CN209836312U - System for improving regeneration and reuse rate of acidic etching solution - Google Patents
System for improving regeneration and reuse rate of acidic etching solution Download PDFInfo
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- CN209836312U CN209836312U CN201920540358.1U CN201920540358U CN209836312U CN 209836312 U CN209836312 U CN 209836312U CN 201920540358 U CN201920540358 U CN 201920540358U CN 209836312 U CN209836312 U CN 209836312U
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- 230000008929 regeneration Effects 0.000 title claims abstract description 96
- 238000011069 regeneration method Methods 0.000 title claims abstract description 96
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 238000002347 injection Methods 0.000 claims abstract description 31
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 29
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- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 23
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- 238000000746 purification Methods 0.000 claims description 47
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 22
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- 239000000654 additive Substances 0.000 claims description 14
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- 210000004027 cell Anatomy 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 2
- 239000002253 acid Substances 0.000 abstract description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 29
- 238000004064 recycling Methods 0.000 abstract description 12
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 239000013043 chemical agent Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910001431 copper ion Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 8
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- 238000000889 atomisation Methods 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 5
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- 230000003203 everyday effect Effects 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
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- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- ing And Chemical Polishing (AREA)
Abstract
The utility model discloses a system for improve acid etching solution regeneration rate of recycling, it is including the etching production line, electrolytic device, add the device, regeneration liquid blending device and regeneration liquid ORP hoisting device, the rich copper acid etching waste liquid of production line becomes chlorine and poor copper electrolysis clear solution after electrolytic device electrolysis, poor copper electrolysis clear solution mixes with the low ORP acid etching solution of production line of etching and forms regeneration acid etching solution, regeneration liquid ORP hoisting device carries out countercurrent injection to acid etching solution, and collide with chlorine, it produces the line to obtain high ORP acid etching regeneration liquid and return the etching again. This application obtains high ORP acid etching regeneration liquid and returns the etching production line through regeneration liquid ORP hoisting device's setting again to improve the ORP of acid etching liquid on the etching production line, replaced the mode that traditional etching production line added oxidant and hydrochloric acid, improved the regeneration rate of reuse of etching waste liquid, reduced the use of chemical agent and the emission of waste water.
Description
Technical Field
The utility model relates to a waste liquid treatment technical field specifically relates to a system for improve acid etching liquid regeneration rate of utilization.
Background
The PCB is a support body of electronic product components and is the most basic hardware carrier of the current information society, and the printed circuit board industry is the pillar industry of the Chinese electronic information industry, and the growth rate of the printed circuit board industry is the same as that of the electronic information industry. Although the PCB production process has been improved greatly with the development of the industry, the method of etching the PCB by using chemical solution is still used for drawing a circuit diagram, and especially the use amount of the acid etching solution is the largest. The main components of the acidic etching solution are copper chloride, organic additives, hydrochloric acid, sodium chloride and the like. In order to maintain the etching performance of the acidic etching solution, hydrochloric acid and sodium chloride solution are continuously added to the etching production line, and meanwhile, the acidic etching waste solution overflows, so that the oxidation-reduction potential of the acidic etching solution is maintained at 500-550mv, and the etching requirement of the PCB is met. The overflowed acidic etching waste liquid contains a large amount of heavy metal copper, hydrochloric acid, organic matters, sodium chloride and the like, belongs to dangerous waste types, and particularly has serious influence on the environment. The research on the current situation of the copper-containing etching waste liquid treatment and utilization industry and management strategies in Jiangsu province shows that the data in the data of the journal of the environmental engineering, 3 months in 2018, volume 8 and 2 nd period show that in 2016, only circuit board enterprises in Jiangsu province generate 52 million tons of copper-containing etching waste liquid, so that the copper-containing etching waste liquid can cause great harm to the environment if the copper-containing etching waste liquid is not effectively treated in large circuit board copper-containing waste liquid generation amount in the whole country.
The traditional treatment method of the acidic copper-containing etching waste liquid of the PCB comprises the following steps: the waste water is collected and transported to a hazardous waste treatment base, valuable metal copper in the etching waste liquid is comprehensively recycled through processes such as acid-base neutralization and the like, and the waste water is subjected to harmless treatment and then is discharged after reaching the standard. However, in view of the defects that the traditional treatment method needs to collect and dispose the acid etching waste liquid in a centralized way, has the risks of leakage and environmental pollution in the transportation process, and the centralized disposal of the waste water is difficult to reach the standard, the industry in recent years develops the process of on-line recycling and regenerating the acid etching waste liquid, for example, a Chinese patent with an authorization publication number of CN202492581U provides a device for recycling acidic etching solution of printed circuit boards, for example, CN101768742B discloses a method for recycling acidic etching solution and copper and a special device thereof, for example, CN101748430B discloses a copper recycling system of acidic etching waste solution of printed circuit boards and a method for recycling etching solution, the general principle of the patent is that copper in the acidic etching waste liquid is electrolytically deposited in an electrolytic mode, and chlorine generated in an anode area is mixed with the etching liquid for the production line of the printed circuit board through a jet device, so that the aim of regenerating the acidic etching liquid is fulfilled. However, in the actual operation process of the above process, although the ejector can bring the chlorine out of the electrolytic bath, the mixing effect with the acidic etching solution is very poor, the utilization rate of the chlorine in the acidic etching production line of the printed circuit board is less than 10%, wherein more than 90% of the chlorine needs to enter a waste gas treatment system and then a large amount of liquid caustic soda is adopted for absorption treatment. The mixing effect of chlorine and acidic etching solution is poor, so that the regeneration and reuse rate of the etching waste solution is low, the etching production line still needs to supplement a large amount of hydrochloric acid and oxidant, such as sodium chloride, in order to keep the acidic etching solution at an oxidation-reduction potential of 500-.
SUMMERY OF THE UTILITY MODEL
Aiming at the defects of the prior art, the utility model provides a system for improving the regeneration and reuse rate of acidic etching liquid.
The utility model discloses a system for improve acid etching liquid regeneration rate of utilization includes: the etching production line is used for etching the PCB and outputting copper-rich acidic etching waste liquid and low ORP acidic etching liquid;
the electrolytic device receives and electrolyzes the copper-rich acidic etching waste liquid output by the etching production line, and outputs copper-poor electrolytic clear liquid, copper and chlorine;
an addition device for providing an additive;
the regenerated liquid blending device is used for receiving and mixing the low ORP acidic etching liquid output by the etching production line, the copper-poor electrolytic clear liquid output by the electrolytic device and the additive provided by the adding device and outputting the regenerated acidic etching liquid; and
the regeneration liquid ORP lifting device comprises a power wave tube, a tank body and a countercurrent injection piece; the lower end of the power wave tube is communicated with the tank body, and the upper end of the power wave tube is communicated with the electrolysis device; a gas-liquid mixing area is arranged in the power wave tube, the countercurrent injection piece is arranged in the power wave tube and is positioned below the gas-liquid mixing area, and the countercurrent injection piece is communicated with the regenerated liquid blending device; the lower end of the tank body is communicated with an etching production line; the countercurrent injection piece reversely injects the regenerated acidic etching solution to the gas-liquid mixing area, chlorine enters the gas-liquid mixing area through the upper end of the power wave tube, the regenerated acidic etching solution collides with the chlorine to form atomized foam and form high ORP acidic etching regenerated solution, and the high ORP acidic etching regenerated solution is transmitted to an etching production line.
According to an embodiment of the present invention, the number of the regeneration liquid ORP lifting apparatuses is two; the upper end of one of the power wave tubes is communicated with the electrolysis device, the other countercurrent injection piece is communicated with the regenerated liquid preparation device, the upper end of one of the tank bodies is communicated with the upper end of the other power wave tube, the lower end of the other tank body is communicated with the countercurrent injection piece, and the lower end of one of the tank bodies is communicated with the etching production line.
According to one embodiment of the present invention, a defogging layer and an oxidizing liquid are further disposed in the tank body; the defogging layer is positioned above the position where the power wave tube is communicated with the tank body; the oxidizing liquid is positioned below the position where the power wave tube is communicated with the tank body.
According to an embodiment of the present invention, the system further comprises an exhaust gas treatment device; the exhaust gas treatment device comprises a purification device and an exhaust device; the purification device is communicated with the upper end of the tank body, and the exhaust device is communicated with the purification device.
According to one embodiment of the present invention, the purification device comprises a purification pipe, a purification tank, and a circulation member; a purification layer and alkali liquor are arranged in the purification tank, and the purification layer is positioned above the alkali liquor; one end of the purifying pipe is communicated with the purifying tank, and the communicating position is positioned between the purifying layer and the alkali liquor; the other end of the purifying pipe is communicated with the upper end of the tank body; the lower end of the purification tank is communicated with the purification pipe through a circulating piece; the upper end of the purification tank is communicated with an exhaust device.
According to one embodiment of the present invention, the electrolysis apparatus comprises a diaphragm electrolyzer, a filter member, an electro-supernatant collection tank, and a chlorine gas extraction member; the diaphragm electrolytic cell has a cell body, an anode portion and a cathode portion; the chlorine gas extraction piece is respectively communicated with the anode part and the upper end of the power wave tube; the tank body is communicated with the electro-clear liquid collecting and storing tank through a filtering piece, and the electro-clear liquid collecting and storing tank is used for storing the lean copper electrolysis clear liquid.
The utility model discloses a countercurrent injection spare carries out countercurrent injection to regeneration acid etching solution, countercurrent injection's regeneration acid etching solution collides with the chlorine that the power wave pipe top got into and forms the atomizing foam district, the area of contact of chlorine and regeneration acid etching solution has been increased, cuprous in the regeneration acid etching solution obtains abundant oxidation, and chlorine is changeed and is dissolved in regeneration acid etching solution, improve regeneration acid etching solution absorption efficiency to chlorine, thereby high ORP acid etching regeneration solution has been obtained, then high ORP acid etching regeneration solution is carried to the etching production line, mix with the acid etching solution on the etching production line, so as to improve the ORP of acid etching solution on the etching production line, accomplish the stable etching to the PCB board, replace the mode that traditional etching production line adds oxidant and hydrochloric acid, the regeneration rate of acid etching waste liquid has been improved, the use of chemical agent and the emission of waste water have been reduced, therefore, the production cost of enterprises is saved, and the environment is not influenced.
In addition, the system can be transformed and realized on the existing etching production line, the etching mode of the existing PCB production line is not changed, the popularization is easy to realize, and the system has great economic benefit prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic diagram illustrating a system for increasing the recycling rate of acidic etching liquid according to an embodiment;
fig. 2 is a schematic structural diagram of a system for increasing the recycling rate of acidic etching liquid in the second embodiment.
Detailed Description
In the following description, numerous implementation details are set forth in order to provide a more thorough understanding of the present invention. It should be understood, however, that these implementation details should not be used to limit the invention. That is, in some embodiments of the invention, details of these implementations are not necessary. In addition, some conventional structures and components are shown in simplified schematic form in the drawings.
It should be noted that all the directional indications in the embodiments of the present invention, such as up, down, left, right, front, and back, are only used to explain the relative position relationship between the components, the motion situation, etc. in a specific posture as shown in the drawings, and if the specific posture is changed, the directional indication is changed accordingly.
Furthermore, the descriptions of the components in the present invention as "second" and the like are provided for descriptive purposes only, not for purposes of specifically referring to the order or sequence, nor for limiting the invention, but merely for purposes of distinguishing between components or operations that are described in the same technical language, and are not intended to indicate or imply relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "", "second" may explicitly or implicitly include at least one of the feature. In addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
For further understanding of the contents, features and functions of the present invention, the following embodiments will be exemplified in conjunction with the accompanying drawings as follows:
example one
Referring to fig. 1, fig. 1 is a schematic structural diagram of a system for increasing the regeneration and reuse rate of acidic etching liquid in this embodiment. The system for improving the regeneration and reuse rate of the acidic etching liquid in the embodiment comprises an etching production line 1, an electrolysis device 2, an adding device 3, a regenerated liquid blending device 4 and a regenerated liquid ORP lifting device 5. The etching production line 1 etches the PCB and outputs copper-rich acidic etching waste liquid and low ORP acidic etching liquid. The electrolysis device 2 receives the copper-rich acidic etching waste liquid output by the etching production line 1, carries out electrolysis, and outputs copper-poor electrolytic clear liquid, copper and chlorine. The adding device 3 is used for providing an additive. The regenerated liquid mixing device 4 receives and mixes the low ORP acidic etching liquid output by the etching production line 1, the copper-poor electrolytic clear liquid output by the electrolysis device 2 and the additive provided by the adding device 3, and outputs the regenerated acidic etching liquid. The regeneration liquid ORP lift device 5 includes a power wave tube 51, a tank 52, and a reverse flow jet 53. The lower end of the power wave tube 51 is communicated with the tank 52, and the upper end thereof is communicated with the electrolysis device 2. The power wave tube 51 is provided with a gas-liquid mixing zone 511, and the counter-flow injection piece 53 is arranged on the power wave tube 51 and is positioned below the gas-liquid mixing zone 511. The reverse-flow injection member 53 communicates with the regeneration liquid preparing apparatus 4. The lower end of the tank 52 communicates with the etching line 1. The countercurrent injection piece 53 is used for countercurrent injection of the regenerated acidic etching solution to the gas-liquid mixing area 511, the chlorine enters the gas-liquid mixing area 511 through the upper end of the power wave tube 51, the regenerated acidic etching solution collides with the chlorine to form atomized foam and form high ORP acidic etching regeneration solution, and the high ORP acidic etching regeneration solution is transmitted to the etching production line 1.
The regenerated acid etching solution is subjected to countercurrent injection through the countercurrent injection piece 53, the countercurrent injected regenerated acid etching solution collides with chlorine entering above the power wave tube 51 to form an atomized foam area, the contact area between the chlorine and the regenerated acid etching solution is increased, cuprous in the regenerated acid etching solution is fully oxidized, the chlorine is more easily dissolved in the regenerated acid etching solution, the absorption efficiency of the regenerated acid etching solution on the chlorine is improved, so that the high ORP acid etching regeneration solution is obtained, the high ORP acid etching regeneration solution is conveyed to the etching production line 1 to be mixed with the acid etching solution on the etching production line 1, the ORP of the acid etching solution on the etching production line 1 is improved, the stable etching of a PCB is completed, the traditional mode of adding an oxidant and hydrochloric acid to the etching production line is replaced, the regeneration recycling rate of the acid etching waste solution is improved, the use of a chemical agent and the discharge of waste water are reduced, therefore, the production cost of enterprises is saved, and the environment is not influenced. In addition, the system can be transformed and realized on the existing etching production line, the etching mode of the existing PCB production line is not changed, the popularization is easy to realize, and the system has great economic benefit prospect.
Referring to fig. 1 again, the etching line 1 further includes an etching solution buffer tank 11 and a waste solution collecting tank 12. It can be understood that the etching line 1 mainly performs the following chemical reactions for etching the PCB: cu2++Cu→2Cu+After the etching reaction of the PCB, the ORP of the acidic etching solution is reduced, and in order to ensure the stable etching performance of the acidic etching solution on the PCB, when the etching line 1 etches the PCB, the ORP value of the acidic etching solution generally needs to be maintained between 500-550mv, which requires to add the high ORP acidic etching regeneration solution to the etching line 1 to increase the ORP value of the acidic etching solution. In this embodiment, the ORP value of the high ORP acidic etching regeneration liquid is between 800-1000mv, and at the same time, the chlorine carried by the high ORP acidic etching regeneration liquid reacts with the copper ions in the acidic etching liquid as follows: 2Cu++Cl2→2Cu2+Further, the ORP of the acidic etching solution is increased, so that the ORP value of the etching production line 1 is kept between 500-550mv, and the stable etching performance of the etching production line 1 is ensured. In specific application, the flow rate of the acidic etching solution in the etching production line 1 is between 190L/min and 800L/min, and the copper ion concentration of the acidic etching solution is required to be kept between 120-140g/L to prevent the etching solution system from crystallizing, preferably, the copper ion concentration of the acidic etching solution is kept between 130-140g/L。
The high ORP acidic etching regeneration liquid output by the regeneration liquid ORP lifting device 5 is added from the upper part of the etching liquid buffer cylinder 11, the ORP value of the acidic etching liquid in the etching liquid buffer cylinder 11 is lifted, then the PCB is etched, the ORP value of the etched acidic etching liquid is reduced, the low ORP acidic etching liquid is extracted from the bottom of the etching liquid buffer cylinder 11, the adding flow rate of the high ORP acidic etching regeneration liquid is set to be larger than the extracting flow rate of the low ORP acidic etching liquid, so that the acidic etching liquid in the etching liquid buffer cylinder 11 is always kept between 500-550mv, for example, in specific application, the adding flow rate of the high ORP acidic etching regeneration liquid can be set to be 190L/min-800L/min, and the extracting flow rate of the low ORP acidic etching liquid can be set to be 180L/min-700L/min. Meanwhile, the copper-rich acidic etching waste liquid generated after etching overflows from the outer edge of the upper opening of the etching liquid buffer tank 11, and the overflowing copper-rich acidic etching waste liquid is collected in the waste liquid collecting tank 12.
The ORP value of the acidic etching solution in the etching solution buffer cylinder 11 can be stabilized at 500-550mv by adjusting the flow of the high ORP acidic etching regeneration solution, so that the acidic etching solution can maintain stable etching performance. Meanwhile, the overflow amount of the copper-rich acidic etching waste liquid is controlled by adjusting the flow of the low ORP acidic etching liquid, so that the concentration of copper ions in the acidic etching liquid is kept at 140g/L and the crystallization of an etching liquid system is prevented.
Referring back to fig. 1, further, the electrolyzer 2 comprises a diaphragm electrolyzer 21, a filter 22, a collected electrolyte storage tank 23 and a chlorine gas extraction unit (not shown). The diaphragm electrolytic cell 21 has a cell body 211, an anode portion 212, and a cathode portion 213. The chlorine gas extraction member is disposed in the tank body 211 and is respectively communicated with the anode portion 212 and the upper end of the power wave tube 51. The tank body 211 is communicated with the electric clear liquid collecting and storing tank 23 through the filter member 22, and the electric clear liquid collecting and storing tank 23 is used for storing the copper-deficient electrolytic clear liquid.
The copper-rich acidic etching waste liquid in the waste liquid collecting tank 12 is pumped into the tank body 211 transferred to the diaphragm electrolytic tank 21 for electrolysis, and the copper ion concentration in the copper-rich acidic etching waste liquid in the embodiment is between 120 and 140 g/L. During electrolysis, the following chemical reactions occur in the cell body 211: CuCl2→Cu+Cl2Wherein, copper is deposited on the cathode portion, chlorine gas is generated on the anode portion 212, and the chlorine gas is extracted by the chlorine gas extraction member from the anode portion 212 and transmitted to the upper end of the power wave tube 51. The copper ion concentration in the tank body 211 after the electrolysis is reduced to 30-50g/L to obtain a copper-depleted electrolytic clear solution, preferably, the copper ion concentration in the copper-depleted electrolytic clear solution is 40-50g/L, which prevents the generation of hydrogen gas in the cathode portion 213. The copper-depleted electrolytic clear liquid is drawn out and filtered through the filter member 22, and then stored in the electric clear liquid collecting tank 23.
In a specific application, the anode part 212 is composed of a titanium plate coated with noble metal, the cathode part 213 is composed of an activated titanium plate, the conductive part is composed of a titanium-clad copper strip, the diaphragm of the anode part 212 is composed of a PVC support and polypropylene filter cloth, the chlorine gas extraction piece can adopt a corrosion-resistant fan, and the filter element 22 can adopt a filter with a folding filter element.
In this embodiment, the additive provided by the adding device 3 is an aqueous solution prepared from thiourea, urea and sodium chloride, and specifically, the ratio of thiourea, urea, sodium chloride and pure water may be 1: 5: 8. The adding device 3 in this embodiment may be a storage tank, and the prepared additive is stored in the storage tank for standby.
The low ORP acidic etching solution extracted from the bottom of the etching solution buffer tank 11, the copper-poor electrolytic clear solution stored in the electro-clear solution collecting storage tank 23 and the additive stored in the adding device 3 are respectively output to the regenerated solution preparing device 4 for mixing to obtain the regenerated acidic etching solution, and finally the copper ion concentration of the obtained regenerated acidic etching solution is between 100 and 120 g/L. Wherein the flow rate of the low ORP acidic etching solution added into the regeneration solution preparation device 4 is 180L/min-700L/min, the flow rate of the copper-poor electrolyte clear solution added into the regeneration solution preparation device 4 is 10/min-80L/min, and the additive accounts for 1% -2% of the volume of the copper-poor electrolyte clear solution. The regeneration liquid preparing device 4 in this embodiment is a tank.
Referring to fig. 1 again, further, the power wave tube 51 is tubular, the chlorine gas pumped by the chlorine gas pumping unit enters from the upper end of the power wave tube 51, the lower end of the power wave tube 51 is bent into an L shape, the lower end of the power wave tube 51 is communicated with the tank 52, and the position where the lower end of the power wave tube 51 is communicated with the tank 52 is close to the lower end of the tank 52.
Preferably, a defogging layer 521 and an oxidizing solution are further arranged in the tank body 52; the defogging layer 521 is positioned above the position where the dynamic wave tube 51 is communicated with the tank body 52; the oxidation liquid is positioned below the position where the dynamic wave tube 51 is communicated with the tank 52. In this embodiment, the oxidation liquid is located at the bottom of the tank 52, and the oxidation liquid may be a 20% sodium chlorate solution.
The countercurrent injection piece 53 is arranged on the outer wall of the power wave tube 51, one end of the countercurrent injection piece 53 is communicated with the regenerated liquid preparation device 4, the other end of the countercurrent injection piece is opposite to the gas-liquid mixing area 511, the regenerated acidic etching liquid of the regenerated liquid preparation device 4 is pumped into the countercurrent injection piece 53 through the corrosion-resistant pump, and the countercurrent injection piece 53 carries out countercurrent injection on the regenerated acidic etching liquid, so that the regenerated acidic etching liquid collides with chlorine to form atomized foam, the regenerated acidic etching liquid is oxidized while being atomized, and the acidic etching regeneration liquid with high ORP is formed. Specifically, the chlorine gas is dissolved in the regenerated acidic etching solution, and the following chemical reactions occur: cl2+H2O → HClO + HCl, the cuprous in the regenerated acid etching solution is fully oxidized, and the following chemical reaction occurs: cl2+2Cu+→2Cu2+Therefore, the ORP value of the regenerated acidic etching solution is improved, and the high ORP acidic etching regenerated solution is obtained.
In this embodiment, the counter-flow injection member 53 may be an injector having a power wave nozzle, which may spray and atomize the regenerated acidic etching solution in a counter-flow manner, and a throat may be disposed at the upper end of the power wave tube 51 to control the speed of the chlorine gas in the power wave tube 51, so as to control the height of the atomized foam area formed by the collision of the atomized acidic etching solution and the chlorine gas in the gas-liquid mixing area 511, so that the atomized foam area is adjustable within 1-5 meters, and further adjust the ORP value of the regenerated acidic etching solution.
Referring to fig. 1 again, in the present embodiment, the system for increasing the regeneration and reuse rate of the acidic etching liquid further includes an exhaust gas treatment device 6. The exhaust gas treatment device 6 includes a purification device 61 and an exhaust device 62, the purification device 61 communicates with the upper end of the tank 52, and the exhaust device 62 communicates with the purification device 61.
Specifically, the purification apparatus 61 includes a purification pipe 611, a purification tank 612, and a circulation member 613. A purification layer 6121 and alkali liquor are arranged in the purification tank 612, and the purification layer 6121 is positioned above the alkali liquor. One end of the purification pipe 611 is connected to the purification tank 612, and the connection position is located between the purification layer 6121 and the alkaline solution, and the other end of the purification pipe 611 is connected to the upper end of the tank 52. The lower end of the purge tank 612 is communicated with the purge pipe 611 through a circulation piece 613; the upper end of the purge tank 612 communicates with the exhaust device 62. The alkali liquor in this embodiment may be 30% sodium hydroxide solution.
The small part of the atomized regenerated acidic etching solution in the tank 52 is subjected to defogging filtration through the defogging layer 521, so that the small part of the acidic gas enters the purification pipe 611. The circulation device 613 extracts the alkali solution in the purification tank 612 and performs counter-current spraying on the alkali solution to neutralize the acid of the atomized regenerated acid etching solution, and the alkali solution is purified by the purification layer 6121 and then discharged by the exhaust device 62. The defogging layer 521 in this embodiment can be a filter screen, the circulation piece 613 can be a pump and ejector, and the purification layer 6121 can be activated carbon.
Preferably, the bottom of the purification tank 612 is provided with an observation liquid charging port 6122 and an alkali liquor discharging port 6123, wherein the observation liquid charging port 6122 is used for charging alkali liquor or observing the condition in the purification tank 612, and the alkali liquor discharging port 6123 is used for discharging alkali liquor.
Preferably, the exhaust device 62 includes an induced draft fan 621 and an exhaust pipe 622. The induced draft fan 621 exhausts the purified exhaust gas through the exhaust pipe 622.
Example two
Referring to fig. 2, fig. 2 is a schematic structural diagram of a system for increasing the regeneration and reuse rate of acidic etching liquid in the second embodiment. The system for improving the regeneration recycling rate of the acidic etching liquid in the embodiment is different from that in the first embodiment in that the number of the regeneration liquid ORP lifting devices 5 is two.
Of the two regeneration liquid ORP elevating devices 5, the upper end of the power wave tube 51 of one of the regeneration liquid ORP elevating devices 5 communicates with the electrolysis device 2, the counter-current injection piece 53 of the other one of the regeneration liquid ORP elevating devices 5 communicates with the regeneration liquid preparing device 4, the upper end of the tank 52 of the one of the regeneration liquid ORP elevating devices 5 communicates with the upper end of the power wave tube 51 of the other one of the regeneration liquid ORP elevating devices 5, the lower end of the tank 52 of the other one of the regeneration liquid ORP elevating devices 5 communicates with the counter-current injection piece 53 of the one of the regeneration liquid ORP elevating devices 5, and the lower end of the tank 52 of the one of the regeneration liquid ORP elevating devices 5 communicates.
The two regeneration liquid ORP lifting devices 5 are arranged, so that the regenerated acidic etching liquid in the regeneration liquid preparation device 4 firstly passes through the other regeneration liquid ORP lifting device 5, is subjected to countercurrent injection through the countercurrent injection piece 53 of the other regeneration liquid ORP lifting device 5 to form an atomized state, is collided with chlorine input from the upper end of the tank body 52 of the regeneration liquid ORP lifting device 5 to form atomized foam, then passes through the oxidation liquid of the other regeneration liquid ORP lifting device 5, enters the countercurrent injection piece 53 of the one regeneration liquid ORP lifting device 5 to be subjected to countercurrent injection to form an atomized state, is collided with chlorine input from the chlorine extraction piece to form atomized foam, and then forms high-acidity etching regeneration liquid through the oxidation liquid of the one regeneration liquid ORP lifting device 5 to return to the etching production line 1. Thus, a two-stage regeneration system can be formed, so that the ORP of the high ORP acidic etching regeneration liquid is higher, and the high ORP acidic etching regeneration liquid can reach 1000mv in a short time.
EXAMPLE III
The method for improving the regeneration and reuse rate of the acidic etching solution in the embodiment comprises the following steps:
the etching production line 1 etches the PCB to obtain low ORP acidic etching solution and copper-rich acidic etching waste solution.
The electrolytic device 2 electrolyzes the copper-rich acidic etching waste liquid to obtain copper-poor electrolytic clear liquid, copper and chlorine gas.
And mixing the low ORP acidic etching solution with the copper-poor electrolytic clear solution, and adding an additive to obtain a regenerated acidic etching solution.
The regenerated acidic etching solution is sprayed counter-currently by the counter-current spray member 53 and then collides with chlorine gas to form atomized foam.
After the atomized foam passes through the oxidizing liquid, the high ORP acidic etching regeneration liquid is formed and returned to the etching production line 1 again.
Preferably, the atomized foam passes through the oxidizing solution and then is subjected to secondary collision atomization, and the secondary atomized foam passes through the oxidizing solution and then returns to the etching production line 1. The method in this embodiment is performed by implementing the system for improving the regeneration and reuse rate of the acidic etching liquid in the first embodiment or the second embodiment, wherein the preferred secondary collision atomization is the case that the system in the second embodiment uses two regeneration liquid ORP lifting devices 5 for collision atomization, and details are not repeated here.
Comparative example 1
An acid etching line of a PCB production enterprise produces 4 tons of acid etching waste liquid per day, wherein the specific gravity of the acid etching waste liquid is 1.3g/ml, the copper content is 140g/L, the hydrochloric acid concentration is 2.0-2.5mol/L, and the oxidation-reduction potential ORP is 500-550 mv.
The traditional method for electrolytic deposition of copper by using a diaphragm is adopted to recover metal copper in the acidic etching waste liquid, 2.4 tons of hydrochloric acid and 1.6 tons of sodium chlorate solution with the mass concentration of 20% are needed every day, and chlorine dioxide are generated by simultaneously adding the hydrochloric acid and the sodium chlorate into the acidic etching liquid to oxidize cuprous ions in the etching liquid so as to keep the oxidation performance in the etching liquid. Meanwhile, 4 tons of sodium chlorate solution with the concentration of 200g/L and acid copper-containing wastewater with the concentration of copper ions of 5-10g/L are needed to be sent to a wastewater treatment station room.
Example four
The system for improving the regeneration and reuse rate of the acidic etching liquid in the first embodiment is adopted to treat 4 tons of acidic etching waste liquid every day. Wherein, the copper-poor electrolytic clear liquid stored in the electro-clear liquid collecting and storing tank 23 is added to the regenerated liquid blending device 4 at a flow rate of 10L/min; the low ORP acidic etching solution pumped out from the bottom of the etching solution buffer tank 11 is added into the regenerated solution preparation device 4 at the flow rate of 100L/min; the additive stored in the adding device 3 is added into the regenerated liquid blending device 4 at the flow rate of 0.1L/min; the regenerated acidic etching solution formed in the regenerated solution blending device 4 is pumped to the regenerated solution ORP lifting device 5 at the speed of 190.1L/min for oxidation, wherein the height of an atomized foam area formed by the atomization of the regenerated acidic etching solution and the collision of chlorine in the gas-liquid mixing area 511 is 3 meters, and the high ORP acidic etching regeneration solution with the ORP up to 800mv can be obtained. The high ORP acidic etching regeneration liquid returns to the etching production line 1 at 190.1L/min for etching production, 720 kg of hydrochloric acid is consumed by the PCB acidic etching production line every day after one month of continuous operation, 480 kg of oxidant of 20% sodium chlorate solution is reduced by 70% compared with the consumption in the comparative example.
EXAMPLE five
4 tons of acidic etching waste liquid are treated by the system for improving the regeneration and reuse rate of the acidic etching liquid in the second embodiment every day. Adding the copper-poor electrolytic clear liquid stored in the electro-clear liquid collecting and storing tank 23 into the regenerated liquid blending device 4 at a flow rate of 80L/min; the low ORP acidic etching solution pumped out from the bottom of the etching solution buffer tank 11 is added into the regenerated solution preparation device 4 at the flow rate of 700L/min; the additive stored in the adding device 3 is added into the regenerated liquid blending device 4 at the flow rate of 1.6L/min; the regenerated acid etching solution formed in the regenerated solution mixing device 4 is pumped into another regenerated solution ORP lifting device 5 at the speed of 781.6L/min for pre-oxidation, and then enters the first regenerated solution ORP lifting device 5 for secondary oxidation, wherein the height of an atomized foam area formed by the atomization of the regenerated acid etching solution and the collision of chlorine gas in a gas-liquid mixing area 511 is 4 meters, and the high ORP acid etching regeneration solution with the ORP up to 1000mv can be obtained. The high ORP acidic etching regeneration liquid is returned to the etching production line 1 at 781.6L/min for etching production, and after one month of continuous operation, the PCB acidic etching production line consumes 240 kg of hydrochloric acid daily, and 160 kg of oxidant of 20% sodium chlorate solution is reduced by 90% relative to the consumption in the comparative example.
EXAMPLE six
4 tons of acidic etching waste liquid are treated by the system for improving the regeneration and reuse rate of the acidic etching liquid in the second embodiment every day. Adding the copper-poor electrolytic clear liquid stored in the electro-clear liquid collecting and storing tank 23 into the regenerated liquid blending device 4 at a flow rate of 60L/min; the low ORP acidic etching solution pumped out from the bottom of the etching solution buffer tank 11 is added into the regenerated solution preparation device 4 at the flow rate of 500L/min; the additive stored in the adding device 3 is added into the regenerated liquid blending device 4 at the flow rate of 0.75L/min; the regenerated acid etching solution formed in the regenerated solution mixing device 4 is pumped into another regenerated solution ORP lifting device 5 at the speed of 560.75L/min for pre-oxidation, and then enters the first regenerated solution ORP lifting device 5 for secondary oxidation, wherein the height of an atomized foam area formed by the atomization of the regenerated acid etching solution and the collision of chlorine gas in a gas-liquid mixing area 511 is 1 meter, and the high ORP acid etching regeneration solution with the ORP reaching 900mv can be obtained. The high ORP acidic etching regeneration liquid is returned to the etching production line 1 at 560.75L/min for etching production, 480 kg of hydrochloric acid is consumed daily by the PCB acidic etching production line after one month of continuous operation, 320 kg of oxidant of 20% sodium chlorate solution is reduced by 80% compared with the consumption in the comparative example.
Compared with the comparative example 1 and the fourth to sixth embodiments, it can be seen that the system for improving the recycling rate of the acidic etching liquid in the embodiment, especially the two-stage regeneration system formed by the two regeneration liquid ORP lifting devices 5 disclosed in the second embodiment, significantly improves the recycling rate of chlorine gas in the treatment process of the acidic etching waste liquid, saves the consumption of hydrochloric acid, sodium chlorate and liquid caustic soda, realizes the cyclic utilization of hazardous waste in enterprises, does not discharge incremental waste liquid, does not pollute the environment, does not change the etching production mode of the existing PCB production line, is easy to popularize, and has good market prospect.
The above is only an embodiment of the present invention, and is not intended to limit the present invention. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (6)
1. A system for improving the regeneration and reuse rate of an acidic etching solution is characterized by comprising:
an etching production line (1) which etches the PCB and outputs copper-rich acidic etching waste liquid and low ORP acidic etching liquid;
an electrolysis device (2) which receives and electrolyzes the copper-rich acidic etching waste liquid output by the etching production line (1) and outputs copper-poor electrolytic clear liquid, copper and chlorine gas;
an adding device (3) for providing an additive;
a regenerated liquid mixing device (4) which receives and mixes the low ORP acidic etching liquid output by the etching production line (1), the copper-poor electrolytic clear liquid output by the electrolysis device (2) and the additive provided by the adding device (3) and outputs a regenerated acidic etching liquid; and
a regenerative liquid ORP lift device (5) comprising a power wave tube (51), a tank (52) and a reverse flow jet (53); the lower end of the power wave tube (51) is communicated with the tank body (52), and the upper end of the power wave tube is communicated with the electrolysis device (2); a gas-liquid mixing area (511) is arranged in the power wave tube (51), the countercurrent injection piece (53) is arranged on the power wave tube (51) and is positioned below the gas-liquid mixing area (511), and the countercurrent injection piece (53) is communicated with the regenerated liquid blending device (4); the lower end of the tank body (52) is communicated with the etching production line (1); the countercurrent injection piece (53) injects the regenerated acidic etching solution to the gas-liquid mixing zone (511) in a countercurrent mode, the chlorine enters the gas-liquid mixing zone (511) through the upper end of the power wave tube (51), the regenerated acidic etching solution collides with the chlorine to form atomized foam and form high-ORP acidic etching regeneration solution, and the high-ORP acidic etching regeneration solution is transmitted to the etching production line (1).
2. The system for improving the regeneration and reuse rate of acidic etching solution according to claim 1, characterized in that the number of the regeneration solution ORP lifting devices (5) is two; the upper end of one of the dynamic wave tubes (51) is communicated with the electrolysis device (2), the other countercurrent injection piece (53) is communicated with the regenerated liquid blending device (4), the upper end of one of the tank bodies (52) is communicated with the upper end of the other dynamic wave tube (51), the lower end of the other tank body (52) is communicated with the countercurrent injection piece (53), and the lower end of one of the tank bodies (52) is communicated with the etching production line (1).
3. The system for improving the regeneration and reuse rate of the acidic etching solution according to claim 1, wherein a defogging layer (521) and an oxidizing solution are further disposed in the tank body (52); the defogging layer (521) is positioned above the position where the dynamic wave tube (51) is communicated with the tank body (52); the oxidizing liquid is positioned below the position where the dynamic wave tube (51) is communicated with the tank body (52).
4. The system for improving the regeneration and reuse rate of acidic etching solution according to claim 3, further comprising an exhaust gas treatment device (6); the exhaust gas treatment device (6) comprises a purification device (61) and an exhaust device (62); the purification device (61) is communicated with the upper end of the tank body (52), and the exhaust device (62) is communicated with the purification device (61).
5. The system for improving the regeneration and reuse rate of acidic etching solution according to claim 4, wherein the purification device (61) comprises a purification pipe (611), a purification tank (612) and a circulation piece (613); a purification layer (6121) and alkali liquor are arranged in the purification tank (612), and the purification layer (6121) is positioned above the alkali liquor; one end of the purification pipe (611) is communicated with the purification tank (612), and the communication position is positioned between the purification layer (6121) and the alkali liquor; the other end of the purification pipe (611) is communicated with the upper end of the tank body (52); the lower end of the purification tank (612) is communicated with the purification pipe (611) through a circulating piece (613); the upper end of the purification tank (612) is communicated with the exhaust device (62).
6. The system for improving the regeneration and reuse rate of the acidic etching solution according to claim 1, wherein the electrolysis device (2) comprises a diaphragm electrolysis cell (21), a filter element (22), an electric clear solution collection storage tank (23) and a chlorine gas extraction element; the diaphragm electrolytic cell (21) has a cell body (211), an anode section (212), and a cathode section (213); the chlorine gas extraction piece is respectively communicated with the anode part (212) and the upper end of the power wave tube (51); the cell body (211) pass through filter piece (22) with electricity clear solution collection storage jar (23) intercommunication, electricity clear solution collection storage jar (23) are used for saving poor copper electrolysis clear solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201920540358.1U CN209836312U (en) | 2019-04-19 | 2019-04-19 | System for improving regeneration and reuse rate of acidic etching solution |
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| CN201920540358.1U CN209836312U (en) | 2019-04-19 | 2019-04-19 | System for improving regeneration and reuse rate of acidic etching solution |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943850A (en) * | 2019-04-19 | 2019-06-28 | 惠州市臻鼎环保科技有限公司 | Improve the system and method for acidic etching liquid regeneration rate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943850A (en) * | 2019-04-19 | 2019-06-28 | 惠州市臻鼎环保科技有限公司 | Improve the system and method for acidic etching liquid regeneration rate |
| CN109943850B (en) * | 2019-04-19 | 2023-12-22 | 惠州市臻鼎环保科技有限公司 | System and method for improving regeneration and reuse rate of acidic etching solution |
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