CN204607752U - Chemical nickel plating waste solution treatment facility up to standard - Google Patents
Chemical nickel plating waste solution treatment facility up to standard Download PDFInfo
- Publication number
- CN204607752U CN204607752U CN201420870894.5U CN201420870894U CN204607752U CN 204607752 U CN204607752 U CN 204607752U CN 201420870894 U CN201420870894 U CN 201420870894U CN 204607752 U CN204607752 U CN 204607752U
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- nickel plating
- chemical nickel
- ion exchange
- waste solution
- waste water
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Abstract
The utility model relates to a kind of chemical nickel plating waste solution treatment facility up to standard, comprising: ion exchange column, comprises ion exchange resin to adsorb the nickel ion in this chemical nickel plating waste solution; Fenton oxidation reactor, processes the chemical nickel plating waste solution through ion exchange method, with the some organic pollutants in oxygenolysis waste water, reach the effect of oxidation contact break, make complex state metal ion nickel be converted into free state, the organism in simultaneous oxidation waste liquid, reduce the COD in waste water; Settling tank, uses magnesium ammonium phosphate sediment method to process the chemical nickel plating waste solution through Fenton oxidation, carries out reacting the magnesium ammonium phosphate sediment thing generating indissoluble, thus by the ammonia nitrogen removal in waste water; Break point chlorination pond, uses break point chlorination method to remove ammonia nitrogen further; And Losantin settling tank, utilize ozone as oxygenant in conjunction with the phosphorus in Losantin precipitation removal waste water.The utility model can solve the qualified discharge problem of nickel, phosphorus, COD, ammonia nitrogen simultaneously.
Description
Technical field
The utility model relates to plating or Surface Processing Industry wastewater treatment and technical field of water pollution control, particularly a kind of chemical nickel plating waste solution treatment facility up to standard.
Background technology
Chemical nickel plating developed process for treating surface faster in recent years, and it is a kind of coating method generating Ni, P coating with the effect such as nickel salt and hypophosphite.Owing to having coating, chemical nickel plating evenly, does not need that external power, hardness are high, wear resisting property good, plating is not widely used in every field by advantages such as part dimension shape restrictions.Along with chemical nickel plating range of application and industrial scale constantly expand, the chemical nickel plating waste solution environmental pollution thereupon produced is also more and more serious.There is the complex compound of nickel in chemical nickel-plating liquid, and these complex compounds are mostly outer rail types, have stronger complexing to nickel.Also there is relatively large hypophosphite and the phosphite with reductibility in plating solution, a large amount of pH value buffer reagent (as acetic acid, succinic acid etc.), also have brightening agent and stablizer.In chemical nickel-plating liquid, because the existence of complexing agent and reductive agent must cause COD sharply to raise, the nickel containing 2 ~ 7g/L in chemical nickel plating waste solution, the phosphorus of 30 ~ 200g/L and large amount of organic.Nickel is a kind of heavy metal resources of costliness, is again a kind of strong carcinogen simultaneously, belongs to first kind pollutent; Phosphorus is then one of main pollution factor causing body eutrophication phenomenon.Waste liquid, as dealt with improperly, is a kind of wasting of resources, may causes heavy metal contamination and body eutrophication again.Therefore, most important to dealing carefully with of chemical nickel plating waste solution.
An existing chemical nickel plating waste solution treatment process part is for the purpose of recycling, as Oak Ridge K-25 institute of the U.S. develops ENVIR-CP chemical nickel-plating liquid reclaiming process.This technique sets up the bypath system except sodium phosphite of one-period and continous way at trough rim, to control plating solution phosphorous acid sodium and sodium sulfate at lower concentration level, keeps the stable of the composition of chemical nickel-plating liquid and plating speed.
Some is to process for the purpose of qualified discharge, but is one or both pollutents of process mostly, as nickel, phosphorus etc.If a kind of already known processes is with Ca (OH)
2for precipitation agent, pH=12,80 DEG C of reactions, in Ageing solution, the mass concentration of nickel drops to 1mg/L; Solution sulfuric acid after precipitation separation regulates pH=8, by Ca (ClO)
2be 3.5:1.0 with the mass ratio of total phosphorus, add Ca (ClO)
2, the phosphoric acid salt in Ageing solution is removed by forming precipitation.To Ni (OH)
2precipitation, dissolves the nickel reclaimed wherein with dilute sulphuric acid, residue sediment landfill disposal.
Utility model content
Technical problem to be solved in the utility model is to provide a kind of chemical nickel plating waste solution treatment facility up to standard, solves the qualified discharge problem of nickel, phosphorus, COD, ammonia nitrogen simultaneously.
The utility model is that to solve the problems of the technologies described above the technical scheme adopted be propose a kind of chemical nickel plating waste solution treatment facility up to standard, comprising: ion exchange column, comprises ion exchange resin to adsorb the nickel ion in this chemical nickel plating waste solution; Fenton oxidation reactor, connect this ion exchange column, this Fenton oxidation reactor processes the chemical nickel plating waste solution through ion exchange method, with the some organic pollutants in oxygenolysis waste water, reach the effect of oxidation contact break, make complex state metal ion nickel be converted into free state, organism in simultaneous oxidation waste liquid, destroy its carbon-chain structure, organism is finally converted into carbonic acid gas and water, reduce the COD in waste water; Magnesium ammonium phosphate sediment pond, connects this Fenton oxidation reactor, uses magnesium ammonium phosphate sediment method to process the chemical nickel plating waste solution through Fenton oxidation, carries out reacting the magnesium ammonium phosphate sediment thing generating indissoluble, thus by the ammonia nitrogen removal in waste water; Break point chlorination pond, connects this magnesium ammonium phosphate sediment pond, uses break point chlorination method to remove ammonia nitrogen further; And Losantin settling tank, connect this break point chlorination pond, utilize ozone as oxygenant in conjunction with the phosphorus in Losantin precipitation removal waste water.
In an embodiment of the present utility model, this ion exchange resin is macrovoid phenylethylene chelating ion exchange resin.
A kind of chemical nickel plating waste solution treatment facility up to standard that the utility model proposes, adopt ion-exchange-Fenton oxidation-magnesium ammonium phosphate (MAP) precipitation-break point chlorination-Losantin precipitate combination technical finesse chemical nickel plating waste solution, solve the qualified discharge problem of nickel, phosphorus, COD, ammonia nitrogen simultaneously.
Accompanying drawing explanation
For above-mentioned purpose of the present utility model, feature and advantage can be become apparent, below in conjunction with accompanying drawing, embodiment of the present utility model is elaborated, wherein:
Fig. 1 illustrates the chemical nickel plating waste solution treatment facility up to standard of the utility model one embodiment.
Fig. 2 illustrates the chemical nickel plating waste solution treatment scheme up to standard of the utility model one embodiment.
Embodiment
Embodiment of the present utility model proposes a kind of chemical nickel plating waste solution treatment process up to standard, adopt ion-exchange-Fenton oxidation-magnesium ammonium phosphate (MAP) precipitation-break point chlorination-Losantin precipitate combination technical finesse chemical nickel plating waste solution, solve the qualified discharge problem of nickel, phosphorus, COD, ammonia nitrogen simultaneously.
Fig. 1 illustrates the chemical nickel plating waste solution treatment facility up to standard of the utility model one embodiment.Shown in figure 1, chemical nickel plating waste solution treatment facility 10 up to standard mainly comprises wastewater collection pond 11, ion exchange column 12, Fenton oxidation reactor 13, magnesium ammonium phosphate sediment pond 14, break point chlorination pond 15 and Losantin settling tank 16.Wastewater collection pond 11, ion exchange column 12, Fenton oxidation reactor 13, magnesium ammonium phosphate sediment pond 14, break point chlorination pond 15 are connected successively with Losantin settling tank 16.Ion exchange column 11 comprises ion exchange resin to adsorb the nickel ion in this chemical nickel plating waste solution.Wastewater collection pond 11 is used for collecting and hold waste water with pending.Ion exchange column 12 is used for carrying out ion-exchange with adsorbing metal nickel.Fenton oxidation reactor 13 is used for performing Fenton process, and magnesium ammonium phosphate sediment pond 14 is used for carrying out magnesium ammonium phosphate sediment, and break point chlorination pond 15 is used for removing ammonia nitrogen further.Losantin settling tank 16 is with removing phosphorus.
Treatment facility 10 up to standard also can comprise concentrated nickel accumulator tank 17, and it connects ion exchange column 12, receives the concentrated solution containing nickel, after reclaiming, obtain nickel salt product.
Treatment facility 10 up to standard also can comprise mud receiving tank 18 and pressure filter 19.Mud receiving tank 18 connects Fenton oxidation reactor 13 and magnesium ammonium phosphate sediment pond 14, from these two collect mud.The mud collected enters after pressure filter 19 processes and transports.
Fig. 2 illustrates the chemical nickel plating waste solution treatment scheme up to standard of the utility model one embodiment.Shown in figure 2, flow process comprises the following steps:
In step 21, use the nickel ion in ion exchange method sorption chemical nickel-plating waste liquid.
As shown in Figure 1, ion exchange column 11 comprises ion exchange resin with the nickel ion in sorption chemical nickel-plating waste liquid.Ion-exchange resins is as used macrovoid phenylethylene chelating ion exchange resin, and the selectivity of resin to metal ion is analogous to EDTA, and higher than strongly-acid or weakly acidic cation-exchange resin.When coexist in solution 1 valency and divalent metal ion time, resin has high avidity and strong Selective adsorption to divalent metal ion, a selective adsorption divalent metal ion.In order to ensure the adsorption effect to nickel ion, 3-4 ion exchange column of can connecting is general by nickel ion concentration≤0.5mg/l after ion exchange treatment.
In step 22, Fenton process is used to process the chemical nickel plating waste solution through ion exchange method.
Fenton oxidation method receives concern both domestic and external day by day at the investigation and application of wastewater treatment, and Fenton reagent can be oxidized dirty Organic substance in water well and reducing substances is because in acid condition, H
2o
2at Fe
2+catalyst action under produce two kinds of active hydroxyl free radical (HO
2and OH), wherein the oxidation capacity of OH is up to 2.80V, be only second to fluorine, and OH free radical has very high electronegativity or Electron Affinities, its electron affinity power, up to 569.3kJ, has very strong addition reaction characteristic, thus causes and propagate radical chain reaction, accelerate the oxidation of organism and reducing substances, simultaneously Fe
2+be oxidized to Fe
3+produce coagulating sedimentation, remove a large amount of pollutent.Therefore, Fenton reagent has oxidation and coagulation two kinds effect in water treatment.
Shown in figure 1, Fenton oxidation reactor 13 can input waste water from ion exchange column 12, by its medicating mechanism optionally acid adding, add hydrogen peroxide (H
2o
2) and add ferrous sulfate.
Chemical nickel plating waste solution, by utilizing some organic pollutants in Fenton oxidation Decomposition Wastewater, reaches two kinds of effects.One, be oxidized the effect of contact break, make complex state metallic nickel be converted into free state, improve the coagulating sedimentation efficiency of follow-up heavy metal ion.Two, be oxidized the organism in waste liquid, destroy its carbon-chain structure, organism is finally converted into carbonic acid gas and water, reduce the COD in waste water.
The preferred process condition of Fenton oxidation is: initial pH value 2 ~ 4, and the ferrous mass concentration added maintains 1-2g/l.The dioxygen water yield that adds maintain ORP 550mv and more than.Reaction times 1 ~ 2h.
Preferred embodiment of the present utility model controls by ORP the amount adding hydrogen peroxide, avoids the fluctuation because of pollutant load, the phenomenon that caused dosage is not enough or too much.I haven't seen you for ages causes treatment effect to decline for hydrogen peroxide dosage; It is excessive to add, and medicament not only can be caused to waste, and can cause Mud up-floating, affect treatment effect.
In step 23, use magnesium ammonium phosphate sediment method to process the chemical nickel plating waste solution through Fenton process, carry out reacting the magnesium ammonium phosphate sediment thing generating indissoluble, thus by the ammonia nitrogen removal in waste water.
Magnesium ammonium phosphate (struvite) precipitator method, except ammonia nitrogen, are add containing Mg in waste water
2+(MgCl
26H
2and P0 O)
4 3-(Na
2hPO
412H
2o) medicament, makes it and the NH in waste water
4+carry out reacting the magnesium ammonium phosphate sediment thing generating indissoluble, thus by the method for the ammonia nitrogen removal in waste water.Its action principle is shown in following formula:
Mg
2++NH
4++PO
4 3-+6H
2O＝MgNH
4PO
4·6H
2O↓
KSP＝2.5×10
-13(25℃)
Shown in figure 1, magnesium ammonium phosphate sediment pond 14 inputs waste water from Fenton oxidation reactor 13, adds Mg respectively as required
2+(MgCl
26H
2and P0 O)
4 3-(Na
2hPO
412H
2o) medicament.The magnesium ammonium phosphate that precipitation produces can be discharged.
This method can not only remove nitrogen, phosphorus in waste water, and the throw out (magnesium ammonium phosphate) generated can be used as slow release fertilizer for planting landscape plant, forest, flowers etc., even can make sanitising agent, makeup and animal-feed.
Preferably, the processing condition of magnesium ammonium phosphate (MAP) precipitator method are: add MgCl by 1.5 times of theoretical dosages
26H
2o and Na
2hPO
412H
2o precipitation agent, controls reaction pH at 8.0-9.0, fully stirs, react 20 minutes.
In step 24, break point chlorination method is used to remove ammonia nitrogen further.
When adopting break point chlorination method to remove ammonia nitrogen further, the NH in waste water
3-N can, in suitable pH value, utilize the oxygenant of chlorine system (as Cl
2, NaOCl) make it to be oxidized to chloramines (NH
2cl, NHCl
2, NCl
3) after, reoxidize and resolve into N
2gas and reach the object removed.Breakpoint chlorination deamination net reaction:
NH
4++1.5HClO→0.5N
2+1.5H
2O+2.5H
++1.5Cl
-
Consider from security standpoint, usually replace liquid chlorine with sodium chlorate or chlorine dioxide generating device.Cl/N actual demand amount is greater than theoretical value 7.6:1, and when Cl/N is 10:1-12:1, treatment effect is better.
Shown in figure 1, break point chlorination pond 15 inputs waste water from magnesium ammonium phosphate sediment pond 14, adds the oxygenant of chlorine system as required as Cl
2, NaClO is oxidized.
In step 25, utilize ozone as oxygenant in conjunction with the phosphorus in Losantin precipitation removal waste water.
Utilize the method that ozone precipitates in conjunction with Losantin as oxygenant, have obvious removal effect to total phosphorus.Select Losantin as oxidation precipitation agent, hypochlorite provides oxygenizement on the one hand, and Hypophosphite and orthophosphite are oxidized to ortho-phosphoric acid root, and calcium ion provides precipitating action on the other hand, makes it form calcium phosphate precipitation further, is shown below:
1) H
2pO
2 -and HPO
3 2-:
2ClO
-+H
2PO
2-→PO
4 3-+2Cl
-+2H
+
ClO
-+HPO
3 2-→PO
4 3-+Cl
-+H
+
2) PO
4 3-precipitation:
2PO
4 3-+3Ca
2+→Ca
3(PO
4)
2↓
The preferred process condition of Losantin dephosphorization is: pass into 80mg/L ozone 10h, then is 9 at pH, under temperature is 80 DEG C of conditions, makes ratio of calcium and phosphorus be 5:1, continuous stirring reaction 5h.
Shown in figure 1, Losantin settling tank 16 inputs waste water from break point chlorination pond 15, adds ozone and Losantin as required, forms calcium phosphate precipitation.
Exemplify the example of the actual enforcement of the utility model below.
Embodiment:
Get certain enterprise's chemical nickel plating waste solution, first use chelating ion exchange resin absorbed Ni, then add 6g ferrous sulfate+3ml hydrogen peroxide by often liter of waste liquid, after reaction 1h.Then MgCl is added by 1.5 times of theoretical dosages
26H
2o and Na
2hPO
412H
2o precipitation agent, controls reaction pH at 8.0-9.0, abundant stirring reaction 20 minutes, precipitation, filtration; Add clorox by Cl/N mass ratio 10:1 again, and constantly stir, leave standstill 15min after reaction, precipitation, filtration, obtain supernatant liquor.First pass into 80mg/L ozone 10h to supernatant liquor, then be 9 at pH, temperature is under 80 DEG C of conditions, makes ratio of calcium and phosphorus be 5:1, continuous stirring reaction 5h, leaves standstill 15min, and precipitation, filtration, obtain supernatant liquor, detect supernatant liquor.
The chemical nickel plating waste solution that the utility model embodiment provides treatment facility up to standard, has the following advantages:
1, adopt ion-exchange-Fenton oxidation-break point chlorination-chemical precipitation combination technique Treatment of Electroless Nickel Plating Wastewater, solve the qualified discharge problem of nickel, phosphorus, COD, ammonia nitrogen, combination technique has novelty simultaneously.
2, table 2 standard that the water outlet after chemical nickel plating waste solution process can be stablized and reached " plating pollutant emission standard GB21900-2008 ".
3, the utility model is simple, practical, can realize automatic red-tape operati; Can reclaim nickel salt resource, magnesium ammonium phosphate can effectively reduce equipment cost as agriculture fertilizer and drop into, and effectively reduces running cost.
Although the utility model discloses as above with preferred embodiment; so itself and be not used to limit the utility model; any those skilled in the art; not departing from spirit and scope of the present utility model; when doing a little amendment and perfect, therefore protection domain of the present utility model is when being as the criterion of defining with claims.
Claims (2)
1. a chemical nickel plating waste solution treatment facility up to standard, is characterized in that comprising:
Ion exchange column, comprises ion exchange resin to adsorb the nickel ion in this chemical nickel plating waste solution;
Fenton oxidation reactor, connect this ion exchange column, this Fenton oxidation reactor processes the chemical nickel plating waste solution through ion exchange method, with the some organic pollutants in oxygenolysis waste water, reach the effect of oxidation contact break, make complex state metal ion nickel be converted into free state, organism in simultaneous oxidation waste liquid, destroy its carbon-chain structure, organism is finally converted into carbonic acid gas and water, reduce the COD in waste water;
Magnesium ammonium phosphate sediment pond, connects this Fenton oxidation reactor, uses magnesium ammonium phosphate sediment method to process the chemical nickel plating waste solution through Fenton oxidation, carries out reacting the magnesium ammonium phosphate sediment thing generating indissoluble, thus by the ammonia nitrogen removal in waste water;
Break point chlorination pond, connects this magnesium ammonium phosphate sediment pond, uses break point chlorination method to remove ammonia nitrogen further; And
Losantin settling tank, connects this break point chlorination pond, utilizes ozone as oxygenant in conjunction with the phosphorus in Losantin precipitation removal waste water.
2. chemical nickel plating waste solution treatment facility up to standard as claimed in claim 1, it is characterized in that, this ion exchange resin is macrovoid phenylethylene chelating ion exchange resin.
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| CN201420870894.5U CN204607752U (en) | 2014-12-30 | 2014-12-30 | Chemical nickel plating waste solution treatment facility up to standard |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800822A (en) * | 2014-12-30 | 2016-07-27 | 上海轻工业研究所有限公司 | Method and equipment for standards-reaching treatment of chemical nickel plating waste liquid |
| CN106430705A (en) * | 2016-09-21 | 2017-02-22 | 上海晶宇环境工程股份有限公司 | Electroplating wastewater reverse osmosis concentrated liquor treatment process and special device thereof |
| CN106630389A (en) * | 2016-11-22 | 2017-05-10 | 北京交通大学 | Treatment system and method for high-speed-railway passenger-transport washing sewage |
| CN107974255A (en) * | 2017-11-27 | 2018-05-01 | 贵州欧瑞欣合环保股份有限公司 | Medicament is repaired in a kind of soil pollution |
| CN108483616A (en) * | 2018-04-26 | 2018-09-04 | 天津兴嘉德环保科技有限公司 | A kind of ammonia nitrogen removal agent |
| CN109293170A (en) * | 2018-11-22 | 2019-02-01 | 深圳瑞赛环保科技有限公司 | A kind of nickel-contained wastewater treatment device and method |
| CN110563218A (en) * | 2019-08-15 | 2019-12-13 | 广州科城环保科技有限公司 | method for recovering phosphorus resource from chemical nickel waste liquid |
-
2014
- 2014-12-30 CN CN201420870894.5U patent/CN204607752U/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800822A (en) * | 2014-12-30 | 2016-07-27 | 上海轻工业研究所有限公司 | Method and equipment for standards-reaching treatment of chemical nickel plating waste liquid |
| CN106430705A (en) * | 2016-09-21 | 2017-02-22 | 上海晶宇环境工程股份有限公司 | Electroplating wastewater reverse osmosis concentrated liquor treatment process and special device thereof |
| CN106430705B (en) * | 2016-09-21 | 2023-09-12 | 上海晶宇环境工程股份有限公司 | Reverse osmosis concentrated solution treatment process for electroplating wastewater and special device thereof |
| CN106630389A (en) * | 2016-11-22 | 2017-05-10 | 北京交通大学 | Treatment system and method for high-speed-railway passenger-transport washing sewage |
| CN107974255A (en) * | 2017-11-27 | 2018-05-01 | 贵州欧瑞欣合环保股份有限公司 | Medicament is repaired in a kind of soil pollution |
| CN108483616A (en) * | 2018-04-26 | 2018-09-04 | 天津兴嘉德环保科技有限公司 | A kind of ammonia nitrogen removal agent |
| CN109293170A (en) * | 2018-11-22 | 2019-02-01 | 深圳瑞赛环保科技有限公司 | A kind of nickel-contained wastewater treatment device and method |
| CN109293170B (en) * | 2018-11-22 | 2023-12-19 | 深圳瑞赛环保科技有限公司 | Nickel-containing wastewater treatment device and method |
| CN110563218A (en) * | 2019-08-15 | 2019-12-13 | 广州科城环保科技有限公司 | method for recovering phosphorus resource from chemical nickel waste liquid |
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