CN109626659A - A kind of processing method of copper sulphate electroplating wastewater - Google Patents
A kind of processing method of copper sulphate electroplating wastewater Download PDFInfo
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- CN109626659A CN109626659A CN201910068073.7A CN201910068073A CN109626659A CN 109626659 A CN109626659 A CN 109626659A CN 201910068073 A CN201910068073 A CN 201910068073A CN 109626659 A CN109626659 A CN 109626659A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- 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
Abstract
The present invention provides a kind of processing methods of copper sulphate electroplating wastewater, and steps are as follows: (1) copper sulphate electroplating wastewater successively being passed through active carbon and ion exchange resin adsorbent bed, obtain acid waste water；(2) sodium ethylene diamine tetracetate is added in the acid waste water obtained to step (1), it is 1-2 that pH is adjusted after dissolution, obtains solution A；(3) PET powder is dissolved in solvent, modified PET powder is cleaned and dried to obtain after reaction；(4) the modified PET powder that step (3) obtains is added in the solution A that step (2) obtains, hypo solution is added, filter residue and filtrate is obtained by filtration after reaction；(5) filtrate for obtaining step (4) is handled using ion-exchange.The present invention using modified PET powder as matrix, in aqueous solution with forerunner's precursor reactant of copper ion so that copper ion in-situ preparation cuprous sulfide/polyester composite on modified PET powder.
Description
Technical field
The present invention relates to electroplating wastewater processing fields, and in particular to a kind of processing method of copper sulphate electroplating wastewater.
Background technique
Electroplating waste processing process has very much, such as: physisorphtion, ion-exchange, evaporation concentration method, chemistry are heavy
Shallow lake method, oxidation-reduction method, biochemical treatment process, membrane separation process, etc..Electroplating wastewater composition is different, and processing method is not also identical, only
Be applicable in, can individually be handled using a certain kind in the above method, also can be used in the above method it is several combine into
Row processing.
In electroplating process, copper plate improves parent metal usually as nickel plating, tin plating, chromium plating, silver-plated, gold-plated bottom
With the binding force of overlay coating and the Corrosion Protection of coating, therefore, copper-contained electroplating waste water is very universal in electroplating industry, and
And this kind of industrial wastewater usually contains various heavy.Not appropriately processed this kind of waste water of discharge, not only causes environmental pollution,
It results in waste of resources, is unfavorable for industry Green Sustainable.
Electro-coppering is a kind of most popular pre-plating layer done to improve binding force of cladding material, and copper coating is important
Protecting decorative coating copper/ni cr system component part, flexible and copper coating that porosity is low, for improving plating interlayer
Binding force and corrosion resistance play an important role.Copper coating is also used to local anti-carburizi ng, printed board hole metallization, and as print roller
Superficial layer.Colored layers of copper after chemically treated, coats organic film, it may also be used for decoration.
Copper sulphate plating accounts for particularly important status in PCB plating, and the quality of sour copper plating directly affects electro-coppering
The quality and related mechanical properties of layer, and certain influence is generated on following process.
Currently, mainly using neutralization precipitation method, ion-exchange, electrolysis method, film point for the processing of copper-contained electroplating waste water
From method, absorption method, bioanalysis etc..Ion-exchange can effectively remove the metal ion in waste water, while water can be with reuse, still
This method amount of resin is big, and regenerated liquid processing is difficult, processing cost is high；And in regenerative process, resin there may be shrink or
It expands and causes to rupture, economy is not high.The treatment process of electrolysis method is mature, stable, but as defined in discharge standard
Controlled substance content is extremely low, so processing method power consumption in electrolysis wastewater is larger, processing cost is high, and is also easy to produce toxic
Gas, it is difficult to which qualified discharge is arrived in processing.Membrane separation process has empty phase change, energy conversion efficiency height, does not consume chemical reagent
The advantages that, but since equipment cost is higher, processing economy is lower.Absorption method handle electroplated heavy metals waste water operations it is simple,
Small investment, but main problem is that treated that water outlet is difficult up to standard for simple absorption method, can only generally be used as preprocessing means.Biology
Method processing electroplating wastewater is adaptable, and equipment is simple, and without secondary pollution, processing cost is low, but main problem is function bacterium breeding
Speed is slower, reaction it is inefficient, processing water outlet be relatively inaccessible to reuse standard.
Summary of the invention
The invention proposes a kind of processing methods of copper sulphate electroplating wastewater, can utilize copper sulphate Sewage treatment, drop
Low production cost realizes energy conservation and clean manufacturing.
It realizes the technical scheme is that a kind of processing method of copper sulphate electroplating wastewater, steps are as follows:
(1) copper sulphate electroplating wastewater is successively passed through into active carbon and ion exchange resin adsorbent bed, obtains acid waste water；
(2) sodium ethylene diamine tetracetate is added in the acid waste water obtained to step (1), it is 1-2 that pH is adjusted after dissolution, obtains solution
A；
(3) PET powder is dissolved in solvent, in 60-80 DEG C of reaction 0.5-1h, modified PET powder is cleaned and dried to obtain after reaction
End；
(4) the modified PET powder that step (3) obtains is added in the solution A that step (2) obtains, after mixing is impregnated, sulphur is added
Filter residue and filtrate is obtained by filtration after reaction in sodium thiosulfate solution, temperature reaction；
(5) filtrate for obtaining step (4) is handled using ion-exchange.
Step (1) ion exchange resin is macroporous absorbent resin.
Cu in step (2) acid waste water2+Molar ratio with sodium ethylene diamine tetracetate is 1:(0.06-1).
Solvent is ethylenediamine or normal propyl alcohol in the step (3).
The mass ratio of solution A, modified PET powder and hypo solution sum is 1:(10-15 in the step (4)):
(1-5)；The mass concentration of hypo solution is 0.5-3%.
The temperature that mixing is impregnated in the step (4) is 30-50 DEG C, soaking time 10-20min；The temperature of temperature reaction
Degree is 70-90 DEG C, reaction time 20-60min.
Step (5) ion exchange methods are cation bed resin with resin.
Copper sulphate electroplating wastewater is that sour copper electroplating liquid is brought into rinse bath by workpiece to be formed with after ejected wash water mixing
, mainly contain the successions such as copper sulphate, sulfuric acid, chloride ion and micro brightening agent for acid copper electroplating.
Active carbon is very abundant to the absorption of this type organic of dyestuff therein and/or polyethet surfactant, and ion is handed over
It is very excellent to the absorption property of latter type organic to change resin.
The beneficial effects of the present invention are:
(1) present invention using modified PET powder as matrix, in aqueous solution with forerunner's precursor reactant of copper ion so that copper ion exists
In-situ preparation cuprous sulfide/polyester composite on modified PET powder, composite material can be used to prepare conductive fiber, realize
The regeneration of copper ion；
(2) present invention handles filtrate using ion-exchange, can be by the Na in filtrate+、SO4 2-And Cl-Deng purification, and then
To the waste water for meeting discharge standard.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
Electroplating wastewater using the discharge of certain factory is process object, and the main component in waste water is 10.5 grams per liter of copper sulphate, sulfuric acid
3.25 grams per liters, chloride ion 3.3ppm, brightening agent for acid copper electroplating debris concentration 50ppm.
A kind of processing method of copper sulphate electroplating wastewater, steps are as follows:
(1) copper sulphate electroplating wastewater is successively passed through into active carbon and ion exchange resin adsorbent bed (macroporous absorbent resin), obtained
Acid waste water；
(2) sodium ethylene diamine tetracetate, Cu in acid waste water is added in the acid waste water obtained to step (1)2+With ethylenediamine tetrem
The molar ratio of sour sodium is 1:0.06, and it is 1 that vinegar acid for adjusting pH is utilized after dissolution, obtains solution A；
(3) in the ethylenediamine or normal propyl alcohol for being 10% by 100g PET powder dissolution 2500g mass fraction, in 60 DEG C of reaction 1h, instead
Should after be cleaned and dried to obtain modified PET powder；
(4) the 100g modified PET powder that step (3) obtains is added in the solution A that 1000g step (2) obtains, is soaked at 30 DEG C
After steeping 20min, the hypo solution that 100g mass concentration is 3% is added, heats up 70 DEG C and reacts 60min, filtered after reaction
To filter residue and filtrate；
(5) mainly it is left Na in filtrate+、SO4 2-And Cl-, described can will be given up using the technique that ion-exchange prepares pure water
Water warfare, using the cations such as sodium ion in cation bed removal electroplating wastewater, in cation bed, the sun such as sodium ion in waste water from
Son is by resin adsorption, and the hydrogen ion on resin is replaced out, becomes free hydrogen ion and enters mobile phase；Preferred cation bed tree
Rouge is gel-like strongly acidic cation-exchange.Such as: 001*7, C100E etc..
Embodiment 2
Electroplating wastewater using the discharge of certain factory is process object, and the main component in waste water is 10.5 grams per liter of copper sulphate, sulfuric acid
3.25 grams per liters, chloride ion 3.3ppm, brightening agent for acid copper electroplating debris concentration 50ppm.
A kind of processing method of copper sulphate electroplating wastewater, steps are as follows:
(1) copper sulphate electroplating wastewater is successively passed through into active carbon and ion exchange resin adsorbent bed (macroporous absorbent resin), obtained
Acid waste water；
(2) sodium ethylene diamine tetracetate, Cu in acid waste water is added in the acid waste water obtained to step (1)2+With ethylenediamine tetrem
The molar ratio of sour sodium is 1:0.08, and it is 1.5 that vinegar acid for adjusting pH is utilized after dissolution, obtains solution A；
(3) in the ethylenediamine or normal propyl alcohol for being 10% by 100g PET powder dissolution 2500g mass fraction, in 70 DEG C of reaction 0.8h,
Modified PET powder is cleaned and dried to obtain after reaction；
(4) the 100g modified PET powder that step (3) obtains is added in the solution A that 1300g step (2) obtains, is soaked at 40 DEG C
After steeping 15min, the hypo solution that 300g mass concentration is 2% is added, heats up 80 DEG C and reacts 50min, filtered after reaction
To filter residue and filtrate；
(5) mainly it is left Na in filtrate+、SO4 2-And Cl-, described can will be given up using the technique that ion-exchange prepares pure water
Water warfare, using the cations such as sodium ion in cation bed removal electroplating wastewater, in cation bed, the sun such as sodium ion in waste water from
Son is by resin adsorption, and the hydrogen ion on resin is replaced out, becomes free hydrogen ion and enters mobile phase；Preferred cation bed tree
Rouge is gel-like strongly acidic cation-exchange.Such as: 001*7, C100E etc..
Embodiment 3
Electroplating wastewater using the discharge of certain factory is process object, and the main component in waste water is 10.5 grams per liter of copper sulphate, sulfuric acid
3.25 grams per liters, chloride ion 3.3ppm, brightening agent for acid copper electroplating debris concentration 50ppm.
A kind of processing method of copper sulphate electroplating wastewater, steps are as follows:
(1) copper sulphate electroplating wastewater is successively passed through into active carbon and ion exchange resin adsorbent bed (macroporous absorbent resin), obtained
Acid waste water；
(2) sodium ethylene diamine tetracetate, Cu in acid waste water is added in the acid waste water obtained to step (1)2+With ethylenediamine tetrem
The molar ratio of sour sodium is 1:1, and it is 2 that vinegar acid for adjusting pH is utilized after dissolution, obtains solution A；
(3) in the ethylenediamine or normal propyl alcohol for being 10% by 100g PET powder dissolution 2500g mass fraction, in 80 DEG C of reaction 0.5h,
Modified PET powder is cleaned and dried to obtain after reaction；
(4) the 100g modified PET powder that step (3) obtains is added in the solution A that 1500g step (2) obtains, is soaked at 50 DEG C
After steeping 10min, the hypo solution that 500g mass concentration is 3% is added, heats up 90 DEG C and reacts 20min, filtered after reaction
To filter residue and filtrate；
(5) mainly it is left Na in filtrate+、SO4 2-And Cl-, described can will be given up using the technique that ion-exchange prepares pure water
Water warfare, using the cations such as sodium ion in cation bed removal electroplating wastewater, in cation bed, the sun such as sodium ion in waste water from
Son is by resin adsorption, and the hydrogen ion on resin is replaced out, becomes free hydrogen ion and enters mobile phase；Preferred cation bed tree
Rouge is gel-like strongly acidic cation-exchange.Such as: 001*7, C100E etc..
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of processing method of copper sulphate electroplating wastewater, it is characterised in that steps are as follows:
(1) copper sulphate electroplating wastewater is successively passed through into active carbon and ion exchange resin adsorbent bed, obtains acid waste water；
(2) sodium ethylene diamine tetracetate is added in the acid waste water obtained to step (1), it is 1-2 that pH is adjusted after dissolution, obtains solution
A；
(3) PET powder is dissolved in solvent, in 60-80 DEG C of reaction 0.5-1h, modified PET powder is cleaned and dried to obtain after reaction
End；
(4) the modified PET powder that step (3) obtains is added in the solution A that step (2) obtains, after mixing is impregnated, sulphur is added
Filter residue and filtrate is obtained by filtration after reaction in sodium thiosulfate solution, temperature reaction；
(5) filtrate for obtaining step (4) is handled using ion-exchange.
2. the processing method of copper sulphate electroplating wastewater according to claim 1, it is characterised in that: in the step (1) from
Sub-exchange resin is macroporous absorbent resin.
3. the processing method of copper sulphate electroplating wastewater according to claim 1, it is characterised in that: the step (2) is acid
Cu in waste water2+Molar ratio with sodium ethylene diamine tetracetate is 1:(0.06-1).
4. the processing method of copper sulphate electroplating wastewater according to claim 1, it is characterised in that: molten in the step (3)
Agent is ethylenediamine or normal propyl alcohol.
5. the processing method of copper sulphate electroplating wastewater according to claim 1, it is characterised in that: molten in the step (4)
The mass ratio of liquid A, modified PET powder and hypo solution sum are 1:(10-15): (1-5)；The matter of hypo solution
Amount concentration is 0.5-3%.
6. the processing method of copper sulphate electroplating wastewater according to claim 1, it is characterised in that: mixed in the step (4)
Closing the temperature impregnated is 30-50 DEG C, soaking time 10-20min；The temperature of temperature reaction is 70-90 DEG C, and the reaction time is
20-60min。
7. the processing method of copper sulphate electroplating wastewater according to claim 1, it is characterised in that: in the step (5) from
Sub- exchange process is cation bed resin with resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921691A (en) * | 2019-12-05 | 2020-03-27 | 安徽皖东树脂科技有限公司 | Treatment process of mother liquor pigment in magnesium sulfate production |
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| JP2000328449A (en) * | 1999-05-25 | 2000-11-28 | Chubu Kiresuto Kk | Metal chelate-forming fiber, its production, scavenging of metal ion using the same fiber and metal chelate fiber |
| WO2014113895A1 (en) * | 2013-01-24 | 2014-07-31 | Sonitec-Vortisand Technologies Inc. | Reactor with antimicrobial medium for liquid disinfection |
| CN205133311U (en) * | 2015-10-08 | 2016-04-06 | 殷嘉仪 | Copper -containing is electroplated and is washd effluent disposal system |
| CN105565533A (en) * | 2014-10-08 | 2016-05-11 | 深圳市汇利龙科技有限公司 | Zero-discharge on-line treatment process for preparing deionized water from copper sulphate electroplating waste water |
| CN105565532A (en) * | 2014-10-08 | 2016-05-11 | 深圳市汇利龙科技有限公司 | Zero-discharge on-line treatment process for preparing deionized water from copper sulphate electroplating wastewater |
| CN105714404A (en) * | 2016-04-07 | 2016-06-29 | 中原工学院 | Preparation method of cuprous sulfide/PET (polyethylene terephthalate) composite conductive fiber |
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2019
- 2019-01-24 CN CN201910068073.7A patent/CN109626659A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000328449A (en) * | 1999-05-25 | 2000-11-28 | Chubu Kiresuto Kk | Metal chelate-forming fiber, its production, scavenging of metal ion using the same fiber and metal chelate fiber |
| WO2014113895A1 (en) * | 2013-01-24 | 2014-07-31 | Sonitec-Vortisand Technologies Inc. | Reactor with antimicrobial medium for liquid disinfection |
| CN105565533A (en) * | 2014-10-08 | 2016-05-11 | 深圳市汇利龙科技有限公司 | Zero-discharge on-line treatment process for preparing deionized water from copper sulphate electroplating waste water |
| CN105565532A (en) * | 2014-10-08 | 2016-05-11 | 深圳市汇利龙科技有限公司 | Zero-discharge on-line treatment process for preparing deionized water from copper sulphate electroplating wastewater |
| CN205133311U (en) * | 2015-10-08 | 2016-04-06 | 殷嘉仪 | Copper -containing is electroplated and is washd effluent disposal system |
| CN105714404A (en) * | 2016-04-07 | 2016-06-29 | 中原工学院 | Preparation method of cuprous sulfide/PET (polyethylene terephthalate) composite conductive fiber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921691A (en) * | 2019-12-05 | 2020-03-27 | 安徽皖东树脂科技有限公司 | Treatment process of mother liquor pigment in magnesium sulfate production |
| CN110921691B (en) * | 2019-12-05 | 2022-04-22 | 安徽皖东树脂科技有限公司 | Treatment process of mother liquor pigment in magnesium sulfate production |
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