CN112830556A - Method for combined treatment of cyanide copper plating wastewater and acidic copper plating wastewater - Google Patents
Method for combined treatment of cyanide copper plating wastewater and acidic copper plating wastewater Download PDFInfo
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Abstract
The invention provides a method for combined treatment of cyanide copper plating wastewater and acidic copper plating wastewater, belonging to the technical field of sewage treatment. The cyanide copper plating wastewater is positioned in an anode chamber of a diaphragm electrolytic cell, the acidic copper plating wastewater is positioned in a cathode chamber of the diaphragm electrolytic cell, and an inert material is used as an anode and copper is used as a cathode to carry out electrolysis; the diaphragm of the diaphragm electrolytic cell is an anion exchange membrane. The method provided by the invention can be used for simultaneously treating cyanide copper plating wastewater and acidic copper plating wastewater, can be used for recovering copper in the acidic copper plating wastewater when cyanide in the cyanide copper plating wastewater is subjected to oxidative decomposition, is simple and efficient, has a high recovery rate of copper in the wastewater, and can be used for recovering the recovered copper with high purity. The purity of the copper metal recovered by the method reaches more than 95 percent, and the removal rate of cyanide and copper in the wastewater is more than 70 percent, so that the method is suitable for industrial application.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for combined treatment of cyanide copper plating wastewater and acidic copper plating wastewater.
Background
Copper plating is one of the most widely used pre-plating layers in the electroplating industry, and includes copper plating of tin welding parts, lead-tin alloy and zinc die casting parts before nickel plating, gold plating and silver plating, and is used for improving the bonding force of the plating layers. The copper plating layer is an important constituent of a protective and decorative plating layer copper/nickel/chromium system, and the copper plating layer with flexibility and low porosity plays an important role in improving the bonding force and corrosion resistance between the plating layers. The most used copper plating solutions at present are cyanide plating solutions and sulfate plating solutions. Copper-containing wastewater can be divided into cyanide copper plating wastewater and acidic copper plating wastewater based on different plating solution components.
Because the two copper-containing electroplating wastewater have different compositions, the treatment methods of the two wastewater are different. The conventional treatment method of cyanide copper plating wastewater is an oxidation method, wherein an oxidant is usually sodium hypochlorite or bleaching powder, cyanide is broken under the alkaline condition, and complex copper ions in the wastewater are converted into insoluble copper hydroxide precipitate; the treatment method of the acidic copper plating wastewater is simple, and the liquid caustic soda or lime cream is added to convert copper ions in the wastewater into insoluble copper hydroxide precipitate.
There are two main methods for recovering copper from copper-containing electroplating wastewater, one is to separate copper from wastewater in the form of copper compound, and to convert copper or complex copper ions in solution into copper hydroxide or copper sulfide precipitate for separation from wastewater. Patent 201810381168.X discloses a method for treating copper-containing electroplating wastewater and recovering copper by using a sulfide precipitation method, wherein copper ions are converted into insoluble copper sulfide, and then the copper sulfide is comprehensively utilized. The precipitation method has two disadvantages in the practical application process, one is that the precipitation process is not easy to control, and the generated floc is fine and not easy to settle. Another disadvantage is that the precipitation method is not selective, and other ions in the solution, such as iron, nickel and zinc, can enter the slag, resulting in complex slag components and low utilization value. Another method for recovering copper is to recover copper in a simple substance manner, and reduce copper ions in the solution to the simple substance copper, the common reduction manner includes electric reduction or chemical reduction, and the reducing agent includes iron powder, zinc powder, formaldehyde, and the like. Patent 201210182220.1 discloses a method for recovering copper from copper-containing electroplating wastewater by electrolysis, which uses expensive platinum electrode and because sodium chloride and potassium chloride are added to the wastewater, chlorine gas escapes during electrolysis to pollute the operation environment.
As can be seen from the above, in the prior art, cyanide copper plating wastewater, acidic copper plating wastewater and copper recovery from copper-containing wastewater are treated separately, and the efficiency is low.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for combined treatment of cyanide copper plating wastewater and acidic copper plating wastewater, which can simultaneously treat cyanide copper plating wastewater and acidic copper plating wastewater, can recover copper in the acidic copper plating wastewater, is simple and efficient, has a high recovery rate of copper in the wastewater, and has a high purity of the recovered copper.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a method for combined treatment of cyanide copper plating wastewater and acidic copper plating wastewater, wherein the cyanide copper plating wastewater is positioned in an anode chamber of a diaphragm electrolytic cell, the acidic copper plating wastewater is positioned in a cathode chamber of the diaphragm electrolytic cell, and electrolysis is carried out by taking an inert material as an anode and copper as a cathode; the diaphragm of the diaphragm electrolytic cell is an anion exchange membrane.
Preferably, the cyanide copper plating wastewater comprises scrapped tank liquor and/or conventional rinsing water of cyanide copper plating, the concentration of copper ions in the cyanide copper plating wastewater is 500-2000 mg/L, and the concentration of cyanide ions is 500-5000 mg/L.
Preferably, the acidic copper plating wastewater comprises scrapped bath solution and/or conventional rinsing water of acidic sulfate copper plating, and the concentration of copper ions in the acidic copper plating wastewater is 500-10000 mg/L.
Preferably, the inert material is titanium-coated lead dioxide, titanium-coated ruthenium iridium, titanium-coated tantalum iridium or graphite, and the copper is a copper plate or a copper mesh.
Preferably, the current density in the electrolysis process is 50A/m2～500A/m2。
Preferably, the pH value of the cyanide copper plating wastewater in the electrolysis process is 10-13.
Preferably, the pH value of the acidic copper plating wastewater in the electrolysis process is 0.5-2.
Preferably, the time for electrolyzing the cyanide copper-plating wastewater in the anode chamber in the electrolysis process is calculated according to the formula I:
t1＝C1V1/k1i formula I
T in the formula I1The unit is h for the electrolysis time of the cyanide copper plating wastewater in the anode chamber; c1The concentration of cyanide ions in the cyanide copper plating wastewater is g/L; v1The volume of the cyanide copper plating wastewater is L; k is a radical of1Represents the electrolytic constant, k, of cyanide ions1The value of (A) is 0.15 to 0.19 g/Ah; i is the current in the electrolysis process and has the unit of A.
Preferably, the electrolysis time of the acidic copper-plating wastewater in the cathode chamber in the electrolysis process is calculated according to the formula II:
t2＝C2V2/k2formula I formula II
In said formula II, t2The electrolysis time of the acidic copper plating wastewater in the cathode chamber is h; c2The concentration of copper ions in the acidic copper plating wastewater is g/L; v2The volume of the acidic copper plating wastewater is L; k is a radical of2Is the electrolytic constant, k, of copper ions2The value is 0.8 to 1.42 g/Ah; i is the current in the electrolysis process and has the unit of A.
The beneficial technical effects are as follows: the invention provides a method for combined treatment of cyanide copper plating wastewater and acidic copper plating wastewater, wherein the cyanide copper plating wastewater is positioned in an anode chamber of a diaphragm electrolytic cell, the acidic copper plating wastewater is positioned in a cathode chamber of the diaphragm electrolytic cell, and electrolysis is carried out by taking an inert material as an anode and copper as a cathode; the diaphragm of the diaphragm electrolytic cell is an anion exchange membrane. The method provided by the invention can be used for simultaneously treating cyanide copper plating wastewater and acid copper plating wastewater, can be used for recovering copper in the acid copper plating wastewater, is simple and efficient, has high recovery rate of copper in the wastewater, and can be used for recovering the obtained copper with high purity. The purity of the copper metal recovered by the method reaches more than 97 percent, the removal rate of cyanide and copper in the wastewater is more than 70 percent, and the method is suitable for industrial application
Drawings
FIG. 1 is a device for combined treatment of cyanide copper plating wastewater and acidic copper plating wastewater in examples 1 to 3;
wherein, the 1-NaOH solution reservoir; 2-cyanide copper plating wastewater reservoir; 3-anode chamber; 4-a cathode chamber; 5-acid copper plating wastewater reservoir; 6-a cathode; 7-an anode; 8-a direct current power supply; 9-pH meter; 10-anion exchange membrane.
Detailed Description
The invention provides a method for combined treatment of cyanide copper plating wastewater and acidic copper plating wastewater, wherein the cyanide copper plating wastewater is positioned in an anode chamber of a diaphragm electrolytic cell, the acidic copper plating wastewater is positioned in a cathode chamber of the diaphragm electrolytic cell, and electrolysis is carried out by taking an inert material as an anode and copper as a cathode; the diaphragm of the diaphragm electrolytic cell is an anion exchange membrane.
In the invention, the cyanide copper plating waste water preferably comprises scrap tank liquor and/or conventional rinse water of cyanide copper plating. In the invention, the concentration of copper ions in the cyanide copper plating wastewater is preferably 500-2000 mg/L, and more preferably 1000-1500 mg/L; the concentration of cyanide ions in the cyanide copper plating wastewater is preferably 500-5000 mg/L, more preferably 1000-4000 mg/L, and most preferably 2000-3000 mg/L.
In the invention, the acidic copper plating waste water preferably comprises waste tank liquor and/or conventional rinsing water of acidic sulfate copper plating. In the invention, the concentration of copper ions in the acidic copper plating wastewater is preferably 500-10000 mg/L, more preferably 10000-90000 mg/L, and most preferably 50000-80000 mg/L.
In the invention, the inert material is preferably titanium-coated lead dioxide, titanium-coated ruthenium iridium, titanium-coated tantalum iridium or graphite; the copper is preferably a copper plate or a copper mesh. In the invention, when the copper is a copper mesh, the pore diameter of the copper mesh is preferably 20-200 meshes, and more preferably 50-150 meshes. The area of the copper plate or the copper mesh is not specially limited, and the copper mesh is properly adjusted according to the volume of cyanide copper plating wastewater and acid copper plating wastewater.
In the present invention, the current density in the electrolysis is preferably 50A/m2～500A/m2More preferably 100A/m2～400A/m2Most preferably 200A/m2～250A/m2。
In the invention, the pH value of the cyanide copper plating wastewater in the electrolysis process is preferably 10-13, and more preferably 10.5-11.5. The pH is preferably adjusted in the present invention by using sodium hydroxide or aqueous ammonia, preferably sodium hydroxide.
In the invention, the pH value of the acidic copper plating wastewater in the electrolysis process is preferably 0.5-2, and more preferably 1-1.5.
In the invention, the time of the cyanide copper plating wastewater in the anode chamber during the electrolysis process is preferably calculated according to the formula I:
t1＝C1V1/k1i formula I
T in the formula I1The unit is h for the electrolysis time of the cyanide copper plating wastewater in the anode chamber; c1The concentration of cyanide ions in the cyanide copper plating wastewater is g/L; v1The volume of the cyanide copper plating wastewater is L; k is a radical of1Represents the electrolytic constant, k, of cyanide ions1The value of (A) is 0.14 to 0.19 g/Ah; i is the current in the electrolysis process and has the unit of A.
In the invention, when the electrolysis time of the cyanide copper plating wastewater reaches a specified time, the cyanide copper plating wastewater after electrolysis is discharged and the non-electrolyzed cyanide copper plating wastewater is injected. In one embodiment of the invention, the anode chamber of the diaphragm electrolytic cell is connected with a cyanide copper plating wastewater storage tankThe cyanide copper plating wastewater in the anode chamber of the diaphragm electrolytic cell and the cyanide copper plating wastewater in the cyanide copper plating wastewater reservoir can flow circularly during the electrolysis process, and the V is1Is the sum of the volume of the cyanide copper plating wastewater in the anode chamber of the diaphragm electrolytic cell and the volume of the cyanide copper plating wastewater in the cyanide copper plating wastewater reservoir.
The method controls the circulating electrolysis time of the cyanide wastewater in the anode chamber, and generates the electrolytic oxidation reaction in the interval with higher cyanide ion concentration, thereby reducing the proportion of side reaction as much as possible and further improving the current efficiency of cyanide ion oxidation.
In the present invention, the time for electrolyzing the acidic copper plating wastewater in the cathode chamber in the electrolysis process is preferably calculated according to formula II:
t2＝C2V2/k2formula I formula II
In said formula II, t2The electrolysis time of the acidic copper plating wastewater in the cathode chamber is h; c2The concentration of copper ions in the acidic copper plating wastewater is g/L; v2The volume of the acidic copper plating wastewater is L; k is a radical of2Is the electrolytic constant, k, of copper ions2The value is 0.8 to 1.42 g/Ah; i is the current in the electrolysis process and has the unit of A.
When the circulating electrolysis time of the acidic copper plating wastewater reaches the specified time, discharging the electrolyzed acidic copper plating wastewater, and injecting the electrolyzed acidic copper plating wastewater. In one embodiment of the invention, the cathode chamber of the diaphragm electrolytic tank is connected with the acidic copper plating waste water storage tank, the acidic copper plating waste water in the cathode chamber of the diaphragm electrolytic tank and the acidic copper plating waste water in the acidic copper plating waste water storage tank can flow circularly in the electrolytic process, and the V is1The sum of the volumes of the acidic copper plating wastewater in the cathode chamber of the diaphragm electrolytic cell and the acidic copper plating wastewater in the acidic copper plating wastewater reservoir
According to the invention, the electrolytic reduction reaction is carried out in the region with higher copper ion concentration by controlling the electrolytic time of the acidic copper plating wastewater in the cathode chamber, so that the proportion of side reactions is reduced as much as possible, and the current efficiency of copper ion reduction is further improved.
In the present invention, the anode reaction in the electrolysis process is:
2CN-+8OH--10e-＝2CO2+N2+4H2O
CN-+2OH--2e-＝CNO-+H2O
4OH--4e-＝2H2O+O2
Cu+-e-＝Cu2+
the cathode reaction in the electrolysis process is as follows:
Cu++2e-＝Cu
2H++2e-＝H2
the invention utilizes the property that the cathode and the anode respectively generate reduction and oxidation reactions in the electrochemical process, respectively treats the acidic copper plating and cyanide copper plating wastewater in the cathode and anode chambers of the electrolytic cell, respectively reduces and oxidizes copper ions and cyanogen in the electrolytic process along with the cathode and the anode, and obtains metal copper at the cathode through electrolysis, so that the copper ions in the wastewater are recycled. The invention utilizes the selectivity of the anion membrane, almost only sulfate radicals migrate in the electrolytic process, the migration of copper ions and cyanide radicals is less (the concentration of the sulfate radicals in the acidic copper plating wastewater is far higher than that of the cyanide radicals in the cyanide copper plating wastewater), and the loss of copper in the acidic copper plating wastewater is small.
After the electrolysis is finished, the treatment difficulty of the electrolyzed acidic copper plating wastewater and the electrolyzed cyanide copper plating wastewater is greatly reduced, and the discharge or recycling standard can be reached only by simple treatment.
In the invention, the simple treatment method of the electrolyzed acidic copper plating wastewater comprises the following steps:
and mixing the electrolyzed acidic copper plating wastewater, a pH regulator and a flocculating agent for flocculation reaction, and performing solid-liquid separation to obtain a first supernatant and a first solid.
In the present invention, the flocculant is preferably PAC and PAM; the pH regulator is preferably liquid caustic soda or lime milk, and the pH value of the flocculation reaction is preferably 8.5-9.5.
In the invention, the concentration of copper ions in the electrolyzed acidic copper plating wastewater is 50-2000 mg/L; the concentration of copper ions in the first supernatant is less than 0.1 mg/L.
In the invention, the simple treatment method of the cyanide copper plating wastewater after electrolysis comprises the following steps:
mixing the electrolyzed cyanide copper plating wastewater with an oxidant for oxidation reaction to obtain oxidized cyanide copper plating wastewater;
and mixing the oxidized cyanide copper plating wastewater with a flocculating agent for flocculation reaction, and performing solid-liquid separation to obtain a second supernatant and a second solid.
The method mixes the electrolyzed cyanide copper plating wastewater with an oxidant for oxidation reaction to obtain the oxidized cyanide copper plating wastewater. In the present invention, the oxidizing agent is preferably sodium hypochlorite or calcium hypochlorite; the oxidation reaction preferably has an oxidation-reduction potential of not less than 350 mv; the pH value of the oxidation reaction is preferably 8.5-9.5.
After oxidized cyanide copper plating wastewater is obtained, the oxidized cyanide copper plating wastewater is mixed with a flocculating agent for flocculation reaction, and solid-liquid separation is carried out to obtain a second supernatant and a second solid.
In the present invention, the flocculant is preferably PAC and PAM.
In the invention, the concentration of cyanide ions in the oxidized cyanide copper plating wastewater is 50-600 mg/L; the concentration of cyanide ions in the second supernatant is 0.1-0.2 mg/L, and the concentration of copper ions is less than 0.1 mg/L.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
The components of the acidic copper plating wastewater and the cyanide copper plating wastewater are as follows:
TABLE 1 composition of acidic copper plating wastewater and cyanide copper plating wastewater before treatment in example 1
As shown in figure 1, cyanide copper plating wastewater 4L is injected into an anode area (comprising an anode chamber and a cyanide wastewater storage tank) of the electrolytic tank, acid copper plating wastewater 4L is injected into a cathode area (comprising a cathode chamber and an acid copper plating wastewater storage tank), the anode material is titanium-coated ruthenium-iridium, and the cathode material is a 50-mesh purple copper mesh. The effective area of the cathode and the anode is 300cm2The current was set to 6A during electrolysis (the current density of the cathode and anode was set to 200A/m)2) And dripping liquid caustic soda into the anolyte during the electrolysis process, and controlling the pH value of the anolyte to be between 11.0 and 11.5. And calculating the electrolysis time of the anolyte according to the formula I.
t1＝C1V1/k1I，C1＝1.8g/L，V1＝4L，k10.15g/Ah, I6A, then t1＝7.06h。
The electrolysis time of the catholyte was calculated according to formula II.
t2＝C2V2/k2I，C2＝8g/L，V2＝4L，k21g/Ah, I6A, then t2＝5.3h。
The components of the treated acidic copper plating wastewater and cyanide copper plating wastewater after the completion of the electrolysis are shown in Table 2.
TABLE 2 composition of acidic copper plating wastewater and cyanide copper plating wastewater after treatment in example 1
| Kind of treated wastewater | pH value | Cu,g/L | CN,g/L | SO4,g/L |
| Cyanide copper plating wastewater | 11.0 | 0.5 | 0.37 | / |
| Acidic copper plating wastewater | 2.3 | 1.25 | / | 39 |
As is clear from tables 1 and 2, the removal rate of cyanide in the anolyte was 78.9%, and the recovery rate of copper in the catholyte was 84.3%. The detection shows that the purity of the metal copper precipitated on the cathode plate is 98.5%.
Through electrolysis, the cyanide ion concentration in cyanide copper plating wastewater is reduced from 1800mg/L to 370mg/L, a proper amount of sodium hypochlorite is added into residual liquid after electrolysis, the oxidation-reduction potential is controlled to be more than 350mv, the pH value is maintained to be more than 9.0, a proper amount of PAC and PAM are added for flocculation after reaction for a period of time, the residual copper concentration in supernatant is reduced to be less than 0.1mg/L, and the cyanide ion concentration is 0.1 mg/L. After the electrolysis is finished, the concentration of copper ions in the acidic copper plating wastewater is reduced from 8000mg/L to 1250mg/L, lime milk is added into the electrolyzed residual liquid to adjust the pH value to about 9.0, a proper amount of PAC and PAM is added for flocculation after a period of reaction, and the concentration of the residual copper in the supernatant is reduced to be less than 0.1 mg/L.
Example 2
The components of the acidic copper plating wastewater and the cyanide copper plating wastewater are as follows:
TABLE 3 composition of acidic copper plating wastewater and cyanide copper plating wastewater before treatment in example 2
As shown in figure 1, 10L of cyanide copper plating wastewater is injected into an anode area (comprising an anode chamber and a cyanide wastewater reservoir) of the electrolytic cell, 10L of acid copper plating wastewater is injected into a cathode area (comprising a cathode chamber and an acid copper plating wastewater reservoir), a titanium-based lead dioxide anode is selected as an anode material, and a 25-mesh violet copper mesh is selected as a cathode material. The effective area of the cathode and the anode is 500cm2The current was set to 7.5A during electrolysis (current density of cathode and anode was set to 150A/m)2) And dripping liquid caustic soda into the anolyte during the electrolysis process, and controlling the pH value of the anolyte to be between 11.0 and 11.5. And calculating the circulating electrolysis time of the anolyte according to the formula I.
t1＝C1V1/k1I，C1＝2.8g/L，V1＝10L，k10.17g/Ah, I is 7.5A, then t1＝21.9h。
The electrolysis time of the catholyte was calculated according to formula II.
t2＝C2V2/k2I，C2＝7g/L，V2＝10L，k20.9g/Ah, I7.5A, then t2＝10.4h。
The components of the treated acidic copper plating wastewater and cyanide copper plating wastewater after the completion of the electrolysis are shown in Table 2.
TABLE 4 composition of acidic copper plating wastewater and cyanide copper plating wastewater after treatment in example 2
| Kind of treated wastewater | pH value | Cu,g/L | CN,g/L | SO4,g/L |
| Cyanide copper plating wastewater | 11.0 | 0.6 | 0.29 | / |
| Acidic copper plating wastewater | 2.3 | 1.68 | / | 30 |
As is clear from tables 3 and 4, the removal rate of cyanide in the anolyte was 89.5%, and the recovery rate of copper in the catholyte was 75.8%. The detection proves that the purity of the metal copper precipitated on the cathode plate is 96.5%.
Through electrolysis, the concentration of cyanide ions in cyanide copper plating wastewater is reduced from 2800mg/L to 290mg/L, a proper amount of bleaching powder is added into residual liquid after electrolysis, the oxidation-reduction potential is controlled to be more than 350mv, the pH value is maintained to be more than 9.0, a proper amount of PAC and PAM are added for flocculation after reaction for a period of time, the concentration of residual copper in supernatant is reduced to be less than 0.1mg/L, and the concentration of cyanide ions is 0.12 mg/L. After the electrolysis is finished, the concentration of copper ions in the acidic copper plating wastewater is reduced from 7000mg/L to 1680mg/L, liquid alkali is added into the electrolyzed residual liquid to adjust the pH value to about 9.0, a proper amount of PAC and PAM is added for flocculation after a period of reaction, and the concentration of the residual copper in the supernatant is reduced to be less than 0.1 mg/L.
Example 3
The components of the acidic copper plating wastewater and the cyanide copper plating wastewater are as follows:
TABLE 5 composition of acidic copper plating wastewater and cyanide copper plating wastewater before treatment in example 3
| Kind of waste water | pH value | Cu,g/L | CN,g/L | SO4,g/L |
| Cyanide copper plating wastewater | 11.5 | 1.5 | 4.5 | / |
| Acidic copper plating wastewater | 1.1 | 3 | / | 18 |
As shown in figure 1, 15L of cyanide copper plating wastewater is injected into an anode area (comprising an anode chamber and a cyanide wastewater storage tank) of the electrolytic tank, 15L of acid copper plating wastewater is injected into a cathode area (comprising a cathode chamber and an acid copper plating wastewater storage tank), a graphite electrode is selected as an anode material, and a copper plate is selected as a cathode material. The effective area of the cathode and the anode is 350cm2Setting the current at 7A (Yin Yang) during electrolysisThe current density of the pole is set to 200A/m2) And dropwise adding ammonia water into the anolyte in the electrolysis process, and controlling the pH value of the anolyte to be 11.0-11.5. And calculating the circulating electrolysis time of the anolyte according to the formula I.
t1＝C1V1/k1I，C1＝4.5g/L，V1＝15L，k10.18g/Ah, I is 7A, then t1＝53.5h。
The electrolysis time of the catholyte was calculated according to formula II.
t2＝C2V2/k2I，C2＝3g/L，V2＝15L，k20.85g/Ah, I is 7.5A, then t2＝7.5h。
The components of the treated acidic copper plating wastewater and cyanide copper plating wastewater after the completion of the electrolysis are shown in Table 2.
TABLE 6 composition of acidic copper plating wastewater and cyanide copper plating wastewater after treatment in example 3
| Kind of treated wastewater | pH value | Cu,g/L | CN,g/L | SO4,g/L |
| Cyanide copper plating wastewater | 11.0 | 1.5 | 0.24 | / |
| Acidic copper plating wastewater | 2.1 | 0.85 | / | 30 |
As is clear from tables 5 and 6, the removal rate of cyanide in the anolyte was 94.7%, and the recovery rate of copper in the catholyte was 71.7%. The detection proves that the purity of the metal copper precipitated on the cathode plate is 96.1%.
Through electrolysis, the cyanide ion concentration in cyanide copper plating wastewater is reduced from 4500mg/L to 240mg/L, proper amount of bleaching powder is added into residual liquid after electrolysis, the oxidation-reduction potential is controlled to be above 350mv, the pH value is maintained to be above 9.0, proper amount of PAC and PAM are added for flocculation after reaction for a period of time, and the concentration of residual copper in supernatant is reduced to be below 0.1mg/L, and the concentration of cyanide ions is 0.08 mg/L. After the electrolysis is finished, the concentration of copper ions in the acidic copper plating wastewater is reduced from 3000mg/L to 850mg/L, the pH value of the electrolyzed residual liquid is adjusted to about 9.0 by adding liquid caustic soda, a proper amount of PAC and PAM is added for flocculation after a period of reaction, and the concentration of the residual copper in the supernatant is reduced to be less than 0.1 mg/L.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The method for combined treatment of cyanide copper plating wastewater and acid copper plating wastewater is characterized in that the cyanide copper plating wastewater is positioned in an anode chamber of a diaphragm electrolytic cell, the acid copper plating wastewater is positioned in a cathode chamber of the diaphragm electrolytic cell, and electrolysis is carried out by taking an inert material as an anode and copper as a cathode; the diaphragm of the diaphragm electrolytic cell is an anion exchange membrane.
2. The method as claimed in claim 1, wherein the cyanide copper plating wastewater comprises scrap tank liquor and/or conventional rinse water of cyanide copper plating, the concentration of copper ions in the cyanide copper plating wastewater is 500-2000 mg/L, and the concentration of cyanide ions is 500-5000 mg/L.
3. The method as claimed in claim 1, wherein the acidic copper plating wastewater comprises scrapped bath solution and/or conventional rinse water of acidic sulfate copper plating, and the concentration of copper ions in the acidic copper plating wastewater is 500-10000 mg/L.
4. The method of claim 1, wherein the inert material is titanium-coated lead dioxide, titanium-coated ruthenium iridium, titanium-coated tantalum iridium, or graphite, and the copper is a copper plate or a copper mesh.
5. The method of claim 1, wherein the current density during electrolysis is 50A/m2～500A/m2。
6. The method according to claim 1, wherein the pH value of the cyanide copper plating wastewater in the electrolysis process is 10-13.
7. The method according to claim 1, wherein the pH value of the acidic copper plating wastewater in the electrolysis process is 0.5-2.
8. The method as claimed in claim 1, wherein the time for which the cyanide copper plating wastewater is electrolyzed in the anode chamber during the electrolysis is calculated according to formula I:
t1＝C1V1/k1i formula I
T in the formula I1The unit is h for the electrolysis time of the cyanide copper plating wastewater in the anode chamber; c1The concentration of cyanide ions in the cyanide copper plating wastewater is g/L; v1The volume of the cyanide copper plating wastewater is L; k is a radical of1Represents the electrolytic constant, k, of cyanide ions1The value of (A) is 0.15 to 0.19 g/Ah; i isThe current in the electrolysis process is given in A.
9. The method of claim 1, wherein the electrolysis time of the acidic copper plating wastewater in the cathode chamber during the electrolysis process is calculated according to formula II:
t2＝C2V2/k2formula I formula II
In said formula II, t2The electrolysis time of the acidic copper plating wastewater in the cathode chamber is h; c2The concentration of copper ions in the acidic copper plating wastewater is g/L; v2The volume of the acidic copper plating wastewater is L; k is a radical of2Is the electrolytic constant, k, of copper ions2The value is 0.8 to 1.42 g/Ah; i is the current in the electrolysis process and has the unit of A.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116199312A (en) * | 2023-04-06 | 2023-06-02 | 苏州融和福天宝环保科技有限责任公司 | Method for combined treatment of cyanide copper plating wastewater and acid chromium plating wastewater |
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