High-value utilization method of copper material pickle liquor

Abstract

The invention provides a high-valued utilization method of copper material pickle liquor, which comprises the following steps: introducing oxygen into the copper material pickle liquor, and heating to 30-50 DEG C for reaction; then adding a sodium hydroxide solution into the copper material pickle liquor, controlling the final pH value of the pickle liquor to be 4-5, generating precipitates, and carrying out solid-liquid separation to obtain first filtrate; adding a reducing agent which is 1.5-3 times of the theoretical dosage into the first filtrate for reaction, and after the reaction is finished, carrying out solid-liquid separation to obtain a solid and a second filtrate; washing and drying the solid to obtain superfine copper powder; adding quick lime or slaked lime into the second filtrate, and separating to obtain calcium sulfate and third filtrate; the reducing agent comprises sodium metabisulfite and / or potassium metabisulfite; according to the method, the copper material pickle liquor is subjected to impurity removal, then the copper ions in the copper material pickle liquor are reduced through the specific reducing agent, the superfine copper powder is obtained, the preparation technology process is simple, and agents used in the treatment process are small in toxicity and environmentally friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of metal extraction, and more specifically, to a method for highly valuable utilization of acid leaching solution of copper materials. Background Art

[0002] The acid leaching solution of copper materials is the mother liquor generated during the extraction of copper by wet processing of copper-containing materials, mainly from industries such as copper ore smelting, electronic waste recycling, and electroplating processes. At present, the main methods for extracting copper from the acid leaching solution of copper materials include electrolysis, displacement, and extraction methods, etc. Due to the relatively high liquid-solid ratio during the copper leaching process and the low copper ion concentration in the acid leaching solution, when using the electrolysis method for treatment, the current efficiency is low, and problems such as high energy consumption and high cost are faced. Although the displacement method has a fast reaction rate and a relatively high copper recovery rate, the consumption of displacement agents (such as iron, zinc) is large. Especially when the copper concentration in the solution is low, the economy declines, and the residual displacement agent ions (such as Fe2+) in the waste liquid after the reaction need to be precipitated for treatment, otherwise it may cause environmental pollution and the environmental protection cost is relatively high. When using the extraction method, multi-stage extraction and stripping operations are required, the process is complex, the equipment investment is large, the cost of the extractant is relatively high, and when the copper concentration is low, the extraction efficiency decreases significantly.

[0003] Directly preparing ultrafine copper powder from copper acid leaching solution by chemical methods can achieve short-process extraction and highly valuable utilization of copper. The liquid-phase reduction method is currently the most widely used method for preparing ultrafine copper powder from copper solutions. This method uses a reducing agent to reduce copper ions to prepare copper powder. For example, Kochnev et al. used hydrazine hydrate as a reducing agent and synthesized hexagonal and triangular nanosheets of copper at a lower reaction temperature with a stabilizer. Lai et al. synthesized copper particles with an average particle size of 80 nm and highly dispersed by using sodium hypophosphite under the condition of polyvinylpyrrolidone as a stabilizer. However, common reducing agents in the liquid-phase method such as hydrazine hydrate (N2H4·H2O), formaldehyde (HCHO), sodium hypophosphite (NaH2PO2), sodium borohydride (BH4Na), etc. are highly toxic, and the post-treatment of the waste generated is difficult, and the pollution is serious. Summary of the Invention

[0004] Based on the above problems existing in the prior art, the present invention provides a method for highly valuable utilization of acid leaching solution of copper materials. On the basis of adjusting the pH value of the solution to precipitate and remove other ions in the acid leaching solution, a specific reducing agent is used to reduce copper ions in the copper-containing solution to obtain ultrafine copper powder. The preparation process flow is simple, the reducing agent used has low toxicity, and the waste liquid generated after the reaction can be recycled, which is environmentally friendly.

[0005] In order to achieve the above object, the technical solution of the present invention is as follows:

[0006] A method for highly valuable utilization of acid leaching solution of copper materials, comprising the following steps:

[0007] S1. Introduce oxygen into the acid leaching solution of copper materials, and raise the temperature to 30 - 50 °C for reaction;

[0008] S2. After the reaction is completed, add sodium hydroxide solution to the acid leaching solution of copper materials, control the final pH of the acid leaching solution to be 4 - 5. Wait until the precipitation no longer increases, then perform solid-liquid separation to obtain the first filtrate;

[0009] S3. Add a reducing agent with a theoretical dosage of 1.5 - 3 times to the filtrate for reaction. After the reaction is completed, perform solid-liquid separation to obtain a solid and a second filtrate; Wash and dry the solid to obtain ultrafine copper powder;

[0010] S4. Add quicklime or slaked lime to the second filtrate. After the reaction is completed, perform solid-liquid separation to obtain calcium sulfate and a third filtrate. The calcium sulfate can be used as building materials, and the third filtrate is recycled and used in the precipitation process of step S2;

[0011] The reducing agent includes sodium metabisulfite and / or potassium metabisulfite.

[0012] In some embodiments, the concentrations of various ions in the acid leaching solution of copper materials are as follows: Cu 2+ : 0.5 - 2.0 g / L, Fe 2+ : 0.1 - 1.0 g / L, Fe 3+ : 0.05 - 0.5 g / L, Zn 2+ : 0.1 - 0.5 g / L, Al 3+ : 0.1 - 0.5 g / L, Cu + : 0.05 - 0.5 g / L, Mn 2+ : 0.01 - 0.1 g / L, Ca 2+ : 0 - 0.1 g / L.

[0013] The technical solution of the present invention has the following specific reaction principles:

[0014] In step S1, after introducing oxygen and raising the temperature for reaction, Fe 2+ , Cu + and Mn 2+ in the acid leaching solution of copper materials undergo oxidation reactions to respectively generate Fe 3+ , Cu 2+ and MnO2;

[0015] In step S2, add sodium hydroxide and control the final pH of the solution to be 4 - 5. Fe 3+ and Al 3+ respectively react with OH - to generate precipitates Fe(OH)3 and Al(OH)3, effectively removing Fe 2+ , Fe 3+ , Al 3+, Mn 2+ ;

[0016] In step S3, copper ions react with the reducing agent to generate copper and SO4 2- ;

[0017] In step S4, after adding quicklime or slaked lime, SO4 2- With Ca 2+ Produces CaSO4.

[0018] In some embodiments, in step S3, after adding the reducing agent, the stirring rate is 100-800 rpm; preferably, 200-600 rpm.

[0019] In some embodiments, in step S3, after the reducing agent is added, the reaction is carried out with the assistance of ultrasound, and the ultrasonic power is 100-400w.

[0020] In some embodiments, in step S3, the reaction temperature is 20-40°C.

[0021] In some embodiments, the concentration of the sodium hydroxide solution is 0.1-2 mol / L.

[0022] In some embodiments, in step S3, the reaction time is 0.5-4 h.

[0023] In some embodiments, in step S3, a dispersant is further added to the first filtrate, and the dispersant is at least one of polyethylene glycol, sodium dodecylbenzene sulfonate, and carboxymethyl cellulose.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The present invention removes impurity metal ions in the copper material acid leaching solution, and then uses sodium metabisulfite and / or potassium metabisulfite as a reducing agent, and adds the treated copper material acid leaching solution to react to obtain ultrafine copper powder, thereby realizing high-value utilization of copper in the acid leaching solution. The reducing agent used in the present invention has low toxicity, does not generate harmful gases during the reaction, and the waste liquid generated after the reaction can be recycled, with little pollution to the environment and green environmental protection; in addition, the method of the present invention has simple reaction conditions, can be carried out at a relatively low temperature, and has a simple process flow, low equipment requirements, and is easy to operate, and is suitable for batch processing of low-concentration copper ions in the copper material acid leaching solution that does not contain precious metals. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is a process flow chart of an embodiment of the present invention;

[0027] Figure 2 This is a particle size analysis diagram of the copper powder obtained in Example 1;

[0028] Figure 3 SEM image of the copper powder obtained in Example 1;

[0029] Figure 4 Particle size analysis chart of the copper powder obtained in Example 2;

[0030] Figure 5 SEM image of the copper powder obtained in Example 2;

[0031] Figure 6 SEM image of the copper powder obtained in Example 3; Figure 7 SEM image of the copper powder obtained in Example 4. Detailed implementation manners

[0032] A lot of specific details are set forth in the following description in order to provide a thorough understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific implementations disclosed below.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this invention belongs. The terms used in the description of the present invention herein are for the purpose of describing specific embodiments only and are not intended to limit the present invention.

[0034] Example 1

[0035] The acid leaching solution of copper materials used in this example is the mother liquor after copper extraction by acid leaching from a certain copper mine in Yunnan. The metal element composition and content are as follows:

[0036] Ion <![CDATA[Cu 2+ / Cu + > <![CDATA[Fe 2+ / Fe 3+ > <![CDATA[Zn 2+ > <![CDATA[Al 3+ > <![CDATA[Mn 2+ > Content (g / L) 1.9 0.4 0.3 0.3 0.08

[0037] As Figure 1 shown, a method for the high-value utilization of an acid leaching solution of copper materials includes the following steps:

[0038] S1. Take 1000 mL of the acid leaching solution of copper materials, introduce oxygen into the acid leaching solution of copper materials, and raise the temperature to 30 °C for reaction;

[0039] S2. After the reaction is completed, add a sodium hydroxide solution with a concentration of 0.5 mol / L dropwise to the acid leaching solution of copper materials, control the final pH to 4.5, wait until the precipitation no longer increases, perform solid-liquid separation, and obtain a first filtrate;

[0040] S3. Add 1 g of polyethylene glycol - 6000 to the first filtrate. After stirring evenly, add 11.4 g of sodium metabisulfite and carry out a reduction reaction at room temperature (25 ± 1 °C) with stirring for 2 h at a stirring rate of 400 rpm. After the reaction is completed, perform solid - liquid separation to obtain a solid and a second filtrate. Wash the solid with water until it is neutral, and then dry it under vacuum at 40 °C to obtain ultrafine copper powder.

[0041] S4. Add slaked lime to the second filtrate obtained in step S3 for reaction. After the reaction is completed, perform solid - liquid separation to obtain calcium sulfate precipitate and a third filtrate. The calcium sulfate can be used as a building material, and the third filtrate can be directly recycled after adding a higher concentration of sodium hydroxide for the precipitation to remove impurity metal ions.

[0042] After testing, the particle size distribution results of the copper powder obtained in this example are as Figure 2 shown, and the SEM image is as Figure 3 shown; as Figure 2 and Figure 3 , the average particle size of the copper powder obtained in this example is 480 nm.

[0043] Example 2

[0044] The acid - leaching solution of copper materials in this example is the same as that in Example 1, and its treatment method includes the following steps:

[0045] S1. Take 1000 mL of the acid - leaching solution of copper materials, introduce oxygen into the acid - leaching solution of copper materials, and raise the temperature to 30 °C for reaction.

[0046] S2. After the reaction is completed, add a sodium hydroxide solution with a concentration of 0.5 mol / L dropwise to the acid - leaching solution of copper materials, control the final pH to 5, and wait until the precipitation no longer increases. Then perform solid - liquid separation to obtain a first filtrate.

[0047] S3. Add 1 g of polyethylene glycol - 6000 to the first filtrate. After stirring evenly, add 11.4 g of sodium metabisulfite, raise the temperature to 35 °C and stir for a reduction reaction for 3 h at a stirring rate of 400 rpm. After the reaction is completed, perform solid - liquid separation to obtain a solid and a second filtrate. Wash the solid with water until it is neutral, and then dry it under vacuum at 40 °C to obtain ultrafine copper powder.

[0048] S4. Add slaked lime to the second filtrate obtained in step S3 for reaction. After the reaction is completed, perform solid - liquid separation to obtain calcium sulfate precipitate and a third filtrate. The calcium sulfate can be used as a building material, and the third filtrate can be directly recycled after adding a higher concentration of sodium hydroxide for the precipitation to remove impurity metal ions.

[0049] After testing, the particle size distribution results of the copper powder obtained in this example are as Figure 4 shown, and the SEM image is as Figure 5 shown; as Figure 4and Figure 5 The average particle size of the obtained copper powder is 565 nm.

[0050] Example 3

[0051] The acid leaching solution of copper materials in this example is the same as that in Example 1, and its treatment method includes the following steps:

[0052] S1. Take 1000 mL of the acid leaching solution of copper materials, introduce oxygen into the acid leaching solution of copper materials, and raise the temperature to 50 °C for reaction;

[0053] S2. After the reaction is completed, add a sodium hydroxide solution with a concentration of 0.5 mol / L to the acid leaching solution of copper materials, control the final pH to 5, wait until the precipitation no longer increases, perform solid-liquid separation to obtain the first filtrate;

[0054] S3. Add 1 g of polyethylene glycol-6000 to the first filtrate, stir evenly, then add 11.4 g of sodium metabisulfite, stir at room temperature (25 ± 1 °C) for a reduction reaction for 2.5 h, and the stirring rate is 400 rpm; after the reaction is completed, perform solid-liquid separation to obtain a solid and a second filtrate; wash the solid with water until it is neutral, and then dry it in vacuum at 40 °C to obtain ultrafine copper powder;

[0055] S4. Add slaked lime to the second filtrate obtained in step S3 for reaction. After the reaction is completed, perform solid-liquid separation to obtain calcium sulfate precipitate and a third filtrate; the calcium sulfate can be used as a building material, and the third filtrate can be directly recycled after adding a higher concentration of sodium hydroxide to remove impurity metal ions by precipitation.

[0056] After testing, the SEM image of the copper powder obtained in this example is as Figure 6 shown, and the average particle size is 580 nm.

[0057] Example 4

[0058] The acid leaching solution of copper materials in this example is the same as that in Example 1, and its treatment method includes the following steps:

[0059] S1. Take 1000 mL of the acid leaching solution of copper materials, introduce oxygen into the acid leaching solution of copper materials, and raise the temperature to 30 °C for reaction;

[0060] S2. After the reaction is completed, add a sodium hydroxide solution with a concentration of 0.5 mol / L to the acid leaching solution of copper materials, control the final pH to 5, wait until the precipitation no longer increases, perform solid-liquid separation to obtain the first filtrate;

[0061] S3. Add 1 g of polyethylene glycol - 6000 to the first filtrate. After stirring evenly, add 11.4 g of sodium metabisulfite and stir at room temperature (25 ± 1 °C) for 2 h for the reduction reaction at a stirring rate of 400 rpm. After the reaction is completed, perform solid - liquid separation to obtain a solid and a second filtrate. Wash the solid with water until it is neutral, and then dry it under vacuum at 40 °C to obtain ultrafine copper powder.

[0062] S4. Add slaked lime to the second filtrate obtained in step S3 for reaction. After the reaction is completed, perform solid - liquid separation to obtain calcium sulfate precipitate and a third filtrate. The calcium sulfate can be used as a building material, and the third filtrate can be directly recycled after adding a higher - concentration sodium hydroxide for removing impurity metal ions by precipitation.

[0063] After testing, the SEM image of the copper powder obtained in this example is as Figure 7 shown, with an average particle size of 560 nm.

[0064] Example 5

[0065] The copper material acid - leaching solution used in this example is the mother liquor after acid - leaching and copper extraction from a certain copper mine in Tibet. Its metal element composition and content are as follows:

[0066] Ion <![CDATA[Copper 2+ / Copper + > <![CDATA[Fe 2+ / Fe 3+ > <![CDATA[Zn 2+ > <![CDATA[Al 3+ > <![CDATA[Mn 2+ > <![CDATA[Ca 2+ > Content (g / L) 1.6 1.0 0.3 0.2 0.09 0.1

[0067] A method for the high - value utilization of a copper material acid - leaching solution, comprising the following steps:

[0068] S1. Take 1000 mL of the copper material acid - leaching solution, introduce oxygen into the copper material acid - leaching solution, and raise the temperature to 30 °C for reaction.

[0069] S2. After the reaction is completed, add a sodium hydroxide solution with a concentration of 0.5 mol / L to the copper material acid - leaching solution, control the final pH to 4.5, and wait until the precipitation no longer increases. Then perform solid - liquid separation to obtain a first filtrate.

[0070] S3. Add 1 g of polyethylene glycol - 6000 to the first filtrate. After stirring evenly, add 7.6 g of sodium metabisulfite and stir at room temperature (25 ± 1 °C) for 2 h for the reduction reaction at a stirring rate of 600 rpm. After the reaction is completed, perform solid - liquid separation to obtain a solid and a second filtrate. Wash the solid with water until it is neutral, and then dry it under vacuum at 40 °C to obtain ultrafine copper powder.

[0071] S4. Add slaked lime to the second filtrate obtained in step S3 for reaction. After the reaction is completed, perform solid - liquid separation to obtain calcium sulfate precipitate and a third filtrate. The calcium sulfate can be used as a building material, and the third filtrate can be directly recycled after adding a higher - concentration sodium hydroxide for removing impurity metal ions by precipitation.

[0072] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0073] The above-described embodiments only express several implementation manners of the present invention. The description is relatively specific and detailed, but it cannot be understood as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A method for the high-value utilization of acid leaching solution of copper materials, characterized in that It includes the following steps: S1. Introduce oxygen into the acid leaching solution of copper materials, and raise the temperature to 30 - 50 °C for reaction; S2. After the reaction is completed, add sodium hydroxide solution to the acid leaching solution of copper materials, control the final pH of the acid leaching solution to be 4 - 5. Wait until the precipitation no longer increases, then perform solid-liquid separation to obtain the first filtrate; S3. Add a reducing agent with a theoretical dosage of 1.5 - 3 times to the first filtrate for reaction. After the reaction ends, perform solid-liquid separation to obtain a solid and a second filtrate; Wash and dry the solid to obtain ultrafine copper powder; S4. Add quicklime or slaked lime to the second filtrate for reaction. After the reaction is completed, perform solid-liquid separation to obtain calcium sulfate and a third filtrate. The calcium sulfate can be used as building materials, and the third filtrate is recycled and used in the precipitation process of step S2; The reducing agent includes sodium metabisulfite and / or potassium metabisulfite.

2. The method for highly valuable utilization of the acid leaching solution of copper materials according to claim 1, wherein The concentrations of various ions in the acid leaching solution of the copper material are as follows: Cu 2+ : 0.5 - 2.0 g / L, Fe 2+ : 0.1 - 1.0 g / L, Fe 3+ : 0.05 - 0.5 g / L, Zn 2+ : 0.1 - 0.5 g / L, Al 3+ : 0.1 - 0.5 g / L, Cu + : 0.05 - 0.5 g / L, Mn 2+ : 0.01 - 0.1 g / L, Ca 2+ : 0 - 0.1 g / L.

3. The high-value utilization method of the acid leaching solution of copper materials according to claim 1, characterized in that, In step S3, after adding the reducing agent, stir for reaction, and the stirring rate is 100 - 800 rpm.

4. The method for high-value utilization of the acid leaching solution of copper materials according to claim 1, characterized in that, In step S3, after adding the reducing agent, perform the reaction under ultrasonic assistance, and the ultrasonic power is 100 - 400 W.

5. The method for highly valuable utilization of the acid leaching solution of copper materials according to claim 1, characterized in that, In step S3, the reaction temperature is 20 - 40 °C.

6. The method for high-value utilization of the acid leaching solution of copper materials according to claim 1, characterized in that The concentration of the sodium hydroxide solution is 0.1 - 2 mol / L.

7. The method for high-value utilization of the acid leaching solution of copper materials according to claim 1, characterized in that, In step S3, the reaction time is 0.5 - 4 h.

8. The green method for preparing ultrafine copper powder from a copper-containing solution according to any one of claims 1-7, characterized in that, A dispersant is also added to the first filtrate, and the dispersant is at least one of polyethylene glycol, sodium dodecylbenzenesulfonate, and carboxymethyl cellulose.

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