded with Ni, wherein the content of Ni in the organic phase loaded with Ni is 0.15 mol/L.

And (3) carrying out back extraction on the Ni-loaded organic phase by using a 1mol/L sulfuric acid aqueous solution, wherein the back extraction rate is more than 99.5% when the phase ratio is 10: 1.

And the Ni-loaded P507 organic phase is generally back-extracted by 2mol/L sulfuric acid, and the primary back-extraction rate is about 85 percent. The results show that when the carboxylic acid compound is applied to extracting metal ions, higher back extraction rate can be obtained on the premise of lower back extraction acidity.

Effect example 3 Compound BC194 on Ni²⁺Saturated capacity test

The experimental method comprises the following steps: compound BC194 was dissolved in dodecane and formulated into a 0.6mol/L organic phase. Preparing 50g/L NiSO₄The aqueous solution serves as the aqueous phase.

Taking a 50mL separating funnel, adding 15mL of organic phase, saponifying with 10mol/L NaOH aqueous solution at a saponification ratio of 60%, directly adding 15mL of aqueous phase without phase separation of the saponified organic phase, and shaking and mixing for 15 min; separating out the water phase, and adding fresh NiSO 50g/L₄Shaking the aqueous solution (15mL) for 15 min; the foregoing operations are repeated until the ion concentration in the aqueous phase is not changing, at which point the concentration of metal in the organic phase is the saturation capacity of the extractant. The organic phase is back extracted to obtain a compound BC194 to Ni²⁺The saturated capacity of (2) was 17 g/L.

Effect example 4 stripping Performance after Metal ion Loading of Compound BC195

The structure of compound BC195 is:

(acid content 95%).

Dissolving a compound BC195 in Escaid110 to prepare a 0.16mol/L organic phase and 0.02mol/L Ni²⁺The organic phase is saponified with 10mol/L NaOH aqueous solution as feed liquid, and the saponification ratio is50%, the organic phase after saponification was compared to 1:2, extracting the feed liquid, wherein the balance time is 15min and the temperature is 25 ℃. Obtaining an organic phase loaded with Ni, wherein the content of Ni in the organic phase loaded with Ni is 0.04 mol/L.

And (3) carrying out back extraction on the Ni-loaded organic phase by using a 1mol/L sulfuric acid aqueous solution, wherein the phase ratio in the back extraction is 15:1, and the back extraction rate is more than 99.5%.

Effect example 5 solubility experiments of extractant BC199 and extractant CA12 in extraction system

The extractant BC199 is prepared by mixing the following compounds in a molar ratio of 1:1:

(acid content 99%).

And (3) extraction: the extractant BC199 and the diluent Escaid110 are prepared into 0.6mol/L solution to be used as an organic phase, the concentration of each compound in the organic phase is 0.15mol/L, and the water phase is 0.2mol/L NiSO₄Taking a 250mL separating funnel, adding 100mL organic phase, adding 10mol/L sodium hydroxide aqueous solution for saponification, wherein the saponification proportion is 24%, adding 100mL aqueous phase after saponification, and carrying out extraction equilibrium for 30min at the temperature of 25 ℃.

And (3) oil content testing: adding 50mL of the balanced water phase into a 100mL separating funnel, adding a proper amount of HCl to enable the pH value of the water phase to be less than or equal to 2, accurately measuring 25mL of tetrafluoroethylene into the separating funnel by using a liquid transfer gun, shaking for 10min, standing, placing tetrachloroethylene at the lower part of the separating funnel into a conical flask, adding about 1g/L of anhydrous sodium sulfate into the conical flask, shaking, observing that the sodium sulfate does not cake, and ensuring that the water in the tetrachloroethylene can be completely removed. Tetrachloroethylene is used as a blank group, and an infrared oil tester is adopted to measure the oil content in the sample.

Comparative Effect example 2

Effect example 5 differs in that extractant BC199 was replaced with extractant CA12 (commercially available, acid content 98%), and extractant CA12 was tested for solubility in the extraction system.

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	Extracting agent BC199	Diluent blank
				System equilibrium pH	8.09	8.10	-
Organic soluble amount mg/L	6000	115	45

From the above experiment, it can be seen that the diluent blank (i.e. without the addition of the extractant, the other operation steps are the same as those in effect example 5) has an extracted oil content of 45mg/L after being equilibrated with the aqueous phase, the extracted oil content of BC199 at an equilibrium pH of 8.10 of the extraction system is about 115mg/L, and the extracted oil content of CA12 at an equilibrium pH of 8.09 of the extraction system is about 6000 mg/L. The result shows that the CA12 in the extraction system has great dissolution loss and is easy to cause unstable process operation, and when the extractant BC199 is used for metal ion extraction and separation, the problem of great solubility of the extractant in a water phase is solved, the process cost is greatly reduced, and the process can operate stably.

Effect example 6

Preparing a 0.62mol/L solution from a compound BC196 and a diluent Escaid110, wherein a water phase is a high-magnesium nickel chloride feed liquid containing 1.33g/L Ni and 4g/L Mg, taking a 250mL separating funnel, adding 100mL of an organic phase, adding 10mol/L of a sodium hydroxide aqueous solution for saponification, wherein the saponification ratio is 24%, adding 100mL of the water phase after saponification, carrying out extraction equilibrium for 30min, and the temperature is 25 ℃.

And (3) testing the oil content: separating the aqueous phase and adding H₂SO₄At this point the aqueous solution [ H ]⁺]The concentration is about 1 mol/L. By CH₂Cl₂Extraction (30 mL. times.3), and collection of CH by extraction₂Cl₂Layer of 1g of anhydrous Na₂SO₄Drying to remove CH₂Cl₂Filtering the water, evaporating the filtrate, and drying with oil pump for 30 min. System CH is obtained by weighing the flask before and after rotary evaporation₂Cl₂Oil content extracted.

Effect comparative example 3

Effect example 6 differs in that compound BC196 was replaced with 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 the extraction System

	CA12	Compound BC196	Diluent blank
				Equilibrium pH	7.15	7.20	-
Organic soluble amount (mg/L)	4180	73	45

From the above experiment, it was found that the diluent blank (without addition of extractant, the other operation steps are the same as those in effect example 6) and the water phase were balanced to obtain an oil content of 45mg/L, the compound BC196 was at about 73mg/L when the equilibrium pH of the extraction system was about 7.2, and the oil content of CA12 was at about 4180mg/L, which resulted in a significant loss of CA12 in the extraction system. When the compound BC196 is used for metal ion extraction and separation, the problem of high solubility of an extracting agent in a water phase is solved, the process is stable, and the operation cost is reduced.

Claims

1. A carboxylic acid compound represented by the formula I: it is characterized in that the preparation method is characterized in that,

R₁is C₄～C₉A linear or branched alkyl group; r₂Is composed of

2. The carboxylic acid compounds or salts thereof according to claim 1, represented by formula I: it is characterized in that the preparation method is characterized in that,

R₁is n-butyl, n-pentyl, n-hexyl or n-octyl.

3. A carboxylic acid compound or its salt shown in formula I, which is characterized in that,

the carboxylic acid compounds shown in the formula I are selected from any one of the following compounds,

4. the method for preparing carboxylic acid compounds as claimed in any of claims 1 to 3, wherein the compound as shown in formula II is reacted with the compound as shown in formula III in a solvent under the action of alkali;

wherein X is halogen, R₁And R₂Is as defined in any one of claims 1 to 3.

5. The method for preparing carboxylic acid compounds as shown in the formula I in claim 4, wherein the halogen is fluorine, chlorine, bromine or iodine;

and/or the solvent is an ether solvent;

and/or the dosage range of the volume-mass ratio of the solvent to the compound shown in the formula III is 1-8 mL/g;

and/or the base is an alkali metal or an alkali metal hydride;

and/or the molar ratio of the alkali to the compound shown in the formula II is (1-1.5): 1;

and/or the molar ratio of the compound shown in the formula II to the compound shown in the formula III is 1: (1-1.5);

and/or the reaction temperature is 60-70 ℃;

and/or the reaction time is 6-12 hours.

6. The method for preparing carboxylic acids represented by the formula I in claim 5, wherein the ether solvent is tetrahydrofuran;

and/or, the base is sodium or sodium hydride;

and/or the molar ratio of the base to the compound shown in formula II is 1.1:1, 1.2:1 or 1.35: 1;

and/or the molar ratio of the compound shown in the formula II to the compound shown in the formula III is 1:1.1 or 1: 1.2;

and/or the reaction temperature is 60-70 ℃;

and/or the reaction time is 10 h.

7. The application of the carboxylic acid compounds shown in the formula I or the salts thereof as the extracting agent according to any one of claims 1 to 3, characterized in that the extracting agent is one of the carboxylic acid compounds shown in the formula I or a mixture thereof; the carboxylic acid compound or the salt thereof shown in the formula I is used as an extracting agent for extracting and separating metal ions; the metal ion is' Ni²⁺、Co²⁺And Mn²⁺At least one of "and/or" Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺、Ca²⁺、Mg²⁺And Li⁺At least one of them ".

8. The use of carboxylic acid compounds or their salts as claimed in claim 7, wherein the extractant is selected from any one or mixture of the following compounds:

9. use according to claim 8, wherein the metal ion is Ni²⁺、Co²⁺、Mn²⁺、Fe³⁺、Al³⁺、Cu² ⁺、Zn²⁺、Cd²⁺、Ca²⁺、Mg²⁺And Li⁺And (3) mixing.

10. An extraction composition, characterized by comprising an extractant and a diluent, wherein the extractant comprises the carboxylic acid compound shown in the formula I and/or the salt thereof according to any one of claims 1 to 3.

11. The extraction composition of claim 10, wherein the molar ratio of the carboxylic acid compound of formula I to the salt of the carboxylic acid compound of formula I is (0.4-9): 1; and/or the diluent is one or a mixture of solvent naphtha, kerosene, Escaid110, hexane, heptane and dodecane; and/or the molar volume ratio of the extracting agent to the diluting agent is 0.1 mol/L-1.5 mol/L.

12. The extraction composition according to claim 11, characterized in that the molar ratio between the carboxylic acid of formula I and the salt of the carboxylic acid of formula I is 1: 1; and/or the diluent is one or a mixture of No. 200 solvent naphtha or No. 260 solvent naphtha, kerosene, Escaid110, hexane, heptane and n-dodecane; and/or the molar volume ratio of the extracting agent to the diluting agent is 0.16 mol/L-0.85 mol/L.

13. An extraction process, comprising the steps of: extracting the organic phase containing the extracting agent from the aqueous phase containing the metal ions to obtain an organic phase containing the metal ions;

in the organic phase containing the extracting agent, the extracting agent comprises the carboxylic acid compound shown in the formula I according to any one of claims 1 to 3 and/or the salt of the carboxylic acid compound shown in the formula I according to any one of claims 1 to 3;

the aqueous phase containing metal ions including Ni²⁺、Co²⁺、Mn²⁺、Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺And Ca²⁺Or a mixture thereof.

14. The extraction process of claim 13, wherein the metal ion is "Ni²⁺、Co²⁺And Mn²⁺At least one kind of "and" Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺、Ca²⁺、Mg²⁺And Li⁺A mixture of at least one of the foregoing;

and/or in the organic phase containing the extracting agent, the molar ratio of the carboxylic acid compound shown in the formula I to the salt of the carboxylic acid compound shown in the formula I is (0.4-9): 1;

and/or the organic phase containing the extracting agent comprises a diluent, wherein the diluent is one or a mixture of solvent naphtha, kerosene, Escaid110, hexane, heptane and dodecane;

the molar volume ratio of the extracting agent to the diluting agent is 0.1-1.5 mol/L;

and/or the volume ratio of the organic phase containing the extracting agent to the aqueous phase containing the metal ions is 1 (1-10);

and/or, in the extraction method, mass transfer is carried out by oscillation;

and/or the extraction temperature is 10-50 ℃;

and/or the extraction time is 5-60 minutes.

15. The extract of claim 14The method is characterized in that the metal ions are Ni²⁺、Co²⁺、Mn²⁺、Fe³⁺、Al³⁺、Cu²⁺、Zn²⁺、Cd²⁺、Ca²⁺、Mg²⁺And Li⁺Mixing;

and/or in the organic phase containing the extracting agent, the molar ratio of the carboxylic acid compound shown in the formula I to the salt of the carboxylic acid compound shown in the formula I is 1: 1;

and/or the organic phase containing the extracting agent comprises a diluent, wherein the diluent is one or a mixture of No. 200 solvent naphtha or No. 260 solvent naphtha, kerosene, Escaid110, hexane, heptane and n-dodecane; the molar volume ratio of the extracting agent to the diluting agent is 0.1-1.5 mol/L;

and/or the volume ratio of the organic phase containing the extracting agent to the aqueous phase containing the metal ions is 1 (1-5);

and/or, in the extraction method, mass transfer is carried out by oscillation;

and/or the extraction temperature is 25-40 ℃;

and/or the extraction time is 5-60 minutes.

16. The extraction process of claim 14,

the diluent is one or a mixture of No. 260 solvent oil, n-dodecane and Escaid 110;

the molar volume ratio of the extracting agent to the diluting agent is 0.16mol/L, 0.33mol/L or 0.6 mol/L;

and/or the volume ratio of the organic phase containing the extractant to the aqueous phase containing the metal ions is 1:1, 1:2 or 1: 4;

and/or, in the extraction process, mass transfer by shaking;

and/or the extraction temperature is 25-40 ℃;

and/or the time of the extraction is 15 minutes or 30 minutes.

17. The back extraction method is characterized by comprising the following steps: mixing the metal ion-containing organic phase obtained by the extraction process of any one of claims 14 to 16 with an aqueous acid solution.

18. The stripping process according to claim 17, characterized in that the molar concentration of the aqueous acid solution is 1 to 3 mol/L;

and/or, the acid in the aqueous acid solution is an inorganic acid;

and/or the volume ratio of the organic phase containing the metal ions to the aqueous solution of the acid is (1-50): 1.

19. The stripping process according to claim 17, characterized in that the molar concentration of the aqueous acid solution is 1 to 3 mol/L;

and/or the acid in the acid water solution is inorganic acid, and the inorganic acid is one or more of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid;

and/or the volume ratio of the organic phase containing the metal ions to the aqueous solution of the acid is (10-20): 1.