CN113336260B - Method for recovering copper sulfate in acidic copper sulfate waste liquid - Google Patents
Method for recovering copper sulfate in acidic copper sulfate waste liquid Download PDFInfo
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Abstract
The application relates to a waste liquid treatment collarThe method for recovering the copper sulfate in the acidic copper sulfate waste liquid comprises the following steps: s1, collecting the acidic copper sulfate waste liquid; s2, adding Cu (OH) into the acidic copper sulfate waste liquid2Carrying out neutralization treatment; s3, pumping the acidic copper sulfate waste liquid in the step S2 to a first evaporation crystallization device for crystallization and evaporation; s4, after the material in the step S3 passes through a solid-liquid separation system, a copper sulfate product is obtained, and separated evaporation mother liquor is discharged into an impurity removal reactor; s5, adding NaOH solid into the impurity removal reactor to generate Cu (OH)2The precipitate is dehydrated and washed and then returns to the step S2, and the supernatant enters a second evaporative crystallization device or enters a factory sewage treatment station for further treatment; and S6, crystallizing and evaporating the supernatant by using a second evaporative crystallizer. The method has the advantages of high purity of the recovered product, no introduction of new impurity ions in the medicament adding process, stable operation of the treatment process and no secondary pollutants.
Description
Technical Field
The application relates to the technical field of waste liquid treatment, in particular to a method for recovering copper sulfate in acid copper sulfate waste liquid.
Background
The acidic copper sulfate waste liquid is copper sulfate consumption liquid in an electroplating bath discharged by a semiconductor wafer in copper plating process and other processes, the main components of the acidic copper sulfate waste liquid are copper sulfate and sulfuric acid, wherein the content of copper ions is dozens of grams to hundreds of grams per liter, the weight ratio of the sulfuric acid is about 15%, according to national hazardous waste records, the acidic copper sulfate waste liquid belongs to HW 22-class hazardous waste, and if the acidic copper sulfate waste liquid is not effectively treated, the acidic copper sulfate waste liquid can pollute the environment and is also waste of resources. At present, the resource technology of the acidic copper sulfate waste liquid mainly comprises an extraction-electrodeposition recovery technology, an eddy current electrolysis technology, an ion exchange method, an iron powder replacement copper recovery technology and a copper sulfate production technology by neutralizing an acid etching solution and an alkaline etching solution.
The extraction-electrodeposition recovery technology is characterized in that the pH value of acidic copper sulfate waste liquid is adjusted to 3.5-6.0 by using alkaline etching waste liquid or ammonia water, sodium hydroxide, sodium carbonate and the like, organic copper extractant is used for extracting the acidic waste liquid after the pH value is adjusted, the ratio of the extracted organic phase to the extracted organic phase is 2-3: 1.0 in an extraction unit, copper ions enter an organic phase, then sulfuric acid-copper sulfate solution is used for carrying out back extraction on the organic phase, the copper ions enter a sulfuric acid-copper sulfate solution system, direct current electrolysis is carried out in an electrolytic bath, and finally the high-purity copper plate is electrolyzed. The technology has the advantages of recovering high-purity copper products with the purity of 99.9 percent, and has the defects of small treatment capacity, loss problems of emulsification, invalidation and the like of organic copper extractants, volume increment of waste liquid caused by the process of adjusting the pH value, and introduction of NH4 +、Na+、CO3 2-The plasma and COD, increment part are transferred to a waste liquid disposal company, and the standard discharge treatment difficulty is increased.
Chinese patent CN201220369211 describes a vortex electrolysis technology, which is characterized in that a vortex generator is added at the bottom of a traditional electrolytic tank, the waste liquid forms a fluid which rotates rapidly after the action of the vortex generator, and the fluid is fully contacted with the surface of the cathode and the anode of the electrolytic tank, so that the electrolysis efficiency is greatly improved, and the problems of cathode burning caused by large electrolysis current density in large flow and short circuit easily caused by needle-shaped electrolyte generated on the upper part of the cathode are solved.
The ion exchange method is to make the acidic copper sulfate waste liquid pass through cation exchange resin, copper can be directly concentrated and recycled to the electroplating bath, and water is recycled to the process. The technology has the advantages of high-quality metal copper recovery and the disadvantages of high price of ion exchange resin, limited exchange capacity, frequent regeneration and high operation cost, and is only suitable for treating acidic copper-containing waste liquid with low copper content at present.
The technology of replacing copper by iron powder is the most traditional treatment technology, and the main principle is to replace acidic copper sulfate by iron powder, iron filings or waste ironCopper in the waste liquid. The process has the advantages of large treatment capacity, but has the disadvantages of large iron consumption, low purity of the recovered copper product, generation of a large amount of ferrous chloride waste liquid, and subsequent production of a water treatment medicament FeCl3The additional value of resource utilization is low.
Therefore, a treatment technology of copper sulfate etching waste liquid, which has the advantages of stable operation of a treatment process, high product recovery purity, no introduction of new impurity ions in the medicament adding process and less secondary pollutants, needs to be researched.
Disclosure of Invention
In order to overcome the defects of the prior art, the method for recovering the copper sulfate in the acidic copper sulfate waste liquid has the advantages of high purity of recovered products, no introduction of new impurity ions in the process of adding the medicament, stable operation of a treatment process and no secondary pollutants.
The application provides a method for recovering copper sulfate in acidic copper sulfate waste liquid, which adopts the following technical scheme:
a method for recovering copper sulfate in acidic copper sulfate waste liquid is characterized by comprising the following steps:
s1, collecting the acidic copper sulfate waste liquid;
s2, adding Cu (OH) into the acidic copper sulfate waste liquid2Carrying out neutralization treatment;
s3, pumping the acidic copper sulfate waste liquid subjected to neutralization treatment in the step S2 into a first evaporative crystallization device for evaporative crystallization to obtain a solid-liquid mixture, purifying the waste gas by a flue gas purification system and then discharging the waste gas, and discharging condensed water into a sewage pipe network;
s4, after the solid-liquid mixture subjected to evaporative crystallization in the step S3 passes through a solid-liquid separation system, naturally drying the obtained solid at room temperature to obtain a copper sulfate product, and discharging the separated evaporation mother liquor into an impurity removal reactor;
s5, adding NaOH into the impurity removal reactor to generate Cu (OH)2Precipitating, returning the precipitate to the step S2 after dehydration and washing to be used as a neutralizing agent, and enabling the clear liquid to enter a second evaporative crystallization device or enter a plant sewage treatment system for further treatment;
s6, crystallizing and evaporating the clear liquid by the second evaporative crystallizer, discharging the waste gas after passing through the flue gas purification system, discharging the condensed water into a sewage pipe network, and burying the waste salt obtained by evaporation and crystallization.
By adopting the technical scheme, the components and the content of the acidic copper sulfate waste liquid treated by the method are shown in the table 1.
TABLE 1 composition and content of acidic copper sulfate waste liquid
In order to improve the purity of copper sulfate and avoid the reduction of the concentration of copper sulfate caused by the introduction of other ions, copper hydroxide powder is adopted as a neutralizing agent. According to the method, copper hydroxide powder is added in the initial stage, in the subsequent process, after the non-crystallized copper sulfate in the mother liquor reacts with the added sodium hydroxide, copper hydroxide precipitate is generated and returned to the neutralization reactor for further utilization, the adding amount of a neutralizing agent can be reduced, the method has the advantage of not introducing extra impurity ions, and meanwhile, a loop is closed, and the circular economy is realized. The method adopts the treatment process of neutralization reaction, evaporative crystallization and solid-liquid separation, the recovered copper sulfate product has high purity, and the requirement of industrial copper sulfate superior products can be met. The method for recovering the copper sulfate has the advantages that the generation amount of secondary pollutants is small, only a small amount of waste water and waste gas are generated in primary and secondary evaporative crystallization, a small amount of solid waste is generated in mother liquor evaporative crystallization, secondary pollutants are not generated in other process links, and the operation is stable.
Preferably, in step S1, the acidic copper sulfate waste liquid is collected in the regulating reservoir to equalize the water quantity and water quality.
By adopting the technical scheme, the front end of the device is provided with the regulating tank, so that a certain buffering effect can be achieved, the water quantity and the water quality of the acidic copper sulfate waste liquid are uniform, and the stability of the subsequent treatment process condition is ensured.
Preferably, in step S2, Cu (OH) is added2Adjusting the pH value to 3-4.
By adopting the technical scheme, Cu (OH) is added2And adjusting the pH value to 3-4, and neutralizing sulfuric acid in the acidic copper sulfate waste liquid to enable sulfate ions in the acidic copper sulfate waste liquid to react with copper ions to generate copper sulfate, so that the yield of copper sulfate generated by subsequent crystallization and evaporation is higher.
Preferably, in step S3, the crystallization temperature is controlled to be 120-160 ℃, and the crystallization evaporation time is 2-5 h.
By adopting the technical scheme, the crystallization of the copper sulfate is a complex heat-mass transfer process, any parameter or operation can have great influence on the generation of crystal nucleus, and the copper sulfate product with higher purity can be obtained by adopting the process parameters.
Preferably, in step S4, the solid-liquid separation system is a filter press, a plate filter or a centrifuge.
By adopting the technical scheme, the copper sulfate product obtained by crystallization can be quickly separated from the evaporation mother liquor, so that the purity of the copper sulfate product is further improved.
Preferably, the molar ratio of the sodium hydroxide added in the step S5 to the copper ions in the evaporation mother liquor is 2.0-2.2: 1.
by adopting the technical scheme, copper ions in the evaporation mother liquor generate copper hydroxide precipitate, and the residual copper ions in the evaporation mother liquor are precipitated, so that the waste of the copper ions is reduced, and the resource maximization treatment of copper ion recovery is realized.
Preferably, in the step S6, the crystallization temperature is controlled to be 140 to 180 ℃, and the crystallization evaporation time is 2 to 4 hours.
By adopting the technical scheme and the process parameters, the time for evaporative crystallization is shortened, the processing time of the clear liquid is shortened, and the processing efficiency is improved.
Preferably, the first evaporative crystallization device and the second evaporative crystallization device are multi-effect evaporative crystallizers or MVR evaporative crystallizers.
By adopting the technical scheme, the condensed water obtained by the treatment of the multiple-effect evaporative crystallizer or the MVR evaporative crystallizer meets the nano-tube standard, can be directly discharged into a sewage pipe network, and meanwhile, the equipment has the advantages of higher evaporation efficiency and effect, stable performance and continuous operation, can achieve the purposes of energy conservation and emission reduction, and greatly saves the cost.
Preferably, the vacuum degree in the first evaporative crystallization device and the second evaporative crystallization device is-0.09 to-0.01 MPa.
By adopting the technical scheme, in industrial production, the reaction is generally carried out in a pressurization, normal pressure or decompression (vacuum) mode, the reaction is carried out in vacuum, the vacuum degree is-0.09 to-0.01 MPa, the required steam quantity is less compared with normal pressure heat treatment, the evaporation speed of liquid (water) is high, and the crystallization rate is high.
Preferably, in the step S5, in the adding process of NaOH, the stirring speed of the impurity removal reactor is 100-200 r/min, the stirring reaction is carried out for 0.5-1 h, and the standing is carried out for 2-4 h.
By adopting the technical scheme, the NaOH is added into the evaporation mother liquor in a solid mode, so that the introduction of the solution is reduced, the volume of the mother liquor is not increased, the initial evaporation temperature of the evaporation mother liquor can be increased, and the pressure and energy consumption of subsequent process treatment are reduced. By adopting the process parameters, copper ions in the evaporation mother liquor can fully react with sodium hydroxide to generate copper hydroxide precipitate, the generated copper hydroxide precipitate is conveniently returned to the step S2 for recycling, the new addition of copper hydroxide is reduced, and the recycling economy is realized.
In summary, the present application has the following beneficial effects:
1. according to the method, copper hydroxide powder is added in the initial stage, in the subsequent process, after the copper sulfate which is not crystallized in the mother liquor reacts with the added sodium hydroxide, copper hydroxide precipitate is produced and returned to the neutralization reactor for further utilization, the adding amount of the neutralizing agent can be reduced, the method has the advantage that extra impurity ions are not introduced, and meanwhile, a closed loop is adopted, and the circular economy is realized.
2. The method adopts the treatment process of neutralization reaction, evaporative crystallization and solid-liquid separation, the recovered copper sulfate product has high purity, and the requirement of industrial copper sulfate superior products can be met.
3. The method for recovering the copper sulfate has the advantages that the generation amount of secondary pollutants is small, only a small amount of waste water and waste gas are generated in primary and secondary evaporative crystallization, a small amount of solid waste is generated in mother liquor evaporative crystallization, secondary pollutants are not generated in other process links, and the operation is stable.
4. The front end of the device is provided with the regulating tank, so that a certain buffering effect can be achieved, and the water quantity and the water quality of the acidic copper sulfate waste liquid are uniform, so that the stability of subsequent treatment process conditions is ensured.
Drawings
Fig. 1 is a flow chart of a method provided herein.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
The first evaporative crystallization device and the second evaporative crystallization device are multi-effect evaporative crystallizers or MVR evaporative crystallizers; the solid-liquid separation system is a filter press, a plate filter or a centrifuge.
The raw material is copper sulfate waste liquid discharged from an electroplating bath of a semiconductor wafer in a copper process, and the specific components and contents of the acidic copper sulfate waste liquid used in the examples and the comparative examples of the application are shown in the following table:
TABLE 2 composition and content of acidic copper sulfate waste
Example 1
S1, collecting 500L of the acidic copper sulfate waste liquid in an adjusting tank to homogenize the water quantity and the water quality;
s2, pumping the copper sulfate waste liquid with uniform water quality into a neutralization reaction tank, and adding Cu (OH)2Adjusting the pH value of the powder to 3.56;
s3, pumping the acidic copper sulfate waste liquid subjected to neutralization treatment in the step S2 to a first evaporative crystallization device, vacuumizing the interior of the first evaporative crystallization device to-0.01 MPa, and carrying out evaporative crystallization for 2 hours at the temperature of 120 ℃ to obtain a solid-liquid mixture, wherein the waste gas is purified by a flue gas purification system and then discharged, and condensed water is discharged into a sewage pipe network;
s4, carrying out solid-liquid separation on the solid-liquid mixture subjected to evaporation crystallization in the step S3 through a filter press, a plate filter or a centrifuge, naturally drying the obtained solid at room temperature to obtain a copper sulfate product, and discharging the separated evaporation mother liquor into an impurity removal reactor;
s5, adding NaOH solid into the impurity removal reactor, wherein the molar ratio of the added sodium hydroxide to the copper ion content in the evaporation mother liquor is 2.0-2.2: 1, stirring and reacting for 0.5h at the rotating speed of 100r/min, standing for 1.5h, and removing Cu (OH) at the bottom of an impurity reactor2The precipitate is dehydrated and washed and then returns to the step S2 to be used as a neutralizing agent, and clear liquid is discharged into a second evaporative crystallization device or enters a factory sewage treatment system for further treatment;
s6, vacuumizing the second evaporative crystallizer to-0.01 MPa, crystallizing the evaporated clear liquid for 3 hours at the temperature of 150 ℃, discharging the waste gas through a flue gas purification system, discharging the condensed water into a sewage pipe network, and sending a small amount of waste salt obtained through evaporation and crystallization to a dangerous waste rigid landfill for treatment.
Example 2
S1, collecting 500L of the acidic copper sulfate waste liquid in an adjusting tank to homogenize the water quantity and the water quality;
s2, pumping the copper sulfate waste liquid with uniform water quality into a neutralization reaction tank, and adding Cu (OH)2Adjusting the pH value of the powder to 3.56;
s3, pumping the acidic copper sulfate waste liquid subjected to neutralization treatment in the step S2 to a first evaporation crystallization device, vacuumizing the first evaporation device to-0.06 MPa, carrying out evaporation crystallization for 3.5 hours at the temperature of 140 ℃ to obtain a solid-liquid mixture, purifying the waste gas by a flue gas purification system, discharging, and discharging condensed water into a sewage pipe network;
s4, carrying out solid-liquid separation on the liquid-solid mixture subjected to evaporative crystallization in the step S3 through a filter press, a plate filter or a centrifuge, naturally drying the obtained solid at room temperature to obtain a copper sulfate product, and discharging the separated evaporation mother liquor into an impurity removal reactor;
s5, adding NaOH solid into the impurity removal reactor, wherein the molar ratio of the added sodium hydroxide to the copper ion content in the evaporation mother liquor is 2.0-2.2: 1, stirring and reacting for 0.75h at the rotating speed of 130r/min, and standingStanding for 3.0h, removing Cu (OH) at the bottom of the impurity reactor2The precipitate is dehydrated and washed and then returns to the step S2 to be used as a neutralizing agent, and clear liquid is discharged into a second evaporative crystallization device or enters a factory sewage treatment system for further treatment;
s6, vacuumizing the second evaporative crystallizer to-0.09 MPa, crystallizing the evaporated clear liquid for 2 hours at the temperature of 180 ℃, discharging the waste gas through a flue gas purification system, discharging the condensed water into a sewage pipe network, and sending a small amount of waste salt obtained through evaporation and crystallization to a dangerous waste rigid landfill for treatment.
Example 3
S1, collecting 500L of the acidic copper sulfate waste liquid in an adjusting tank to homogenize the water quantity and the water quality;
s2, pumping the copper sulfate waste liquid with uniform water quality into a neutralization reaction tank, and adding Cu (OH)2Adjusting the pH value of the powder to 3.56;
s3, pumping the acidic copper sulfate waste liquid subjected to neutralization treatment in the step S2 to a first evaporative crystallization device, vacuumizing the first evaporative crystallization device to-0.09 MPa, carrying out evaporative crystallization for 5 hours at the temperature of 160 ℃ to obtain a solid-liquid mixture, purifying the waste gas by a flue gas purification system, and then discharging the waste gas, and discharging condensed water into a sewage pipe network;
s4, carrying out solid-liquid separation on the liquid-solid mixture subjected to evaporative crystallization in the step S3 through a filter press, a plate filter or a centrifuge, naturally drying the obtained solid at room temperature to obtain a copper sulfate product, and discharging the separated evaporation mother liquor into an impurity removal reactor;
s5, adding NaOH solid into the impurity removal reactor, wherein the molar ratio of the added sodium hydroxide to the copper ion content in the evaporation mother liquor is 2.0-2.2: 1, stirring and reacting for 1h at the rotating speed of 150r/min, standing for 4h, and removing Cu (OH) at the bottom of an impurity reactor2The precipitate is dehydrated and washed and then returns to the step S2 to be used as a neutralizing agent, and clear liquid is discharged into a second evaporative crystallization device or enters a factory sewage treatment system for further treatment;
s6, vacuumizing the second evaporative crystallizer to-0.06 MPa, crystallizing the evaporated clear liquid for 2 hours at the temperature of 140 ℃, discharging the waste gas through a flue gas purification system, discharging the condensed water into a sewage pipe network, and sending a small amount of waste salt obtained through evaporation and crystallization to a dangerous waste rigid landfill for treatment.
Comparative example
Comparative example 1
The difference between the comparative example 1 and the example 1 is that the acid copper sulfate waste liquid is directly introduced into the neutralization reaction tank for treatment without arranging a regulating tank for uniform water quantity and water quality, and the rest steps are the same as those in the example 1.
Comparative example 2
A method for producing copper sulfate by using acidic etching waste liquid comprises the following steps,
(1) collecting the acidic copper sulfate waste liquid;
carrying out homogenization treatment on 500L of acidic copper sulfate waste liquid to ensure the stability of the control of a subsequent treatment process;
(2) oxidizing the acidic copper sulfate waste liquid by using hydrogen peroxide, precipitating metal ions with stronger metal activity than copper in the acidic copper sulfate waste liquid, and adjusting the pH value of the solution to be between 0 and 1; filtering the oxidized acidic copper sulfate waste liquid to obtain a filtrate;
(3) evaporating the filtrate obtained in the step (2), stopping evaporation when the filtrate is supersaturated with copper chloride, cooling, and performing crystallization separation to obtain crystallized copper chloride; the evaporation concentration temperature is controlled to be 90-120 ℃, and the pressure is controlled to be-0.06-0 Mpa. Evaporating for 30min, discharging certain concentrated solution at certain intervals to determine the content of copper chloride, and cooling and crystallizing when the copper chloride is supersaturated;
placing the crystallized copper chloride obtained in the step (3) into a replacement reaction kettle, adding concentrated sulfuric acid for acidification reaction, cooling, and performing crystallization separation to obtain crystallized copper sulfate; the molar ratio of the added concentrated sulfuric acid to the copper content in the acidic etching waste liquid is 1.8: 1.
comparative example 3
S1, collecting 500L of the acidic copper sulfate waste liquid in an adjusting tank to homogenize the water quantity and the water quality;
s2, pumping the copper sulfate waste liquid with uniform water quality into a neutralization reaction tank, and adding Cu (OH)2Adjusting the pH value of the powder to 3.56;
s3, pumping the acidic copper sulfate waste liquid subjected to neutralization treatment in the step S2 to a first evaporative crystallization device, wherein the interior of the first evaporative crystallization device is in a normal pressure state, evaporative crystallization is carried out for 1.5 hours at the temperature of 110 ℃ to obtain a solid-liquid mixture, the waste gas is purified by a flue gas purification system and then discharged, and condensed water is discharged into a sewage pipe network;
s4, carrying out solid-liquid separation on the liquid-solid mixture subjected to evaporative crystallization in the step S3 through a filter press or a plate filter, naturally drying the obtained solid at room temperature to obtain a copper sulfate product, and discharging the separated evaporation mother liquor into an impurity removal reactor or into a plant sewage treatment system for further treatment;
s5, adding NaOH solid into the impurity removal reactor, wherein the molar ratio of the added sodium hydroxide to the copper ion content in the evaporation mother liquor is 2.0-2.2: 1, stirring and reacting for 0.5h at the rotating speed of 100r/min, standing for 1.5h, and removing Cu (OH) at the bottom of an impurity reactor2The precipitate is dehydrated and washed and then returned to the step S2 to be used as a neutralizing agent, and clear liquid is discharged into a second evaporative crystallization device;
s6, vacuumizing the second evaporative crystallizer to-0.01 MPa, crystallizing the evaporated clear liquid for 3 hours at the temperature of 150 ℃, discharging the waste gas through a flue gas purification system, discharging the condensed water into a sewage pipe network, and sending a small amount of waste salt obtained through evaporation and crystallization to a dangerous waste rigid landfill for treatment.
Performance test
The copper sulfate products obtained in examples 1-3 and comparative examples 1-2 of the present application were tested by using standard industrial copper sulfate "HG/T5215-2017", and the test results are shown in Table 3:
table 3 comparative results of examples and comparative examples
Combining the examples 1-3 and the comparative examples 1-2 and combining the table 3, it can be seen that the copper hydroxide powder is added in the initial stage, in the subsequent process, the non-crystallized copper sulfate in the mother liquor reacts with the added sodium hydroxide to generate copper hydroxide precipitate, and the copper hydroxide precipitate is returned to the neutralization reactor for further removal, so that the adding amount of the neutralization agent can be reduced, and the method has the advantages of no introduction of additional impurity ions, and meanwhile, the loop is closed, and the circulation is economical. The method adopts the treatment process of neutralization reaction, evaporative crystallization and solid-liquid separation, the recovered copper sulfate product has high purity, and the requirement of industrial copper sulfate superior products can be met. The method for recovering the copper sulfate has the advantages that the generation amount of secondary pollutants is small, only a small amount of waste water and waste gas are generated in primary and secondary evaporative crystallization, a small amount of solid waste is generated in mother liquor evaporative crystallization, secondary pollutants are not generated in other process links, and the operation is stable.
From the embodiment 1 and the comparative example 1, it can be seen that the adjusting tank arranged at the front end of the device can play a certain buffering role, and the water quantity and the water quality of the acidic copper sulfate waste liquid are uniform, so that the stability of the subsequent treatment process conditions is ensured.
Combining example 1 and comparative example 3 with table 3, it can be seen that the purity of the final copper sulfate product is affected by the adjustment of parameters, particularly the control of pressure and temperature, and a higher purity copper sulfate product can be obtained using the process parameters defined in the application.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. A method for recovering copper sulfate in acidic copper sulfate waste liquid is characterized by comprising the following steps:
s1, collecting the acidic copper sulfate waste liquid;
s2, adding Cu (OH) into the acidic copper sulfate waste liquid2Carrying out neutralization treatment;
s3, pumping the acidic copper sulfate waste liquid after neutralization treatment in the step S2 into a first evaporative crystallization device for evaporative crystallization to obtain a solid-liquid mixture, controlling the crystallization temperature to be 120-160 ℃, controlling the crystallization evaporation time to be 2-5 h, controlling the vacuum degree in the first evaporative crystallization device to be-0.09-0.01 MPa, purifying waste gas by a flue gas purification system, discharging, and discharging condensed water into a sewage pipe network;
s4, after the solid-liquid mixture subjected to evaporative crystallization in the step S3 passes through a solid-liquid separation system, naturally drying the obtained solid at room temperature to obtain a copper sulfate product, and discharging the separated evaporation mother liquor into an impurity removal reactor;
s5, adding NaOH into the impurity removal reactor to generate Cu (OH)2Precipitating, returning the precipitate to the step S2 after dehydration and washing to be used as a neutralizing agent, and enabling the clear liquid to enter a second evaporative crystallization device or enter a plant sewage treatment system for further treatment;
s6, crystallizing and evaporating the clear liquid by the second evaporative crystallizer, discharging the waste gas after passing through the flue gas purification system, discharging the condensed water into a sewage pipe network, and burying the waste salt obtained by evaporation and crystallization.
2. The method for recovering copper sulfate in acidic copper sulfate waste liquid as claimed in claim 1, wherein the method comprises the following steps: in step S1, the acidic copper sulfate waste liquid is collected in a regulating reservoir to equalize the water quantity and quality.
3. The method for recovering copper sulfate in acidic copper sulfate waste liquid as claimed in claim 1, wherein the method comprises the following steps: in step S2, Cu (OH) is added2Adjusting the pH value to 3-4.
4. The method for recovering copper sulfate in acidic copper sulfate waste liquid as claimed in claim 1, wherein the method comprises the following steps: in step S4, the solid-liquid separation system is a filter press, a plate filter or a centrifuge.
5. The method for recovering copper sulfate in acidic copper sulfate waste liquid as claimed in claim 1, wherein the method comprises the following steps: the molar ratio of the amount of the sodium hydroxide added in the step S5 to the content of the copper ions in the evaporation mother liquor is 2.0-2.2: 1.
6. the method for recovering copper sulfate in acidic copper sulfate waste liquid as claimed in claim 1, wherein the method comprises the following steps: in the step S6, the crystallization temperature is controlled to be 140-180 ℃, and the crystallization evaporation time is 2-4 h.
7. The method for recovering copper sulfate in acidic copper sulfate waste liquid as claimed in claim 1, wherein the method comprises the following steps: the second evaporative crystallization device is a multi-effect evaporative crystallizer or MVR evaporative crystallizer.
8. The method for recovering copper sulfate in acidic copper sulfate waste liquid as claimed in claim 1, wherein the method comprises the following steps: the vacuum degree in the first evaporative crystallization device and the second evaporative crystallization device is-0.09 to-0.01 MPa.
9. The method for recovering copper sulfate in acidic copper sulfate waste liquid as claimed in claim 1, wherein the method comprises the following steps: in the step S5, in the adding process of NaOH, the stirring speed of the impurity removal reactor is 100-200 r/min, the stirring reaction is carried out for 0.5-1 h, and the standing is carried out for 2-4 h.
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