Resourceful treatment method for waste oil washing water in alkaline extraction system
By using Na+-type copper removal resin and electrolyte in an alkaline extraction system to treat waste washing water, the problem of direct discharge pollution from waste washing water was solved, Cu2+ recovery and resin recycling were achieved, treatment costs were reduced and water quality was improved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-09
- Publication Date
- 2026-03-10
AI Technical Summary
In existing technologies, the direct discharge of waste washing water from alkaline extraction systems can pollute the environment, and the treatment costs are high and useful substances cannot be effectively recovered.
The waste washing water is treated with Na+ type copper removal resin by ion exchange, combined with water, sulfuric acid electrolyte and alkaline solution, to achieve the collection and recycling of Cu2+, and to achieve recycling through resin regeneration and transformation.
It effectively reduces the treatment cost of waste washing oil, improves the treatment effect, realizes the recycling of Cu2+, and meets the needs of continuous industrial production.
Smart Images
Figure CN121629166A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of copper recycling technology, and in particular to a method for the resource-based treatment of waste washing water in an alkaline extraction system. Background Technology
[0002] In the copper recycling industry, alkaline extraction systems are hydrometallurgical processes that selectively separate and enrich copper in copper-containing materials (such as copper smelting slag, waste circuit boards, electroplating sludge, etc.) under alkaline conditions using extractants. The core function is to achieve efficient separation of copper from impurities such as iron, aluminum, and silicon, providing high-purity copper-containing liquid for subsequent copper purification and recycling. These systems are widely used in the resource-based treatment of complex copper-containing waste.
[0003] The key auxiliary wash waters in the extraction system are oil wash water and acid wash water, which need to be replaced regularly. The oil wash water is alkaline, and its core indicator is Cu. 2+ The content is ≤5g / L, and it contains a certain amount of ammonia nitrogen; the washing acid water is acidic, and the core indicator is Cu. 2+ Content ≤5g / L. Direct discharge of washing oil and acid wastewater will cause serious environmental pollution: for example, acidic / alkaline wastewater will disrupt the pH balance of water bodies and soil, leading to the death of aquatic organisms and soil compaction; Cu 2+ Ammonia nitrogen is a heavy metal with bioaccumulation properties, which can harm human health through the food chain; it can also cause eutrophication of water bodies, leading to water pollution problems such as cyanobacterial blooms. Therefore, in current technologies, the wastewater from washing oil and acid washing is generally discharged to a wastewater treatment plant for treatment. However, this method is costly and cannot effectively recover useful substances (such as Cu) from the wastewater. 2+ wait). Summary of the Invention
[0004] The purpose of this invention is to propose a method for the resource-based treatment of waste washing water in an alkaline extraction system, which is beneficial for realizing the utilization of Cu in the waste washing water. 2+ The collection and recycling of these technologies can overcome the shortcomings of existing technologies.
[0005] To achieve this objective, the present invention adopts the following technical solution: A method for resource recovery of waste washing water in an alkaline extraction system includes the following steps: A. Mix waste washing water with Na + The copper-removing resin is subjected to ion exchange to obtain copper-free washing oil and copper-loaded resin. B. Use clean water to clean the copper-carrying resin to obtain water-washed copper-carrying resin and a first backwash solution; C. The copper-loaded resin is regenerated by using the sulfuric acid electrolyte in the alkaline extraction system to wash the water, resulting in regenerated resin and copper-rich electrolyte. D. Wash the regenerated resin with clean water to obtain H. + Type II copper removal resin and secondary backwash solution; E. Using alkaline solutions to treat H + The copper-removing resin was transformed to obtain Na + The copper-removing resin is then used again in step A.
[0006] Preferably, in step E, the alkaline solution is the copper-free washing oil from step A, and the copper-free washing oil after the transformation treatment is mixed with the waste washing oil from step A.
[0007] Preferably, it further includes step F1, which is located after step E. F1 includes: F11. Ion exchange is performed between copper-free washing oil and ammonia-removing nitrogen resin to obtain copper-free and ammonia-free nitrogen washing oil and ammonia-loaded nitrogen resin. F12. Mix the copper-free and ammonia-free washing water with the waste washing water from step A.
[0008] Preferably, it further includes step F2, which is located after step E. F2 includes: F21. Mix and neutralize the copper-free washing oil with the waste acid washing water to obtain mixed washing water; F22. Mix the mixed wash water with the waste wash water from step A.
[0009] Preferably, step B further includes: Mix the backwash solution with the waste wash water from step A.
[0010] Preferably, step D further includes: The secondary backwash solution is mixed with the acid wash water in the alkaline extraction system.
[0011] Preferably, in step A, the Na + The copper removal resin is a weakly acidic cation exchange resin.
[0012] Preferably, in step E, the H + The copper removal resin is a weakly acidic cation exchange resin.
[0013] Preferably, in step F11, the ammonia nitrogen removal resin is a strong acid type cation exchange resin.
[0014] The technical solution provided by this invention may include the following beneficial effects: 1. Use Na + Type II copper removal resin for Cu in waste washing water 2+ Collect, and then collect Cu 2+ The solution is washed into the sulfuric acid electrolyte in the alkaline extraction system, allowing the Cu in the electrolyte to be removed. 2+The content was increased and the material was reused in the alkaline extraction system to remove Cu from waste wash water. 2+ The recycling of waste oil washing water can effectively reduce the treatment cost of waste oil washing water and improve its treatment effect and water quality.
[0015] 2. The copper removal resin in this solution can achieve Cu... 2+ After collection, the material is recycled and transformed, which helps meet the needs of continuous industrial production. Attached Figure Description
[0016] Figure 1 This is a schematic flowchart of a method for the resource-based treatment of waste washing water in an alkaline extraction system according to the present invention. Detailed Implementation
[0017] This technical solution provides a method for the resource-based treatment of waste washing water in an alkaline extraction system, including the following steps: A. Mix waste washing water with Na + The copper-removing resin is subjected to ion exchange to obtain copper-free washing oil and copper-loaded resin. B. Use clean water to clean the copper-carrying resin to obtain water-washed copper-carrying resin and a first backwash solution; C. The copper-loaded resin is regenerated by using the sulfuric acid electrolyte in the alkaline extraction system to wash the water, resulting in regenerated resin and copper-rich electrolyte. D. Wash the regenerated resin with clean water to obtain H. + Type II copper removal resin and secondary backwash solution; E. Using alkaline solutions to treat H + The copper-removing resin was transformed to obtain Na + The copper-removing resin is then used again in step A.
[0018] To achieve Cu in waste wash oil water 2+ Regarding the collection and recycling of waste washing water in alkaline extraction systems, this technical solution proposes a resource-based treatment method, such as... Figure 1 As shown, using Na + Type II copper removal resin for Cu in waste washing water 2+ Collect, and then collect Cu 2+ The solution is washed into the sulfuric acid electrolyte in the alkaline extraction system, allowing the Cu in the electrolyte to be removed. 2+ The content was increased and the material was reused in the alkaline extraction system to remove Cu from waste wash water. 2+ The recycling of this material can effectively reduce the treatment cost of waste oil washing water and improve its treatment effect and water quality. In addition, copper removal resin can achieve Cu... 2+ After collection, the material is recycled and transformed, which helps meet the needs of continuous industrial production.
[0019] Specifically, the resource recovery method in this scheme first involves reacting the waste washing oil with Na... + A copper-removing resin is used for ion exchange to remove Cu from waste washing oil water. 2+ Removal; then, the adsorbed Cu 2+ The copper-containing resin was cleaned to remove any residual OH groups. - The copper-loaded resin reacts directly with the sulfuric acid electrolyte in step C to form a precipitate; then, the copper-loaded resin is regenerated by washing with the sulfuric acid electrolyte in the alkaline extraction system, thereby removing the Cu. 2+ The transfer of copper from the copper-loaded resin to the electrolyte achieved Cu in the electrolyte. 2+ The content was increased; then, the residual SO4 in the regenerated resin was washed away with clean water. 2- This facilitates the transformation and adsorption in step E; finally, an alkaline solution is used to transform the copper removal resin from its protonated deactivated form to its sodium-active form, restoring the Cu in the highly efficient adsorption solution. 2+ This capability enables the recycling of resins, meeting the needs of continuous industrial production.
[0020] It should be noted that the sulfuric acid electrolyte in step C includes Cu. 2+ and SO4 2- Additionally, based on ionic form, resins other than copper can include Na+. + Type Copper Removal Resin, H + Type of copper removal resin and Cu 2+ The three types of copper-removing resins (i.e., the copper-carrying resins in this solution) represent different working states of the same copper-removing resin, with Na... + Type-A copper removal resin is a working state with copper adsorption activity, Cu 2+ Type II copper removal resin is used to adsorb Cu 2+ The state after H + The copper removal resin is in a deactivated state after sulfuric acid regeneration and needs to be converted using an alkaline solution to restore its Cu adsorption capacity. 2+ The ability.
[0021] To further explain, in step E, the alkaline solution is the copper-free washing oil from step A, and the copper-free washing oil after the transformation treatment is mixed with the waste washing oil from step A.
[0022] In a preferred embodiment of this technical solution, the alkalinity of copper-free washing water can be used to treat H + The copper-removing resin is transformed, and then the copper-free washing water after transformation is mixed with the waste washing water from step A to dilute the waste washing water.
[0023] Diluted waste oil wash water reduces solution viscosity, decreasing the risk of resin pores being blocked by impurities and complexes, ensuring full contact and reaction of resin functional groups, and improving copper adsorption efficiency. Furthermore, the diluted waste oil wash water has a milder alkalinity and its pH is easier to control, thus meeting the Na+ adsorption requirements. + The type of resin adsorbs the alkalinity required, while also preventing the resin from deteriorating due to localized excessive alkalinity, thus extending the resin's service life.
[0024] To further explain, it also includes step F1, which follows step E. F1 includes: F11. Ion exchange is performed between copper-free washing oil and ammonia-removing nitrogen resin to obtain copper-free and ammonia-free nitrogen washing oil and ammonia-loaded nitrogen resin. F12. Mix the copper-free and ammonia-free washing water with the waste washing water from step A.
[0025] In another preferred embodiment of this technical solution, the copper-free washing oil can be further treated with ammonia nitrogen removal to obtain copper-free and ammonia nitrogen-free washing oil, thereby further diluting the ammonia nitrogen content of the waste washing oil and reducing the processing pressure of the subsequent ammonia nitrogen removal process.
[0026] To further explain, it also includes step F2, which follows step E. F2 includes: F21. Mix and neutralize the copper-free washing oil with the waste acid washing water to obtain mixed washing water; F22. Mix the mixed wash water with the waste wash water from step A.
[0027] In another preferred embodiment of this technical solution, the copper-free washing water can also consume part of the waste washing acid water in the alkaline extraction system, and remove the Cu from the waste washing acid water. 2+ Collecting and recycling waste washing water through resource-based treatment methods can further improve the Cu content of the washing water. 2+ The overall recycling effect.
[0028] To elaborate further, step B also includes: Mix the backwash solution with the waste wash water from step A.
[0029] Since the primary backwash solution is alkaline, it can be used to dilute the waste wash water from step A.
[0030] To further explain, step D also includes: The secondary backwash solution is mixed with the acid wash water in the alkaline extraction system.
[0031] Since the secondary backwash solution is acidic, it can be used as acid washing water in alkaline extraction systems, thus avoiding the waste of water resources.
[0032] To further explain, in step A, the Na+ The copper removal resin is a weakly acidic cation exchange resin.
[0033] To further explain, in step E, the H + The copper removal resin is a weakly acidic cation exchange resin.
[0034] To further clarify, in step F11, the ammonia nitrogen removal resin is a strong acid type cation exchange resin.
[0035] Embodiments of the present invention are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.
[0036] Example A. Mix waste washing water with Na + The copper-removing resin is subjected to ion exchange to obtain copper-free washing oil and copper-loaded resin.
[0037] The pH of the waste oil washing water was 10.33, and the Cu content was... 2+ 1.14 g / L, OH - : 0.8N; During the ion exchange process, the waste washing water is transported at a rate of 40 L / h. After 60 minutes of uniform transport, the pH of the copper-free washing water is 9.10, Cu 2+ 2.86 mg / L, OH - : 0.3N, with an adsorption rate of over 99%.
[0038] B. Use clean water to clean the copper-carrying resin to obtain water-washed copper-carrying resin and a primary backwash solution.
[0039] C. The copper-loaded resin is regenerated by using the sulfuric acid electrolyte in the alkaline extraction system to wash the water, resulting in regenerated resin and copper-rich electrolyte. Among them, Cu in the sulfuric acid system electrolyte 2+ 15.89 g / L, H + : 2.8N; Cu in copper-rich electrolyte 2+ 22.87 g / L, H + : 2.0N; Regeneration rate reaches 96.56%.
[0040] D. Wash the regenerated resin with clean water to obtain H. + Type II copper removal resin and secondary backwash solution; E. Using alkaline solutions to treat H + The copper-removing resin was transformed to obtain Na + Type of copper removal resin.
[0041] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are merely for explaining the principles of the invention and should not be construed as limiting the scope of protection of the invention in any way. Based on this explanation, those skilled in the art can readily conceive of other specific embodiments of the invention without inventive effort, and these embodiments will all fall within the scope of protection of the present invention.
Claims
1. A method for resource recovery of spent wash oil water in an alkaline extraction system, characterized by, The method comprises the following steps: A, the waste oil water is ion exchanged with Na + Copper-loaded resin; B, the copper-loaded resin is eluted with HCl solution to obtain the copper-free oil water and the regenerated resin; B. cleaning the copper-loaded resin with clean water to obtain water-washed copper-loaded resin and primary backwashing liquid; C. regenerating the water-washed copper-loaded resin with sulfuric acid system electrolyte in the alkaline extraction system to obtain regenerated resin and copper-rich electrolyte; D, the regenerated resin is washed with clean water to obtain H + type copper-removing resin and secondary backwashing liquid; E. The H + type copper-removing resin was transformed by using a basic solution to obtain Na + type copper-removing resin and used again in step A.
2. The method of reclaiming waste wash oil water in an alkaline extraction system according to claim 1, characterized by, In step E, the alkaline solution is the copper-free oil washing water in step A, and the copper-free oil washing water after the transformation treatment is mixed with the waste oil washing water in step A.
3. The method of reclaiming waste wash oil water in an alkaline extraction system according to claim 1, wherein Step F1 is further included and is located after step E, and F1 comprises: F11. ion exchanging the copper-free oil washing water with ammonia-nitrogen-removing resin to obtain copper-free and ammonia-nitrogen-free oil washing water and ammonia-nitrogen-loaded resin; F12. mixing the copper-free and ammonia-nitrogen-free oil washing water with the waste oil washing water in step A.
4. The method of reclaiming waste wash oil water in an alkaline extraction system according to claim 1, wherein Step F2 is further included and is located after step E, and F2 comprises: F21. mixing and neutralizing the copper-free oil washing water with waste acid washing water to obtain mixed washing water; F22. mixing the mixed washing water with the waste oil washing water in step A.
5. The method of reclaiming spent wash oil water in an alkaline extraction system according to claim 1, wherein, Step B further comprises: mixing the primary backwashing liquid with the waste oil washing water in step A.
6. The method of reclaiming waste wash oil water in an alkaline extraction system according to claim 1, wherein Step D further comprises: mixing the secondary backwashing liquid with acid washing water in the alkaline extraction system.
7. The method of reclaiming waste wash oil water in an alkaline extraction system according to claim 1, wherein In Step A, the Na + The copper-removing resin is a weak acid type cation exchange resin.
8. The method of reclaiming waste wash oil water in an alkaline extraction system according to claim 1, wherein, In Step E, the H + The copper-removing resin is a weak acid type cation exchange resin.
9. The method of claim 3, wherein the spent wash oil water is treated in a resource recovery system, characterized by, In step F11, the ammonia-nitrogen-removing resin is strong acid cation exchange resin.