CN102603102B - Processing method of browning liquid - Google Patents
Processing method of browning liquid Download PDFInfo
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- CN102603102B CN102603102B CN201210090682.0A CN201210090682A CN102603102B CN 102603102 B CN102603102 B CN 102603102B CN 201210090682 A CN201210090682 A CN 201210090682A CN 102603102 B CN102603102 B CN 102603102B
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Abstract
The invention provides a processing method of a browning liquid. The processing method particularly comprises the following steps: step one, adding at least one cationic polymer in the browning liquid so as to form electrolyzable complexing copper in the browning liquid; and step two, electrolyzing the browning liquid in the step one to separate out simple substance copper. According to the processing method of the browning liquid, the cationic polymer is added in the browning liquid, and the copper in the browning liquid is recovered by adopting a direct electrolysis method; the operation method is simple, the recovery rate of copper in the browning liquid is increased due to the addition of an electrolysis additive, and recovered copper is very high in utilization value, in addition, the processing cost of a sewage plant is lowered, and the discharging amount of heavy metal pollutants is reduced.
Description
Technical field
The present invention relates to the heavy metal waste liquid and reclaim field, especially, relate to a kind of brown liquid processing method.
Background technology
Fast development and the market requirement along with the printing plate industry, the manufacturing technology of printing plate is just towards the future development of thin plate, small-bore, highly denseization, after the internal layer bare copper wire road deck of completing circuit plate, then carry out multilayer build-up and pressing, finally also will carry out the brown processing.
Carrying out along with the brown processing, copper ion concentration in brown liquid can constantly rise, when copper ion concentration surpass a certain amount of after, brown liquid just can because cupric ion too much produces, the brown copper face turns white, the unequal quality problems of brown copper face color and luster, therefore, now in the brown groove, need to change new liquid or constantly supplement new brown liquid, by all discharge or constantly discharges of waste liquid, thereby guarantee the quality of brown product.
The treatment process of the waste liquid after current circuit board plant is processed brown is mainly to adopt traditional chemical precipitation method, heavy metal copper ion content higher (general content is at 30-50g/L) due to waste liquid, contain a large amount of organic complexing agents in waste liquid, copper just exists in waste liquid with the form of complex state simultaneously.While adopting chemical precipitation method to dispose waste liquid, chemical consumption is very large, and the filtration mud copper mass of output is low, and not only its economic worth is not high, and easily causes the secondary pollution to environment when this mud is carried out to purification processes.
At Chinese invention patent application prospectus CN201713399 a kind of brown liquid is disclosed by the device of crystallisation by cooling regeneration, the method cost recovery is high, and cycle index is limited, and the mantoquita that crystallization is reclaimed is owing to containing a large amount of organism, added value is very low, and economic benefit is not high.
Summary of the invention
The object of the invention is to provide a kind of brown liquid processing method, not high to solve the copper utilization ratio reclaimed in brown liquid, causes the technical problem of the wasting of resources.
For achieving the above object, according to an aspect of the present invention, provide a kind of brown liquid processing method, comprised the following steps: step 1: added at least one cationic polymers in brown liquid, make in brown liquid and form eletrolyzable complex copper; Step 2: the brown liquid in step 1 is carried out to electrolysis treatment, separate out elemental copper.
Further, also add at least one electrolysis additive in step 1.
Further, every 1L brown liquid adds the electrolysis additive of 0.01～1g.
Further, one or more in the group that electrolysis additive selects free sodium polydithio-dipropyl sulfonate, polymine alkyl salt, phenyl two sulphur two propane sulfonic acid sodium, pure mercapto propyl-sulfonate, aliphatic amide oxyethyl group sulfonated bodies, ethylene thiourea, 2-coloured glaze base benzene, polymine alkylate, polymine alkyl salt, the thin base benzimidazolyl (M) of 2-and polyoxyethylene glycol to form.
Further, one or more in the group that cationic polymers selects free benzyl trimethyl ammonium chloride, chlorination tributyl hexadecyldimethyl benzyl ammonium and distearyl dimethyl ammonium chloride to form.
Further, the brown liquid of every 1L adds the cationic polymers of 0.0001～1g.
Further, the brown liquid of every 1L adds the cationic polymers of 0.05～0.5g.
Temperature when further, brown liquid is processed is controlled between 25 ℃～40 ℃.
Temperature when further, brown liquid is processed is 35 ℃.
The present invention has following beneficial effect: brown liquid processing method of the present invention, and than prior art, added cationic polymers in brown liquid after, adopt the method for Direct Electrolysis to reclaim the copper in brown liquid, working method is simple.Add electrolysis additive, make the rate of recovery of the copper in brown liquid very high, the copper of recovery has very high utility value, and can alleviate the processing costs of sewage plant and the discharge of heavy metal contaminants.
Except purpose described above, feature and advantage, the present invention also has other purpose, feature and advantage.Below, with reference to figure, the present invention is further detailed explanation.
The accompanying drawing explanation
The accompanying drawing that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention the present invention does not form inappropriate limitation of the present invention for explaining.In the accompanying drawings:
Fig. 1 is the schema for the treatment of process of the waste liquid of the preferred embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
Brown liquid of the present invention is the waste liquid of brown after processing in circuit card technique, in above-mentioned brown liquid, contain can not Direct Electrolysis complex copper.Referring to Fig. 1, the preferred embodiments of the present invention provide a kind for the treatment of process of brown liquid, at first in brown liquid, add a certain amount of cationic polymers, make complex copper in brown liquid convert eletrolyzable complex copper to; Then be injected in electrolyzer and carry out electrolysis, to separate out elemental copper.
Temperature general control in above-mentioned brown liquid treating processes is between 25 ℃～40 ℃.Preferably, temperature is 35 ℃.
Brown liquid processing method detailed process of the present invention is as follows:
Step S1: add at least one cationic polymers in brown liquid, make in brown liquid and form eletrolyzable complex copper;
Cupric ion in brown liquid, be present in organism, with the form of complex state, exists, and the molecular structure of this kind of complex copper is more stable, and Direct Electrolysis is difficult to by cupric electrolysis out.
In the preferred embodiment of the present invention, add a certain amount of at least one cationic polymers in brown liquid, add the cationic polymers of 0.0001～1g in the above-mentioned brown liquid of every 1L, when the cationic polymers added in the brown liquid of every 1L is less than 0.0001g, the addition of cationic polymers is very few, with complex copper, reacts not obvious; When the cationic polymers added in the brown liquid of every 1L is greater than 1g, the addition of cationic polymers is too much, can cause the waste of cationic polymers.
One or more in the group that cationic polymers selects free benzyl trimethyl ammonium chloride, chlorination tributyl hexadecyldimethyl benzyl ammonium and distearyl dimethyl ammonium chloride to form.In other embodiment, it can also be other cationic polymers, as the diallyl dimethyl ammonium chloride, these cationic polymerss can be robbed original cupric ion in can not the complex copper of electrolysis to dispossess, and regroup into new eletrolyzable complex copper.
After adding cationic polymers, cationic polymers is robbed the cupric ion in original complex copper to dispossess, and reformulates new complex copper, and the complex copper reconfigured copper ion releasing after electrolysis forms copper at negative electrode.The valence state that the complex compound that these cupric ions form shows is nominal price, has the copper complex of the characteristic that can follow the impressed current motion, as cupric ammine complex etc., all has these characteristics.
Usually, after adding cationic polymers, the copper ion concentration in brown liquid is in 30～50g/L left and right.
In the preferred embodiment of the present invention, when adding cationic polymers in brown liquid, in order to obtain the high and ganoid electrolytic copper of purity, can further add a certain amount of electrolysis additive, add the electrolysis additive of 0.01～1g in the above-mentioned waste liquid of every 1L, when the electrolysis additive added in the brown liquid of every 1L is less than 0.01g, the addition of electrolysis additive is very few, and the effect of electrolysis additive is not obvious; When the electrolysis additive added in the brown liquid of every 1L is greater than 1g, the addition of electrolysis additive is too much, the copper Chan Sheng that can cause the circuit card electrolysis to produce ?lilac band, and copper is rough.
One or more in the group that this electrolysis additive selects free sodium polydithio-dipropyl sulfonate, polymine alkyl salt, phenyl two sulphur two propane sulfonic acid sodium, pure mercapto propyl-sulfonate, aliphatic amide oxyethyl group sulfonated bodies, ethylene thiourea, 2-coloured glaze base benzene, polymine alkylate, polymine alkyl salt, the thin base benzimidazolyl (M) of 2-and polyoxyethylene glycol to form.
The current efficiency when electrolysis additive added can improve electrolysis, and can guarantee that electrodeposition goes out purity in the elemental copper more than 99%, and the compact structure of this elemental copper in higher current density and the lower solution of copper ion concentration.
Step S2: the brown liquid in above-mentioned steps S1 is carried out to electrolysis treatment, separate out elemental copper;
In the preferred embodiment of the present invention, adopt titanium coated anode and stainless steel cathode.Waste liquid is injected in electrolyzer, then negative plate and positive plate is inserted in electrolyzer, energising, and to make current density in electrolyzer be 250～500A/m
2, following reaction occurs respectively near negative plate and near positive plate in brown liquid:
Negative electrode Cu
2++ 2e
-=Cu
Anode O
2+ 2H
2o+4e
-=4OH
-
After above-mentioned electrolysis, the cupric ion in brown liquid has been gradually transformed into elemental copper, and these elemental copper are attached on negative plate.Now, in brown liquid, the content of cupric ion descends, the density loss to 0.5 of its cupric ion～1.0g/L; Near pH value positive plate increases.
When the copper on negative plate no longer increases, negative plate is taken out, the copper-stripping that then will be attached on negative plate reclaims, and these steel structures are fine and close, it is block to be, fragility slightly.
The concentration of brown liquid institute copper ions after treatment is very low, this brown liquid directly can be discharged into to sewage works and be processed.
Embodiment
In following examples, medicine used and instrument are commercially available.Copper content in following examples in the long-pending * brown liquid of the theoretical yield of copper=brown liquid.
Embodiment 1:
When temperature is 25 ℃, get brown liquid 2000L, copper content is 34.9g/L, and theoretical product copper is 69.8Kg, and current density is 250A/m
2, add the benzyl trimethyl ammonium chloride of 0.2g and the sodium polydithio-dipropyl sulfonate of 20g in brown liquid, after carrying out electrolysis, the output of the actual copper obtained is 67.8Kg, and current efficiency now is 97.7%, and now in brown liquid, the content of copper is 1g/L.
Embodiment 2:
When temperature is 28 ℃, get brown liquid 2000L, copper content is 37.4g/L, and theoretical product copper is 74.8Kg, and current density is 300A/m
2, add the chlorination tributyl hexadecyldimethyl benzyl ammonium of 5g and the polymine alkyl salt of 80g in brown liquid, after carrying out electrolysis, the output of the actual copper obtained is 72.9Kg, and current efficiency now is 97.4%, and now in brown liquid, the content of copper is 0.95g/L.
Embodiment 3:
When temperature is 30 ℃, get brown liquid 2000L, copper content is 40g/L, and theoretical product copper is 80Kg, and current density is 350A/m
2add the distearyl dimethyl ammonium chloride of 10g and the phenyl two sulphur two propane sulfonic acid sodium of 100g in brown liquid, after carrying out electrolysis, the output of the actual copper obtained is 78.7Kg, current efficiency now is 98.3%, and now in brown liquid, the content of copper is 0.65g/L.
Embodiment 4:
When temperature is 35 ℃, get brown liquid 2000L, copper content is 42.3g/L, and theoretical product copper is 84.6Kg, and current density is 400A/m
2add the benzyl trimethyl ammonium chloride of 500g and composition and the sodium polydithio-dipropyl sulfonate of 800g and the composition of polymine alkyl salt of chlorination tributyl hexadecyldimethyl benzyl ammonium in brown liquid, after carrying out electrolysis, the output of the actual copper obtained is 83.6Kg, current efficiency now is 98.8%, and now in brown liquid, the content of copper is 0.5g/L.
Embodiment 5:
When temperature is 36 ℃, get brown liquid 2000L, copper content is 42g/L, and theoretical product copper is 84Kg, and current density is 450A/m
2toward adding benzyl trimethyl ammonium chloride and the composition of distearyl dimethyl ammonium chloride and phenyl two sulphur two propane sulfonic acid sodium and the pure mercapto propyl-sulfonate compositions of 1000g of 1000g in brown liquid, after carrying out electrolysis, the output of the actual copper obtained is 82.4Kg, current efficiency now is 98%, and now in brown liquid, the content of copper is 0.8g/L.
Embodiment 6:
When temperature is 38 ℃, get brown liquid 2000L, copper content is 44.9g/L, and theoretical product copper is 89.8Kg, and current density is 500A/m
2composition toward aliphatic amide oxyethyl group sulfonated bodies, ethylene thiourea, 2-coloured glaze base benzene and the polymine alkyl salt of the composition of the benzyl trimethyl ammonium chloride, chlorination tributyl hexadecyldimethyl benzyl ammonium and the distearyl dimethyl ammonium chloride that add 2000g in brown liquid and 2000g, after carrying out electrolysis, the output of the actual copper obtained is 88Kg, current efficiency now is 97.9%, and now in brown liquid, the content of copper is 0.9g/L.
Embodiment 7:
When temperature is 40 ℃, get brown liquid 2000L, copper content is 44g/L, and theoretical product copper is 88Kg, and current density is 300A/m
2add the diallyl dimethyl ammonium chloride of 1000g and phenyl two sulphur two propane sulfonic acid sodium and the pure mercapto propyl-sulfonate compositions of 1000g in brown liquid, after carrying out electrolysis, the output of the actual copper obtained is 86.6Kg, current efficiency now is 98.4%, and now in brown liquid, the content of copper is 0.7g/L.
Embodiment 8:
When temperature is 38 ℃, get brown liquid 2000L, copper content is 38.4g/L, and theoretical product copper is 76.8Kg, and current density is 300A/m
2, toward adding the chlorination tributyl hexadecyldimethyl benzyl ammonium of 100g in brown liquid, after carrying out electrolysis, the output of the actual copper obtained is 63Kg, and current efficiency now is 82%, and now in brown liquid, the content of copper is 6.9g/L.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (3)
1. a brown liquid processing method, is characterized in that, comprises the following steps:
Step S1: add at least one cationic polymers in described brown liquid, make in described brown liquid and form eletrolyzable complex copper;
Step S2: the brown liquid in step S1 is carried out to electrolysis treatment, and temperature when described brown liquid is processed is controlled between 25 ℃～40 ℃ separates out elemental copper,
One or more in the group that described cationic polymers selects free benzyl trimethyl ammonium chloride, chlorination tributyl hexadecyldimethyl benzyl ammonium and distearyl dimethyl ammonium chloride to form, and the described brown liquid of every 1L adds the described cationic polymers of 0.0001～1g;
Also add at least one electrolysis additive in described step S1, one or more in the group that described electrolysis additive selects free sodium polydithio-dipropyl sulfonate, polymine alkyl salt, phenyl two sulphur two propane sulfonic acid sodium, pure mercapto propyl-sulfonate, aliphatic amide oxyethyl group sulfonated bodies, ethylene thiourea, 2-coloured glaze base benzene, polymine alkylate, polymine alkyl salt, the thin base benzimidazolyl (M) of 2-and polyoxyethylene glycol to form, and the described brown liquid of every 1L adds the described electrolysis additive of 0.01～1g.
2. brown liquid processing method according to claim 1, is characterized in that, the described brown liquid of every 1L adds the described cationic polymers of 0.05～0.5g.
3. brown liquid processing method according to claim 1, is characterized in that, temperature when described brown liquid is processed is 35 ℃.
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| CN201210090682.0A CN102603102B (en) | 2012-03-30 | 2012-03-30 | Processing method of browning liquid |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103233244B (en) * | 2013-05-16 | 2015-08-05 | 广东工业大学 | A kind of method utilizing useless brown liquid to extract copper |
| CN103510107B (en) * | 2013-09-24 | 2015-12-23 | 湖南凯天重金属污染治理工程有限公司 | A kind of method reclaiming copper from brown oxide waste liquid |
| CN104724861A (en) * | 2013-12-24 | 2015-06-24 | 张逸 | Device for treating waste brownification liquid by electro-catalysis |
| CN104773794A (en) * | 2015-04-30 | 2015-07-15 | 湖南富莱明节能环保科技有限公司 | Composite additive for electrolysis |
| CN106191919A (en) * | 2016-07-13 | 2016-12-07 | 深圳市京中康科技有限公司 | A kind of technique reclaiming copper from brown oxide waste liquid |
| CN106350678B (en) * | 2016-08-30 | 2018-08-17 | 盛隆资源再生（无锡）有限公司 | A method of recycling corrosion inhibiter and copper from brown oxide waste liquid |
| CN112125449B (en) * | 2020-09-21 | 2022-09-06 | 深圳市祺鑫环保科技有限公司 | Method for treating brownification waste liquid |
| CN112573726A (en) * | 2020-11-24 | 2021-03-30 | 苏州美源达环保科技股份有限公司 | Brown liquid wastewater treatment method |
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| CN1584129A (en) * | 2003-08-20 | 2005-02-23 | 李德良 | Method and apparatus for separating copper from copper-containing waste liquid |
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| CN102295321A (en) * | 2011-09-06 | 2011-12-28 | 冯云香 | Method for treating acid copper-containing waste liquor of printed-circuit board and producing electrolytic copper |
| JP2012036058A (en) * | 2010-08-11 | 2012-02-23 | Japan Organo Co Ltd | Method for recovering copper sulfate and apparatus for recovering copper sulfate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6869519B2 (en) * | 2001-09-27 | 2005-03-22 | National Institute Of Advanced Industrial Science And Technology | Electrolytic process for the production of metallic copper and apparatus therefor |
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- 2012-03-30 CN CN201210090682.0A patent/CN102603102B/en active Active
Patent Citations (6)
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|---|---|---|---|---|
| CN1584129A (en) * | 2003-08-20 | 2005-02-23 | 李德良 | Method and apparatus for separating copper from copper-containing waste liquid |
| CN101550488A (en) * | 2009-05-13 | 2009-10-07 | 中南大学 | Method of preparing high pure cathode copper by using PCB acid chlorine copper etching solution sewage |
| CA2732486A1 (en) * | 2010-03-17 | 2011-09-17 | Jx Nippon Mining & Metals Corporation | Recovery method for cobalt |
| JP2012036058A (en) * | 2010-08-11 | 2012-02-23 | Japan Organo Co Ltd | Method for recovering copper sulfate and apparatus for recovering copper sulfate |
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