A system for recycling etching waste liquid and recovering cuprous chloride and copper

Abstract

The present invention provides an etching waste liquid recycling and regeneration and cuprous chloride and copper recovery system, wherein the etching waste liquid recycling and regeneration system comprises an acid-base etching waste liquid collecting and neutralizing device, a cuprous chloride filtering and recovering device and an acid-base etching liquid regeneration device which are fixedly connected in sequence, the acid-base etching waste liquid collecting and neutralizing device is respectively connected to the etching waste liquid outlet of the acid etching production line, the etching waste liquid outlet of the alkaline etching production line, and the cuprous chloride filtering and recovering device, the cuprous chloride filtering and recovering device is respectively connected to the acid-base etching liquid regeneration device, the cuprous chloride purification system, and the electrolytic copper recovery system, and the acid-base etching liquid regeneration device is also respectively connected to the acid etching production line and the alkaline etching production line. The beneficial effects of the present invention are: different recycling and regeneration systems of acid-base etching waste liquids are integrated into a set of recycling and regeneration systems, the etching waste liquid recycling and regeneration quality is high, the copper extraction efficiency is high, and the production cost of cuprous chloride is low.

Description

Technical Field

[0001] The invention relates to the field of recycling of etching waste liquid, and in particular to a recycling system for etching waste liquid and a system for recovering cuprous chloride and copper. Background Art

[0002] At present, in the circuit board etching production line, the recycling system of printed circuit board etching waste liquid has been widely used. Printed circuit board etching is divided into two categories: acid etching and alkaline etching. At present, the recycling and regeneration of etching waste liquid is basically carried out separately. The main component of the etching liquid is cuprous chloride, which is widely used in catalysts, fungicides, mordants, decolorants and metallurgical industries. The current production process of cuprous chloride is the reaction of cupric chloride and copper powder, and the production cost is high. The copper extraction method in the alkaline recycling system is divided into alkaline extraction electrolytic copper extraction and direct electrolytic copper extraction. In the acidic recycling system, there is also acid membrane electrolytic copper extraction, which requires multiple sets of etching waste liquid recycling systems.

[0003] Moreover, due to the characteristics of the electrolytic copper extraction process, the actual production of the cuprous chloride crude product and etching waste liquid recycling system will have the following disadvantages:

[0004] 1. Different recycling equipment is required for different systems, which has high equipment cost and large supporting area;

[0005] 2. The existing copper extraction process can generally only reduce the copper ion concentration of the regenerated sub-liquid from 100g per liter to 30g-50g. The copper extraction efficiency is not high, and the efficiency of different copper recovery systems is different;

[0006] 3. In the prior art, the etching waste liquid needs to enter the copper extraction equipment, and a small amount of additives need to be added, which will bring impurities into the etching liquid and affect the quality of the etching liquid after regeneration. Summary of the invention

[0007] In order to solve the problems in the prior art, the present invention provides an etching waste liquid recycling and regeneration system and a cuprous chloride and copper recovery system. By arranging the etching waste liquid recycling and regeneration system, a cuprous chloride purification system and an electrolytic copper recovery system that cooperate with each other in the etching waste liquid recycling and regeneration system, a cuprous chloride precipitate crude product can be precipitated by neutralization of the acidic etching waste liquid and the alkaline etching waste liquid, no additives need to be added, the etching waste liquid does not enter the copper extraction equipment, and no impurities are brought in. The etching waste liquid is easy to regenerate and circulate, and the quality of the regenerated acid-base etching liquid is significantly improved. The amount of the acid-base etching liquid used is only 1 / 5 of the acid-base etching liquid regenerated by the existing process, which effectively reduces the production material cost and integrates different recycling and regeneration systems of the acid-base etching waste liquid. A set of recycling system is synthesized, the equipment occupies a small area and has low equipment cost; the crude cuprous chloride precipitate can be purified and processed into a finished cuprous chloride product with a purity of more than 99%, and the purification process only has a small amount of hydrochloric acid and ethanol volatiles, the tail gas treatment cost is low, and the production cost is reduced; the crude cuprous chloride precipitate can also be dissolved and then electrolyzed to extract copper, and the copper ion of the etching waste liquid can be processed from 100g per liter to 5g-10g per liter, which greatly improves the copper extraction efficiency, and solves the problems that the etching waste liquid in the current etching production line needs to be equipped with different recycling equipment, the existing copper extraction process is not efficient, the etching liquid quality of the existing etching waste liquid recycling system is low, and the existing cuprous chloride production cost is high.

[0008] The invention provides an etching waste liquid recycling and regeneration and cuprous chloride and copper recovery system, comprising an etching waste liquid recycling and regeneration system, a cuprous chloride purification system and an electrolytic copper extraction and recovery system, wherein the etching waste liquid recycling and regeneration system comprises an acid-base etching waste liquid collecting and neutralizing device, a cuprous chloride filtering and recovery device and an acid-base etching liquid regeneration device which are fixedly connected in sequence, wherein the acid-base etching waste liquid collecting and neutralizing device is provided with an acid-base etching waste liquid water inlet and a neutralized etching waste liquid water outlet, wherein the acid-base etching waste liquid water inlet is respectively connected to the etching waste liquid outlet of the acid etching production line and the etching waste liquid outlet of the alkaline etching production line, wherein the neutralized etching waste liquid water outlet is connected to the cuprous chloride filtering and recovery device, wherein the cuprous chloride filtering and recovery device is provided with a post-filter etching waste liquid drainage port and a cuprous chloride precipitate drainage port, wherein the post-filter etching waste liquid drainage port is provided with a cuprous chloride precipitate drainage port, wherein the post-filter etching waste liquid drainage port is provided with a cuprous chloride precipitate drainage port, wherein the cuprous chloride precipitate ... The outlet is connected to the acid-base etching liquid regeneration device, and the acid-base etching liquid regeneration device is also connected to the acid etching production line and the alkaline etching production line respectively. The cuprous chloride precipitate discharge outlet is respectively connected to the cuprous chloride purification system and the electrolytic copper extraction recovery system. The acid-base etching waste liquid collecting and neutralizing device is also provided with a pH value detection sensor. The cuprous chloride filtering and recovery device can separate the etching waste liquid neutralized in the acid-base etching waste liquid collecting and neutralizing device from the cuprous chloride precipitate, and adjust the etching waste liquid after neutralization to a new acid-base etching liquid through the acid-base etching liquid regeneration device to provide it to the etching production line for etching production, purify the cuprous chloride precipitate through the cuprous chloride purification system to recover it as a cuprous chloride finished product, and recover the cuprous chloride precipitate as a copper finished product through the electrolytic copper extraction recovery system.

[0009] The present invention is further improved, the acid-base etching waste liquid collecting and neutralizing device comprises an alkaline etching waste liquid collecting tank, an acid etching waste liquid collecting tank and an acid-base etching waste liquid neutralizing tank, the acid-base etching waste liquid neutralizing tank is respectively connected with the alkaline etching waste liquid collecting tank and the acid etching waste liquid collecting tank, the neutralizing etching waste liquid water outlet is fixedly arranged on the acid-base etching waste liquid neutralizing tank, the acid-base etching waste liquid water inlet comprises an acid etching waste liquid water inlet and an alkaline etching waste liquid water inlet, the alkaline etching waste liquid collecting tank is connected with the etching waste liquid outlet of the alkaline etching production line through the alkaline etching waste liquid water inlet, and the acid etching waste liquid collecting tank is connected with the etching waste liquid outlet of the acid etching production line through the acid etching waste liquid water inlet.

[0010] The present invention is further improved, the cuprous chloride filtering and recovery device comprises a cuprous chloride filtering tank, the filtered etching waste liquid drainage port is arranged on the bottom side of the cuprous chloride filtering tank, the cuprous chloride precipitate drainage port is arranged at the bottom of the cuprous chloride filtering tank, and the neutralized etching waste liquid outlet is connected to the cuprous chloride filtering tank.

[0011] The present invention is further improved, the acid-base etching liquid regeneration device comprises a regeneration liquid collecting tank, an acid etching liquid regenerator, an alkaline etching liquid regenerator, an acid etching liquid sub-tank and an alkaline etching liquid sub-tank which are fixedly connected in sequence, the regeneration liquid collecting tank is connected to the post-filtration etching waste liquid drain port, the regeneration liquid collecting tank is respectively connected to the acid etching liquid regenerator and the alkaline etching liquid regenerator, the acid etching liquid regenerator is connected to the acid etching liquid sub-tank, the alkaline etching liquid regenerator is connected to the alkaline etching liquid sub-tank, the acid etching liquid sub-tank is connected to the acid etching production line, and the alkaline etching liquid sub-tank is connected to the alkaline etching production line.

[0012] The present invention is further improved in that the additive added to the etching waste liquid in the acidic etching liquid regenerator is hydrochloric acid, and the additive added to the etching waste liquid in the alkaline etching liquid regenerator is ammonia water.

[0013] The present invention is further improved, the cuprous chloride purification system comprises a dilute hydrochloric acid cleaning tank, a dilute hydrochloric acid filter tank, an ethanol cleaning tank and an ethanol filter tank which are fixedly connected in sequence, the cuprous chloride precipitate discharge port is connected to the dilute hydrochloric acid cleaning tank, the dilute hydrochloric acid filter tank is provided with a cuprous chloride post-acid pickling discharge port and a dilute hydrochloric acid filtrate discharge port, the cuprous chloride post-acid pickling discharge port is connected to the ethanol cleaning tank, the dilute hydrochloric acid filtrate discharge port is connected to the dilute hydrochloric acid cleaning tank, the ethanol filter tank is provided with a cuprous chloride finished product discharge port and an ethanol filtrate discharge port, and the ethanol filtrate discharge port is connected to the ethanol cleaning tank.

[0014] The present invention is further improved, the electrolytic copper extraction and recovery system is an extraction electrolytic copper extraction system, including a cuprous chloride crude product extraction and dissolution tank, an alkaline extraction high-copper solution collection tank, an alkaline extraction low-copper solution collection tank and an extraction copper extraction device, the cuprous chloride crude product extraction and dissolution tank is respectively connected to the cuprous chloride precipitate discharge port and the alkaline extraction high-copper solution collection tank, the alkaline extraction high-copper solution collection tank is connected to the extraction copper extraction device, the extraction copper extraction device is connected to the alkaline extraction low-copper solution collection tank, and the alkaline extraction low-copper solution collection tank is connected to the cuprous chloride crude product extraction and dissolution tank.

[0015] The present invention is further improved, the extraction and copper extraction device comprises an extraction tank, a water washing tank, a back extraction tank and a copper recovery electrolytic tank, the extraction tank is respectively connected with the alkaline extraction high-copper solution collection tank and the alkaline extraction low-copper solution collection tank, the extraction tank, the water washing tank, the back extraction tank and the copper recovery electrolytic tank are fixedly connected in sequence, the alkaline high-copper solution in the alkaline extraction high-copper solution collection tank can be extracted in the extraction tank, the extracted copper solution can flow into the water washing tank to wash away the residual alkaline high-copper solution, and then flow into the back extraction tank to complete the back extraction, and then flow into the copper recovery electrolytic tank for electrolytic copper extraction.

[0016] The present invention is further improved, the electrolytic copper extraction and recovery system is an alkaline direct electrolytic copper extraction system, including an alkaline dissolution tank for crude cuprous chloride, an alkaline electrolytic copper extraction high-copper solution collection tank, an alkaline electrolytic copper extraction low-copper solution collection tank and an alkaline direct electrolytic copper extraction solution tank, the alkaline dissolution tank for crude cuprous chloride, the alkaline electrolytic copper extraction high-copper solution collection tank, the alkaline electrolytic copper extraction low-copper solution collection tank and the alkaline direct electrolytic copper extraction solution tank are fixedly connected in sequence, and the alkaline direct electrolytic copper extraction solution tank is also connected to the alkaline dissolution tank for crude cuprous chloride.

[0017] The present invention is further improved, the electrolytic copper extraction and recovery system is an acidic direct membrane electrolytic copper extraction system, including a crude cuprous chloride acidic dissolution tank, an acidic electrolytic copper extraction high-copper solution collection tank, an acidic electrolytic copper extraction low-copper solution collection tank and an acidic direct membrane electrolytic copper extraction solution tank, the crude cuprous chloride acidic dissolution tank, the acidic electrolytic copper extraction high-copper solution collection tank, the acidic electrolytic copper extraction low-copper solution collection tank and the acidic direct membrane electrolytic copper extraction solution tank are fixedly connected in sequence, and the acidic direct electrolytic copper extraction solution tank is also connected to the crude cuprous chloride acidic dissolution tank and the acidic etching production line.

[0018] Compared with the prior art, the invention has the following beneficial effects: the invention provides an etching waste liquid recycling and regeneration system and a cuprous chloride and copper recovery system; by arranging the etching waste liquid recycling and regeneration system, a cuprous chloride purification system and an electrolytic copper recovery system that cooperate with each other in the etching waste liquid recycling and regeneration system; the cuprous chloride filtering and recovery device can separate the etching waste liquid neutralized in the acid-base etching waste liquid collection and neutralization device from the cuprous chloride precipitate; and the etching waste liquid neutralized is treated and adjusted into a new acid-base etching liquid by the acid-base etching liquid regeneration device and provided to the etching production line for etching production; the cuprous chloride precipitate is purified and recovered as a cuprous chloride product by the cuprous chloride purification system; and the cuprous chloride precipitate is recovered as a copper product by the electrolytic copper recovery system; a crude cuprous chloride precipitate can be precipitated by neutralization of the acidic etching waste liquid and the alkaline etching waste liquid; no additives are needed; the etching waste liquid does not enter the copper recovery equipment and does not bring in impurities; and the etching The waste liquid is easy to regenerate and circulate, the quality of the regenerated acid-base etching liquid is significantly improved, and the amount used is only 1 / 5 of the acid-base etching liquid regenerated by the existing process, which effectively reduces the production material cost, integrates different recycling and regeneration systems of acid-base etching waste liquid into a recycling and regeneration system, and the equipment occupies a small area and has low equipment cost; the crude cuprous chloride precipitate can be purified and processed into a finished cuprous chloride product with a purity of more than 99%, and the purification process only has a small amount of hydrochloric acid and ethanol volatiles, and the tail gas treatment cost is low, which reduces the production cost; the crude cuprous chloride precipitate can also be dissolved and then electrolyzed to extract copper, and the copper ions of the etching waste liquid can be processed from 100g per liter to 5g-10g per liter, which greatly improves the copper extraction efficiency, and solves the problems that the etching waste liquid in the current etching production line needs to be equipped with different recycling and regeneration equipment, the existing copper extraction process is not efficient, the etching liquid quality of the existing etching waste liquid recycling and regeneration system is low, and the existing cuprous chloride production cost is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the etching waste liquid recycling and cuprous chloride and copper recovery system of the present invention;

[0020] Figure 2 It is the principle diagram of the cuprous chloride purification system in the present invention;

[0021] Figure 3 The schematic diagram of the copper extraction system of the present invention is shown in FIG.

[0022] Figure 4 It is a schematic diagram of the alkaline direct electrolytic copper extraction system of the present invention;

[0023] Figure 5 The schematic diagram of the acidic direct membrane electrolysis copper extraction system of the present invention;

[0024] Figure 6This is a table recording the content of copper ions before and after filtration of the etching waste liquid recycling system in the present invention.

[0025] In the figure, 1-etching waste liquid recycling system, 11-acid-base etching waste liquid collecting and neutralizing device, 111-alkaline etching waste liquid collecting tank, 112-acid etching waste liquid collecting tank, 113-acid-base etching waste liquid neutralizing tank, 12-cuprous chloride filtering and recovering device, 121-cuprous chloride filtering tank, 13-acid-base etching liquid regenerating device, 131-regenerating liquid collecting tank, 132-acid etching liquid regenerator, 133-alkaline etching liquid regenerator, 134-acid etching liquid sub-tank, 135-alkaline etching liquid sub-tank, 14-acid etching production line, 15-alkaline etching production line, 2-cuprous chloride purification system, 21-dilute hydrochloric acid cleaning tank, 22-dilute hydrochloric acid filtering tank, 23-ethanol cleaning tank, 24-ethanol filtering tank, 3-electrolytic copper recovery system, 4 -Extraction electrolytic copper extraction system, 41-cuprous chloride extraction and dissolution tank, 42-alkaline extraction high-copper solution collection tank, 43-alkaline extraction low-copper solution collection tank, 44-extraction copper extraction device, 441-extraction tank, 442-water washing tank, 443-back extraction tank, 444-copper recovery electrolytic tank, 5-alkaline direct electrolytic copper extraction system, 51-cuprous chloride alkaline dissolution tank, 52-alkaline electrolytic copper extraction high-copper solution collection tank, 53-alkaline electrolytic copper extraction low-copper solution collection tank, 54-alkaline direct electrolytic copper extraction solution tank, 6-acidic direct membrane electrolytic copper extraction system, 61-cuprous chloride acidic dissolution tank, 62-acidic electrolytic copper extraction high-copper solution collection tank, 63-acidic electrolytic copper extraction low-copper solution collection tank, 64-acidic direct membrane electrolytic copper extraction solution tank. DETAILED DESCRIPTION

[0026] The present invention is further described in detail below with reference to the accompanying drawings and embodiments.

[0027] like Figure 1-6As shown, the present invention provides an etching waste liquid recycling and regeneration and cuprous chloride, copper recovery system, comprising an etching waste liquid recycling and regeneration system 1, a cuprous chloride purification system 2 and an electrolytic copper recovery system 3, wherein the etching waste liquid recycling and regeneration system 1 comprises an acid-base etching waste liquid collecting and neutralizing device 11, a cuprous chloride filtering and recovering device 12 and an acid-base etching liquid regeneration device 13 which are fixedly connected in sequence, the acid-base etching waste liquid collecting and neutralizing device 11 is provided with an acid-base etching waste liquid water inlet and a neutralized etching waste liquid water outlet, the acid-base etching waste liquid water inlet is respectively connected to the etching waste liquid outlet of the acid etching production line 14 and the alkaline etching production line 15, and the acid-base etching waste liquid water outlet is connected to the acid-base etching waste liquid water outlet. The etching waste liquid outlet of line 15 is connected, and the neutralization etching waste liquid outlet is connected to the cuprous chloride filtering and recovery device 12. The cuprous chloride filtering and recovery device 12 is provided with a post-filter etching waste liquid drain port and a cuprous chloride precipitate discharge port. The post-filter etching waste liquid drain port is connected to the acid-base etching liquid regeneration device 13. The acid-base etching liquid regeneration device 13 is also respectively connected to the acid etching production line 14 and the alkaline etching production line 15. The cuprous chloride precipitate discharge port is respectively connected to the cuprous chloride purification system 2 and the electrolytic copper recovery system 3. A pH value detection sensor is also provided in the acid-base etching waste liquid collecting and neutralizing device 11. In this embodiment, the cuprous chloride filtering and recovery device can collect the acid-base etching waste liquid and separate the neutralized etching waste liquid from the cuprous chloride precipitate in the neutralization device, and adjust the neutralized etching waste liquid to a new acid-base etching liquid through the acid-base etching liquid regeneration device to provide it to the etching production line for etching production, purify the cuprous chloride precipitate through the cuprous chloride purification system to recover it as a finished cuprous chloride product, and recover the cuprous chloride precipitate through the electrolytic copper extraction recovery system to recover it as a copper product. The crude cuprous chloride precipitate can be precipitated by neutralization of the acidic etching waste liquid and the alkaline etching waste liquid, without adding any additives, the etching waste liquid does not enter the copper extraction equipment, and will not bring in impurities, and the etching waste liquid is easy to regenerate The quality of the acid-base etching liquid after recycling is significantly improved, and the amount used is only 1 / 5 of the acid-base etching liquid after regeneration in the existing process, which effectively reduces the production material cost, integrates different recycling and regeneration systems of acid-base etching waste liquid into a set of recycling and regeneration systems, and the equipment occupies a small area and has low equipment cost; the crude cuprous chloride precipitate can be purified and processed into a finished cuprous chloride product with a purity of more than 99%, and the purification process only has a small amount of hydrochloric acid and ethanol volatiles, and the tail gas treatment cost is low, which reduces the production cost; the crude cuprous chloride precipitate can also be dissolved and then electrolyzed to extract copper, and the copper ion of the etching waste liquid can be processed from 100g per liter to 5g-10g per liter, which greatly improves the copper extraction efficiency.

[0028] like Figure 1As shown, the acid-base etching waste liquid collecting and neutralizing device 11 includes an alkaline etching waste liquid collecting tank 111, an acid etching waste liquid collecting tank 112 and an acid-base etching waste liquid neutralizing tank 113, the acid-base etching waste liquid neutralizing tank 113 is connected to the alkaline etching waste liquid collecting tank 111 and the acid etching waste liquid collecting tank 112 respectively, the neutralized etching waste liquid outlet is fixedly arranged on the acid-base etching waste liquid neutralizing tank 113, and the acid-base etching waste liquid inlet includes an acid etching waste liquid inlet and an alkaline etching waste liquid inlet. The alkaline etching waste liquid collecting tank 111 is connected to the etching waste liquid outlet of the alkaline etching production line 15 through the alkaline etching waste liquid inlet, and the acid etching waste liquid collecting tank 112 is connected to the etching waste liquid outlet of the acid etching production line 14 through the acid etching waste liquid inlet; the cuprous chloride filtering and recovering device 12 comprises a cuprous chloride filtering tank 121, the drainage port of the filtered etching waste liquid is arranged on the bottom side of the cuprous chloride filtering tank 121, and the drainage port of the cuprous chloride precipitate is arranged on the bottom side of the cuprous chloride filtering tank 121, and the drainage port of the cuprous chloride precipitate is arranged on the bottom side of the cuprous chloride filtering tank 121. At the bottom of the filter tank 121, the outlet of the neutralized etching waste liquid is connected to the cuprous chloride filter tank 121; the acid-base etching liquid regeneration device 13 includes a regeneration liquid collecting tank 131, an acid etching liquid regenerator 132, an alkaline etching liquid regenerator 133, an acid etching liquid sub-tank 134 and an alkaline etching liquid sub-tank 135 which are fixedly connected in sequence, the regeneration liquid collecting tank 131 is connected to the drainage port of the post-filter etching waste liquid, and the regeneration liquid collecting tank 131 is respectively connected to the acid etching liquid regenerator 132, the alkaline etching liquid regenerator 133, the acid etching liquid sub-tank 134 and the alkaline etching liquid sub-tank 135. The regenerator 133 is connected, the acid etching liquid regenerator 132 is connected to the acid etching liquid sub-tank 134, the alkaline etching liquid regenerator 133 is connected to the alkaline etching liquid sub-tank 135, the acid etching liquid sub-tank 134 is connected to the acid etching production line 14, and the alkaline etching liquid sub-tank 135 is connected to the alkaline etching production line 15; the additive added to the etching waste liquid in the acid etching liquid regenerator 132 is hydrochloric acid, and the additive added to the etching waste liquid in the alkaline etching liquid regenerator 133 is ammonia water.

[0029] In this embodiment, if Figure 6 As shown, Figure 6 This is a record table of the content of copper ions before and after filtration of the etching waste liquid recycling and regeneration system in the present invention. The etching waste liquid in the acid etching production line and the alkaline etching production line is neutralized in the acid-base etching waste liquid neutralization tank by utilizing the characteristic that cuprous chloride, the main component of the acid-base etching waste liquid, will precipitate in large quantities when the pH value is neutral. The acid-base etching waste liquid is neutralized to precipitate cuprous chloride, and the crude cuprous chloride can be filtered out; the filtered etching waste liquid is sent to the regeneration liquid collection tank, and then sent to the acid etching liquid regenerator and the alkaline etching liquid regenerator respectively. When the waste liquid is sent to the acid etching liquid regenerator, hydrochloric acid and additives are added to the waste liquid for mixing, and then it is sent to the acid etching liquid sub-tank for etching production in the acid etching production line; when the waste liquid is sent to the alkaline etching liquid regenerator, ammonia water and additives are added to the waste liquid for mixing, and then it is sent to the alkaline etching liquid sub-tank for etching production in the alkaline etching production line. Among them, the main chemical principle of the neutralization of the etching waste liquid in the acid-base etching waste liquid neutralization tank is:

[0030] Acidic complex reaction, CuCl + HCl = H[CuCl2];

[0031] Alkaline complex reaction, CuCl + 2NH3·H2O = 2H2O + [Cu(NH3)2]Cl;

[0032] Acid-base neutralization and complex breaking reaction, 2H[CuCl2]+[Cu(NH3)2]Cl=2CuCl↓+2NH4Cl+2H2O. .

[0033] like Figure 2 As shown, the cuprous chloride purification system 2 comprises a dilute hydrochloric acid cleaning tank 21, a dilute hydrochloric acid filter tank 22, an ethanol cleaning tank 23 and an ethanol filter tank 24 which are fixedly connected in sequence, the cuprous chloride precipitate discharge port is communicated with the dilute hydrochloric acid cleaning tank 21, the dilute hydrochloric acid filter tank 22 is provided with a cuprous chloride hydrochloric acid post-pickling discharge port and a dilute hydrochloric acid filtrate drain port, the cuprous chloride hydrochloric acid post-pickling discharge port is communicated with the ethanol cleaning tank 23, the dilute hydrochloric acid filtrate drain port is communicated with the dilute hydrochloric acid cleaning tank 21, the ethanol filter tank 24 is provided with a cuprous chloride finished product discharge port and an ethanol filtrate drain port, and the ethanol filtrate drain port is communicated with the ethanol cleaning tank 23. In this embodiment, the cuprous chloride crude product is cleaned and purified by utilizing the principle that cuprous chloride is insoluble in dilute hydrochloric acid and ethanol, and a cuprous chloride finished product with a purity of more than 99% can be obtained, and the purification process has only a small amount of hydrochloric acid and ethanol volatiles, and the tail gas treatment cost is low, thereby reducing the production cost.

[0034] like Figure 3As shown, the electrolytic copper recovery system 3 is an extraction electrolytic copper system 4, comprising a cuprous chloride crude product extraction and dissolution tank 41, an alkaline extraction high-copper solution collection tank 42, an alkaline extraction low-copper solution collection tank 43 and an extraction copper extraction device 44, wherein the cuprous chloride crude product extraction and dissolution tank 41 is connected to the cuprous chloride precipitate discharge port and the alkaline extraction high-copper solution collection tank 42, respectively, the alkaline extraction high-copper solution collection tank 42 is connected to the extraction copper extraction device 44, and the extraction copper extraction device 44 is connected to the alkaline extraction low-copper solution collection tank 43. The solution collection tank 43 is connected, the alkaline extraction low-copper solution collection tank 43 is connected to the cuprous chloride crude product extraction and dissolution tank 41, and the extraction and copper extraction device 44 includes an extraction tank 441, a water washing tank 442, a back extraction tank 443 and a copper recovery electrolytic tank 444. The extraction tank 441 is respectively connected to the alkaline extraction high-copper solution collection tank 42 and the alkaline extraction low-copper solution collection tank 43, and the extraction tank 441, the water washing tank 442, the back extraction tank 443 and the copper recovery electrolytic tank 444 are fixedly connected in sequence. In this embodiment, the cuprous chloride precipitate crude product is dissolved in the cuprous chloride crude product extraction and dissolution tank and then sent to the alkaline extraction high-copper solution collection tank. The alkaline high-copper solution in the alkaline extraction high-copper solution collection tank can be extracted in the extraction tank, and the extracted copper solution can flow into the water washing tank to wash away the residual alkaline high-copper solution and then flow into the back extraction tank to complete the back extraction and then flow into the copper recovery electrolytic tank for electrolytic copper extraction.

[0035] like Figure 4 As shown, the electrolytic copper extraction recovery system 3 is an alkaline direct electrolytic copper extraction system 5, including a cuprous chloride crude alkaline dissolution tank 51, an alkaline electrolytic copper extraction high-copper solution collection tank 52, an alkaline electrolytic copper extraction low-copper solution collection tank 53 and an alkaline direct electrolytic copper extraction solution tank 54. The cuprous chloride crude alkaline dissolution tank 51, the alkaline electrolytic copper extraction high-copper solution collection tank 52, the alkaline electrolytic copper extraction low-copper solution collection tank 54 and the alkaline direct electrolytic copper extraction solution tank 54 are fixedly connected in sequence, and the alkaline direct electrolytic copper extraction solution tank 54 is also connected to the cuprous chloride crude alkaline dissolution tank 51. In this embodiment, the cuprous chloride precipitate crude product is dissolved in the cuprous chloride crude product alkaline dissolution tank and then sent to the alkaline electrolytic copper extraction high-copper solution collection tank, and the alkaline high-copper solution in the alkaline electrolytic copper extraction high-copper solution collection tank can flow into the alkaline direct electrolytic copper extraction solution tank for electrolytic copper extraction.

[0036] like Figure 5As shown, the electrolytic copper recovery system 4 is an acidic direct membrane electrolytic copper system 6, including a cuprous chloride crude acid dissolution tank 61, an acidic electrolytic copper high-copper solution collection tank 62, an acidic electrolytic copper low-copper solution collection tank 63 and an acidic direct membrane electrolytic copper solution tank 64. The cuprous chloride crude acid dissolution tank 61, the acidic electrolytic copper high-copper solution collection tank 62, the acidic electrolytic copper low-copper solution collection tank 63 and the acidic direct membrane electrolytic copper solution tank 64 are fixedly connected in sequence, and the acidic direct electrolytic copper solution tank 64 is also connected to the cuprous chloride crude acid dissolution tank 61 and the acidic etching production line 24. In this embodiment, the cuprous chloride precipitate crude product is dissolved in the cuprous chloride crude acid dissolution tank and then sent to the acidic electrolytic copper high-copper solution collection tank, and the acidic high-copper solution in the acidic electrolytic copper high-copper solution collection tank can flow into the acidic direct membrane electrolytic copper solution tank for electrolytic copper extraction.

[0037] As can be seen from the above, the present invention provides an etching waste liquid recycling and regeneration and cuprous chloride and copper recovery system. By arranging the etching waste liquid recycling and regeneration system, the cuprous chloride purification system and the electrolytic copper extraction and recovery system that cooperate with each other in the etching waste liquid recycling and regeneration system, the cuprous chloride filtering and recovery device can collect the acid-base etching waste liquid and separate the etching waste liquid neutralized in the neutralization device from the cuprous chloride precipitate, and the acid-base etching liquid regeneration device can adjust the neutralized etching waste liquid to a new acid-base etching liquid for etching production, and the cuprous chloride precipitate is purified and recovered as a cuprous chloride product by the cuprous chloride purification system, and the cuprous chloride precipitate is recovered as a copper product by the electrolytic copper extraction and recovery system. The crude cuprous chloride precipitate can be precipitated by neutralization of the acidic etching waste liquid and the alkaline etching waste liquid, and no additives need to be added. The etching waste liquid does not enter the copper extraction equipment and will not bring in impurities. The etching waste liquid is easy to regenerate and recycle. The quality of the acid-base etching liquid after regeneration is significantly improved, and the amount used is only 1 / 5 of the acid-base etching liquid after regeneration in the existing process, which effectively reduces the production material cost, integrates different recycling and regeneration systems of acid-base etching waste liquid into a recycling and regeneration system, and the equipment occupies a small area and has low equipment cost; the crude cuprous chloride precipitate can be purified and processed into a finished cuprous chloride product with a purity of more than 99%, and the purification process only has a small amount of hydrochloric acid and ethanol volatiles, and the tail gas treatment cost is low, which reduces the production cost; the crude cuprous chloride precipitate can also be dissolved and then electrolyzed to extract copper, and the copper ion of the etching waste liquid can be processed from 100g per liter to 5g-10g per liter, which greatly improves the copper extraction efficiency, and solves the problems that the etching waste liquid in the current etching production line needs to be equipped with different recycling and regeneration equipment, the existing copper extraction process is not efficient, the etching liquid quality of the existing etching waste liquid recycling and regeneration system is low, and the existing cuprous chloride production cost is high.

[0038] The specific implementation modes described above are preferred implementation modes of the present invention, and are not intended to limit the specific implementation scope of the present invention. The scope of the present invention includes but is not limited to the specific implementation modes, and all equivalent changes made according to the present invention are within the protection scope of the present invention.

Claims

1. A system for recycling etching waste liquid and recovering cuprous chloride and copper, characterized in that: The invention comprises an etching waste liquid recycling and regeneration system, a cuprous chloride purification system and an electrolytic copper extraction and recovery system. The etching waste liquid recycling and regeneration system comprises an acid-base etching waste liquid collecting and neutralizing device, a cuprous chloride filtering and recovering device and an acid-base etching liquid regeneration device which are fixedly connected in sequence. The acid-base etching waste liquid collecting and neutralizing device is provided with an acid-base etching waste liquid water inlet and a neutralized etching waste liquid water outlet. The acid-base etching waste liquid water inlet is respectively connected with the etching waste liquid outlet of the acid etching production line and the etching waste liquid outlet of the alkaline etching production line. The neutralized etching waste liquid water outlet is connected with the cuprous chloride filtering and recovering device. The cuprous chloride filtering and recovering device is provided with a filter after filtration. The etching waste liquid drainage port and the cuprous chloride precipitate drainage port are connected to the acid-base etching liquid regeneration device, and the acid-base etching liquid regeneration device is also connected to the acid etching production line and the alkaline etching production line respectively. The cuprous chloride precipitate drainage port is connected to the cuprous chloride purification system and the electrolytic copper extraction recovery system respectively. The acid-base etching waste liquid collection and neutralization device is also provided with a pH value detection sensor. The cuprous chloride filtering and recovery device can separate the etching waste liquid neutralized in the acid-base etching waste liquid collection and neutralization device from the cuprous chloride precipitate, and neutralize the neutralized waste liquid through the acid-base etching liquid regeneration device. The etching waste liquid is treated and adjusted to a new acid-base etching liquid and provided to the etching production line for etching production; the cuprous chloride precipitate is purified and recovered as a cuprous chloride product through a cuprous chloride purification system; the cuprous chloride precipitate is recovered as a copper product through an electrolytic copper recovery system; the acid-base etching waste liquid collection and neutralization device comprises an alkaline etching waste liquid collection tank, an acid etching waste liquid collection tank and an acid-base etching waste liquid neutralization tank, the acid-base etching waste liquid neutralization tank is respectively connected to the alkaline etching waste liquid collection tank and the acid etching waste liquid collection tank, the neutralization etching waste liquid water outlet is fixedly arranged on the acid-base etching waste liquid neutralization tank, and the acid-base etching waste liquid water inlet is The inlet comprises an acidic etching waste liquid inlet and an alkaline etching waste liquid inlet, the alkaline etching waste liquid collecting tank is connected to the etching waste liquid outlet of the alkaline etching production line through the alkaline etching waste liquid inlet, and the acidic etching waste liquid collecting tank is connected to the etching waste liquid outlet of the acidic etching production line through the acidic etching waste liquid inlet; the cuprous chloride filtering and recovering device comprises a cuprous chloride filter tank, the filtered etching waste liquid drainage port is arranged on the bottom side of the cuprous chloride filter tank, the cuprous chloride precipitate drainage port is arranged at the bottom of the cuprous chloride filter tank, and the neutralized etching waste liquid outlet is connected to the cuprous chloride filter tank;The acid-base etching liquid regeneration device comprises a regeneration liquid collecting tank, an acid etching liquid regenerator, an alkaline etching liquid regenerator, an acid etching liquid sub-tank and an alkaline etching liquid sub-tank which are fixedly connected in sequence, the regeneration liquid collecting tank is connected to the post-filtration etching waste liquid drain port, the regeneration liquid collecting tank is connected to the acid etching liquid regenerator and the alkaline etching liquid regenerator respectively, the acid etching liquid regenerator is connected to the acid etching liquid sub-tank, the alkaline etching liquid regenerator is connected to the alkaline etching liquid sub-tank, the acid etching liquid sub-tank is connected to the acid etching production line, and the alkaline etching liquid sub-tank is connected to the alkaline etching production line; The additive added to the etching waste liquid in the acidic etching liquid regenerator is hydrochloric acid, and the additive added to the etching waste liquid in the alkaline etching liquid regenerator is ammonia water; the cuprous chloride purification system comprises a dilute hydrochloric acid cleaning tank, a dilute hydrochloric acid filter tank, an ethanol cleaning tank and an ethanol filter tank which are fixedly connected in sequence, the cuprous chloride precipitate discharge port is connected to the dilute hydrochloric acid cleaning tank, the dilute hydrochloric acid filter tank is provided with a cuprous chloride post-acid pickling discharge port and a dilute hydrochloric acid filtrate discharge port, the cuprous chloride post-acid pickling discharge port is connected to the ethanol cleaning tank, the dilute hydrochloric acid filtrate discharge port is connected to the dilute hydrochloric acid cleaning tank, and the ethanol filter tank is provided with a chlorine The copper leaching product outlet and the ethanol filtrate outlet are connected, and the ethanol filtrate outlet is connected to the ethanol cleaning tank; the electrolytic copper extraction recovery system is an extraction electrolytic copper extraction system, including a cuprous chloride crude product extraction and dissolution tank, an alkaline extraction high-copper solution collection tank, an alkaline extraction low-copper solution collection tank and an extraction copper extraction device, the cuprous chloride crude product extraction and dissolution tank is respectively connected to the cuprous chloride precipitate outlet and the alkaline extraction high-copper solution collection tank, the alkaline extraction high-copper solution collection tank is connected to the extraction copper extraction device, the extraction copper extraction device is connected to the alkaline extraction low-copper solution collection tank, and the alkaline extraction low-copper solution collection tank is connected to the extraction copper extraction device. The collecting tank is connected to the copper chloride crude product extraction and dissolution tank; the extraction and copper extraction device includes an extraction tank, a water washing tank, a stripping tank and a copper recovery electrolytic tank, the extraction tank is respectively connected to the alkaline extraction high copper solution collection tank and the alkaline extraction low copper solution collection tank, the extraction tank, the water washing tank, the stripping tank and the copper recovery electrolytic tank are fixedly connected in sequence, the alkaline high copper solution in the alkaline extraction high copper solution collection tank can be extracted in the extraction tank, the extracted copper solution can flow into the water washing tank to wash away the residual alkaline high copper solution, and then flow into the stripping tank to complete the stripping, and then flow into the copper recovery electrolytic tank to electrolyze and extract copper. ;

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