CN111635994A - Method for recovering copper from acidic copper-containing etching solution and preparing cuprous oxide - Google Patents
Method for recovering copper from acidic copper-containing etching solution and preparing cuprous oxide Download PDFInfo
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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Abstract
The invention discloses a method for recovering copper from acidic copper-containing etching solution and preparing cuprous oxide, which comprises the following steps: s1, filtering the acidic copper-containing etching waste liquid to obtain a crude copper-containing solution; s2, adjusting the pH value of the crude copper-containing solution to 2-4, adding an extracting agent, mixing and stirring, standing and layering, wherein the upper layer is a primary copper-containing organic phase, and the lower layer is a primary water phase; recovering the primary aqueous phase for use in an etching production line; s3, washing the copper-containing organic phase with deionized water, and separating to obtain a secondary copper-containing organic phase and a primary washing water phase; s4, adding sulfuric acid into the secondary copper-containing organic phase, fully stirring, standing for layering, wherein the upper layer is an organic phase containing an extractant, and the lower layer is an organic phase containing CuSO4An aqueous phase; s5, adding the primary washing water phase into the organic phase containing the extracting agent for water washing, standing for layeringObtaining a pure extractant organic phase for use in step S2; s6 preparation of CuSO-containing material by hydrothermal method or chemical precipitation method4And preparing the cuprous oxide from the water phase.
Description
Technical Field
The invention relates to the field of copper resource recycling, in particular to a method for recycling copper from an acidic copper-containing etching solution and preparing cuprous oxide.
Background
Printed circuit boards can generate a large amount of copper-containing waste etching solution after being etched, and the emission amount of the copper-containing waste etching solution is increasing along with the development of the electronic industry. The waste etching solution can be divided into acidic and alkaline types, and is mainly acidic in China. The acidic waste liquid mainly contains copper chloride, hydrochloric acid and the like, the content of copper ions is generally 10-250 g/L, and the concentration of free hydrochloric acid is generally 0.5-6 mol/L. If the acidic etching waste liquid is directly discharged, the environment can be seriously polluted, and the heavy metal copper resource is greatly wasted. Therefore, the effective treatment of the acidic etching waste liquid and the recycling of copper have important economic and environmental significance for environmental protection and high-efficiency utilization of copper resources. At present, the methods for recovering copper from acidic etching waste liquid mainly comprise a chemical precipitation method, an adsorption method, an electrolytic deposition method, a solvent extraction method and the like. The recycled products mainly comprise copper oxide, copper sulfate and the like, the product quality is low, the market value is low, and compared with the product, cuprous oxide has better market prospect. On one hand, cuprous oxide can be used as a ship antifouling paint, has the advantages of less pollution, low toxicity, long validity period, low cost and the like, and the demand of the cuprous oxide increases year by year along with the development of the ship industry and the navigation industry in China; on the other hand, cuprous oxide also has ideal photovoltage and optical memory properties, and has wide application prospect in the field of photoelectrons. In addition, the application of cuprous oxide in organic catalysis, agriculture, photocatalysis, glass, ceramics and the like is also developed to a certain extent.
However, the current method for extracting and separating copper ions from acidic copper-containing etching waste liquid and preparing cuprous oxide has the following problems:
1. the preparation process is only suitable for laboratory research and cannot realize large-scale industrial application;
2. the treatment equipment for the acidic copper-containing etching waste liquid has a complex structure and is difficult to operate and maintain;
3. the preparation process is mostly prepared by adopting an electrodeposition method, the prepared product is mainly pure copper, and the electrodeposition equipment has the advantages of complex structure, high energy consumption and lower economic value.
Disclosure of Invention
The invention aims to solve the problems and provides a method for recovering copper from an acidic copper-containing etching solution and preparing cuprous oxide, which has high reaction rate and high recovery efficiency.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for recovering copper and preparing cuprous oxide from acidic copper-containing etching solution comprises the following steps:
s1, filtering the acidic copper-containing etching waste liquid to remove insoluble particles in the acidic copper-containing etching waste liquid, adding NaOH to adjust the pH value of the acidic copper-containing etching waste liquid to 2-4, and sequentially adding Na2SO4And BaCO3Standing for 60 minutes, and removing precipitates to obtain a crude copper-containing solution;
s2, adjusting the pH value of the crude copper-containing solution obtained in the step S1 to 2-4 by using ammonia water, transferring the solution into an extraction cylinder, adding an extracting agent, mixing and stirring, standing and layering, wherein the upper layer is a primary copper-containing organic phase, and the lower layer is a primary water phase; recovering the primary aqueous phase for use in an etching production line;
s3, washing the copper-containing organic phase obtained in the step S2 with deionized water, and separating to obtain a secondary copper-containing organic phase and a primary washing water phase;
s4, transferring the secondary copper-containing organic phase obtained in the step S3 into a back extraction cylinder, simultaneously adding sulfuric acid, fully stirring, standing and layering, wherein the upper layer is an extractant-containing organic phase, and the lower layer is a CuSO-containing organic phase4An aqueous phase;
s5, adding the primary washing water phase obtained in the step S3 into an extractant-containing organic phase for washing, standing and layering to obtain a pure extractant organic phase for use in the step S2;
s6, adding CuSO obtained in step S44And adding NaOH or KOH into the water phase to adjust the pH value to be alkaline, adding a reducing agent, and preparing the cuprous oxide by adopting a hydrothermal method or a chemical precipitation method.
Further, the extractant is Mextral984H, the concentration is 10-50%, the diluent used for the extractant is Mextral DT100, and the volume ratio of the extractant to the acidic copper-containing etching waste liquid is 5-15: 1, the number of extraction stages is 1-5.
Further, the concentration of the sulfuric acid in the step S4 is 100-220 g/L, and the volume ratio of the sulfuric acid to the secondary copper-containing organic phase is 1:1 to 5.
Further, the step S6 of preparing cuprous oxide by using a hydrothermal method includes the following steps:
s61, adding CuSO4Adding the water phase into a hydrothermal reaction kettle, adjusting the pH to be alkaline by using a 1mol/L NaOH solution or KOH solution, then adding a reducing agent, and sealing, wherein the hydrothermal reaction temperature is 150-200 ℃, and the hydrothermal reaction time is 1-24 hours, so as to obtain a cuprous oxide solution;
and S62, performing centrifugal separation on the cuprous oxide solution obtained in the step S61, alternately cleaning and filtering with water and ethanol, putting the filtered cuprous oxide solid into a vacuum drying oven after the filtrate is neutral, and drying for 6-12 hours to obtain the high-purity cuprous oxide.
Further, the step S6 of preparing cuprous oxide by using a chemical precipitation method includes the following steps:
s63, adding CuSO4Adding the water phase into a stirring reactor, adjusting the pH to be alkaline by using 1mol/L NaOH solution or KOH solution, then adding a reducing agent, and reacting for 1-6 h;
and S64, performing centrifugal separation on the cuprous oxide solution obtained in the step S63, alternately cleaning and filtering with water and ethanol, putting the filtered cuprous oxide solid into a vacuum drying oven after the filtrate is neutral, and drying for 6-12 hours to obtain the high-purity cuprous oxide.
Further, the reducing agent in step S6 is one or more of sulfite, glucose, tartaric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, and sodium hypophosphite; the reducing agent and the catalyst contain CuSO4The molar ratio of copper ions in the water phase is 1-5: 1.
compared with the prior art, the invention has the advantages and positive effects that:
1. the preparation process can effectively treat the acidic copper-containing etching solution, avoids environmental pollution caused by the discharge of the copper-containing etching solution, simultaneously has the copper recovery rate of 99.5 percent and has excellent metal copper recovery rate;
2. the purity of the cuprous oxide product prepared by the process can reach 99.9 percent, and the cuprous oxide product has extremely high additional value;
3. the extraction agent in the process is convenient to recover and can be recycled, so that the emission pollution of the extraction agent is reduced, and the process cost is saved;
4. the water produced in the process can meet the water requirement of the etching production line after being recovered, and has remarkable water saving and environmental protection properties.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow block diagram of the present invention;
FIG. 2 is an SEM image of cuprous oxide produced by the present invention;
FIG. 3 is an XRD spectrum of cuprous oxide prepared by the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived from the embodiments of the present invention by a person skilled in the art without any creative effort, should be included in the protection scope of the present invention.
Example 1
Certain acidic etching waste liquid, Cu2+The concentration is 200g/L, H+The concentration is 2.5mol/L, and a large amount of chloride ions are contained. As shown in the process flow diagram of fig. 1, the acidic copper-containing etching waste liquid is filtered to remove fine insoluble particles in the industrial acidic copper-containing etching waste liquid, then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4, and an appropriate amount of Na is sequentially added2SO4And BaCO3And standing for 60 minutes, removing precipitates by using a precision filter, adding a proper amount of ammonia water, and adjusting the pH value to 2-4 again to obtain a crude copper-containing solution. Extracting copper ions in the crude copper solution by using an extractant Mextral984H diluted by Mextral DT100, wherein the concentration of the extractant is 50%, the volume ratio of the extractant to the copper-containing etching waste liquid is (O/A)15:1, the extraction grade is 5 grades, and a blue copper-containing extract phase (organic phase) and a raffinate phase (aqueous phase) are obtained after extraction. And adjusting the components of the raffinate phase (water phase) to be used as a regenerated etching solution. And carrying out first water washing on the copper-containing extract phase (organic phase) to obtain a blue transparent copper-containing organic phase and first washing water. Fully mixing a blue transparent copper-containing organic phase with a sulfuric acid solution with the concentration of 220g/L according to the volume ratio of 2:1 for back extraction, standing for phase separation, wherein the upper layer is an organic phase, and the lower layer is a copper sulfate-containing water phase. And (3) washing the upper organic phase for the second time by adopting primary washing water, standing for phase splitting, and separating the organic phase to be used as an extracting agent for reuse. Adding a proper amount of KOH into the back-extracted copper sulfate-containing aqueous phase to adjust the pH value to be alkaline, then adding tartaric acid according to the molar ratio of copper ions to the reducing agent tartaric acid of 1:2, stirring strongly, transferring into a reaction kettle to perform hydrothermal reaction at the hydrothermal temperature of 180 ℃ for 24 hours. After the reaction is finished, performing centrifugal separation, respectively washing with deionized water and ethanol for 2 times in a circulating manner, then placing the washed product into a vacuum drying oven, and drying for 12 hours to obtain nano cuprous oxide powder with the purity of 99.9 percent and the copper recovery rate of 99.5 percent.
Example 2
Certain acidic etching waste liquid, Cu2+The concentration is 150g/L, H+The concentration is 2mol/L, and a large amount of chloride ions are contained. As shown in the process flow diagram of fig. 1, the acidic copper-containing etching waste liquid is filtered to remove fine insoluble particles in the industrial acidic copper-containing etching waste liquid, and then a proper amount of NaOH is added to adjust the pH of the solution to 2-4, and the pH is sequentially adjusted to 2-4Adding a proper amount of Na2SO4And BaCO3And standing for 60 minutes, removing precipitates by using a precision filter, adding a proper amount of ammonia water, and adjusting the pH value to 2-4 again to obtain a crude copper-containing solution. Extracting copper ions in the crude copper solution by using an extractant Mextral984H diluted by Mextral DT100, wherein the concentration of the extractant is 40%, the volume ratio of the extractant to the copper-containing etching waste liquid is (O/A)10:1, the extraction grade is 3 grades, and a blue copper-containing extract phase (organic phase) and a raffinate phase (aqueous phase) are obtained after extraction. And adjusting the components of the raffinate phase (water phase) to be used as a regenerated etching solution. And carrying out first water washing on the copper-containing extract phase (organic phase) to obtain a blue transparent copper-containing organic phase and first washing water. Fully mixing a blue transparent copper-containing organic phase with a sulfuric acid solution with the concentration of 180g/L according to the volume ratio of 2:1 for back extraction, standing for phase separation, wherein the upper layer is an organic phase, and the lower layer is a copper sulfate-containing water phase. And (3) washing the upper organic phase for the second time by adopting primary washing water, standing for phase splitting, and separating the organic phase to be used as an extracting agent for reuse. Adding a proper amount of NaOH into the copper sulfate solution subjected to back extraction to adjust the pH value to be alkaline, then adding glucose according to the molar ratio of copper ions to the reducing agent glucose of 1:1, magnetically stirring, transferring into a reaction kettle to perform hydrothermal reaction at the hydrothermal temperature of 150 ℃ for 12h, after the reaction is finished, performing centrifugal separation, washing with deionized water and ethanol for 2 times respectively, then placing into a vacuum drying oven, and drying for 6h to obtain nano cuprous oxide powder with the purity of 99.5% and the copper recovery rate of 99%.
Example 3
Certain acidic etching waste liquid, Cu2+The concentration is 50g/L, H+The concentration is 0.7mol/L, and a large amount of chloride ions are contained. As shown in the process flow diagram of fig. 1, the acidic copper-containing etching waste liquid is filtered to remove fine insoluble particles in the industrial acidic copper-containing etching waste liquid, then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4, and an appropriate amount of Na is sequentially added2SO4And BaCO3And standing for 60 minutes, removing precipitates by using a precision filter, adding a proper amount of ammonia water, and adjusting the pH value to 2-4 again to obtain a crude copper-containing solution. Extraction of copper ions from crude copper solutions with extraction agent Mextral984H diluted with Mextral DT100, wherein extraction is carried outThe concentration of the extractant is 20 percent, the volume ratio of the extractant to the copper-containing etching waste liquid is (O/A)5:1, the extraction stage number is 1 stage, and a blue copper-containing extract phase (organic phase) and a raffinate phase (aqueous phase) are obtained after extraction. And adjusting the components of the raffinate phase (water phase) to be used as a regenerated etching solution. And carrying out first water washing on the copper-containing extract phase (organic phase) to obtain a blue transparent copper-containing organic phase and first washing water. Fully mixing a blue transparent copper-containing organic phase with a sulfuric acid solution with the concentration of 100g/L according to the volume ratio of 2:1 for back extraction, standing for phase separation, wherein the upper layer is an organic phase, and the lower layer is a copper sulfate-containing water phase. And (3) washing the upper organic phase for the second time by adopting primary washing water, standing for phase splitting, and separating the organic phase to be used as an extracting agent for reuse. Adding a proper amount of NaOH into the copper sulfate solution after back extraction to adjust the pH value to be alkaline, then adding sodium sulfite according to the molar ratio of copper ions to the reducing agent sodium sulfite of 1:1.2, reacting in a beaker for 6 hours, after the reaction is finished, performing centrifugal separation, washing for 2 times by deionized water and ethanol respectively, then placing in a vacuum drying oven, and drying for 8 hours to obtain nano cuprous oxide powder with the purity of 99.5 percent and the copper recovery rate of 98 percent.
Example 4
Certain acidic etching waste liquid, Cu2+The concentration is 180g/L, H+The concentration is 3mol/L, and a large amount of chloride ions are contained. As shown in the process flow diagram of fig. 1, the acidic copper-containing etching waste liquid is filtered to remove fine insoluble particles in the industrial acidic copper-containing etching waste liquid, then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4, and an appropriate amount of Na is sequentially added2SO4And BaCO3And standing for 60 minutes, removing precipitates by using a precision filter, adding a proper amount of ammonia water, and adjusting the pH value to 2-4 again to obtain a crude copper-containing solution. Extracting copper ions in the crude copper solution by using an extractant Mextral984H diluted by Mextral DT100, wherein the concentration of the extractant is 20%, the volume ratio of the extractant to the copper-containing etching waste liquid is (O/A)8:1, the extraction grade is 3 grades, and a blue copper-containing extract phase (organic phase) and a raffinate phase (aqueous phase) are obtained after extraction. And adjusting the components of the raffinate phase (water phase) to be used as a regenerated etching solution. And carrying out first water washing on the copper-containing extract phase (organic phase) to obtain a blue transparent copper-containing organic phase and first washing water. Mixing blue transparent solution withFully mixing the copper organic phase with a sulfuric acid solution with the concentration of 150g/L according to the volume ratio of 2:1 for back extraction, standing for phase separation, wherein the upper layer is an organic phase, and the lower layer is a copper sulfate-containing water phase. And (3) washing the upper organic phase for the second time by adopting primary washing water, standing for phase splitting, and separating the organic phase to be used as an extracting agent for reuse. Adding a proper amount of NaOH into the copper sulfate solution subjected to back extraction to adjust the pH value to be alkaline, then adding hydrazine hydrate according to the molar ratio of copper ions to the reducing agent hydrazine hydrate of 1:3, reacting for 2 hours in a beaker, after the reaction is finished, performing centrifugal separation, washing for 2 times by using deionized water and ethanol respectively, then placing into a vacuum drying oven, and drying for 3 hours to obtain nano cuprous oxide powder with the purity of 99% and the copper recovery rate of 90%.
Example 5
Certain acidic etching waste liquid, Cu2+The concentration is 80g/L, H+The concentration is 1mol/L, and the chlorine ion content is large. As shown in the process flow diagram of fig. 1, the acidic copper-containing etching waste liquid is filtered to remove fine insoluble particles in the industrial acidic copper-containing etching waste liquid, then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4, and an appropriate amount of Na is sequentially added2SO4And BaCO3And standing for 60 minutes, removing precipitates by using a precision filter, adding a proper amount of ammonia water, and adjusting the pH value to 2-4 again to obtain a crude copper-containing solution. Extracting copper ions in the crude copper solution by using an extractant Mextral984H diluted by Mextral DT100, wherein the concentration of the extractant is 10%, the volume ratio of the extractant to the copper-containing etching waste liquid is (O/A)12:1, the number of extraction stages is 3, and a blue copper-containing extract phase (organic phase) and a raffinate phase (aqueous phase) are obtained after extraction. And adjusting the components of the raffinate phase (water phase) to be used as a regenerated etching solution. And carrying out first water washing on the copper-containing extract phase (organic phase) to obtain a blue transparent copper-containing organic phase and first washing water. Fully mixing a blue transparent copper-containing organic phase with a sulfuric acid solution with the concentration of 150g/L according to the volume ratio of 2:1 for back extraction, standing for phase separation, wherein the upper layer is an organic phase, and the lower layer is a copper sulfate-containing water phase. And (3) washing the upper organic phase for the second time by adopting primary washing water, standing for phase splitting, and separating the organic phase to be used as an extracting agent for reuse. Adding a proper amount of NaOH into the copper sulfate solution after back extraction to adjust the pH value to be alkaline, and then adding a proper amount of NaOH into the copper sulfate solution after back extraction to adjust the pH value to be alkalineAdding sodium borohydride according to the molar ratio of the copper ions to the reducing agent sodium borohydride of 1:2, reacting in a beaker for 1h, after the reaction is finished, performing centrifugal separation, washing with deionized water and ethanol for 2 times respectively, then placing in a vacuum drying oven, and drying for 12h to obtain nano cuprous oxide powder with the purity of 99.5% and the copper recovery rate of 96%.
Example 6
Certain acidic etching waste liquid, Cu2+The concentration is 120g/L, H+The concentration is 2mol/L, and a large amount of chloride ions are contained. As shown in the process flow diagram of fig. 1, the acidic copper-containing etching waste liquid is filtered to remove fine insoluble particles in the industrial acidic copper-containing etching waste liquid, then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4, and an appropriate amount of Na is sequentially added2SO4And BaCO3And standing for 60 minutes, removing precipitates by using a precision filter, adding a proper amount of ammonia water, and adjusting the pH value to 2-4 again to obtain a crude copper-containing solution. Extracting copper ions in the crude copper solution by using an extractant Mextral984H diluted by Mextral DT100, wherein the concentration of the extractant is 30%, the volume ratio of the extractant to the copper-containing etching waste liquid is (O/A)8:1, the extraction grade is 4 grades, and a blue copper-containing extract phase (organic phase) and a raffinate phase (aqueous phase) are obtained after extraction. And adjusting the components of the raffinate phase (water phase) to be used as a regenerated etching solution. And carrying out first water washing on the copper-containing extract phase (organic phase) to obtain a blue transparent copper-containing organic phase and first washing water. Fully mixing a blue transparent copper-containing organic phase with a sulfuric acid solution with the concentration of 220g/L according to the volume ratio of 2:1 for back extraction, standing for phase separation, wherein the upper layer is an organic phase, and the lower layer is a copper sulfate-containing water phase. And (3) washing the upper organic phase for the second time by adopting primary washing water, standing for phase splitting, and separating the organic phase to be used as an extracting agent for reuse. Adding a proper amount of NaOH into the copper sulfate solution after back extraction to adjust the pH value to be alkaline, then adding the mixed reducing agent according to the molar ratio of copper ions to the mixed reducing agent (ascorbic acid and glucose) of 1:5, magnetically stirring, transferring into a reaction kettle to perform hydrothermal reaction at the hydrothermal temperature of 200 ℃ for 2h, after the reaction is finished, performing centrifugal separation, washing with deionized water and ethanol for 2 times respectively, then placing into a vacuum drying oven, drying for 6h to obtain nano cuprous oxide powder,the purity of the copper is 99.8 percent, and the recovery rate of the copper is 99 percent.
Example 7
Certain acidic etching waste liquid, Cu2+The concentration is 100g/L, H+The concentration is 1.5mol/L, and a large amount of chloride ions are contained. As shown in the process flow diagram of fig. 1, the acidic copper-containing etching waste liquid is filtered to remove fine insoluble particles in the industrial acidic copper-containing etching waste liquid, then an appropriate amount of NaOH is added to adjust the pH of the solution to 2-4, and an appropriate amount of Na is sequentially added2SO4And BaCO3And standing for 60 minutes, removing precipitates by using a precision filter, adding a proper amount of ammonia water, and adjusting the pH value to 2-4 again to obtain a crude copper-containing solution. Extracting copper ions in the crude copper solution by using an extractant Mextral984H diluted by Mextral DT100, wherein the concentration of the extractant is 25%, the volume ratio of the extractant to the copper-containing etching waste liquid is (O/A)10:1, the extraction grade is 3 grades, and a blue copper-containing extract phase (organic phase) and a raffinate phase (aqueous phase) are obtained after extraction. And adjusting the components of the raffinate phase (water phase) to be used as a regenerated etching solution. And carrying out first water washing on the copper-containing extract phase (organic phase) to obtain a blue transparent copper-containing organic phase and first washing water. Fully mixing a blue transparent copper-containing organic phase with a sulfuric acid solution with the concentration of 220g/L according to the volume ratio of 2:1 for back extraction, standing for phase separation, wherein the upper layer is an organic phase, and the lower layer is a copper sulfate-containing water phase. And (3) washing the upper organic phase for the second time by adopting primary washing water, standing for phase splitting, and separating the organic phase to be used as an extracting agent for reuse. Adding a proper amount of NaOH into the copper sulfate solution after the back extraction to adjust the pH value to be alkaline, then adding a mixed reducing agent according to the molar ratio of copper ions to the mixed reducing agent (glucose and sodium hypophosphite) of 1:4, magnetically stirring, transferring into a reaction kettle to perform hydrothermal reaction at 200 ℃ for 2h, after the reaction is finished, performing centrifugal separation, washing with deionized water and ethanol for 2 times respectively, then placing into a vacuum drying oven, and drying for 6h to obtain nano cuprous oxide powder with the purity of 99.5% and the copper recovery rate of 99.5%.
Example 8
Certain acidic etching waste liquid, Cu2+The concentration is 160g/L, H+The concentration is 3mol/L, and a large amount of chloride ions are contained. As shown in the figure1, filtering and pretreating the acidic copper-containing etching waste liquid to remove fine insoluble particles in the industrial acidic copper-containing etching waste liquid, adding a proper amount of NaOH to adjust the pH value of the solution to 2-4, and sequentially adding a proper amount of Na2SO4And BaCO3And standing for 60 minutes, removing precipitates by using a precision filter, adding a proper amount of ammonia water, and adjusting the pH value to 2-4 again to obtain a crude copper-containing solution. Extracting copper ions in the crude copper solution by using an extractant Mextral984H diluted by Mextral DT100, wherein the concentration of the extractant is 25%, the volume ratio of the extractant to the copper-containing etching waste liquid is (O/A)10:1, the extraction grade is 2 grades, and a blue copper-containing extract phase (organic phase) and a raffinate phase (aqueous phase) are obtained after extraction. And adjusting the components of the raffinate phase (water phase) to be used as a regenerated etching solution. And carrying out first water washing on the copper-containing extract phase (organic phase) to obtain a blue transparent copper-containing organic phase and first washing water. Fully mixing a blue transparent copper-containing organic phase with a sulfuric acid solution with the concentration of 220g/L according to the volume ratio of 2:1 for back extraction, standing for phase separation, wherein the upper layer is an organic phase, and the lower layer is a copper sulfate-containing water phase. And (3) washing the upper organic phase for the second time by adopting primary washing water, standing for phase splitting, and separating the organic phase to be used as an extracting agent for reuse. Adding a proper amount of NaOH into the copper sulfate solution subjected to back extraction to adjust the pH value to be alkaline, then adding a mixed reducing agent according to the molar ratio of copper ions to the mixed reducing agent (glucose and tartaric acid) of 1:4, magnetically stirring, transferring into a reaction kettle to perform hydrothermal reaction at the hydrothermal temperature of 200 ℃ for 1h, after the reaction is finished, performing centrifugal separation, washing with deionized water and ethanol for 2 times respectively, then placing into a vacuum drying oven, and drying for 6h to obtain nano cuprous oxide powder with the purity of 99.5% and the copper recovery rate of 95%.
Fig. 2 and 3 are SEM and XRD spectra of cuprous oxide prepared in the above example, respectively; the above embodiments show that the present invention has the following beneficial effects:
1. the preparation process can effectively treat the acidic copper-containing etching solution, avoids environmental pollution caused by the discharge of the copper-containing etching solution, simultaneously has the copper recovery rate of 99.5 percent and has excellent metal copper recovery rate;
2. the purity of the cuprous oxide product prepared by the process can reach 99.9 percent, and the cuprous oxide product has extremely high additional value;
3. the extraction agent in the process is convenient to recover and can be recycled, so that the emission pollution of the extraction agent is reduced, and the process cost is saved;
4. the water produced in the process can meet the water requirement of the etching production line after being recovered, and has remarkable water saving and environmental protection properties.
Claims (6)
1. A method for recovering copper from acidic copper-containing etching solution and preparing cuprous oxide is characterized in that: the method comprises the following steps:
s1, filtering the acidic copper-containing etching waste liquid to remove insoluble particles in the acidic copper-containing etching waste liquid, adding NaOH to adjust the pH value of the acidic copper-containing etching waste liquid to 2-4, and sequentially adding Na2SO4And BaCO3Standing for 60 minutes, and removing precipitates to obtain a crude copper-containing solution;
s2, adjusting the pH value of the crude copper-containing solution obtained in the step S1 to 2-4 by using ammonia water, transferring the solution into an extraction cylinder, adding an extracting agent, mixing and stirring, standing and layering, wherein the upper layer is a primary copper-containing organic phase, and the lower layer is a primary water phase; recovering the primary aqueous phase for use in an etching production line;
s3, washing the copper-containing organic phase obtained in the step S2 with deionized water, and separating to obtain a secondary copper-containing organic phase and a primary washing water phase;
s4, transferring the secondary copper-containing organic phase obtained in the step S3 into a back extraction cylinder, simultaneously adding sulfuric acid, fully stirring, standing and layering, wherein the upper layer is an extractant-containing organic phase, and the lower layer is a CuSO-containing organic phase4An aqueous phase;
s5, adding the primary washing water phase obtained in the step S3 into an extractant-containing organic phase for washing, standing and layering to obtain a pure extractant organic phase for use in the step S2;
s6, adding CuSO obtained in step S44Adding NaOH or KOH into the water phase to adjust the pH to be alkaline, adding a reducing agent, and adopting a hydrothermal method orAnd (4) preparing cuprous oxide by a chemical precipitation method.
2. The process for the recovery of copper and the production of cuprous oxide from acidic copper-containing etching solution according to claim 1, wherein: the extractant is Mextral984H, the concentration is 10-50%, the diluent for the extractant is Mextral DT100, and the volume ratio of the extractant to the acidic copper-containing etching waste liquid is 5-15: 1, the number of extraction stages is 1-5.
3. The process for the recovery of copper and the production of cuprous oxide from acidic copper-containing etching solution according to claim 1, wherein: the concentration of sulfuric acid in the step S4 is 100-220 g/L, and the volume ratio of the sulfuric acid to the secondary copper-containing organic phase is 1:1 to 5.
4. The process for the recovery of copper and the production of cuprous oxide from acidic copper-containing etching solution according to claim 1, wherein: the step S6 of preparing cuprous oxide by using a hydrothermal method comprises the following steps:
s61, adding CuSO4Adding the water phase into a hydrothermal reaction kettle, adjusting the pH to be alkaline by using a 1mol/L NaOH solution or KOH solution, then adding a reducing agent, and sealing, wherein the hydrothermal reaction temperature is 150-200 ℃, and the hydrothermal reaction time is 1-24 hours, so as to obtain a cuprous oxide solution;
and S62, performing centrifugal separation on the cuprous oxide solution obtained in the step S61, alternately cleaning and filtering with water and ethanol, putting the filtered cuprous oxide solid into a vacuum drying oven after the filtrate is neutral, and drying for 6-12 hours to obtain the high-purity cuprous oxide.
5. The process for the recovery of copper and the production of cuprous oxide from acidic copper-containing etching solution according to claim 1, wherein: the step S6 of preparing cuprous oxide by using a chemical precipitation method comprises the following steps:
s63, adding CuSO4Adding the water phase into a stirring reactor, adjusting the pH to be alkaline by using 1mol/L NaOH solution or KOH solution, then adding a reducing agent, and reacting for 1-6 h;
and S64, performing centrifugal separation on the cuprous oxide solution obtained in the step S63, alternately cleaning and filtering with water and ethanol, putting the filtered cuprous oxide solid into a vacuum drying oven after the filtrate is neutral, and drying for 6-12 hours to obtain the high-purity cuprous oxide.
6. The process for the recovery of copper and the production of cuprous oxide from acidic copper-containing etching solution according to claim 1, wherein: the reducing agent in the step S6 is one or a combination of more of sulfite, glucose, tartaric acid, hydrazine hydrate, sodium borohydride, ascorbic acid and sodium hypophosphite; the reducing agent and the catalyst contain CuSO4The molar ratio of copper ions in the water phase is 1-5: 1.
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| CN112376049A (en) * | 2020-11-09 | 2021-02-19 | 江苏净拓环保科技有限公司 | Method for recovering acidic etching solution |
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| CN113403134A (en) * | 2021-06-23 | 2021-09-17 | 江西省科学院能源研究所 | Copper wire drawing oil waste liquid treatment method |
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