A method for recovering copper from a copper-containing feed solution having a pH of 0.1 to 2.5

Abstract

The application discloses a method for recovering copper from a copper-containing solution with a pH value of 0.1-2.5, which comprises the following steps: 1) using a solid-phase extraction agent to extract the solution to obtain a copper or copper-nickel loaded solid-phase extraction agent and a pH value of 2.5 or less raffinate; 2) sequentially washing and stripping the copper or copper-nickel loaded solid-phase extraction agent obtained in step 1) to obtain a copper or copper-nickel stripping solution and a post-stripping solid-phase extraction agent. Through the method, the copper or copper-nickel in the copper-containing solution can be extracted and recovered, and the separation effect of copper or copper-nickel from impurity elements such as iron is good.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrometallurgy and environmental protection, and particularly relates to a method for recovering copper from a copper-containing solution with a pH value of 0.1-2.5. BACKGROUND

[0002] Some copper-containing materials such as leaching solution of waste lithium batteries, raw ore, slag and chemical wastewater contain copper or copper-nickel, which may need to be removed as impurity elements.

[0003] The resin solid phase extraction method can make the atoms on the functional groups on the resin and the metal ions have a coordination reaction to form a stable structure of chelate, so as to selectively separate the metal ions in the solution. Compared with the traditional solvent extraction method, the resin solid phase extraction method has the characteristics of fast phase separation, simple operation and small pollution.

[0004] However, the existing resin solid phase extraction method cannot well extract and recover copper or copper-nickel, and the separation effect of copper or copper-nickel from iron and other elements is not ideal.

[0005] Therefore, it is necessary to develop a process method with good recovery effect of copper or copper-nickel. SUMMARY

[0006] In view of the deficiencies of the prior art, the purpose of the present application is to provide a method for recovering copper from a copper-containing solution with a pH value of 0.1-2.5, which has good extraction effect of copper or copper-nickel, can effectively remove copper or copper-nickel from the copper-containing solution, and has good separation effect from iron and other elements.

[0007] To achieve the above purpose, the present application provides the following technical scheme: a method for recovering copper from a copper-containing solution with a pH value of 0.1-2.5, comprising the following steps:

[0008] 1) using a solid phase extraction agent to extract the solution to obtain a copper or copper-nickel loaded solid phase extraction agent and a pH value ≤2.5 raffinate; and

[0009] 2) sequentially washing and stripping the copper or copper-nickel loaded solid phase extraction agent obtained in step 1) to obtain a copper or copper-nickel stripping solution and a solid phase extraction agent after stripping;

[0010] The solid phase extraction agent comprises a chelating resin of formula (I) and / or formula (II):

[0011] (I) (II)

[0012] wherein:

[0013] P is a base resin;

[0014] R1 and R2 are each independently a nitrogen-containing heterocyclic group.

[0015] R3is an acyl-containing group or hydrogen; and

[0016] M is ( ) x wherein n and m are independently integers from 2 to 10; and x is 0 or 1.

[0017] The base resin P is not particularly limited, and preferably, the base resin P is selected from the group consisting of polystyrene resins, styrene copolymers with divinylbenzene, phenol formaldehyde resin polymers, polyacrylic resins, and silicon-based resins. More preferably, the base resin P is selected from the group consisting of polystyrene resins and styrene copolymers with divinylbenzene.

[0018] In particular, n and m are independently 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0019] Preferably, the nitrogen-containing heterocyclic groups R1and R2are each independently selected from the group consisting of pyridine groups, imidazole groups, benzimidazole groups, pyrazole groups, quinoline groups, pyrazine groups, triazine groups, and triazole groups.

[0020] More particularly, the nitrogen-containing heterocyclic groups R1and R2are each independently selected from the group consisting of:

[0021] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,

[0022] Preferably, the nitrogen-containing heterocyclic groups R1and R2are each independently selected from the following groups:

[0023]

[0024] Preferably, the copper-containing feed solution comprises Cu 0.001-5 g / L, Fe 0.1-100 g / L, Ni ≤ 50 g / L, and optionally further comprises a combination of one or more of Co, Al, Cr, Cd, Zn, Mn, Ca, Mg, Na, K, P and Li.

[0025] Preferably, the extraction in step 1) is single-stage, or multi-stage extraction in series and / or in parallel, and the number of extraction stages is 1-10, preferably 2-7.

[0026] Preferably, the extraction flow rate is 1-25 Bv / h, preferably 1.5-10 Bv / h.

[0027] ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Preferably, the stripping agent used in step 2) is any one of inorganic acid solution, ammonia water, disodium EDTA or a combination of disodium EDTA and inorganic acid solution or ammonia water, wherein the inorganic acid solution includes hydrochloric acid and / or sulfuric acid, the concentration of the sulfuric acid is 1-6 mol / L, preferably 2-3 mol / L; the concentration of the ammonia water is 1-6 mol / L, preferably 2-4 mol / L; and the concentration of the disodium EDTA is 0.05-0.3 mol / L, preferably 0.1-0.2 mol / L.

[0028] Preferably, the stripping flow rate is 0.5-5 Bv / h, preferably 0.5-3 Bv / h.

[0029] Preferably, the washing stage is 1-10 stages, preferably 2-7 stages.

[0030] Preferably, the washing flow rate is 1-25 Bv / h, preferably 2-10 Bv / h.

[0031] Preferably, the pH value of the washing liquid used in the washing is 0.1-7, preferably 0.5-2, more preferably 0.8-1.

[0032] In the present application, the washing liquid with a pH value of 0.8-1 is not particularly limited, and is preferably a hydrochloric acid and / or sulfuric acid solution.

[0033] Preferably, the solid phase extraction agent after the stripping in step 2) is recycled after regeneration, and preferably, the regeneration is controlled to generate water with a pH value of 0.2-3, further preferably 0.5-2.5.

[0034] In the present application, the regenerant used in the regeneration is not particularly limited, and is preferably water, such as any one or more of pure water, soft water, tap water.

[0035] In the present application, the copper stripping solution can be directly or concentrated to prepare metallic copper by electrodeposition or to prepare sponge copper by adding iron powder.

[0036] Compared with the prior art, the present application provides a method for recovering copper from a copper-containing solution with a pH value of 0.1-2.5, which has the following beneficial effects:

[0037] 1. The method provided by the present application has good extraction and recovery effect on copper or copper-nickel, and can effectively separate copper or copper-nickel from other metal ions such as iron. In addition, the chelating resin used can be recycled after regeneration, and the operation cost is low.

[0038] 2. In the method provided by the present application, the copper or copper-nickel content in the raffinate is ≤0.005 g / L, and the loss of iron is less than 2%. DETAILED DESCRIPTION

[0039] In the following, aspects of the present application will be described in more detail as well as further objects, features and advantages.

[0040] The present application provides a method for recovering copper from a copper-containing feed solution with a pH value of 0.1-2.5, comprising the following steps:

[0041] 1) extracting the feed solution with a solid phase extractant to obtain a copper or copper-nickel loaded solid phase extractant and a pH value ≤2.5 raffinate; and

[0042] 2) sequentially washing and stripping the copper or copper-nickel loaded solid phase extractant obtained in step 1) to obtain a copper or copper-nickel stripping solution and a post-stripping solid phase extractant;

[0043] wherein the solid phase extractant comprises a chelating resin of formula (I) and / or formula (II):

[0044] (I) (II)

[0045] wherein:

[0046] P is a base resin;

[0047] R1 and R2 are each independently a nitrogen-containing heterocyclic group;

[0048] R3 is an acyl-containing group or hydrogen; and

[0049] M is ( ) x wherein n and m are independently an integer of 2-10; and x is 0 or 1.

[0050] The chelating resin according to the present application has a good selectivity to metal ions, and can achieve good separation of copper or copper-nickel from metal ions such as iron in an acidic solution (pH ≤2.5); in addition, controlling the pH value of the feed solution to be ≤2.5 in the present application can control the extraction of iron by the chelating resin at a low level, thereby reducing the washing cost.

[0051] The base resin P is not particularly limited in the present application, and preferably, the base resin P is selected from polystyrene resins, copolymers of styrene and divinylbenzene, phenolic resin polymers, polyacrylic acid resins and silicon-based resins. More preferably, the base resin P is selected from polystyrene resins and copolymers of styrene and divinylbenzene.

[0052] Specifically, n and m are independently 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0053] Preferably, the nitrogen-containing heterocyclic groups R1and R2are each independently selected from pyridine-based groups, imidazole-based groups, benzimidazole-based groups, pyrazole-based groups, quinoline-based groups, pyrazine-based groups, triazine-based groups and triazole-based groups.

[0054] More particularly, the nitrogen-containing heterocyclic groups R1and R2are each independently selected from the following groups:

[0055] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0056] Preferably, the nitrogen-containing heterocyclic groups R1and R2are each independently selected from the following groups:

[0057] , , , , , , , , , , , , , , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 and .

[0058] Preferably, the acyl group is -(CO)R4or -CH2(CO)R4, wherein R4is a straight or branched alkyl group having a carbon chain number of 1 to 5, -N-(R5)2or a nitrogen containing heterocyclic group as defined for R1or R2, wherein R5is a straight or branched alkyl group having a carbon chain number of 1 to 5.

[0059] Preferably, the chelating resin of formula (I) has a structure selected from the group consisting of:

[0060] 、 、 、 、 、 、 、 、 、 、 、 、 .

[0061] Preferably, the chelating resin of formula (II) has a structure selected from the group consisting of:

[0062] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , 、 、 、 、 、 、 、 .

[0063] More preferably, the chelating resin comprises:

[0064] and , or and , or and , or , or , or , or and , or and , or , or and , or , or and ,

[0065] wherein P is independently selected from polystyrene resins, copolymers of styrene with divinylbenzene, phenol-formaldehyde resin polymers, polyacrylic resins and silicon-based resins.

[0066] In some embodiments of the present application, the pH value of the copper-containing feed solution can be divided into three ranges: greater than or equal to 0.1 and less than 0.8, greater than or equal to 0.8 and less than 1.5, and greater than or equal to 1.5 and less than or equal to 2.5.

[0067] Preferably, the copper-containing feed solution comprises Cu 0.001-5 g / L, Fe 0.1-100 g / L, Ni≤50 g / L, and optionally further comprises one or more of Co, Al, Cr, Cd, Zn, Mn, Ca, Mg, Na, K, P and Li.

[0068] Preferably, when the copper-containing feed solution further comprises P, the pH value of the raffinate in step 1) is controlled to be less than 0.8, more preferably less than 0.7.

[0069] Preferably, the extraction in step 1) is single-stage, or multi-stage extraction in series and / or in parallel, and the number of extraction stages is 1-10, more preferably 2-7.

[0070] Preferably, the flow rate of the extraction is 1-25 Bv / h, more preferably 1.5-10 Bv / h.

[0071] Preferably, the stripping agent used in step 2) is any one of inorganic acid solution, ammonia water, disodium EDTA or a combination of disodium EDTA with inorganic acid solution or ammonia water, wherein the inorganic acid solution includes hydrochloric acid and / or sulfuric acid, the concentration of the sulfuric acid is 1-6 mol / L, preferably 2-3 mol / L; the concentration of the ammonia water is 1-6 mol / L, preferably 2-4 mol / L; and the concentration of the disodium EDTA is 0.05-0.3 mol / L, preferably 0.1-0.2 mol / L.

[0072] Preferably, the stripping flow rate is 0.5-5 Bv / h, more preferably 0.5-3 Bv / h.

[0073] Preferably, the washing stage number in step 2) is 1-10, more preferably 2-7.

[0074] Preferably, the washing flow rate is 1-25 Bv / h, preferably 2-10 Bv / h.

[0075] Preferably, the pH value of the washing liquid used in the washing is 0.1-7, further preferably 0.5-2, more further preferably 0.8-1.

[0076] In the present application, the washing liquid with the pH value of 0.8-1 is not particularly limited, and is preferably a hydrochloric acid and / or sulfuric acid solution.

[0077] In the present application, controlling the pH value of the washing liquid to be 0.5-2, preferably 0.8-1, can more easily wash down the iron and reduce the number of washing, the amount of washing water and acid.

[0078] Advantageously, the solid phase extraction agent after the stripping in step 2) is recycled after regeneration, and preferably, the regeneration controls the pH value of the regenerated water to be 0.2-3, further preferably 0.5-2.5.

[0079] In the present application, the regenerant used in the regeneration is not particularly limited, and is preferably any one or more of water, such as pure water, soft water, tap water.

[0080] In the present application, the copper stripping solution can be directly or concentrated to prepare metallic copper by electrodeposition or to prepare sponge copper by adding iron powder.

[0081] The method provided by the present application has good extraction and recovery effect on copper or copper-nickel, can effectively separate copper or copper-nickel from other metal ions such as iron, is simple to operate and has low running cost.

[0082] Examples

[0083] The concept, specific structure and technical effects of the present application will be further described in combination with the embodiments, so that those skilled in the art can fully understand the purposes, features and effects of the present application. It is easy for those skilled in the art to understand that the embodiments herein are only for illustrative purposes, and the scope of the present application is not limited thereto.

[0084] Embodiment 1

[0085] The content of each element in the waste and old lithium iron phosphate battery leaching solution (pH value is 0.17) is shown in Table 1.

[0086] Table 1 Content of each element in waste and old lithium iron phosphate battery leaching solution

[0087] Element Cu Fe P Al Li Content (g / L) 0.3 67.5 40.2 0.3 0.34

[0088] The chelating resin (structural formula is and , wherein P is a polystyrene resin microsphere) is used to extract copper in the waste and old lithium iron phosphate battery leaching solution, the reaction equipment is an ion exchange resin column, the extraction stage is 3 stages, the control extraction flow rate is 2 Bv / h, after the extraction is completed, the copper-loaded chelating resin and the raffinate with a pH value of 0.1 are obtained. The copper-loaded chelating resin is washed with a sulfuric acid solution with a pH value of 1 to wash down the impurities such as iron, the control washing flow rate is 5 Bv / h, the washing stage is 3 stages, the washed copper-loaded chelating resin and the washing solution after washing are obtained; 2 mol / L sulfuric acid is used for stripping, the control stripping flow rate is 0.5 Bv / h, the copper stripping solution is obtained, and the chelating resin after stripping is washed with pure water until the effluent pH value is 0.5 and then recycled. The copper stripping solution is reduced by adding 1.2 times the molar ratio of iron powder to generate sponge copper.

[0089] In this embodiment, the copper content in the raffinate is 0.003 g / L, and the loss rates of iron and phosphorus are 0.4% and 0.5%, respectively.

[0090] Embodiment 2

[0091] The content of each element in the waste and old lithium iron phosphate battery material leaching solution (pH value is 0.6) is shown in Table 1.

[0092] Table 2 Content of main elements in waste and old lithium iron phosphate battery material leaching solution

[0093] Element Cu Fe P Al Li Content (g / L) 0.32 63.2 40.6 0.31 7.5

[0094] The chelating resin (structural formula is and In a process where P represents polystyrene resin and a copolymer of styrene and divinylbenzene, copper was extracted from the leachate of waste lithium iron phosphate battery materials. The reaction equipment consisted of an ion exchange resin column with three extraction stages, and the extraction flow rate was controlled at 2 Bv / h. After extraction, copper-loaded chelating resin and raffinate were obtained. The copper-loaded chelating resin was washed with a sulfuric acid solution with a pH of 1 to remove impurities such as iron. The washing flow rate was controlled at 3 Bv / h, and the washing stage was three stages, resulting in washed copper-loaded chelating resin and washed solution. Back-extraction was performed using 3 mol / L sulfuric acid, with the back-extraction flow rate controlled at 3 Bv / h, to obtain copper back-extraction solution. The chelating resin after back-extraction was washed with pure water until the pH of the effluent was 0.8, and then recycled.

[0095] In this embodiment, the copper content in the raffinate is 0.003 g / L, and the loss rates of iron and phosphorus are 0.5% and 0.55%, respectively.

[0096] Example 3

[0097] The elemental contents in the copper-containing solution (pH 1.5) are shown in Table 3:

[0098] Table 3. Element content in copper-containing liquid

[0099] Element Ni Co Mn Ca Mg Cr Cd Content (g / L) 0.21 0.014 0.204 0.146 0.277 49.30 0.0004 Element Fe Zn Cu Al Na Li Si Content (g / L) 25.44 0.004 0.013 0.034 0.006 0.0001 0.003

[0100] Chelating resin (structural formula is) is used and In this process, copper and nickel in a copper-containing feed solution were extracted using polystyrene resin microspheres (P being polystyrene resin microspheres). The reaction equipment consisted of an ion exchange resin column with three extraction stages. The extraction flow rate was controlled at 2 Bv / h. After extraction, copper-loaded chelating resin and a raffinate with a pH of 1.35 were obtained. The copper-loaded chelating resin was washed with a sulfuric acid solution at pH 2 to remove impurities such as iron. The washing flow rate was controlled at 3 Bv / h, with three washing stages. Washed copper-loaded chelating resin and a washing solution were obtained. Back-extraction was performed using 2.5 mol / L sulfuric acid at a flow rate of 1.5 Bv / h to obtain a copper back-extraction solution. The back-extracted chelating resin was washed with pure water until the effluent pH reached 2.0 and then recycled. The copper back-extraction solution was concentrated and then electrowinning to prepare electrowinning copper.

[0101] In this embodiment, the copper content in the raffinate is less than 0.001 g / L, the nickel content is 0.002 g / L, and the iron loss rate is 1.4%.

[0102] Example 4

[0103] The elemental contents in the copper-containing solution (pH 1.2) are shown in Table 4:

[0104] Table 4. Element content in copper-containing liquid

[0105] Element Ni Co Mn Ca Mg Cr Cd Content (g / L) 0.0385 0.0018 0.0432 0.0261 0.0176 0.0055 0.0015 Element Fe Ti Cu Al Zn Li Si Content (g / L) 74.3 0.6659 0.0026 0.1722 0.0025 0.2280 0.00246

[0106] The chelating resin (structural formula is The chelating resin (structural formula is

[0107] In the embodiment, the content of copper and nickel in the raffinate is less than 0.001 g / L, and the loss rate of iron is 0.8%.

[0108] Example 5

[0109] The embodiment refers to the process in the extraction example 2, and the difference from the extraction example 2 is that the pH value of the feed liquid is adjusted to 2.5.

[0110] In the embodiment, the content of copper and nickel in the raffinate is less than 0.001 g / L, and the loss rate of iron is 1.5%.

[0111] Example 6

[0112] The content of each element in the copper-containing feed liquid (pH value is 1.4) is shown in Table 5:

[0113] Table 5 Content of each element in the copper-containing feed liquid

[0114] Element Ni Co Mn Ca Mg Cr Cd Content (g / L) 2.0 0.0018 0.045 0.40 0.2 0.0055 0.0015 Element Fe Ti Cu Al Zn Li Si Content (g / L) 65.14 0.005 0.020 0.1673 0.020 0.001 0.0022

[0115] The chelating resin (structural formula is and The copper and nickel in the copper-containing solution are extracted by the chelating resin, the reaction equipment is an ion exchange resin column, the extraction stage is 7, the control extraction flow rate is 5 Bv / h, after the extraction is completed, the copper and nickel loaded chelating resin and the raffinate with a pH value of 1.2 are obtained. The copper and nickel loaded chelating resin is washed by using a sulfuric acid solution with a pH value of 1 to wash the impurities such as iron, the control washing flow rate is 4 Bv / h, the washing stage is 3, the copper loaded chelating resin after washing and the washing liquid after washing are obtained; the back extraction is performed by using 2 mol / L ammonia water, the control back extraction flow rate is 0.5 Bv / h, the copper and nickel back extraction liquid is obtained, and the chelating resin after back extraction is washed by using pure water until the pH value of the effluent is 1.0 and then is recycled.

[0116] In the example, the copper content in the raffinate is less than 0.001 g / L, the nickel content is 0.004 g / L, and the loss rate of iron is 1.0%.

[0117] Comparative Example 1

[0118] In the example, the process in the extraction example 1 is referred to, and the difference from the extraction example 1 is that the structural formula of the chelating resin is wherein P is a polystyrene resin microsphere.

[0119] In the example, the copper content in the raffinate is 0.01 g / L, and the loss rate of iron is 1.6%.

[0120] Comparative Example 2

[0121] In the example, the process in the extraction example 3 is referred to, and the difference from the extraction example 3 is that the structural formula of the chelating resin is wherein P is a polystyrene resin microsphere.

[0122] In the example, the nickel content in the raffinate is greater than 0.01 g / L, and the loss rate of iron is greater than 10%.

[0123] The above only describes the exemplary embodiments or examples of the present application, and is not intended to limit the present application. The present application can be variously changed and modified by those skilled in the art. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application is included in the scope of claims of the present application.

Claims

1. A method for recovering copper and nickel from a copper-nickel-containing feed solution with a pH value of 0.1-2.5, characterized in that, Includes the following steps: 1) The feed solution was extracted using a solid-phase extractant to obtain a copper-nickel loaded solid-phase extractant and a raffinate with a pH value ≤ 2.5; and 2) The copper-nickel loaded solid-phase extractant obtained in step 1) is washed and back-extracted sequentially to obtain a copper-nickel back-extractant and a back-extracted solid-phase extractant. The washing solution used in the washing process has a pH value of 0.8-2. The solid-phase extractant comprises chelating resins of formula (I) and formula (II): (AND) (II) in: P is a base resin; R1 and R2 are each independently nitrogen-containing heterocyclic groups; R3 is an acyl group; and M is ( ) x Where n and m are independent integers from 2 to 10; x is 0, The nitrogen-containing heterocyclic groups R1 and R2 are each independently selected from the following groups: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , R3 is -(CO)R4 or -CH2(CO)R4, where R4 is a straight-chain alkyl group with 1-5 carbon chains, a branched alkyl group with 1-5 carbon chains, or -N-(R5)2, where R5 is a straight-chain or branched alkyl group with 1-5 carbon chains.

2. The method according to claim 1, characterized in that, The base resin P is selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin polymer, polyacrylic acid resin or silicone resin.

3. The method according to claim 1, 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, styrene-based copolymers with divinylbenzene, phenolic resin polymers, polyacrylic resins, or silicone resins.

4. The method according to claim 3, characterized in that, The extractant comprises: and ,or and ,or and ,or and .

5. The method according to claim 1, characterized in that, The copper-nickel molten material contains Cu 0.001-5 g / L, Fe 0.1-100 g / L, Ni≤50 g / L, and also contains one or more of the following elements: Co, Al, Cr, Cd, Zn, Mn, Ca, Mg, Na, K, P, and Li.

6. The method according to claim 1, characterized in that, Step 1) The extraction is a single-stage extraction, or a multi-stage series extraction, or a multi-stage parallel extraction, or a combination of multi-stage series and parallel extraction, and the number of extraction stages is 1-10. And / or, the extraction flow rate is 1-25 Bv / h.

7. The method according to claim 6, characterized in that, The number of extraction stages is 2-7.

8. The method according to claim 6, characterized in that, The extraction flow rate is 1.5-10 Bv / h.

9. The method according to claim 1, characterized in that, Step 2) The back-extraction agent used is any one of inorganic acid solution, ammonia, and disodium EDTA, or a combination of disodium EDTA with inorganic acid solution and ammonia. The inorganic acid solution includes hydrochloric acid and / or sulfuric acid, with the sulfuric acid concentration being 1-6 mol / L; the ammonia concentration being 1-6 mol / L; and the disodium EDTA concentration being 0.05-0.3 mol / L. And / or, the back-extraction flow rate is 0.5-5 Bv / h.

10. The method according to claim 9, characterized in that, The sulfuric acid concentration is 2-3 mol / L.

11. The method according to claim 9, characterized in that, The concentration of the ammonia water is 2-4 mol / L.

12. The method according to claim 9, characterized in that, The concentration of disodium EDTA is 0.1-0.2 mol / L.

13. The method according to claim 9, characterized in that, The back-extraction flow rate is 0.5-3 Bv / h.

14. The method according to claim 1, characterized in that, Step 2) describes a washing level of 1-10. And / or, the washing flow rate is 1-25 Bv / h; And / or, the washing solution used in the washing process has a pH value of 0.8-1.

15. The method according to claim 14, characterized in that, Step 2) describes a washing level of 2-7.

16. The method according to claim 14, characterized in that, The washing flow rate is 2-10 Bv / h.

17. The method according to claim 14, characterized in that, The washing solution with a pH of 0.8-1 is a hydrochloric acid and / or sulfuric acid solution.

18. The method according to claim 1, characterized in that, The solid-phase extractant described in step 2) is recycled after regeneration.

19. The method according to claim 18, characterized in that, The regeneration process controls the pH value of the regenerated effluent to be 0.2-3.

20. The method according to claim 19, characterized in that, The pH value of the regenerated effluent is controlled to be 0.5-2.

5.

21. The method according to claim 18, characterized in that, The regenerant used in the regeneration process is water.

22. The method according to claim 21, characterized in that, The regenerant used in the regeneration process is any one or more of pure water, soft water, and tap water.

23. The method according to claim 1, characterized in that, Step 2) The copper back-extraction solution is used to prepare metallic copper directly or by electrowinning after concentration, or to prepare sponge copper by adding iron powder.

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