CN102162036B - Process for enriching copper and nickel in electroplating copper-nickel mixed waste water - Google Patents
Process for enriching copper and nickel in electroplating copper-nickel mixed waste water Download PDFInfo
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- CN102162036B CN102162036B CN201110088080A CN201110088080A CN102162036B CN 102162036 B CN102162036 B CN 102162036B CN 201110088080 A CN201110088080 A CN 201110088080A CN 201110088080 A CN201110088080 A CN 201110088080A CN 102162036 B CN102162036 B CN 102162036B
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- Treatment Of Water By Ion Exchange (AREA)
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Abstract
The invention relates to a process for enriching copper and nickel in electroplating copper-nickel mixed waste water, belonging to the technical field of environmental protection. The process provided by the invention comprises the following three steps of: pretreatment, ion-exchange absorption and ion-exchange regeneration, wherein in the pretreatment step, Fe3<+> and soluble oil and particle impurities are removed from the waste water, thus effectively preventing resin from being polluted and poisoned, and enabling the ion-exchange method to be successfully applied to enrichment of copper and nickel in the electroplating copper-nickel mixed waste water; and the regeneration step adopts two-step regeneration, improves the reproducibility and ion-exchange treatment capacity of the resin and reduces the operating cost.
Description
Technical field
The present invention relates to a kind of from electro-coppering nickel composite waste the technology of enriching Cu nickel, belong to environmental protection technical field.
Background technology
Plating is one of the current whole world three big contaminated industries, and along with the continuous expansion of electroplating industry scale, the wastewater flow rate of discharging is also increasing.Contain objectionable impuritiess such as heavy metal ion, organic cpds and other mineral compound in these waste water, environment protection is caused greatly pressure, need to be resolved hurrily.At present, cupric that produces in the Electroplating Production or nickeliferous single rinse water can reclaim through the trough rim retrieving arrangement, but collection rate is lower, less than 30%.A large amount of metals ions gets into sewage plant through modes such as " evaporating, emitting, dripping or leaking of liquid or gas " with ground waste water, is the composite waste of cupric nickel ion.Copper is two pollutants in this composite waste, and nickel is a pollutant, but both also are precious resources.Therefore develop electro-coppering nickel composite waste treatment technology, environment protection and raising resource utilization are had a very important role.
The existing plating waste water treatment process mainly contains chemical precipitation method, membrane separation process and ion exchange method.Although the chemical precipitation method cost is low, and is widely applicable, heavy metal ion finally becomes useless admittedly, can cause secondary pollution.Membrane separation process and ion exchange method are current more advanced methods, and through membrane-concentrated or resin concentration regeneration, the metals ion that can obtain high density reclaims liquid, and it is good to handle the back effluent quality.But the membrane separation process energy consumption is high, and investment is big, and is strict to advancing film water matter, is only applicable to the single rinse water on the production line, and pre-treatment is had relatively high expectations.The ion exchange method applicable surface is narrow; For the electro-coppering nickel composite waste that contains a large amount of iron ions and oily substance; Be prone to pollute resin because iron ion contacts the back with oily substance with resin, make the plastic resin treatment ability reduce, even poison; Be difficult to regeneration, therefore limited its application in electro-coppering nickel composite waste is handled.
Summary of the invention
The object of the invention provide a kind of from electro-coppering nickel composite waste the technology of enriching Cu nickel, can effectively prevent resin stain, improve the regeneration of resin rate, expanded the use range of ion exchange method.
Above-mentioned technical purpose of the present invention is achieved through following technical scheme: a kind of from electro-coppering nickel composite waste the technology of enriching Cu nickel, may further comprise the steps:
1. pre-treatment: adjustment electro-coppering nickel composite waste pH value to 4 ~ 5 in neutralization tank, then it is entered settling tank, make Fe (OH)
3Flco and solid impurity are settlement separate, remove solvability oil and granule foreign again, control the redox potential≤30mV of said waste water at last;
2. IX absorption: get into ion exchange unit through above-mentioned pretreated waste water, ion exchange resin adsorption and enrichment copper nickel is until saturated;
3. ion exchange regenerant: be communicated with regeneration tank and ion exchange unit, use regeneration of hydrochloric acid to reclaim copper nickel earlier, re-use the regeneration of complexing agent and organic solvent and recover the resin activity.
As preferably, in the above-mentioned pre-treatment step, adopt the oil suction filtrate to remove solvability oil and granule foreign.
As preferably, use in V-Brite B, thiourea peroxide, the hydrazine any one or more to control the redox potential of waste water in the said pre-treatment step.
As preferably, said complexing agent is one or more in Hydrocerol A, phosphoric acid salt, edetate, the organophosphate.
As preferably, said organic solvent is low-carbon alcohol or acetone.
Contain a large amount of iron ions and oily substance in the electro-coppering nickel composite waste, wherein Fe
3+Make its poisoning with the exchange of resin reactive group or form colloidal obstruction resin internal voids, cause resin to be difficult to regeneration.Pre-treatment step in the technique scheme of the present invention will be to the maximum Fe of resin harm
3+Form Fe (OH)
3Flco is removed, and controlled oxidation reduction potential≤30mV has prevented Fe simultaneously
2+Be oxidized to Fe
3+Further pollute resin.Regeneration step, adopt the regeneration of two steps: the effect of the first step hydrochloric acid provides the required H of regeneration
+, and hydrochloric acid this as non-oxidizing acid, regenerative process can not cause Fe
2+Oxidizing reaction takes place, and has prevented that further resin is by Fe
3+Pollute; Second step added complexing agent and ferrous ion forms complex compound, it is easy to and resin isolation; Add organic solvent and mainly remove greasy dirt, keep the unimpeded of resin surface cleaning and internal capillary runner, prevent to form oil film or moisture film and stop the exchange process of metals ion and reactive group.
In sum, the present invention has following outstanding advantage and beneficial effect:
1, through electro-coppering nickel composite waste is carried out pre-treatment, prevent contacting of resin and iron ion and oily substance, thereby effectively prevented the resin stain poisoning, make ion exchange method successfully be applied to enriching Cu nickel in the electro-coppering nickel composite waste;
2, adopt the regeneration of two steps, improved regeneration of resin rate and ion exchange treatment ability, reduced running cost.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention.
Among the figure, 1 is neutralization tank, and 2 is settling tank, and 3 is intermediate pool, and 4 is topping-up pump, and 5 is strainer, and 6 is the finished product case, and 7 is ion exchange unit, and 8 is regeneration tank.
Embodiment
Below in conjunction with accompanying drawing the present invention is done further explain.
As shown in the figure; Neutralization tank 1, settling tank 2, intermediate pool 3, topping-up pump 4 are connected with strainer 5; Form the technology preprocessing part, ion exchange unit 7 is copper nickel separation and concentration centers, the absorption and two processes of regenerating of being divided in service; Strainer 5 is the IX adsorption process when connecting with ion exchange unit 7, and regeneration tank 8, ion exchange unit 7 are connected with finished product case 6 and be the ion exchange regenerant process.
Embodiment 1
A kind of from electro-coppering nickel composite waste the technology of enriching Cu nickel, may further comprise the steps:
1. pre-treatment: adjustment electro-coppering nickel composite waste pH value to 4 in neutralization tank, then it is entered settling tank, make Fe (OH)
3Flco and solid impurity are settlement separate, remove solvability oil and granule foreign again, control the redox potential≤30mV of said waste water at last;
2. IX absorption: get into ion exchange unit through above-mentioned pretreated waste water, ion exchange resin adsorption and enrichment copper nickel is until saturated;
3. ion exchange regenerant: be communicated with regeneration tank and ion exchange unit, use regeneration of hydrochloric acid to reclaim copper nickel earlier, re-use the regeneration of complexing agent Hydrocerol A and ethanol and recover the resin activity.
Embodiment 2
A kind of from electro-coppering nickel composite waste the technology of enriching Cu nickel, may further comprise the steps:
1. pre-treatment: adjustment electro-coppering nickel composite waste pH value to 5 in neutralization tank, then it is entered settling tank, make Fe (OH)
3Flco and solid impurity are settlement separate, remove solvability oil and granule foreign again, control the redox potential≤30mV of said waste water at last;
2. step is adsorbed in IX: get into ion exchange unit through above-mentioned pretreated waste water, ion exchange resin adsorption and enrichment copper nickel is until saturated;
3. ion exchange regenerant step: be communicated with regeneration tank and ion exchange unit, use regeneration of hydrochloric acid to reclaim copper nickel earlier, re-use complexing agent Hydrocerol A, YD 30 and ethanol, that acetone regeneration recovers resin is active.
This specific embodiment only is to explanation of the present invention; It is not a limitation of the present invention; Those skilled in the art can make any modification to present embodiment as required after reading this specification sheets, but as long as in claim scope of the present invention, all receive the protection of patent law.
Claims (4)
1. the technology of an enriching Cu nickel from electro-coppering nickel composite waste may further comprise the steps:
1. pre-treatment: adjustment electro-coppering nickel composite waste pH value to 4 ~ 5 in neutralization tank, then it is entered settling tank, make Fe (OH)
3Flco and solid impurity are settlement separate, adopt the oil suction filtrate to remove solvability oil and granule foreign, control the redox potential≤30mV of said waste water at last, prevent Fe
2+Be oxidized to Fe
3+Further pollute resin;
2. IX absorption: get into ion exchange unit through above-mentioned pretreated waste water, ion exchange resin adsorption and enrichment copper nickel is until saturated;
3. ion exchange regenerant: be communicated with regeneration tank and ion exchange unit, use regeneration of hydrochloric acid to reclaim copper nickel earlier, re-use the regeneration of complexing agent and organic solvent and recover the resin activity.
2. according to claim 1 a kind of from electro-coppering nickel composite waste the technology of enriching Cu nickel, it is characterized in that: use in V-Brite B, thiourea peroxide, the hydrazine any one or more to control the redox potential of waste water in the said pre-treatment step.
3. according to claim 2 a kind of from electro-coppering nickel composite waste the technology of enriching Cu nickel, it is characterized in that: said complexing agent is one or more in Hydrocerol A, phosphoric acid salt, edetate, the organophosphate.
4. according to claim 3 a kind of from electro-coppering nickel composite waste the technology of enriching Cu nickel, it is characterized in that: said organic solvent is low-carbon alcohol or acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201110088080A CN102162036B (en) | 2011-04-08 | 2011-04-08 | Process for enriching copper and nickel in electroplating copper-nickel mixed waste water |
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|---|---|---|---|
| CN201110088080A CN102162036B (en) | 2011-04-08 | 2011-04-08 | Process for enriching copper and nickel in electroplating copper-nickel mixed waste water |
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| CN102162036A CN102162036A (en) | 2011-08-24 |
| CN102162036B true CN102162036B (en) | 2012-09-26 |
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| CN201110088080A Expired - Fee Related CN102162036B (en) | 2011-04-08 | 2011-04-08 | Process for enriching copper and nickel in electroplating copper-nickel mixed waste water |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464392A (en) * | 2011-10-20 | 2012-05-23 | 常州亚环环保科技有限公司 | Composite dechlorination agent for removing high-concentration chlorine-containing wastewater and application method thereof |
| CN102618882B (en) * | 2012-04-12 | 2014-11-05 | 无锡中天固废处置有限公司 | Electrolysis recovery method of nickel in waste water |
| CN103506632B (en) * | 2013-09-27 | 2015-09-09 | 暨南大学 | A kind of from containing the method reclaiming ultra tiny copper powder complex copper waste liquid |
| CN104561592B (en) * | 2014-11-28 | 2017-04-26 | 深圳前海中盛环保科技有限公司 | Treatment method for nickel-containing electroplating wastewater |
| CN105149610B (en) * | 2015-09-10 | 2018-05-22 | 舒城联科环境科技有限公司 | A kind of chemical nickeling ageing liquid treatment process |
| CN107034364B (en) * | 2017-04-25 | 2019-07-02 | 上海问鼎环保科技有限公司 | A method of metallic nickel is adsorbed and recycled from electroplating wastewater |
| CN112408670A (en) * | 2020-12-09 | 2021-02-26 | 淮安中顺环保科技有限公司 | Treatment method of electroless copper plating rinsing solution |
| CN112850948A (en) * | 2020-12-28 | 2021-05-28 | 南京昆腾化工科技有限公司 | Electroplating wastewater treatment method and system |
| CN113149248A (en) * | 2021-01-19 | 2021-07-23 | 中基(海南)科技有限公司 | Green electroplating wastewater recycling treatment process |
Citations (2)
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|---|---|---|---|---|
| CN101746906A (en) * | 2008-12-03 | 2010-06-23 | 五邑大学 | Method for processing electroplating wastewater with heavy metal ions |
| CN101798131A (en) * | 2009-02-09 | 2010-08-11 | 深圳市蓝水晶环保有限公司 | High-efficiency electroplating wastewater treatment and resource utilization device |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101746906A (en) * | 2008-12-03 | 2010-06-23 | 五邑大学 | Method for processing electroplating wastewater with heavy metal ions |
| CN101798131A (en) * | 2009-02-09 | 2010-08-11 | 深圳市蓝水晶环保有限公司 | High-efficiency electroplating wastewater treatment and resource utilization device |
Non-Patent Citations (4)
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| 丁元海.树脂的污染和复苏.《河北电力科技》.1986,(第2期),26-29. |
| 余健等.应用ORP预测和控制地下水除铁滤池出水含铁量.《中国环境科学》.2003,第23卷(第6期),648-652. |
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Denomination of invention: Process for enriching copper and nickel in electroplating copper-nickel mixed waste water Effective date of registration: 20130723 Granted publication date: 20120926 Pledgee: Bank of Huzhou North Branch of Limited by Share Ltd Pledgor: Huzhou Jintai Technology Co., Ltd.|Huzhou Hurt Jintai Auto Parts Co., Ltd Registration number: 2013990000495 |
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Date of cancellation: 20171116 Granted publication date: 20120926 Pledgee: Bank of Huzhou North Branch of Limited by Share Ltd Pledgor: Huzhou Jintai Science and Technology Co., Ltd.|Huzhou Hete Jintai Auto Parts Co., Ltd. Registration number: 2013990000495 |
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