CN103979625A9 - Printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method - Google Patents
Printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method Download PDFInfo
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Abstract
The present invention provides a kind of sour printed circuit board, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, the following steps are included: step a: acidic etching waste liquid to be processed being added into quartzy evaporation equipment, then quartzy evaporation equipment electrified regulation to 110 °C of collections are obtained the first copper ion mixture；Step b: alkaline etching waste liquid for producing to be processed is added into the quartzy evaporation equipment, collection obtains the second copper ion mixture；Step c: nitric acid stripping and hanging waste liquid to be processed is added into the quartzy evaporation equipment, collection obtains third copper ion mixture；Step d: suitable dilute sulfuric acid is added into the storage pool and obtains copper-bath；Step e: copper-bath continued electrolysis obtained in step d is generated into high purity metal copper.Not only copper content can be with qualified discharge in processed waste water by the present invention, and more have the purity of generation to be up to 99.5% or more metallic copper is product, has apparent economic benefit and social benefit.
Description
[technical field]
The present invention relates to printing manufacturing technology fields, more particularly, to a kind of printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method.
[background technique]
Recently as the fast development of electronics industry, the annual growth rate of 10-20% is always maintained at as electronics industry basic link-printed circuit board industry, domestic there are many more than 3500 families of printed circuit board manufacturing enterprise of scale at present, monthly output reaches 1.2 hundred million square metres.
In the manufacturing process of printed circuit board, need to consume a large amount of refined coppers, domestic printed circuit board manufacturing enterprise refined copper consumption is in 60,000 tons/month or more according to statistics, total amount of copper is in 50,000 tons/month or more in the copper waste etching solution of output, and copper is that one kind is present in soil and the intracorporal heavy metal element of people and animals, generally in 0.2ppm or so, excessive copper can occur precipitating/complex reaction with the intracorporal enzyme of people and animals, poisoning by enzyme occurs and loses physiological function content in soil.Copper in nature is transferred in people and animals' body by water body, plant etc., if intake is excessively high, will be made one to raise intracorporal Equilibrium of Trace Elements and be destroyed, lead to the abnormal accumulation of heavy metal in vivo, generate the results such as denaturation, carcinogenicity of causing a disease.In this way, a large amount of copper waste etching solutions generated in the manufacturing process of printed circuit board, are such as effectively treated not in time, undoubtedly can cause serious pollution hidden trouble to the environment especially water resource of printed circuit board factory surrounding area and soil.
In the industrial wastewater discharge standard of China, the monitor control index of copper is 0.5ppm, drinking water standard 0.03ppm, and American-European relevant criterion is then more severe.In the copper scrap etching solution generated due to printed circuit board processing, copper content is tens supreme hundred grams per liters, and therefore, printed circuit board copper scrap etching solution (useless copper etching liquor) is positioned as dangerous liquid waste, it is specified that treatment in situ, forbids transboundary movement by State Environmental Protection Administration.
There are several types of methods for the recycling copper of acidic etching waste liquid:
1, displacement method: the method is usually that acidic etching liquid and a small amount of alkaline etching liquid or ammonium hydroxide is used to neutralize, reduce the acidity in acidic etching liquid, then industrial iron plate is put into thereto, copper is cemented out using the activity of iron, the method understands heat release in production reaction process and generates a large amount of vapor, chlorine and hydrogen chloride gas, a large amount of waste water must be discharged after the completion of displacement, contain a large amount of Cl-, ammonia nitrogen and Fe3+ in its waste water discharged, not only pollutes in environment but also etching solution that active princlple can not regeneration.
2. membrane electrolysis: the method is to carry out diaphragm electrolysis to acidic etching waste liquid using the anode with resistance to activity Cl-, but since Cl-is higher, the electrolytic metal copper generated after electrolysis is powdery, electrolysis is to be easy to produce a large amount of chlorine and hydrogen, risk is high, and anode and ionic membrane consumption are very fast, production run cost is high.The method that copper waste etching solution recycling utilization is carried out using electrolysis with ion-exchange film, often due to high requirement of the ionic membrane to use environment, deteriorate with the progress of process, cause film properties unstable, anode and cathode plate clearance is small simultaneously, current density is at 600A/ square metres or more, the easily long fastener of cathode plate surface stabs ionic membrane, and to alter anode and cathode liquid logical, lead to systemic breakdown, it produces extremely unstable, expensive (every square metre of 8000 ~ 15000 yuan of RMB) service life of ionic membrane is short (average out to half a year) simultaneously, the presence of chloride ion and certain metal ions when electrolysis, production inevitably has chlorine generation, and the copper powdering of output, the oxidizable purity of product copper-base is low, value is lower than the 30% of standard electrolytic copper.Power consumption also tends to be higher than the three times of standard electrolytic copper or more due to there is the accumulation of certain metal ions in the resistance of copper ion migration, electrolyte etc. ionic membrane, therefore its industrial applications has certain economic, environmental protection and technical difficulty.Waste liquid, which enters extraction raffinate after electrolytic tank electrolysis and is unable to reuse, needs outlet, causes the wasting of resources to environmental protection and brings pressure.
2, sulfuric acid distills electrodeposition method: the method is that sulfuric acid is added in acidic etching liquid to be evaporated under reduced pressure, separation and recovery HCl is distilled using the boiling point and volatility difference of sulfuric acid and hydrochloric acid and produces copper sulphate, the method need to be added a large amount of sulfuric acid and copper chloride is replaced as copper sulphate, and copper chloride can not be completely by sulfate substitution at copper sulphate, cause to generate chlorine when electrolysis, production technology is complicated, and risk is high.
3, direct Water distillation extractor: the method is that the HCl in acidic etching liquid is separated first with vacuum distillation, and still residue recycles metallic copper with solution extraction-electrodeposition method.But it is poor due to directly distilling separation HCl effect, still residue acid concentration is still very high, causes extraction efficiency low, no actual promotional value.
4, acid system extraction: pH value is adjusted to 1 ~ 3 by acidic etching liquid water and alkaline matter, with the extractant extracting copper-back extraction extracted under suitable acid system under acid system, produce cathode copper, acidic etching liquid pH value is adjusted to when 1 ~ 3 that extracting power is low under acid system, after copper extraction is a certain amount of, raffinate pH value decline extraction failure, need to the amount of increasing tap water dilution adjustment pH value to 1 ~ 3 extraction is repeated, ten times of increments of raffinate contain a large amount of dilute hydrochloric acid discharges and result in waste of resources and new environmental pollution, increase environmental protection treatment difficulty to enterprise.
For a large amount of high keto-acid containings, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid generated in printed circuit board process, common processing mode is that simple neutralization precipitation and extracting process is taken to recycle the intermediate products such as copper sulphate, the method has a large amount of discharge of wastewater and comes out, copper content up to number grams per liter in the waste water of discharge, even some relatively large treatment plants, copper concentration is also often higher than 1ppm in its outer draining, and for the copper sulphate of recycling because process characteristic causes purity not high, added value of product is little.
[summary of the invention]
The technical problem to be solved in the present invention is that, in view of the drawbacks of the prior art, there is provided the Cu in waste water content that one kind is not only discharged after this treatment with qualified discharge, can more can produce printed circuit board acid, alkaline etching waste liquid for producing and the nitric acid stripping and hanging waste liquid mixed processing method of metallic copper of high-purity.
In order to solve the above technical problem, the present invention provides a kind of printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing methods, the described method comprises the following steps:
Step a: acidic etching waste liquid to be processed is added into quartzy evaporation equipment, the quartzy evaporation equipment electrified regulation is generated into the first mixed gas to 110 °C again, first mixed gas is cooled to room temperature by condenser system and is collected by collector, obtain the first copper ion mixture in the quartzy evaporation equipment bottom collection and pours into the first copper ion mixture in storage pool；
Step b: alkaline etching waste liquid for producing to be processed is added into the quartzy evaporation equipment, the quartzy evaporation equipment electrified regulation is generated into the second mixed gas to 110 °C again, second mixed gas is cooled to room temperature by the condenser system and is collected by collector, obtain the second copper ion mixture in the quartzy evaporation equipment bottom collection and pours into the second copper ion mixture in the storage pool；
Step c: nitric acid stripping and hanging waste liquid to be processed is added into the quartzy evaporation equipment, the quartzy evaporation equipment electrified regulation is generated into high concentration nitric acid gas to 360 °C again, it is collected by the condenser system to the high concentration nitric acid gas cooling to room temperature and by collector, obtains third copper ion mixture in the quartzy evaporation equipment bottom collection and pours into the third copper ion mixture in the storage pool；
Step d: suitable dilute sulfuric acid being added into the storage pool, is sufficiently stirred, so that the first copper ion mixture, the second copper ion mixture and third copper ion mixture are completely dissolved to obtain copper-bath；
Step e: copper-bath obtained in step d being placed in electrolytic cell and forms electrolyte, by the electrolyte continuous heating to 45 °C, and with the current density continued electrolysis of 0.5 ~ 1.0ASD, generates high purity metal copper.
Further, in above-mentioned printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, the step a further include: appropriate sodium hydroxide solution is added in the acid solution being collected into after cooling and is neutralized, the mixed solution of sodium chloride and ammonium chloride is obtained, obtains the sodium chloride of solid and ammonium chloride by being evaporated to the mixed solution.
Further, in above-mentioned printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, the step b further include: the solution being collected into after the cooling is ammonium chloride solution, obtains the ammonium chloride of solid by being evaporated to the ammonium chloride solution.
Further, in above-mentioned printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, the solution being collected into after cooling in the step c is concentrated nitric acid solution.
Further, in above-mentioned printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, the step d is specifically included:
Detect the copper content of the first copper ion mixture, the second copper ion mixture and third copper ion mixture in the storage pool, suitable dilution heat of sulfuric acid is prepared according to the copper content, suitable dilute sulfuric acid is added into the storage pool, it is sufficiently stirred and passes through the feeding machine of drum drum into the storage pool and support, so that the first copper ion mixture, the second copper ion mixture and third copper ion mixture are completely dissolved to obtain copper-bath.
Further, in above-mentioned printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, after the step e further include: liquid after the electricity after electrolysis is added in the storage pool, step d and step e described in circulating repetition.
Not only copper content can be with qualified discharge in processed waste water for printed circuit board of the present invention acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, more there is the purity of generation to be up to 99.5% or more metallic copper as product, value has apparent economic benefit and social benefit much higher than the thick copper sulphate that common neutralization precipitation method generates.
[specific embodiment]
Illustrate printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method of the invention below in conjunction with specific embodiment.
Embodiment 1:
Acidic etching waste liquid to be processed is entered in special quartzy evaporation equipment by acid-resistant pipeline, the quartzy evaporation equipment electrified regulation is distilled to 110 °C again and generates a large amount of steam, chlorine, ammonia and hydrogen chloride gas, as the first mixed gas, first mixed gas collects to obtain acid solution by collector after being cooled to room temperature by condenser system, appropriate sodium hydroxide solution is added in the acid solution to neutralize, obtain the mixed solution of sodium chloride and ammonium chloride, the sodium chloride and ammonium chloride of solid are obtained by being evaporated to can be recycled to the mixed solution；The first copper ion mixture of a large amount of thick shape high-contents is obtained in addition, collecting in the quartzy evaporation equipment bottom, which is poured into be processed in storage pool；
Alkaline etching waste liquid for producing to be processed is entered in the quartzy evaporation equipment by acid-resistant pipeline, the quartzy evaporation equipment electrified regulation is distilled to 110 °C again and generates a large amount of steam, ammonia and chlorine, as the second mixed gas, second mixed gas collects to obtain ammonium chloride solution by collector after being cooled to room temperature by the condenser system, obtains the ammonium chloride of solid by being evaporated to the ammonium chloride solution；In addition, obtaining the second copper ion mixture of a large amount of thick shape high-contents in the quartzy evaporation equipment bottom collection, which is poured into be processed in the storage pool；
Nitric acid stripping and hanging waste liquid to be processed is entered in the quartzy evaporation equipment by acid-resistant pipeline, the quartzy evaporation equipment electrified regulation is generated into high concentration nitric acid gas to 360 °C again, it is collected to the high concentration nitric acid gas cooling to room temperature and by collector to obtain concentrated nitric acid solution by the condenser system, the concentrated nitric acid solution which comes can be used as the use of nitric acid stripping and hanging liquid raw material；In addition, obtaining third copper ion mixture in the quartzy evaporation equipment bottom collection and pouring into the third copper ion mixture in the storage pool；
Detect the copper content of the first copper ion mixture, the second copper ion mixture and third copper ion mixture in the storage pool, suitable dilution heat of sulfuric acid is prepared according to the copper content, suitable dilute sulfuric acid is added into the storage pool, it is sufficiently stirred and passes through the feeding machine of drum drum into the storage pool and support, for increasing the mobility of solution in storage pool, so that the first copper ion mixture, the second copper ion mixture and third copper ion mixture are completely dissolved to obtain copper-bath；
Copper-bath obtained above is placed in electrolytic cell and forms electrolyte, by the electrolyte continuous heating to 45 °C, and with the current density continued electrolysis of 1.0ASD, generates high purity metal copper；
Liquid after electricity in electrolytic cell is squeezed into after electricity in liquid storage pool with noncorrosive pump by pipeline, again in the storage pool, step d and step e described in circulating repetition are recycled liquid after the electricity after liquid after electricity to be carried out to composition regulation.
Embodiment 2:
Acidic etching waste liquid to be processed is entered in special quartzy evaporation equipment by acid-resistant pipeline, the quartzy evaporation equipment electrified regulation is distilled to 120 °C again and generates a large amount of steam, chlorine, ammonia and hydrogen chloride gas, as the first mixed gas, first mixed gas collects to obtain acid solution by collector after being cooled to room temperature by condenser system, appropriate sodium hydroxide solution is added in the acid solution to neutralize, obtain the mixed solution of sodium chloride and ammonium chloride, the sodium chloride and ammonium chloride of solid are obtained by being evaporated to can be recycled to the mixed solution；The first copper ion mixture of a large amount of thick shape high-contents is obtained in addition, collecting in the quartzy evaporation equipment bottom, which is poured into be processed in storage pool；
Alkaline etching waste liquid for producing to be processed is entered in the quartzy evaporation equipment by acid-resistant pipeline, the quartzy evaporation equipment electrified regulation is distilled to 120 °C again and generates a large amount of steam, ammonia and chlorine, as the second mixed gas, second mixed gas collects to obtain ammonium chloride solution by collector after being cooled to room temperature by the condenser system, obtains the ammonium chloride of solid by being evaporated to the ammonium chloride solution；In addition, obtaining the second copper ion mixture of a large amount of thick shape high-contents in the quartzy evaporation equipment bottom collection, which is poured into be processed in the storage pool；
Nitric acid stripping and hanging waste liquid to be processed is entered in the quartzy evaporation equipment by acid-resistant pipeline, the quartzy evaporation equipment electrified regulation is generated into high concentration nitric acid gas to 360 °C again, it is collected to the high concentration nitric acid gas cooling to room temperature and by collector to obtain concentrated nitric acid solution by the condenser system, the concentrated nitric acid solution which comes can be used as the use of nitric acid stripping and hanging liquid raw material；In addition, obtaining third copper ion mixture in the quartzy evaporation equipment bottom collection and pouring into the third copper ion mixture in the storage pool；
Detect the copper content of the first copper ion mixture, the second copper ion mixture and third copper ion mixture in the storage pool, suitable dilution heat of sulfuric acid is prepared according to the copper content, suitable dilute sulfuric acid is added into the storage pool, it is sufficiently stirred and passes through the feeding machine of drum drum into the storage pool and support, for increasing the mobility of solution in storage pool, so that the first copper ion mixture, the second copper ion mixture and third copper ion mixture are completely dissolved to obtain copper-bath；
Copper-bath obtained above is placed in electrolytic cell and forms electrolyte, by the electrolyte continuous heating to 50 °C, and with the current density continued electrolysis of 0.5ASD, generates high purity metal copper；
Liquid after electricity in electrolytic cell is squeezed into after electricity in liquid storage pool with noncorrosive pump by pipeline, again in the storage pool, step d and step e described in circulating repetition are recycled liquid after the electricity after liquid after electricity to be carried out to composition regulation.
Embodiment 3:
Acidic etching waste liquid to be processed is entered in special quartzy evaporation equipment by acid-resistant pipeline, the quartzy evaporation equipment electrified regulation is distilled to 105 °C again and generates a large amount of steam, chlorine, ammonia and hydrogen chloride gas, as the first mixed gas, first mixed gas collects to obtain acid solution by collector after being cooled to room temperature by condenser system, appropriate sodium hydroxide solution is added in the acid solution to neutralize, obtain the mixed solution of sodium chloride and ammonium chloride, the sodium chloride and ammonium chloride of solid are obtained by being evaporated to can be recycled to the mixed solution；The first copper ion mixture of a large amount of thick shape high-contents is obtained in addition, collecting in the quartzy evaporation equipment bottom, which is poured into be processed in storage pool；
Alkaline etching waste liquid for producing to be processed is entered in the quartzy evaporation equipment by acid-resistant pipeline, the quartzy evaporation equipment electrified regulation is distilled to 105 °C again and generates a large amount of steam, ammonia and chlorine, as the second mixed gas, second mixed gas collects to obtain ammonium chloride solution by collector after being cooled to room temperature by the condenser system, obtains the ammonium chloride of solid by being evaporated to the ammonium chloride solution；In addition, obtaining the second copper ion mixture of a large amount of thick shape high-contents in the quartzy evaporation equipment bottom collection, which is poured into be processed in the storage pool；
Nitric acid stripping and hanging waste liquid to be processed is entered in the quartzy evaporation equipment by acid-resistant pipeline, the quartzy evaporation equipment electrified regulation is generated into high concentration nitric acid gas to 360 °C again, it is collected to the high concentration nitric acid gas cooling to room temperature and by collector to obtain concentrated nitric acid solution by the condenser system, the concentrated nitric acid solution which comes can be used as the use of nitric acid stripping and hanging liquid raw material；In addition, obtaining third copper ion mixture in the quartzy evaporation equipment bottom collection and pouring into the third copper ion mixture in the storage pool；
Detect the copper content of the first copper ion mixture, the second copper ion mixture and third copper ion mixture in the storage pool, suitable dilution heat of sulfuric acid is prepared according to the copper content, suitable dilute sulfuric acid is added into the storage pool, it is sufficiently stirred and passes through the feeding machine of drum drum into the storage pool and support, for increasing the mobility of solution in storage pool, so that the first copper ion mixture, the second copper ion mixture and third copper ion mixture are completely dissolved to obtain copper-bath；
Copper-bath obtained above is placed in electrolytic cell and forms electrolyte, by the electrolyte continuous heating to 45 °C, and with the current density continued electrolysis of 0.8ASD, generates high purity metal copper；
Liquid after electricity in electrolytic cell is squeezed into after electricity in liquid storage pool with noncorrosive pump by pipeline, again in the storage pool, step d and step e described in circulating repetition are recycled liquid after the electricity after liquid after electricity to be carried out to composition regulation.
Compared with the prior art, not only copper content can be with qualified discharge in processed waste water for printed circuit board of the present invention acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, more there is the purity of generation to be up to 99.5% or more metallic copper as product, value has apparent economic benefit and social benefit much higher than the thick copper sulphate that common neutralization precipitation method generates.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, and but it cannot be understood as limitations on the scope of the patent of the present invention.It should be pointed out that for those of ordinary skill in the art, without departing from the inventive concept of the premise, various modifications and improvements can be made, and these are all within the scope of protection of the present invention.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (6)
1. a kind of printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method, which is characterized in that the described method comprises the following steps:
Step a: acidic etching waste liquid to be processed is added into quartzy evaporation equipment, the quartzy evaporation equipment electrified regulation is generated into the first mixed gas to 110 °C again, first mixed gas is cooled to room temperature by condenser system and is collected by collector, obtain the first copper ion mixture in the quartzy evaporation equipment bottom collection and pours into the first copper ion mixture in storage pool；
Step b: alkaline etching waste liquid for producing to be processed is added into the quartzy evaporation equipment, the quartzy evaporation equipment electrified regulation is generated into the second mixed gas to 110 °C again, second mixed gas is cooled to room temperature by the condenser system and is collected by collector, obtain the second copper ion mixture in the quartzy evaporation equipment bottom collection and pours into the second copper ion mixture in the storage pool；
Step c: nitric acid stripping and hanging waste liquid to be processed is added into the quartzy evaporation equipment, the quartzy evaporation equipment electrified regulation is generated into high concentration nitric acid gas to 360 °C again, it is collected by the condenser system to the high concentration nitric acid gas cooling to room temperature and by collector, obtains third copper ion mixture in the quartzy evaporation equipment bottom collection and pours into the third copper ion mixture in the storage pool；
Step d: suitable dilute sulfuric acid being added into the storage pool, is sufficiently stirred, so that the first copper ion mixture, the second copper ion mixture and third copper ion mixture are completely dissolved to obtain copper-bath；
Step e: copper-bath obtained in step d being placed in electrolytic cell and forms electrolyte, by the electrolyte continuous heating to 45 °C, and with the current density continued electrolysis of 0.5 ~ 1.0ASD, generates high purity metal copper.
2. printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method according to claim 1, it is characterized in that, the step a further include: appropriate sodium hydroxide solution is added in the acid solution being collected into after cooling and is neutralized, the mixed solution of sodium chloride and ammonium chloride is obtained, obtains the sodium chloride of solid and ammonium chloride by being evaporated to the mixed solution.
3. printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method according to claim 1, it is characterized in that, the step b further include: the solution being collected into after the cooling is ammonium chloride solution, obtains the ammonium chloride of solid by being evaporated to the ammonium chloride solution.
4. printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method according to claim 1, which is characterized in that the solution being collected into after cooling in the step c is concentrated nitric acid solution.
5. printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method according to claim 1-4, which is characterized in that the step d is specifically included:
Detect the copper content of the first copper ion mixture, the second copper ion mixture and third copper ion mixture in the storage pool, suitable dilution heat of sulfuric acid is prepared according to the copper content, suitable dilute sulfuric acid is added into the storage pool, it is sufficiently stirred and passes through the feeding machine of drum drum into the storage pool and support, so that the first copper ion mixture, the second copper ion mixture and third copper ion mixture are completely dissolved to obtain copper-bath.
6. printed circuit board acid, alkaline etching waste liquid for producing and nitric acid stripping and hanging waste liquid mixed processing method according to claim 5, it is characterized in that, after the step e further include: liquid after the electricity after electrolysis is added in the storage pool, step d and step e described in circulating repetition.
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| 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 |
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| 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 |
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| 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 |
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| CN102303917B (en) * | 2011-08-25 | 2014-01-01 | 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 |
| CN103556152B (en) * | 2013-11-11 | 2015-08-05 | 浙江科菲科技股份有限公司 | A kind of mixed chlorinated copper spent etching solution synthetical recovery treatment process |
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| CI02 | Correction of invention patent application | ||
| CI02 | Correction of invention patent application |
Correction item: Claims|Description Correct: Zheng Que False: Cuo Wu Number: 33 Page: Quan Wen Volume: 30 |
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140813 |