Environment-friendly preparation process of high-purity heavy basic cupric carbonate

Abstract

The invention relates to the technical field of production of basic cupric carbonate, in particular to an environment-friendly preparation process of high-purity heavy basic cupric carbonate. Comprising the following steps: S1, fully and uniformly mixing the acidic copper-containing etching waste liquid and an ethanol water solution in stirring equipment to obtain diluted waste liquid; s2, adding a composite precipitator and an auxiliary agent into the obtained diluted waste liquid, and carrying out precipitation treatment at 22-26 DEG C until the pH value is 6.5-7.5; wherein the addition amount of the composite precipitant is 40-60% of the mass of the diluted waste liquid, and the addition amount of the auxiliary agent is 8-12% of the mass of the diluted waste liquid; s3, washing the obtained precipitation product with deionized water for 2-4 times, and drying to obtain a high-purity heavy basic cupric carbonate finished product; the high-purity heavy basic cupric carbonate prepared by the method disclosed by the invention not only has better purity, but also can realize recycling of the acidic copper-containing etching waste liquid.

Description

Technical Field

[0001] The invention relates to the technical field of basic copper carbonate production, and in particular to an environmentally friendly preparation process for high-purity heavy basic copper carbonate. Background Art

[0002] Basic copper carbonate, also known as copper rust or verdigris, is a substance produced by the reaction of copper with substances such as oxygen, carbon dioxide, and water vapor in the air. When heated in air, it decomposes into copper oxide, water, and carbon dioxide, which dissolves in acid to form the corresponding copper salt. Basic copper carbonate has a wide range of uses, including in the manufacture of flares, fireworks, paints, fungicides, wood preservatives, and feed additives. Ultrafine processing greatly improves and enhances the application performance of basic copper carbonate, and nanomaterials of different particle sizes exhibit different optical, electrical, and magnetic effects. Common methods for preparing basic copper carbonate include the ammonia method, the copper nitrate method, and the copper sulfate method. The copper sulfate method has been the most studied method both domestically and internationally, but it has a high production cost.

[0003] Acid etching is a predominant chemical processing method in the printed circuit board (PCB) industry, generating large quantities of waste acidic etching solutions. This acidic etching solution primarily contains copper, hydrochloric acid, sulfuric acid, and an oxidant. Left untreated, this can lead to the waste of valuable copper and serious environmental pollution. Currently, several methods exist for treating this acidic etching solution, including the sponge copper method, electrolysis, extraction, and neutralization, but each presents various challenges. The sponge copper method involves adding iron powder to the waste acid and copper ions in the acidic etching solution under acidic conditions. This reaction causes a displacement reaction between the iron powder and the copper, oxidizing the iron to form ferrous iron ions. Filtering through a filter press yields the sponge copper and ferrous chloride solution. This method uses the iron to consume the oxidant and acid, preventing the reuse of the hydrochloric acid and oxidant, and requires the addition of numerous chemicals to the production line. The electrolysis method primarily uses an electric current to electrolyze acidic etching wastewater through a diaphragm. Copper is electrolyzed at the cathode and a large amount of chlorine gas is generated at the anode. This chlorine gas is then dissolved and absorbed into the production line. The electrolysis anode uses an insoluble noble metal anode plate, which poses a significant risk. The electrolysis method is costly, energy-intensive, and wastewater growth is also a concern. The extraction method, which extracts copper using an extractant and then electrolyzes the copper, primarily requires a large amount of alkaline material to neutralize the free acid. This results in low extraction efficiency, increased wastewater volume, and significant electrical energy consumption. The neutralization method uses an alkaline material to neutralize the acidic etching wastewater, producing copper hydroxide, which is then dried and dehydrated to form copper oxide. However, the neutralized wastewater cannot be reused and requires secondary treatment. Therefore, effectively utilizing acidic copper-containing etching wastewater to produce basic copper carbonate has become a critical issue facing my country's basic copper carbonate production industry.

[0004] Therefore, the present invention provides an environmentally friendly preparation process for high-purity heavy basic copper carbonate to solve the above-mentioned related technical problems! Summary of the Invention

[0005] The present invention aims to provide an environmentally friendly preparation process for high-purity heavy basic copper carbonate. The prepared high-purity heavy basic copper carbonate not only has good purity and can realize the reuse of acidic copper-containing etching waste liquid, but also meets the requirements of "Industrial Basic Copper Carbonate" HG / T4825-2015, effectively ensuring its quality.

[0006] To achieve the above object, the present invention provides the following technical solutions: The present invention provides an environmentally friendly preparation process for high-purity heavy basic copper carbonate, comprising the following steps: S1, placing the acidic copper-containing etching waste liquid and the ethanol aqueous solution in a stirring device and fully mixing them to obtain a diluted waste liquid; S2. Add a composite precipitant and an auxiliary agent to the obtained diluted waste liquid, and perform precipitation treatment at 22-26° C. until the pH value is 6.5-7.5; The addition amount of the composite precipitant is 40-60% of the mass of the diluted waste liquid, and the addition amount of the auxiliary agent is 8-12% of the mass of the diluted waste liquid; S3. Wash the obtained precipitated product with deionized water 2 to 4 times and dry it to obtain a high-purity heavy basic copper carbonate product.

[0007] Furthermore, in step S1, the ethanol aqueous solution is prepared by mixing anhydrous ethanol and distilled water in a mass ratio of 0.12 to 0.16:1.

[0008] Furthermore, in the step S1, the mixing mass ratio of the acidic copper-containing etching waste liquid and the ethanol aqueous solution in the diluted waste liquid is 1:3.2-3.6.

[0009] Furthermore, in step S2, the composite precipitant is prepared by mixing sodium carbonate and sodium bicarbonate in a mass ratio of 1:0.2 to 0.4.

[0010] Furthermore, in step S2, the preparation process of the auxiliary agent is as follows: The first solution, the second solution and the third solution are placed in a stirring device at a mass ratio of 1:1.2-1.4:0.8-1.2, and treated in a water bath at a temperature of 70-75°C for 50-60 minutes; After filtration, the filter cake is washed with deionized water for 2 to 4 times, dried in a drying oven at 40 to 50° C. for 8 to 10 hours, and then crushed in a crushing device to 100 to 200 meshes to obtain an additive.

[0011] Furthermore, the preparation process of the first solution is as follows: Polyethylene glycol is placed in an appropriate amount of deionized water at a mass ratio of 0.02 to 0.12:1, treated at 95 to 98° C. and 120 to 140 r / min for 30 to 40 minutes, and passed through a 200-mesh sieve. The obtained filtrate is the first solution.

[0012] Furthermore, the preparation process of the second solution is as follows: Perfluoro(2-ethoxyethane)sulfonic acid is placed in an appropriate amount of N,N-dimethylacetamide at a mass ratio of 0.08-0.18:1, and stirred at 90-120 rpm and 30-36° C. for 20-30 minutes to obtain a second solution.

[0013] Furthermore, the preparation process of the third solution is as follows: Polyvinyl alcohol is placed in an appropriate amount of deionized water at a mass ratio of 0.03 to 0.13:1, and stirred at 90 to 120 r / min and 95 to 98° C. for 20 to 30 minutes to obtain a third solution.

[0014] Furthermore, in step S3, the drying temperature is 70-80° C. and the drying time is 30-40 minutes.

[0015] Furthermore, in the step S3, the dried product is placed in a pulverizing device for pulverization, and passed through a 100-120 mesh sieve.

[0016] Compared with the prior art, the present invention has the following beneficial effects: In the present invention, acidic copper-containing etching waste liquid and ethanol aqueous solution are fully mixed, and then a composite precipitant and an auxiliary agent are added for precipitation treatment, and the obtained precipitated product is washed with deionized water and dried to obtain a high-purity heavy basic copper carbonate finished product. The high-purity heavy basic copper carbonate prepared by the present invention not only has good purity and can realize the reuse of acidic copper-containing etching waste liquid, but also meets the requirements of "Industrial Basic Copper Carbonate" HG / T4825-2015, effectively ensuring its quality and quality. The environmentally friendly preparation process of high-purity heavy basic copper carbonate provided by the present invention has a broader market prospect and is more suitable for promotion. DETAILED DESCRIPTION

[0017] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0018] Example 1: This example provides an environmentally friendly preparation process for high-purity heavy basic copper carbonate, comprising the following steps: S1. placing the acidic copper-containing etching waste liquid and the ethanol aqueous solution in a stirring device and fully mixing them to obtain a diluted waste liquid.

[0019] The ethanol aqueous solution is prepared by mixing anhydrous ethanol and distilled water in a mass ratio of 0.12:1.

[0020] The mixing mass ratio of the acidic copper-containing etching waste liquid and the ethanol aqueous solution in the diluted waste liquid is 1:3.6.

[0021] In this embodiment, it should be noted that the acidic copper-containing etching waste liquid has a density of 1.31 g / mL, a Cu2+ mass concentration of 117.5 g / L, a H+ concentration of 1.85 mol / L, and a Cl- mass concentration of 273.62 g / L.

[0022] S2. Add a composite precipitant and an auxiliary agent to the obtained diluted waste liquid, and carry out precipitation treatment at 22° C. until the pH value reaches 6.5.

[0023] The addition amount of the composite precipitant is 40% of the mass of the diluted waste liquid, and the addition amount of the auxiliary agent is 8% of the mass of the diluted waste liquid.

[0024] The composite precipitant is prepared by mixing sodium carbonate and sodium bicarbonate in a mass ratio of 1:0.2.

[0025] Furthermore, the preparation process of the auxiliary agent is as follows: The first solution, the second solution, and the third solution were placed in a stirring device at a mass ratio of 1:1.2:0.8 and treated in a water bath at 70°C for 50 minutes; After filtration, the filter cake was washed twice with deionized water, dried in a drying oven at 40° C. for 8 h, and then crushed in a crushing device to 100 mesh to obtain an additive.

[0026] The preparation process of the first solution is as follows: Polyethylene glycol was placed in an appropriate amount of deionized water at a mass ratio of 0.02:1, and treated at 95° C. and 120 r / min for 30 min. The solution was passed through a 200-mesh sieve, and the obtained filtrate was the first solution.

[0027] The preparation process of the second solution is as follows: Perfluoro(2-ethoxyethane)sulfonic acid was added to an appropriate amount of N,N-dimethylacetamide at a mass ratio of 0.08:1, and stirred at 90 rpm and 30° C. for 20 minutes to obtain a second solution.

[0028] The preparation process of the third solution is as follows: Polyvinyl alcohol was added to an appropriate amount of deionized water at a mass ratio of 0.03:1, and stirred at 90 rpm and 95° C. for 20 minutes to obtain a third solution.

[0029] S3. Wash the obtained precipitated product twice with deionized water and dry it to obtain a high-purity heavy basic copper carbonate product.

[0030] The drying temperature is 70°C and the drying time is 30 minutes.

[0031] In addition, the method further comprises placing the dried product in a pulverizing device for pulverization, and passing the pulverized product through a 100-mesh sieve.

[0032] Example 2: An environmentally friendly preparation process for high-purity heavy basic copper carbonate, comprising the following steps: S1. placing the acidic copper-containing etching waste liquid and the ethanol aqueous solution in a stirring device and fully mixing them to obtain a diluted waste liquid.

[0033] The ethanol aqueous solution is prepared by mixing anhydrous ethanol and distilled water in a mass ratio of 0.13:1.

[0034] The mixing mass ratio of the acidic copper-containing etching waste liquid and the ethanol aqueous solution in the diluted waste liquid is 1:3.3.

[0035] In this embodiment, it should be noted that the acidic copper-containing etching waste liquid has a density of 1.31 g / mL, a Cu2+ mass concentration of 117.5 g / L, a H+ concentration of 1.85 mol / L, and a Cl- mass concentration of 273.62 g / L.

[0036] S2. Add a composite precipitant and an auxiliary agent to the obtained diluted waste liquid, and carry out precipitation treatment at 23° C. until the pH value reaches 6.6.

[0037] The addition amount of the composite precipitant is 42% of the mass of the diluted waste liquid, and the addition amount of the auxiliary agent is 9% of the mass of the diluted waste liquid.

[0038] The composite precipitant is prepared by mixing sodium carbonate and sodium bicarbonate in a mass ratio of 1:0.3.

[0039] Furthermore, the preparation process of the auxiliary agent is as follows: The first solution, the second solution, and the third solution were placed in a stirring device at a mass ratio of 1:1.3:0.9 and treated in a water bath at 72°C for 52 minutes; After filtration, the filter cake was washed three times with deionized water, dried in a drying oven at 42° C. for 9 h, and then crushed in a crushing device to 120 mesh to obtain an additive.

[0040] The preparation process of the first solution is as follows: Polyethylene glycol was placed in an appropriate amount of deionized water at a mass ratio of 0.04:1, and treated at 96° C. and 1220 r / min for 32 min. The solution was passed through a 200-mesh sieve, and the obtained filtrate was the first solution.

[0041] The preparation process of the second solution is as follows: Perfluoro(2-ethoxyethane)sulfonic acid was added to an appropriate amount of N,N-dimethylacetamide at a mass ratio of 0.09:1, and stirred at 2 r / min and 32° C. for 22 min to obtain a second solution.

[0042] The preparation process of the third solution is as follows: Polyvinyl alcohol was added to an appropriate amount of deionized water at a mass ratio of 0.04:1, and stirred at 92 rpm and 96° C. for 22 minutes to obtain a third solution.

[0043] S3. Wash the obtained precipitated product with deionized water three times and dry it to obtain a high-purity heavy basic copper carbonate product.

[0044] The drying temperature was 72°C and the drying time was 32 minutes.

[0045] In addition, the method further comprises placing the dried product in a pulverizing device for pulverization, and passing the pulverized product through a 110-mesh sieve.

[0046] Example 3: An environmentally friendly preparation process for high-purity heavy basic copper carbonate, comprising the following steps: S1. placing the acidic copper-containing etching waste liquid and the ethanol aqueous solution in a stirring device and fully mixing them to obtain a diluted waste liquid.

[0047] The ethanol aqueous solution is prepared by mixing anhydrous ethanol and distilled water in a mass ratio of 0.14:1.

[0048] The mixing mass ratio of the acidic copper-containing etching waste liquid and the ethanol aqueous solution in the diluted waste liquid is 1:3.4.

[0049] In this embodiment, it should be noted that the acidic copper-containing etching waste liquid has a density of 1.31 g / mL, a Cu2+ mass concentration of 117.5 g / L, a H+ concentration of 1.85 mol / L, and a Cl- mass concentration of 273.62 g / L.

[0050] S2. Add a composite precipitant and an auxiliary agent to the obtained diluted waste liquid, and carry out precipitation treatment at 24° C. until the pH value reaches 7.0.

[0051] The addition amount of the composite precipitant is 50% of the mass of the diluted waste liquid, and the addition amount of the auxiliary agent is 10% of the mass of the diluted waste liquid.

[0052] The composite precipitant is prepared by mixing sodium carbonate and sodium bicarbonate in a mass ratio of 1:0.3.

[0053] Furthermore, the preparation process of the auxiliary agent is as follows: The first solution, the second solution, and the third solution were placed in a stirring device at a mass ratio of 1:1.3:1.0 and treated in a water bath at 72°C for 55 minutes; After filtration, the filter cake was washed three times with deionized water, dried in a drying oven at 45° C. for 9 h, and then crushed in a crushing device to 150 mesh to obtain an additive.

[0054] The preparation process of the first solution is as follows: Polyethylene glycol was placed in an appropriate amount of deionized water at a mass ratio of 0.07:1, and treated at 96° C. and 130 r / min for 35 min. The solution was passed through a 200-mesh sieve, and the obtained filtrate was the first solution.

[0055] The preparation process of the second solution is as follows: Perfluoro(2-ethoxyethane)sulfonic acid was added to an appropriate amount of N,N-dimethylacetamide at a mass ratio of 0.13:1, and stirred at 105 rpm and 33° C. for 25 minutes to obtain a second solution.

[0056] The preparation process of the third solution is as follows: Polyvinyl alcohol was added to an appropriate amount of deionized water at a mass ratio of 0.08:1, and stirred at 105 rpm and 96° C. for 25 minutes to obtain a third solution.

[0057] S3. Wash the obtained precipitated product with deionized water three times and dry it to obtain a high-purity heavy basic copper carbonate product.

[0058] The drying temperature is 75°C and the drying time is 35 minutes.

[0059] In addition, the method further comprises placing the dried product in a pulverizing device for pulverization, and passing the pulverized product through a 110-mesh sieve.

[0060] Example 4: An environmentally friendly preparation process for high-purity heavy basic copper carbonate, comprising the following steps: S1. placing the acidic copper-containing etching waste liquid and the ethanol aqueous solution in a stirring device and fully mixing them to obtain a diluted waste liquid.

[0061] The ethanol aqueous solution is prepared by mixing anhydrous ethanol and distilled water in a mass ratio of 0.15:1.

[0062] The mixing mass ratio of the acidic copper-containing etching waste liquid and the ethanol aqueous solution in the diluted waste liquid is 1:3.5.

[0063] In this embodiment, it should be noted that the acidic copper-containing etching waste liquid has a density of 1.31 g / mL, a Cu2+ mass concentration of 117.5 g / L, a H+ concentration of 1.85 mol / L, and a Cl- mass concentration of 273.62 g / L.

[0064] S2. Add a composite precipitant and an auxiliary agent to the obtained diluted waste liquid, and carry out precipitation treatment at 25° C. until the pH value reaches 7.2.

[0065] The addition amount of the composite precipitant is 55% of the mass of the diluted waste liquid, and the addition amount of the auxiliary agent is 11% of the mass of the diluted waste liquid.

[0066] The composite precipitant is prepared by mixing sodium carbonate and sodium bicarbonate in a mass ratio of 1:0.3.

[0067] Furthermore, the preparation process of the auxiliary agent is as follows: The first solution, the second solution, and the third solution were placed in a stirring device at a mass ratio of 1:1.3:1.1 and treated in a water bath at 74°C for 58 minutes; After filtration, the filter cake was washed three times with deionized water, dried in a drying oven at 45° C. for 9 h, and then crushed in a crushing device to 150 mesh to obtain an additive.

[0068] The preparation process of the first solution is as follows: Polyethylene glycol was placed in an appropriate amount of deionized water at a mass ratio of 0.1:1, and treated at 97°C and 135 rpm for 38 minutes. The solution was passed through a 200-mesh sieve, and the obtained filtrate was the first solution.

[0069] The preparation process of the second solution is as follows: Perfluoro(2-ethoxyethane)sulfonic acid was added to an appropriate amount of N,N-dimethylacetamide at a mass ratio of 0.16:1, and stirred at 110 r / min and 35° C. for 28 minutes to obtain a second solution.

[0070] The preparation process of the third solution is as follows: Polyvinyl alcohol was added to an appropriate amount of deionized water at a mass ratio of 0.11:1, and stirred at 105 rpm and 97° C. for 28 minutes to obtain a third solution.

[0071] S3. Wash the obtained precipitated product with deionized water three times and dry it to obtain a high-purity heavy basic copper carbonate product.

[0072] The drying temperature was 78°C and the drying time was 38 minutes.

[0073] In addition, the method further comprises placing the dried product in a pulverizing device for pulverization, and passing the pulverized product through a 110-mesh sieve.

[0074] Example 5: An environmentally friendly preparation process for high-purity heavy basic copper carbonate, comprising the following steps: S1. placing the acidic copper-containing etching waste liquid and the ethanol aqueous solution in a stirring device and fully mixing them to obtain a diluted waste liquid.

[0075] The ethanol aqueous solution is prepared by mixing anhydrous ethanol and distilled water in a mass ratio of 0.16:1.

[0076] The mixing mass ratio of the acidic copper-containing etching waste liquid and the ethanol aqueous solution in the diluted waste liquid is 1:3.6.

[0077] In this embodiment, it should be noted that the acidic copper-containing etching waste liquid has a density of 1.31 g / mL, a Cu2+ mass concentration of 117.5 g / L, a H+ concentration of 1.85 mol / L, and a Cl- mass concentration of 273.62 g / L.

[0078] S2. Add a composite precipitant and an auxiliary agent to the obtained diluted waste liquid, and carry out precipitation treatment at 26° C. until the pH value reaches 7.5.

[0079] The amount of the composite precipitant added is 60% of the mass of the diluted waste liquid, and the amount of the auxiliary agent added is 12% of the mass of the diluted waste liquid.

[0080] The composite precipitant is prepared by mixing sodium carbonate and sodium bicarbonate in a mass ratio of 1:0.4.

[0081] Furthermore, the preparation process of the auxiliary agent is as follows: The first solution, the second solution, and the third solution were placed in a stirring device at a mass ratio of 1:1.4:1.2 and treated in a water bath at 75°C for 60 minutes; After filtration, the filter cake was washed four times with deionized water, dried in a drying oven at 50° C. for 10 h, and then crushed in a crushing device to 200 mesh to obtain an additive.

[0082] The preparation process of the first solution is as follows: Polyethylene glycol was placed in an appropriate amount of deionized water at a mass ratio of 0.12:1, and treated at 98° C. and 140 r / min for 40 min. The solution was passed through a 200-mesh sieve, and the obtained filtrate was the first solution.

[0083] The preparation process of the second solution is as follows: Perfluoro(2-ethoxyethane)sulfonic acid was added to an appropriate amount of N,N-dimethylacetamide at a mass ratio of 0.18:1, and stirred at 120 r / min and 36° C. for 30 minutes to obtain a second solution.

[0084] The preparation process of the third solution is as follows: Polyvinyl alcohol was added to an appropriate amount of deionized water at a mass ratio of 0.13:1, and stirred at 120 rpm and 98° C. for 30 minutes to obtain a third solution.

[0085] S3. Wash the obtained precipitated product with deionized water 4 times and dry it to obtain a high-purity heavy basic copper carbonate product.

[0086] The drying temperature is 80°C and the drying time is 40 minutes.

[0087] In addition, the method further comprises placing the dried product in a pulverizing device for pulverization, and passing the pulverized product through a 120-mesh sieve.

[0088] Comparative Example 1: The difference from Example 1 is that the amount of the additive added in this example is 7% of the mass of the diluted waste liquid.

[0089] Comparative Example 2: The difference from Example 1 is that the amount of the additive added in this example is 13% of the mass of the diluted waste liquid.

[0090] Comparative Example 3: The difference from Example 1 is that the composite precipitant in this example is replaced by sodium carbonate.

[0091] Comparative Example 4: The difference from Example 1 is that the auxiliary agent in this example is replaced by polyvinyl alcohol.

[0092] Comparative Example 5: The difference from Example 1 is that the auxiliary agent in this example is replaced by polyethylene glycol.

[0093] Performance test: The high-purity heavy basic copper carbonate samples provided in Examples 1 to 5 and Comparative Examples 1 to 5 are marked as Examples 1 to 5 and Comparative Examples 1 to 5, respectively; and the relevant properties of the high-purity heavy basic copper carbonate provided in Examples 1 to 5 and Comparative Examples 1 to 5 are tested as follows: 1. Copper content test: The test method is to refer to "Industrial Basic Copper Carbonate" HG / T4825-2015 and use the indirect iodine titration method to determine the copper content of the product.

[0094] 2. Chlorine content test: The test method is to use visual turbidimetry to analyze the chlorine content of the product.

[0095] The obtained test data are recorded in Table 1 below.

[0096]

[0097] Comparison and analysis of the relevant data in Table 1 show that the high-purity heavy basic copper carbonate prepared by the present invention not only has good purity but also meets the requirements of "Industrial Basic Copper Carbonate" HG / T4825-2015, effectively ensuring its quality. This shows that the environmentally friendly preparation process for high-purity heavy basic copper carbonate provided by the present invention has a broader market prospect and is more suitable for promotion.

[0098] In the present invention, acidic copper-containing etching waste liquid and ethanol aqueous solution are thoroughly mixed, a composite precipitant and an auxiliary agent are added for precipitation treatment, and the resulting precipitate is washed with deionized water and dried to obtain a high-purity heavy basic copper carbonate product. The high-purity heavy basic copper carbonate prepared by the present invention not only has good purity and can realize the reuse of acidic copper-containing etching waste liquid, but also meets the use requirements of industrial basic copper carbonate.

[0099] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0100] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An environmentally friendly preparation process for high-purity heavy basic copper carbonate, characterized in that: The following steps are involved: S1, placing the acidic copper-containing etching waste liquid and the ethanol aqueous solution in a stirring device and fully mixing them to obtain a diluted waste liquid; S2. Add a composite precipitant and an auxiliary agent to the obtained diluted waste liquid, and perform precipitation treatment at 22-26° C. until the pH value is 6.5-7.5; The addition amount of the composite precipitant is 40-60% of the mass of the diluted waste liquid, and the addition amount of the auxiliary agent is 8-12% of the mass of the diluted waste liquid; S3. Wash the obtained precipitated product with deionized water 2 to 4 times and dry it to obtain a high-purity heavy basic copper carbonate product.

2. The environmentally friendly preparation process for high-purity heavy basic copper carbonate according to claim 1, wherein: In step S1, the ethanol aqueous solution is prepared by mixing anhydrous ethanol and distilled water in a mass ratio of 0.12 to 0.16:

1.

3. The environmentally friendly preparation process for high-purity heavy basic copper carbonate according to claim 1, wherein: In the step S1, the mixing mass ratio of the acidic copper-containing etching waste liquid and the ethanol aqueous solution in the diluted waste liquid is 1:3.2-3.

6.

4. The environmentally friendly preparation process for high-purity heavy basic copper carbonate according to claim 1, wherein: In step S2, the composite precipitant is prepared by mixing sodium carbonate and sodium bicarbonate in a mass ratio of 1:0.2 to 0.

4.

5. The environmentally friendly preparation process for high-purity heavy basic copper carbonate according to claim 1, characterized in that: In step S2, the preparation process of the auxiliary agent is as follows: The first solution, the second solution and the third solution are placed in a stirring device at a mass ratio of 1:1.2-1.4:0.8-1.2, and treated in a water bath at a temperature of 70-75°C for 50-60 minutes; After filtration, the filter cake is washed with deionized water for 2 to 4 times, dried in a drying oven at 40 to 50° C. for 8 to 10 hours, and then crushed in a crushing device to 100 to 200 meshes to obtain an additive.

6. The environmentally friendly preparation process for high-purity heavy basic copper carbonate according to claim 5, characterized in that: The preparation process of the first solution is as follows: Polyethylene glycol is placed in an appropriate amount of deionized water at a mass ratio of 0.02 to 0.12:1, treated at 95 to 98° C. and 120 to 140 r / min for 30 to 40 minutes, and passed through a 200-mesh sieve. The obtained filtrate is the first solution.

7. The environmentally friendly preparation process for high-purity heavy basic copper carbonate according to claim 5, characterized in that: The preparation process of the second solution is as follows: Perfluoro(2-ethoxyethane)sulfonic acid is placed in an appropriate amount of N,N-dimethylacetamide at a mass ratio of 0.08-0.18:1, and stirred at 90-120 rpm and 30-36° C. for 20-30 minutes to obtain a second solution.

8. The environmentally friendly preparation process for high-purity heavy basic copper carbonate according to claim 5, characterized in that: The preparation process of the third solution is as follows: Polyvinyl alcohol is placed in an appropriate amount of deionized water at a mass ratio of 0.03 to 0.13:1, and stirred at 90 to 120 r / min and 95 to 98° C. for 20 to 30 minutes to obtain a third solution.

9. The environmentally friendly preparation process for high-purity heavy basic copper carbonate according to claim 1, characterized in that: In step S3, the drying temperature is 70-80° C. and the drying time is 30-40 minutes.

10. The environmentally friendly preparation process for high-purity heavy basic copper carbonate according to claim 1, characterized in that: In the step S3, the dried product is placed in a pulverizing device for pulverization, and passed through a 100-120 mesh sieve.

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