Efficient recycling process based on panel industry copper etching waste liquid

Abstract

The invention belongs to the technical field of waste liquid treatment processes, and particularly relates to an efficient recycling process based on panel industry copper etching waste liquid. The preparation method comprises the following steps: sequentially carrying out extraction, back extraction and electrolysis to obtain elemental copper, mixing an extracted water phase obtained by extraction with a cooled backwashing agent to obtain a quasi-new solution, comparing the quasi-new solution with a formula of a standard copper etching solution through detection, and blending components to obtain the copper etching regeneration solution. According to the method, the copper etching waste liquid can be re-prepared into the copper etching regeneration liquid after copper is removed, the etching performance of the obtained copper etching regeneration liquid is consistent with that of the copper etching liquid, the treatment cost of organic matter, fluorine ions and other components in the copper etching waste liquid is reduced by recycling the copper etching waste liquid, and the recycling process and cost are greatly reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of waste liquid treatment process, and particularly relates to a high-efficiency recycling process based on copper etching waste liquid in the panel industry. BACKGROUND

[0002] Currently, there are two methods for treating copper etching waste liquid in the panel industry, namely dilution-precipitation method and extraction-electrolysis-enzyme method.

[0003] The dilution-precipitation method is to mix the copper etching waste liquid with other waste water, dilute 50-100 times to obtain copper waste water, then add liquid alkali and calcium chloride into the copper waste water in batches to precipitate copper ions, fluoride ions and part of organic matter in the copper waste water, and decompose hydrogen peroxide in the copper waste water, so that the content of these components is lower than the discharge standard, and after long-time and multi-batch precipitation, the upper clear liquid is finally discharged.

[0004] The extraction-electrolysis-enzyme method is to reduce the copper ions in the copper etching waste liquid to elemental copper through extraction-back extraction and electrolysis, add enzymes into the extracted waste liquid to decompose hydrogen peroxide and precipitate part of organic matter, and the obtained waste liquid is further treated to reach the discharge standard and is finally discharged.

[0005] The above two methods will decompose the high-value hydrogen peroxide in the copper etching waste liquid, and the expensive organic components will be decomposed and precipitated, although the final copper waste water will meet the discharge standard, but there is a great waste of resources. SUMMARY

[0006] In order to overcome the defects in the prior art, the present application provides a high-efficiency recycling process based on copper etching waste liquid in the panel industry. The present application can reconfigure the copper etching waste liquid into copper etching regeneration liquid after removing copper, and recover elemental copper in the copper etching waste liquid.

[0007] To achieve the above purpose, the following technical scheme is adopted: A high-efficiency recycling process based on copper etching waste liquid in the panel industry, the specific steps are as follows: S1, extraction: the cooled copper etching waste liquid is injected into the extraction tank, then the extraction agent is added and stirred uniformly, and then centrifugal separation is performed to obtain the extraction water phase and high-copper extraction agent; S2, back extraction: the high-copper extraction agent is washed and then added into the back extraction tank, then sulfuric acid solution is injected for back extraction, and after stirring uniformly, centrifugal separation is performed to obtain copper sulfate solution and low-copper extraction agent, and the low-copper extraction agent is cooled and then introduced into the extraction tank for recycling; S3, backwashing: the extraction water phase in step S1 is mixed with the cooled backwashing agent, stirred uniformly, and then centrifugal separation is performed to obtain quasi-new liquid; S4, electrolysis of copper sulfate: the copper sulfate solution in step S2 is passed into an electrolytic cell for electrolysis to obtain elemental copper; S5, waste liquid recycling: the component content of the quasi-new liquid in step S3 is detected, compared with the formula of the standard copper etching liquid, then passed into a mixing tank for component adjustment to obtain a copper etching regeneration liquid.

[0008] Preferably, in step S1, the volume ratio of the copper etching waste liquid to the extractant is 1:(0.5-1).

[0009] Preferably, in step S1, the extractant is one of Lix54-100, Lix84, Lix84i, Lix860, Lix984, P204, P507, N-910, N1923, N902, TBP and M5640.

[0010] Preferably, in step S2, the high-copper extractant is washed with high-purity water, and the volume ratio of the high-purity water to the high-copper extractant is 1:(2-5).

[0011] Preferably, in step S2, the volume ratio of the sulfuric acid solution to the high-copper extractant is 1:(2-8).

[0012] Preferably, in step S1, the copper ion concentration of the aqueous phase is 50-150 ppm; in step S2, the copper ion concentration in the copper sulfate solution is 20000-25000 ppm.

[0013] Preferably, in step S3, the volume ratio of the aqueous phase to the backwash agent is 1:(0.01-0.05).

[0014] Preferably, in step S3, the backwash agent is one or more of toluene, petroleum ether, diethyl ether, n-hexane and sulfonated kerosene.

[0015] Preferably, in step S3, the residual amount of the extractant in the quasi-new liquid is <1 ppm.

[0016] Preferably, in step S1, the temperature of the cooled copper etching waste liquid is 1-10℃; in step S2, the temperature of the cooled low-copper extractant is 1-10℃; in step S3, the temperature of the cooled backwash agent is 1-10℃; in step S5, the temperature of the cooled copper etching regeneration liquid is 1-10℃.

[0017] The present application has the following advantages: (1) The extractant of the present application is used as an intermediate medium to transfer / concentrate copper ions in copper etching waste liquid into sulfuric acid solution, and finally to obtain elemental copper. The extractant can be recycled, thereby reducing the processing cost. At the same time, a small amount of organic matter extracted from the waste liquid is contained in the high-copper extractant obtained after extraction. The residual organic matter in the high-copper extractant can be washed into the water phase by high-purity water, thereby avoiding the entry of the residual organic matter into the copper sulfate solution in the stripping step, which leads to the shortening of the service life of the electrode in the electrolytic cell.

[0018] (2) The extraction water phase obtained after extraction of the present application contains a small amount of residual extractant, which will directly affect the etching effect of the copper etching regeneration liquid. The backwashing step is set, and the backwashing agent can extract the extractant in the extraction water phase, thereby effectively avoiding the influence of the extractant on the use of the copper etching regeneration liquid.

[0019] (3) Since the process of the present application is carried out in a closed environment, the copper etching waste liquid contains copper ions. At room temperature, copper can catalyze the decomposition of hydrogen peroxide, and the generated oxygen can cause safety problems. In addition, if hydrogen peroxide is decomposed, it is also not conducive to recycling and reuse. Therefore, the copper etching waste liquid and the like are subjected to cooling treatment in the process of the present application, which can effectively inhibit the decomposition of hydrogen peroxide, thereby ensuring the safety of the overall process, and the hydrogen peroxide in the copper etching waste liquid is also effectively recycled and reused.

[0020] (4) The copper etching waste liquid is removed from the copper etching waste liquid to prepare the copper etching regeneration liquid, and the obtained copper etching regeneration liquid has the same etching performance as the copper etching liquid. Through the recycling and reuse of the copper etching waste liquid, the processing cost of the organic matter, fluoride ions and other components in the copper etching waste liquid is reduced, and the process and cost of recycling are greatly reduced. In addition, the present application can quickly process the copper etching waste liquid, shorten the storage time of the copper etching waste liquid, improve the processing efficiency, and reduce the wastewater discharge, thereby meeting the requirements of green environmental protection. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The process flow diagram of the present application.

[0022] Figure 2 The SEM image of the etching effect of the copper etching regeneration liquid obtained in Example 1 of the present application.

[0023] Figure 3 The SEM image of the etching effect of the copper etching regeneration liquid obtained in Example 2 of the present application.

[0024] Figure 4 The SEM image of the etching effect of the copper etching regeneration liquid obtained in Example 3 of the present application.

[0025] Figure 5 The SEM image of the etching effect of the standard copper etching liquid of the present application. DETAILED DESCRIPTION

[0026] To further illustrate the technical means and effects adopted by the present application to achieve the predetermined inventive objectives, the specific embodiments, structures, features and effects according to the present application are described in detail below in conjunction with the drawings and preferred embodiments.

[0027] Embodiments 1-3 provide a recycling process based on copper etching waste liquid in the panel industry, wherein the composition of the copper etching waste liquid includes: hydrogen peroxide 18-19wt%, copper ions 4000-5000ppm, organic matter 3-5wt%.

[0028] Embodiment 1 The flow chart of the recycling process based on copper etching waste liquid in the panel industry used in this embodiment is shown as follows: Figure 1 The specific steps are as follows: S1, extraction The copper etching waste liquid is cooled to 1℃ by a heat exchanger, and then heavy phase and light phase are injected into the extraction tank, the volume ratio of the heavy phase (copper etching waste liquid) to the light phase (extraction agent) is 1:0.5, and after uniform stirring, centrifugal separation is performed to obtain extraction water phase and high-copper extraction agent. After treatment of the copper etching waste liquid, the concentration of copper ions decreases from 4000ppm to 50ppm.

[0029] The extraction agent is Lix54-100.

[0030] S2, stripping

[0031] Heavy phase and light phase are injected into the washing tank, the volume ratio of the heavy phase (high-purity water) to the light phase (high-copper extraction agent) is 1:2, and after uniform stirring, centrifugal separation is performed to obtain high-copper extraction agent after washing; then heavy phase and light phase are injected into the stripping tank, the volume ratio of the heavy phase (sulfuric acid solution) to the light phase (high-copper extraction agent) is 1:2, and after uniform stirring, centrifugal separation is performed to obtain copper sulfate solution and low-copper extraction agent; the low-copper extraction agent can be used as the extraction agent, and after cooling, it is introduced into the extraction tank for recycling. The concentration of copper ions in the copper sulfate solution is 20000ppm.

[0032] S3, backwashing

[0033] The backwashing agent is cooled to 1℃, and then heavy phase and light phase are injected into the backwashing tank, the volume ratio of the heavy phase (extraction water phase) to the light phase (backwashing agent) is 1:0.01, and after uniform stirring, centrifugal separation is performed to obtain quasi-new liquid. The residual amount of the extraction agent in the quasi-new liquid is 0.5ppm.

[0034] The backwashing agent is toluene.

[0035] S4, electrolysis of copper sulfate

[0036] After the stripping step, the copper sulfate solution enters the electrolysis tank for electrolysis to obtain elemental copper.

[0037] S5, waste liquid recycling

[0038] After the backwashing step, the quasi-new liquid enters the mixing tank, and after detection, the components are adjusted compared with the formula of the standard copper etching liquid. Then through the processes of stirring dissolution, circulating filtration, etc., the copper etching regeneration liquid is obtained, and is stored after cooling.

[0039] Example 2 The flow chart of the recycling process of the copper etching waste liquid based on the panel industry used in this example is shown in Figure 1 The specific steps are as follows: S1, extraction The copper etching waste liquid is cooled to 10℃ by a heat exchanger, and then heavy phase and light phase are injected into the extraction tank. The volume ratio of heavy phase (copper etching waste liquid) to light phase (extractant) is 1:1. After uniform stirring, centrifugal separation is performed to obtain the extraction water phase and high-copper extraction agent. After treatment, the copper ion concentration of the copper etching waste liquid decreases from 5000 ppm to 150 ppm.

[0040] The extractant is M5640.

[0041] S2, stripping

[0042] Heavy phase and light phase are injected into the washing tank. The volume ratio of heavy phase (high-purity water) to light phase (high-copper extraction agent) is 1:5. After uniform stirring, centrifugal separation is performed to obtain the high-copper extraction agent after washing. Then heavy phase and light phase are injected into the stripping tank. The volume ratio of heavy phase (sulfuric acid solution) to light phase (high-copper extraction agent) is 1:8. After uniform stirring, centrifugal separation is performed to obtain the copper sulfate solution and low-copper extraction agent. The low-copper extraction agent can be used as the extractant and is recycled by being injected into the extraction tank after cooling. The copper ion concentration in the copper sulfate solution is 25000 ppm.

[0043] S3, backwashing

[0044] The backwashing agent is cooled to 10℃, and then heavy phase and light phase are injected into the backwashing tank. The volume ratio of heavy phase (extraction water phase) to light phase (backwashing agent) is 1:0.05. After uniform stirring, centrifugal separation is performed to obtain the quasi-new liquid. The residual amount of the extractant in the quasi-new liquid is 0.6 ppm.

[0045] The backwashing agent is ethyl ether.

[0046] S4, electrolytic copper sulfate

[0047] After the stripping step, the copper sulfate solution enters the electrolysis tank for electrolysis to obtain elemental copper.

[0048] S5, waste liquid recycling

[0049] After the backwashing step, the quasi-new liquid enters the mixing tank, and after detection, the components are adjusted compared with the standard copper etching liquid formula. Then through the processes of stirring dissolution, circulating filtration, etc., the copper etching regeneration liquid is obtained, and is stored after cooling.

[0050] Example 3 The flow chart of the recycling process based on the panel industry copper etching waste liquid used in this example is shown in Figure 1 The specific steps are as follows: S1, extraction The copper etching waste liquid is cooled to 5℃ by a heat exchanger, and then heavy phase and light phase are injected into the extraction tank. The volume ratio of heavy phase (copper etching waste liquid) to light phase (extracting agent) is 1:0.8. After uniform stirring, centrifugal separation is performed to obtain the extraction water phase and high-copper extracting agent. After treatment of the copper etching waste liquid, the copper ion concentration decreases from 4500 ppm to 100 ppm.

[0051] The extracting agent is P507.

[0052] S2, stripping

[0053] Heavy phase and light phase are injected into the washing tank. The volume ratio of heavy phase (high-purity water) to light phase (high-copper extracting agent) is 1:3. After uniform stirring, centrifugal separation is performed to obtain the high-copper extracting agent after washing. Then heavy phase and light phase are injected into the stripping tank. The volume ratio of heavy phase (sulfuric acid solution) to light phase (high-copper extracting agent) is 1:5. After uniform stirring, centrifugal separation is performed to obtain the copper sulfate solution and low-copper extracting agent. The low-copper extracting agent can be used as the extracting agent and is recycled after cooling and then introduced into the extraction tank. The copper ion concentration in the copper sulfate solution is 23500 ppm.

[0054] S3, backwashing

[0055] The backwashing agent is cooled to 1℃, and then heavy phase and light phase are injected into the backwashing tank. The volume ratio of heavy phase (extraction water phase) to light phase (backwashing agent) is 1:0.03. After uniform stirring, centrifugal separation is performed to obtain the quasi-new liquid. The residual amount of extracting agent in the quasi-new liquid is 0.8 ppm.

[0056] The backwashing agent is petroleum ether.

[0057] S4, electrolytic copper sulfate

[0058] After the stripping step, the copper sulfate solution enters the electrolysis tank for electrolysis to obtain elemental copper.

[0059] S5, waste liquid recycling

[0060] After the backwashing step, the quasi-new liquid enters the mixing tank, and after detection, the components are adjusted compared with the standard copper etching liquid formula. Then through the processes of stirring dissolution, circulating filtration, etc., the copper etching regeneration liquid is obtained, and is stored after cooling.

[0061] The etching performance of the copper etching regenerating solution in Examples 1-3 and the standard copper etching solution was detected: The copper etching regenerating solution in Examples 1-3 and the standard copper etching solution were added with copper powder for dissolution, and after the copper ions in the etching solution reached 5000 ppm, they were stored at room temperature in the dark. At a temperature of 33°C, the etching machine was used to etch the substrate (MoNb / Cu = 150 / 6000 Å), and the total etching time was 1.5 times EPD. EPD is the time required for the substrate to become transparent during etching, i.e., the etching endpoint time. By controlling the total etching time to be 1.5 times EPD, the formation of the etching taper angle can be ensured, meeting the target requirements. After etching, the substrate was taken out, cleaned and dried, and then the taper angle and CD bias were observed using a scanning electron microscope (SEM) to evaluate the etching effect. The results are shown in Table 1 and Figures 2-5 .

[0062] Table 1

[0063] As can be seen from Table 1 in combination with Figures 2-5 , the etching performance of the copper etching regenerating solution of the present application is consistent with that of the standard copper etching solution, fully demonstrating that the recycling process of the present application is practical and meets the requirements of green environmental protection.

[0064] The above is only a preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement and improvement made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A process for recycling of copper etching waste liquid based on panel industry, characterized in that, The specific steps are as follows: S1, extraction: the copper etching waste liquid after cooling is injected into the extraction tank, then the extractant is added and stirred uniformly, and then centrifugal separation is performed to obtain an extraction water phase and a high-copper extractant; S2, stripping: the high-copper extractant is washed and then added into a stripping tank, and then sulfuric acid solution is injected for stripping, and then stirring is performed uniformly, and then centrifugal separation is performed to obtain a copper sulfate solution and a low-copper extractant, and the low-copper extractant is cooled and then introduced into the extraction tank for recycling; S3, backwashing: the extraction water phase in step S1 is mixed with the backwash agent after cooling, stirred uniformly, and then centrifugal separation is performed to obtain a quasi-new liquid; S4, electrolytic copper sulfate: the copper sulfate solution in step S2 is introduced into an electrolytic tank for electrolysis to obtain elemental copper; S5, waste liquid recycling: the composition content of the quasi-new liquid in step S3 is detected, compared with the formula of the standard copper etching liquid, then introduced into a mixing tank for component adjustment to obtain a copper etching regeneration liquid.

2. A process for recycling of copper etching spent liquor based on panel industry according to claim 1 characterized in that: In step S1, the volume ratio of the copper etching waste liquid to the extractant is 1:(0.5-1).

3. A process for recycling of copper etching spent liquor based on panel industry as claimed in claim 1, wherein: In step S1, the extractant is one of Lix54-100, Lix84, Lix84i, Lix860, Lix984, P204, P507, N-910, N1923, N902, TBP and M5640.

4. The process as claimed in claim 1, wherein the process is based on recycling of copper etching waste liquid of panel industry. In step S2, high-purity water is used to wash the high-copper extractant, and the volume ratio of the high-purity water to the high-copper extractant is 1:(2-5).

5. A process for recycling of copper etching spent liquor based on panel industry as claimed in claim 1, wherein: In step S2, the volume ratio of the sulfuric acid solution to the high-copper extractant is 1:(2-8).

6. A process for recycling of copper etching spent liquor based on panel industry as claimed in claim 1, wherein: In step S1, the copper ion concentration of the extraction water phase is 50-150 ppm; in step S2, the copper ion concentration in the copper sulfate solution is 20000-25000 ppm.

7. A process for recycling of copper etching spent liquor based on panel industry as claimed in claim 1, wherein the said process is characterized by: In step S3, the volume ratio of the extraction water phase to the backwash agent is 1:(0.01-0.05).

8. A process for recycling of copper etching spent liquor based on panel industry as claimed in claim 1, wherein: In step S3, the backwash agent is one or more of toluene, petroleum ether, diethyl ether, n-hexane and sulfonated kerosene.

9. A process for recycling of copper etching spent liquor based on panel industry as claimed in claim 1, wherein: In step S3, the residual amount of the extractant in the quasi-new liquid is <1 ppm.

10. A process for recycling of copper etching spent liquor based on panel industry as claimed in claim 1, wherein: In step S1, the temperature of the copper etching waste liquid after cooling is 1-10℃; in step S2, the temperature of the low-copper extractant after cooling is 1-10℃; in step S3, the temperature of the backwash agent after cooling is 1-10℃; in step S5, the temperature of the copper etching regeneration liquid after cooling is 1-10℃.

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