CN112831786B - Regeneration method for extracting copper from ferric trichloride copper-containing etching waste liquid - Google Patents
Regeneration method for extracting copper from ferric trichloride copper-containing etching waste liquid Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 133
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 123
- 238000005530 etching Methods 0.000 title claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000007788 liquid Substances 0.000 title claims abstract description 60
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 238000011069 regeneration method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 26
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 238000012546 transfer Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 46
- 229960002089 ferrous chloride Drugs 0.000 claims description 30
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 239000012263 liquid product Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 235000015073 liquid stocks Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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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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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a regeneration method for extracting copper from copper-containing etching waste liquid of ferric trichloride, which adopts an iron powder reduction-membrane electrolysis combined process, uses an advanced anode box, optimizes the circulation mode of anolyte, improves the mass transfer efficiency, obtains a copper plate and a regenerated etching liquid product which have high purity and are easy to strip, and greatly reduces the cost for extracting copper from the copper-containing etching liquid of ferric trichloride; the defects that the existing etching waste liquid treatment cost is high, the electrolysis energy consumption is high, the purity of the recovered copper is low, the treatment is difficult and the like are overcome.
Description
Technical Field
The invention relates to the technical field of printed circuit board waste liquid recycling, in particular to a copper extraction regeneration method of ferric trichloride copper-containing etching waste liquid.
Background
Ferric trichloride is used as an important chemical reagent and chemical raw material, and is mainly used as a water purifying agent of drinking water, a sewage treatment flocculating agent, a printed circuit board, a stainless steel etching agent and the like.
Printed Circuit Boards (PCBs) are important components in electronic devices. With the full development of the electronic industry, china also becomes the largest production country and use market of PCBs, PCBs also become an industry with strong competition, and the requirement of the industry is reduced. FeCl 3 The etching solution has strong oxidation corrosion effect on metals such as Fe, cu and the like, and in addition, the etching solution has lower price and higher etching speed than other etching solutions such as copper chloride etching solution, so FeCl 3 The etching solution is still widely used in the etching process of the PCB. However, a large amount of FeCl is generated during the etching process 3 Waste etching solution with strong corrosivity and a large amount of Fe 3+ 、Cu 2+ The direct discharge of the metal ions can cause resource waste and environmental pollution. In recent years, with the development of PCB and shortage of metal resources in China, feCl is regenerated 3 The use of waste etching solutions and the recovery of copper have become a major problem in the fields of metal resource recovery and environmental protection.
Currently, iron powder replacement regenerationMethods, ferrous sulfide precipitation, solvent extraction, crystal electrolysis and ion-membrane electrolysis are commonly used to regenerate FeCl 3 Spent etching solution and recovered copper product, but the use of these processes has many problems. For example, the purity of copper recovered by the iron powder displacement regeneration method is not high, and the first reduction and second oxidation processes not only waste expensive iron powder but also increase the consumption of chlorine. The ferrous sulfide precipitation method needs iron powder and sulfur powder to generate ferrous sulfide, but the reaction is violent, and secondary pollution is easy to cause. Although the extraction regeneration method realizes good separation of iron and copper, the process is complex, and the purity of the regeneration liquid is reduced by introducing an extracting agent. The purity of the metal recovered by the electrolytic regeneration method is very high, but most of the recovered copper products are in a state of copper powder, copper sludge or the like and are not easy to handle. Meanwhile, the energy consumption in the electrolytic process is very high, and a large amount of toxic gas chlorine is easily generated nearby the anode. In the ion membrane electrolysis process, feCl may be generated in the anode compartment 3 The etching solution is exhausted, and Cu is removed 2+ The catholyte may then be returned to the anode chamber for oxidative regeneration. Although ion membrane electrolysis is environmentally friendly, the high power consumption limits the wide application of this process.
Disclosure of Invention
The invention aims to provide a regeneration method for extracting copper from copper-containing etching waste liquid of ferric trichloride, which adopts an iron powder reduction-membrane electrolysis combined process, uses an advanced anode box, optimizes an anolyte circulation mode, improves mass transfer efficiency, obtains a copper plate and a regenerated etching liquid product which have high purity and are easy to strip, and greatly reduces the cost for extracting copper from the copper-containing etching liquid of ferric trichloride; the defects that the existing etching waste liquid treatment cost is high, the electrolysis energy consumption is high, the purity of the recovered copper is low, the treatment is difficult and the like are overcome.
In order to achieve the purpose, the invention adopts the following technical scheme:
s010, transferring the etching waste liquid into a stirring reduction cylinder, adding iron powder and mechanically stirring, and adding Fe 3+ Reduction to Fe 2+ The ion equation for the major reactions is as follows:
2Fe 3+ +Fe＝3Fe 2+
wherein the amount of the added iron powder is determined according to the Fe content in the etching waste liquid 3+ In a molar ratio of n (Fe) 3+ ): n (Fe) = (2-3): 1
Wherein a high-copper ferrous chloride solution is obtained after the reaction is finished, and the solution components are controlled as follows: cu 2+ ％2-6％，TFe％8-15％，Fe 3+ ＜1％；
S011, performing plate-and-frame filter pressing on the solution after the reaction in the S010 step to finish solid-liquid separation to obtain a high-copper ferrous chloride solution, and transferring the filtrate to the next step;
s012 is an electrolytic reaction system which comprises an electrolytic cell, an anode chamber, a cathode chamber, an anion membrane, a cathode plate, an anode plate and a rectification power supply system;
the catholyte is a mixed solution of the high-copper ferrous chloride and the low-copper ferrous chloride from the low-copper ferrous chloride tank in the step S011, and the reaction conditions are that the current density is 1.5-2.5ASD and the temperature is 20-50 ℃;
the cathode mainly reacts:
2HCl+2e-＝H 2 ↑+2Cl-
CuCl 2 +2e-＝Cu↓+2Cl-
Fe 3+ +e-＝Fe 2+
and (4) electrodepositing a copper plate on the negative plate, and directly stripping the copper plate after the negative plate is taken out to obtain the product copper plate.
The anode chamber is an independent optimal anode box, the anion membranes are arranged on two sides of the anode box and are separated from the cathode chamber, the plating anode plate is arranged in the anode box, and the mass transfer rate of the anode liquid on the anode plate is greatly enhanced by adopting a mode of directly jetting the liquid into the anode plate and bubbling air at the bottom of the anode box.
The anolyte is a mixed solution of low-copper ferrous chloride and low-copper ferric trichloride from a tail gas absorption tower and a low-copper ferric trichloride tank. The main reaction of the anode chamber:
FeCl 2 -e-+Cl-＝FeCl 3
2Cl - -2e-＝Cl 2 ↑
s013 is a low-copper ferrous chloride groove, is connected with a feed inlet and a discharge outlet of a cathode chamber of the electrolytic cell through pipelines, a liquid phase circulating system is established, an ORP detector is arranged on a backflow pipeline, and an ORP is controlled through a backflow pipe: 300mv-500mv of Cu 2+ ＜1％；
S014 is a low copper ferric trichloride tank, which is connected with the feed inlet and the discharge outlet of the anode chamber of the electrolytic cell by a pipeline, a liquid phase circulating system is established, an ORP detector is also arranged on a backflow pipeline, and the backflow pipeline controls ORP: ORP800mv-1100mv 2+ ＜1％，TFe：8％-15％；
S015 is the tail gas absorption tower, and low copper ferrous chloride solution passes through the tail gas absorption tower earlier, absorbs a small amount of chlorine that the electrolysis trough produced and ferrous chloride is oxidized into ferric chloride simultaneously, and the absorption liquid is being sent to the electrolysis trough positive pole, and the tail gas both can discharge to reach standard and can reduce the electrolysis energy consumption, and the main reaction equation of emergence is as follows:
Cl 2 +2FeCl 2 ＝2FeCl 3
s016 is a mixing tank, the ferric trichloride solution with high ORP from the electrolysis anode is mixed with the original ferric trichloride etching waste liquid after physical filtration according to a certain proportion, and the regenerated etching liquid which is suitable for the requirement of an etching line is mixed and sent to an etching production line.
Wherein, the mixing ratio of the effluent of the anode chamber of the electrolytic cell and the filtered stock solution is as follows: volume ratio (3-10): 1, the standard of the regenerated etching solution is as follows: ORP:500-1000mv of Fe 2+ ＜1％，TFe：8％-14％，Cu 2+ ＜2％。
The invention provides a copper extraction regeneration method of ferric trichloride copper-containing etching waste liquid, compared with the prior art, the method has good environmental and economic benefits, and the advantages are as follows:
adding iron powder into the waste etching solution through pretreatment, and adding Fe in the waste etching solution in advance 3+ The content is reduced to a certain degree, and the requirement of reducing Fe electrically in the electrolytic process of the cathode chamber of the electrolytic cell 3+ The content of (2) reduces the whole energy consumption;
by adjusting the current density, copper is deposited on the negative plate to be a fine compact plate-shaped structure, the purity is high, and the copper can be directly sold after being stripped from the negative plate; the recovery process is convenient and fast, and the economic value is higher;
by improving the anode box, fe is accelerated 2+ The mass transfer rate in the solution reduces the chlorine gas generated by the chlorine evolution reaction of the side reaction, reduces the cell voltage and further reduces the electrolysis energy consumption.
Drawings
FIG. 1 is a flow chart of a method for regenerating copper from a copper-containing etching waste solution of ferric trichloride;
fig. 2 is a schematic structural diagram of a preferred anode box of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, but the technical solutions in the embodiments of the present invention are not limited to the scope of the present invention.
Referring to the attached figures 1-2, the invention provides a method for extracting copper from a ferric trichloride copper-containing etching waste liquid and regenerating the copper, which comprises the following steps:
s010, transferring the etching waste liquid into a stirring reduction cylinder, adding iron powder and mechanically stirring, wherein the amount of the added iron powder is determined according to Fe in the etching waste liquid 3+ In a molar ratio of n (Fe) 3+ ): n (Fe) = (2-3): 1 is added in a proportion of;
s011, after the reaction is finished, filtering to obtain a high-copper ferrous chloride solution, wherein the solution components are controlled as follows: cu (copper) 2+ ％2－6％，TFe％8－15％，Fe 3+ ＜1％；
And S012 is an electrolysis reaction system which comprises an electrolytic bath, an anode chamber, a cathode chamber, an anion membrane, a cathode plate, an anode plate and a rectification power supply system. The reaction conditions are that the current density is 1.5-2.5ASD and the temperature is 20-50 ℃;
wherein, the catholyte is the mixed solution of the high-copper ferrous chloride and the low-copper ferrous chloride from the step S011, and the liquid inlet mode of the catholyte is as follows: the high copper ferrous chloride pipeline and the low copper ferrous chloride tank cathode chamber pipeline are converged and then enter the cathode chamber, and the pipeline is provided with a flow meter and an adjusting valve.
The anode chamber is an independent preferred anode box, anion membranes are arranged on two sides of the anode box and are separated from the cathode chamber, and a plating anode plate is arranged in the anode box. The bottom of the anode box adopts a mode of directly facing the anode plate to inject liquid and bubbling air, so that the mass transfer rate of the anolyte on the anode plate is enhanced.
The inlet and outlet of the anode box is shown in fig. 2, which is marked as: a liquid outlet 10, an aeration port 11, a liquid inlet pipe 12, an air inlet groove 13, a liquid inlet 14 and an air inlet 15.
The anolyte is a mixed solution of low-copper ferrous chloride from a tail gas absorption tower and low-copper ferric trichloride from a low-copper ferric trichloride tank. The liquid inlet mode of the anode box is as follows: the pipeline from the absorption tower is converged with a pipeline from the low-copper ferric trichloride tank to the anode chamber and then enters the anode chamber, and a flowmeter and an adjusting valve are arranged on the pipeline.
S013 is a low-copper ferrous chloride groove, is connected with a feed inlet and a discharge outlet of a cathode chamber of the electrolytic cell through pipelines, a liquid phase circulating system is established, an ORP detector is arranged on a backflow pipeline, and an ORP is controlled through a backflow pipe: 300mv-500mv of Cu 2+ ＜1％；
S014 is a low copper ferric trichloride tank, which is connected with the feed inlet and the discharge outlet of the anode chamber of the electrolytic cell by a pipeline, a liquid phase circulating system is established, an ORP detector is also arranged on a backflow pipeline, and the backflow pipeline controls ORP: ORP800mv-1100mv 2+ ＜1％，TFe：8％－15％；
S015 is a tail gas absorption tower, the low-copper ferrous chloride solution passes through the tail gas absorption tower firstly, a small amount of chlorine generated by the electrolytic cell is absorbed, meanwhile, ferrous chloride is oxidized into ferric chloride, the absorption solution is sent to the anode of the electrolytic cell, and the tail gas can reach the standard and be discharged and the electrolysis energy consumption can be reduced;
s016 is a mixing tank, the ferric trichloride solution with high ORP from the electrolysis anode is mixed with the original ferric trichloride etching waste liquor after physical filtration according to a certain proportion, and the regenerated etching liquor which is suitable for the requirements of the etching line is mixed and sent to an etching production line;
wherein, the mixing ratio of the effluent of the anode chamber of the electrolytic cell and the filtered stock solution is as follows: volume ratio (3-10): 1, the standard of the regenerated etching solution is as follows: ORP:500-1000mv of Fe 2+ ＜1％，TFe：8％－14％，Cu 2+ ＜2％。
Example 1
The method is adopted to treat the ferric trichloride copper-containing etching waste liquid generated by a certain PCB enterprise, and the etching waste liquid contains 9.34 percent of acidity (calculated by HCl) and Cu 2+ ：6.4％，TFe：7.44％，Fe 3+ :5.86 percent and the specific gravity of 1.297g/cm 3 (ii) a According to the method of the invention, the processing steps are as follows:
s010, adding iron powder into the etching waste liquid stock solution according to the Fe content in the etching waste liquid 3+ In a molar ratio n (Fe) 3+ ): n (Fe) = (2-3): adding iron powder at the ratio of 1 to react and stirring.
S011, filtering the filtrate by a plate frame filter press, and then entering the next step.
S012, controlling the current density of the electrolysis system to be 1.5ASD for electrolysis at 30 ℃. Copper ions are deposited on the negative plate to form a copper plate, and the copper plate is stripped to obtain an electrolytic copper plate, wherein the mass fraction of the electrolytic copper plate is 99.5%.
S013, a low-copper ferrous chloride groove is connected with a feed inlet and a discharge outlet of a cathode chamber of the electrolytic cell through pipelines, a liquid phase circulating system is established, an ORP detector is arranged on a backflow pipeline, and an ORP is controlled through a backflow pipe: 430mv, cu 2+ ＜1％。
S014, connecting a low-copper ferric trichloride tank with a feed inlet and a discharge outlet of an anode chamber of an electrolytic cell by a pipeline, establishing a liquid phase circulating system, and arranging an ORP detector on a return pipeline. The anode chamber is an independent preferred anode box, an anion membrane is arranged on two sides of the anode box and is separated from the cathode chamber, and a plating anode plate is arranged in the anode box. The bottom of the anode box adopts a mode of directly facing the anode plate to inject liquid and bubbling air, so that the mass transfer rate of the anolyte on the anode plate is greatly enhanced. The anolyte is a mixed solution of low-copper ferrous chloride and low-copper ferric chloride from a tail gas absorption tower, and an ORP (oxidation-reduction potential) control pipe of the anolyte is controlled to be 700mv.
S016, a mixing tank, wherein the ferric trichloride solution with high ORP from the electrolysis anode and the original ferric trichloride etching waste liquid after physical filtration are mixed according to the volume ratio of 8:1, mixing the raw materials in a ratio of 1, mixing the raw materials to obtain regenerated etching solution which meets the requirements of an etching line, and conveying the regenerated etching solution to an etching production line.
Thus, the copper-containing etching waste liquor of ferric trichloride in example 1 is treated to obtain a plate-shaped electrolytic copper product with the mass fraction of 99.5 percentFrets and ORP:564mv of Fe 3+ ：9.52％，Fe 2+ ：0.43％，Cu 2+ :1.56% regenerated ferric chloride etching liquid product.
Wherein, the energy consumption comparison under the treatment of the two methods is as follows:
| processing method | Anode | Current Density/ASD | Average voltage/V | Copper/kg | Power consumption/kw.h.t -1 |
| Direct electrolysis | Common anode box | 1.5 | 3.18 | 86.2 | 7070.15 |
| The method of the invention | Preferred anode box | 1.5 | 2.21 | 80.5 | 4031.01 |
Compared with direct electrolysis, by adopting the method, the cell voltage is reduced from 3.18V to 2.21V, and the power consumption of each ton of copper is reduced from 7070.15kw.h to 4031.01kw.h.
Example 2
The method is adopted to treat the ferric trichloride copper-containing etching waste liquid generated by a certain PCB enterprise, and the etching waste liquid contains 2.38 percent of acidity (calculated by HCl) and Cu 2+ ％6.19％、TFe％13.46％、Fe 3+ %5.15% gravity 1.564; according to the method of the invention, the processing steps are as follows:
s010, adding iron powder into the etching waste liquid stock solution according to the Fe content in the etching waste liquid 3+ In a molar ratio n (Fe) 3+ ): n (Fe) = (2-3): adding iron powder at the ratio of 1 to react and stirring.
And S011, performing plate and frame filter pressing, and then enabling the filtrate to enter the next step.
S012, controlling the current density of the electrolysis system to be 2.0ASD for electrolysis at the temperature of 40 ℃. Copper ions are deposited on the negative plate to form a copper plate, and the copper plate is stripped to obtain an electrolytic copper plate, wherein the mass fraction of the electrolytic copper plate is 99.6%.
S013, a low-copper ferrous chloride groove is connected with a feed inlet and a discharge outlet of a cathode chamber of the electrolytic cell through pipelines, a liquid phase circulating system is established, an ORP detector is arranged on a backflow pipeline, and an ORP is controlled through a backflow pipe: 350mv, cu 2+ ＜1％。
S014, connecting a low-copper ferric trichloride tank with a feed inlet and a discharge outlet of an anode chamber of an electrolytic cell by a pipeline, establishing a liquid phase circulating system, and arranging an ORP detector on a return pipeline. The anode chamber is an independent preferred anode box, anion membranes are arranged on two sides of the anode box and are separated from the cathode chamber, and a plating anode plate is arranged in the anode box. The bottom of the anode box adopts a mode of directly injecting liquid inlet to the anode plate and bubbling air, so that the mass transfer rate of the anolyte on the anode plate is greatly enhanced. The anolyte is a mixed solution of low-copper ferrous chloride and low-copper ferric chloride from a tail gas absorption tower, and an anolyte return pipe ORP is controlled to be 1000mv.
S016, a mixing tank, namely mixing the ferric trichloride solution with high ORP from the electrolysis anode with the physically filtered ferric trichloride etching waste liquid according to a volume ratio of 4:1, mixing the raw materials in a ratio of 1, mixing the raw materials to obtain regenerated etching solution which meets the requirements of an etching line, and conveying the regenerated etching solution to an etching production line.
Thus, the ferric trichloride copper-containing etching waste liquid obtained in example 2 is treated by the method to obtain a plate-shaped copper product with the mass fraction of 99.6%, and the obtained parameter is Fe 3+ ％：13.23％，Fe 2+ ％：1.03％，Cu 2+ Percent: 1.32% regenerated ferric chloride etching liquid product
Wherein, the energy consumption comparison under two methods:
while the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A regeneration method for extracting copper from ferric trichloride copper-containing etching waste liquid is characterized by comprising the following steps:
s010, transferring the etching waste liquid into a stirring reduction cylinder, adding iron powder, and adding Fe 3+ Reduction to Fe 2+ ；
S011, filtering after the reaction is finished to obtain a high-copper ferrous chloride solution, wherein the solution components of the high-copper ferrous chloride solution are controlled to be Cu 2+ ％2－6％，TFe％8－15％，Fe 3+ ＜1％；
S012, mixing the high-copper ferrous chloride solution with the low-copper ferrous chloride in the low-copper ferrous chloride tank, and then introducing the mixture into a cathode chamber of an electrolytic tank, wherein a feed inlet and a discharge outlet of the cathode chamber of the electrolytic tank are connected with a feed inlet and a discharge outlet of the low-copper ferrous chloride tank through a pipeline, and a liquid phase circulating system is established; electrolyzing to deposit copper ions on the cathode plate to obtain a copper plate;
s013, connecting a feed inlet and a discharge outlet of the anode chamber of the electrolytic cell with a feed inlet and a discharge outlet of the low-copper ferric trichloride cell through pipelines, and establishing a liquid phase circulating system;
s014, the anolyte in the anode chamber of the electrolytic tank is a mixed solution of low-copper ferrous chloride in the tail gas absorption tower and low-copper ferric trichloride in the low-copper ferric trichloride tank; electrolyzing to obtain a ferric trichloride solution with high ORP;
s015, mixing: and (4) mixing the high OPR ferric trichloride solution from the electrolysis anode with the high copper ferric trichloride solution obtained in the step (S11) according to a certain proportion, and mixing to obtain a regenerated etching solution suitable for the requirements of etching lines.
2. The method for recovering copper from the copper-containing etching waste liquid of ferric trichloride according to claim 1, wherein the method comprises the following steps: the adding amount of the iron powder in the S010 is determined by the Fe in the etching waste liquid 3+ In a molar ratio of n (Fe) 3+ ): n (Fe) = (2-3): 1 in a ratio of 1.
3. The method for recovering copper from the copper-containing etching waste liquid of ferric trichloride according to claim 2, wherein the method comprises the following steps: the electrolysis reaction condition in S012 is current density 1.5-2.5ASD, temperature 20-50 ℃.
4. The method for recovering copper from the copper-containing etching waste liquid of ferric trichloride according to claim 3, wherein the method comprises the following steps: an ORP detector is arranged on a backflow pipeline of the cathode chamber of the electrolytic cell in S012, and the backflow pipeline controls ORP:300mv-500mv of Cu 2+ ＜1％。
5. The method for recovering copper from the copper-containing etching waste liquid of ferric trichloride according to claim 4, wherein the method comprises the following steps: an ORP detector is arranged on a return pipe of the anode chamber of the electrolytic cell in S013, and the ORP is controlled by the return pipe: ORP800mv-1100mv 2+ ＜1％，TFe：8％－15％。
6. The method for recovering copper from the copper-containing etching waste liquid of ferric trichloride according to claim 5, wherein the method comprises the following steps: in S015, the high OPR ferric trichloride solution and the high copper ferric trichloride solution are mixedVolume ratio (3-10): 1, the effluent standard of the regenerated etching solution is as follows: ORP:500-1000mv of Fe 2+ ＜1％，TFe：8％－14％，Cu 2+ ＜2％。
7. The method for recovering copper from the copper-containing etching waste liquid of ferric trichloride according to any of claims 1 to 6, wherein: the low-copper ferrous chloride and the low-copper ferric trichloride are Cu 2+ < 1% solution.
8. The method for recovering copper from the copper-containing etching waste liquid of ferric trichloride according to any of claims 1 to 6, characterized by comprising the following steps: the electrolytic cell anode chamber is provided with an anode box, two sides of the anode box are provided with anion membranes which are separated from the cathode chamber, a plating anode plate is arranged in the anode box, and air is introduced into the bottom of the anode box in a mode of directly facing the anode plate to inject liquid and bubble air so as to enhance the mass transfer speed of the anode liquid on the anode plate.
9. The method for extracting copper from the ferric trichloride copper-containing etching waste liquid according to claim 8, which is characterized in that: an air inlet groove is formed in the bottom of the anode box, a plurality of air exposure ports are formed in the air inlet groove, and an air inlet communicated with the air inlet groove is formed in the side wall of the anode box; the bottom of the anode box is provided with a liquid inlet pipe, the liquid inlet pipe is provided with a plurality of liquid outlets, and the side wall of the anode box is provided with a liquid inlet communicated with the liquid inlet pipe.
10. The method for recovering copper from the copper-containing etching waste liquid of ferric trichloride according to claim 9, wherein the method comprises the following steps: the position of the liquid inlet pipe is higher than that of the air inlet groove.
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| JPH1112768A (en) * | 1997-06-25 | 1999-01-19 | Astec Irie:Kk | Method for regenerating waste iron chloride-base liquid etchant |
| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
| CN103936081B (en) * | 2013-01-21 | 2015-07-08 | 解付兵 | Method and system for preparing ferric chloride, electrodeposited copper and copper powder from copper-containing hydrochloric acid waste liquid |
| CN105177583B (en) * | 2015-09-09 | 2018-05-08 | 成都虹华环保科技股份有限公司 | A kind of zero-emission acidic etching waste liquid circulation regeneration method and system |
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