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CN-119019034-B - Method for treating high-purity copper industrial copper nitrate-containing copper sulfate wastewater

CN119019034BCN 119019034 BCN119019034 BCN 119019034BCN-119019034-B

Abstract

The invention relates to the technical field of environmental engineering, and discloses a method for treating high-purity copper industrial wastewater containing copper nitrate and copper sulfate, which comprises the steps of respectively filtering copper nitrate and copper sulfate wastewater into a A, B reaction tank, adding a flocculating agent, monitoring the pH value of the reaction tank in the reaction process through an on-line monitoring instrument, independently adding hydrogen peroxide into the reaction tank A, breaking complex state copper into Cu 2+ , treating supernatant as effluent, carrying out diffusion dialysis technology, further removing residual copper ions by using an activated carbon adsorption and reverse osmosis separation technology, carrying out 8 times of washing treatment on sludge through circulating water, converting the sludge into an organic fertilizer through a composting technology on the basis of sludge stabilization, carrying out neutralization treatment on the treated wastewater by utilizing the interaction of microorganisms or metabolites thereof and metal in the sludge, and then discharging the treated wastewater into a comprehensive wastewater tank, and preparing the recovered copper into a copper product with the purity of 98 percent through electrolysis.

Inventors

  • CHEN YUHONG
  • SONG BAOSHAN
  • YANG YANCHUN

Assignees

  • 河南新国玺半导体材料有限公司

Dates

Publication Date
20260505
Application Date
20240823

Claims (8)

  1. 1. The method for treating the wastewater containing copper nitrate and copper sulfate in the high-purity copper industry is characterized by comprising the following steps of: Firstly, preprocessing, namely respectively filtering copper nitrate and copper sulfate wastewater, and respectively collecting the filters into A, B reaction tanks; adding a flocculating agent, namely adding the flocculating agent into a reaction tank of copper nitrate and copper sulfate; optimizing the pH value of the reaction tank, namely monitoring the pH value of the reaction tank in the reaction process by an online monitoring instrument, and adjusting the pH value in real time; Step four, breaking the collaterals, namely adding hydrogen peroxide into the reaction tank A, breaking the collaterals of the complex copper, converting the complex copper into Cu 2+ , and taking supernatant as effluent; Step five, conversion, namely respectively carrying out diffusion dialysis technology treatment on copper nitrate and copper sulfate wastewater of the reaction tank A, B; step six, advanced treatment, namely further removing residual copper ions by using an activated carbon adsorption and reverse osmosis separation technology; step seven, sludge stabilization treatment, namely stabilizing sludge generated by advanced treatment; step eight, sludge washing, namely washing the sludge for 8 times through circulating water; step nine, sludge composting, namely on the basis of sludge stabilization, converting sludge into organic fertilizer through a composting technology; step ten, heavy metal recovery, namely leaching valuable metals by adopting a biological leaching technology and utilizing the interaction of microorganisms or metabolites thereof and metals in sludge; step eleven, final treatment, namely neutralizing the treated wastewater, and then discharging the wastewater into a comprehensive wastewater pool; Step twelve, recycling, namely preparing the recycled copper into a copper product with the purity of 98% through electrolysis; the pretreatment in the first step is that copper nitrate and copper sulfate wastewater are respectively filtered to obtain copper nitrate filtrate and copper sulfate filtrate, the copper nitrate filtrate is collected into a reaction tank A, and the copper sulfate filtrate is collected into a reaction tank B; in the step ten, the biological leaching technical process comprises the steps of keeping the temperature of pool water of a A, B reaction pool between 30 and 35 ℃ and the pH value between 6 and 9, putting a combination of thiobacillus ferrooxidans, thiobacillus thiooxidans and aspergillus niger in a ratio of 3:1:2 into the reaction pool to interact with copper ions in sludge, simultaneously introducing 50% of oxygen at the bottom of the A, B reaction pool, and starting a stirring paddle to stir for 2 to 4 hours.
  2. 2. The method for treating the wastewater containing copper nitrate and copper sulfate in the high-purity copper industry, which is characterized in that a flocculating agent is added in the second step, wherein 15% of polyaluminum chloride is added in a reaction tank A, and 20% of polyacrylamide is added in a reaction tank B.
  3. 3. The method for treating the wastewater containing copper nitrate and copper sulfate in the high-purity copper industry according to claim 1, wherein the pH value of the reaction tank is optimized in the third step, when the pH value of the reaction tank A is less than 6, 20% of sodium hydroxide is added for adjustment, when the pH value of the reaction tank A is more than 9, 10% of hydrochloric acid is added for adjustment, when the pH value of the reaction tank B is less than 6, 10% of potassium hydroxide is added for adjustment, and when the pH value of the reaction tank A is more than 9, 5% of sulfuric acid is added for adjustment.
  4. 4. The method for treating the wastewater containing copper nitrate and copper sulfate in the high-purity copper industry, which is characterized in that the condition of breaking the collaterals in the fourth step is as follows: S1.1, controlling the pH value of the solution to be between 6 and 9; s1.2, adding 80mg and 40mg of polyacrylamide while using hydrogen peroxide.
  5. 5. The method for treating the wastewater containing copper nitrate and copper sulfate in the high-purity copper industry, which is characterized in that the conversion process in the fifth step is as follows: s2.1, a pretreatment step of filtering copper nitrate and copper sulfate waste liquid by using diffusion dialysis equipment; S2.2, using sulfur dioxide as a reducing agent of copper nitrate and copper sulfate filtrate, reducing copper sulfate into copper, controlling the pH value of the copper nitrate and copper sulfate filtrate in a A, B reaction tank to be between 6 and 9, setting the environment temperature to be 20-30 ℃, standing for 2 hours, and controlling the acidity of water to be 5 g/L; s2.3, after the reduction reaction is completed, the mixed product in the reaction tank is treated, and copper and the mixed acid liquid are separated by installing diffusion dialysis equipment at the water outlet position.
  6. 6. The method for treating industrial wastewater containing copper nitrate and copper sulfate with high purity according to claim 1, wherein the step six is characterized in that the activated carbon with the proportion multiple of 3 is used for feeding the wastewater to the reaction tank A to adsorb residual copper ions, the reverse osmosis separation technology is used for further removing the copper ions adsorbed by the activated carbon, and the wastewater of copper sulfate is passed through a reactor filled with ion exchange resin at a flow rate of 10 meters per second in the reaction tank B.
  7. 7. The method for treating wastewater containing copper nitrate and copper sulfate in high purity copper industry according to claim 1, wherein in the step seven, sludge stabilization treatment is carried out by respectively stabilizing sludge generated by advanced treatment when pH of A, B reaction tank is more than 9, combining calcium oxide and magnesium salt with a ratio of 5:1, uniformly mixing with the sludge, and putting the mixture into a A, B reaction tank: reaction of calcium oxide with water: CaO+H2 2 O→Ca(OH) 2 +heat CaO+H 2 O→Ca(OH) 2 +heat Reaction of calcium hydroxide with carbon dioxide: Ca (OH) 2 +CO 2 →CaCO 3 +H2O+heat Ca (OH) 2 +CO 2 →CaCO 3 +H 2 O+heat.
  8. 8. The method for treating wastewater containing copper nitrate and copper sulfate in high-purity copper industry as claimed in claim 1, wherein the step eleven is final treatment, which is to add 20% of sodium hydroxide, 10% of hydrochloric acid, 10% of potassium hydroxide or 5% of sulfuric acid into the wastewater discharged from the A, B reaction tank to neutralize the wastewater, and discharge the neutralized wastewater to a comprehensive wastewater tank or municipal wastewater pipe network when the pH value of the neutralized wastewater is 7-8.

Description

Method for treating high-purity copper industrial copper nitrate-containing copper sulfate wastewater Technical Field The invention relates to the technical field of environmental engineering, in particular to a method for treating high-purity copper industrial wastewater containing copper nitrate and copper sulfate. Background In the high purity copper industry, wastewater containing copper nitrate and copper sulfate is a common contaminant. If the wastewater is directly discharged without treatment, serious pollution can be generated to the water body, and the ecological environment and human health are affected. Therefore, it is important to develop an effective treatment method. Currently, treatment methods for such wastewater mainly include chemical precipitation methods, electrolytic methods, adsorption methods, ion exchange methods, and the like. Among them, the chemical precipitation method is widely used because of its mature technology and low cost. Although the existing treatment method reduces the burden on the environment pollution, the chemical treatment method forms copper hydroxide precipitate by adjusting the pH value of copper ions, and then solid-liquid separation is performed to remove the precipitate. This process produces large amounts of heavy metal-containing sludge which, if improperly treated, may cause secondary pollution. Disclosure of Invention (One) solving the technical problems Aiming at the defects of the prior art, the invention provides a method for treating wastewater containing copper nitrate and copper sulfate in the high-purity copper industry, which has the advantage of low sludge content of heavy metals and solves the problem of high sludge content of heavy metals in the traditional chemical treatment method. (II) technical scheme In order to achieve the purpose, the invention provides the following technical scheme that the method for treating the wastewater containing copper nitrate and copper sulfate in the high-purity copper industry comprises the following steps: Firstly, preprocessing, namely respectively filtering copper nitrate and copper sulfate wastewater, and respectively collecting the filters into A, B reaction tanks; adding a flocculating agent, namely adding the flocculating agent into a reaction tank of copper nitrate and copper sulfate; optimizing the pH value of the reaction tank, namely monitoring the pH value of the reaction tank in the reaction process by an online monitoring instrument, and adjusting the pH value in real time; Step four, breaking the collaterals, namely adding hydrogen peroxide into the reaction tank A, breaking the collaterals of the complex copper, converting the complex copper into Cu 2+, and taking supernatant as effluent; Step five, conversion, namely respectively carrying out diffusion dialysis technology treatment on copper nitrate and copper sulfate wastewater of the reaction tank A, B; step six, advanced treatment, namely further removing residual copper ions by using an activated carbon adsorption and reverse osmosis separation technology; step seven, sludge stabilization treatment, namely stabilizing sludge generated by advanced treatment; step eight, sludge washing, namely washing the sludge for 8 times through circulating water; step nine, sludge composting, namely on the basis of sludge stabilization, converting sludge into organic fertilizer through a composting technology; step ten, heavy metal recovery, namely leaching valuable metals by adopting a biological leaching technology and utilizing the interaction of microorganisms or metabolites thereof and metals in sludge; step eleven, final treatment, namely neutralizing the treated wastewater, and then discharging the wastewater into a comprehensive wastewater pool; and twelve, recycling, namely preparing the recycled copper into a copper product with the purity of 98% through electrolysis. Preferably, the pretreatment in the first step is to filter the copper nitrate and copper sulfate wastewater respectively to obtain copper nitrate filtrate and copper sulfate filtrate, collect the copper nitrate filtrate into the reaction tank A and collect the copper sulfate filtrate into the reaction tank B. Preferably, in the second step, a flocculating agent is added, namely 15% of polyaluminum chloride is added into the reaction tank A, and 20% of polyacrylamide is added into the reaction tank B. Preferably, in the third step, the pH value of the reaction tank is optimized, wherein when the pH value of the reaction tank A is less than 6, 20% of sodium hydroxide is added for adjustment, when the pH value of the reaction tank A is more than 9, 10% of hydrochloric acid is added for adjustment, when the pH value of the reaction tank B is less than 6, 10% of potassium hydroxide is added for adjustment, and when the pH value of the reaction tank A is more than 9, 5% of sulfuric acid is added for adjustment. Preferably, the conditions for breaking the collaterals in the fourth s