CN114990339A - Method for recovering and recycling semiconductor copper alloy etching solution - Google Patents
Method for recovering and recycling semiconductor copper alloy etching solution Download PDFInfo
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- CN114990339A CN114990339A CN202210567278.1A CN202210567278A CN114990339A CN 114990339 A CN114990339 A CN 114990339A CN 202210567278 A CN202210567278 A CN 202210567278A CN 114990339 A CN114990339 A CN 114990339A
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C21—METALLURGY OF IRON
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- C22B15/00—Obtaining copper
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- C22B15/00—Obtaining copper
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- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation processes
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/004—Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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Abstract
The invention discloses a method for recovering and recycling semiconductor copper alloy etching solution, and particularly relates to the technical field of metal recovery, which comprises the following steps: the method comprises the following steps: collecting waste liquid; step two: electrolyzing and extracting copper; step three: recycling chlorine; step four: treating and recycling acid waste liquid; step five: recycling the acid waste liquid, dissolving the acid waste liquid in the hydrochloric acid solution by adding additives, and recycling the dissolved acid waste liquid to a production line for production; step six: precipitating and separating, adding a precipitator for precipitation and separation; step seven: refining and recovering metal, and refining and recovering metal elements in the metal by utilizing high-temperature reducibility. The method has the advantages of simple overall operation process, realization of recovery of copper and other metals, cyclic utilization of acid waste liquid, easy process operation, high waste liquid treatment efficiency and low operation cost, and generates economic benefits and higher environmental benefits.
Description
Technical Field
The invention relates to the technical field of metal recovery, in particular to a method for recovering and recycling semiconductor copper alloy etching solution.
Background
With the progress of science and technology, the semiconductor industry is developed rapidly and more in China, wherein in the semiconductor industry, a part of semiconductors use copper alloy as a conductive material, so that hydrochloric acid + sodium chlorate (hydrogen peroxide and the like) + copper chloride are needed to be used for etching the copper alloy in the manufacturing process, because the copper alloy material contains various chemical elements (such as Si, Zn, P, Ni, Fe and the like), the components of an etching solution generated in the etching process are greatly different from the components of an acid etching solution of a PCB enterprise, the etching solution also contains Si, Zn, Ni, Fe and the like besides the metal copper element, if the metal recovery regeneration process of the acid etching solution of the PCB enterprise is adopted for carrying out metal recovery on the semiconductor etching solution, the copper recovery is very difficult, and meanwhile, when acid wastewater generated after copper metal is recovered is recycled in a production line, the etching speed and the quality are greatly influenced, therefore, some copper recovery enterprises cannot produce the copper alloy after installing copper recovery equipment in the semiconductor industry; therefore, the method not only can recover the useful value in the waste liquid, but also effectively recycle other metals, and the recovered acid wastewater can be recycled to a production line to produce without affecting the etching performance; the invention of the method brings clean production to enterprises, protects the environment and increases economic benefits to the enterprises.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks of the prior art, embodiments of the present invention provide a method for recycling and reusing an etching solution of a semiconductor copper alloy, so as to solve the above-mentioned problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a method for recovering and recycling semiconductor copper alloy etching solution specifically comprises the following steps:
the method comprises the following steps: waste liquid collection, wherein etching liquid is separately collected, and a collection pipeline is cleaned by hot steam before collection;
step two: electrolyzing to extract copper, namely electrolyzing the etching solution by using diaphragm electrolysis;
step three: recycling chlorine, namely recycling the chlorine generated after electrolysis, and detecting the concentration of the chlorine by a detection device;
step four: treating and recycling acid waste liquid, distilling the waste liquid generated in the step at high temperature by using evaporation equipment to recycle hydrochloric acid solution and obtain crystallized concentrated solution;
step five: recycling the acid waste liquid, dissolving the acid waste liquid in the hydrochloric acid solution by adding additives, and recycling the dissolved acid waste liquid to a production line for production;
step six: precipitating and separating, adding a precipitator for precipitation and separation;
step seven: refining and recovering metal, and refining and recovering metal elements in the metal by utilizing high-temperature reducibility.
Preferably, in the first step, the etching solution generated in the production line needs to be collected separately, and the waste solution is collected into the storage barrel from the production line connected with a dedicated pipeline, so that waste solution, washing water and other waste water generated in other processes cannot be mixed.
Preferably, in the second step, a diaphragm electrolysis process is used, the cathode chamber and the anode chamber are divided, the etching solution in the cathode chamber circularly flows, during electrolysis, the temperature of the circulating etching solution is controlled to be 25-35 ℃, the cathode chamber generates an electrolytic copper plate, and the anode chamber generates chlorine; wherein the anode chamber is sealed by a PVC material box, the PVC material is connected with a gas guide tube for collecting chlorine, and the gas is collected to the production line for recycling under the action of external force air draft.
Preferably, in the third step, the electrolytic anode chamber sends the chlorine to the production line through a closed air duct and external air draft to react with the etching solution, and the etching solution is pumped into the chlorine recycling equipment through a pump to be contacted with the chlorine in a spraying manner for reaction and absorption.
Preferably, in the fourth step, after the copper is extracted from the etching waste liquid by diaphragm electrolysis, the copper ions in the etching waste liquid drop to about 5 g/L to stop electrolysis, and then the waste liquid is distilled at a heating temperature of 40-100 ℃ by an evaporation device to recover a hydrochloric acid solution (concentrated to 10 percent of the original) and obtain a crystal concentrated solution (concentrated to the original), wherein the hydrochloric acid solution is called acid waste liquid, and the evaporation device is one of atmospheric distillation and reduced pressure distillation.
Preferably, the hydrochloric acid solution is obtained through distillation and recovery in the fifth step, and then the hydrochloric acid solution is dissolved by supplementing sodium chloride and other materials and then recycled to the production line for production, so that the specific gravity parameter requirement of the etching solution of the production line is maintained stably.
Preferably, in the sixth step, a precipitator is added according to the crystallization concentrated solution generated in the fourth step to precipitate all ions such as copper, zinc, nickel and iron, then the solid precipitate is separated from the liquid, and the solid precipitate is recovered and collected; the settling agent is hydroxide such as sodium hydroxide, potassium hydroxide and calcium hydroxide, or at least one of carbonate and bicarbonate such as sodium carbonate and calcium carbonate and potassium carbonate.
Preferably, in the seventh step, the solid precipitate is recovered and collected according to the above steps, and then enters a high-temperature smelting furnace, a reducing agent is added, the temperature of the smelting furnace is raised to about 1560 ℃, and metals such as zinc, copper, nickel, iron and the like are respectively and sequentially extracted and recovered.
The invention has the technical effects and advantages that:
the invention improves the prior design, has simple integral operation process, can realize the recovery of copper and other metals, and respectively utilizes the acid-base solution additive to carry out precipitation separation on the recovered solution, thereby effectively improving the recovery rate of metal elements.
Drawings
FIG. 1 is an overall schematic view of 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 by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a method for recovering and recycling semiconductor copper alloy etching solution specifically comprises the following steps:
the method comprises the following steps: the method comprises the following steps of waste liquid collection, wherein etching liquid is collected independently, and a collection pipeline is cleaned by hot steam before collection, wherein the etching liquid generated in a production line needs to be collected independently, and the waste liquid is collected into a storage barrel from the production line by a special pipeline and cannot be mixed with waste liquid, washing water and other waste water generated in other processes; the components and the concentration of the liquid medicine collected into the storage barrel are the same as the components of the etching liquid in the production line;
step two: electrolyzing to extract copper, purifying and filtering the etching solution collected via special pipeline with filter element having aperture of 5 μm, pumping into cathode chamber of diaphragm electrolysis equipment, adding electrolysis additive into cathode chamber, and mixing cathode etching solution uniformly by using cathode chamber etching solution circulation flow, controlling cathode etching solution temperature at 25-35 deg.C during electrolysis, and obtaining copper ion from cathode chamber etching solution to obtain electrolytic copper plate (Cu) for generating electrons 2+ +2e ═ Cu), chlorine gas (2 Cl) is produced in the anode compartment by loss of electrons from the chloride ions in the anode compartment - -2e＝Cl 2 )；
Step three: chlorine is recycled, during electrolysis, chlorine is generated in the anode chamber, the chlorine is sent to a production line to react with the etching solution through a closed air duct and external air draft, the etching solution is pumped into chlorine recycling equipment through a pump and is contacted with the chlorine from top to bottom in a spraying mode, monovalent copper in the etching solution and the chlorine undergo redox reaction and are absorbed, and 2Cu is obtained + +Cl 2 ＝2Cu 2+ +2Cl - ；
Step four: treating and recycling acid waste liquid, wherein the concentration of copper ions in the etching liquid obtained after copper is extracted by electrolysis is about 5 g/L, pumping the etching liquid into a reduced pressure evaporation device, heating to maintain the temperature at 40-80 ℃, evaporating the evaporation device under the vacuum degree of 0.098Mpa, introducing hydrochloric acid steam in the etching liquid into a condenser at 5-10 ℃, condensing the volatilized hydrochloric acid steam into hydrochloric acid solution (acid waste liquid) and flowing into a storage barrel through a pipeline for collection, generating concentrated crystal liquid such as zinc salt, iron salt, nickel and copper salt after the hydrochloric acid in the etching liquid is volatilized, and then collecting the concentrated crystal liquid in a container;
step five: recycling the acid waste liquid, obtaining the acid waste liquid through distillation and recovery, and then adding a certain amount of materials such as sodium chloride and the like to perform component adjustment, wherein when the production line is produced, the specific gravity of the etching liquid is gradually increased, and when the specific gravity is increased to more than 1.300, the acid waste liquid is automatically added into the production line through a specific gravity controller, so that the specific gravity parameter requirement of the etching liquid of the production line is maintained stably;
step six: and (3) performing precipitation separation, namely pumping the concentrated crystal liquid into a precipitation stirring barrel, adding a precipitator (sodium hydroxide) to precipitate copper, zinc, nickel, iron and the like, and reacting as follows: cu 2+ +2NaOH＝Cu(OH) 2 ↓+2Na + ；Zn 2+ +2NaOH＝Zn(OH) 2 ↓+2Na + ；Ni 2+ +2NaOH＝Ni(OH) 2 ↓+2Na + ；Fe 3+ +3NaOH＝Fe(OH) 3 ↓+3Na + (ii) a Separating the solid precipitate from the liquid by a filter press, and recovering the solid precipitate;
step seven: refining and recovering metals, adding solid precipitates obtained by filter pressing into a high-temperature smelting furnace, adding a smelting reducing agent, gradually increasing the temperature of the smelting furnace to 500 ℃ to obtain liquid zinc and solid copper-nickel-iron and separating out zinc, increasing the temperature to 1400 ℃ to obtain liquid copper and solid nickel-iron and separating out copper, increasing the temperature to 1460 ℃ to obtain liquid nickel and solid iron and separating out nickel, increasing the temperature to 1560 ℃ to obtain liquid nickel and other solid impurities and separating out nickel, and condensing the separated liquid to obtain metals such as zinc, copper, nickel, iron and the like.
Example two:
a method for recovering and recycling semiconductor copper alloy etching solution specifically comprises the following steps:
the method comprises the following steps: the method comprises the following steps of waste liquid collection, wherein etching liquid is collected independently, and a collection pipeline is cleaned by hot steam before collection, wherein the etching liquid generated in a production line needs to be collected independently, and the waste liquid is collected into a storage barrel from the production line by a special pipeline and cannot be mixed with waste liquid, washing water and other waste water generated in other processes; the components and the concentration of the liquid medicine collected into the storage barrel are the same as the components of the etching liquid in the production line;
step two: electrolyzing to extract copper, purifying and filtering the etching solution collected via a special pipeline by a filter with a filter element with a pore diameter of 5um, pumping into a cathode chamber of a diaphragm electrolysis device, adding an electrolysis additive into the cathode chamber, and uniformly mixing the cathode etching solution by using the circular flow of the etching solution in the cathode chamber, wherein during electrolysis, the temperature of the cathode etching solution is controlled to be 25-35 ℃, and copper ions in the etching solution in the cathode chamber are used for obtaining an electron-generating electrolytic copper plate (Cu) 2+ +2e ═ Cu), chlorine gas (2 Cl) is produced in the anode compartment by loss of electrons from the chloride ions in the anode compartment - -2e＝Cl 2 )；
Step three: chlorine is recycled, during electrolysis, chlorine is generated in the anode chamber, the chlorine is sent to a production line to react with the etching solution through a closed air duct and external air draft, the etching solution is pumped into chlorine recycling equipment through a pump and is contacted with the chlorine from top to bottom in a spraying mode, monovalent copper in the etching solution and the chlorine undergo redox reaction and are absorbed, and 2Cu is obtained + +Cl 2 ＝2Cu 2+ +2Cl - ；
Step four: treating and recovering acid waste liquid, wherein the concentration of copper ions in the etching liquid obtained after copper is extracted by electrolysis is about 5 g/L, pumping the etching liquid into a reduced pressure evaporation device, heating to maintain the temperature at 40-80 ℃, evaporating the evaporation device under the vacuum degree of 0.098Mpa, introducing hydrochloric acid steam in the etching liquid into a condenser at 5-10 ℃, condensing the volatilized hydrochloric acid steam into hydrochloric acid solution (acid waste liquid) and flowing the hydrochloric acid solution into a storage barrel through a pipeline for collection, volatilizing hydrochloric acid in the etching liquid to generate concentrated crystal liquid of zinc salt, iron salt, nickel, copper salt and the like, and then collecting the concentrated crystal liquid in a container;
step five: recycling the acid waste liquid, obtaining the acid waste liquid through distillation and recovery, and then adding a certain amount of materials such as sodium chloride and the like to perform component adjustment, wherein when the production line is produced, the specific gravity of the etching liquid is gradually increased, and when the specific gravity is increased to more than 1.300, the acid waste liquid is automatically added into the production line through a specific gravity controller, so that the specific gravity parameter requirement of the etching liquid of the production line is maintained stably;
step six: and (3) performing precipitation separation, namely pumping the concentrated crystal liquid into a precipitation stirring barrel, adding a precipitator (sodium carbonate) to precipitate copper, zinc, nickel, iron and other ions, and reacting as follows: cu 2+ +Na 2 CO 3 ＝CuCO 3 ↓+2Na + ；；Zn 2+ +Na 2 CO 3 ＝ZnCO 3 ↓+2Na + ；Ni 2+ +Na 2 CO3＝NiCO3↓+2Na+；2Fe 3+ +3Na 2 CO 3 ＝Fe 2 (CO3) 3 ↓+6Na + (ii) a Separating the solid precipitate from the liquid by using a filter press, and recovering the solid precipitate;
step seven: refining and recovering metals, adding solid precipitates obtained by filter pressing into a high-temperature smelting furnace, adding a smelting reducing agent, gradually increasing the temperature of the smelting furnace to 500 ℃ to obtain liquid zinc and solid copper-nickel-iron and separate out zinc, increasing the temperature to 1400 ℃ to obtain liquid copper and solid nickel-iron and separate out copper, increasing the temperature to 1460 ℃ to obtain liquid nickel and solid iron and separate out nickel, increasing the temperature to 1560 ℃ to obtain liquid nickel and other solid impurities and separate out nickel, and condensing the separated liquid to obtain metals such as zinc, copper, nickel, iron and the like.
The points to be finally explained are: first, in the description of the present application, it should be noted that, unless otherwise specified and limited, the terms "mounted," "connected," "connecting," and "connecting" should be understood broadly, and may be a mechanical connection or an electrical connection, or a communication between two elements, and may be directly connected, and "upper," "lower," "left," and "right" are only used to indicate relative positional relationships, and when the absolute position of the object to be described is changed, the relative positional relationships may be changed;
secondly, the method comprises the following steps: in the drawings of the disclosed embodiments of the invention, only the structures related to the disclosed embodiments are referred to, other structures can refer to common designs, and the same embodiment and different embodiments of the invention can be combined with each other without conflict;
and finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (8)
1. A method for recovering and recycling semiconductor copper alloy etching solution is characterized by comprising the following steps: the method specifically comprises the following steps:
the method comprises the following steps: waste liquid collection, wherein etching liquid is separately collected, and a collection pipeline is cleaned by hot steam before collection;
step two: electrolyzing and extracting copper, namely electrolyzing the etching solution by using diaphragm electrolysis;
step three: recycling chlorine, namely recycling the chlorine generated after electrolysis, and detecting the concentration of the chlorine by using a detection device;
step four: treating and recycling acid waste liquid, distilling the waste liquid generated in the step at high temperature through evaporation equipment to recycle hydrochloric acid solution and obtain crystallized concentrated solution;
step five: recycling the acid waste liquid, dissolving the acid waste liquid in the hydrochloric acid solution by adding additives, and recycling the dissolved acid waste liquid to a production line for production;
step six: precipitating and separating, adding a precipitator for precipitation and separation;
step seven: refining and recovering metal, and refining and recovering metal elements in the metal by utilizing high-temperature reducibility.
2. The method for recycling and reusing the etching solution for copper alloy of semiconductor according to claim 1, wherein: in the first step, the etching solution generated by the production line needs to be collected separately, and waste liquid is collected into a storage barrel from a pipeline special for the production line, so that waste liquid, washing water and other waste water generated in other processes cannot be mixed.
3. The method for recycling and reusing the etching solution for copper alloy of semiconductor according to claim 1, wherein: in the second step, a diaphragm electrolysis process is used, a cathode chamber and an anode chamber are divided, etching solution in the cathode chamber flows circularly, during electrolysis, the temperature of the circulating etching solution is controlled to be 25-35 ℃, an electrolytic copper plate is generated in the cathode chamber, and chlorine is generated in the anode chamber; wherein the anode chamber is sealed by a PVC material box, the PVC material is connected with a gas guide tube for collecting chlorine, and the gas is collected to the production line for recycling under the action of external force air draft.
4. The method for recycling and reusing the etching solution for copper alloy of semiconductor according to claim 1, wherein: in the third step, the electrolytic anode chamber sends chlorine to the production line through a closed air duct and external air draft to react with the etching solution, and the etching solution is pumped into the chlorine recycling equipment through a pump and is contacted with the chlorine in a spraying mode for reaction and absorption.
5. The method for recycling and reusing the etching solution for copper alloy of semiconductor according to claim 1, wherein: and in the fourth step, after the copper is extracted from the etching waste liquid through diaphragm electrolysis, the copper ions in the etching waste liquid are reduced to about 5 g/L to stop electrolysis, the waste liquid is distilled and recovered by evaporation equipment at the heating temperature of 40-100 ℃ to obtain a hydrochloric acid solution (concentrated to 10 percent of the original solution), the hydrochloric acid solution is called acid waste liquid, and the evaporation equipment is one of normal pressure distillation and reduced pressure distillation.
6. The method for recycling and reusing the etching solution for copper alloy of semiconductor according to claim 1, wherein: and in the fifth step, the hydrochloric acid solution is obtained through distillation recovery, and then the hydrochloric acid solution is added with sodium chloride and other materials to be dissolved and then recycled to the production line for production, so that the specific gravity parameter requirement of the etching solution of the production line is maintained stably.
7. The method for recycling and reusing the etching solution for copper alloy of semiconductor according to claim 1, wherein: in the sixth step, precipitating agent is added according to the crystallization concentrated solution generated in the fourth step to completely precipitate copper, zinc, nickel, iron and other ions, then solid precipitate is separated from liquid, and the solid precipitate is recovered and collected; the settling agent is hydroxide such as sodium hydroxide, potassium hydroxide and calcium hydroxide, or at least one of carbonate and bicarbonate such as sodium carbonate and calcium carbonate and potassium carbonate.
8. The method for recycling and reusing the etching solution for copper alloy of semiconductor according to claim 1, wherein: and seventhly, recovering and collecting solid precipitates according to claim 7, putting the solid precipitates into a high-temperature smelting furnace, adding a reducing agent, raising the temperature of the smelting furnace to about 1560 ℃, and respectively and sequentially extracting and recovering metals such as zinc, copper, nickel, iron and the like.
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- 2022-05-23 CN CN202210567278.1A patent/CN114990339A/en active Pending
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| CN106498401A (en) * | 2017-01-06 | 2017-03-15 | 深圳市新锐思环保科技有限公司 | A kind of recoverying and utilizing method of acidic etching waste liquid and recovery and processing system |
| CN106958021A (en) * | 2017-05-03 | 2017-07-18 | 中南大学 | A kind of regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing |
| CN110453225A (en) * | 2019-08-29 | 2019-11-15 | 深圳市祺鑫天正环保科技有限公司 | The processing method of acidic etching waste liquid |
| CN111020633A (en) * | 2019-12-23 | 2020-04-17 | 广东臻鼎环境科技有限公司 | Treatment method of acidic etching waste liquid |
| CN114016034A (en) * | 2021-11-04 | 2022-02-08 | 兴平市秦兴环保科技有限公司 | Recycling treatment method of etching waste liquid mixed acid |
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