CN212335352U

CN212335352U - Stainless steel etching solution cyclic regeneration system of ferric trichloride

Info

Publication number: CN212335352U
Application number: CN202021606080.2U
Authority: CN
Inventors: 徐麟; 杨代军; 黄勇
Original assignee: Shanghai Elo Technology Co ltd
Current assignee: Shanghai Elo Technology Co ltd
Priority date: 2020-08-05
Filing date: 2020-08-05
Publication date: 2021-01-12
Anticipated expiration: 2030-08-05

Abstract

The utility model discloses a stainless steel etching solution circulation regeneration system of ferric trichloride, this system is including the etching machine, crystallizing pond, plate and frame filter and the electrolysis trough that connect gradually, and a hydrochloric acid supplements the bucket, a water supplements the bucket and a ferric trichloride supplements the bucket and feeds through the etching machine respectively, and bucket intercommunication, other end and electrolysis trough intercommunication are supplemented with ferric trichloride to a regeneration pond one end. By the system implementation method, Fe in the ferric trichloride etching waste liquid in the electrolytic tank is extracted near the anode of the electrolytic tank²⁺Is oxidized into Fe³⁺And realizing H near the cathode of the electrolytic cell by auxiliary catalytic cathode selective catalytic reduction⁺And hydrogen gas is evolved. The utility model can effectively avoid other substances from being mixed into the etching solution, and keeps etchingThe purity of the etching solution, the stability of components and the activity of the regenerated ferric trichloride etching solution.

Description

Stainless steel etching solution cyclic regeneration system of ferric trichloride

Technical Field

The utility model relates to a stainless steel etching solution cyclic regeneration system of ferric trichloride.

Background

Etching of stainless steel products such as lead frame, elevator decorative plate, template mold, electronic reinforcing sheet, speaker mesh, and the likeThe manufacturing process is a process of etching patterns on stainless steel by adopting ferric trichloride etching solution, and meanwhile, the ferric trichloride etching waste solution which is rich in nickel, chromium, ferrous iron and ferric ions and has complex components is generated. The stainless steel etching solution of ferric trichloride generally comprises 150-200g/L ferric ion and 0.3-2mol/L H⁺220 and 350g/L of chloride ions and water, and the specific gravity of the etching solution is generally 38-40 Baume degrees. With the etching solution of ferric trichloride etching the stainless steel, the etching solution is Fe in the etching solution³⁺To Fe²⁺Saturation of total iron concentration (specific gravity outside the operating parameters) and hydrochloric acid volatilization (H)⁺Below the operating parameter range) and the like to become etching waste liquid. The environment-friendly treatment difficulty of the ferric trichloride etching waste liquid rich in nickel and chromium is high, the wastewater in the traditional acid-base neutralization treatment method is difficult to discharge after reaching the standard, the sludge production amount is high, and the great waste of resources is caused. At present, the domestic aims at FeCl₃The regeneration and recycling method of the etching waste liquid is more, and can be classified into a freezing or concentration crystallization method, a chemical oxidation regeneration method, an extraction or precipitation separation method, an electrochemical method and the like.

FeCl3 crystals obtained by a freezing or concentration crystallization method (patents CN200310120087.8, CN03116558.3, CN201510415221.X and CN201210464703.0) are recycled, the method has high energy consumption, ferrous iron cannot be effectively oxidized into ferric iron, and the regenerated ferric trichloride etching solution has insufficient etching capacity. The chemical oxidation regeneration method (patents CN200910028729.9, CN201720551958.9, CN201210464703.0 and the like) mainly adopts ozone, chlorine and H₂O₂、NaClO₃The chemical reagents such as the oxidant and the like regenerate the ferric trichloride, so that the oxidant is flammable and explosive, is not easy to store and has safe use risks. The extraction or precipitation method (patent CN200810065306.X, CN00127588.7, etc.) mainly separates iron, nickel and other ions in the etching solution through an organic solvent or a precipitator, and has the problems of complex process, high cost, pollution of the etching solution by the extraction or precipitator, and the like, and is not suitable for regeneration, circulation, etching and recycling of the etching solution. In recent years, electrochemical methods (patents CN201310719974.0, cn201310163584.x, cn201410764425.x, cn201710306127.x, cn201710213368.x, CN201710349396.4, cn201810970052.x, CN201621023926.3, CN201720340689.1, etc.) is applied to more regeneration techniques of the ferric trichloride waste liquid, at present, diaphragms or ionic membranes are mostly adopted to separate the cathode and the anode of an electrolytic cell, Fe2+ in the waste liquid of an anode area is oxidized into Fe3+ during electrolysis, the regeneration and the cyclic utilization of partial waste liquid are realized, the solution components of a cathode area and the anode area are inconsistent, when the diaphragms or the ionic membranes are damaged, the cathode liquid pollutes the ferric trichloride etching liquid recycled in the anode area, the etching liquid cannot be effectively and stably recycled, and the requirements of production and application cannot be met.

SUMMERY OF THE UTILITY MODEL

The utility model discloses mainly to the above-mentioned problem in the present electrochemistry method, provide a stainless steel etching solution cyclic regeneration system of ferric trichloride.

In order to achieve the above purpose, the utility model discloses the following technical scheme of accessible realizes:

the utility model provides a stainless steel etching solution circulation regeneration system of ferric trichloride, includes etching machine, crystallization tank, plate and frame filter and the electrolysis trough that connects gradually, and a hydrochloric acid supplements the bucket, a water supplements the bucket and a ferric trichloride supplements the bucket and communicates respectively the etching machine, a regeneration tank one end with the bucket intercommunication is supplemented to the ferric trichloride, the other end with the electrolysis trough intercommunication.

Further, the device also comprises an iron trichloride online detection and automatic dosing system which is connected with the etching machine.

Further, a component detection control system and a liquid level control system of the ferric trichloride etching solution are arranged in the electrolytic bath, H₂And a chlorine concentration monitoring and alarming system, a safe negative pressure explosion-proof air draft system and a plate frame automatic filtering system.

Furthermore, the electrolytic cell is connected with an acidity detection control system, and the polar plate of the electrolytic cell is composed of an anode, a cathode and an auxiliary catalytic cathode.

Further, the anode, the cathode and the auxiliary catalytic cathode are titanium or graphite insoluble materials treated by surface catalytic 3D coating, and the surface catalytic 3D coating is Pt, Au or PbO₂One or more composite coatings of Ru, W or Ir platinum group metals, wherein the coating contains one of perfluorosulfonic acid resin and perfluorocarboxylic acid resinOr two composite components.

Advantageous effects

The utility model discloses well electrolysis trough need not to divide into negative pole and positive pole district, all is the same ferric trichloride etching waste liquid of composition, and near electrolysis trough positive pole Fe of whole waste liquids²⁺Is oxidized into Fe³⁺Realizing the complete regeneration and cyclic utilization of the waste liquid, and realizing the H near the cathode of the electrolytic cell by detecting and controlling the acidity of the etching solution and assisting the selective catalytic reduction of the catalytic cathode⁺Hydrogen is separated out, other substances are effectively prevented from being mixed into the etching solution, and the purity, the component stability and the activity of the regenerated ferric trichloride etching solution are maintained.

Drawings

FIG. 1 is a schematic view of an electrolytic cell structure

In the figure, A is a 3D coating composite polar plate, B is an anode, and C is an electrolytic tank

FIG. 2 is a schematic view of a 3D coating composite plate structure

In the figure, A1 is a cathode corrosion-resistant polar plate base material, A2 is A3D coating platinum group and other catalytic centers, the grain diameter is 0.1-5um, A3 is 3D coating perfluorinated sulfuric acid resin filling, and the total thickness is 10-25 um.

FIG. 3 is a schematic view of the connection of the stainless steel etching solution recycling system of ferric trichloride

In the figure, C is an electrolytic bath; d is a plate and frame filter; e is a crystallization tank; f is an etching machine; g1 hydrochloric acid supplement barrel; g2 is a water supplement barrel; g3 is a ferric trichloride supplement barrel; g4 is a regeneration tank; h is ferric trichloride on-line measuring and automatic reagent feeding system

Detailed Description

The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein.

As shown in figure 3, for the utility model discloses a stainless steel etching solution cyclic regeneration system of ferric trichloride connects the sketch map, including etching machine F, crystallizer E, plate and frame filter D and the electrolysis trough C that connect gradually, a hydrochloric acid supplements bucket G1, a water and supplements bucket G2 and a ferric trichloride and supplyes bucket G3 and communicate respectively to etching machine F, and a regeneration pond G4 one end and ferric trichloride supplyes bucket G3 intercommunication, and the other end and electrolysis trough C communicate.

Wherein, still include a ferric trichloride on-line measuring and automatic reagent feeding system H, it is connected with etching machine F.

Wherein, the electrolytic bath C is internally provided with a ferric trichloride etching solution component detection control system, a liquid level control system and H₂And a chlorine concentration monitoring and alarming system, a safe negative pressure explosion-proof air draft system and a plate frame automatic filtering system.

Wherein, the electrolytic cell C is connected with an acidity detection control system, and the polar plate thereof consists of an anode, a cathode and an auxiliary catalytic cathode. The anode, the cathode and the auxiliary catalytic cathode are titanium or graphite insoluble materials treated by surface catalytic 3D coating, and the surface catalytic 3D coating is Pt, Au or PbO₂One or more composite coatings of Ru, W or Ir platinum group metal, wherein the coating contains one or two composite components of perfluorinated sulfonic acid resin and perfluorinated carboxylic acid resin. (FIG. 1 is a schematic diagram of an electrolytic cell structure, A is A3D coating composite polar plate, B is an anode, C is an electrolytic cell; FIG. 2 is a schematic diagram of A3D coating composite polar plate structure, A1 is a cathode corrosion-resistant polar plate base material, A2 is A3D coating platinum system and other catalytic centers, the particle size is 0.1-5um, A3 is 3D coating perfluorinated sulfuric acid resin filling, and the total thickness is 10-25 um).

The stainless steel etching solution recycling method of ferric trichloride realized by the system uses an electrolytic tank without distinguishing a cathode chamber and an anode chamber, and ferric trichloride etching waste liquid with the same components is filled in the electrolytic tank; the polar plate consists of an anode, a cathode and an auxiliary cathode, wherein the anode, the cathode and the auxiliary catalytic cathode are insoluble materials such as titanium or graphite subjected to surface special catalytic 3D coating treatment; the surface catalytic coating is Pt, Au, PbO₂One or more composite coatings of platinum metals such as Ru, W and Ir, wherein the coating contains one or two composite components of perfluorosulfonic acid resin and perfluorocarboxylic acid resin, such as Nafion series produced by DuPont company or perfluorosulfonic acid resin series produced by Shandong Yue; fe in ferric trichloride waste liquid near anode in electrolytic cell during electrolysis²⁺Is oxidized into Fe³⁺Cathodic special catalysisH is effectively transferred in the 3D coating due to one or two composite components of perfluorinated sulfonic acid resin and perfluorinated carboxylic acid resin⁺Let H stand for⁺Is reduced to H₂(ii) a Effectively block Fe³⁺Prevent Fe³⁺Reduction to Fe²⁺。

The process flow of the ferric trichloride etching solution cyclic regeneration sequentially comprises the following steps: the device comprises an etching machine, a crystallization tank, a plate and frame filter, an electrolytic tank, a regeneration tank and the etching machine, wherein the electrolytic tank is connected with an acidity detection control system; the method specifically comprises the following steps: FeCl flowing out of etching machine₃And (2) allowing the etching waste liquid to enter a crystallization tank, standing at 0-15 ℃, crystallizing, settling for 24 hours, periodically discharging sediments rich in nickel chloride and chromium chloride from an inverted conical bottom valve, filtering the supernatant through a plate-and-frame filter, performing in-situ catalytic electrolysis regeneration in an electrolytic cell to obtain a regenerated liquid, and automatically adding the regenerated liquid in the regenerated liquid tank into an etching machine according to the change of the ORP oxidation-reduction potential of the etching liquid in the etching machine to complete the one-time cyclic utilization of the ferric trichloride etching liquid. The electrolytic cell is connected with an acidity detection control system, and hydrochloric acid is automatically supplemented according to the acidity change of the etching waste liquid in the electrolytic cell; the current voltage of the electrolysis rectifier is reduced along with the increase of ORP of the ferric trichloride etching waste liquid in the electrolytic bath. In the regeneration cycle process, automatic control is adopted, and the system mainly comprises a voltage and current control system of a rectifier, a detection control system of the components of the ferric trichloride etching solution in an electrolytic bath, a liquid level control system and H₂And a chlorine concentration monitoring and alarming system, a safe negative pressure explosion-proof air draft system, a plate frame automatic filtering system and an on-line detection and automatic dosing system in the etching machine (containing acidity, specific gravity and ORP on-line detection and automatic supplementing functions of corresponding hydrochloric acid, water and ferric trichloride).

Wherein, the interface reaction of the anode catalytic coating electrode is as follows: fe²⁺-e→Fe³⁺，Fe²⁺Ions are gradually oxidized to Fe³⁺The etching solution is regenerated; the cathode catalyzed 3D coating electrode interface reaction is as follows: 2H⁺+2e→H₂And @, the generated H2 is directly introduced into an air outlet for emptying, and hydrochloric acid is automatically supplemented by a component detection control system of the ferric trichloride etching solution in the electrolytic bath. Inside the cathodic special catalytic 3D coatingBecause the composite component containing one or two of the perfluorosulfonic acid resin and the perfluorocarboxylic acid resin effectively transfers H⁺Let H stand for⁺Is reduced to H₂Preferably maintains H⁺Infiltration and catalytic reduction at the cathode surface; the perfluorosulfonic acid resin coating effectively blocks Fe³⁺Transfer and block Fe³⁺Reduction to Fe²⁺Effectively prevent Fe²⁺Approach of (3) suppressing Fe³⁺+e→Fe²⁺The method is carried out at the interface of a cathode catalytic 3D coating electrode, and the stability of the concentration of ferric ions in the etching solution is maintained.

Wherein, the etching machine is connected with an on-line detection and automatic dosing system of ferric trichloride, the system detects the acidity of the ferric trichloride etching solution by 0.3-2mol/L, the specific gravity of 38-42 baume degree and ORP 550-650mv on line in real time, hydrochloric acid is automatically supplemented along with the real-time volatilization reduction of the acidity, water is automatically added when the specific gravity rises, and the ORP is reduced and the ferric trichloride etching regeneration solution is automatically supplemented. And (3) overflowing the ferric trichloride etching waste liquid in the etching machine from the etching machine to a crystallization tank to wait for cyclic regeneration along with continuous replenishment of the liquid medicine.

The specific implementation case one:

in a certain hardware etching plant in Jiangsu, the specific gravity of the components of the etching waste liquid is 40 Baume degrees and 0.5mol/L of H⁺ORP550, 150g/L ferric ion, 10g/L ferrous ion, 5g/L nickel ion, 5g/L chromium ion, plate-frame filtration after 24 hours of freezing crystallization at 10 ℃, 0.8V @10A/dm²In-situ catalytic electrolysis, the consumption time is 3 hours, the divalent ferrous ion is reduced to 0.1g/L, the conversion rate reaches 99 percent, and the etching speed of the etching regeneration liquid reaches 10 um/min.

The specific implementation case two:

in a certain template etching plant in Zhejiang, the specific gravity of the components of the waste etching solution is 41 Baume degrees and 0.5mol/L of H⁺ORP600, 160g/L ferric ion, 5g/L ferrous ion, 2g/L nickel ion, 2g/L chromium ion, plate-frame filtration after 5 ℃ freezing crystallization for 24 hours, 0.9V @15A/dm²In-situ catalytic electrolysis, the use time is 1.5 hours, the divalent ferrous ions are reduced to 0.2g/L, the conversion rate reaches 98 percent, and the etching speed of the etching regeneration liquid reaches 10 um/min.

The above description is only exemplary of the present invention and should not be taken as limiting the scope of the present invention, as any modifications, equivalents, improvements and the like made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.

Claims

1. The stainless steel etching solution recycling system of ferric trichloride is characterized by comprising an etching machine, a crystallization tank, a plate frame filter and an electrolytic bath which are sequentially connected, wherein a hydrochloric acid supplementing barrel, a water supplementing barrel and a ferric trichloride supplementing barrel are respectively communicated with the etching machine, one end of a regeneration tank is communicated with the ferric trichloride supplementing barrel, and the other end of the regeneration tank is communicated with the electrolytic bath.

2. The stainless steel etching solution recycling system of ferric trichloride of claim 1, further comprising an on-line ferric trichloride detection and automatic dosing system connected to the etching machine.

3. The stainless steel etching solution recycling system of ferric trichloride of claim 2, wherein a component detection control system of ferric trichloride etching solution, a liquid level control system and H are arranged in the electrolytic bath₂And a chlorine concentration monitoring and alarming system, a safe negative pressure explosion-proof air draft system and a plate frame automatic filtering system.

4. The system of claim 2 or 3, wherein the electrolytic cell is connected to an acidity detection control system, and the plates of the system are composed of an anode, a cathode and an auxiliary catalytic cathode.

5. The system of claim 4, wherein the anode, the cathode and the auxiliary catalytic cathode are titanium or graphite insoluble materials treated by surface catalytic 3D coating, and the surface catalytic 3D coating is Pt, Au, PbO₂One or more composite coatings of Ru, W or Ir platinum group metals,the coating contains one or two composite components of perfluorosulfonic acid resin and perfluorocarboxylic acid resin.