CN103991935B - A kind of method removing Copper in Electroplating Waste Water ion - Google Patents
A kind of method removing Copper in Electroplating Waste Water ion Download PDFInfo
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- CN103991935B CN103991935B CN201410255458.1A CN201410255458A CN103991935B CN 103991935 B CN103991935 B CN 103991935B CN 201410255458 A CN201410255458 A CN 201410255458A CN 103991935 B CN103991935 B CN 103991935B
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Abstract
The invention discloses a kind of method of efficient removal Copper in Electroplating Waste Water ion, belong to field of waste water treatment, comprise the following steps successively: one-step electrolysis: the pH of electroplating wastewater is transferred to 6-9, with Graphite Electrodes, or Graphite Electrodes and metal electrode are negative and positive the two poles of the earth, carry out electrolysis; Two one-step electrolysis: add sulfide, stir, and continue electrolysis; Three one-step electrolysis: add polyaluminium sulfate, stir, and continue electrolysis; Four one-step electrolysis: add polyacrylamide, stir, and continue electrolysis to terminating.The present invention be a kind of can rapidly and efficiently, the method for the actual copper-contained electroplating waste water of processing plant at low cost.
Description
Technical field
The invention belongs to field of waste water treatment, particularly in actual electrical waste electroplating with the treatment process of cupric ion that complex form exists.
Background technology
Cupric ion discharge excessive in electroplating wastewater, can affect hydrobiological existence, polluted water, Soil Surrounding and growing plant.The most basic toxic effect of copper is that it can disturb root system of plant enzyme system, and affects the synthesis of photosynthesis of plant and lipid acid, causes that plant-growth is slow, root system development is poor, the withered jaundice of blade.People eats the fishery products such as periphery vegetables or fish, and be easy to cause heavy metal poisoning, serious threat is healthy.
At present Copper in Electroplating Waste Water ion processing method mainly contains chemical precipitation method, membrane filter method, ion exchange method, physisorphtion, ferrite process and biosorption process etc.Chemical precipitation method be start to walk comparatively early, relatively ripe electroplating effluent treatment method, its research in recent years is mainly preparing more efficient flocculation agent and heavy metal chelating agent.The heavy metal chelating agent XMT that Wang Fenghe etc. prepare, can reach more than 99% to the clearance of starting point concentration cupric ion in the copper ion solution of 100mg/L, extraneous copper ionic concn is less than 0.05mg/L.Microbial flocculant is also extensively pursued in recent years, as microbial flocculant MBFGA1 to the clearance of cupric ion up to 99.68%, extraneous copper ionic concn is less than 0.08mg/L.Membrane filter method presses isolating ions size, can be divided into micro-filtration, ultrafiltration, reverse osmosis, nanofiltration etc.Membrane separation process has empty phase change, and energy conversion efficiency is high, does not consume the advantages such as chemical reagent.But because equipment cost is higher, be mainly used for reuse water process.Physical adsorption mainly contains charcoal absorption, the absorption of waste material ferric oxide, polyacrylic ester absorption, starch base absorption, cellulose base absorption etc.Biosorption process causes the extensive concern of people because having efficient, cheap potential advantages.At present this area research person is mainly with bacterium, fungi, algae as research object, and obtains certain achievement.But when these methods process heavy metal wastewater thereby under low consistency conditions, have poor removal effect, the treatment time is long, microorganism is difficult to cultivate, and easily produces the shortcoming of secondary pollution, in addition process cost and material cost too high, its application receives limit value.
Existing electroplating wastewater cupric ion treatment process is mainly for the copper of ionic state, and the less copper considering complex state.And due to containing EDTA, NH4+, Cl in electroplating wastewater
-, CN
-deng material and Cu
2+form complex compound, cause part Cu
2+exist with the form of complex state.Just because of the existence of complex state copper, so that process Copper in Electroplating Waste Water ion is still a global problem, and the aqueous concentration of cupric ion remains high always, has not yet to see the report of Copper in Electroplating Waste Water ion aqueous concentration lower than 0.05mg/L so far.
Summary of the invention
The object of the invention is to: propose a kind of can rapidly and efficiently, the method for the actual copper-contained electroplating waste water of processing plant at low cost.
The object of the invention is realized by following technical proposals:
A method for efficient removal Copper in Electroplating Waste Water ion, comprises the following steps successively:
One-step electrolysis: the pH of electroplating wastewater is transferred to 6-9, with Graphite Electrodes, or Graphite Electrodes and metal electrode are negative and positive the two poles of the earth, carry out electrolysis;
Two one-step electrolysis: add sulfide, stir, and continue electrolysis;
Three one-step electrolysis: add polyaluminium sulfate (PAS), stir, and continue electrolysis;
Four one-step electrolysis: add polyacrylamide (PAM), stir, and continue electrolysis to terminating.
In such scheme, waste water handled by the present invention is the actual copper-contained electroplating waste water of factory, but not laboratory simulation waste water.Actual copper-contained electroplating waste water comprises acid waste water, alkaline waste water and complexing waste water, and cupric ion starting point concentration is 10-200mg/L.Metal electrode comprises Ti electrode, copper electrode, platinum electrode or silver electrode.
Overall electrolytic process:
Alive effect is be Cu on the one hand
2+reduction; On the other hand mainly according to the H that electrofloatation principle utilizes electrolysis to produce
2and O
2cu (OH) in absorption waste water
2, Cu
2+, CuS and rise to the water surface, play the effect that impurity is separated with water.
The effect of control pH mainly when pH=6 ~ 9 electrolysis to remove the effect of cupric ion best.When pH=1 ~ 6, cupric ion clearance raises along with pH value and raises; When pH=9 ~ 14, cupric ion clearance raises along with pH value and reduces.In addition, under neutrality or meta-alkalescence condition, add sulfide, can not H be produced
2s, avoids H
2s pollutes, and according to electrolysis order S
2-> I
-> Br
-> Cl
-> OH
-> oxygen acid radical ion > F
-, remaining S
2-also electrolysis can separate out, stench can not be caused to produce secondary pollution.The reaction of its electrolysis is: S
2-2e
-=S ↓.
Sulfonium ion (the S of the effect adding sulfide mainly in sulfide
2-) destroy Cu
2+with EDTA, NH
4 +, Cl
-, CN
-deng the chelation structure formed.Part Cu
2+with S
2-generate more stable Compound C uS; Part Cu
2+outside under alive condition, copper simple substance can be generated in negative electrode generation reduction reaction.
The effect adding PAS mainly makes the impurity in waste water condense, and more easily precipitates and filters, realizing being separated with water.Polyaluminium sulfate is compound macromolecular polymer, high adsorption capacity, and sedimentation speed is fast, and active high, filterableness is good.And the strong adaptability to former water, on pH value impact minimum (pH value 4-11) of water.
The effect adding a PAM mainly nearly step makes the impurity in waste water condense.The flocculating effect adding PAM in the process of copper-contained electroplating waste water is better than and adds PAS, and PAM flocculating effect in the impurity waste water of lower concentration is better.But due to PAM price costly, coordinate the use of PAS, good effect can be reached and can reduce costs again.
Particularly, in process of the present invention, add sulfide, PAS, PAM, the order of three can not change, and indispensable, is the effect for reaching first contact break precipitation reflocculation.
The reaction of negative electrode is: Cu
2++ 2e
-=Cu ↓
H
++2e
-=H
2↑
The reaction of anode is: 40H
--4e=2H
2o+O
2↑
S
2-2e
-=S↓
Final cupric ion of the present invention mainly contains two kinds of forms: one is also with Cu (OH)
2, the compound precipitates form such as CuS exists; And another kind is Cu
2+obtain electronics at negative electrode and generate the copper of elemental.The elemental copper generated at negative electrode can be recycled, and serves the effect of turning waste into wealth.
As selection, described electrolysis voltage scope is 3 ~ 60V.Further selection, described electrolysis voltage scope is 8 ~ 20V.In such scheme, verify by experiment, voltage is all effective at more than 3V, but overtension can make electrolysis temperature too high, destroys former electrolytic equilibrium, and cupric ion clearance reduces, and it is excessive to consume electric energy, and therefore electrolysis temperature is no more than 60V.
As selection, described one-step electrolysis electrolysis time is 5 ~ 20min.In such scheme, electrolysis time is according to Voltage Cortrol, and the time is less than 5min can make electrolysis incomplete.
As selection, described sulfide is sodium sulphite or potassium sulphide, S
2-add-on be (0.01 ~ 0.50) g/L electroplating wastewater, S
2-add-on adjust according to the concentration of former Copper in Electroplating Waste Water ion.S
2-add-on can not make Cu very little
2+precipitation and electrolysis completely.Electrolysis time is 15 ~ 30min, and electrolysis time need according to Voltage Cortrol, passes that I haven't seen you for ages makes electrolysis incomplete the time.
As selection, the add-on of described polyaluminium sulfate is (0.02 ~ 0.50) g/L electroplating wastewater, and polyaluminium sulfate adds the very few effect that can not reach flocculation.Electrolysis time is 10 ~ 15min, passes that I haven't seen you for ages makes electrolysis incomplete the time.
As selection, the add-on of described polyacrylamide is (0.005 ~ 0.20) g/L electroplating wastewater, and adding too much not only according to one-tenth waste of raw materials of polyacrylamide, also can shine into waste water viscosity and increase, follow-up being difficult to processes.Electrolysis time is 15 ~ 25min, passes that I haven't seen you for ages makes electrolysis incomplete the time.
The main scheme of aforementioned the present invention and each further selection scheme thereof can independent assortment to form multiple scheme; be the present invention can adopt and claimed scheme: as the present invention; each selection can select arbitrary combination with other; those skilled in the art can understand there is multiple combination according to prior art and common practise after understanding the present invention program; be the claimed technical scheme of the present invention, do not do exhaustive at this.
Beneficial effect of the present invention: can be reduced to 0.05mg/L by minimum for the cupric ion in high-concentration electroplating wastewater in 1.5h, the clearance of cupric ion can reach more than 99.5%, processing cost is low and rapidly and efficiently, be obviously better than existing electroplating effluent treatment method.
Embodiment
Following non-limiting examples is for illustration of the present invention.
embodiment 1:
A novel method for efficient removal Copper in Electroplating Waste Water ion, comprises the steps:
(1) get 200ml factory electroplating wastewater, the starting point concentration of its cupric ion is 20.07mg/L.PH value is adjusted to 6, is negative and positive the two poles of the earth with Graphite Electrodes, adds 8V potential electrolysis 20min.
(2) first add 0.0244g sodium sulphite, stir, electrolysis 21min.
(3) then add 0.4648g polyaluminium sulfate (PAS), stir, electrolysis 12min.
(4) finally add 0.0056g polyacrylamide (PAM), stir, electrolysis 22min, terminate.
Experimental result shows: be 0.06mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, and the clearance of cupric ion is 99.70%.
embodiment 2:
A novel method for efficient removal Copper in Electroplating Waste Water ion, comprises the steps:
(1) get 200ml factory electroplating wastewater, the starting point concentration of its cupric ion is 132.26mg/L.PH value is adjusted to 8, and take Graphite Electrodes as anode, Ti electrode is negative electrode, adds 60V potential electrolysis 5min.
(2) first add 1.718g potassium sulphide, stir, electrolysis 15min.
(3) then add 0.0910g polyaluminium sulfate (PAS), stir, electrolysis 10min.
(4) finally add 0.0055g polyacrylamide (PAM), stir, electrolysis 15min, terminate.
Experimental result shows: be 0.09mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, and the clearance of cupric ion is 99.93%.
embodiment 3:
A novel method for efficient removal Copper in Electroplating Waste Water ion, comprises the steps:
(1) get 200ml factory electroplating wastewater, the starting point concentration of its cupric ion is 40.15mg/L.PH value is adjusted to 7, and take Graphite Electrodes as anode, Ti electrode is negative electrode, adds 20V potential electrolysis 13min.
(2) first add 0.8658g sodium sulphite, stir, electrolysis 25min.
(3) then add 0.0563g polyaluminium sulfate (PAS), stir, electrolysis 10min.
(4) finally add 0.0658g polyacrylamide (PAM), stir, electrolysis 18min, terminate.
Experimental result shows: be 0.05mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, and the clearance of cupric ion is 99.87%.
embodiment 4:
A novel method for efficient removal Copper in Electroplating Waste Water ion, comprises the steps:
(1) get 200ml factory electroplating wastewater, the starting point concentration of its cupric ion is 76.15mg/L, and pH value is adjusted to 9, is anode with Graphite Electrodes, is negative electrode with copper electrode, adds 15V potential electrolysis 18min.
(2) 0.7245g potassium sulphide is first added, electrolysis 30min.
(3) 0.0226g polyaluminium sulfate (PAS) is then added, electrolysis 10min.
(4) finally add 0.1719g polyacrylamide (PAM) electrolysis 22min, terminate.
Experimental result shows: be 0.06mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, and the clearance of cupric ion is 99.87%.
Above-described embodiment experimental result shows: be all less than 0.10mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, be only in " plating pollutant emission standard " and put 20% of primary standard value 0.50mg/L to total copper bar.
comparative example 1:
(1) get 200ml factory electroplating wastewater, the starting point concentration of its cupric ion is 40.15mg/L.PH value is adjusted to 7, stirs 13min.
(2) first add 0.8658g sodium sulphite, stir 25min.
(3) then add 0.0563g polyaluminium sulfate (PAS), stir 10min.
(4) finally add 0.0658g polyacrylamide (PAM), stir 18min, terminate.
Experimental result shows: be 0.48mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, and the clearance of cupric ion is 98.80%.
comparative example 2:
(1) get 200ml factory electroplating wastewater, the starting point concentration of its cupric ion is 40.15mg/L.PH value is adjusted to 7, and take Graphite Electrodes as anode, Ti electrode is negative electrode, adds 20V potential electrolysis 13min.
(3) first add 0.0563g polyaluminium sulfate (PAS), stir, electrolysis 10min.
(4) then add 0.0658g polyacrylamide (PAM), stir, electrolysis 18min, terminate.
Experimental result shows: be 6.85mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, and the clearance of cupric ion is 82.94%.
comparative example 3:
(1) get 200ml factory electroplating wastewater, the starting point concentration of its cupric ion is 40.15mg/L.PH value is adjusted to 7, and take Graphite Electrodes as anode, Ti electrode is negative electrode, adds 20V potential electrolysis 13min.
(2) first add 0.8658g sodium sulphite, stir, electrolysis 25min.
(4) finally add 0.1858g polyacrylamide (PAM), stir, electrolysis 25min, terminate.
Experimental result shows: be 1.20mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, and the clearance of cupric ion is 97.01%.
comparative example 4:
(1) get 200ml factory electroplating wastewater, the starting point concentration of its cupric ion is 40.15mg/L.PH value is adjusted to 7, and take Graphite Electrodes as anode, Ti electrode is negative electrode, adds 20V potential electrolysis 13min.
(2) first add 0.8658g sodium sulphite, stir, electrolysis 25min.
(3) then add 0.4863g polyaluminium sulfate (PAS), stir, electrolysis 25min, terminate.
Experimental result shows: be 5.64mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, and the clearance of cupric ion is 85.95%.
comparative example 5:
(1) get 200ml factory electroplating wastewater, the starting point concentration of its cupric ion is 40.15mg/L.PH value is adjusted to 7, and take Graphite Electrodes as anode, Ti electrode is negative electrode, adds 20V potential electrolysis 13min.
(2) first add 0.8658g sodium sulphite, stir, electrolysis 25min.
(3) then, add 0.0658g polyacrylamide (PAM), stir, electrolysis 18min.
(4) last, add 0.0563g polyaluminium sulfate (PAS), stir, electrolysis 10min, terminate.
Experimental result shows: be 0.88mg/L by the concentration of Copper in Electroplating Waste Water ion after this method process, and the clearance of cupric ion is 97.80%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1. remove a method for Copper in Electroplating Waste Water ion, it is characterized in that comprising the following steps successively:
One-step electrolysis: the pH of electroplating wastewater is transferred to 6-9, with Graphite Electrodes, or Graphite Electrodes and metal electrode are negative and positive the two poles of the earth, carry out electrolysis; Described electrolysis voltage scope is 3 ~ 60V; Described electrolysis time is 5 ~ 20min;
Two one-step electrolysis: add sulfide, stir, and continue electrolysis; Described sulfide is sodium sulphite or potassium sulphide, S
2-add-on be 0.01 ~ 0.50g/L electroplating wastewater, electrolysis time is 15 ~ 30min;
Three one-step electrolysis: add polyaluminium sulfate, stir, and continue electrolysis; The add-on of described polyaluminium sulfate is 0.02 ~ 0.50g/L electroplating wastewater, and electrolysis time is 10 ~ 15min;
Four one-step electrolysis: add polyacrylamide, stir, and continue electrolysis to terminating; The add-on of described polyacrylamide is 0.005 ~ 0.20g/L electroplating wastewater, and electrolysis time is 15 ~ 25min.
2. the method removing Copper in Electroplating Waste Water ion as claimed in claim 1, is characterized in that: described electrolysis voltage scope is 8 ~ 20V.
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Cited By (1)
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| RU2793617C1 (en) * | 2022-11-02 | 2023-04-04 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева"(РХТУ им. Д.И. Менделеева), | Method for electroflotation extraction of sparingly soluble copper compounds from ammonia systems |
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| CN106915882A (en) * | 2017-04-27 | 2017-07-04 | 安徽省农业科学院棉花研究所 | A kind of dirty low voltage method of abatement pig farm excrement |
| CN109516614A (en) * | 2018-11-23 | 2019-03-26 | 宁波欣辉环保科技有限公司 | A kind of electroplating wastewater oxidation processing technique of reverse osmosis membrane processing complex compound |
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Cited By (2)
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| RU2793617C1 (en) * | 2022-11-02 | 2023-04-04 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева"(РХТУ им. Д.И. Менделеева), | Method for electroflotation extraction of sparingly soluble copper compounds from ammonia systems |
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