CN114606497B - Ferric trichloride etching solution treatment and regeneration circulation process method - Google Patents
Ferric trichloride etching solution treatment and regeneration circulation process method Download PDFInfo
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- CN114606497B CN114606497B CN202210105394.1A CN202210105394A CN114606497B CN 114606497 B CN114606497 B CN 114606497B CN 202210105394 A CN202210105394 A CN 202210105394A CN 114606497 B CN114606497 B CN 114606497B
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- 238000005530 etching Methods 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 51
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 title claims abstract description 30
- 238000011069 regeneration method Methods 0.000 title claims description 31
- 230000008929 regeneration Effects 0.000 title claims description 30
- 238000000605 extraction Methods 0.000 claims abstract description 75
- 239000010949 copper Substances 0.000 claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- 239000012071 phase Substances 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 230000001172 regenerating effect Effects 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000003860 storage Methods 0.000 claims abstract description 9
- 239000008346 aqueous phase Substances 0.000 claims abstract description 7
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 229910001431 copper ion Inorganic materials 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 229910001447 ferric ion Inorganic materials 0.000 claims description 5
- -1 iron ions Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000460 chlorine Substances 0.000 abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 abstract description 15
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 56
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 19
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses a process method for treating and regenerating ferric trichloride etching solution, which mainly comprises the following steps of (1) overflowing the ferric trichloride etching solution of a production line to an etching waste solution storage barrel; (2) The etching waste liquid storage barrel is connected with the extraction tank, the cyclic extraction is carried out, the extracted aqueous phase low copper etching liquid is conveyed to the oxidation tank, and the low copper etching liquid after oxidation is returned to the production line; (3) The oil phase enters a water washing section, sulfuric acid solution is introduced into the oil phase after water washing for back extraction, water after back extraction is introduced into an electrolytic tank for electrolysis, and oxygen generated by electrolysis is introduced into an oxidation tank in the step (2); (4) And introducing the oil phase after back extraction into an extraction tank to carry out the extraction process again. The whole process flow of the invention does not introduce any oxidant, can greatly reduce the cost, and does not generate unsafe factors caused by chlorine during electrolysis.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a treatment and regeneration circulation process method of ferric trichloride etching waste liquid in the PCB production process.
Background
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 the PCB. Along with the continuous development of miniaturization, light weight, high speed and multifunction of electronic products, the attention of the PCB industry on high-precision and high-density circuits is increasing. In the circuit manufacturing process, etching is a process which is critical for realizing circuit patterns after pattern transfer, the quality level and the yield of products are directly determined, and the control of the etching process is a key for ensuring the quality and the performance of the whole PCB.
Since the 60 s of the 20 th century, etching solutions have been updated and improved in various types, mainly including ferric chloride etching solutions, ammonium persulfate etching solutions, sulfuric acid/chromic acid etching solutions, sulfuric acid/hydrogen peroxide etching solutions, alkaline cupric chloride etching solutions, acidic cupric chloride etching solutions, and the like. The method gradually exits from the market due to the problems of difficult regeneration of ferric trichloride etching solution and difficult and large waste liquid treatment capacity. Ammonium persulfate etching solutions and chromium-containing etching solutions and sulfuric acid hydrogen peroxide system etching solutions are not accepted in the market due to the problems of difficult regeneration or toxicity. The acid copper chloride etching system has the advantages of high etching speed, good stability, uniform etching, small side etching, easy regeneration and the like, and the alkaline copper chloride etching system has the characteristics of high copper dissolution, small test, high etching rate and easy control of the etching rate, meets the etching requirements of the current printed circuit board, and is the two etching solutions which are most widely applied at present. However, the acid-base copper chloride system etching solution has high ammonia nitrogen content, secondary pollution caused by ammonia nitrogen wastewater can be generated in the use process, and the resource waste caused by using an oxidant and hydrochloric acid in regeneration or the safety risk caused by chlorine oxidation generated by regeneration cycle electrolysis can be caused.
Chinese patent CN109161895B provides a copper recovery and regeneration system and recovery and regeneration method for acid copper chloride etching solution, and relates to the technical field of etching solution cyclic regeneration. The copper recovery and regeneration system of the acidic copper chloride etching solution comprises an etching solution regeneration system, a waste gas treatment system positioned at the downstream of the etching solution regeneration system and a molten iron washing solution treatment system; the method for recycling and regenerating the copper of the acidic copper chloride etching solution effectively solves the problems of high energy consumption, low recycling rate, high content of cathode copper impurities, secondary pollution of chlorine and the like of the existing recycling and regenerating cycle of the acidic copper chloride etching solution, and provides technical support for the comprehensive application of the electrolytic recycling and regenerating technology of the acidic copper chloride etching solution. The process is a copper chloride etching waste liquid treatment system, the regenerated etching liquid is an electrolytic chlorine oxidation system, and the environmental safety risk coefficient is high.
Chinese patent CN106119852a, an electrolytic recovery and regeneration process for acid copper chloride etching solution, discloses an electrolytic recovery and regeneration process for acid copper chloride etching solution, comprising the following steps: (1) Using acids with addition of iron ionsEtching the circuit board by using the acidic copper chloride etching solution, and controlling the oxidation-reduction potential of the etching solution to be between 360 and 700 mV; (2) Introducing etching waste liquid generated in the step (A) into an electrolytic tank for electrolysis; (3) Under the action of oxidation-reduction potential of electrolyte, the chlorine generated by electrolysis oxidizes the electrolyte in the electrolytic tank to dissolve the chlorine in the electrolyte; (4) After chlorine in the third step is dissolved in the electrolyte, namely Fe in the electrolyte 2+ And Cu+ oxidation to Fe 3+ And Cu 2+ After the chlorine is completely dissolved in the electrolyte, the electrolyte is regenerated into etching solution after the oxidation step is completed; (5) And (3) introducing the oxidized electrolyte obtained in the step (c) onto an etching production line for recycling. The process can absorb most of chlorine generated in the process of consuming electrolysis, ensure safe production and protect environment. The etching system is a copper chloride system, iron is used as a catalyst, the electrolysis generates chlorine to oxidize during regeneration, so that higher environmental safety risks are brought, the diaphragm electrolysis resistance is high, the energy consumption is high, and the cathode copper deposition is seriously influenced by the reverse corrosion during electrolysis due to diaphragm breakage; the ferric iron at the cathode discharges to generate ferrous iron during electrolysis, and then the ferrous iron needs to be reoxidized, so that the energy consumption is increased.
Chinese patent CN111394726B discloses an acid etching solution recycling process, which uses an acid etching solution recycling system, and comprises an etching line (4), an electrolytic cell (30), a circulating tank (20), a chlorine absorption and reuse tower (10), a mother solution storage barrel (5) and a regeneration solution storage barrel (6). The specific process steps are described in the specification. The process of the invention well realizes the on-line circulation and regeneration of the etching waste liquid by the arrangement of the system and the control of the process parameters of each part in the system, has high degree of automation, simple system operation and maintenance, does not influence the production in the installation and the debugging, has zero emission and protects the environment. The method also has a large environmental safety risk coefficient due to absorption oxidation of chlorine generated by electrolysis during regeneration.
Disclosure of Invention
The invention aims to provide a process method for treating and regenerating ferric trichloride etching solution with low treatment cost and less pollution
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a process method for treating and regenerating ferric trichloride etching solution comprises the following steps:
(1) Overflowing the ferric trichloride etching solution of the production line to an etching waste liquid storage barrel;
(2) The etching waste liquid storage barrel is connected with the extraction tank for cyclic extraction, the extractant is added, stirring and mixing are carried out, copper ions and iron ions are separated, copper ions are extracted, then standing and layering are carried out, the extracted aqueous phase low copper etching liquid is conveyed to the oxidation tank, and the low copper etching liquid is returned to the production line after oxidation;
(3) The oil phase enters a water washing section, sulfuric acid solution is introduced into the oil phase after water washing for back extraction, copper ions are back extracted from an extracting agent, water after back extraction is introduced into an electrolytic tank for electrolysis, oxygen generated by electrolysis is introduced into an oxidation tank in the step (2) for oxidizing ferrous ions in low-copper etching solution into ferric ions;
(4) And introducing the oil phase after back extraction into an extraction tank to carry out the extraction process again.
Preferably, the extractant in the step (2) is one or more of ad100, N902 and M5640H, CLX50, the extraction time is 1min-10min, and the stirring rotation speed is 0-2000r/min.
Preferably, the oil phase is 1:1 to 1:5 compared with water during the extraction in the step (2).
Preferably, the copper content of the aqueous phase after extraction in step (2) is less than 20g/l.
Preferably, the sulfuric acid concentration used in step (3) is 1-4 mol/l, and the stripping oil phase used is 1:1-1:3 of water phase.
Preferably, the water phase after back extraction in the step (3) is a copper sulfate solution with copper concentration of 5-40 g/l.
Preferably, the current density in the electrolysis in the step (3) is 0.5-4asd.
Preferably, the reaction pressure of the oxidation tank in the step (2) is 0.06-0.2Mpa, the temperature is 80-100 ℃, and the method further comprises adding a catalyst into the oxidation tank, wherein the catalyst is one or more of sodium nitrite and nitric acid, and the addition amount of the catalyst is 0-0.06%.
By using the ferric trichloride etching solution treatment process, ammonia nitrogen is not contained, wastewater containing the ammonia nitrogen cannot be generated in the DES etching section after water washing, copper and iron separation is carried out after etching through extraction, and the ferric trichloride etching solution is regenerated through oxygen oxidation. The extraction section is used for carrying out water washing on the extracted copper-containing extractant, then sulfuric acid is used for back-extracting copper in the extractant, and then electrolysis is carried out to obtain electrodeposited pure copper; the regeneration section will use oxygen oxidation, and oxidation rate is fast, can guarantee the ferric iron content that the production line is high, guarantees the etching rate of production line, promotes the etching quality of product. The whole process flow does not introduce any oxidant.
The method has the advantages that the etching solution is free of ammonia nitrogen components by utilizing the high oxidation-reduction potential etching of the ferric trichloride, and the extraction agent with large iron-copper separation and the method for efficiently oxidizing and regenerating the ferric trichloride are used, so that the etching efficiency can be effectively improved, the generation of ammonia nitrogen wastewater is stopped, the secondary pollution is reduced, the safety risk caused by the oxidation and regeneration of chlorine generated by electrolysis is reduced, and the method has remarkable economic and social benefits.
Drawings
FIG. 1 is a schematic flow chart of the treatment process 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 scope of protection of the present invention is not limited.
Referring to fig. 1, the invention aims to solve the problem of secondary pollution caused by ammonia nitrogen wastewater in the waste liquid of the copper chloride etching liquid system of the pcb etching section and the problem of chlorine leakage risk during oxidation of regenerated chlorine gas in the copper chloride etching liquid system at present, and provides a method for treating and regenerating the waste liquid of the ferric chloride etching liquid system. The treatment process can obviously reduce the environmental protection problem of ammonia nitrogen wastewater treatment brought in the use process of the etching solution and the safety problem of improving the leakage risk of the chlorine oxidation zone, and brings good economic and social benefits for PCB manufacturers.
The invention aims to provide a process for recycling and regenerating etching waste liquid of a printed circuit board and extracting copper, which has the advantages of no ammonia nitrogen waste water generation, no chlorine gas generation, simple process, safety and environmental protection.
The specific embodiment is as follows:
(1) Etching solution with copper ion concentration of 10-60 g/l and iron ion concentration of 100-180g/l is subjected to extraction process section to separate copper from iron;
(2) In the extraction process section, an extractant with high copper-iron separation coefficient is added, stirred and mixed, and then the mixture is stood for layering. The ratio of the oil phase to water is 1:1-1:5, the extractant is one or more of ad100, N902 and M5640H, CLX, the extraction time is 1min-10min, and the stirring rotation speed is 0-2000r/min;
(3) After layering, the upper oil phase enters a water washing section, the lower water phase enters an etching solution storage barrel for cyclic extraction, and the copper content can be reduced to below 10 g/l-20 g/l through tertiary cyclic extraction through experimental tests, so that the copper-iron separation effect is achieved;
(4) Washing the oil phase to remove water phase which is not completely layered and other impurity anions carried in the oil phase, wherein the anions comprise chloride ions;
(5) After the water washing is finished, the oil phase is introduced into sulfuric acid solution for back extraction, the concentration of the sulfuric acid is 1-4 mol/l, and the back extraction can be completed after the back extraction is carried out twice through experimental tests. The ratio of the back extraction oil to the water phase is 1:1-1:3;
(6) The oil phase after back extraction is subjected to further standing delamination, then is introduced into an extraction section for re-extraction, and the purpose of the further standing delamination is to prevent the oil phase from carrying sulfuric acid into etching liquid, wherein the standing time is 1-10min;
(7) And circulating the water phase after back extraction with a transfer circulation tank in an electrolytic tank, and depositing the copper ions after back extraction on a cathode plate in an electrodeposition mode. The copper concentration of the back extraction solution is 5-40g/l of copper sulfate solution, and the current density is 0.5-4asd during electrolysis;
(8) Introducing the etching solution after copper and iron separation in the step (2) into an oxidation kettle for oxidation; the purpose is that the etching solution after use contains a large amount of ferrous ions, and the ferrous ions are required to be oxidized for regeneration. The oxidized oxygen used is derived from oxygen generated by the electrolysis anode; the pressure is 0.06-0.2Mpa, the temperature is 80-100 ℃, the catalyst is one or more of sodium nitrite and nitric acid, and the adding amount of the catalyst is 0-0.06%;
(9) The oxidized etching liquid can be recycled to a production line to reduce the content of copper ions, improve the content of ferric ions and increase the etching speed and etching rate. The effect of on-line regeneration circulation, zero discharge and zero increment of wastewater is achieved by the circulation.
Example 1
(1) The parameters of the etching solution, namely copper ion content 40g/l, iron ion content 130g/l and acidity 1N, are extracted by an extraction tank, and compared with the oil phase: the water phase is 1:2, the extraction time is 5min, the copper content of raffinate after extraction is 28g/l, and the iron content is 130g/l. The extractant is an ad100 and CLX50 mixed extractant;
(2) Introducing raffinate into a water washing section of the extraction tank for water washing, and carrying out oil phase: aqueous phase 1:1;
(3) Extracting with water to obtain extract oil with copper content of more than 20g/l, re-circulating extraction, extracting with copper content of 19.4g/l and iron content of 129.4g/l under the extraction condition of (1), and washing with water;
(4) Introducing the raffinate obtained in the step (3) into an oxidation kettle, and introducing the extract oil obtained in the step (2) and the extract oil obtained in the step (3) into a back extraction section for back extraction, wherein the back extraction liquid is sulfuric acid solution with the concentration of 2 mol/l;
(5) Adding a catalyst into the oxidation kettle at the temperature of 80 ℃ and the pressure of 0.1Mpa to perform catalytic oxidation of ferric trichloride, wherein the catalyst is sodium nitrate, the catalytic oxidation speed of the oxidation kettle is 1M3/H, and the oxygen transmission speed is 3.5M3/H;
(6) Introducing the extracted oil in the step (4) into a back extraction section, and back extracting an oil phase: the water phase is 1:1, the copper content of the strip raffinate is 10.2g/l, the copper ions in the extractant are not completely stripped completely by the primary stripping, the secondary stripping is carried out, and the copper content of the strip raffinate after the secondary stripping is 1.67g/l;
(7) The back-extracted sulfuric acid solution after back extraction is subjected to electrolysis to extract copper by starting an electrolytic tank power supply until the copper content is more than 20g/l, the current density is 1.5ASD, the current efficiency reaches 98.4%, the power consumption is 1300kwh/T copper, and the recovered copper content is 99.92%;
(8) Testing the ferric ion content of the oxidized regenerated etching solution of (5) to 128.7g/l, the ferrous iron content to 0.06g/l and the copper content to 18.9g/l, and recovering the etching performance of ferric trichloride.
Example 2
(1) The parameters of the etching solution, namely copper ion content of 30g/l, iron ion content of 130g/l and acidity of 1N, are extracted by an extraction tank, and compared with the oil phase: the water phase is 1:2, the extraction time is 5min, the copper content of raffinate after extraction is 19g/l, and the iron content is 130g/l. The extractant is an ad100 and CLX50 mixed extractant;
(2) Introducing raffinate into a water washing section of the extraction tank for water washing, and carrying out oil phase: aqueous phase 1:1;
(3) Recycling extraction of raffinate after extraction in the step (1), and washing the extracted oil according to the extraction condition in the step (1), wherein the copper content of the extracted raffinate is 9.4g/l, the iron content is 130 g/l;
(4) Introducing the raffinate obtained in the step (3) into an oxidation kettle, and introducing the extract oil obtained in the step (2) and the extract oil obtained in the step (3) into a back extraction section for back extraction, wherein the back extraction liquid is sulfuric acid solution with the concentration of 2 mol/l;
(5) Adding a catalyst into the oxidation kettle at the temperature of 90 ℃ and the pressure of 0.1Mpa to perform catalytic oxidation of ferric trichloride, wherein the catalyst is sodium nitrate, the catalytic oxidation speed of the oxidation kettle is 1.8M3/H, and the oxygen conveying speed is 4m < 3 >/H;
(6) Introducing the extracted oil in the step (4) into a back extraction section, and back extracting an oil phase: the water phase is 1:1, the copper content of the back extraction raffinate is increased from 22.3g/l to 32.8g/l, copper ions in the extractant are not completely back extracted by primary back extraction, secondary back extraction is carried out, and the copper content of the raffinate after the secondary back extraction is increased from 28.7g/l to 29.4g/l;
(7) The back extraction liquid circulates with the electrolyte of the electrolytic tank, and the power supply of the electrolytic tank is started to carry out electrolytic copper extraction, the current density is 2ASD, the current efficiency reaches 96.7%, the power consumption is 1420kwh/T copper, and the recovered copper content is 99.95%;
(8) Testing the ferric ion content of the oxidized regenerated etching solution of (5) to be 126.8g/l, the ferrous iron content to be less than 0.1g/l and the copper content to be 9g/l, and recovering the etching performance of ferric trichloride.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (10)
1. A process method for treating and regenerating ferric trichloride etching liquid is characterized by comprising the following steps:
(1) Overflowing the ferric trichloride etching solution of the production line to an etching waste liquid storage barrel;
(2) The etching waste liquid storage barrel is connected with the extraction tank for cyclic extraction, the extractant is added, stirring and mixing are carried out, copper ions and iron ions are separated, copper ions are extracted, then standing and layering are carried out, the extracted aqueous phase low copper etching liquid is conveyed to the oxidation tank, and the low copper etching liquid is returned to the production line after oxidation;
(3) The oil phase enters a water washing section, sulfuric acid solution is introduced into the oil phase after water washing for back extraction, copper ions are back extracted from an extracting agent, water after back extraction is introduced into an electrolytic tank for electrolysis, oxygen generated by electrolysis is introduced into an oxidation tank in the step (2) for oxidizing ferrous ions in low-copper etching solution into ferric ions;
(4) And introducing the oil phase after back extraction into an extraction tank to carry out the extraction process again.
2. The process of ferric trichloride etching solution treatment and regeneration cycle of claim 1, wherein: the extractant in the step (2) is one or more of ad100, N902 and M5640 and H, CLX, the extraction time is 1min-10min, and the stirring rotation speed is 0-2000r/min.
3. The process of treating and regenerating ferric trichloride etching solution according to claim 2, wherein: the oil phase is 1:1-1:5 compared with water during the extraction in the step (2).
4. A process for treating and regenerating a ferric chloride etching solution according to claim 3, wherein: the copper content in the aqueous phase after extraction in step (2) is lower than 20g/l.
5. The process of ferric trichloride etching solution treatment and regeneration cycle of claim 1, wherein: the concentration of sulfuric acid used in the step (3) is 1-4 mol/l, and the water phase of the used stripping oil is 1:1-1:3.
6. The process of ferric trichloride etching solution treatment and regeneration cycle of claim 1, wherein: the water phase after back extraction in the step (3) is copper sulfate solution with copper concentration of 5-40 g/l.
7. The process of ferric trichloride etching solution treatment and regeneration cycle of claim 1, wherein: the current density in the electrolysis in the step (3) is 0.5-4asd.
8. The process of ferric trichloride etching solution treatment and regeneration cycle of claim 1, wherein: the reaction pressure of the oxidation tank in the step (2) is 0.06-0.2Mpa, and the temperature is 80-100 ℃.
9. The process of ferric trichloride etching solution treatment and regeneration cycle of claim 1, wherein: and (2) adding a catalyst into the oxidation tank, wherein the catalyst is one or two of sodium nitrite and nitric acid.
10. The process of ferric chloride etching solution treatment and regeneration cycle as recited in claim 9, wherein: the addition amount of the catalyst is 0-0.06%.
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