CN110408938B - Etching solution recycling process - Google Patents
Etching solution recycling process Download PDFInfo
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- CN110408938B CN110408938B CN201910752735.2A CN201910752735A CN110408938B CN 110408938 B CN110408938 B CN 110408938B CN 201910752735 A CN201910752735 A CN 201910752735A CN 110408938 B CN110408938 B CN 110408938B
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- 238000005530 etching Methods 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 73
- 230000008569 process Effects 0.000 title claims abstract description 64
- 238000004064 recycling Methods 0.000 title claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 215
- 238000005342 ion exchange Methods 0.000 claims abstract description 161
- 239000010949 copper Substances 0.000 claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052802 copper Inorganic materials 0.000 claims abstract description 71
- 238000005273 aeration Methods 0.000 claims abstract description 70
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 61
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 60
- 239000002699 waste material Substances 0.000 claims abstract description 56
- 239000000706 filtrate Substances 0.000 claims abstract description 54
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012452 mother liquor Substances 0.000 claims abstract description 40
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 40
- 238000004537 pulping Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000002378 acidificating effect Effects 0.000 claims abstract description 20
- 238000003825 pressing Methods 0.000 claims abstract description 20
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 19
- 239000012065 filter cake Substances 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 238000005086 pumping Methods 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 14
- 208000005156 Dehydration Diseases 0.000 claims abstract description 13
- 230000018044 dehydration Effects 0.000 claims abstract description 13
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 81
- 230000007246 mechanism Effects 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 230000008929 regeneration Effects 0.000 claims description 22
- 238000011069 regeneration method Methods 0.000 claims description 22
- 238000012546 transfer Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 19
- 239000002351 wastewater Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 13
- 238000005192 partition Methods 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000011001 backwashing Methods 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 abstract description 8
- 239000011343 solid material Substances 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- -1 sulfur ions Chemical class 0.000 description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Removal Of Specific Substances (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention relates to the field of etching solution recovery, in particular to a process for recycling etching solution, which comprises the following steps: carrying out primary hydrogen peroxide treatment on the acidic copper-containing etching waste liquid, carrying out acid-base neutralization treatment on the acidic copper-containing etching waste liquid and the alkaline copper-containing etching waste liquid, and then carrying out filter pressing to generate a filter cake and a filtrate; pulping the filter cake, adding 98% sulfuric acid to generate copper sulfate, water and hydrochloric acid, performing centrifugal dehydration treatment after copper sulfate crystallization to generate copper sulfate pentahydrate and copper sulfate mother liquor, precipitating filtrate, conveying the precipitated filtrate to an ion exchange tank for ion exchange, conveying the waste liquor to a stirring barrel, adding a proper amount of solid materials, stirring to fully mix and dissolve the solid materials, and pumping the etching solution and the tin stripping solution into a storage tank respectively after production is finished; the process can replace copper ions in the copper-containing etching waste liquid with high efficiency through the steps of ion exchange, oxidation aeration and ion exchange, thereby preparing the regenerated etching liquid, and simultaneously can generate a byproduct of copper sulfate pentahydrate, thereby having high economic value.
Description
Technical Field
The invention relates to the field of etching solution recovery, in particular to a process for recycling etching solution.
Background
The Printed Circuit Board (PCB) industry is the basis of the electronic industry, the information industry and the household appliance industry, and the PCB industry, one of the heavy pollution industries, has been shifted to china in recent 20 years, so that the PCB industry in china has been kept at a growth rate of more than 10% in recent years. At present, about 3000 PCB enterprises in various scales exist in China, the annual output reaches more than 2 hundred million square meters, the consumption of refined copper is more than 10 million tons every year, the total copper content in the produced etching waste liquid is more than 5 million tons, and the method poses serious threat and harm to the environment of China, particularly the water resource environment in the peripheral areas of PCB plants. The etching production line is a process with large drug water consumption in PCB production, and is also a process with the largest generation of waste liquid (namely dangerous waste-waste etching liquid, named HW22 according to waste classification of national Central office for environmental protection) and waste water (namely primary washing waste water and secondary washing waste water). Generally, about 2 to 3 liters of etching solution is consumed per one square meter of a double-sided board having a normal thickness (18 μm) produced, and 2 to 3 liters of waste etching solution, 5 to 10 liters of primary washing waste water, and 8 to 12 liters of secondary washing waste water are discharged. The current practice is to periodically or irregularly discharge part of the mother solution with high copper content, namely the waste etching solution, from the etching bath, and simultaneously add new etching solution into the mother solution. The optimal etching copper ion concentration of the etching solution is 100-140 g/L, and when the waste liquid is discharged, the higher the copper ion concentration is better (usually 150-160 g/L), so as to improve the utilization rate of the etching solution as much as possible and reduce the total usage amount of the solution. Therefore, the etching solution is not in its optimum state in actual production, regardless of whether the manual intermittent discharge process or the continuous discharge process of specific gravity control is employed. The current practice is disadvantageous to PCB enterprises in terms of economic cost.
The current practice of alkaline etching waste liquid is to store it in various printing plate factories and place it in sealed pools or storage tanks to wait for the removal of the waste liquid from the outside. The other units are qualified recovery companies which are generally examined and approved by local environmental protection departments, and the recovery companies recover the copper in the waste liquid by using a chemical method (a neutralization method, an electrolysis method and a replacement method) or refine the copper into a copper sulfate product after drawing back the waste liquid. The traditional copper removal purification method is that sodium sulfide solution is added into neutralization pressure filtrate, and sulfur ions react with copper ions to generate insoluble copper sulfide solid precipitate, so that the copper ions in the copper sulfide solid precipitate are removed. However, in the actual production process, the amount of sodium sulfide added is less, the copper removal is not clean, the amount of hydrogen sulfide gas which can generate irritant odor is more, and the precipitated copper sulfide sludge belongs to dangerous waste and is treated by special dangerous waste treatment enterprises, so that the cost is higher. The methods have the disadvantages of backward process, incomplete copper recovery, unobvious economic benefit of treatment and secondary pollutant discharge. Particularly, alkaline etching has a large amount of ammonia ions, and once the ammonia ions are improperly treated and discharged, the ammonia ions have great impact on the water body ecosystem.
Chinese patent CN106119853A discloses a high-efficiency zero-emission waste acidic copper etching solution recovery and regeneration system, which comprises a copper electrolysis recovery device and a regeneration device, wherein chlorine generated in the process of recovering electrolytic copper is used as an oxidant, the chlorine is directly absorbed by the waste etching solution as the oxidant without being discharged, and the element balance of the acidic copper etching solution is maintained without adding an additional oxidant. The structure is simple and reasonable in design, pollution-free, safer, low in maintenance cost, low in requirements on equipment and personnel, further saves cost and is convenient for product popularization.
The system disclosed in this patent is capable of recovering chlorine and copper, but the reaction results in copper chloride, which is of little economic value and generally of low economic success.
Disclosure of Invention
The invention aims to provide a process for recycling etching solution, which can replace copper ions in copper-containing etching waste liquid with high efficiency through the steps of ion exchange, oxidation aeration and ion exchange so as to prepare regenerated etching solution, can generate a byproduct of copper sulfate pentahydrate, and has high economic value.
In order to achieve the purpose, the invention adopts the following technical scheme:
the provided 1. a process for recycling etching solution is characterized by comprising the following steps:
firstly, carrying out primary hydrogen peroxide treatment on the acidic copper-containing etching waste liquid to convert monovalent copper in the waste liquid into divalent copper;
step two, carrying out acid-base neutralization treatment on the acidic copper-containing etching waste liquid and the alkaline copper-containing etching waste liquid in a neutralization reaction tank;
thirdly, performing filter pressing on the neutralized solution through a filter press to generate a filter cake and filtrate;
fourthly, carrying out filter cake pulping on the filter cake generated by filter pressing through a pulping machine;
step five, adding 98% sulfuric acid into the solution generated by pulping in an acid dissolution reaction kettle to perform acid dissolution reaction to generate copper sulfate, water and hydrochloric acid, and then cooling the acid dissolution reaction kettle;
step six, enabling the copper sulfate solution to enter a crystallization tank for crystallization;
step seven, carrying out centrifugal dehydration treatment on the copper sulfate crystals and water through a centrifugal dehydrator to generate copper sulfate pentahydrate and copper sulfate mother liquor, shunting the copper sulfate mother liquor separated from the centrifugal dehydrator through a copper sulfate mother liquor circulating device, conveying the low-chlorine copper sulfate mother liquor to a beater, and conveying the high-chlorine copper sulfate mother liquor separated from the centrifugal dehydrator to a neutralization reaction tank;
step eight, precipitating the filtrate generated in the filter pressing process in a filtrate precipitation tank, and conveying the precipitate to a filter press;
step nine, conveying the filtrate to an ion exchange tank, and performing ion exchange through an ion exchange column;
step ten, conveying the waste liquid generated after ion exchange into a stirring barrel, adding a proper amount of solid materials, stirring to fully mix and dissolve the solid materials, and pumping the etching solution and the tin stripping solution into a storage tank respectively after production is finished;
and eleventh, carrying out backwashing regeneration on the ion exchange column through hydrochloric acid, and conveying the generated regeneration wastewater to a neutralization reaction tank.
As a preferable scheme of the etching solution recycling process, between the step nine and the step ten, the method further comprises the following steps of:
step 9.1, pumping the filtrate into an aeration type ion exchange device, and carrying out secondary hydrogen peroxide treatment on the filtrate generated after primary ion exchange to convert monovalent copper in the filtrate into divalent copper;
step 9.2, removal of excess H by aeration2O2；
And 9.3, carrying out secondary ion exchange.
As a preferred scheme of the etching solution recycling process, the copper sulfate mother solution circulating device in the third step comprises a circulating tank, a liquid transfer mechanism, a liquid inlet pipe, a first liquid outlet pipe, a second liquid outlet pipe and a circulating device controller, wherein a separating mechanism for separating the circulating tank into a first tank cavity and a second tank cavity is arranged in the circulating tank, and the top end of the separating mechanism is not in contact with the top end of the inner wall of the circulating tank;
the input end of the liquid transferring mechanism is communicated with the bottom end of the first tank cavity, the output end of the liquid transferring mechanism is communicated with the top end of the second tank cavity, the height of the output end of the liquid transferring mechanism is lower than that of the separating mechanism, and a first electromagnetic valve is installed at the joint of the circulating tank and the liquid transferring mechanism;
the centrifugal dehydrator is communicated with the top end of the first tank cavity through a liquid inlet pipe;
the bottom end of the second tank cavity is communicated with the pulping machine through a first liquid outlet pipe, and a second electromagnetic valve is installed at the joint of the circulating tank and the first liquid outlet pipe;
the bottom end of the second tank cavity is communicated with the neutralization reaction tank through a second liquid outlet pipe, and a third electromagnetic valve is arranged at the joint of the circulating tank and the second liquid outlet pipe;
the first solenoid valve, the second solenoid valve and the third solenoid valve are all electrically connected with the circulating device controller.
As a preferred scheme of the etching solution recycling process, the liquid transfer mechanism comprises a liquid transfer pipe and a liquid pump arranged at the middle end of the liquid transfer pipe, two ends of the liquid transfer pipe are respectively communicated with the bottom end of the first tank cavity and the top end of the second tank cavity, and the liquid pump is electrically connected with the circulating device controller.
As a preferable scheme of the etching solution recycling process, a first flow meter is installed on the liquid inlet pipe, a second flow meter is installed on the liquid transferring mechanism, and the first flow meter and the second flow meter are both electrically connected with the circulating device controller.
As a preferred scheme of the etching solution recycling process, a chloride ion sensor is installed in the second tank cavity and electrically connected with the circulating device controller.
As a preferable scheme of the etching solution recycling process, the separating mechanism comprises a separating ring and a vent pipe, the separating ring is arranged at the middle end of the interior of the circulating tank, the separating ring is in a bowl shape with an upward opening and an opening at the bottom, and the vent pipe is in a cylindrical shape vertically extending upwards along the edge of the opening of the separating ring.
As a preferable scheme of the etching solution recycling process, the aeration type ion exchange device in the step 9.1 comprises a first ion exchange column, an aeration device and a second ion exchange column, wherein the aeration device comprises an aeration tank, a fourth electromagnetic valve and a hydrogen peroxide storage tank;
the input end of the first ion exchange column is communicated with the output end of the filtrate tank through a first liquid inlet valve, and the output end of the first ion exchange column is communicated with the input end of the aeration tank through a first liquid outlet valve;
the input end of the aeration tank is communicated with the output end of the hydrogen peroxide storage tank through a fourth electromagnetic valve;
the output end of the aeration tank is communicated with the input end of the second ion exchange column through a second liquid inlet valve, and the output end of the second ion exchange column is communicated with the input end of the stirring barrel through a second liquid outlet valve.
As a preferable scheme of the etching solution recycling process, the etching solution recycling process further comprises a third ion exchange column;
the output end of the filtrate tank is communicated with the input end of the third ion exchange column through a third liquid inlet valve, and the output end of the aeration tank is communicated with the input end of the third ion exchange column through a fourth liquid inlet valve;
the output end of the third ion exchange column is communicated with the input end of the aeration tank through a third liquid outlet valve, and the output end of the third ion exchange column is communicated with the input end of the stirring barrel through a fourth liquid outlet valve.
As a preferred scheme of the etching solution recycling process, the etching solution recycling process further comprises a display device arranged outside the aeration type ion exchange device, copper ion sensors are arranged inside the first ion exchange column, the second ion exchange column and the third ion exchange column, and the copper ion sensors are electrically connected with the display device.
The invention has the beneficial effects that:
the circulating device controller is used for sending signals to the first electromagnetic valve, the second electromagnetic valve and the third electromagnetic valve to open or close the first electromagnetic valve, the second electromagnetic valve and the third electromagnetic valve; the first tank cavity is used for storing and transferring, and the second tank cavity is used for discharging liquid to the pulping machine or the neutralization reaction tank, so that the centrifugal dehydrator or the pulping machine does not need to be stopped; when the liquid is fed, the first electromagnetic valve is closed, and the centrifugal dehydrator pumps the copper sulfate mother liquor into the first tank cavity through the liquid feeding pipe; after the centrifugal dehydration process is finished, the first electromagnetic valve and the liquid transfer mechanism are opened, the liquid in the first tank cavity is moved into the second tank cavity through the liquid transfer mechanism, and then the first electromagnetic valve and the liquid transfer mechanism are closed to wait for the next centrifugal dehydration process; when liquid is drained to the pulping machine, the third electromagnetic valve is kept closed, and the second electromagnetic valve is intermittently opened, so that the liquid in the second tank cavity is intermittently conveyed to the pulping machine through the first liquid outlet pipe for recycling; after the centrifugal dehydration process is repeated for four times, the second electromagnetic valve is kept closed, and the third electromagnetic valve is intermittently opened, so that the liquid in the second tank cavity is intermittently conveyed to the neutralization reaction tank through the second liquid outlet pipe for recycling; the gas in first tank cavity and the second tank cavity flows through the clearance between partition mechanism top and the circulation jar inner wall top to avoid first tank cavity and the inside high pressure or the negative pressure that produces of second tank cavity, avoid gaseous loss to the external world simultaneously.
The first liquid inlet valve, the first liquid outlet valve, the second liquid inlet valve and the second liquid outlet valve are opened, other liquid inlet valves and liquid outlet valves are closed, the filtrate tank, the first ion exchange column, the aeration tank, the second ion exchange column and the stirring barrel are sequentially communicated, the first ion exchange column carries out primary ion exchange, the aeration tank carries out oxidation-aeration, the second ion exchange column carries out secondary ion exchange, and the third ion exchange column carries out regeneration analysis;
the first liquid inlet valve, the first liquid outlet valve, the fourth liquid inlet valve and the fourth liquid outlet valve are opened, other liquid inlet valves and other liquid outlet valves are closed, the filtrate tank, the first ion exchange column, the aeration tank, the third ion exchange column and the stirring barrel are sequentially communicated, the first ion exchange column carries out primary ion exchange, the aeration tank carries out oxidation-aeration, the third ion exchange column carries out secondary ion exchange, and the second ion exchange column carries out regeneration analysis;
the third liquid inlet valve, the third liquid outlet valve, the second liquid inlet valve and the second liquid outlet valve are opened, other liquid inlet valves and liquid outlet valves are closed, the filtrate tank, the third ion exchange column, the aeration tank, the second ion exchange column and the stirring barrel are sequentially communicated, the third ion exchange column carries out primary ion exchange, the aeration tank carries out oxidation-aeration, the second ion exchange column carries out secondary ion exchange, and the first ion exchange column carries out regeneration analysis.
1. The process can replace copper ions in the copper-containing etching waste liquid with high efficiency through the steps of ion exchange, oxidation aeration and ion exchange;
2. the process can prepare the copper-containing etching waste liquid into regenerated etching liquid;
3. the process can produce side product copper sulfate pentahydrate and has high economic value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention will be briefly described below. It is obvious that the drawings described below are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a system diagram of an etching solution recycling process according to an embodiment of the present invention;
FIG. 2 is a front view of a copper sulfate mother liquor recycling apparatus of an etching solution recycling process according to an embodiment of the present invention;
FIG. 3 is a side sectional view of a copper sulfate mother liquor circulating apparatus of an etching solution recycling process according to an embodiment of the present invention;
FIG. 4 is a side view of a copper sulfate mother liquor recycling apparatus for an etching solution recycling process according to an embodiment of the present invention;
FIG. 5 is a front sectional view of a copper sulfate mother liquor circulating apparatus of an etching solution recycling process according to an embodiment of the present invention;
FIG. 6 is a first perspective view of a copper sulfate mother liquor recycling apparatus for an etching solution recycling process according to an embodiment of the present invention;
FIG. 7 is a second perspective view of a recycling process of the etching solution according to an embodiment of the present invention;
FIG. 8 is a system diagram of an aerated ion exchange unit for recycling the etching solution according to an embodiment of the present invention;
FIG. 9 is a structural diagram of an aerated ion exchange unit for an etching solution recycling process according to an embodiment of the present invention;
in the figure:
1. a circulation tank; 1a, a separation mechanism; 1a1, spacer ring; 1a2, vent pipe; 1b, a first electromagnetic valve;
2. a pipetting mechanism; 2a, a pipette; 2b, a liquid pump;
3. a liquid inlet pipe;
4. a first liquid outlet pipe; 4a, a second electromagnetic valve;
5. a second liquid outlet pipe; 5a, a third electromagnetic valve;
6. a first ion exchange column;
7a, an aeration tank; 7b, a fourth electromagnetic valve; 7c, a hydrogen peroxide storage tank;
8. a second ion exchange column; 9. a third ion exchange column.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Wherein the showings are for the purpose of illustration only and are shown by way of illustration only and not in actual form, and are not to be construed as limiting the present patent; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The same or similar reference numerals in the drawings of the embodiments of the present invention correspond to the same or similar components; in the description of the present invention, it should be understood that if the terms "upper", "lower", "left", "right", "inner", "outer", etc. are used for indicating the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, it is only for convenience of description and simplification of description, but it is not indicated or implied that the referred device or element must have a specific orientation, be constructed in a specific orientation and be operated, and therefore, the terms describing the positional relationship in the drawings are only used for illustrative purposes and are not to be construed as limitations of the present patent, and the specific meanings of the terms may be understood by those skilled in the art according to specific situations.
In the description of the present invention, unless otherwise explicitly specified or limited, the term "connected" or the like, if appearing to indicate a connection relationship between the components, is to be understood broadly, for example, as being fixed or detachable or integral; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or may be connected through one or more other components or may be in an interactive relationship with one another. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Referring to fig. 1, the etching solution recycling process includes the following steps:
firstly, carrying out primary hydrogen peroxide treatment on the acidic copper-containing etching waste liquid to convert monovalent copper in the waste liquid into divalent copper;
step two, carrying out acid-base neutralization treatment on the acidic copper-containing etching waste liquid and the alkaline copper-containing etching waste liquid in a neutralization reaction tank;
thirdly, performing filter pressing on the neutralized solution through a filter press to generate a filter cake and filtrate;
fourthly, carrying out filter cake pulping on the filter cake generated by filter pressing through a pulping machine;
step five, adding 98% sulfuric acid into the solution generated by pulping in an acid dissolution reaction kettle to perform acid dissolution reaction to generate copper sulfate, water and hydrochloric acid, and then cooling the acid dissolution reaction kettle;
step six, enabling the copper sulfate solution to enter a crystallization tank for crystallization;
step seven, carrying out centrifugal dehydration treatment on the copper sulfate crystals and water through a centrifugal dehydrator to generate copper sulfate pentahydrate and copper sulfate mother liquor, shunting the copper sulfate mother liquor separated from the centrifugal dehydrator through a copper sulfate mother liquor circulating device, conveying the low-chlorine copper sulfate mother liquor to a beater, and conveying the high-chlorine copper sulfate mother liquor separated from the centrifugal dehydrator to a neutralization reaction tank;
step eight, precipitating the filtrate generated in the filter pressing process in a filtrate precipitation tank, and conveying the precipitate to a filter press;
step nine, conveying the filtrate to an ion exchange tank, and performing ion exchange through an ion exchange column;
step ten, conveying the waste liquid generated after ion exchange into a stirring barrel, adding a proper amount of solid materials, stirring to fully mix and dissolve the solid materials, and pumping the etching solution and the tin stripping solution into a storage tank respectively after production is finished;
and eleventh, carrying out backwashing regeneration on the ion exchange column through hydrochloric acid, and conveying the generated regeneration wastewater to a neutralization reaction tank.
Between the ninth step and the tenth step, the following steps are also included:
step 9.1, pumping the filtrate into an aeration type ion exchange device, and carrying out secondary hydrogen peroxide treatment on the filtrate generated after primary ion exchange to convert monovalent copper in the filtrate into divalent copper;
step 9.2, removal of excess H by aeration2O2；
And 9.3, carrying out secondary ion exchange.
Referring to the copper sulfate mother liquor circulating device shown in fig. 2 to 7, the copper sulfate mother liquor circulating device in step three comprises a circulating tank 1, a liquid transfer mechanism 2, a liquid inlet pipe 3, a first liquid outlet pipe 4, a second liquid outlet pipe 5 and a circulating device controller, wherein a separating mechanism 1a for separating the circulating tank 1 into a first tank cavity and a second tank cavity is arranged in the circulating tank 1, and the top end of the separating mechanism 1a is not contacted with the top end of the inner wall of the circulating tank 1;
the input end of the liquid transferring mechanism 2 is communicated with the bottom end of the first tank cavity, the output end of the liquid transferring mechanism 2 is communicated with the top end of the second tank cavity, the height of the output end of the liquid transferring mechanism 2 is lower than that of the separating mechanism 1a, and a first electromagnetic valve 1b is installed at the joint of the circulating tank 1 and the liquid transferring mechanism 2;
the centrifugal dehydrator is communicated with the top end of the first tank cavity through a liquid inlet pipe 3;
the bottom end of the second tank cavity is communicated with the pulping machine through a first liquid outlet pipe 4, and a second electromagnetic valve 4a is installed at the joint of the circulating tank 1 and the first liquid outlet pipe 4;
the bottom end of the second tank cavity is communicated with the neutralization reaction tank through a second liquid outlet pipe 5, and a third electromagnetic valve 5a is arranged at the joint of the circulating tank 1 and the second liquid outlet pipe 5;
the first solenoid valve 1b, the second solenoid valve 4a and the third solenoid valve 5a are all electrically connected to the circulation device controller.
The liquid transferring mechanism 2 comprises a liquid transferring pipe 2a and a liquid pump 2b installed at the middle end of the liquid transferring pipe 2a, two ends of the liquid transferring pipe 2a are respectively communicated with the bottom end of the first tank cavity and the top end of the second tank cavity, and the liquid pump 2b is electrically connected with the circulating device controller.
After the first solenoid valve 1b is opened, the liquid pump 2b pumps liquid from the first tank chamber into the second tank chamber via the pipette 2 a.
The liquid inlet pipe 3 is provided with a first flowmeter, the liquid transfer mechanism 2 is provided with a second flowmeter, and the first flowmeter and the second flowmeter are both electrically connected with the circulating device controller.
The first flow meter is used for counting the liquid discharge amount of each centrifugal dehydration process, the second flow meter is used for counting the liquid transfer amount moving from the first tank cavity to the second tank cavity, and when the total liquid transfer amount of multiple liquid transfers reaches five times of the average liquid discharge amount, the circulating device controller sends signals to the second electromagnetic valve 4a and the third electromagnetic valve 5a, so that the second electromagnetic valve 4a is closed, and the third electromagnetic valve 5a is intermittently opened, and the automatic switching of liquid discharge from the second tank cavity to the pulping machine or the neutralization reaction tank is realized.
And a chloride ion sensor is arranged in the second tank cavity and is electrically connected with the circulating device controller.
The chloride ion sensor is a Shanghai Lei magnet PCL-1 type chloride ion electrode and is used for sensing the concentration of chloride ions in the second tank cavity and sending data to the circulating device controller, and when the content of chloride ions in the solution in the second tank cavity is high, the circulating device controller sends signals to the second electromagnetic valve 4a and the third electromagnetic valve 5a, so that the second electromagnetic valve 4a is closed, the third electromagnetic valve 5a is intermittently opened, and the automatic switching of the liquid drainage of the second tank cavity to the pulping machine or the neutralization reaction tank is realized.
The partition mechanism 1a comprises a partition ring 1a1 and a vent pipe 1a2, the partition ring 1a1 is arranged at the middle end of the interior of the circulation tank 1, the partition ring 1a1 is bowl-shaped with an opening facing upwards and a bottom opening, and the vent pipe 1a2 is cylindrical and extends vertically upwards along the opening edge of the partition ring 1a 1.
The partition ring 1a1 and the vent pipe 1a2 form a circular-ring-shaped container for containing copper sulfate mother liquor, and the first tank cavity and the second tank cavity exchange gas through the vent pipe 1a2, so that the internal gas pressure is constant when the first tank cavity and the second tank cavity alternately feed liquid and discharge liquid; the second tank cavity is positioned right above the first tank cavity, so that the center of gravity inside the circulating tank 1 is always stable, and the liquid in the second tank cavity can move to a beater or a neutralization reaction tank through the self gravity without adding a liquid pump.
Referring to the aeration type ion exchange device shown in fig. 8 to 9, the aeration type ion exchange device in step 9.1 comprises a first ion exchange column 6, an aeration device 7 and a second ion exchange column 8, wherein the aeration device 7 comprises an aeration tank 7a, a fourth electromagnetic valve 7b and a hydrogen peroxide storage tank 7 c;
the input end of the first ion exchange column 6 is communicated with the output end of the filtrate tank through a first liquid inlet valve 6a, and the output end of the first ion exchange column 6 is communicated with the input end of an aeration tank 7a through a first liquid outlet valve 6 b;
the input end of the aeration tank 7a is communicated with the output end of the hydrogen peroxide storage tank 7c through a fourth electromagnetic valve 7 b;
the output end of the aeration tank 7a is communicated with the input end of the second ion exchange column 8 through a second liquid inlet valve 8a, and the output end of the second ion exchange column 8 is communicated with the input end of the stirring barrel through a second liquid outlet valve 8 b.
Pumping the precipitated filtrate from the filtrate tank into a first ion exchange column 6 for primary ion exchange;
then pumping the waste liquid in the first ion exchange column 6 into an aeration tank 7a, simultaneously opening a fourth electromagnetic valve 7b to pump the hydrogen peroxide in a hydrogen peroxide storage tank 7c into the aeration tank 7a, after pumping a certain amount of hydrogen peroxide, closing the fourth electromagnetic valve 7b, starting the aeration tank 7a and operating for a period of time until univalent copper in the waste liquid is almost completely converted into bivalent copper, and simultaneously, redundant H in the aeration tank 7a2O2Removing by aeration;
pumping the waste liquid in the aeration tank 7a into a second ion exchange column 8 for secondary ion exchange;
and pumping the waste liquid in the second ion exchange column 8 into a stirring barrel for processing so as to generate regenerated etching liquid.
A third ion exchange column 9 is also included;
the output end of the filtrate tank is communicated with the input end of a third ion exchange column 9 through a third liquid inlet valve 9a, and the output end of an aeration tank 7a is communicated with the input end of the third ion exchange column 9 through a fourth liquid inlet valve 9 c;
the output end of the third ion exchange column 9 is communicated with the input end of the aeration tank 7a through a third liquid outlet valve 9b, and the output end of the third ion exchange column 9 is communicated with the input end of the stirring barrel through a fourth liquid outlet valve 9 d.
The third ion exchange column 9 is used for regenerating a standby ion exchange column for analysis, the first ion exchange column 6, the second ion exchange column 8 and the third ion exchange column 9 can work in series by switching the circulation pipeline of the waste liquid, and the ion exchange columns which do not work carry out regeneration analysis, so that the aeration type ion exchange device can continuously run for 24 hours.
The device also comprises a display device arranged outside the aeration type ion exchange device, copper ion sensors are arranged inside the first ion exchange column 6, the second ion exchange column 8 and the third ion exchange column 9, and the copper ion sensors are electrically connected with the display device.
The copper ion sensor is a Shanghai Leima Pcu-1 copper ion electrode and is used for detecting the concentration of copper ions in the ion exchange column, the display device is used for displaying the value of the concentration of the copper ions, and when a worker reads out that the content of copper in the ion exchange column is more than 0.5mg/L through the display device, the worker needs to immediately perform regeneration analysis on the ion exchange column.
The working principle of the invention is as follows:
step one, carrying out primary hydrogen peroxide treatment on the acidic copper-containing etching waste liquid to further oxidize monovalent copper in the waste liquid into divalent copper; the acidic copper-containing etching waste liquid collected from a circuit board factory contains more cuprous chloride (about 1%), cuprous chloride cannot generate basic copper chloride precipitate during neutralization reaction, cuprous remains in a press filtrate, and the press filtrate containing too high copper brings great difficulty to subsequent treatment, so the acidic copper-containing etching waste liquid must be pretreated after entering the factory, and the pretreatment method comprises the following steps: adding hydrogen peroxide as oxidant into the single-liquid acidic etching waste liquid containing copper to further oxidize the monovalent copper in the waste liquid containing copper into divalent copper. The hydrogen peroxide oxidant is safer than the common sodium chlorate oxidant, does not generate toxic chlorine gas and bring harmful components, and even if the hydrogen peroxide oxidant is added in an excessive amount, the excessive part can be completely decomposed in the neutralization reaction, and the next working procedure can not be influenced.
Step two, carrying out acid-base neutralization treatment on the acidic copper-containing etching waste liquid and the alkaline copper-containing etching waste liquid in a neutralization reaction tank; conveying the acidic and alkaline copper-containing etching waste liquid to a neutralization reaction tank by a water pump to neutralize Cu in the solution2+Content of about 80g/L, NH4+The content is about 100g/L, the pH value of the solution after reaction is 5-6, and the solution density is about 1.2 kg/L; the single neutralization reaction tank can treat about 5.67m at one time3Acidic, alkaline copper-containing etching waste liquor of (a); the reaction is carried out at normal temperature for about half an hour, and basic copper chloride (Cu) is generated in the reaction2(OH)3Cl) is precipitated, the amount of precipitate is about 1.5 tons, and the neutralization and sedimentation conditions are controlled to avoid ammonium ions from being mixed into the precipitate.
Thirdly, performing filter pressing on the neutralized solution through a filter press to generate a filter cake and filtrate; conveying the solution neutralized by the neutralization reaction tank to a filter press by a slurry pump for filter pressing, conveying about 1.5 tons of filter cakes which can be filtered by pressing into the beater tank for treatment, wherein about 30min is consumed by a single filter press, firstly discharging about 5.0 tons of filtrate which is filtered by pressing into a filtrate sedimentation tank, returning the sedimentation part to the filter press, and cleaning the filter cake and the filter press by using water which is equal to the amount of the filter cake each time, then carrying out filter pressing, and cleaning for 2 times in total; the precipitate cake formed in the neutralization reaction is Cu2(OH)3Cl，Cu2+The content is 30 percent and the content of chloride ion is 8.32 percent.
Fourthly, carrying out filter cake pulping on the filter cake generated by filter pressing through a pulping machine; 1.5 tons of basic copper chloride filter cakes and the same amount of water are pressed by a filter press and sent into a beater tank for half an hour for treatment.
Step five, adding 98% sulfuric acid into the solution generated by pulping in an acid dissolution reaction kettle to perform acid dissolution reaction to generate copper sulfate, water and hydrochloric acid, and then cooling the acid dissolution reaction kettle; pumping the pulped basic copper chloride solution into an acid dissolution reaction kettle, adding 98% sulfuric acid after pumping, reacting, and treating acid mist by an alkali spray absorption tower, wherein the reaction is exothermic reaction, so heating is not needed, and the reaction time is about 25 minutes; after the reaction is finished, because the temperature is too high and is not beneficial to crystallization, cooling water needs to be introduced for cooling, and the materials can be discharged after being cooled to about 45 ℃; the cooling water amount in the reaction kettle is about 8t, the cooling water is recycled and not discharged, a small amount of evaporation exists in the self cooling process, the evaporation amount is about 5%, and the cooling water needs to be supplemented periodically, wherein 0.4 t/time is supplemented each time; the cooling time required was about 70 minutes.
Step six, enabling the copper sulfate solution to enter a crystallization tank for crystallization; discharging materials into a crystallization tank, placing filter cloth in the crystallization tank, wherein the filtrate is copper sulfate mother liquor which can be recycled, adding an anti-corrosion material on the inner wall of the crystallization tank, continuously crystallizing supersaturated copper sulfate solution and crystals sent from a reaction kettle in the crystallization tank, and separating copper sulfate crystals from the copper sulfate solution by a filter membrane in the crystallization tank to generate copper sulfate crystals with the water content of about 10%.
Step seven, carrying out centrifugal dehydration treatment on copper sulfate crystals and water through a centrifugal dehydrator to generate copper sulfate pentahydrate mother liquor, shunting the copper sulfate mother liquor separated from the centrifugal dehydrator through a copper sulfate mother liquor circulating device, conveying the low-chlorine copper sulfate mother liquor to a beater, and conveying the high-chlorine copper sulfate mother liquor separated from the centrifugal dehydrator to a neutralization reaction tank; dehydrating the water and the copper sulfate crystals generated by the crystallization tank by a centrifugal machine (a small amount of water is added in the dehydration process to remove free acid), thus obtaining a primary product of the copper sulfate pentahydrate; the components of the liquid removed by the centrifuge are the same as those of the copper sulfate mother liquor and can be returned to the pulping process for recycling, the mother liquor after cooling and crystallizing the copper sulfate contains about 8-10 percent of copper and mainly contains a large amount of sulfate radicals and chloride ions, and because the chloride ions in the alkali copper chloride and the sulfuric acid are acidified in the step five, the chloride ions cannot be completely volatilized, and a large amount of chloride ions are remained in the copper sulfate mother liquor, so that the newly generated chloride ions in the copper sulfate mother liquor are too high to generate copper chloride crystals to cause the reduction of the greening quality of the copper sulfate if the copper sulfate mother liquor is completely returned to the pulping process, a step-by-step recycling method is adopted to solve the problem, the former four mother liquor is returned to the pulping process to be pulped together with basic copper chloride, and the latter fifth mother liquor is returned to the neutralizing process to be acid-base neutralized together with acidic and basic copper-containing etching waste liquor, thereby leading the chloride ions enriched in the mother solution to enter the neutralization and filter pressing water and avoiding the enrichment of the chloride ions.
Step eight, precipitating the filtrate generated in the filter pressing process in a filtrate precipitation tank, and conveying the precipitate to a filter press; discharging the filter liquor into a filter liquor sedimentation tank after filter pressing, wherein the main component of the filter liquor is NH4Cl, and further a small amount of Cu which is not precipitated2+。
Step nine, conveying the filtrate to an ion exchange tank, and performing ion exchange through an ion exchange column; conveying the precipitated filtrate to an ion exchange tank, dividing an ion exchange column into an anode bed and a cathode bed, contacting the resin in the ion exchange column with the flowing wastewater, and then utilizing hydrogen ions on the resin to contact Cu in the wastewater2+Performing replacement to make Cu in the wastewater2+Are collected together.
Step 9.1, pumping the filtrate into an aeration type ion exchange device, and performing secondary hydrogen peroxide treatment on the filtrate generated after primary ion exchange to convert monovalent copper in the filtrate into divalent copper; the ion exchange resin only adsorbs bivalent copper ions, has poor adsorption effect on monovalent copper, and in order to ensure that the copper content of the neutralized press filtration water after ion exchange does not exceed the standard, H is carried out once again after the ion exchange resin removes most of copper2O2Oxidizing to fully oxidize the residual monovalent copper into divalent copper;
step 9.2, removal of excess H by aeration2O2(ii) a Removing most of excessive H in filtrate by aeration2O2。
9.3, performing secondary ion exchange in the ion exchange tank through an ion exchange column; thereby sufficiently exchanging copper ions in the filtrate.
Step ten, conveying the waste liquid generated after ion exchange into a stirring barrel, adding a proper amount of solid materials, stirring to fully mix and dissolve the solid materials, and pumping the etching solution and the tin stripping solution into a storage tank respectively after production is finished;
the main components of the solution generated after the copper-containing etching waste liquid is subjected to neutralization, filter pressing and ion exchange copper removal are chloride ions, ammonium ions, sodium ions and water, the main components of the acidic etching sub-solution are chloride ions, hydrogen ions, sodium ions, ammonium ions and water, and the main components of the alkaline etching solution are chloride ions, ammonia, sodium ions and hydroxide ions; the main components are the same, so the solution can be used as a raw material for preparing new acidic and alkaline etching sub-solutions, and the addition amount of ammonium chloride, sodium chloride and water can be reduced compared with the preparation of water, thereby reducing the preparation cost of the acidic and alkaline etching solutions.
And eleventh, carrying out backwashing regeneration on the ion exchange column through hydrochloric acid, and conveying the generated regeneration wastewater to a neutralization reaction tank. With the continuous proceeding of the exchange process, the hydrogen ions in the resin are released and lose the exchange function, and at this time, hydrochloric acid solution is used to regenerate the resin, so as to adsorb Cu on the resin2+The resin absorbs hydrogen ions again after replacement, and the exchange capacity is recovered; after backwashing regeneration, Cu in the wastewater2+Gather in the regeneration wastewater to generate Cu as the main pollutant2+The regeneration wastewater of (2); the copper-containing alloy contains Cu2+The wastewater is recycled to a neutralization reaction tank for production; according to the actual production condition, the ion exchange regeneration wastewater mainly contains copper, and all the copper is directly recycled to the neutralization reaction tank without being discharged.
The working principle of the copper sulfate mother liquor circulating device is as follows:
the circulating device controller is used for sending signals to the first electromagnetic valve 1b, the second electromagnetic valve 4a and the third electromagnetic valve 5a to open or close the first electromagnetic valve, the second electromagnetic valve and the third electromagnetic valve;
the first tank cavity is used for storing and transferring, and the second tank cavity is used for discharging liquid to the pulping machine or the neutralization reaction tank, so that the centrifugal dehydrator or the pulping machine does not need to be stopped;
when liquid is fed, the first electromagnetic valve 1b is closed, and the centrifugal dehydrator pumps the copper sulfate mother liquor into the first tank cavity through the liquid inlet pipe 3;
after the centrifugal dehydration process is finished, the first electromagnetic valve 1b and the liquid transfer mechanism 2 are opened, the liquid in the first tank cavity is moved into the second tank cavity through the liquid transfer mechanism 2, and then the first electromagnetic valve 1b and the liquid transfer mechanism 2 are closed to wait for the next centrifugal dehydration process;
when the liquid is drained to the pulping machine, the third electromagnetic valve 5a is kept closed, and the second electromagnetic valve 4a is intermittently opened, so that the liquid in the second tank cavity is intermittently conveyed to the pulping machine through the first liquid outlet pipe 4 for recycling;
after the centrifugal dehydration process is repeated for four times, the second electromagnetic valve 4a is kept closed, and the third electromagnetic valve 5a is intermittently opened, so that the liquid in the second tank cavity is intermittently conveyed to the neutralization reaction tank through the second liquid outlet pipe 5 for recycling;
the gas in first tank cavity and the second tank cavity flows through the clearance between 1a top end of partition mechanism and the 1 inner wall top end of circulation tank to avoid first tank cavity and the inside high pressure or the negative pressure that produces of second tank cavity, avoid gaseous loss to the external world simultaneously.
The working principle of the aeration type ion exchange device is as follows:
a first liquid inlet valve 6a, a first liquid outlet valve 6b, a second liquid inlet valve 8a and a second liquid outlet valve 8b are opened, other liquid inlet valves and liquid outlet valves are closed, a filtrate tank, a first ion exchange column 6, an aeration tank 7a, a second ion exchange column 8 and a stirring barrel are communicated in sequence, the first ion exchange column 6 carries out primary ion exchange, the aeration tank 7a carries out oxidation-aeration, the second ion exchange column 8 carries out secondary ion exchange, and a third ion exchange column 9 carries out regeneration analysis;
the first liquid inlet valve 6a, the first liquid outlet valve 6b, the fourth liquid inlet valve 9c and the fourth liquid outlet valve 9d are opened, other liquid inlet valves and liquid outlet valves are closed, the filtrate tank, the first ion exchange column 6, the aeration tank 7a, the third ion exchange column 9 and the stirring barrel are sequentially communicated, the first ion exchange column 6 carries out primary ion exchange, the aeration tank 7a carries out oxidation-aeration, the third ion exchange column 9 carries out secondary ion exchange, and the second ion exchange column 8 carries out regeneration analysis;
the third liquid inlet valve 9a, the third liquid outlet valve 9b, the second liquid inlet valve 8a and the second liquid outlet valve 8b are opened, other liquid inlet valves and liquid outlet valves are closed, the filtrate tank, the third ion exchange column 9, the aeration tank 7a, the second ion exchange column 8 and the stirring barrel are communicated in sequence, the third ion exchange column 9 carries out primary ion exchange, the aeration tank 7a carries out oxidation-aeration, the second ion exchange column 8 carries out secondary ion exchange, and the first ion exchange column 6 carries out regeneration analysis.
It should be understood that the above-described embodiments are merely preferred embodiments of the invention and the technical principles applied thereto. It will be understood by those skilled in the art that various modifications, equivalents, changes, and the like can be made to the present invention. However, such variations are within the scope of the invention as long as they do not depart from the spirit of the invention. In addition, certain terms used in the specification and claims of the present application are not limiting, but are used merely for convenience of description.
Claims (10)
1. The etching solution recycling process is characterized by comprising the following steps of:
firstly, carrying out primary hydrogen peroxide treatment on the acidic copper-containing etching waste liquid to convert monovalent copper in the waste liquid into divalent copper;
step two, carrying out acid-base neutralization treatment on the acidic copper-containing etching waste liquid and the alkaline copper-containing etching waste liquid in a neutralization reaction tank;
thirdly, performing filter pressing on the neutralized solution through a filter press to generate a filter cake and filtrate;
fourthly, carrying out filter cake pulping on the filter cake generated by filter pressing through a pulping machine;
step five, adding 98 percent by mass of sulfuric acid into the solution generated by pulping in an acid dissolution reaction kettle to perform acid dissolution reaction to generate copper sulfate, water and hydrochloric acid, and then cooling the acid dissolution reaction kettle;
step six, enabling the copper sulfate solution to enter a crystallization tank for crystallization;
step seven, carrying out centrifugal dehydration treatment on the copper sulfate crystals and water through a centrifugal dehydrator to generate anhydrous copper sulfate and copper sulfate mother liquor, shunting the copper sulfate mother liquor separated from the centrifugal dehydrator through a copper sulfate mother liquor circulating device, conveying the low-chlorine copper sulfate mother liquor to a beater, and conveying the high-chlorine copper sulfate mother liquor separated from the centrifugal dehydrator to a neutralization reaction tank;
step eight, precipitating the filtrate generated in the filter pressing process in a filtrate precipitation tank, and conveying the precipitate to a filter press;
step nine, conveying the filtrate to an ion exchange tank, and performing ion exchange through an ion exchange column;
step ten, conveying the waste liquid generated after ion exchange into a stirring barrel, adding a proper amount of sodium chloride and ammonium chloride, stirring to fully mix and dissolve the sodium chloride and the ammonium chloride, and pumping the etching solution and the tin stripping solution into a storage tank respectively after production is finished;
and eleventh, carrying out backwashing regeneration on the ion exchange column through hydrochloric acid, and conveying the generated regeneration wastewater to a neutralization reaction tank.
2. The process of claim 1, further comprising the following steps between step nine and step ten:
step 9.1, pumping the filtrate into an aeration type ion exchange device, and carrying out secondary hydrogen peroxide treatment on the filtrate generated after primary ion exchange to convert monovalent copper in the filtrate into divalent copper;
step 9.2, removal of excess H by aeration2O2；
And 9.3, carrying out secondary ion exchange.
3. The etching solution recycling process according to claim 1, wherein the copper sulfate mother solution circulating device in the third step comprises a circulating tank (1), a liquid transfer mechanism (2), a liquid inlet pipe (3), a first liquid outlet pipe (4), a second liquid outlet pipe (5) and a circulating device controller, a separating mechanism (1a) for separating the circulating tank (1) into a first tank cavity and a second tank cavity is arranged in the circulating tank (1), and the top end of the separating mechanism (1a) is not in contact with the top end of the inner wall of the circulating tank (1);
the input end of the liquid transfer mechanism (2) is communicated with the bottom end of the first tank cavity, the output end of the liquid transfer mechanism (2) is communicated with the top end of the second tank cavity, the height of the output end of the liquid transfer mechanism (2) is lower than that of the separation mechanism (1a), and a first electromagnetic valve (1b) is installed at the joint of the circulating tank (1) and the liquid transfer mechanism (2);
the centrifugal dehydrator is communicated with the top end of the first tank cavity through a liquid inlet pipe (3);
the bottom end of the second tank cavity is communicated with the pulping machine through a first liquid outlet pipe (4), and a second electromagnetic valve (4a) is installed at the joint of the circulating tank (1) and the first liquid outlet pipe (4);
the bottom end of the second tank cavity is communicated with the neutralization reaction tank through a second liquid outlet pipe (5), and a third electromagnetic valve (5a) is arranged at the joint of the circulating tank (1) and the second liquid outlet pipe (5);
the first electromagnetic valve (1b), the second electromagnetic valve (4a) and the third electromagnetic valve (5a) are all electrically connected with the circulating device controller.
4. The etching solution recycling process according to claim 3, wherein the liquid transferring mechanism (2) comprises a liquid transferring tube (2a) and a liquid pump (2b) installed at the middle end of the liquid transferring tube (2a), the two ends of the liquid transferring tube (2a) are respectively communicated with the bottom end of the first tank cavity and the top end of the second tank cavity, and the liquid pump (2b) is electrically connected with the circulating device controller.
5. The etching solution recycling process according to claim 3, wherein a first flow meter is installed on the liquid inlet pipe (3), a second flow meter is installed on the liquid transferring mechanism (2), and both the first flow meter and the second flow meter are electrically connected with the controller of the circulating device.
6. The process of claim 3, wherein the second tank chamber is provided with a chloride ion sensor, and the chloride ion sensor is electrically connected with the circulator controller.
7. The etching solution recycling process according to claim 3, wherein the partition mechanism (1a) comprises a partition ring (1a1) and a vent pipe (1a2), the partition ring (1a1) is disposed at the middle end of the interior of the circulation tank (1), the partition ring (1a1) is bowl-shaped with an opening facing upwards and a bottom opening, and the vent pipe (1a2) is cylindrical-shaped with a vertical upward extension along the opening edge of the partition ring (1a 1).
8. The etching solution recycling process according to claim 2, wherein the aeration type ion exchange device in step 9.1 comprises a first ion exchange column (6), an aeration device (7) and a second ion exchange column (8), the aeration device (7) comprises an aeration tank (7a), a fourth electromagnetic valve (7b) and a hydrogen peroxide storage tank (7 c);
the input end of the first ion exchange column (6) is communicated with the output end of the filtrate tank through a first liquid inlet valve (6a), and the output end of the first ion exchange column (6) is communicated with the input end of the aeration tank (7a) through a first liquid outlet valve (6 b);
the input end of the aeration tank (7a) is communicated with the output end of the hydrogen peroxide storage tank (7c) through a fourth electromagnetic valve (7 b);
the output end of the aeration tank (7a) is communicated with the input end of a second ion exchange column (8) through a second liquid inlet valve (8a), and the output end of the second ion exchange column (8) is communicated with the input end of a stirring barrel through a second liquid outlet valve (8 b).
9. The process of claim 8, further comprising a third ion exchange column (9);
the output end of the filtrate tank is communicated with the input end of a third ion exchange column (9) through a third liquid inlet valve (9a), and the output end of an aeration tank (7a) is communicated with the input end of the third ion exchange column (9) through a fourth liquid inlet valve (9 c);
the output end of the third ion exchange column (9) is communicated with the input end of the aeration tank (7a) through a third liquid outlet valve (9b), and the output end of the third ion exchange column (9) is communicated with the input end of the stirring barrel through a fourth liquid outlet valve (9 d).
10. The process of claim 9, further comprising a display device disposed outside the aeration type ion exchange device, wherein the first ion exchange column (6), the second ion exchange column (8) and the third ion exchange column (9) are each internally provided with a copper ion sensor, and the copper ion sensors are electrically connected to the display device.
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| CN111394730B (en) * | 2020-04-29 | 2022-06-07 | Tcl华星光电技术有限公司 | Etching solution regeneration device and etching solution regeneration method |
| CN115747805A (en) * | 2022-11-29 | 2023-03-07 | 南通卓力达金属制品有限公司 | Electrolytic oxidation regeneration equipment and system for ferric trichloride etching old liquid |
| CN117403055B (en) * | 2023-10-17 | 2024-06-07 | 广东诚一环保科技有限公司 | Method for recycling rare metals in waste residues |
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| US3785944A (en) * | 1971-10-07 | 1974-01-15 | Duval Corp | Hydrometallurgical process for the production of copper |
| CN1865166A (en) * | 2005-05-18 | 2006-11-22 | 陈晶 | Microwave circulating disposal process for printed plate board etching waste liquor |
| CN101391800B (en) * | 2007-09-20 | 2011-06-15 | 深圳市东江环保股份有限公司 | Method for producing basic copper chloride, cupric sulfate pentahydrate from copper-containing etching waste liquid |
| CN104829003B (en) * | 2015-04-24 | 2016-12-07 | 温州金源化工有限公司 | A kind of recoverying and utilizing method of cupric industrial wastes |
| CN105129838A (en) * | 2015-07-02 | 2015-12-09 | 清远市新绿环境技术有限公司 | Method for producing copper sulphate by using copper-containing waste solution of PCB circuit board plant |
| CN106637215B (en) * | 2016-10-21 | 2020-07-07 | 东莞市广华化工有限公司 | Method for recycling electrolytic oxidant of circuit board acidic etching waste liquid resource |
| CN106976902A (en) * | 2016-11-30 | 2017-07-25 | 佛山市兴华源机械设备有限公司 | A kind of method for preparing basic copper carbonate using industrial copper-containing etching waste solution |
| CN108862365A (en) * | 2017-05-09 | 2018-11-23 | 广东省博罗县湘澧精细化工有限公司 | A kind of circuit board acidic and alkaline waste etching solution recovery processing technique |
| CN207221480U (en) * | 2017-05-16 | 2018-04-13 | 广东省博罗县湘澧精细化工有限公司 | A kind of filter press multistage washing system |
| CN108677192A (en) * | 2018-07-09 | 2018-10-19 | 南京舜业环保科技有限公司 | A kind of copper recovery system and method for alkaline etching waste liquid for producing |
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