CN105565533A - Zero-discharge on-line treatment process for preparing deionized water from copper sulphate electroplating waste water - Google Patents
Zero-discharge on-line treatment process for preparing deionized water from copper sulphate electroplating waste water Download PDFInfo
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- CN105565533A CN105565533A CN201410529317.4A CN201410529317A CN105565533A CN 105565533 A CN105565533 A CN 105565533A CN 201410529317 A CN201410529317 A CN 201410529317A CN 105565533 A CN105565533 A CN 105565533A
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Abstract
The invention relates to a zero-discharge on-line treatment process for preparing deionized water from copper sulphate electroplating waste water. The treatment process comprises 1, adsorbing organic matters in the copper sulphate electroplating waste water through combination of active carbon and ion exchange resin, 2, adsorbing heavy metal ions in the waste water treated through the step 1 through ion exchange resin and 3, purifying the electroplating waste water without the organic matters and heavy metal ions through a purified water ion exchange preparation method to obtain deionized water. The organic matters in the copper sulphate electroplating waste water are removed through the combination of active carbon and ion exchange resin so that the organic matters in the copper sulphate electroplating waste water are completely removed and a regeneration period and a service life of the later resin are prolonged. Through the zero-discharge on-line treatment process, the copper sulphate electroplating waste water is completely purified to form deionized water satisfying electroplating water quality requirements and the prepared deionized water is returned to a copper sulphate electroplating unit so that water use and waste water treatment processes in the copper sulphate electroplating unit form a closed cycle and thus 100% recycle is realized.
Description
Technical field
The present invention relates to a kind of zero release online treatment and the reuse technology of being prepared deionized water by copper sulfate electroplating wastewater, belong to industrial waste water treatment.
Background technology
Electroplating waste processing process has a lot, such as: physisorphtion, ion exchange method, evaporation concentration method, chemical precipitation method, oxidation reduction process, biochemical treatment process, membrane separation process, etc.Electroplating wastewater composition is different, and treatment process is also not identical, as long as be suitable for, can to adopt in aforesaid method a certain processes separately, and also can to adopt in aforesaid method several is combined into row relax.
Common waste water treatment process uses combined method to carry out two-section type end to focus on electroplating wastewater.Electroplating wastewater is entered hexavalent chromium wastewater pond, cyanide wastewater pond, comprehensive wastewater pond according to the pipeline of regulation by plating shop respectively.The process of first paragraph utilizes reductive agent the hexavalent chrome reduction in hexavalent chromium wastewater pond to be become trivalent chromium, with oxygenant, the cyanide ion in cyanide wastewater pond is oxidized to harmless carbonic acid gas and nitrogen, then enter comprehensive wastewater equalizing tank, be merged into as comprehensive wastewater with other waste water.Second segment process comprehensive wastewater, after adjusting pH value, removes COD and activated carbon decolorizing through precipitation, flocculation, press filtration, readjustment, biochemistry in comprehensive wastewater equalizing tank successively, become reach emission standard can discharge water.
In order to saving water resource, the recycling realizing electroplating wastewater, on the basis of above-mentioned two-phase method, added again the Treated sewage reusing device based on membrane separation technique and ion exchange technique in the last few years, defined so-called three-stage process technique.Common comprehensive wastewater process and Treated sewage reusing technical process as follows:
Comprehensive wastewater → comprehensive wastewater equalizing tank → settling tank → flocculation basin → press filteration system → equalizing tank → biochemical treatment system → charcoal absorption system → filtering basin → reverse osmosis membrane treatment system → concentrated water discharge, pure water enter ion exchange treatment system and are further purified → pure water recycling.
No matter be two-phase method technique or three-stage process technique, main flow be all adopt end concentrate the pattern of electroplating wastewater processing (as application number be 200910055677.4 and application number be the document of 200910066905.8).Because waste water composition is too complicated, wastewater treatment capacity is excessive, be difficult to process thoroughly, still the reasons such as chemical reaction may be there is between different components residual after process, this end focuses on pattern and there is a following difficult problem: processing cost is high, after process, water quality is difficult to the requirement reaching emission standard, there is the risk of secondary pollution, heavy metal resources reclaims difficulty, Treated sewage reusing cost is too expensive, reclaim water quality to be difficult to reach electroplating water water quality standard, and Treated sewage reusing rate can only reach 60% ~ 80% at most.
Pattern is focused on relative to end, single wastewater treatment pattern is because waste water composition is more single, wastewater treatment capacity is less, analyze theoretically and solve the above-mentioned difficult problem that end focuses on pattern well, therefore become electroplating wastewater processing and the focus recycling area research in recent years.The core of single wastewater treatment pattern is the chemical constitution according to electroplating wastewater, carries out wastewater treatment and renovation and useful matter targetedly as the recycling of copper and mickel etc.
US6162361A, CN102336481A, CN203498176U, CN202754870U and CN201874981A etc. are some patented technologies based on membrane separation technique, although overcome the some drawbacks that end focuses on pattern preferably, still there is the defects such as system complex, processing cost is high, waste water reclamation utilization ratio is not high, evaporation concentration energy consumption is large.Especially by the pure water of membrane separation unit output, its specific conductivity is minimum can only reach 5 μ s/cm, if do not carry out further purification process, such water quality can not meet the water quality requirement of high-quality plating at all.
CN101717136A, CN103374743A, CN201660466U and application number are the technology disclosing some recycles in the patent of 200810219643.X, but, disclosed in above-mentioned each patent, technology all comes with some shortcomings, water quality after online treatment can't meet electroplating technology requirement, namely cannot realize recycle truly.
Summary of the invention
An object of the present invention is to provide a kind of copper sulfate electroplating waste processing process, and the production water of this technique is the deionized water that specific conductivity is very low, purity is very high, and its water quality can meet electroplating technology requirement completely.
Two of object of the present invention is to provide a kind of zero release online treatment and the reuse technology of being prepared deionized water by copper sulfate electroplating wastewater, the Waste Water Treatment of this technique is combined online with electroplating system, form a water closed cycle, thus realize the zero release recycle of electroplating wastewater.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of copper sulfate electroplating waste processing process, comprises the steps:
1) with the organism in gac and ion exchange resin combine adsorption copper sulfate electroplating wastewater;
2) spent ion exchange resin adsorption step 1) in heavy metal ion in the waste water that obtains;
3) organics removal is become deionized water with the purifying electroplating wastewater of heavy metal ion by the technique adopting ion exchange method to prepare pure water.
Sour copper electroplating liquid is brought in rinse bath by workpiece and is formed after rinse water mixing, the successions such as the brightening agent for acid copper electroplating mainly containing copper sulfate, sulfuric acid, chlorion and trace by copper sulfate electroplating wastewater.
According to the present invention, in step 1) in, described organism mainly refers to the organism in brightening agent for acid copper electroplating.The main component of described brightening agent for acid copper electroplating is several combination in the organism such as dyestuff, polyethet surfactant, sodium polydithio-dipropyl sulfonate, polydithio-dipropyl sodium sulfate and substituting thioureido.In order to extend regeneration period and the work-ing life of follow-up resin, need before subsequent processing these organism to be removed totally.Applicant studies discovery, gac to dyestuff wherein and/or this kind of organic absorption of polyethet surfactant very abundant, and it is very little to the adsorptive capacity of this kind of compositions such as sodium polydithio-dipropyl sulfonate, polydithio-dipropyl sodium sulfate and substituting thioureido, otherwise, the absorption property of ion exchange resin to a rear type organic is very excellent, and very limited to the adsorptive power of last type organic, just form extraordinary complementation with gac.Therefore, the present invention adopts the combination of activated carbon adsorption bed and resin absorption bed to adsorb the organism in copper sulfate electroplating wastewater.
According to the present invention, in step 1) in, preferably, first adopt charcoal absorption to remove the organism such as dyestuff and/or polyethet surfactant, then adopt ion exchange resin to adsorb the organism such as sodium polydithio-dipropyl sulfonate, polydithio-dipropyl sodium sulfate and substituting thioureido.Reason is, in order to prevent some Organic pollutants ion exchange resin, lowers efficiency.
According to the present invention, in step 1) in, described ion exchange resin is selected from macropore deacidite.Can be a kind of macroporous strong basic ion exchange resin, also can be a kind of macroreticular weakly base ion exchange resin, preferred macroporous strong basic ion exchange resin, such as:
vPOC1071,
xAD4,
a860 etc.When resin absorption bed reach absorption saturated time, utilize the technique known, as by NaOH solution, the regeneration to resin can be completed.
According to the present invention, in step 2) in, the described ion exchange resin for Adsorption of Heavy Metal Ions is selected from Zeo-karb or/and chelating ion exchange resin.Preferred, described Zeo-karb is weak-type Zeo-karb, such as polyacrylic acid ion exchange resin; Preferred, described chelating ion exchange resin is the resin containing functional groups such as imino-diacetic acetoxy groups.Also preferred, above-mentioned ion exchange resin is sodium form resin.
According to the present invention, in step 3) in, the electroplating wastewater purifying of organics removal and heavy metal ion is deionized water by the described employing ion exchange method technique of preparing pure water, is realized: A by following steps) by all non-H in the electroplating wastewater of organics removal and heavy metal ion
+positively charged ion all changes into H
+; B) by all non-OH
-negatively charged ion all converts OH to
-, and and H
+combine on the spot and generate water.Or, realized by following steps: A ') and by all non-OH in the electroplating wastewater of organics removal and heavy metal ion
-negatively charged ion all converts OH to
-; B ') by all non-H
+positively charged ion all changes into H
+, and and OH
-combine on the spot and generate water.
Preferred embodiments of the present invention, described steps A) or B ') in be adopt resin cation (R.C.) in cation bed by all non-H
+positively charged ion such as Na+ etc. carries out adsorption treatment and is replaced as H
+.
Preferred embodiments of the present invention, described step B) or A ') in be adopt resin anion(R.A) in anion bed by all non-OH
-negatively charged ion is as SO
4 2-, Cl
-etc. carrying out adsorption treatment and being replaced as OH
-.
Ion exchange method well known in the prior art prepares cation bed resin and the anion bed resin of pure water, can be used as cation bed resin and the anion bed resin of this technique.
Described anion bed resin is gel-like strongly basic anion exchange resin.
In order to improve water quality further, extend the regeneration period, a mixed bed can be increased after cation bed and anion bed.Ion exchange method well known in the prior art prepares the mixed-bed resin of pure water, all can be used as the mixed-bed resin of this technique.
According to the present invention, the flow process of the online waste water treatment process of copper sulfate electroplating wastewater is as follows:
Step 1): with the organism in gac and ion exchange resin combine adsorption copper sulfate electroplating wastewater.Specifically, the organism that described absorption is removed is the organism such as the brightening agent for acid copper electroplating residue in copper sulfate electroplating wastewater.
As previously mentioned, the main component of described brightening agent for acid copper electroplating is dyestuff and/or polyethet surfactant etc., in addition also containing a small amount of sodium polydithio-dipropyl sulfonate or the composition such as polydithio-dipropyl sodium sulfate and substituting thioureido.The adsorptive capacity of gac to the such as this kind of composition such as sodium polydithio-dipropyl sulfonate, polydithio-dipropyl sodium sulfate and substituting thioureido is very little; Otherwise ion exchange resin is very excellent to the Adsorption of Organic performance showing negative ion characteristic after dissociation or partial dissociation, for the organism of not dissociation and difficult dissociation, its adsorptive power is very limited, just forms extraordinary complementation with gac.Therefore, the present invention adopts the combination of activated carbon adsorption bed and resin absorption bed to carry out the organism such as the ketone acid brightening agent in adsorber acid copper electroplating wastewater.
For conventional ion exchange resin, this kind of organic molecules such as polydithio-dipropyl sodium sulfate and substituting thioureido are larger, easy desorption when considering regeneration, shortens the recovery time, and the present invention is preferably macropore deacidite for the ion exchange resin of resin absorption bed.As
xAD4,
vPOC1071,
a860 etc.
When resin absorption bed reach absorption saturated time, according to the technique known, as by NaOH solution, the regeneration to resin can be completed.
Step 2): spent ion exchange resin adsorption step 1) in heavy metal ion in the waste water that obtains.Specifically, the heavy metal ion of described Adsorption is the Cu in copper sulfate electroplating wastewater
2+.
Principal pollutant in copper sulfate electroplating wastewater are copper sulfate.Consider adsorptive capacity, be easy to the factors such as regeneration and cost, the resin for Adsorption of Heavy Metal Ions (as bivalent cupric ion) that the present invention selects is that Zeo-karb is or/and chelating ion exchange resin.Preferred Zeo-karb is weak-type Zeo-karb, such as polyacrylic acid ion exchange resin; Preferred chelating ion exchange resin is the resin containing functional groups such as imino-diacetic acetoxy groups.
Because advantage of lower cost, conventional above-mentioned ion exchange resin mostly is sodium form resin.The absorption replacement(metathesis)reaction of described sodium form resin and bivalent cupric ion is as follows:
2Na-A+Cu
2+＝Cu-A
2+2Na
+
(in formula, A represents resin matrix).
As shown in above formula, when copper sulfate electroplating wastewater flows through this resin column, Cu
2+be adsorbed on resin stationary phase, and the Na on original resin stationary phase
+replaced out ingoing stream moves mutually.
When absorption reaches capacity, with sulfuric acid or hydrochloric acid, the bivalent cupric ion of absorption is carried out desorption, bivalent cupric ion be desorbed attached while, resin is made the transition as Hydrogen structural resin, and then with NaCl or NaOH by Hydrogen structural resin transition be sodium form structural resin, complete regeneration.
The copper sulfate that desorption is got off or cupric chloride can be processed into copper sulfate crystal or cupric chloride crystal is recycled, and also by electrolysis mode, cupric ion wherein can be electrolyzed to produce metallic copper and recycle.
Step 3): online pure water preparation, organics removal is become deionized water with the purifying electroplating wastewater of heavy metal ion by the technique namely adopting ion exchange method to prepare pure water.
The organism such as removal brightening agent and heavy metal ion are as Cu
2+after, the pollutent in copper sulfate electroplating wastewater is remaining Na mainly
+, SO
4 2-and Cl
-, described purification of waste water just can be become deionized water by the technique adopting ion exchange method to prepare pure water.Described method comprises the steps:
A, all non-H+ positively charged ion in the electroplating wastewater of organics removal and heavy metal ion is all changed into H
+.In other words, cation bed is utilized to remove the positively charged ions such as the sodium ion in electroplating wastewater.
The same with the technique that conventional ion exchange process prepares pure water, in cation bed, the positively charged ions such as the sodium ion in waste water are by resin absorption, and hydrogen ion on resin is out replaced, becomes free hydrogen ion and enters moving phase.
Ion exchange method well known in the prior art prepares the cation bed resin of pure water, all can be used as cation bed resin of the present invention.Based on Chemical Composition and the cost consideration of waste water, the preferred cation bed resin of the present invention is gel-like strongly acidic cation-exchange.Such as: 001*7,
c100E, etc.
When cation bed resin reach absorption saturated time, utilizing the technique known, as adopted sulfuric acid or hydrochloric acid, just can complete the regeneration to cation bed resin.
B, by all non-OH
-negatively charged ion all converts OH to
-, and and H
+combine on the spot and generate water.In other words, the sulfate ion in anion bed absorption electroplating wastewater and chlorion is utilized.
The same with the technique that conventional ion exchange process prepares pure water, in anion bed, the negatively charged ion such as the sulfate ion in waste water and chlorion are by resin absorption, and hydroxide ion on resin is out replaced, become free hydroxide ion, and the hydrogen ion cemented out from cation bed in moving phase is on the spot combined generation deionized water.
Ion exchange method well known in the prior art prepares the anion bed resin of pure water, all can be used as anion bed resin of the present invention.Based on Chemical Composition and the cost consideration of waste water, the preferred anion bed resin of the present invention is gel-like strongly basic anion exchange resin.Such as: 201*7,
a600, etc.
When anion bed resin reach absorption saturated time, utilize the technique known, as by NaOH solution, the regeneration to anion bed resin can be completed.
As mentioned above, above-mentioned step A and step B can be exchanged, namely first by all non-OH
-negatively charged ion all converts OH to
-, then by all non-H
+positively charged ion all changes into H
+, and and OH
-combine on the spot and generate water.
C, optional, utilize mixed bed to improve water quality further
The same with the technique that conventional ion exchange process prepares pure water, in order to promote water quality further, extend the regeneration period, a mixed bed can be increased after cation bed and anion bed.Ion exchange method well known in the prior art prepares the mixed-bed resin of pure water, and e.g., 001*7MB, 201*7MB etc., all can be used as mixed-bed resin of the present invention.
The present invention preferably judges water quality and the system regeneration time of production water online by electrical conductivity method.The production water of system, its specific conductivity can control according to electroplating water water quality standard, such as: according to generally electroplating water quality standard, can control at 5 below μ s/cm, also according to the water quality standard of ultrapure water, can control at 1 below μ s/cm.Under often kind of situation, when production water specific conductivity is higher than control limit, system ion exchange resin used must carry out manipulation of regeneration according to related process.
Present invention also offers a kind of plating close circulation technology, comprising: electroplating technology and copper sulfate electroplating waste processing process of the present invention, described electroplating waste processing process is combined online with electroplating technology, forms a closed circuit circulatory system.
Technique of the present invention is one and prepares zero release online treatment and the reuse technology of deionized water by copper sulfate electroplating wastewater, both zero release online treatment and the reuse of the decoration plating copper sulfate electroplating wastewater of the low acid of high-copper be can be applied to, zero release online treatment and the reuse of the copper sulfate electroplating wastewaters such as the PCB printed circuit board of low copper peracid also can be applied to.
Above technique both can be applied to copper sulfate electroplating wastewater zero online treatment in an electroplating assembly line and reuse, and the zero release end that also can be applied to all copper sulfate electroplating wastewaters in many electroplating assembly lines focuses on and reuse.As in the waste water processing station in Ji Kong district, the container that one is collected all copper sulfate electroplating wastewaters in Ji Kong district is specially set, then utilize present invention process to carry out individual curing to the copper sulfate electroplating wastewater in this container, the high-purity deionized water of output returns for Electroplating Production again.
Treatment process of the present invention, can remove the organism in copper sulfate electroplating wastewater completely, extends regeneration period and the work-ing life of follow-up resin.And the deionized water that copper sulfate electroplating wastewater can be purified completely as satisfied plating water quality requirement, directly return for copper sulfate electroplating system, define the water closed cycle of electroplating waste water treatment system and copper sulfate electroplating system online, thus realize the zero release recycle of electroplating wastewater.
Accompanying drawing explanation
Fig. 1 is the closed cycle figure of a kind of online wastewater treatment in embodiment 1 and electroplating water
Fig. 2 is the closed cycle figure of the online wastewater treatment of another kind in embodiment 2 and electroplating water
Embodiment
embodiment 1: the comparison of adsorb organic compound
In the first step of copper sulfate electroplating waste processing process, make the combine adsorption organism wherein of spent ion exchange resin and gac, especially adopt macropore deacidite and gac combination, there is excellent absorption property, improve organic removal rate to greatest extent.For this absorption property, invention has been simultaneous test, have detected different adsorbent respectively for the organic removal rate of brightening agent for acid copper electroplating residual in copper sulfate electroplating wastewater, result is as table 1.
The different adsorbent of table 1 is for the organic removal rate of brightening agent for acid copper electroplating
It is known by contrasting,
vPOC1071+ gac,
a860+ gac,
the combination of XAD4+ gac, is used alone adsorb organic compound relative to them, has more excellent effect.And aforesaid combination, relative to the combination of alkaline adsorption resin D293+ gac, also has better adsorption effect.Visible by gac and the combination of macropore deacidite, almost can remove the organism (reaching 99%) in copper sulfate electroplating wastewater completely.
Find after deliberation, gac is to sodium polydithio-dipropyl sulfonate, the adsorptive capacity of this kind of compositions such as polydithio-dipropyl sodium sulfate and substituting thioureido is very little, but it can fully absorb the type organic such as dyestuff and polyethet surfactant, otherwise, macropore deacidite is to the sodium polydithio-dipropyl sulfonate showing negative ion characteristic after dissociation or partial dissociation, the absorption property of this kind of compositions such as polydithio-dipropyl sodium sulfate and substituting thioureido is very excellent, for the type organic such as dyestuff and polyethet surfactant of not dissociation and difficult dissociation, its adsorptive power is very limited, it is visible that they can form perfect complementation, therefore, it is possible to almost remove the organism (reaching 99%) in copper sulfate electroplating wastewater completely.
Embodiment 2: copper sulfate electroplating wastewater zero online treatment technique
Technical process is as follows:
1, the technical process of copper sulfate electroplating unit is: sour copper plating → first step washing → second stage washing → third stage washing → subsequent disposal.This electroplating unit with current direction be: pure water storage tank → third stage washing bath → second stage washing bath → first step washing bath → comprehensive wastewater treating pond.The color of copper sulfate electroplating wastewater flowed out from first step washing bath is light blue black.On-site sampling is analyzed, and the electroplating wastewater composition of discharging from first step washing bath is as follows: copper sulfate 10.60 grams per liter, sulfuric acid 3.43 grams per liter, chlorion 3.5ppm, brightening agent for acid copper electroplating debris concentration 58ppm.
2, the treatment process of sour copper electroplating wastewater is:
Acid copper electroplating wastewater → gac+macropore deacidite adsorption bed → bivalent cupric ion adsorption tower → cation bed → anion bed → deionized water
The ion exchange resin used in macropore deacidite adsorption bed is PuroliteA860, and it is a kind of macroporous strong basic anionite-exchange resin of easy regeneration.Bed body bulk is 100 liters, and resin loading capacity is 70 liters.D009 ion exchange resin is housed in bivalent cupric ion adsorption tower, and for adsorbing bivalent cupric ion, it is a kind of polyacrylie-type ion exchange resin.Cation bed is equipped with 001*7 gel-type strongly acidic cation exchange resin, for adsorbing other positively charged ion in waste water.201*7 gel type strong basic anion exchange resin is housed, for adsorbing the negatively charged ion such as sulfate ion and chlorion in waste water in anion bed.The volume of each body is 100 liters, and the loading capacity of gac and resin is 70 liters.
3, with pipeline, the water port of the influent waste water end of this Waste Water Treatment with the first step washing bath of production line is connected, the product water end (W.E.) of this system is connected with the water-in of third stage washing bath, close the pure water water intaking valve of third stage washing bath, material is thus formed the closed cycle of online wastewater treatment as shown in Figure 1 and electroplating water, sewage treatment technology process is as follows: sour copper electroplating wastewater → activated carbon adsorption bed → resin absorption bed → bivalent cupric ion adsorption bed → cation bed → anion bed → deionized water.The online wastewater treatment of such formation and the closed cycle of electroplating water are as shown in Figure 1.
4, when online water treatment device is started working, specific conductivity is beyond the maximum range 200 μ s/cm of specific conductivity, shows that the water quality of rinse water is very poor.Run about 30 minutes, conductivity values one tunnel is descending, until be shown as " 0.3 ".Show after halfhour operation, the water quality of Waste Water Treatment production water has obviously been better than not running the water quality before waste water treatment process of the present invention, meets the requirement of high-quality electroplating water completely.Continuous operation is until production water specific conductivity reaches threshold value 5.0 μ s/cm.
5, after running 70 hours continuously, conductivity data has risen to 5.0 μ s/cm, shows that resin needs have regenerated.
6, after regenerating resin according to related process flow process, after stable, conductivity values is shown as again " 0.3 ".
7, after connecting by the method described in step 3, repeating step 4 and 6, the conductivity data display recorded online, the conductivity values under normal operating condition and after regeneration is all shown as " 0.3 ", shows the water quality requirement meeting electroplating water by the water quality after this waste water treatment process process completely.
In above each concrete implementation step, unique external water source water intaking valve " third stage washing bath pure water water intaking valve " on electroplating assembly line is in closing condition always, electroplating cleaning water is supplied by the deionized water of online Waste Water Treatment output completely, shows that the wastewater treatment and renovation rate of present invention process reaches 100%.
It should be noted that, in above-mentioned embodiment, such as waste water composition is different, content is different, institute uses resin model and loading capacity difference and discharge on an equal basis factor all can not form the substantial change to present invention process.
Embodiment 3: copper sulfate electroplating wastewater zero online treatment technique
Technical process is as follows:
1, the technical process of copper sulfate electroplating unit is: sour copper plating → first step washing → second stage washing → third stage washing → subsequent disposal.This electroplating unit with current direction be: pure water storage tank → third stage washing bath → second stage washing bath → first step washing bath → comprehensive wastewater treating pond.On-site sampling is analyzed, and the electroplating wastewater composition of discharging from first step washing bath is as follows: copper sulfate 10.60 grams per liter, sulfuric acid 3.43 grams per liter, chlorion 3.5ppm, brightening agent for acid copper electroplating debris concentration 58ppm.
2, the treatment process of sour copper electroplating wastewater is:
Acid copper electroplating wastewater → gac+macropore deacidite adsorption bed → bivalent cupric ion adsorption tower → cation bed → anion bed → mixed bed → deionized water
The ion exchange resin used in macropore deacidite adsorption bed is
a860, it is a kind of macroporous strong basic anionite-exchange resin of easy regeneration.Bed body bulk is 100 liters, and resin loading capacity is 70 liters.Be equipped with in bivalent cupric ion adsorption tower
s930 ion exchange resin, for adsorbing bivalent cupric ion, it is a kind of functional group is imino-diacetic acetoxy group resin.Cation bed is equipped with 001*7 gel-type strongly acidic cation exchange resin, for adsorbing other positively charged ion in waste water.201*7 gel type strong basic anion exchange resin is housed, for adsorbing the negatively charged ion such as sulfate ion and chlorion in waste water in anion bed.The volume of each body is 100 liters, and the loading capacity of gac and resin is 70 liters.The resin used in this mixed bed is 001*7 and the 201*7 hybrid resin of 1:1.Mixed bed bed body bulk is 100 liters, and resin loading capacity is 70 liters.
3, with pipeline, the water port of the influent waste water end of this Waste Water Treatment with the first step washing bath of production line is connected, the product water end (W.E.) of this system is connected with the water-in of third stage washing bath, close the pure water water intaking valve of third stage washing bath, material is thus formed following online wastewater treatment and the closed cycle of electroplating water, sewage treatment technology process is as follows: sour copper electroplating wastewater → resin absorption bed → activated carbon adsorption bed → bivalent cupric ion adsorption bed → cation bed → anion bed → mixed bed → deionized water.The online wastewater treatment of such formation and the closed cycle of electroplating water are as shown in Figure 2.
4, when online water treatment device is started working, specific conductivity is beyond the maximum range 200 μ s/cm of specific conductivity, shows that the water quality of rinse water is very poor.Run about 30 minutes, conductivity values one tunnel is descending, until be shown as " 0.2 ", after showing to install mixed bed additional, the water quality of production water makes moderate progress.Also show, after halfhour operation, the water quality of Waste Water Treatment production water has obviously been better than not running the water quality before waste water treatment process of the present invention, meets the requirement of high-quality electroplating water completely simultaneously.Continuous operation is until production water specific conductivity reaches threshold value 5.0 μ s/cm.
5, after running 85 hours continuously (after showing to increase mixed bed, the regeneration period of wastewater treatment equipment extended to 85 hours by 70 hours), conductivity data has risen to 5.0 μ s/cm, shows that resin needs have regenerated.
6, after regenerating resin according to related process flow process, after stable, conductivity values is shown as again " 0.2 ".
7, after connecting by the method described in step 3, repeating step 4 and 6, the conductivity data display recorded online, the conductivity values under normal operating condition and after regeneration is all shown as " 0.2 ", shows the water quality requirement meeting electroplating water by the water quality after this waste water treatment process process completely.
In above each concrete implementation step, unique external water source water intaking valve " third stage washing bath pure water water intaking valve " on electroplating assembly line is in closing condition always, electroplating cleaning water is supplied by the deionized water of online Waste Water Treatment output completely, shows that the wastewater treatment and renovation rate of present invention process reaches 100%.
It should be noted that, in above-mentioned embodiment, such as waste water composition is different, content is different, institute uses resin model and loading capacity difference and discharge on an equal basis factor all can not form the substantial change to present invention process.
Claims (10)
1. a copper sulfate electroplating waste processing process, comprising: 1) with the organism in gac and ion exchange resin combine adsorption copper sulfate electroplating wastewater; 2) spent ion exchange resin adsorption step 1) in heavy metal ion in the waste water that obtains; 3) organics removal is become deionized water with the purifying electroplating wastewater of heavy metal ion by the technique adopting ion exchange method to prepare pure water.
2. a kind of copper sulfate electroplating waste processing process according to claim 1, it is characterized in that: in step 1) in, described organism comprises the organism in brightening agent for acid copper electroplating, such as: dyestuff and/or polyethet surfactant, and the organism such as sodium polydithio-dipropyl sulfonate, polydithio-dipropyl sodium sulfate and substituting thioureido.
Preferably, in step 1) in, first adopt charcoal absorption, then adopt ion exchange resin Adsorption organism.
3. a kind of copper sulfate electroplating waste processing process according to claim 1 and 2, is characterized in that: in step 1) in, described ion exchange resin is macropore deacidite.Can be a kind of macroporous strong basic ion exchange resin, also can be a kind of macroreticular weakly base ion exchange resin, preferred macroporous strong basic ion exchange resin.
4. a kind of copper sulfate electroplating waste processing process according to claim 3, is characterized in that, described macroporous strong basic ion exchange resin is AmberliteXAD4, LewatitVPOC1071, PuroliteA860 resin.
5. a kind of copper sulfate electroplating waste processing process according to any one of claim 1-4, it is characterized in that: the ion exchange resin for Adsorption of Heavy Metals be resin or/and Zeo-karb, preferred ion exchange resin is that weakly acidic cation-exchange resin is or/and resin.
6. a kind of copper sulfate electroplating waste processing process according to any one of claim 1-5, it is characterized in that: step 3) in organics removal is become deionized water with the purifying electroplating wastewater of heavy metal ion, realized by following steps: A) by all non-H in the electroplating wastewater of organics removal and heavy metal ion
+positively charged ion all changes into H
+; B) by all non-OH
-negatively charged ion all converts OH to
-, and and H
+combine on the spot and generate water.
Or, realized by following steps: A ') and by all non-OH in the electroplating wastewater of organics removal and heavy metal ion
-negatively charged ion all converts OH to
-; B ') by all non-H
+positively charged ion all changes into H
+, and and OH
-combine on the spot and generate water.
7. a kind of copper sulfate electroplating waste processing process according to claim 6, is characterized in that: after cation bed and anion bed, adopts hybrid resin to carry out adsorption treatment to electroplating wastewater in mixed bed.
8. a kind of copper sulfate electroplating waste processing process according to claim 7, is characterized in that: described hybrid resin is 001*7 and 201*7 of 1:1, described mixed bed bed body bulk is 100 liters, and resin loading capacity is 70 liters.
9. a kind of copper sulfate electroplating waste processing process according to any one of claim 1-8, it is characterized in that: described technique may be used for the copper sulfate electroplating wastewater zero online treatment in an electroplating assembly line, also the zero release end that may be used for all copper sulfate electroplating wastewaters in many electroplating assembly lines focuses on, such as in the waste water processing station in Ji Kong district, the container that one is collected all copper sulfate electroplating wastewaters in Ji Kong district is specially set, then utilizes described technique to carry out individual curing to the copper sulfate electroplating wastewater in described container.
10. electroplate a close circulation technology, comprising: electroplating technology and the waste water treatment process described in any one of claim 1-9, described waste water treatment process is combined online with electroplating technology flow process, forms a closed circuit circulatory system.
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| CN109626658A (en) * | 2019-01-24 | 2019-04-16 | 黄河水利职业技术学院 | A kind of processing method of copper-contained electroplating waste water |
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