TW201938493A - Method for processing and recycling copper ion from copper etching (cupric acid) waste liquid comprising an extraction reaction, a regeneration reaction, an electrolysis treatment and a recycling treatment - Google Patents

Abstract

A method for processing and recycling copper ion from copper etching (cupric acid) waste liquid, the method for processing and recycling comprising an extraction reaction, a regeneration reaction, an electrolysis treatment and a recycling treatment. With the processes above, this invention can eliminate the interference of complex ingredients in the copper etching (cupric acid) waste liquid to the direct electrolytic recovery method, wherein copper ion in the waste liquid is first converted into regenerated cupric sulfate solution, followed by the electrolytic recovery method, so as to recycle the copper ion in the copper etching (cupric acid) waste liquid as valuable metal copper.

Description

Copper etching (copper acid) waste liquid copper ion treatment and recovery method

The invention relates to a treatment method for recovering valuable metals from a waste liquid, in particular to a copper ion etching (copper acid) waste liquid copper ion treatment and recovery method.

With the increasingly strict requirements for the treatment of industrial waste water by environmental protection regulations, many industrial waste water must use more advanced treatment procedures, high energy consumption treatment procedures or new inventions of treatment methods in order to reach their prescribed discharge water standards.

Among them, the copper etching (copper acid) waste liquid produced by the optoelectronics industry has been developed in recent years. With the improvement of image resolution and additional functions, the original aluminum process has been improved and converted to a copper process. As a result, copper etching has begun. (Copper acid) waste liquid. This is a new type of waste liquid. Due to the special requirements of the panel process, the composition of copper etching solution (copper acid solution) is extremely complicated (hydrogen peroxide / organic acid / base compound / phosphate / amine / iminodiacetic acid / 5-aminotetrazolium / hydrogen fluoride / confidential additives ... and other ingredients, mixed according to different types / different ratios), several suppliers of copper etching solution (copper acid solution) all over the world have their own ingredients, Proportion, and even added several secret secret formulas.

Therefore, since the main function of the copper etching solution (copper acid solution) is to etch metal copper on the circuit board, the main metal contaminant is copper ions (currently the concentration of copper emitted by the photovoltaic industry process is about 5000 ~ 10000mg / L). However, the complex composition of copper etching (copper acid) waste liquid makes the treatment of this copper-containing waste liquid or further copper treatment and recycling more difficult.

In addition, due to the complex components contained in the copper etching (copper acid) waste liquid of the photovoltaic industry, if the direct electrolytic recovery method is used for copper recovery, many of the components (hydrogen peroxide / organic acid ...) will not only interfere with the direct electrolytic recovery method. The copper reduction reaction will damage the electrolytic equipment. Therefore, the method of directly recycling copper etching (copper acid) waste liquid by electrolytic treatment and recovery cannot successfully achieve the purpose of efficiently removing copper ions and treating and recycling them into valuable metal copper.

In view of this, the present inventors have engaged in the manufacturing, development and design of related products for many years. After careful design and careful evaluation of the above-mentioned goals, they finally have a practical invention.

The technical problem to be solved by the present invention is to provide a method for treating and recovering copper ions from copper etching (copper acid) waste liquid in view of the above-mentioned defects existing in the prior art.

The above-mentioned treatment and recovery method includes an extraction reaction, a regeneration reaction, an electrolytic treatment, and a recovery treatment. Among them: the extraction reaction is to concentrate the waste liquid to be treated in a waste liquid concentration tank and then transfer it to an extraction reaction tank. The extraction reaction An extraction agent is introduced into the tank system, and the copper ions in the waste liquid are adsorbed and separated by the extractant. The extraction agent having the copper ions adsorbed is subjected to regeneration reaction treatment, and the waste liquid from which copper ions have been removed will be discharged out of the extraction reaction tank; The regeneration reaction is to transfer the extractant with the adsorbed copper ions into a regeneration reaction tank, and then introduce the sulfuric acid solution. The copper ions are regenerated by the sulfuric acid solution and mixed into a regenerated copper sulfate solution. At the same time, the extractant will be separated out, and Recovered for extraction reaction, and the regenerated copper sulfate solution is further subjected to electrolytic treatment; the electrolytic treatment is electrolytic treatment of the copper sulfate solution through an electrolytic system, so that the ionic copper of the copper sulfate solution is electrolytically reduced to metallic copper and recovered Treatment, and the sulfuric acid solution after the electrolytic treatment is recovered for regeneration reaction, thereby completing the waste liquid treatment and returning Valuable metals are copper process.

Preferably, the extractant is a resin capable of effectively adsorbing copper ions, and further adsorbing and separating copper ions from the waste liquid.

Preferably, the extraction reaction further includes an extractant storage tank and a low copper waste liquid storage tank. The extractant storage tank introduces the extractant into the extraction reaction tank and recovers the extractant after the regeneration reaction.

Preferably, after the extraction reaction, a washing treatment may be performed, and a trace of waste liquid in the extractant may be washed and discharged, and then a regeneration reaction treatment may be performed.

Preferably, the cleaning treatment is performed by using clean water or a sulfuric acid solution containing less than 5% sulfur.

Preferably, the regeneration reaction further includes an electrolytic circulation tank. A sulfuric acid solution is contained in the electrolytic circulation tank, which is introduced into the regeneration reaction tank for the regeneration reaction, and the regenerated copper sulfate solution after the regeneration reaction is re-introduced into the electrolytic cycle. In the tank, the copper sulfate solution is introduced into the electrolytic system through the electrolytic circulation tank for electrolytic treatment, and the sulfuric acid solution after the electrolytic treatment is recovered and concentrated in the electrolytic circulation tank for use in the regeneration reaction.

Preferably, the concentration of the sulfuric acid solution used in the regeneration reaction is between 5-50%.

Preferably, the extraction reaction, the regeneration reaction, and the electrolytic treatment are a batch matching process or a continuous matching process.

Preferably, the hydraulic retention time of the introduction of the extractant in the extraction reaction is 0.1 to 60 minutes.

Preferably, the hydraulic retention time of the sulfuric acid solution introduced during the regeneration reaction is 0.1 to 60 minutes.

Preferably, the visual recovery plan of the electrolytic system is designed as multiple groups connected in series or in parallel, and the operating current density of the electrolytic system is between 10 and 1000 A / m ² .

Contrast with the efficacy of the prior art: The main purpose of this treatment and recovery method is to eliminate the interference of the complex components of copper etching (copper acid) waste liquid on the direct electrolytic recovery method. The copper ions in the waste liquid are first converted into regenerated copper sulfate solution, and then An electrolytic recovery method is performed to treat and recover copper ions in the copper etching (copper acid) waste liquid into valuable metal copper.

The secondary purpose of this treatment and recovery method is to treat and recover the copper ion pollutants of copper etching (copper acid) waste liquid into valuable metal copper, to achieve the recovery and reuse of industrial pollutants, and to sell the electrolytically recovered metal copper. Profit.

The secondary purpose of this treatment and recovery method, using the treatment method of the present invention, saves a large amount of outsourcing treatment costs compared to other methods (concentrated outsourcing treatment / coagulation sedimentation pressure filtration to copper-containing sludge, etc.) Or copper sludge outsourcing treatment costs.

The secondary purpose of this treatment and recovery method can effectively reduce the amount of copper sludge. The removal rate of copper ions is over 99%. In contrast, the amount of copper sludge produced by subsequent wastewater treatment is less than 1% of the original.

The secondary purpose of this treatment and recovery method can greatly reduce the amount of drugs used to remove copper ions in wastewater treatment and the subsequent copper sludge filter press operation / copper sludge inventory.

The secondary purpose of this treatment and recovery method is to treat and recover copper ion pollutants of copper etching (copper acid) waste liquid into metallic copper, thereby avoiding the possibility of secondary pollution.

〔this invention〕

10‧‧‧ Extraction reaction

11‧‧‧Waste liquid concentration tank

12‧‧‧extraction reaction tank

13‧‧‧Extractant tank

14‧‧‧Low copper waste liquid storage tank

20‧‧‧Regeneration reaction

21‧‧‧ regeneration reaction tank

22‧‧‧Electrolytic circulation tank

30‧‧‧ Electrolytic treatment

31‧‧‧electrolysis system

40‧‧‧Recycling

A‧‧‧waste liquid

B‧‧‧Metal Copper

FIG. 1 is a block diagram showing the flow of the processing and recycling method of the present invention.

FIG. 2 is a schematic flow chart of the processing and recycling method of the present invention.

In order for your reviewers to have a better understanding and understanding of the purpose, features and effects of the present invention, the following please cooperate with [Simplified Description of the Drawings] as detailed below: First, please refer to Figure 1 first, a copper Etching (copper acid) waste liquid copper ion treatment and recovery method, the treatment and recovery method includes extraction reaction 10, regeneration reaction 20, electrolytic treatment 30, and recovery treatment 40, wherein: extraction reaction 10 includes a waste liquid concentration tank 11, an extraction reaction Tank 12, an extractant storage tank 13, and a low-copper waste liquid storage tank 14. The waste liquid A to be processed is first concentrated in a waste liquid concentration tank 11 and then transferred to an extraction reaction tank 12, and the extractant The storage tank 13 is used for containing the extractant, and the extractant is introduced into the extraction reaction tank 12. The extractant is a resin (such as a liquid or solid resin) that can effectively adsorb copper ions, and the hydraulic force of the extractant is retained. The time is from 0.1 to 60 minutes. The copper ion in the waste liquid A is adsorbed and separated by the extractant. The copper ion-containing extractant will continue to perform the regeneration reaction 20, and the waste liquid A from which copper ions have been removed will be discharged. The extraction reaction Outside the tank 12, it is collected to the low copper waste liquid storage tank 14 for other reprocessing operations; the regeneration reaction 20 includes a regeneration reaction tank 21 and an electrolytic circulation tank 22, and the extractant system adsorbing copper ions is transferred to the In the regeneration reaction tank 21, a sulfuric acid solution is contained in the electrolytic circulation tank 22. The concentration of the sulfuric acid solution ranges from 5 to 50% and is introduced into the regeneration reaction tank 21 for the regeneration reaction. The hydraulic retention time for the introduction of the sulfuric acid solution is In 0.1 ~ 60 minutes, the copper ions are regenerated and mixed into a regenerated copper sulfate solution through a sulfuric acid solution. At the same time, the extractant will be separated out, and the extractant will be recovered into the extractant storage tank 13 for the extraction reaction. The regenerated copper sulfate solution after the regeneration reaction is re-introduced into the electrolytic circulation tank 22, and the copper sulfate solution is led out through the electrolytic circulation tank 22 and subjected to electrolytic treatment. The electrolytic treatment 30 is an electrolytic treatment of the copper sulfate solution through an electrolytic system 31. the electrolysis system 31 visualization program designed to recover metal copper, an amount B of a plurality of groups in series or in parallel, and the operating current density electrolysis system is between 10 ~ 1000 a / m ^2, the copper sulfate solution The copper is electrolytically reduced to metallic copper B and subjected to recovery treatment 40, and the sulfuric acid solution after the electrolytic treatment 30 will be recovered and concentrated in the electrolytic circulation tank 22 for regeneration reaction, thereby completing waste liquid treatment and recovering valuable metals Processer of copper B.

In the above method, after the extraction reaction 10, a cleaning treatment may be performed first, and a small amount of waste liquid in the extractant may be cleaned and discharged, and then the regeneration reaction 20 treatment may be performed. The cleaning treatment is performed by using clean water or a sulfuric acid solution containing less than 5%. Cleaning.

The extraction reaction, regeneration reaction, and electrolytic treatment of the above method can be performed in batch or continuous processing depending on the amount of waste liquid.

The extraction reaction equation of the above method is: Cu ²⁺ + 2HR (O) → CuR ₂ (O) + 2H ⁺

The regeneration reaction equation of the above method is: CuR ₂ (O) + H ₂ SO ₄ → CuSO ₄ + 2HR (O)

The electrolytic treatment reaction of the above method is:

Anodizing:

In an acidic solution, the anode reacts only with electrolyzed water. The reaction is as follows: H ₂ O → 2H ⁺ + 1 / 2O ₂ + 2e

Cathode reaction:

Main ^{_{reaction: CuSO 4 + 2e - → Cu}} ( copper) + SO ₄ ²

Side ^{reaction: 2H + + 2e - → H} 2

The first embodiment of the method is a copper etching (copper acid) waste liquid of MGC. By adopting the processing and recovery method of the present invention, copper ions in the waste liquid are processed and recovered into valuable metal copper. The detailed operating conditions and processing results are shown in the following list:

The second embodiment of the method is a copper etching (copper acid) waste liquid of PPC. By adopting the treatment and recovery method of the present invention, copper ions in the waste liquid are treated and recovered into valuable metal copper. The detailed operating conditions and processing results are shown in the following list:

The third embodiment of the method is a copper etching (copper acid) waste liquid of ENF. By adopting the treatment recovery method of the present invention, the copper ions in the waste liquid are treated and recovered into valuable metal copper. The detailed operating conditions and processing results are shown in the following list:

The fourth embodiment of the method is a copper etching (copper acid) waste liquid of DAXIN. The treatment and recovery method of the present invention is adopted to treat and recover copper ions in the waste liquid into valuable metal copper. The detailed operating conditions and processing results are shown in the following list:

As can be seen from the above examples and their tables, the treatment and recovery method of the present invention can indeed efficiently remove copper ions in a variety of copper etching (copper acid) waste liquid A of the photovoltaic industry (the average removal rate is over 99%), and The copper ions extracted and removed can be regenerated into regenerated copper sulfate solution, and the regenerated copper sulfate solution can be further electrolyzed and recovered to become valuable metal copper B. Therefore, the treatment and recovery method of the present invention is very suitable for the copper ion removal treatment and recovery application of copper etching (copper acid) waste liquid A.

By the structure of the above specific embodiment, the following benefits can be obtained:

(1) The copper ion pollutants of copper etching (copper acid) waste liquid A can be processed and recovered into valuable metal copper B, and industrial pollutants can be recovered and reused. The electrolytic copper metal B can also be sold for profit. .

(2) By adopting the treatment and recovery method of the present invention, compared with other methods (concentrated outsourcing treatment / coagulation sedimentation, pressure filtration to copper-containing sludge, etc.), a large outsourcing treatment cost or copper sludge is saved. Outsourced processing costs.

(3) Effectively reduce the amount of copper sludge. The removal rate of copper ions is as high as 99% or higher. The amount of copper sludge produced by wastewater treatment is only less than 1% of the original.

(4) It can greatly reduce the amount of drugs used to remove copper ions in wastewater treatment and subsequent copper sludge filter press operations / copper sludge inventory.

(5) Treatment and recovery of copper ion pollutants of copper etching (copper acid) waste liquid A into metallic copper B, avoiding the possibility of secondary pollution.

To sum up, the present invention has indeed achieved a breakthrough structural design, with improved content of the invention, and at the same time, it can achieve industrial applicability and progress, and the present invention is not seen in any publications, and it is also novel. In accordance with the relevant provisions of the Patent Law, I filed an application for an invention patent in accordance with the law.

The above is only one of the preferred embodiments of the present invention. When it cannot be used to limit the scope of the present invention; that is, all equal changes and modifications made in accordance with the scope of the patent application for the present invention should still belong to the present invention. Within the scope of the patent.

Claims (10)

A copper ion etching (copper acid) waste liquid copper ion treatment and recovery method. The treatment and recovery method includes extraction reaction, regeneration reaction, electrolytic treatment, and recovery treatment. Among them, the extraction reaction is to concentrate the waste liquid to be treated in a waste liquid first. The concentration tank is then transported to an extraction reaction tank. The extraction reaction tank is introduced with an extractant, and the copper ion in the waste liquid is adsorbed and separated by the extractant. The copper ion-absorbing extractant is subjected to regeneration reaction treatment. The waste liquid from which copper ions are removed will be discharged out of the extraction reaction tank; the regeneration reaction is to transfer the extractant that has adsorbed copper ions to a regeneration reaction tank, and then introduce a sulfuric acid solution, and the copper ions are regenerated by the sulfuric acid solution and Mixed into a regenerated copper sulfate solution, the extractant will be separated at the same time and recovered for use in the extraction reaction, and the regenerated copper sulfate solution is further subjected to electrolytic treatment; the electrolytic treatment is to electrolyze the copper sulfate solution through an electrolytic system Treatment, the ionic copper of the copper sulfate solution is electrolytically reduced to metallic copper and recovered, and the sulfuric acid solution after the electrolytic treatment is Receiving the reaction used for regeneration, thereby completing waste water treatment and recovery of valuable metals as copper by the process. According to the method for treating and recovering copper ions from copper etching (copper acid) waste liquid according to item 1 of the scope of the patent application, wherein the extraction agent is a resin that can effectively adsorb copper ions, and then the copper ions are separated from the waste liquid by adsorption. According to the copper ion etching (copper acid) waste liquid copper ion treatment and recovery method according to item 1 of the scope of the patent application, the extraction reaction further includes an extractant storage tank and a low copper waste liquid storage tank. The extractant storage tank is The extractant is introduced into the extraction reaction tank, and the extractant after the regeneration reaction is recovered at the same time. According to the copper ion etching (copper acid) waste liquid copper ion treatment and recovery method described in the scope of the patent application, the cleaning process can be performed after the extraction reaction, and the trace waste liquid in the extractant can be washed out and then regenerated. Reactive treatment. According to the copper ion etching (copper acid) waste liquid copper ion treatment and recovery method according to item 4 of the scope of the patent application, the cleaning treatment is performed by using clean water or a sulfuric acid solution containing less than 5% sulfuric acid. According to the copper ion etching (copper acid) waste liquid copper ion treatment and recovery method according to item 1 of the scope of the patent application, the regeneration reaction further includes an electrolytic circulation tank, which contains a sulfuric acid solution and is introduced into the regeneration A regeneration reaction is performed in the reaction tank, and the regenerated copper sulfate solution after the regeneration reaction is re-introduced into the electrolytic circulation tank. The copper sulfate solution is introduced into the electrolytic system for electrolytic treatment through the electrolytic circulation tank, and the sulfuric acid solution after electrolytic treatment is Recycling will be concentrated in the electrolytic circulation tank for regeneration reaction. According to the copper ion etching (copper acid) waste liquid copper ion treatment and recovery method according to item 1 or 6 of the scope of the patent application, the concentration of the sulfuric acid solution used in the regeneration reaction is between 5-50%. According to the copper etching (copper acid) waste liquid copper ion treatment and recovery method according to item 1 of the scope of the patent application, the extraction reaction, the regeneration reaction, and the electrolytic treatment are batch matching processing or continuous matching processing. According to the copper etching (copper acid) waste liquid copper ion treatment and recovery method according to item 1 of the scope of the patent application, wherein the hydraulic retention time of the extraction reaction introduction of the extraction agent into the extraction reaction tank and the sulfuric acid solution of the regeneration reaction are introduced into the regeneration reaction tank. The hydraulic retention time is between 0.1 and 60 minutes. According to the copper etching (copper acid) waste liquid copper ion treatment and recovery method according to item 1 of the scope of the patent application, the electrolytic system can be designed according to the plan to recover the amount of copper in series or parallel, and the operating current density of the electrolytic system Between 10 ~ 1000A / m ² .