A recovery treatment process for copper acid waste liquor based on high-concentration hydrogen peroxide

Abstract

The application discloses a kind of based on high-concentration hydrogen peroxide copper acid waste liquid recovery processing process, belong to copper acid waste liquid processing technical field, including the following steps: after mixing copper acid waste liquid with concentrated sulfuric acid is transported to mixed decomposition tank, heating and holding treatment, obtain except hydrogen peroxide copper acid waste liquid;Adjust the pH value of except hydrogen peroxide copper acid waste liquid and be mixed evenly with extractant, stratify after standing, obtain low copper waste liquid and high copper extraction liquid, sulfuric acid solution is added to high copper extraction liquid, obtain low copper extraction liquid and copper sulfate solution, low copper extraction liquid goes to extraction tank and is used cyclically;Copper sulfate solution is electrolyzed, obtain metal copper and sulfuric acid solution, sulfuric acid solution goes to back extraction tank and is used cyclically;Low copper waste liquid is treated using ion exchange resin, complete high-concentration hydrogen peroxide copper acid waste liquid recovery processing process, the application processing operation step is simple, safety is high, does not involve the use of additive such as enzyme, low in cost, and treatment effect is good.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of copper acid waste liquid treatment, and particularly relates to a recovery treatment process for copper acid waste liquid based on high-concentration hydrogen peroxide. BACKGROUND

[0002] The copper etching process is an important process in the production of PCBs, panels and the like. Under this process, a large amount of copper acid waste liquid containing hydrogen peroxide and divalent copper ions will be generated. The copper acid waste liquid cannot be directly discharged and needs to be treated for its chemical components harmful to the environment, especially hydrogen peroxide and copper ions.

[0003] Currently, the hydrogen peroxide in the copper acid waste liquid is mostly treated by reduction using alkali or enzymes, and the treatment scheme for copper is mainly based on the settlement method, extraction method and electrolysis method. The processes for simultaneously treating hydrogen peroxide and copper ions in the copper acid waste liquid mainly include the following three kinds:

[0004] 1) Dilution-settlement process: A large amount of waste liquid not containing copper ions and hydrogen peroxide is added to dilute the concentration of hydrogen peroxide and copper ions in the copper acid waste liquid, and then alkali is added to increase the pH value of the system. Under the condition of high pH value, the hydrogen peroxide in the waste liquid will decompose and the copper ions will precipitate.

[0005] 2) Extraction-electrolysis-decomposition of hydrogen peroxide process: The copper ions in the copper acid waste liquid are extracted into a certain concentration of sulfuric acid solution by extraction / back-extraction to obtain a copper sulfate solution. Elemental copper is obtained by electrolyzing the copper sulfate, and the low-copper waste liquid is diluted and the hydrogen peroxide is decomposed by adding enzymes.

[0006] 3) Decomposition of hydrogen peroxide-acid dilution-electrolysis process: The hydrogen peroxide is decomposed by kettle heating, then the COD concentration in the waste liquid is reduced by dilution with sulfuric acid, and finally the elemental copper is electrolyzed.

[0007] However, when the above three processes are used to treat copper acid waste liquid containing high-concentration hydrogen peroxide, the following problems often exist:

[0008] 1. When the dilution-alkali addition settlement method is used, the copper acid waste liquid needs to be greatly diluted. Considering the concentration of hydrogen peroxide in the waste liquid and the safety requirements, the dilution ratio is often more than 50 times, which is high in treatment cost and low in efficiency.

[0009] 2. When the extraction-electrolysis method is used to recover copper ions, it is difficult to reduce the concentration of treated copper ions to below the discharge standard due to the presence of a large amount of organic chelating compounds in the waste liquid.

[0010] 3. High-concentration hydrogen peroxide has great safety hazards, and the scheme of first recovering copper and then using enzymes to degrade hydrogen peroxide will greatly increase the safety cost of the process.

[0011] 4, The oxidizability of high-concentration hydrogen peroxide can cause corrosion to equipment and pipelines, and the treatment of waste liquid containing high-concentration hydrogen peroxide can increase the corrosion prevention cost of equipment;

[0012] 5, In the decomposition of hydrogen peroxide-acid dilution-electrolysis process, the decomposition time of hydrogen peroxide is too long, the decomposition efficiency is low, and part of the hydrogen peroxide remains in the waste liquid after decomposition; even if the waste liquid is diluted several times by sulfuric acid before electrolysis, the organic matter contained in the waste liquid will still affect the electrolysis of copper, which will reduce the service life of the electrode; and the electrolysis efficiency is low, so that the copper ions in the waste liquid far fail to reach the safe discharge standard. SUMMARY

[0013] The purpose of the present application is to provide a recovery treatment process for copper acid waste liquid based on high-concentration hydrogen peroxide, to solve the problems of high treatment cost and poor effect in the existing recovery treatment process for copper acid waste liquid.

[0014] The purpose of the present application can be achieved by the following technical solutions:

[0015] A recovery treatment process for copper acid waste liquid based on high-concentration hydrogen peroxide, the treatment process comprising the following steps:

[0016] (1) Decomposition of hydrogen peroxide by adding acid-heating method: the copper acid waste liquid is mixed with concentrated sulfuric acid and then sent to a mixed decomposition tank for heating and holding treatment, to obtain hydrogen peroxide-free copper acid waste liquid;

[0017] The copper acid waste liquid is first mixed with concentrated sulfuric acid by a pipeline mixer, and then enters the heating zone of the mixed decomposition tank. During this period, the hydrogen peroxide in the copper acid waste liquid starts to heat and decompose rapidly, and then gradually flows into the holding zone. The holding zone ensures efficient decomposition, and also ensures the stability and safety of hydrogen peroxide decomposition. Finally, the waste liquid with completely decomposed hydrogen peroxide flows out of the mixed decomposition tank through the pipeline, and the hydrogen peroxide-free copper acid waste liquid is obtained;

[0018] (2) Extraction / back-extraction: adjust the pH value of the hydrogen peroxide-free copper acid waste liquid and mix it uniformly with the extractant, and then separate it into layers to obtain low-copper waste liquid and high-copper extraction liquid. Add sulfuric acid solution to the high-copper extraction liquid for back-extraction to obtain low-copper extraction liquid and copper sulfate solution. The low-copper extraction liquid is recycled to the extraction tank;

[0019] (3) Electrolysis of copper sulfate: electrolysis of copper sulfate solution to obtain metallic copper and sulfuric acid solution, and the sulfuric acid solution is recycled to the back-extraction tank;

[0020] (4) Resin adsorption: ion exchange resin is used to treat the low-copper waste liquid, and the recovery treatment process for high-concentration hydrogen peroxide copper acid waste liquid is completed.

[0021] Further, the amount of concentrated sulfuric acid added in step (1) is 0.5% to 5% of the mass of the copper acid waste liquid. If the amount of concentrated sulfuric acid is too low, the hydrogen peroxide is not stable and the safety cannot be guaranteed. If the amount of concentrated sulfuric acid is too high, the decomposition rate of hydrogen peroxide is greatly reduced, and too much acid will reduce the recovery effect of copper ions in the subsequent process.

[0022] Further, the interior of the mixed decomposition tank in step (1) is separated into a curved channel by a partition, and the mixed decomposition tank includes a heating zone and a heat preservation zone. The temperature of the heating zone is 70℃ to 98℃, and the temperature of the heat preservation zone is 80℃ to 98℃.

[0023] Further, the heating and heat preservation treatment time in step (1) is 5min to 20min.

[0024] Further, the mass fraction of the concentrated sulfuric acid is 95% to 98%.

[0025] Further, the pH value of the copper acid waste liquid is 2 to 5, the copper ion content is 2000ppm to 5000ppm, and the hydrogen peroxide content is 5wt% to 22wt%.

[0026] Further, the hydrogen peroxide content in the hydrogen peroxide-removed copper acid waste liquid is less than 0.1wt%.

[0027] Further, step (2) is specifically operated as follows:

[0028] The hydrogen peroxide-removed copper acid waste liquid is transported to a pretreatment tank, and concentrated sulfuric acid is added to the pretreatment tank to adjust the pH value to 1 to 3, obtaining an acidified hydrogen peroxide-removed copper acid waste liquid. The acidified hydrogen peroxide-removed copper acid waste liquid is transported to an extraction tank, and an extractant is added to the extraction tank, stirred uniformly, and allowed to stand and separate into layers. After phase separation, a low-copper waste liquid and a high-copper extraction liquid are obtained. The high-copper extraction liquid is transported to a back-extraction tank, and a sulfuric acid solution is added to the back-extraction tank, stirred uniformly, and allowed to stand and separate into layers, obtaining a low-copper extraction liquid and a copper sulfate solution. The low-copper extraction liquid is recycled to the extraction tank.

[0029] Further, the mass ratio of the hydrogen peroxide-removed copper acid waste liquid to the extractant in step (2) is 1 to 10:1.

[0030] Further, the mass ratio of the high-copper extraction liquid to the sulfuric acid solution in step (2) is 1 to 5:1, and the mass fraction of the sulfuric acid solution is 10% to 30%.

[0031] Further, the extractant is one of Lix54-100, Lix84, Lix84i, Lix860, Lix984, P204, P507, N-910, N1923, N902, TBP (tributyl phosphate), and M5640.

[0032] Further, the copper ion content in the low-copper extraction solution is 10-50 ppm, and the copper sulfate content in the copper sulfate solution is greater than or equal to 20,000 ppm.

[0033] Further, the electrolysis temperature in step (3) is 40-50 DEG C, the current density is 200 A / m 2 ~ 250 A / m 2 , the electrolysis voltage is 3-5 V, and the electrolysis time is 8-15 h.

[0034] Further, in step (3), the positive electrode of the electrolytic cell is connected to the electrolyte, the negative electrode is connected to the copper sulfate solution, and a reverse osmosis diaphragm is arranged between the copper sulfate solution and the electrolyte.

[0035] Further, the specific operation of step (4) is as follows: the low-copper waste liquid is transported to a resin tower filled with ion exchange resin, the flow rate is 0.5-2.8 BV / h, and the temperature is 15-50 DEG C; the copper ions in the low-copper waste liquid are adsorbed by the ion exchange resin, the effluent of the resin tower is collected in a storage tank, and the treated waste liquid is obtained; when the ion exchange resin adsorption reaches saturation, stop feeding the low-copper waste liquid, add concentrated sulfuric acid to the resin tower, use the concentrated sulfuric acid to clean the ion exchange resin, and restore the adsorption capacity of the ion exchange resin, and the cleaning liquid is obtained and sent to the pretreatment tank to participate in the pH adjustment.

[0036] Further, the ion exchange resin is one of LSC-485, LSC-495, LSC-855, LX-1850H, LX-1850NH, 001x7 and LX-300C.

[0037] Further, the copper ion content in the treated waste liquid is less than or equal to 0.5 ppm.

[0038] The beneficial effects of the present application are as follows:

[0039] 1. The present application adopts the acid-heat method to decompose hydrogen peroxide, and then uses the extraction-electrolysis method to recover the copper in the copper acid waste liquid after removing the hydrogen peroxide, and finally uses the ion exchange resin adsorption method to adsorb a small amount of copper ions in the low-copper waste liquid to meet the discharge standard, the process operation steps of the present application are simple, safe, do not involve the use of additives such as enzymes, the cost is low, and the treatment effect is good.

[0040] 2. The application adopts the acid-heat method to decompose high-concentration hydrogen peroxide in copper acid waste liquid, which is safe, stable and efficient. By adjusting the acid ratio, heating temperature and treatment time, the decomposition time and intensity of hydrogen peroxide in copper acid waste liquid with different concentrations of copper ions can be effectively adjusted. Compared with the heating method alone, the acid-heat method can effectively control the intensity of the reaction and better handle high-concentration hydrogen peroxide, improving the safety of production.

[0041] 3. The copper acid waste liquid of the application is continuously heated and decomposed by mixing the decomposition tank, which greatly improves the decomposition efficiency of hydrogen peroxide and quickly and effectively removes hydrogen peroxide in copper acid waste liquid while ensuring safety.

[0042] 4. The application preferentially handles hydrogen peroxide in copper acid waste liquid, effectively avoiding its corrosion of equipment, pipelines and materials in the remaining steps, greatly reducing the cost of equipment corrosion and material cost.

[0043] 5. The application selects efficient extractants and uses extraction-electrolysis method to recover copper in copper acid waste liquid, avoiding the interference of organic matter in copper acid waste liquid in direct electrolysis of copper acid waste liquid containing hydrogen peroxide, increasing the concentration of copper ions in the electrolyte, and greatly improving the electrolysis efficiency. In this system, the extractant and sulfuric acid solution can be recycled, greatly reducing the cost of copper recovery.

[0044] 6. The application uses ion exchange resin treatment to effectively reduce the copper ion content in copper acid waste liquid after extraction, so that it meets the emission standard. At the same time, the copper ions adsorbed in the resin tower are effectively recovered by strong acid solution backwashing, and the ion exchange resin can be recycled, reducing the cost of raw materials. BRIEF DESCRIPTION OF DRAWINGS

[0045] The application will be further described below in conjunction with the drawings.

[0046] Figure 1 is a flowchart of a copper acid waste liquid recovery treatment process based on high-concentration hydrogen peroxide according to the application;

[0047] Figure 2 is a flowchart of the acid-heat method for decomposing hydrogen peroxide according to the application;

[0048] Figure 3 is a flowchart of the extraction / back-extraction step according to the application;

[0049] Figure 4 is a flowchart of the copper electrolysis step according to the application;

[0050] Figure 5 is a flowchart of the resin adsorption step according to the application. DETAILED DESCRIPTION

[0051] In order to make the technical problems, technical solutions and beneficial effects to be solved in the present application clearer, the present application will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only intended to explain the present application and not intended to limit the present application.

[0052] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or similar expressions means any combination of the items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can represent a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0053] The terms used in the embodiments of the present application are merely intended for the purpose of describing specific embodiments and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0054] It should be understood that in various embodiments of the present application, the size of the sequence number of each process does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence, and the execution order of each process should be determined according to its function and inherent logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0055] The weight of the related components mentioned in the specification of the embodiments of the present application can not only refer to the specific content of each component, but also represent the weight ratio relationship between each component, therefore, as long as the content of the related components in the specification of the embodiments of the present application is enlarged or reduced in proportion, it is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass mentioned in the specification of the embodiments of the present application can be μg, mg, g, kg and other mass units commonly known in the chemical field.

[0056] Unless otherwise defined, all professional terms used herein have the same meaning as generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present application.

[0057] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.

[0058] In view of the problems of high treatment cost and poor effect of the existing copper acid waste liquid recovery treatment process, the application provides a copper acid waste liquid recovery treatment process based on high-concentration hydrogen peroxide, which comprises the following steps:

[0059] (1) Hydrogen peroxide decomposition by adding acid and heating: the copper acid waste liquid is mixed with concentrated sulfuric acid and then sent to a mixed decomposition tank for heating and holding treatment to obtain a hydrogen peroxide-free copper acid waste liquid;

[0060] The copper acid waste liquid is first mixed with concentrated sulfuric acid by a pipeline mixer and then enters the heating zone of the mixed decomposition tank. During this period, the hydrogen peroxide in the copper acid waste liquid starts to heat and decompose rapidly, and then gradually flows into the holding zone. The holding zone ensures efficient decomposition and also ensures the stability and safety of hydrogen peroxide decomposition. Finally, the waste liquid with completely decomposed hydrogen peroxide flows out of the mixed decomposition tank through a pipeline to obtain a hydrogen peroxide-free copper acid waste liquid;

[0061] (2) Extraction / back-extraction: adjust the pH value of the hydrogen peroxide-free copper acid waste liquid and mix it uniformly with an extractant, and then separate it by layers to obtain a low-copper waste liquid and a high-copper extraction liquid. Add sulfuric acid solution to the high-copper extraction liquid for back-extraction to obtain a low-copper extraction liquid and a copper sulfate solution. The low-copper extraction liquid is recycled to the extraction tank;

[0062] (3) Electrolytic copper sulfate: electrolyze the copper sulfate solution to obtain metallic copper and sulfuric acid solution. The sulfuric acid solution is recycled to the back-extraction tank;

[0063] (4) Resin adsorption: use ion exchange resin to treat the low-copper waste liquid to complete the recovery treatment process of the high-concentration hydrogen peroxide copper acid waste liquid.

[0064] In some embodiments, the amount of concentrated sulfuric acid added in step (1) is 0.5% to 5% of the mass of the copper acid waste liquid. In exemplary embodiments, the mass ratio can be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4.0%, 4.5%, 5.0%, etc. or any range between any two of the above ratios. Within this mass ratio range, the hydrogen peroxide decomposition is stable and does not affect the subsequent recovery effect of copper ions. It should be noted that the amount of concentrated sulfuric acid added should not exceed the above range. Otherwise, if the amount of concentrated sulfuric acid added is too low, the hydrogen peroxide decomposition is unstable and the safety cannot be guaranteed. If the amount of concentrated sulfuric acid added is too high, the decomposition rate of hydrogen peroxide is greatly reduced, and too much acid will reduce the recovery effect of copper ions in the subsequent step.

[0065] In some embodiments, the mixing tank in step (1) is divided into a curved channel by a partition, including a heating zone and a heat preservation zone, the temperature of the heating zone is 70℃-98℃, in exemplary but non-limiting examples, it can be 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 98℃ or a range between any two of the above temperatures; the temperature of the heat preservation zone is 80℃-98℃, in exemplary but non-limiting examples, it can be 80℃, 85℃, 90℃, 95℃, 98℃ or a range between any two of the above temperatures.

[0066] In some embodiments, the heating and heat preservation treatment time in step (1) is 5min-20min.

[0067] In some embodiments, the mass fraction of the concentrated sulfuric acid is 95%-98%.

[0068] In some embodiments, the pH value of the copper acid waste liquid is 2-5, the copper ion content is 2000ppm-5000ppm, and the hydrogen peroxide content is 5wt%-22wt%.

[0069] In some embodiments, the hydrogen peroxide content in the hydrogen peroxide-removed copper acid waste liquid is <0.1wt%.

[0070] In some embodiments, step (2) is specifically as follows:

[0071] The hydrogen peroxide-removed copper acid waste liquid is transported to a pretreatment tank, concentrated sulfuric acid is added to the pretreatment tank to adjust the pH value to 1-3, obtaining an acidified hydrogen peroxide-removed copper acid waste liquid, the acidified hydrogen peroxide-removed copper acid waste liquid is transported to an extraction tank, an extractant is added to the extraction tank, stirring is performed until uniform, and then the mixture is left to separate into layers, obtaining a low-copper waste liquid and a high-copper extraction liquid; the high-copper extraction liquid is transported to a back-extraction tank, and a sulfuric acid solution is added to the back-extraction tank, stirring is performed until uniform, and then the mixture is left to separate into layers, obtaining a low-copper extraction liquid and a copper sulfate solution, and the low-copper extraction liquid is recycled to the extraction tank.

[0072] In some embodiments, the mass ratio of the hydrogen peroxide-removed copper acid waste liquid to the extractant in step (2) is 1-10:1.

[0073] In some embodiments, the mass ratio of the high-copper extraction liquid to the sulfuric acid solution in step (2) is 1-5:1, and the mass fraction of the sulfuric acid solution is 10%-30%.

[0074] In some embodiments, the extractant is one of Lix54-100, Lix84, Lix84i, Lix860, Lix984, P204, P507, N-910, N1923, N902, TBP (tributyl phosphate) and M5640.

[0075] In some embodiments, the low-copper extraction solution has a copper ion content of 10 ppm to 50 ppm, and the copper sulfate solution has a copper sulfate content of ≥20,000 ppm.

[0076] In some embodiments, the electrolysis temperature in step (3) is 40°C to 50°C, the current density is 200 A / m 2 to 250 A / m 2 , the electrolysis voltage is 3 V to 5 V, and the electrolysis time is 8 h to 15 h.

[0077] In some embodiments, in step (3), the positive electrode of the electrolytic cell is connected to the electrolyte, and the negative electrode is connected to the copper sulfate solution. A reverse osmosis membrane is provided between the copper sulfate solution and the electrolyte. During operation, oxygen is generated at the positive electrode, and elemental copper is generated at the negative electrode.

[0078] In some embodiments, step (4) is specifically performed as follows: the low-copper waste liquid is transported to a resin tower filled with ion exchange resin, the flow rate is 0.5 BV / h to 2.8 BV / h, and the temperature is 15°C to 50°C. The copper ions in the low-copper waste liquid are adsorbed by the ion exchange resin. The effluent from the resin tower is collected in a storage tank to obtain treated waste liquid. When the ion exchange resin reaches saturation, stop feeding the low-copper waste liquid, and add concentrated sulfuric acid to the resin tower. The ion exchange resin is cleaned with concentrated sulfuric acid to restore its adsorption capacity, and the cleaning liquid is obtained and sent to the pretreatment tank to participate in pH adjustment.

[0079] In some embodiments, the ion exchange resin is one of the following types: LSC-485, LSC-495, LSC-855, LX-1850H, LX-1850NH, 001×7, and LX-300C.

[0080] In some embodiments, the treated waste liquid has a copper ion content of ≤0.5 ppm.

[0081] In the following Examples 1-5 and Comparative Examples 1-5, the copper acid waste liquid is a copper-containing waste liquid from the panel industry, with a pH of 3.5, a copper ion content of 5000 ppm, a hydrogen peroxide content of 18 wt%, and a concentrated sulfuric acid mass fraction of 98.3%.

[0082] Example 1

[0083] Please refer to Figures 1-5 As shown in FIG. 1, a recovery treatment process for copper acid waste liquid based on high-concentration hydrogen peroxide includes the following steps:

[0084] (1) adding acid-heating method to decompose hydrogen peroxide: 9 kg of copper acid waste liquid is mixed with 45 g of concentrated sulfuric acid and then transported to a mixed decomposition tank. The inside of the mixed decomposition tank is divided into a curved channel by a partition, including a heating zone and a heat preservation zone. The temperature of the heating zone in the mixed decomposition tank is controlled at 70°C, and the temperature of the heat preservation zone is 80°C. After 20 minutes of heating and heat preservation treatment, the copper acid waste liquid without hydrogen peroxide is obtained. The copper acid waste liquid without hydrogen peroxide is sampled and detected, and no hydrogen peroxide is detected.

[0085] (2) extraction / back-extraction: the copper acid waste liquid without hydrogen peroxide is transported to a pretreatment tank, and concentrated sulfuric acid is added to the pretreatment tank to adjust the pH value to 3, obtaining the acidified copper acid waste liquid without hydrogen peroxide. The acidified copper acid waste liquid without hydrogen peroxide is transported to an extraction tank, and an extractant N902 is added to the extraction tank. The mass ratio of the copper acid waste liquid without hydrogen peroxide to the extractant is controlled at 1:1, and the mixture is stirred uniformly and then separated into layers. After phase separation, low-copper waste liquid and high-copper extraction liquid are obtained. The high-copper extraction liquid is transported to a back-extraction tank, and 10wt% sulfuric acid solution is added to the back-extraction tank. The mass ratio of the high-copper extraction liquid to the 10wt% sulfuric acid solution is 1:1, and the mixture is stirred uniformly and then separated into layers, obtaining low-copper extraction liquid and copper sulfate solution. The low-copper extraction liquid is recycled to the extraction tank.

[0086] (3) electrolysis of copper sulfate: the copper sulfate solution is transported to an electrolysis tank. The positive electrode of the electrolysis tank is connected to an electrolyte, and the negative electrode is connected to the copper sulfate solution. A reverse osmosis diaphragm is arranged between the copper sulfate solution and the electrolyte. The electrolysis temperature is 40°C, the current density is 200 A / m 2 , the electrolysis voltage is 3V, and the electrolysis time is 8h. Oxygen is generated at the positive electrode, and elemental copper is generated at the negative electrode. 38g of metallic copper and sulfuric acid solution are obtained. The sulfuric acid solution is recycled to the back-extraction tank.

[0087] (4) resin adsorption: the low-copper waste liquid is transported to a resin tower filled with LSC-855 type ion exchange resin. The flow rate is 0.5BV / h, and the temperature is 15°C. The copper ions in the low-copper waste liquid are adsorbed by the ion exchange resin. The effluent of the resin tower is collected in a storage tank, obtaining treated waste liquid. When the ion exchange resin adsorption reaches saturation, the low-copper waste liquid is stopped. Concentrated sulfuric acid is added to the resin tower to clean the ion exchange resin and restore its adsorption capacity. The cleaning liquid is obtained and recycled to the pretreatment tank for pH adjustment.

[0088] The treated waste liquid obtained in this embodiment is sampled and detected. The copper ion content in the treated waste liquid is 0.5ppm, reaching the discharge standard.

[0089] Example 2

[0090] A copper acid waste liquid recovery treatment process based on high-concentration hydrogen peroxide includes the following steps:

[0091] (1) Decomposition of hydrogen peroxide by adding acid and heating: 9 kg of copper acid waste liquid is mixed with 250 g of concentrated sulfuric acid and then fed into a mixed decomposition tank. The inside of the mixed decomposition tank is divided into a curved channel by a partition, including a heating zone and a heat preservation zone. The temperature of the heating zone in the mixed decomposition tank is controlled at 80°C, and the temperature of the heat preservation zone is 85°C. After 10 minutes of heating and heat preservation treatment, the copper acid waste liquid without hydrogen peroxide is obtained. The copper acid waste liquid without hydrogen peroxide is sampled and detected, and no hydrogen peroxide is detected.

[0092] (2) Extraction / reextraction: The copper acid waste liquid without hydrogen peroxide is fed into a pretreatment tank, and concentrated sulfuric acid is added to the pretreatment tank to adjust the pH value to 2, obtaining the acidified copper acid waste liquid without hydrogen peroxide. The acidified copper acid waste liquid without hydrogen peroxide is fed into an extraction tank, and an extractant N902 is added to the extraction tank. The mass ratio of the copper acid waste liquid without hydrogen peroxide to the extractant is controlled at 5:1, and the mixture is stirred uniformly and then separated into layers. After phase separation, low-copper waste liquid and high-copper extraction liquid are obtained. The high-copper extraction liquid is fed into a reextraction tank, and 20wt% sulfuric acid solution is added to the reextraction tank. The mass ratio of the high-copper extraction liquid to the 20wt% sulfuric acid solution is 3:1, and the mixture is stirred uniformly to obtain low-copper extraction liquid and copper sulfate solution. The low-copper extraction liquid is recycled to the extraction tank.

[0093] (3) Electrolysis of copper sulfate: The copper sulfate solution is fed into an electrolysis tank. The positive electrode of the electrolysis tank is connected to an electrolyte, and the negative electrode is connected to the copper sulfate solution. A reverse osmosis diaphragm is arranged between the copper sulfate solution and the electrolyte. The electrolysis temperature is 45°C, the current density is 250 A / m 2 , the electrolysis voltage is 5V, and the electrolysis time is 12h. Oxygen is generated at the positive electrode, and elemental copper is generated at the negative electrode. 38g of metallic copper and sulfuric acid solution are obtained. The sulfuric acid solution is recycled to the reextraction tank.

[0094] (4) Resin adsorption: The low-copper waste liquid is fed into a resin tower filled with LSC-855 type ion exchange resin. The flow rate is 1.8BV / h, and the temperature is 30°C. The copper ions in the low-copper waste liquid are adsorbed by the ion exchange resin. The effluent of the resin tower is collected in a storage tank to obtain treated waste liquid. When the ion exchange resin adsorption reaches saturation, the flow of low-copper waste liquid is stopped, and concentrated sulfuric acid is added to the resin tower to clean the ion exchange resin and restore its adsorption capacity. The cleaning liquid is obtained and fed into the pretreatment tank to participate in pH adjustment.

[0095] The treated waste liquid obtained in this example is sampled and detected. The copper ion content in the treated waste liquid is 0.4ppm, which meets the discharge standard.

[0096] Example 3

[0097] A copper acid waste liquid recovery treatment process based on high-concentration hydrogen peroxide includes the following steps:

[0098] (1) Hydrogen peroxide decomposition by adding acid and heating: 9 kg of copper acid waste liquid is mixed with 450 g of concentrated sulfuric acid and then fed into a mixed decomposition tank. The inside of the mixed decomposition tank is divided into a curved channel by a partition, including a heating zone and a heat preservation zone. The temperature of the heating zone in the mixed decomposition tank is controlled at 95°C, and the temperature of the heat preservation zone is 93°C. After heating and heat preservation treatment for 5 min, the copper acid waste liquid without hydrogen peroxide is obtained. The copper acid waste liquid without hydrogen peroxide is sampled and detected, and no hydrogen peroxide is detected.

[0099] (2) Extraction / back-extraction: The copper acid waste liquid without hydrogen peroxide is fed into a pretreatment tank, and concentrated sulfuric acid is added to the pretreatment tank to adjust the pH value to 1.8, obtaining the acidified copper acid waste liquid without hydrogen peroxide. The acidified copper acid waste liquid without hydrogen peroxide is fed into an extraction tank, and an extractant N902 is added to the extraction tank. The mass ratio of the copper acid waste liquid without hydrogen peroxide to the extractant is controlled at 10:1, and the mixture is stirred uniformly and then allowed to separate into layers. After phase separation, low-copper waste liquid and high-copper extraction liquid are obtained. The high-copper extraction liquid is fed into a back-extraction tank, and 30wt% sulfuric acid solution is added to the back-extraction tank. The mass ratio of the high-copper extraction liquid to the 30wt% sulfuric acid solution is 5:1, and the mixture is stirred uniformly to obtain low-copper extraction liquid and copper sulfate solution. The low-copper extraction liquid is recycled to the extraction tank.

[0100] (3) Electrolysis of copper sulfate: The copper sulfate solution is fed into an electrolysis tank. The positive electrode of the electrolysis tank is connected to an electrolyte, and the negative electrode is connected to the copper sulfate solution. A reverse osmosis diaphragm is arranged between the copper sulfate solution and the electrolyte. The electrolysis temperature is 50°C, the current density is 200 A / m 2 , the electrolysis voltage is 5V, and the electrolysis time is 15h. Oxygen is generated at the positive electrode, and elemental copper is generated at the negative electrode. 36g of metallic copper and sulfuric acid solution are obtained. The sulfuric acid solution is recycled to the back-extraction tank.

[0101] (4) Resin adsorption: The low-copper waste liquid is fed into a resin tower filled with LSC-855 type ion exchange resin. The flow rate is 2.8 BV / h, and the temperature is 50°C. The copper ions in the low-copper waste liquid are adsorbed by the ion exchange resin. The effluent from the resin tower is collected in a storage tank to obtain treated waste liquid. When the ion exchange resin adsorption reaches saturation, the flow of low-copper waste liquid is stopped, and concentrated sulfuric acid is added to the resin tower to clean the ion exchange resin and restore its adsorption capacity. The cleaning liquid is obtained and fed into the pretreatment tank to participate in pH adjustment.

[0102] The treated waste liquid obtained in this example is sampled and detected. The copper ion content in the treated waste liquid is 0.3 ppm, reaching the discharge standard.

[0103] Example 4

[0104] A recovery treatment process for copper acid waste liquor based on high concentration hydrogen peroxide, which differs from example 1 only in that the extractant used in the extraction / back-extraction process is extractant M5640 and the ion exchange resin used in the resin adsorption process is LSC-495 type ion exchange resin.

[0105] The hydrogen peroxide-free copper acid waste liquor obtained in this example was sampled and tested, and no hydrogen peroxide was detected;

[0106] The treated waste liquor obtained in this example was sampled and tested, and the copper ion content in the treated waste liquor was 0.2 ppm, reaching the discharge standard.

[0107] Example 5

[0108] A recovery treatment process for copper acid waste liquor based on high concentration hydrogen peroxide, which differs from example 1 only in that the extractant used in the extraction / back-extraction process is extractant N-910 and the ion exchange resin used in the resin adsorption process is LSC-495 type ion exchange resin.

[0109] The hydrogen peroxide-free copper acid waste liquor obtained in this example was sampled and tested, and no hydrogen peroxide was detected;

[0110] The treated waste liquor obtained in this example was sampled and tested, and the copper ion content in the treated waste liquor was 0.4 ppm, reaching the discharge standard.

[0111] Example 6

[0112] A recovery treatment process for copper acid waste liquor based on high concentration hydrogen peroxide, which differs from example 1 only in that the composition of the copper acid waste liquor is different, and in this example the pH value of the copper acid waste liquor is 3.7, the copper ion content is 3000 ppm, and the hydrogen peroxide content is 22 wt%.

[0113] The hydrogen peroxide-free copper acid waste liquor obtained in this example was sampled and tested, and no hydrogen peroxide was detected;

[0114] The treated waste liquor obtained in this example was sampled and tested, and the copper ion content in the treated waste liquor was 0.2 ppm, reaching the discharge standard.

[0115] Example 7

[0116] A recovery treatment process for copper acid waste liquor based on high concentration hydrogen peroxide, which differs from example 1 only in that the composition of the copper acid waste liquor is different, and in this example the pH value of the copper acid waste liquor is 4.2, the copper ion content is 2000 ppm, and the hydrogen peroxide content is 20 wt%.

[0117] The hydrogen peroxide-free copper acid waste liquor obtained in this example was sampled and tested, and no hydrogen peroxide was detected;

[0118] The treated waste liquid obtained in this example was sampled and detected, and the copper ion content in the treated waste liquid was 0.1 ppm, reaching the discharge standard.

[0119] Comparative Example 1

[0120] A recovery treatment process for copper acid waste liquid based on high-concentration hydrogen peroxide includes the following steps:

[0121] 9 kg of copper acid waste liquid was added to 36 g of concentrated sulfuric acid (the amount of concentrated sulfuric acid added was 0.4% of the mass of the copper acid waste liquid), and after being uniformly mixed, it was fed into a mixed decomposition tank. The inside of the mixed decomposition tank was separated into a curved channel by a partition, including a heating zone and a heat preservation zone. The temperature of the heating zone was 70°C, and then it was decomposed with violent bubbling, with the bubbling amount being greater than 10 times the volume of the liquid. Considering the safety of the experiment, 9 kg of cold water (5°C) was directly added to the system, and the experiment was ended.

[0122] Comparative Example 2

[0123] A recovery treatment process for copper acid waste liquid based on high-concentration hydrogen peroxide, compared with Example 3, the only difference is that in step (1) of Example 3, "9 kg of copper acid waste liquid was mixed with 450 g of concentrated sulfuric acid and then fed into a mixed decomposition tank" is adjusted to "9 kg of copper acid waste liquid was mixed with 540 g of concentrated sulfuric acid (the amount of concentrated sulfuric acid added was 6% of the mass of the copper acid waste liquid) and then fed into a mixed decomposition tank". In step (2), except that the hydrogen peroxide copper acid waste liquid does not need to be acidified through a pretreatment tank, it is directly fed into an extraction tank.

[0124] The hydrogen peroxide copper acid waste liquid obtained in this comparative example was sampled and detected, and the hydrogen peroxide content was 5.8 wt%, and the pH value of the obtained hydrogen peroxide copper acid waste liquid was <1.0;

[0125] The treated waste liquid obtained in this comparative example was sampled and detected, and the copper ion content in the treated waste liquid was 56 ppm, which did not reach the discharge standard.

[0126] Comparative Example 3

[0127] A recovery treatment process for copper acid waste liquid based on high-concentration hydrogen peroxide includes the following steps:

[0128] 9 kg of copper acid waste liquid was added to a mixed decomposition tank. The inside of the mixed decomposition tank was separated into a curved channel by a partition, including a heating zone and a heat preservation zone. The temperature of the heating zone was 70°C, and then it was immediately decomposed with violent bubbling, with the bubbling amount being greater than 10 times the volume of the liquid. Considering the safety of the experiment, 9 kg of cold water (5°C) was directly added to the system, and the experiment was ended.

[0129] Comparative Example 4

[0130] A recovery treatment process for copper acid waste liquid based on high-concentration hydrogen peroxide (dilution-settling process) includes the following steps:

[0131] 9 kg of copper acid waste liquid was added to the degradation tank, 450 kg of water was added, and it was stirred uniformly to obtain 459 kg of copper acid dilution liquid waste liquid; 200 kg of liquid alkali (36 wt% NaOH solution) was added to the copper acid dilution liquid waste liquid, the pH value of the system was 9, and it was stirred uniformly to generate a small amount of bubbles; it was left to stand for 24 h, 65 g of blue mud-like precipitate was generated, it was filtered, the filtrate was sampled and measured, no hydrogen peroxide was detected, and the copper ion content was 15 ppm, which did not reach the discharge standard.

[0132] Comparative Example 5

[0133] A copper acid waste liquid recovery treatment process based on high-concentration hydrogen peroxide (extraction-electrolysis-decomposition hydrogen peroxide process) includes the following steps:

[0134] (1) 10 kg of copper acid waste liquid was added to the pretreatment tank, 50 g of concentrated sulfuric acid was added to adjust the pH to 3; the waste liquid with adjusted pH value was added to the extraction tank, 1 kg of extraction agent N902 was added, stirred for 5 min, left to stand until phase separation, repeated three times, and high-copper extraction liquid and low-copper waste liquid was obtained;

[0135] (2) The high-copper extraction liquid was added to the back-extraction tank, 3 kg of 10 wt% sulfuric acid solution was added, stirred for 5 min, left to stand until phase separation, and the aqueous phase was injected into the electrolysis tank;

[0136] (3) In the electrolysis tank, copper sulfate solution was electrolyzed using a 5V electrode, the electrolysis temperature was 40℃, the current density was 200 A / m 2 , and electrolysis was performed for 8 h, finally 15 g of metallic copper was obtained on the cathode;

[0137] (4) 20 g of sodium hydroxide was added to the low-copper waste liquid, the pH was adjusted to 6.5, 40 g of enzyme was added, the temperature was raised to 37℃, and after stirring for 4 h, sampling and measurement were performed, no hydrogen peroxide was detected, and the copper ion content was 12 ppm, which did not reach the discharge standard.

[0138] Comparative Example 6

[0139] A copper acid waste liquid recovery treatment process based on high-concentration hydrogen peroxide (decomposition hydrogen peroxide-dilution with acid-electrolysis process) includes the following steps:

[0140] (1) 10 kg of copper acid waste liquid (pH value of 4, copper ion content of 5000 ppm, and hydrogen peroxide content of 5 wt%) was supplied to a heating device and heated to 80℃, then introduced into a heat preservation tank for 7 h to decompose hydrogen peroxide, sampling and measurement were performed, the hydrogen peroxide content was 1.1 wt%, and the initial treatment copper acid waste liquid was obtained;

[0141] (2) to the initial treatment copper acid waste liquid, 10 kg of 10wt% sulfuric acid solution is added, after being diluted sufficiently, it is added into the electrolytic cell, direct current 500A is passed, constant current electrolysis is carried out for 48 hours, 45.8g of copper metal is collected at the negative electrode, after treatment, the waste liquid is sampled and detected, the hydrogen peroxide content is 0.4wt%, the copper ion content is 100ppm, which does not reach the discharge standard.

[0142] It should be noted that the relational terms herein such as first and second and the like are used solely to distinguish one entity or action from another, without necessarily requiring or implying any such actual relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can also include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0143] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, alternatives, and variations can be made in the embodiments without departing from the spirit and scope of the present application as defined by the appended claims and their equivalents.

Claims

1. A process for recovering and treating copper acid waste liquid based on high-concentration hydrogen peroxide, characterized in that, Includes the following steps: (1) The copper acid waste liquid is mixed with concentrated sulfuric acid and then transported to a mixing decomposition tank for heating and heat preservation treatment to obtain copper acid waste liquid without hydrogen peroxide. (2) Adjust the pH value of the copper acid waste liquid to remove hydrogen peroxide and mix it evenly with the extractant. Let it stand and separate into layers to obtain low copper waste liquid and high copper extract. Add sulfuric acid solution to the high copper extract for back extraction to obtain low copper extract and copper sulfate solution. The low copper extract is recycled to the extraction tank. (3) Electrolyze the copper sulfate solution to obtain metallic copper and sulfuric acid solution. The sulfuric acid solution is then recycled to the back-extraction tank. (4) Ion exchange resin is used to treat low-copper waste liquid to complete the recovery and treatment of copper acid waste liquid with high concentration of hydrogen peroxide; In step (1), the amount of concentrated sulfuric acid added is 0.5% to 5% of the mass of the copper acid waste liquid; In step (1), the interior of the mixing and decomposition tank is divided into curved channels by a partition. The mixing and decomposition tank includes a heating zone and a heat preservation zone. The temperature of the heating zone is 70℃~98℃, and the temperature of the heat preservation zone is 80℃~98℃. The copper acid waste liquid has a pH value of 2-5, a copper ion content of 2000ppm-5000ppm, and a hydrogen peroxide content of 5wt%-22wt%.

2. The process for recovering and treating copper acid waste liquid based on high-concentration hydrogen peroxide according to claim 1, characterized in that, The heating and heat preservation treatment time in step (1) is 5 min to 20 min.

3. The process for recovering and treating copper acid waste liquid based on high-concentration hydrogen peroxide according to claim 1, characterized in that, In step (2), the pH adjuster for adjusting the pH of the copper acid waste liquid is concentrated sulfuric acid, and the pH is adjusted to 1-3.

4. The process for recovering and treating copper acid waste liquid based on high-concentration hydrogen peroxide according to claim 1, characterized in that, In step (2), the mass ratio of copper peroxide waste liquid to extractant is 1 to 10:

1.

5. The process for recovering and treating copper acid waste liquid based on high-concentration hydrogen peroxide according to claim 1, characterized in that, In step (2), the mass ratio of the high copper extract to the sulfuric acid solution is 1 to 5:1, and the mass fraction of the sulfuric acid solution is 10% to 30%.

6. The process for recovering and treating copper acid waste liquid based on high-concentration hydrogen peroxide according to claim 1 or 4, characterized in that, The extractant is one of Lix54-100, Lix84, Lix84i, Lix860, Lix984, P204, P507, N-910, N1923, N902, TBP and M5640.

7. The process for recovering and treating copper acid waste liquid based on high-concentration hydrogen peroxide according to claim 1, characterized in that, The electrolysis temperature is 40℃~50℃, the current density is 200A / m2~250A / m2, the electrolysis voltage is 3V~5V, and the electrolysis time is 8h~15h.

8. The process for recovering and treating copper acid waste liquid based on high-concentration hydrogen peroxide according to claim 1, characterized in that, The ion exchange resin is one of the following: LSC-485, LSC-495, LSC-855, LX-1850H, LX-1850NH, 001×7, and LX-300C.

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