CN111394730B

CN111394730B - Etching solution regeneration device and etching solution regeneration method

Info

Publication number: CN111394730B
Application number: CN202010355366.6A
Authority: CN
Inventors: 何毅烽
Original assignee: TCL Huaxing Photoelectric Technology Co Ltd
Current assignee: TCL Huaxing Photoelectric Technology Co Ltd
Priority date: 2020-04-29
Filing date: 2020-04-29
Publication date: 2022-06-07
Anticipated expiration: 2040-04-29
Also published as: CN111394730A

Abstract

The application provides an etching solution regeneration device and an etching solution regeneration method. The etching solution regeneration device comprises: the device comprises a first storage container, a second storage container, a third storage container, a fourth storage container and a regeneration container positioned between the first storage container and the fourth storage container, wherein the first storage container is used for storing the etching waste liquid, the second storage container is used for storing desorption liquid, the third storage container is used for storing the desorption waste liquid, the fourth storage container is used for storing regenerated etching liquid, and the regeneration container is used for regenerating the etching waste liquid. The first storage container, the second storage container, the third storage container and the fourth storage container are selectively communicated with the regeneration container through pipelines. This application is through the setting of regeneration container, adsorbs the copper ion in the etching waste liquid, has realized the regeneration of etching solution, has improved the availability factor of etching solution, has reduced the use of etching solution regeneration in-process organic solvent, has alleviateed the pollution that causes the environment.

Description

Etching solution regeneration device and etching solution regeneration method

Technical Field

The present disclosure relates to display devices, and particularly to an etching solution regeneration device and an etching solution regeneration method.

Background

As the demand for display devices increases, the production capacity of display devices increases, and the amount of etching solution used in the manufacturing process of display devices increases.

The existing etching solution treatment and regeneration device mainly adopts a liquid-liquid extraction mode, so that the problems of long extraction time consumption and environmental pollution caused by using a large amount of organic solvents exist.

Therefore, a new etching solution regeneration apparatus and a new etching solution regeneration method are needed to solve the above-mentioned technical problems.

Disclosure of Invention

The application provides an etching solution regeneration device and an etching solution regeneration method, which are used for solving the problems that the existing etching solution regeneration device is long in time consumption for extracting copper ions in etching waste liquid and easy to cause environmental pollution by using a large amount of organic solvents.

In order to solve the technical problem, the technical scheme provided by the application is as follows:

the application provides an etching solution regeneration device, which comprises a first storage container, a second storage container, a third storage container, a fourth storage container and a regeneration container positioned between the first storage container and the fourth storage container;

wherein the first storage container is used for storing etching waste liquid;

The second storage container is used for storing desorption liquid;

the third storage container is used for storing desorption waste liquid;

the fourth storage container is used for storing the regenerated etching solution;

the regeneration container is used for regenerating the etching waste liquid;

the first storage container, the second storage container, the third storage container and the fourth storage container are selectively communicated with the regeneration container through pipelines.

In the etching solution regenerating unit that this application provided, the pipeline includes be located first storage container with first pipeline between the regeneration container, be located second storage container with second pipeline between the regeneration container, be located third storage container with third pipeline between the regeneration container, and be located fourth storage container with the fourth pipeline between the regeneration container.

In the etching solution regeneration device provided by the application, the first pipeline, the second pipeline, the third pipeline and the fourth pipeline are arranged independently; or

The first pipeline and one side of the second pipeline, which is close to the regeneration container, are integrally arranged, and/or the third pipeline and one side of the fourth pipeline, which is close to the regeneration container, are integrally arranged.

In the etching solution regenerating unit that this application provided, the pipeline is still including being located be close to on the first pipeline first valve of first storage container one side, being located be close to on the second pipeline the second valve of second storage container one side, being located be close to on the third pipeline the third valve of third storage container one side and being located be close to on the fourth pipeline the fourth valve of fourth storage container one side.

In the etching solution regenerating unit that this application provided, etching solution regenerating unit links to each other with the etching device.

In the etching solution regeneration device provided by the application, the regeneration container comprises at least one packed column;

the stationary phase of the packed column is made of a composite material of a silicon-based/metal-organic framework compound.

In the etching solution regenerating device provided by the application, the desorption solution at least comprises dilute nitric acid.

The application also provides an etching solution regeneration method, which comprises the steps of S1, opening the first valve and the fourth valve to enable the etching waste liquid from the first storage container to pass through the regeneration container and regenerate the etching solution into the fourth storage container;

s2, closing the first valve and the fourth valve;

s3, opening a second valve and a third valve to enable desorption liquid from a second storage container to pass through the regeneration container to carry copper ions out of the regeneration container to enter a third storage container;

Wherein, the regeneration container at least comprises a packed column.

In the regeneration method of the etching solution provided by the application, the stationary phase of the packed column is filled into the packed column by a homogenization method.

In the etching solution regeneration method provided by the present application, the preparation method of the stationary phase material includes:

synthesizing silicon dioxide through a first reaction;

carrying out a second reaction on the synthesized silicon dioxide and copper ions to form a first silicon dioxide/copper hydroxide compound;

the first composite is subjected to a third reaction to form a second composite of a silica/metal organic framework compound;

the second complex is subjected to a fourth reaction to form a third complex of an amino and carboxyl modified silica/metal organic framework compound.

Has the advantages that: this application is through the setting of regeneration container, adsorbs the copper ion in the etching waste liquid, has realized the regeneration of etching solution, has improved the availability factor of etching solution, has reduced the use of etching solution regeneration in-process organic solvent, has alleviateed the pollution that causes the environment.

Drawings

The technical solution and other advantages of the present application will become apparent from the detailed description of the embodiments of the present application with reference to the accompanying drawings.

Fig. 1 is a first structural schematic diagram of an etching solution regeneration device according to the present application.

Fig. 2 is a second structural schematic diagram of the etching solution regeneration device of the present application.

Fig. 3 is a schematic view of a third structure of the etching solution regeneration device of the present application.

Fig. 4 is a flowchart of an etching solution regeneration method according to the present application.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the embodiments described are only a few embodiments of the present application and not all 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 application.

In the description of the present application, it is to be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present application and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated in a particular manner, and are not to be construed as limiting the present application. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", may explicitly or implicitly include one or more of the described features. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.

In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; may be mechanically connected, may be electrically connected or may be in communication with each other; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.

In this application, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may comprise direct contact of the first and second features, or may comprise contact of the first and second features not directly but through another feature in between. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.

The following disclosure provides many different embodiments or examples for implementing different features of the application. To simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, examples of various specific processes and materials are provided herein, but one of ordinary skill in the art may recognize applications of other processes and/or use of other materials.

In the existing etching solution regeneration device, because a liquid-liquid extraction mode is adopted, the problems of long extraction time consumption and large use of organic solvent exist, and environmental pollution is easily caused. Based on this, the application provides an etching solution regeneration device and an etching solution regeneration method.

Referring to fig. 1 to 3, the etching solution regeneration apparatus 100 includes a first storage container 101, a second storage container 102, a third storage container 103, a fourth storage container 104, and a regeneration container 105 disposed between the first storage container 101 and the fourth storage container 104.

Wherein the first storage container 101 is used for storing etching waste liquid.

The second storage container 102 is used for storing desorption liquid.

The third storage vessel 103 is used for storing desorption waste liquid.

The fourth storage container 104 is used for storing the regenerated etching solution.

The regeneration vessel 105 is used for regeneration of the etching waste liquid.

The first storage vessel 101, the second storage vessel 102, the third storage vessel 103, and the fourth storage vessel 104 are in selective communication with the regeneration vessel 105 via piping.

In this embodiment, the desorption waste liquid may be replaced with iron powder or may be used to recover copper element by an electrochemical deposition method, which is beneficial to avoiding heavy metal pollution caused by the desorption waste liquid.

This application passes through regeneration container 105's setting, adsorbs the copper ion in the etching waste liquid, has realized the regeneration of etching solution, has improved the availability factor of etching solution, has reduced the use of etching solution regeneration in-process organic solvent, has alleviateed the pollution that causes the environment.

Referring to fig. 1-3, the regeneration vessel 105 includes at least one packed column 117.

The stationary phase of the packed column 117 is made of a composite material of a silicon-based/metal-organic framework compound.

In this embodiment, one or more packing columns 117 may be provided. When the number of the packed columns 117 is plural, a plurality of the packed columns 117 may be connected in parallel in the etching solution regeneration apparatus 100, which is advantageous for accelerating the treatment of the etching waste solution by the regeneration vessel 105; a plurality of the packed columns 117 may be connected in series to the etching solution regeneration apparatus 100, which is advantageous for improving the adsorption efficiency of the regeneration vessel 105 on the copper ions in the etching waste solution.

In this embodiment, the inner diameter and length of the packed column 117 are determined by factors such as the total amount of the etching waste liquid to be treated and the required treatment speed.

In this embodiment, the material of the stationary phase may be a silica/metal organic framework compound modified by amino and carboxyl groups.

In this embodiment, the stationary phase may be made of SiO₂@ HKUST-1@ L-Cys material.

Referring to fig. 1-3, the desorption solution at least comprises dilute nitric acid.

The inventor carries out desorption on the material of the stationary phase adsorbing the same amount of copper ions by using a plurality of acids with the same concentration, including dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid, a mixture of dilute nitric acid and ethylene diamine tetraacetic acid and the like, and finds that the desorption rates of the dilute nitric acid and the mixture of the dilute nitric acid and the ethylene diamine tetraacetic acid are both more than 98%, and complete desorption can be realized.

The technical solution of the present application will now be described with reference to specific embodiments.

Example one

Referring to fig. 1, the pipelines include a first pipeline 106 between the first storage container 101 and the regeneration container 105, a second pipeline 107 between the second storage container 102 and the regeneration container 105, a third pipeline 108 between the third storage container 103 and the regeneration container 105, and a fourth pipeline 109 between the fourth storage container 104 and the regeneration container 105.

In this embodiment, the first pipe 106 is provided integrally with the second pipe 107 on the side close to the regeneration vessel 105, and/or the third pipe 108 is provided integrally with the fourth pipe 109 on the side close to the regeneration vessel 105.

In this embodiment, the pipeline may further include a first valve 110 located on the first pipeline 106 near the first storage container 101, a second valve 111 located on the second pipeline 107 near the second storage container 102, a third valve 112 located on the third pipeline 108 near the third storage container 103, and a fourth valve 113 located on the fourth pipeline 109 near the fourth storage container 104.

In this embodiment, the first valve 110, the second valve 111, the third valve 112, and the fourth valve 113 are respectively used to control the communication and the closing of the first storage container 101, the second storage container 102, the third storage container 103, the fourth storage container 104, and the regeneration container 105.

In this embodiment, the pipeline may further include a fifth valve located at the intersection where the first pipeline and the second pipeline 107 are not integrally disposed and integrally disposed, and a sixth valve located at the intersection where the third pipeline 108 and the fourth pipeline 109 are not integrally disposed and integrally disposed.

In this embodiment, the fifth valve and the sixth valve are multi-directional valves.

For example, when the first storage container 101 and the regeneration container 105 are communicated, the fifth valve disconnects the communication between the side of the second pipe 107 near the second storage container 102 and the side of the second pipe 107 near the regeneration container 105, and maintains the communication between the side of the first pipe 106 near the first storage container 101 and the side of the first pipe 106 near the regeneration container 105.

When the third storage container 103 and the regeneration container 105 are communicated, the sixth valve disconnects the communication between the side of the fourth pipeline 109 close to the fourth storage container 104 and the side of the fourth pipeline 109 close to the regeneration container 105, and keeps the communication between the side of the third pipeline 108 close to the third storage container 103 and the side of the third pipeline close to the regeneration container 105.

In this embodiment, the connection and the disconnection between the first storage container 101, the second storage container 102, the third storage container 103, the fourth storage container 104 and the regeneration container 105 are controlled by the valves located on the pipes, which is beneficial to prevent the mixing of the solutions stored in the storage containers, and to prevent the etching solution regeneration efficiency of the etching solution regeneration apparatus 100 from being reduced due to the mixing of the solutions stored in the storage containers.

Example two

Referring to fig. 2, the present embodiment is the same as or similar to the first embodiment, except that:

in this embodiment, the first duct 106, the second duct 107, the third duct 108, and the fourth duct 109 are provided independently of each other.

In this embodiment, the first valve 110, the second valve 111, the third valve 112, and the fourth valve 113 may be respectively located at any positions on the first pipe 106, the second pipe 107, the third pipe 108, and the fourth pipe 109.

In this embodiment, the first pipe 106, the second pipe 107, the third pipe, and the fourth pipe 109, which are independently disposed, are advantageous to avoid a decrease in the regeneration efficiency of the etching solution regeneration apparatus 100, which is caused by a possibility of solution mixing at a portion where the first pipe 106 and the second pipe 107 and/or the third pipe 108 and the fourth pipe 109 are integrally disposed, when the first pipe 106 and the second pipe 107 are integrally disposed at a side close to the regeneration container 105 and/or the third pipe 108 and the fourth pipe 108 are integrally disposed at a side close to the regeneration container 105.

EXAMPLE III

Referring to fig. 3, the etching solution regenerating apparatus 100 is connected to the etching apparatus 114.

In this embodiment, the pipes may further include a fifth pipe 115 located at a side of the first storage container 101 and the etching apparatus adjacent to the first storage container 101, and a sixth pipe 116 located at a side of the fourth storage container 104 and the etching apparatus 114 adjacent to the fourth storage container 104.

In this embodiment, the etching solution regeneration apparatus 100 is in communication with the etching apparatus 114 through the fifth pipe 115 and the sixth pipe 116.

In this embodiment, the fifth conduit 115 may include a seventh valve and/or the sixth conduit may include an eighth valve for controlling the selective communication of the etching regeneration device 100 with the etching device 114.

In this embodiment, the etching solution regeneration device 100 is connected to the etching device 114, so that the etching waste solution generated by the etching device 114 can be timely treated by the etching solution regeneration device 100, and the regenerated etching solution can be timely conveyed to the etching device 114 for recycling.

In the above embodiments, the etching solution regeneration apparatus 100 may further include a pressure pump, where the pressure pump accelerates the outflow of the solutions in the first storage container 101 and the second storage container 102 into the regeneration container 105, and accelerates the outflow of the solutions from the regeneration container 105 into the third storage container 103 and the fourth storage container 104, which is beneficial to increasing the speed of the regeneration apparatus 100 for the etching solution.

In the above embodiment, the etching solution regeneration apparatus 100 may further include a monitoring probe for monitoring each storage container, the regeneration container 105, and the pipeline in real time, which is beneficial to timely finding and handling the abnormal condition of the etching solution regeneration apparatus 100, and avoiding the damage to the etching solution regeneration apparatus 100.

In the above embodiment, the regeneration container 105 is arranged to adsorb copper ions in the etching waste liquid, so that the regeneration of the etching liquid is realized, the use efficiency of the etching liquid is improved, the use of organic solvent in the regeneration process of the etching liquid is reduced, and the pollution to the environment is reduced.

Referring to fig. 1 to 4, the present application further provides a method for regenerating an etching solution, including:

s1, opening the first valve 110 and the fourth valve 113 to regenerate the etching waste liquid from the first storage container 101 into the etching liquid into the fourth storage container 104 through the regeneration container 105;

s2, closing the first valve 110 and the fourth valve 113;

s3, opening the second valve 111 and the third valve 112 to allow the desorption solution from the second storage container 102 to pass through the regeneration container 105 to carry the copper ions in the regeneration container 105 to the third storage container 103;

Wherein the regeneration vessel 105 includes at least one packed column 117.

Example four

Referring to fig. 1 to 4, in the present embodiment, the stationary phase of the packed column 117 is filled into the packed column 117 by a homogenization method.

In this embodiment, the method for filling the stationary phase into the packed column 117 includes:

packing material is packed at the outlet of the packing column 117.

In this embodiment, the filling material may be silanized glass wool.

In this embodiment, the filler material serves to prevent a large amount of the stationary phase from leaking out of the packed column 117 during and after the packing process.

The inlet of the packed column 117 is connected to the outlet at one end of the packing pool.

In this embodiment, the material of the stationary phase is dispersed in the first solvent in the packing pool.

The first solvent may be ethanol.

And introducing a first gas from an outlet at the other end of the packing pool to press the material of the stationary phase dispersed in the first solvent into the packed column.

In this embodiment, the first gas may be nitrogen or other gases such as air that do not react with the first solvent and the material of the stationary phase.

In this embodiment, the first solvent is filtered out by the packing material after entering the packing column 117, and the material of the stationary phase stays in the packing column 117 to form the stationary phase.

In this embodiment, the material of the stationary phase can be filled more uniformly in the packed column 117 by knocking the column shaft of the packed column 117.

The inlet of the packing column 117 is filled with the packing material.

In this embodiment, the preparation method of the material of the stationary phase includes:

silica is synthesized by a first reaction.

In this embodiment, the second solution is added to the first solution, and after the first reaction, the second solution is centrifuged to obtain silica.

In this embodiment, the first solution may be a mixed solution of concentrated ammonia water, ethanol, and deionized water, and the second solution may be an ethanol solution of tetraethoxysilane.

In this embodiment, the first reaction may be performed at 20 to 30 ℃, preferably at 25 ℃.

In this embodiment, the rotation speed for centrifugation is preferably 8000 rpm to 10000 rpm.

The synthesized silica undergoes a second reaction with copper ions to form a first composite of silica/copper hydroxide.

In this embodiment, the first composite may be prepared by a coprecipitation method of the silica and the copper ions.

The first composite undergoes a third reaction to form a second composite of a silica/metal organic framework compound.

In this embodiment, the first composite is dispersed in deionized water to form a first mixture;

dropwise adding a third solution into the first mixture under continuous stirring to obtain a second mixture;

and stirring the second mixture at the first reaction temperature for a first reaction time, washing the mixture by deionized water and ethanol, and drying the mixture to obtain the second compound.

In this embodiment, the first reaction temperature may be 20 to 30 ℃, and preferably 25 ℃.

The first reaction time may be 10 to 14 hours, and preferably 12 hours.

In this embodiment, the third solution may be an ethanol solution of trimesic acid.

In this example, the second composite was ultrasonically dispersed in ethanol to obtain a third mixture;

adding L-cysteine with the same mass as the second compound into the third mixture under stirring to obtain a fourth mixture;

and stirring the fourth mixture at a second reaction temperature for a second reaction time, washing with deionized water and ethanol, and drying to obtain the third compound.

In this embodiment, the third complex may be a complex of an amino group-and carboxyl group-modified silica/metal organic framework compound.

Wherein, the content range of the amino and the carboxyl is 1.2 to 2.4mmol/g, preferably 1.5 to 2.0 mmol/g. When the content of the amino group and the carboxyl group is less than 1.2mmol/g, the content of the amino group and the carboxyl group in the third compound is too low, so that the third compound is not favorable for adsorbing copper ions; when the content of the amino group and the carboxyl group is more than 2.4mmol/g, the degree of the adsorption effect of the third compound on the copper ions is limited along with the further increase of the content of the amino group and the carboxyl group in the third compound, and the further increase of the content of the amino group and the carboxyl group in the third compound has the limited effect of further enhancing the adsorption effect of the third compound on the copper ions; when the content of amino and carboxyl in the third compound is 1.5-2.0 mmol/g, the third compound can effectively adsorb copper ions.

In this embodiment, the third compound may be SiO₂@HKUST-1@L-Cys。

When the material of the stationary phase is SiO₂@ HKUST-1@ L-Cys, the inventor introduces a certain volume of the etching waste liquid containing copper into the packed column 117, and then introduces a desorption liquid into the packed column 117 for desorption, wherein the flow rate of the desorption liquid introduced into the packed column 117 does not exceed the flow rate of the etching waste liquid containing copper introduced into the packed column 117, and detection shows that the recovery rate of copper ions is greater than 95%.

The inventor carries out the adsorption and desorption experiments of copper ions after soaking the material of the stationary phase for a period of time by using strong acid or strong alkali or baking the material at high temperature for a period of time, and the result shows that the recovery rate of the copper ions is more than 95 percent.

The inventor conducts repeated adsorption and desorption experiments on the material of the stationary phase, the recovery rate of the material to copper ions is still more than 95% after the material is repeatedly adsorbed and desorbed for 10 times, and the material of the stationary phase has excellent stability, can be regenerated and reused and saves cost.

Experiments carried out by the inventor on adsorption and desorption time show that the material of the stationary phase has faster adsorption-desorption kinetics, which is beneficial to accelerating the regeneration speed of the etching solution.

The inventor shows through the adsorption and desorption experiments of the material of the stationary phase on copper ions under different pH conditions that when the pH is under a neutral condition, namely the pH value is 7, the adsorption capacity of the material of the stationary phase is maximized, and the removal efficiency on the copper ions is maximized.

In this embodiment, by the arrangement of the packing column 117 in the regeneration container and the packing of the stationary phase of the packing column 117, copper ions in the etching waste liquid can be removed by solid phase extraction, so that the use of organic solvents in the regeneration process of the etching waste liquid is reduced, and the pollution to the environment is reduced.

In the above embodiments, the regeneration container 105 is arranged to adsorb copper ions in the etching waste liquid, so that the regeneration of the etching liquid is realized, the use efficiency of the etching liquid is improved, the use of organic solvents in the regeneration process of the etching liquid is reduced, and the pollution to the environment is reduced.

In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.

The etching solution regeneration apparatus and the etching solution regeneration method provided in the embodiments of the present application are described in detail above, and specific examples are applied herein to explain the principles and embodiments of the present application, and the description of the embodiments is only used to help understanding the technical solutions and the core ideas of the present application; those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure as defined by the appended claims.

Claims

1. An etching solution regeneration device is characterized by comprising a first storage container, a second storage container, a third storage container, a fourth storage container and a regeneration container positioned between the first storage container and the fourth storage container;

wherein the first storage container is used for storing etching waste liquid;

The second storage container is used for storing desorption liquid;

the third storage container is used for storing desorption waste liquid;

the regeneration container is used for regenerating the etching waste liquid and comprises at least one packed column;

the stationary phase of the packed column is made of a silicon dioxide/metal organic framework compound modified by amino and carboxyl, wherein the content range of the amino and carboxyl is between 1.2mmol/g and 2.4 mmol/g;

2. The etching liquid regeneration apparatus according to claim 1,

the conduits include a first conduit between the first storage vessel and the regeneration vessel, a second conduit between the second storage vessel and the regeneration vessel, a third conduit between the third storage vessel and the regeneration vessel, and a fourth conduit between the fourth storage vessel and the regeneration vessel.

3. The etching liquid regeneration apparatus according to claim 2,

The first pipeline, the second pipeline, the third pipeline and the fourth pipeline are arranged independently; or

4. The etching liquid regeneration apparatus according to claim 3,

the pipeline is characterized by further comprising a first valve, a second valve, a third valve and a fourth valve, wherein the first valve is positioned on the first pipeline and close to one side of the first storage container, the second valve is positioned on the second pipeline and close to one side of the second storage container, the third valve is positioned on the third pipeline and close to one side of the third storage container, and the fourth valve is positioned on the fourth pipeline and close to one side of the fourth storage container.

5. The etching liquid regeneration apparatus according to claim 1,

the etching solution regeneration device is connected with the etching device.

6. The etching liquid regeneration apparatus according to claim 1,

the desorption liquid at least comprises dilute nitric acid.

7. The method for regenerating the etching solution is characterized by comprising

S1, opening the first valve and the fourth valve to enable the etching waste liquid from the first storage container to pass through the regeneration container to regenerate the etching liquid into the fourth storage container;

S2, closing the first valve and the fourth valve;

wherein, the regeneration container at least comprises a packed column, and the preparation method of the stationary phase material of the packed column comprises the following steps:

synthesizing silicon dioxide through a first reaction;

and the second complex is subjected to a fourth reaction to form a third complex of the silica/metal organic framework compound modified by amino and carboxyl, wherein the content of the amino and carboxyl is in a range of between 1.2mmol/g and 2.4 mmol/g.

8. The method according to claim 7, wherein the etching solution is introduced into the chamber,

the stationary phase of the packed column is packed into the packed column by a homogenization method.