Chelating resin composition, preparation method therefor and use thereof

Abstract

The present invention relates to a chelating resin composition, a preparation method therefor and a use thereof. The chelating resin composition comprises a chelating resin of formula (I) and a chelating resin of formula (II), wherein: P is a base resin; R1 and R2 are each independently a nitrogen-containing heterocyclic group; R3 is an acyl-containing group; and M is formula (A), n and m independently being integers between 2 and 10, and x being 0 or 1. The chelating resin composition of the present invention is effective in metal ion extraction, can achieve separation of copper, nickel and cobalt from metals such as iron, or separation of copper from metals such as nickel, cobalt and iron under strong acidic conditions (pH < 3), and can also achieve separation of copper from manganese and calcium under acidic conditions (pH < 7), with good selectivity; in addition, the composition has relatively high adsorption capacity, and can be recycled after recovery.

Description

Chelating resin composition and its preparation method and use Technical Field

[0001] The present invention relates to the technical field of organic compound preparation, in particular to a chelate resin composition and a preparation method and application thereof. Background Art

[0002] Metal extractants are the most important materials in metal purification and separation processes and are widely used in metal separation and purification. In traditional liquid-liquid extraction processes, the design and application of extractants are limited by issues such as solubility and difficulty in preparation.

[0003] In recent years, with the rise of the new energy industry, the demand for metals such as nickel and cobalt, as well as the purity requirements, have increased significantly. With the popularization of electric vehicles, the recycling of used batteries has also placed higher demands on the separation and purification of related metals.

[0004] Therefore, it is necessary to develop an extractant and method that has a better separation effect on valuable metals, especially copper, nickel, cobalt and other metals.

[0005] Summary of the Invention

[0006] An object of the present invention is to provide an extractant which is effective in separating valuable metals, especially copper, nickel, and cobalt.

[0007] Another object of the present invention is to provide a method for separating valuable metals, especially metals such as copper, nickel and cobalt, which is more effective.

[0008] Therefore, according to a first aspect, the present invention provides a kind of chelate resin composition, it is characterized in that, comprise the chelate resin of formula (I) and the chelate resin of formula (II):

[0009] in:

[0010] P is the base resin;

[0011] R1 and R2 are each independently a nitrogen-containing heterocyclic group;

[0012] R3 is an acyl-containing group; and

[0013] M is wherein n and m are independently integers of 2-10; and x is 0 or 1.

[0014] According to a second aspect, the present invention provides a method for preparing the above-mentioned chelating resin composition, characterized in that a resin having a primary amino group is subjected to a substitution reaction with nitrogen-containing heterocyclic chlorides R1Cl, R2Cl and an acyl chloride R3Cl in sequence, wherein R1, R2 and R3 are as described above for formulas (I) and (II).

[0015] According to a third aspect, the present invention provides use of the chelate resin composition for adsorbing metals.

[0016] According to a fourth aspect, the present invention provides a method for solid phase extraction of metals, characterized in that the above-mentioned chelating resin composition is used as an adsorbent.

[0017] The chelate resin composition of the present invention has a good extraction effect on metal ions, especially copper, nickel and cobalt. It can separate copper, nickel and cobalt from metals such as iron or copper from metals such as nickel, cobalt and iron under strongly acidic conditions (pH<3). It can also separate copper from manganese and calcium under acidic conditions (pH<7) with good selectivity. At the same time, the chelate resin composition has a high adsorption capacity, and the resin can be recycled after recovery. DETAILED DESCRIPTION

[0018] Various aspects of the invention as well as further objects, features and advantages will appear more fully hereinafter.

[0019] Chelating resin composition

[0020] According to a first aspect, the present invention provides a chelate resin composition, characterized in that it comprises a chelate resin of formula (I) and a chelate resin of formula (II):

[0021] in:

[0022] P is the base resin;

[0023] R1 and R2 are each independently a nitrogen-containing heterocyclic group;

[0024] R3 is an acyl-containing group; and

[0025] M is wherein n and m are independently integers of 2-10; and x is 0 or 1.

[0026] Preferably, the molar ratio of the chelating resin of formula (I) to the chelating resin of formula (II) is 0.7-19:1, more preferably, 1-5:1.

[0027] The present invention does not particularly limit the base resin P. Preferably, the base resin P is selected from polystyrene resins, copolymers of styrene and divinylbenzene, phenolic resin polymers, polyacrylic resins, and silicone-based resins. More preferably, the base resin P is selected from polystyrene resins and copolymers of styrene and divinylbenzene.

[0028] Specifically, n and m are independently 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0029] Preferably, the nitrogen-containing heterocyclic groups R1 and R2 are each independently selected from a pyridine group, an imidazole group, a benzimidazole group, a pyrazole group, a quinoline group, a pyrazine group, a triazine group and a triazole group.

[0030] More specifically, the nitrogen-containing heterocyclic groups R1 and R2 are each independently selected from the following groups:

[0031] Preferably, the nitrogen-containing heterocyclic groups R1 and R2 are each independently selected from the following groups:

[0032] Preferably, R3 is -(CO)R4 or -CH2(CO)R4, wherein R4 is a straight chain or branched alkyl group with a carbon chain number of 1-5, -N-(R5)2 or a nitrogen-containing heterocyclic group defined for R1 or R2, wherein R5 is a straight chain or branched alkyl group with a carbon chain number of 1-5.

[0033] The inventors have found that the presence of acyl groups improves the selectivity of the chelating resin composition to metal ions, especially copper.

[0034] Preferably, the chelating resin of formula (I) has a structure selected from the following:

[0035] Preferably, the chelating resin of formula (II) has a structure selected from the following:

[0036] Wherein P is independently selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin polymer, polyacrylic resin and silicon-based resin.

[0037] Preferably, the chelate resin composition comprises:

[0038] or or or or or or or or or or or

[0039] Wherein P is independently selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin polymer, polyacrylic resin and silicon-based resin.

[0040] Method for preparing the above-mentioned chelate resin composition

[0041] The above-mentioned chelate resin composition can be obtained by subjecting a resin containing primary amino groups to substitution reactions with nitrogen-containing heterocyclic chlorides R1Cl, R2Cl and acyl chlorides R3Cl, wherein R1, R2 and R3 are as described above for formulas (I) and (II).

[0042] Therefore, according to a second aspect, the present invention provides a method for preparing the above-mentioned chelating resin composition, characterized in that a resin having a primary amino group is subjected to a substitution reaction with nitrogen-containing heterocyclic chlorides R1Cl, R2Cl and an acyl chloride R3Cl in sequence, wherein R1, R2 and R3 are as described above for formulas (I) and (II).

[0043] Specifically, the above-mentioned chelate resin composition can be prepared by the following steps:

[0044] SS1: A resin containing a primary amino group is subjected to a substitution reaction with a nitrogen-containing heterocyclic chloride R1Cl in an alkaline solution under heating conditions to obtain a compound of formula (1):

[0045] SS2: The intermediate compound of formula (1) is subjected to a substitution reaction with a nitrogen-containing heterocyclic chloride R2Cl under the same conditions as in step SS1 to obtain a mixture comprising a compound of formula (1) and a compound of formula (2):

[0046] SS3: make the mixture of the compound comprising the compound of formula (1) and the compound of formula (2) and contain acyl chloride R3Cl generation substitution reaction, obtain comprising the composition of the chelating resin of formula (I) and the chelating resin of formula (II):

[0047] Preferably, the resin containing a primary amino group is selected from the group consisting of a polystyrene resin containing a primary amino group, a modified phenolic resin containing a primary amino group, a polyacrylic resin containing a primary amino group, and a silicon-based resin containing a primary amino group.

[0048] Preferably, the molar ratio of the resin containing primary amino groups to the nitrogen-containing heterocyclic chlorides R1Cl and R2Cl to the acyl chloride R3Cl is 1:1-1.9:0.1-1.5, more preferably 1:1-1.9:0.5-1.5.

[0049] The molar ratio of the nitrogen-containing heterocyclic chloride R1Cl and the nitrogen-containing heterocyclic chloride R2Cl to the primary amino resin is not particularly limited, as long as the sum of the molar ratios of the two to the primary amino resin is 1-1.9. Preferably, in step SS1, the alkaline compound contained in the alkaline solution is 1-3 times the equivalent of the nitrogen-containing heterocyclic chloride R1Cl, the solvent of the alkaline solution is 2-50 times the mass of the nitrogen-containing heterocyclic chloride R1Cl, preferably 2-10 times the mass, the heating temperature is 40-120°C, preferably 50-85°C, and the reaction time is 2-36 hours, preferably 2-8 hours.

[0050] Preferably, in step SS2, the alkaline compound contained in the alkaline solution is 1-3 times the equivalent of the nitrogen-containing heterocyclic chloride R2Cl, the solvent of the alkaline solution is 2-50 times the mass of the nitrogen-containing heterocyclic chloride R2Cl, preferably 2-10 times the mass, the heating temperature is 40-120°C, preferably 50-85°C, and the reaction time is 2-36 hours, preferably 2-8 hours.

[0051] Preferably, in steps SS1 and SS2, the alkaline compound is selected from sodium carbonate, magnesium hydroxide, calcium oxide, magnesium oxide, calcium hydroxide, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, triethylamine and N,N-diisopropylethylamine.

[0052] Preferably, in steps SS1 and SS2, the solvent is selected from water, N,N-dimethylformamide, dimethyl sulfoxide, toluene, tetrahydrofuran, ethanol, acetonitrile and acetone.

[0053] Advantageously, step SS3 is performed at room temperature for 0.5-36 hours, preferably 2-8 hours.

[0054] Advantageously, step SS3 is carried out in a solvent, preferably, the solvent is selected from tetrahydrofuran, dichloromethane and dichloroethane.

[0055] In some embodiments, R1 and R2 are the same nitrogen-containing heterocyclic substituent.

[0056] In this case, the above-mentioned chelating resin composition can be prepared by following steps:

[0057] SS1+SS2: A resin containing a primary amino group is subjected to a substitution reaction with a nitrogen-containing heterocyclic chloride R1Cl in an alkaline solution under heating conditions to obtain a mixture comprising a compound of formula (1) and a chelating resin of formula (3):

[0058] SS3: make the mixture of the compound comprising the compound of formula (1) and the compound of formula (3) and contain acyl chloride R3Cl generation substitution reaction, obtain comprising the composition of the chelating resin of formula (3) and the chelating resin of formula (II):

[0059] Preferably, the molar ratio of the resin containing primary amino groups to the nitrogen-containing heterocyclic chloride R1Cl and the acyl chloride R3Cl is 1:1-1.9:0.1-1.5, more preferably 1:1-1.9:0.5-1.5.

[0060] Preferably, in the SS1+SS2 step, the alkaline compound contained in the alkaline solution is 1-3 times the equivalent of the nitrogen-containing heterocyclic chloride R1Cl, the solvent of the alkaline solution is 2-50 times the mass of the nitrogen-containing heterocyclic chloride R1Cl, preferably 2-10 times the mass, the heating temperature is 40-120°C, preferably 50-85°C, and the reaction time is 2-36 hours, preferably 2-8 hours.

[0061] Preferably, in step SS1+SS2, the alkaline compound is selected from sodium carbonate, magnesium hydroxide, calcium oxide, magnesium oxide, calcium hydroxide, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, triethylamine and N,N-diisopropylethylamine.

[0062] Preferably, in the SS1+SS2 step, the solvent is selected from water, N,N-dimethylformamide, dimethyl sulfoxide, toluene, tetrahydrofuran, ethanol, acetonitrile and acetone.

[0063] Advantageously, step SS3 is performed at room temperature for 0.5-36 hours, preferably 2-8 hours.

[0064] Advantageously, step SS3 is carried out in a solvent, preferably, the solvent is selected from tetrahydrofuran, dichloromethane and dichloroethane.

[0065] The preparation method of the present invention can obtain a high yield, which can reach more than 90%.

[0066] Application of chelate resin composition

[0067] According to a third aspect, the present invention provides use of the chelate resin composition for adsorbing metals.

[0068] More specifically, the chelate resin composition can be used for adsorbing metals in hydrometallurgy, waste disposal, recycling industries, or electroplating.

[0069] In particular, the metal is one or more of copper, cobalt and nickel.

[0070] According to a fourth aspect, the present invention provides a method for recovering copper, nickel and cobalt, characterized in that the above-mentioned chelating resin composition is used as an adsorbent.

[0071] More specifically, the method comprises the following steps:

[0072] S1: contacting the chelate resin composition with a copper-nickel-cobalt solution for extraction, and then performing solid-liquid separation to obtain a copper-nickel-cobalt loaded chelate resin composition and a raffinate;

[0073] S2: stripping the copper-nickel-cobalt loaded chelating resin composition using an acid solution, and then performing solid-liquid separation to obtain a stripping chelating resin composition and a copper-nickel-cobalt stripping solution; and

[0074] S3: Separate copper, nickel and cobalt from the copper, nickel and cobalt stripping solution.

[0075] Advantageously, the extraction time is more than 1 min, such as 1-120 min, such as 5-100 min, such as 10-80 min, preferably 10-60 min.

[0076] Advantageously, the pH value of the copper-nickel-cobalt solution is 0.5-7, such as 0.5-6, such as 0.5-5, such as 0.5-3.5, such as 0.5-3; when containing iron metal, the copper-nickel-cobalt solution is preferably 0.5-3.

[0077] Advantageously, the copper-nickel-cobalt loaded chelate resin is first washed with a dilute acid solution before stripping to wash away the extracted impurity metals;

[0078] Advantageously, the acid solutions used for washing and stripping are independently selected from sulfuric acid solution and hydrochloric acid solution. Preferably, the concentration of the sulfuric acid solution used for stripping is 0.5-6 mol / L, the concentration of the hydrochloric acid solution is 1-8 mol / L, and the pH value of the acid solution used for washing is between 0.5-2.

[0079] The chelate resin composition of the present invention has improved selectivity for metal elements, especially copper metal elements, and can effectively separate copper, nickel and cobalt from impurities such as iron, manganese, calcium and magnesium, or effectively separate copper from nickel and cobalt.

[0080] The "selectivity" described in this application is represented by the separation coefficient β of the metal elements. Further, the separation coefficient is obtained by the following formula:

[0081] β A / B =D A / D B =E A .(1-E B ) / ((1-E A ).E B )

[0082] Where D A It represents the ratio of the content of metal element A in the resin to the content of metal element A in the raffinate water phase after one extraction is completed;

[0083] D B It represents the ratio of the content of metal element B in the resin to the content of metal element B in the raffinate water phase after one extraction is completed;

[0084] E A and E B They represent the extraction rates of metal element A and metal element B respectively (extraction rate E=content of metal element in resin after one extraction / content of metal element in initial aqueous phase×100%).

[0085] The metal extraction rate in the formula can be measured by the following method:

[0086] Resin pretreatment: Mix the resin with 2 mol / L sulfuric acid and stir at 250 rpm / min for 30 min, wash with pure water until the supernatant is colorless, then wash with 0.25 mol / L sodium hydroxide solution until the supernatant is alkaline, then wash the resin with pure water until it is neutral, filter and obtain the pretreated resin for use;

[0087] 30 mL of sulfate solution containing 0.05 g / L of each metal element was prepared as the initial aqueous phase, and the pH value of the initial aqueous phase was adjusted. Then, it was mixed and stirred with 5 g of pretreated resin at room temperature for 60 min at a rotation speed of 250 rpm / min to allow the adsorption to reach equilibrium. After stirring, solid-liquid separation was performed to obtain a raffinate (equilibrium) aqueous phase. The concentration of each metal element in the raffinate aqueous phase was determined by inductively coupled plasma emission spectroscopy (ICP), and the content of the metal elements in the resin was calculated by subtraction.

[0088] The "loading capacity" described in this application can be measured by the following method:

[0089] Prepare a 0.5 mol / L sulfate solution of each metal element, adjust the pH of the initial aqueous phase, and then place 2g of the pretreated resin in a beaker. Add 20mL of each prepared metal solution to each beaker. Stir at room temperature for 60 minutes at 250 rpm. After stirring, perform solid-liquid separation to obtain a raffinate aqueous phase. Repeat this process three times, contacting the resin with a fresh initial aqueous phase each time. Determine the concentration of each metal element in the raffinate aqueous phase using inductively coupled plasma emission spectroscopy (ICP). The metal element content in the resin is determined by subtraction to determine the resin's loading capacity for each metal element.

[0090] In the present application, the terms “comprise” and “include” encompass the case where the phrases “comprise” and “include” also include or comprise other elements not explicitly mentioned as well as the case where the phrases are composed of the mentioned elements.

[0091] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention belongs. When the definition of a term in this specification conflicts with the meaning commonly understood by those skilled in the art to which the invention belongs, the definition described in this article shall prevail.

[0092] Unless otherwise indicated, all numbers expressing amounts of ingredients, temperatures, times, and so forth used in the specification and claims are to be understood as being modified by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties sought to be obtained.

[0093] Example

[0094] The following will further illustrate the concept, specific structure and technical effects of the present invention in conjunction with the embodiments, so that those skilled in the art can fully understand the purpose, features and effects of the present invention. It will be readily understood by those skilled in the art that the embodiments herein are for illustrative purposes only and the scope of the present invention is not limited thereto.

[0095] Preparation Example 1: Preparation of Resin Mixture 1

[0096] Prepare resin mixture 1 according to the following process:

[0097] Specifically, 10 g (30 mmol) of primary amino polystyrene microspheres (Lanxiao Technology, model LX-D30) and 9.3 g (57 mmol) of 2-chloromethylpyridine hydrochloride were placed in a 100 ml three-necked flask, and 60 g of N,N-dimethylformamide and 2.88 g (72 mmol) of sodium hydroxide were added in sequence. The mixture was heated to 80° C. under mechanical stirring and reacted for 2 hours to generate intermediate 1 microspheres with a yield of 80%.

[0098] The intermediate 1 microspheres were filtered out by suction, rinsed twice with water, and then rinsed twice with ethanol. The intermediate 1 microspheres were placed in a 100 ml three-necked flask, and 2.2 g (15 mmol) of N,N-diethyl-2-chloroacetamide and 30 g of dichloromethane were added in sequence. The reaction was continued at room temperature for 2 hours to obtain a resin mixture 1 with a yield of 98.5%.

[0099] Preparation Example 2: Preparation of Resin Mixture 2

[0100] Prepare resin mixture 2 according to the following process:

[0101] Specifically, 10 g (30 mmol) of primary amino polystyrene microspheres (Lanxiao Technology, model LX-D30) and 5.7 g (45 mmol) of 2-chloromethylpyridine hydrochloride were placed in a 100 ml three-necked flask, and 57 g of acetone and 4.6 g (45 mmol) of triethylamine were added in sequence. The mixture was heated to 60° C. under mechanical stirring and reacted for 4 hours to generate intermediate 2 microspheres with a yield of 62%.

[0102] The intermediate 2 microspheres were filtered out by suction and rinsed twice with acetone. The intermediate 2 microspheres were placed in a 100 ml three-necked flask, and 2.36 g (30 mmol) of acetyl chloride and 60 g of tetrahydrofuran were added in sequence. The reaction was continued at room temperature for 8 hours to obtain mixture 2 with a yield of 99%.

[0103] Preparation Example 3: Preparation of Resin Mixture 3

[0104] Prepare resin mixture 3 according to the following process:

[0105] Specifically, 10 g (30 mmol) of primary amino polystyrene microspheres (Lanxiao Technology, model LX-D30) and 7.4 g (45 mmol) of 2-chloromethylpyrazine hydrochloride were placed in a 100 ml three-necked flask, and 74 g of tetrahydrofuran and 5.44 g (135 mmol) of magnesium oxide (MgO) were added in sequence. The mixture was heated to 60° C. under mechanical stirring and reacted for 3 hours to generate intermediate 3 microspheres with a yield of 63%.

[0106] The intermediate 3 microspheres were filtered out by suction and rinsed twice with water and ethanol respectively. The intermediate 3 microspheres were placed in a 100 ml three-necked flask, and 2.83 g (20 mmol) of acetyl chloride and 60 g of dichloroethane were added in sequence. The reaction was continued at room temperature for 4 hours to obtain mixture 3 with a yield of 90%.

[0107] Preparation Example 4: Preparation of Resin Mixture 4

[0108] Prepare resin mixture 4 according to the following process:

[0109] Specifically, 10 g (30 mmol) of primary amino polystyrene microspheres (Lanxiao Technology, model LX-D30) and 9.4 g (50 mmol) of the intermediate of pantoprazole were placed in a 100 ml three-necked flask, and 60 g of acetone and 7.3 g (72 mmol) of triethylamine were added in sequence. Under mechanical stirring, the mixture was heated to 85° C. and reacted for 4 hours to generate intermediate 4 microspheres with a yield of 70%.

[0110] The intermediate 4 microspheres were filtered out by suction and rinsed twice with acetone. The intermediate 4 microspheres were placed in a 100 ml three-necked flask, and 2.36 g (30 mmol) of acetyl chloride and 20 g of tetrahydrofuran were added in sequence. The reaction was continued at room temperature for 8 hours to obtain mixture 4 with a yield of 99.6%.

[0111] Preparation Example 5: Preparation of Resin Mixture 5

[0112] Prepare resin mixture 5 according to the following process:

[0113] Specifically, 10 g (30 mmol) of primary amino polystyrene microspheres (Lanxiao Technology, model LX-D30) and 8.3 g (36 mmol) of 2-(chloromethyl)-4-(3-methoxypropoxy)-3-methylpyridine were placed in a 100 ml three-necked flask, and 60 g of acetone and 7.3 g (72 mmol) of triethylamine were added in sequence. The mixture was heated to 60° C. under mechanical stirring and reacted for 3 hours to generate intermediate 5 microspheres with a yield of 50%.

[0114] The intermediate 5 microspheres were filtered out by suction and rinsed twice with acetone. The intermediate 5 microspheres were placed in a 100 ml three-necked flask, and 2.8 g (36 mmol) of acetyl chloride and 30 g of tetrahydrofuran were added in sequence. The reaction was continued at room temperature for 8 hours to obtain a mixture 5 with a yield of 98.6%.

[0115] Preparation Example 6: Preparation of Resin Mixture 6

[0116] Prepare resin mixture 6 according to the following process:

[0117] Specifically, 10 g (30 mmol) of primary amino polystyrene microspheres (Lanxiao Technology, model LX-D30) and 7.9 g (56 mmol) of 2-chloromethyl-6-methylpyridine were placed in a 100 ml three-necked flask, and 60 g of N,N-dimethylformamide and 2.88 g (72 mmol) of sodium hydroxide were added in sequence. Under mechanical stirring, the mixture was heated to 60°C and reacted for 3 hours to generate intermediate 6 microspheres with a yield of 78%.

[0118] The intermediate 6 microspheres were filtered out by suction and rinsed twice with water, ethanol, and acetone, respectively. The intermediate 6 microspheres were placed in a 100 ml three-necked flask, and 2.83 g (20 mmol) of acetyl chloride and 30 g of dichloroethane were added in sequence. The reaction was continued at room temperature for 8 hours to obtain a mixture 6 with a yield of 99.6%.

[0119] Extraction Example 1

[0120] Configure 5 parts containing Ni 2+ 、Co 2+ 、Al 3+、Fe 3+ 、Mn 2+ 、Cd 2+ 、Zn 2+ , Ca 2+ Mg 2+ Cr 2+ 、Li + 30 mL of each 50 mg / L sulfate solution was used as the aqueous phase to be extracted, and the pH values ​​of the residual aqueous phase to be extracted were adjusted to 0.9, 1.2, 2.0, 3.9 and 4.0, respectively. Then, it was mixed with 5 g of resin mixture 1 and stirred for 60 minutes to allow the adsorption to reach equilibrium. After stirring, solid-liquid separation was performed to obtain the residual (equilibrium) aqueous phase, and the concentration of each metal ion in the equilibrium aqueous phase was determined by inductively coupled plasma emission spectroscopy (ICP). The content of metal ions in the resin mixture 1 was calculated by subtraction.

[0121] Table 1 shows the extraction rates of various metal ions by resin 1 at different equilibrium aqueous phase pH values.

[0122] Table 1. Extraction rate of each metal ion by resin mixture 1 / %

[0123] As shown in Table 1, when the pH value of the equilibrium aqueous phase is about 0.9, the resin mixture 1 has a strong 2+ 、Ni 2+ and Co 2+ The extraction rates of Zn were 99.6%, 64.2% and 30.6% respectively. 2+ 、Cd 2+ The extraction rate of Cu is less than 21%, and the extraction rate of other impurity metals is less than 10%. When the pH value of the equilibrium aqueous phase is about 1.2, the resin mixture has a good effect on Cu 2+ 、Ni 2+ and Co 2+ The extraction rates of Zn 2+ 、Cd 2+ The extraction rate of Cu is less than 31%, and the extraction rate of other impurity metals is less than 16%. When the pH value of the equilibrium aqueous phase is 4.0, the extraction rate of resin 1 for Cu is less than 31%. 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ 、Cd 2+ and Fe 3+ The extraction rates of Al 3+ 、Mn + Cr 2+ The extraction rates of Ca 2+ Mg 2+ 、Li +The extraction rates were all less than 5%.

[0124] Table 2 shows the separation coefficients of the resin mixture 1 for various ions when the equilibrium pH value of the aqueous phase is 1.2.

[0125] Table 2. Separation coefficients of resin 1 for various ions

[0126] It can be seen from Table 2 that when the pH value of the equilibrium aqueous phase is about 1.2, Cu 2+ The separation coefficients of Ni and other impurity metals are between 283-24676. 2+ The separation coefficient with each impurity metal is between 11-1029, Co 2+ The separation coefficient from each impurity metal is between 2-257.

[0127] The above results show that the resin mixture 1 has a good extraction and separation effect on various metal ions and can selectively separate copper, nickel and cobalt (especially copper and nickel) from impurity metal ions.

[0128] Comparative Extraction Example 1

[0129] This example was carried out with reference to the process in Extraction Example 1. The difference from Extraction Example 1 was that the resin mixture 1 was replaced with a resin B having the following structure:

[0130] Wherein P is polystyrene resin microspheres.

[0131] Table 3 shows the separation coefficients of resin mixture 1 and resin B for various ions when the equilibrium pH value of the aqueous phase is 1.2.

[0132] Table 3. Separation coefficients of resin 1 and resin B for various ions

[0133] As shown in Table 3, compared with resin B, resin mixture 1 has a higher separation coefficient for Cu / Fe, Ni / Fe, and Co / Fe, which is about 70%-97% higher.

[0134] The results showed that compared with resin B, resin mixture 1 had a more significant selective separation effect on copper, nickel, cobalt and iron.

[0135] Extraction Example 2

[0136] This example was carried out with reference to the process in Extraction Example 1, except that resin mixture 1 was replaced by resin mixture 2, and the pH value of the equilibrium aqueous phase was controlled to be 2.0.

[0137] Table 4 shows the extraction rates of various metal ions by resin mixture 2 under the condition that the equilibrium pH value of the aqueous phase is 2.0.

[0138] Table 4. Extraction rate of each metal ion by resin mixture 2 / %

[0139] It can be seen from Table 4 that the resin mixture 2 has a strong 2+ 、Ni 2+ and Co 2+ The extraction rates of Zn 2+ 、Cd 2+ 、Fe 3+ The extraction rates of 2, 3, 4 and 5 impurity metals are 73.5%, 73.2% and 51.5% respectively, and the extraction rates of other impurity metals are all less than 10%.

[0140] Comparative Extraction Example 2

[0141] This example was carried out with reference to the process in Extraction Example 2, except that the resin mixture 2 was replaced by resin B.

[0142] Table 5 shows the separation coefficients of resin mixture 2 and resin B for various ions when the equilibrium aqueous phase pH value is 2.0.

[0143] Table 5. Separation coefficients of resin mixture 2 and resin B for various ions

[0144] As shown in Table 5, the separation coefficients of resin mixture 2 for Cu / Fe, Ni / Fe, and Co / Fe are higher by about 26%-36% compared with resin B. When the equilibrium pH value of the aqueous phase is about 2.0, the separation coefficients of resin mixture 2 for Cu / Fe, Ni / Fe, and Co / Fe are 84.7, 20.5, and 4.3, respectively, while the separation coefficients of resin B for Cu / Fe, Ni / Fe, and Co / Fe are 64.9, 15.0, and 3.4, respectively.

[0145] The results showed that compared with resin B, resin mixture 2 had a more significant selective separation effect on copper, nickel, cobalt and iron.

[0146] Extraction Example 3

[0147] This example was carried out with reference to the process in Extraction Example 1, except that resin mixture 1 was replaced by resin mixture 3, and the pH value of the equilibrium aqueous phase was controlled to be 1.5.

[0148] The results show that the resin mixture 3 has a great 2+ 、Ni 2+ 、Co 2+ The extraction rates of Zn 2+ 、Cd 2+ 、Fe 3+, Ca 2+ 、Mn 2+ Mg 2+ 、Al 3+ Cr 2+ 、Li + The extraction rates of metals were all less than 15%.

[0149] Comparative Extraction Example 3

[0150] This example was carried out with reference to the process in Extraction Example 3, except that the resin mixture 3 was replaced by resin B.

[0151] Table 6 shows the separation coefficients of resin mixture 3 and resin B for various ions when the equilibrium pH value of the aqueous phase is 1.5.

[0152] Table 6. Separation coefficients of resin mixture 3 and resin B for various ions

[0153] As shown in Table 6, the separation coefficients of resin mixture 3 for Cu / Fe, Ni / Fe, and Co / Fe are higher than those of resin B, ranging from 42% to 270%. When the equilibrium pH value of the aqueous phase is about 1.5, the separation coefficients of resin mixture 3 for Cu / Fe, Ni / Fe, Ni / Zn, and Ni / Cd are 524, 30.2, 30.0, and 15.0, respectively, while the separation coefficients of resin B for Cu / Fe, Ni / Fe, Ni / Zn, and Ni / Cd are 179, 21.3, 8.1, and 8.6, respectively.

[0154] The results showed that compared with resin B, resin mixture 3 had a more significant selective separation effect on copper and nickel from iron, zinc and cadmium.

[0155] Extraction Example 4

[0156] This example was carried out with reference to the process in Extraction Example 1. The difference from Extraction Example 1 was that resin mixture 1 was replaced by resin mixture 4 and resin mixture 5, and the pH value of the equilibrium aqueous phase was controlled to be 1.0.

[0157] The results show that the resin mixture 4 has a good 2+ The extraction rate of Fe 3+ The extraction rate of Ni was 29.7%. 2+ 、Co 2+ 、Zn 2+ 、Cd 2+ 、Fe 3+ , Ca 2+ 、Mn 2+ Mg 2+ 、Al 3+ Cr 2+ 、Li+ The extraction rates of the resin mixture were less than 20%; 2+ The extraction rate of Fe 3+ The extraction rate of Ni was 29.8%. 2+ 、Co 2+ 、Zn 2+ 、Cd 2+ 、Fe 3+ , Ca 2+ 、Mn 2+ Mg 2+ 、Al 3+ Cr 2+ 、Li + The extraction rates were all less than 20%.

[0158] Comparative Extraction Example 4

[0159] This example was carried out with reference to the process in Extraction Example 4. The difference from Extraction Example 4 was that resin mixture 4 and resin mixture 5 were replaced with resin A having the following structure:

[0160] Wherein P is polystyrene resin microspheres.

[0161] Table 7 shows the separation coefficients of resin mixture 4, resin mixture 5, and resin A for various ions when the equilibrium aqueous phase pH value is 1.0.

[0162] Table 7. Separation coefficients of resin mixture 4, resin mixture 5, and resin A for various ions

[0163] As shown in Table 7, compared with resin A, resin mixture 4 and resin mixture 5 have higher separation coefficients for Cu / Fe, Cu / Ni, and Cu / Co, which are about 33%-460% higher.

[0164] The results show that compared with resin A, resin mixture 4 and resin mixture 5 have significant selective separation effects on copper and iron, nickel and cobalt.

[0165] Comparative Extraction Example 5

[0166] This example was carried out with reference to the process in Extraction Example 1, except that resin mixture 1 was replaced with resin mixture 2-6 and resin A, and the pH value of the equilibrium aqueous phase was controlled to be 3.0.

[0167] Table 8 shows the separation coefficients of resin mixtures 1-6 and resin A for various ions when the equilibrium aqueous phase pH value is 3.0.

[0168] Table 8. Separation coefficients of resin mixtures 1-6 and resin A for various ions

[0169] As shown in Table 8, compared with resin A, resin mixtures 1-6 have higher separation coefficients for Cu / Mn and Cu / Ca, and resin 6 has higher separation coefficients for Cu / Ni, Cu / Co, and Cu / Fe.

[0170] The results showed that compared with resin A, resin mixtures 1-6 had a significant effect on the separation of copper from manganese and calcium, and resin mixture 6 also had a significant effect on the selective separation of copper from iron, nickel and cobalt.

[0171] Extraction Example 6

[0172] Prepare a 0.5 mol / L copper sulfate solution and adjust the initial aqueous phase pH to 1.2. Take 2g of pretreated resin mixtures 1 and 2 in separate beakers, add 20mL of the prepared copper sulfate solution to each beaker, and stir at room temperature for 60 minutes at 250 rpm. After stirring, perform solid-liquid separation to obtain a raffinate aqueous phase. Repeat this process three times, contacting the fresh initial aqueous phase each time. Determine the copper concentration in the raffinate aqueous phase using inductively coupled plasma emission spectroscopy (ICP). The copper content in the resin is determined by subtraction to obtain the copper loading capacity of the resin.

[0173] Table 9 shows the copper and nickel loadings for each resin mixture.

[0174] Table 9. Loading of copper and nickel by resin mixture / mg / g

[0175] As can be seen from Table 9, resin mixtures 1-3 have high loadings on copper and nickel, and resin mixtures 4-6 have high loadings on copper.

[0176] The resin mixture 1-6 was subjected to six extraction and regeneration cycles. The results showed that the metal element loading of the resin mixture 1-6 during the sixth extraction was not much different from that during the first extraction.

[0177] The above merely describes exemplary embodiments or examples of the present invention and is not intended to limit the present invention. It will be apparent to those skilled in the art that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention are intended to be included within the scope of the claims of this application.

Claims

1. A chelating resin composition, characterized in that, A chelating resin comprising formula (I) and a chelating resin comprising formula (II): in: P is the base resin; R1 and R2 are each independently a nitrogen-containing heterocyclic group; R3 is an acyl-containing group; and M is wherein n and m are independently integers of 2-10; and x is 0 or 1.

2. Chelating resin composition according to claim 1, is characterized in that, The base resin P is selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin polymer, polyacrylic resin and silicon-based resin.

3. The chelating resin composition according to claim 1 or 2, characterized in that, The nitrogen-containing heterocyclic groups R1 and R2 are each independently selected from pyridine groups, imidazole groups, benzimidazole groups, pyrazole groups, quinoline groups, pyrazine groups, triazine groups and triazole groups. Preferably, the nitrogen-containing heterocyclic groups R1 and R2 are each independently selected from the following groups:

4. The chelate resin composition according to any one of claims 1 to 3, characterized in that R3 is -(CO)R4 or -CH2(CO)R4, wherein R4 is a straight chain or branched alkyl group having a carbon chain number of 1-5, -N-(R5)2 or a nitrogen-containing heterocyclic group as defined for R1 or R2, wherein R5 is a straight chain or branched alkyl group having a carbon chain number of 1-5.

5. The chelate resin composition according to any one of claims 1 to 4, characterized in that The chelating resin of formula (I) has a structure selected from the following: and / or The chelating resin of formula (II) has a structure selected from the following: Wherein P is independently selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin polymer, polyacrylic resin and silicon-based resin.

6. The chelate resin composition according to any one of claims 1 to 5, characterized in that Include: or Include: or or or or or or or or or or Wherein P is independently selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin polymer, polyacrylic resin and silicon-based resin.

7. The chelating resin composition according to any one of claims 1 to 6, characterized in that The molar ratio of the chelating resin of formula (I) to the chelating resin of formula (II) is 0.7-19:1, more preferably, 1-5:

1.

8. A method for preparing the chelating resin composition according to any one of claims 1 to 7, characterized in that: The resin having primary amino groups is subjected to substitution reaction with nitrogen-containing heterocyclic chlorides R1Cl, R2Cl and acyl chlorides R3Cl in sequence, wherein R1, R2 and R3 are as described in claim 1 for formulas (I) and (II).

9. The method according to claim 8, characterized in that The chelating resin composition is prepared by the following steps: SS1: A resin containing a primary amino group is subjected to a substitution reaction with a nitrogen-containing heterocyclic chloride R1Cl in an alkaline solution under heating conditions to obtain a compound of formula (1): SS2: subjecting the intermediate compound of formula (1) to a substitution reaction with a nitrogen-containing heterocyclic chloride R2Cl under the same conditions as in step SS1 to obtain a mixture comprising a compound of formula (1) and a compound of formula (2): SS3: Make the mixture of the compound comprising the compound of formula (1) and the compound of formula (2) and contain the acyl chloride R3Cl generation substitution reaction, obtain the composition comprising the chelating resin of formula (I) and the chelating resin of formula (II): in: M is x is 0 or 1; P, n, m, R1-R3 are as defined in claims 1-8.

10. The method according to claim 9, characterized in that The resin containing primary amino groups is selected from the group consisting of polystyrene resin containing primary amino groups, modified phenolic resin containing primary amino groups, polyacrylic acid resin containing primary amino groups, and silicon-based resin containing primary amino groups.

11. The method according to claim 9 or 10, characterized in that: The molar ratio of the resin containing primary amino groups to the nitrogen-containing heterocyclic chlorides R1Cl and R2Cl to the acyl chloride R3Cl is 1:1-1.9:0.1-1.5, preferably 1:1-1.9:0.5-1.

5.

12. The method according to any one of claims 9 to 11, characterized in that In step SS1, the base contained in the alkaline solution is 1-3 times the equivalent of the nitrogen-containing heterocyclic chloride R1Cl, the solvent of the alkaline solution is 2-50 times the mass of the nitrogen-containing heterocyclic chloride R1Cl, the heating temperature is 40-120° C., and the reaction time is 2-36 hours.

13. The method according to any one of claims 9 to 12, characterized in that In step SS2, the alkaline compound contained in the alkaline solution is 1-3 times the equivalent of the nitrogen-containing heterocyclic chloride R2Cl, the solvent of the alkaline solution is 2-50 times the mass of the nitrogen-containing heterocyclic chloride R1Cl, the heating temperature is 40-120° C., and the reaction time is 2-36 hours.

14. The method according to any one of claims 13, characterized in that The alkaline compound is selected from sodium carbonate, magnesium hydroxide, calcium oxide, magnesium oxide, calcium hydroxide, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, triethylamine and N,N-diisopropylethylamine, and / or, the solvent is selected from water, N,N-dimethylformamide, dimethyl sulfoxide, toluene, tetrahydrofuran, ethanol, acetonitrile and acetone.

15. The method according to any one of claims 9 to 14, characterized in that Step SS3 is performed at room temperature for 0.5-36 hours, preferably 2-8 hours.

16. The method according to any one of claims 9 to 15, characterized in that Step SS3 is carried out in a solvent, preferably, the solvent is selected from tetrahydrofuran, dichloromethane and dichloroethane.

17. Use of the chelate resin composition according to any one of claims 1 to 7 for adsorbing metals, preferably, the metal is one or more of copper, cobalt and nickel.

18. A method for recovering copper, nickel and cobalt, characterized in that: The chelate resin composition according to any one of claims 1 to 7 is used as an adsorbent.

19. The method according to claim 18, characterized in that The following steps are involved: S1: contacting the chelate resin composition according to any one of claims 1 to 7 with a copper-nickel-cobalt-containing solution for extraction, and then performing solid-liquid separation to obtain a copper-nickel-cobalt-loaded chelate resin composition and a raffinate; S2: stripping the copper-nickel-cobalt loaded chelating resin composition using an acid solution, and then performing solid-liquid separation to obtain a stripping chelating resin composition and a copper-nickel-cobalt stripping solution; and S3: Separation of copper, nickel and cobalt from copper, nickel and cobalt stripping solution

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