CN103979625A - Mixing method for treating acid and alkaline etching waste liquid and nitric acid stripping waste liquid of printed-circuit boards - Google Patents
Mixing method for treating acid and alkaline etching waste liquid and nitric acid stripping waste liquid of printed-circuit boards Download PDFInfo
- Publication number
- CN103979625A CN103979625A CN201410169013.1A CN201410169013A CN103979625A CN 103979625 A CN103979625 A CN 103979625A CN 201410169013 A CN201410169013 A CN 201410169013A CN 103979625 A CN103979625 A CN 103979625A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- ion mixture
- cupric ion
- nitric acid
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 90
- 239000002699 waste material Substances 0.000 title claims abstract description 66
- 238000005530 etching Methods 0.000 title claims abstract description 49
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 48
- 239000002253 acid Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002156 mixing Methods 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 72
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000010949 copper Substances 0.000 claims abstract description 49
- 238000001704 evaporation Methods 0.000 claims abstract description 49
- 230000008020 evaporation Effects 0.000 claims abstract description 49
- 229910052802 copper Inorganic materials 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 47
- 235000019270 ammonium chloride Nutrition 0.000 claims description 25
- 238000003672 processing method Methods 0.000 claims description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000005611 electricity Effects 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000003929 acidic solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 229910001431 copper ion Inorganic materials 0.000 abstract description 4
- 239000010453 quartz Substances 0.000 abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 238000007599 discharging Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000009972 noncorrosive effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The present invention provides a mixing method for treating acid and alkaline etching waste liquid and nitric acid stripping waste liquid of printed-circuit boards. The method comprises the following steps: step a: adding acid etching waste liquid requiring treatment to a quartz evaporation apparatus, electrifying the quartz evaporation apparatus and heating to a temperature of 110 DEG C, and collecting a first copper ion mixture; step b: adding alkaline etching waste liquid requiring treatment to the quartz evaporation apparatus, collecting a second copper ion mixture; step c: adding nitric acid stripping waste liquid requiring treatment to the quartz evaporation apparatus, collecting a third copper ion mixture; step d: adding an appropriate amount of dilute sulfuric acid to a storage pool to obtain a copper sulfate solution; and step e: continuously electrolyzing the copper sulfate solution obtained in step d to generate high-purity metal copper. According to the present invention, not only the copper content of the treated wastewater can meet the discharging standard, but also a metal copper product with a high purity of more than 99.5% can be generated. The method has obvious economic benefits and social benefits.
Description
[technical field]
The present invention relates to print manufacturing technology field, especially relate to a kind of printed circuit board (PCB) acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method.
[background technology]
In recent years along with the fast development of electron trade, the annual growth rate that always keeps 10-20% as electronic industry basic link-printed electronic circuit board industry, the current domestic family more than 3500 of printed circuit board manufacturing enterprise that has multiple scale, monthly output reaches 1.2 hundred million square metres.
In the manufacturing processed of printed circuit board, need to consume a large amount of smart copper, domestic printed circuit board manufacturing enterprise essence copper consumption is more than 60,000 tons/month according to statistics, in the copper waste etching solution of output, total copper amount is more than 50,000 tons/month, and copper is a kind of heavy metal element being present in soil and people's carcass, in soil, content is generally in about 0.2ppm, excessive copper can with people's carcass in precipitate/complex reaction of enzyme, generation poisoning by enzyme and lose physiological function.The copper of occurring in nature is transferred in people's carcass by water body, plant etc., if intake is too high, will the Equilibrium of Trace Elements in people's carcass be destroyed, and causes heavy metal undesired accumulation in vivo, produces the results such as sex change, carinogenicity of causing a disease.Like this, a large amount of copper waste etching solutions that produce in the manufacturing processed of printed circuit board, as effectively processed not in time, can cause severe contamination hidden danger to water resources and the soil of environment especially printed circuit board factory surrounding area undoubtedly.
In the industrial wastewater discharge standard of China, the monitor control index of copper is 0.5ppm, and drinking water standard is 0.03ppm, and American-European relevant criterion is severeer.In copper scrap etching solution due to printed circuit board processing generation, copper content is tens supreme hundred grams per liters, and therefore, State Environmental Protection Administration orientates printed circuit board copper scrap etching solution (useless copper etching liquor) as dangerous liquid refuse, and regulation is processed on the spot, forbids transboundary movement.
The recovery copper of acidic etching waste liquid has following several method:
1, substitution method: this method is generally with acidic etching liquid and a small amount of alkaline etching liquid or ammonia neutralization, acidity in acidic etching liquid is reduced, then drop into wherein industrial iron plate, utilize the activity of iron that copper is cemented out, this method is understood heat release and is produced a large amount of water vapour, chlorine and hydrogen chloride gas in production reaction process, after having replaced, must discharge a large amount of waste water, in the waste water of its discharge, contain a large amount of Cl-, ammonia nitrogen and Fe3+, not only in contaminate environment but also etching solution, active princlple cannot regeneration.
2. membrane electrolysis: this method be adopt there is resistance to active Cl-anode acidic etching waste liquid is carried out to diaphragm electrolysis, but due to Cl-higher, the electrolytic metal copper producing after electrolysis is powdery, electrolysis is easily to produce a large amount of chlorine and hydrogen, dangerous high, and anode and ionic membrane consumption are very fast, and production run cost is high.Adopt electrolysis with ion-exchange film to carry out the method for copper waste etching solution recycling utilization, often due to the high requirement of ionic membrane to environment for use, along with the carrying out of process, worsen, cause film properties unstable, cathode-anode plate interpole gap is little simultaneously, current density is more than 600A/ square metre, negative plate surface easily long fastener is stabbed ionic membrane that anode and cathode liquid is altered is logical, cause systemic breakdown, produce extremely unstable, ionic membrane expensive (every square metre Renminbi 8000 ~ 15000 yuan) work-ing life short (average out to half a year) simultaneously, the existence of chlorion and some metal ion during electrolysis, produce and have unavoidably chlorine to produce, and the copper powdering of output, the oxidizable purity of product copper-base is low, value is lower than 30% of standard electrolytic copper.Power consumption is also often because ionic membrane is former thereby higher than the more than three times of standard electrolytic copper, therefore its industrial applications exists certain economy, environmental protection and technical difficulty to accumulation existence of some metal ion in the resistance of copper ion migration, electrolytic solution etc.After waste liquid enters electrolytic tank electrolysis, remaining liquid can not reuse need outer row, has caused the wasting of resources to bring pressure to environmental protection.
2, sulfuric acid distillation electrodeposition method: this method is to add sulfuric acid to carry out underpressure distillation in acidic etching liquid, utilize sulfuric acid reclaim HCl and produce copper sulfate from the boiling point fractionation by distillation different from volatility of hydrochloric acid, this method need add a large amount of sulfuric acid that cupric chloride is replaced as to copper sulfate, and cupric chloride can not be replaced as copper sulfate by sulfuric acid completely, while causing electrolysis, produce chlorine, complex manufacturing is dangerous high.
3, straight run distillation extraction process: this method is first to utilize underpressure distillation, separates the HCl in acidic etching liquid, and still residue reclaims metallic copper by the method for solution extraction-electrodeposition.But due to the separated HCl weak effect of straight run distillation, still residue acid concentration is still very high, causes extraction efficiency low, without actual promotional value.
4, acid system extraction process: acidic etching liquid water and alkaline matter adjust to 1 ~ 3 by pH value, under acid system, use the extraction agent extracting copper-back extraction extracting under applicable acid system, produce electrolytic copper, it is low that acidic etching liquid pH value is adjusted under 1 ~ 3 o'clock acid system extracting power, after copper extraction is a certain amount of, raffinate pH value decline extraction was lost efficacy, need be added a large amount of tap water dilution adjustment pH value to 1 ~ 3 and repeatedly extracted, ten times of increments of raffinate contain a large amount of dilute hydrochloric acid discharges and cause the wasting of resources and new environmental pollution, to enterprise, have increased environmental protection treatment difficulty.
For a large amount of high keto-acid containing producing in the printed circuit board course of processing, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid, common processing mode is to take the intermediates such as simple neutralization precipitation and extracting process reclaim(ed) sulfuric acid copper, this method has a large amount of discharge of wastewater out, in the waste water of discharge, copper content is up to several grams per liters, even the treatment plant that some are relatively large, in its outer draining, copper concentration is also often higher than 1ppm, the copper sulfate reclaiming is because process characteristic causes purity not high, and added value of product is little.
[summary of the invention]
The technical problem to be solved in the present invention is, defect for prior art, provide that a kind of not only the Cu in waste water content of discharge can qualified discharge after this processes, more can produce printed circuit board (PCB) acid, alkaline etching waste liquid for producing and the nitric acid stripping and hanging waste liquid mixed processing method of highly purified metallic copper.
In order to solve the problems of the technologies described above, the invention provides a kind of printed circuit board (PCB) acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, said method comprising the steps of:
Step a: pending acidic etching waste liquid is added in quartzy evaporation equipment, again described quartzy evaporation equipment energising is heated to 110 ° of C(and please provides a value range) and produce the first mixed gas, by condenser system, this first mixed gas be cooled to normal temperature and collected by collector, in described quartzy evaporation equipment bottom, collecting and obtain the first cupric ion mixture and this first cupric ion mixture is poured in storage pool;
Step b: pending alkaline etching waste liquid for producing is added in described quartzy evaporation equipment, again described quartzy evaporation equipment energising is heated to 110 ° of C(and please provides a value range) and produce the second mixed gas, by described condenser system, this second mixed gas be cooled to normal temperature and collected by collector, in described quartzy evaporation equipment bottom, collecting and obtain the second cupric ion mixture and this second cupric ion mixture is poured in described storage pool;
Step c: pending nitric acid stripping and hanging waste liquid is added in described quartzy evaporation equipment, again described quartzy evaporation equipment energising is heated to 360 ° of C(and please provides a value range) and produce high density nitric acid gas, by described condenser system, this high density nitric acid gas cooling is collected to normal temperature and by collector, in described quartzy evaporation equipment bottom, collect and obtain the 3rd cupric ion mixture and the 3rd cupric ion mixture is poured in described storage pool;
Steps d: add appropriate dilute sulphuric acid in described storage pool, fully stir, described the first cupric ion mixture, the second cupric ion mixture and the 3rd cupric ion mixture are dissolved completely and obtain copper-bath;
Step e: the copper-bath obtaining in steps d is positioned over and forms electrolytic solution in electrolyzer, described electrolytic solution continuous heating to 45 ° C(please be provided to a value range), and continue electrolysis (please provide the current density of electrolysis) with the current density of 0.5 ~ 1.0ASD, generate high purity metal copper.
Further, in above-mentioned printed circuit board (PCB) acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, described step a also comprises: add appropriate sodium hydroxide solution to neutralize the acidic solution of collecting after cooling, obtain the mixing solutions of sodium-chlor and ammonium chloride, by this mixing solutions being evaporated to sodium-chlor and the ammonium chloride that obtains solid.
Further, in above-mentioned printed circuit board (PCB) acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, described step b also comprises: the described solution of collecting after cooling is ammonium chloride solution, by this ammonium chloride solution being evaporated to the ammonium chloride that obtains solid.
Further, in the acid of above-mentioned printed circuit board (PCB), alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, the solution of collecting after cooling in described step c is concentrated nitric acid solution.
Further, in above-mentioned printed circuit board (PCB) acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, described steps d specifically comprises:
Detect the copper content of the first cupric ion mixture in described storage pool, the second cupric ion mixture and the 3rd cupric ion mixture, according to this copper content, prepare appropriate dilution heat of sulfuric acid, in described storage pool, add described appropriate dilute sulphuric acid, fully stir and support machine to bulging foster in described storage pool by drum, described the first cupric ion mixture, the second cupric ion mixture and the 3rd cupric ion mixture being dissolved completely and obtain copper-bath.
Further, in above-mentioned printed circuit board (PCB) acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, after described step e, also comprise: liquid after the electricity after electrolysis is added in described storage pool, is cycled to repeat described steps d and step e.
Not only copper content can qualified discharge in processed waste water for printed circuit board (PCB) of the present invention acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, more having the purity of generation is product up to more than 99.5% metallic copper, the thick copper sulfate that value produces far above common neutralization precipitation method, has obvious economic benefit and social benefit.
[embodiment]
Below in conjunction with specific embodiment, printed circuit board (PCB) acid of the present invention, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method are described.
Embodiment 1:
Pending acidic etching waste liquid is entered in special quartzy evaporation equipment by acid-resistant pipeline, again described quartzy evaporation equipment energising is heated to 110 ° of C and a large amount of steam of generation that distils, chlorine, ammonia and hydrogen chloride gas, be the first mixed gas, this first mixed gas is collected and is obtained acidic solution by collector after being cooled to normal temperature by condenser system, add appropriate sodium hydroxide solution to neutralize this acidic solution, obtain the mixing solutions of sodium-chlor and ammonium chloride, by this mixing solutions is evaporated, be recyclable sodium-chlor and the ammonium chloride that obtains solid, separately, in described quartzy evaporation equipment bottom, can collect the first cupric ion mixture that obtains a large amount of thick shape high-contents, this first cupric ion mixture is poured in storage pool pending,
Pending alkaline etching waste liquid for producing is entered in described quartzy evaporation equipment by acid-resistant pipeline, again described quartzy evaporation equipment energising is heated to 110 ° of C and distil generation a large amount of steam, ammonia and chlorine, be the second mixed gas, this second mixed gas is collected and is obtained ammonium chloride solution by collector after being cooled to normal temperature by described condenser system, by this ammonium chloride solution being evaporated to the ammonium chloride that obtains solid; Separately, in described quartzy evaporation equipment bottom, collect the second cupric ion mixture that obtains a large amount of thick shape high-contents, this second cupric ion mixture is poured in described storage pool pending;
Pending nitric acid stripping and hanging waste liquid is entered in described quartzy evaporation equipment by acid-resistant pipeline, again described quartzy evaporation equipment energising is heated to 360 ° of C and produces high density nitric acid gas, by described condenser system, this high density nitric acid gas cooling is collected and obtained concentrated nitric acid solution to normal temperature and by collector, the concentrated nitric acid solution that this collection comes can be used as nitric acid stripping and hanging liquid raw material and uses; Separately, in described quartzy evaporation equipment bottom, collect and obtain the 3rd cupric ion mixture and the 3rd cupric ion mixture is poured in described storage pool;
Detect the copper content of the first cupric ion mixture in described storage pool, the second cupric ion mixture and the 3rd cupric ion mixture, according to this copper content, prepare appropriate dilution heat of sulfuric acid, in described storage pool, add described appropriate dilute sulphuric acid, fully stir and support machine to bulging foster in described storage pool by drum, for increasing the mobility of solution in storage pool, described the first cupric ion mixture, the second cupric ion mixture and the 3rd cupric ion mixture are dissolved completely and obtain copper-bath;
Copper-bath obtained above is positioned in electrolyzer and forms electrolytic solution, by described electrolytic solution continuous heating to 45 ° C, and continue electrolysis with the current density of 1.0ASD, generate high purity metal copper;
Liquid after electricity in electrolyzer is squeezed into after electricity in liquid storage pool by pipeline with noncorrosive pump, liquid after electricity is carried out after the electricity after composition regulation to liquid again in described storage pool, be cycled to repeat described steps d and step e recycles.
Embodiment 2:
Pending acidic etching waste liquid is entered in special quartzy evaporation equipment by acid-resistant pipeline, again described quartzy evaporation equipment energising is heated to 120 ° of C and a large amount of steam of generation that distils, chlorine, ammonia and hydrogen chloride gas, be the first mixed gas, this first mixed gas is collected and is obtained acidic solution by collector after being cooled to normal temperature by condenser system, add appropriate sodium hydroxide solution to neutralize this acidic solution, obtain the mixing solutions of sodium-chlor and ammonium chloride, by this mixing solutions is evaporated, be recyclable sodium-chlor and the ammonium chloride that obtains solid, separately, in described quartzy evaporation equipment bottom, can collect the first cupric ion mixture that obtains a large amount of thick shape high-contents, this first cupric ion mixture is poured in storage pool pending,
Pending alkaline etching waste liquid for producing is entered in described quartzy evaporation equipment by acid-resistant pipeline, again described quartzy evaporation equipment energising is heated to 120 ° of C and distil generation a large amount of steam, ammonia and chlorine, be the second mixed gas, this second mixed gas is collected and is obtained ammonium chloride solution by collector after being cooled to normal temperature by described condenser system, by this ammonium chloride solution being evaporated to the ammonium chloride that obtains solid; Separately, in described quartzy evaporation equipment bottom, collect the second cupric ion mixture that obtains a large amount of thick shape high-contents, this second cupric ion mixture is poured in described storage pool pending;
Pending nitric acid stripping and hanging waste liquid is entered in described quartzy evaporation equipment by acid-resistant pipeline, again described quartzy evaporation equipment energising is heated to 360 ° of C and produces high density nitric acid gas, by described condenser system, this high density nitric acid gas cooling is collected and obtained concentrated nitric acid solution to normal temperature and by collector, the concentrated nitric acid solution that this collection comes can be used as nitric acid stripping and hanging liquid raw material and uses; Separately, in described quartzy evaporation equipment bottom, collect and obtain the 3rd cupric ion mixture and the 3rd cupric ion mixture is poured in described storage pool;
Detect the copper content of the first cupric ion mixture in described storage pool, the second cupric ion mixture and the 3rd cupric ion mixture, according to this copper content, prepare appropriate dilution heat of sulfuric acid, in described storage pool, add described appropriate dilute sulphuric acid, fully stir and support machine to bulging foster in described storage pool by drum, for increasing the mobility of solution in storage pool, described the first cupric ion mixture, the second cupric ion mixture and the 3rd cupric ion mixture are dissolved completely and obtain copper-bath;
Copper-bath obtained above is positioned in electrolyzer and forms electrolytic solution, by described electrolytic solution continuous heating to 50 ° C, and continue electrolysis with the current density of 0.5ASD, generate high purity metal copper;
Liquid after electricity in electrolyzer is squeezed into after electricity in liquid storage pool by pipeline with noncorrosive pump, liquid after electricity is carried out after the electricity after composition regulation to liquid again in described storage pool, be cycled to repeat described steps d and step e recycles.
Embodiment 3:
Pending acidic etching waste liquid is entered in special quartzy evaporation equipment by acid-resistant pipeline, again described quartzy evaporation equipment energising is heated to 105 ° of C and a large amount of steam of generation that distils, chlorine, ammonia and hydrogen chloride gas, be the first mixed gas, this first mixed gas is collected and is obtained acidic solution by collector after being cooled to normal temperature by condenser system, add appropriate sodium hydroxide solution to neutralize this acidic solution, obtain the mixing solutions of sodium-chlor and ammonium chloride, by this mixing solutions is evaporated, be recyclable sodium-chlor and the ammonium chloride that obtains solid, separately, in described quartzy evaporation equipment bottom, can collect the first cupric ion mixture that obtains a large amount of thick shape high-contents, this first cupric ion mixture is poured in storage pool pending,
Pending alkaline etching waste liquid for producing is entered in described quartzy evaporation equipment by acid-resistant pipeline, again described quartzy evaporation equipment energising is heated to 105 ° of C and distil generation a large amount of steam, ammonia and chlorine, be the second mixed gas, this second mixed gas is collected and is obtained ammonium chloride solution by collector after being cooled to normal temperature by described condenser system, by this ammonium chloride solution being evaporated to the ammonium chloride that obtains solid; Separately, in described quartzy evaporation equipment bottom, collect the second cupric ion mixture that obtains a large amount of thick shape high-contents, this second cupric ion mixture is poured in described storage pool pending;
Pending nitric acid stripping and hanging waste liquid is entered in described quartzy evaporation equipment by acid-resistant pipeline, again described quartzy evaporation equipment energising is heated to 360 ° of C and produces high density nitric acid gas, by described condenser system, this high density nitric acid gas cooling is collected and obtained concentrated nitric acid solution to normal temperature and by collector, the concentrated nitric acid solution that this collection comes can be used as nitric acid stripping and hanging liquid raw material and uses; Separately, in described quartzy evaporation equipment bottom, collect and obtain the 3rd cupric ion mixture and the 3rd cupric ion mixture is poured in described storage pool;
Detect the copper content of the first cupric ion mixture in described storage pool, the second cupric ion mixture and the 3rd cupric ion mixture, according to this copper content, prepare appropriate dilution heat of sulfuric acid, in described storage pool, add described appropriate dilute sulphuric acid, fully stir and support machine to bulging foster in described storage pool by drum, for increasing the mobility of solution in storage pool, described the first cupric ion mixture, the second cupric ion mixture and the 3rd cupric ion mixture are dissolved completely and obtain copper-bath;
Copper-bath obtained above is positioned in electrolyzer and forms electrolytic solution, by described electrolytic solution continuous heating to 45 ° C, and continue electrolysis with the current density of 0.8ASD, generate high purity metal copper;
Liquid after electricity in electrolyzer is squeezed into after electricity in liquid storage pool by pipeline with noncorrosive pump, liquid after electricity is carried out after the electricity after composition regulation to liquid again in described storage pool, be cycled to repeat described steps d and step e recycles.
Than prior art, not only copper content can qualified discharge in processed waste water for printed circuit board (PCB) of the present invention acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, more having the purity of generation is product up to more than 99.5% metallic copper, the thick copper sulfate that value produces far above common neutralization precipitation method, has obvious economic benefit and social benefit.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (6)
1. printed circuit board (PCB) acid, alkaline etching waste liquid for producing and a nitric acid stripping and hanging waste liquid mixed processing method, is characterized in that, said method comprising the steps of:
Step a: pending acidic etching waste liquid is added in quartzy evaporation equipment, again described quartzy evaporation equipment energising is heated to 110 ° of C(and please provides a value range) and produce the first mixed gas, by condenser system, this first mixed gas be cooled to normal temperature and collected by collector, in described quartzy evaporation equipment bottom, collecting and obtain the first cupric ion mixture and this first cupric ion mixture is poured in storage pool;
Step b: pending alkaline etching waste liquid for producing is added in described quartzy evaporation equipment, again described quartzy evaporation equipment energising is heated to 110 ° of C(and please provides a value range) and produce the second mixed gas, by described condenser system, this second mixed gas be cooled to normal temperature and collected by collector, in described quartzy evaporation equipment bottom, collecting and obtain the second cupric ion mixture and this second cupric ion mixture is poured in described storage pool;
Step c: pending nitric acid stripping and hanging waste liquid is added in described quartzy evaporation equipment, again described quartzy evaporation equipment energising is heated to 360 ° of C(and please provides a value range) and produce high density nitric acid gas, by described condenser system, this high density nitric acid gas cooling is collected to normal temperature and by collector, in described quartzy evaporation equipment bottom, collect and obtain the 3rd cupric ion mixture and the 3rd cupric ion mixture is poured in described storage pool;
Steps d: add appropriate dilute sulphuric acid in described storage pool, fully stir, described the first cupric ion mixture, the second cupric ion mixture and the 3rd cupric ion mixture are dissolved completely and obtain copper-bath;
Step e: the copper-bath obtaining in steps d is positioned over and forms electrolytic solution in electrolyzer, described electrolytic solution continuous heating to 45 ° C(please be provided to a value range), and continue electrolysis (please provide the current density of electrolysis) with the current density of 0.5 ~ 1.0ASD, generate high purity metal copper.
2. printed circuit board (PCB) according to claim 1 acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, it is characterized in that, described step a also comprises: add appropriate sodium hydroxide solution to neutralize the acidic solution of collecting after cooling, obtain the mixing solutions of sodium-chlor and ammonium chloride, by this mixing solutions being evaporated to sodium-chlor and the ammonium chloride that obtains solid.
3. printed circuit board (PCB) according to claim 1 acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, it is characterized in that, described step b also comprises: the described solution of collecting after cooling is ammonium chloride solution, by this ammonium chloride solution being evaporated to the ammonium chloride that obtains solid.
4. printed circuit board (PCB) according to claim 1 acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, is characterized in that, the solution of collecting after cooling in described step c is concentrated nitric acid solution.
5. according to printed circuit board (PCB) acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method described in claim 1-4 any one, it is characterized in that, described steps d specifically comprises:
Detect the copper content of the first cupric ion mixture in described storage pool, the second cupric ion mixture and the 3rd cupric ion mixture, according to this copper content, prepare appropriate dilution heat of sulfuric acid, in described storage pool, add described appropriate dilute sulphuric acid, fully stir and support machine to bulging foster in described storage pool by drum, described the first cupric ion mixture, the second cupric ion mixture and the 3rd cupric ion mixture being dissolved completely and obtain copper-bath.
6. printed circuit board (PCB) according to claim 5 acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, it is characterized in that, after described step e, also comprise: liquid after the electricity after electrolysis is added in described storage pool, is cycled to repeat described steps d and step e.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410169013.1A CN103979625A (en) | 2014-04-25 | 2014-04-25 | Mixing method for treating acid and alkaline etching waste liquid and nitric acid stripping waste liquid of printed-circuit boards |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410169013.1A CN103979625A (en) | 2014-04-25 | 2014-04-25 | Mixing method for treating acid and alkaline etching waste liquid and nitric acid stripping waste liquid of printed-circuit boards |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103979625A true CN103979625A (en) | 2014-08-13 |
| CN103979625A9 CN103979625A9 (en) | 2018-12-18 |
Family
ID=51271831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410169013.1A Pending CN103979625A (en) | 2014-04-25 | 2014-04-25 | Mixing method for treating acid and alkaline etching waste liquid and nitric acid stripping waste liquid of printed-circuit boards |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103979625A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319563A (en) * | 2016-09-13 | 2017-01-11 | 广沣金源（北京）科技有限公司 | Electrolytic copper and method for producing electrolytic copper from concentrated nitric acid copper-containing wastewater |
| CN109628935A (en) * | 2019-01-16 | 2019-04-16 | 成都虹华环保科技股份有限公司 | A kind of the alkaline etching liquid circular regeneration processing system and regeneration method of efficient electrolysis copper |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3738996A1 (en) * | 1986-12-02 | 1988-06-30 | Robotron Veb K | Method and appliance for the deposition of copper from ammoniacal copper chloride solutions |
| CN102303917A (en) * | 2011-08-25 | 2012-01-04 | 石祥阁 | Method for mixed treatment of waste liquid from acid etching and micro etching of printed circuit boards |
| CN103523977A (en) * | 2012-07-03 | 2014-01-22 | 库特勒自动化系统(苏州)有限公司 | Printing plate etching waste liquid treatment system and method |
| CN103556152A (en) * | 2013-11-11 | 2014-02-05 | 浙江科菲冶金科技股份有限公司 | Comprehensive recovery processing method for waste hybrid copper chloride etching liquid |
-
2014
- 2014-04-25 CN CN201410169013.1A patent/CN103979625A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3738996A1 (en) * | 1986-12-02 | 1988-06-30 | Robotron Veb K | Method and appliance for the deposition of copper from ammoniacal copper chloride solutions |
| CN102303917A (en) * | 2011-08-25 | 2012-01-04 | 石祥阁 | Method for mixed treatment of waste liquid from acid etching and micro etching of printed circuit boards |
| CN103523977A (en) * | 2012-07-03 | 2014-01-22 | 库特勒自动化系统(苏州)有限公司 | Printing plate etching waste liquid treatment system and method |
| CN103556152A (en) * | 2013-11-11 | 2014-02-05 | 浙江科菲冶金科技股份有限公司 | Comprehensive recovery processing method for waste hybrid copper chloride etching liquid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319563A (en) * | 2016-09-13 | 2017-01-11 | 广沣金源（北京）科技有限公司 | Electrolytic copper and method for producing electrolytic copper from concentrated nitric acid copper-containing wastewater |
| CN109628935A (en) * | 2019-01-16 | 2019-04-16 | 成都虹华环保科技股份有限公司 | A kind of the alkaline etching liquid circular regeneration processing system and regeneration method of efficient electrolysis copper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103979625A9 (en) | 2018-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102303917B (en) | Method for mixed treatment of waste liquid from acid etching and micro etching of printed circuit boards | |
| CN103936081B (en) | Method and system for preparing ferric chloride, electrodeposited copper and copper powder from copper-containing hydrochloric acid waste liquid | |
| CN204779821U (en) | Etching solution recycle and regeneration and carry copper device | |
| CN101658941B (en) | Technology for extracting copper powder from waste materials generated in circuit board manufacturing plants by compound extraction method | |
| CN104911596A (en) | Device and method for cyclic regeneration and copper extraction of etching liquid | |
| CN102912352A (en) | Method for recycling acidic copper-etching waste solution | |
| CN104152905A (en) | Acidic copper chloride etching liquid electrolytic regeneration recycling and copper plate recovery device and method | |
| CN103966607A (en) | Method for recovering copper and hydrochloric acid from acid etching solution | |
| CN101914785B (en) | Method for recycling silver and copper from silver-copper alloy scrap | |
| CN106495404A (en) | A kind of processing method of the high salinity cupric organic wastewater of highly acidity | |
| CN102912375B (en) | Method and the special purpose device thereof of copper is reclaimed from acidic etching liquid | |
| CN106350678B (en) | A method of recycling corrosion inhibiter and copper from brown oxide waste liquid | |
| CN104711636B (en) | Method for processing acidic etching waste solution of printed circuit board | |
| CN114016034A (en) | Recycling treatment method of etching waste liquid mixed acid | |
| CN111663155B (en) | Comprehensive recovery treatment method for waste copper cutting liquid of copper nitrate | |
| CN103979625A (en) | Mixing method for treating acid and alkaline etching waste liquid and nitric acid stripping waste liquid of printed-circuit boards | |
| CN203065178U (en) | System for preparing ferric chloride, electrodeposited copper and copper powder from copper-containing hydrochloric acid waste liquid | |
| CN104947155A (en) | Process for recovering copper from waste circuit board to prepare high purity and high strength copper foil based on electrochemical method | |
| CN101003394A (en) | System and method for treating waste solution from acidity etching printed circuit board | |
| CN103060842A (en) | Method for preparing electrodeposited cobalt under large flow | |
| CN204982072U (en) | Acid etching waste liquid copper recovery device | |
| CN111943423A (en) | Method and system for treating acidic copper-containing etching liquid | |
| CN104726866A (en) | Acidic etching waste liquid regeneration and copper recovery device | |
| CN103979755A (en) | Comprehensive treatment method of electro-plating sludge and sludge containing low amount of copper | |
| CN110790427A (en) | Treatment and recovery process of alkaline etching wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CI02 | Correction of invention patent application | ||
| CI02 | Correction of invention patent application |
Correction item: Claims|Description Correct: Zheng Que False: Error Number: 33 Page: full text Volume: 30 |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140813 |