CN205528097U - Processing system of nickeliferous waste water that anodic oxidation hole sealing produced - Google Patents

Abstract

The utility model provides a processing system of nickeliferous waste water that anodic oxidation hole sealing produced that organic pollutant is got rid of to nickel ion, the effective degradation of while ability that the equipment investment is little, treatment cost low, can thoroughly detach in the waste water. It includes nickeliferous wastewater collection groove, a plurality of liquid lifting pumps, broken twine preliminary treatment pond, a plurality of dosing pumps, fenton reaction ware, thoughtlessly congeals reaction tank, flocculation reaction tank, sedimentation tank and ion exchange column. It passes through efficient processing technique in advance, form free state nickel with the broken twine of nickel of strong complexing attitude, and break destruction with difficult oxidative degradation's organic matter strand, form the little molecular compound of tractability, then through the further exhaustive oxidation organic matter of fenton reaction, release the nickel ion of complexing attitude, later mixing and reacting the link adoption with fixed attention with alkali, the coagulant is got rid of the nickel ion in the waste water again, the back is through the flocculation again, precipitation deposits most nickel ions get off, adsorb remaining nickel ion in this supernatant once more through the cationic resin interchanger.

Description

The processing system of the nickel-containing waste water that anodic oxidation sealing of hole produces

Technical field

This utility model relates to a kind of nickel-containing waste water processing method and equipment, particularly to a kind of aluminium material surface anodic oxidation The processing method of sealing of hole nickel-containing waste water and processing system used.

Background technology

Aluminum alloy materials has excellent physics, chemistry, mechanics and processing characteristics, be widely used in space flight and aviation, automobile, The field such as electronics, household electrical appliances.But, aluminum alloy materials hardness is low, wear no resistance, and abrasion breakage often occurs, and therefore, aluminium alloy makes With going to toward processing through corresponding surface.

The process that aluminum alloy material surface processes generally comprises: defat, alkaline etching, neutralization, anodic oxidation, coloring and sealing of hole Deng.Anodic oxidation can generate layer oxide film in aluminum alloy surface, and it can significantly improve the corrosion resisting property of aluminium alloy, improves aluminum The hardness of alloy surface and wearability.But the oxide-film in the aluminum alloy surface of anodized is cellular micropore Structure, these micropores have extremely strong chemism and physical absorption performance, easily the corrosive medium in absorption air and pollution Thing and affect outward appearance, can cause the corrosion of oxide-film time serious, reduce hardness and the wearability of aluminum alloy materials.Therefore, it is necessary to Use appropriate hole sealing technology to be closed by the micropore in oxide-film, make this oxide-film play the work effectively protecting aluminum alloy surface With.

China mainly uses low temperature or middle temperature oxide-film sealer at present, and it is the sealer of nickel salt type, every liter of this envelope Closing Contents of Main Components in agent is: the nickel ion of 0.8-1.8g/L, the non-nickel metal ion of 0.1-0.2g/L, 0.3-0.5g/L Surfactant, the hydration accelerator of 0.2-0.6g/L and the chelating agent of 0.2-0.5g/L.The waste water that thus closing process produces In nickel content 0.1-1.8g/L, the content 0.3-1.2g/L of other additive.

Due to Long contact time nickel, the lighter can cause dermatitis, and severe one may have carcinogenic danger, therefore China increase right The control dynamics of nickel contamination, since 2008, environmental bearing capacity weakened area higher for territorial development density, such as pearl Some areas strict implement National Standard of the People's Republic of China " plating pollutant emission standard " of Triangle and the Yangtze River Delta (GB21900-2008) table 3 in specifies the special emission limit of water pollutant, and wherein the content of total nickel is less than 0.1mg/L.For Meeting the requirement of environmental protection standard, this kind of nickel-containing waste water is separated by most enterprises with other waste water, individual processing.

At present, conventional process nickel-containing waste water method has chemical precipitation method (i.e. to regulate nickel-containing waste water pH value with alkali, and add gold Belong to neutralization, the coagulation such as supplementary set agent, flocculate, precipitate), ion exchange, absorption method, electroosmose process, evaporation concentration method and reverse osmosis method Deng.The macromole of complex state cannot effectively be abolished by its ion exchange methods and absorption method；Electroosmose process and reverse osmosis are to film Require the highest, easily cause the destruction of film；Evaporation concentration method is high to equipment requirements, needs to use thermal source, processes energy consumption high.

Chinese patent CN201310706434.9 discloses a kind of electroplating waste water treatment system and uses chemical precipitation method.

Chinese patent CN201010503812 uses the anodic coloration waste water of anion exchange resin absorption nickel ion to process Method.

Waste water after above two method processes all cannot reach national grade one discharge standard sustainedly and stably, can cause ring Environment pollution hidden danger.The reason causing nickel ion to exceed standard be in hole sealing solution containing can with nickel ion formed stable comple network Mixture, such as acetic acid, ammonia, fluorion, ethylenediaminetetraacetic acid, organic phosphate etc..Nickel ion once with these chelating agent complexations Afterwards, sufficiently stable, it is impossible to the method exchanged by flocculation sediment or ion is removed it, therefore in deliquescent complex state Nickel easily causes waste water to exceed standard.

Chinese patent CN102443709 discloses a kind of employing acidization contact break conjunction technology and electronickelling waste water is carried out front place Reason, under strongly acidic conditions, conventional complexation such as citric acid, ammonia, oxalic acid etc. lose or weaken and nickel ion complexing power, from And the metallic nickel of complex state can be made free out, the chelating agent that the method can make part the most weak discharges nickel ion, but the party The deficiency that method exists is: it cannot discharge the nickel of organic phosphate chelating agent such as ethylenediamine tetraacetic methene sodium phosphate institute complexation.This After outer acid adding, the process procedure at follow-up resin absorption nickel ion can reduce this resin to the adsorption capacity of nickel and performance.

Chinese patent CN104528987 proposes to use Fenton oxidation technology to make the complex of nickel abolish the side forming free nickel Method.The method has certain redox ability, to network according to the hydroxyl radical free radical produced by Fenton oxidation and ferrous ion Compound is degraded, thus the nickel abolishing complex pattern forms free nickel.Though Fenton oxidation can be effectively in oxidative degradation water body Organic pollution, however relatively low to the degraded release efficiency of Ni-EDTA complexation.Therefore, the method can only abolish complexing power relatively The complex of weak part nickel, the nickel complex stronger for complexing power abolishes DeGrain, it is impossible to reach the most steady Fixed except nickel effect, equally, the method is also easily caused nickel discharge and exceeds standard.

Utility model content

The technical problems to be solved in the utility model is to provide that a kind of equipment investment is little, processing cost is low, can thoroughly remove Nickel ion in waste water, can effectively degrade the process of nickel-containing waste water that the anodic oxidation sealing of hole of removal organic polluter produces simultaneously System.

In order to solve above-mentioned technical problem, the technical solution adopted in the utility model is:

The processing system of nickel-containing waste water that anodic oxidation sealing of hole of the present utility model produces, including nickel-containing waste water collecting tank, Some lifting liquid pumps, contact break pretreatment pool and some dosing pumps, it is characterised in that: also include Fenton reactor, coagulation Reaction tank, flocculation tank, sedimentation tank and ion exchange column, wherein,

Contact break pretreatment pool for the strong complex state nickel contact break of the Ni-EDTA form in collecting tank become free state nickel and The little molecule of the weak complex state of small part；

Fenton reactor for carrying out aoxidizing by the one-level nickel-containing waste water that contact break pretreatment pool flows into, resolution process is with life Become the partly precipitated thing containing small organic molecule and nickel compound at the interior secondary waste water in float；

Coagulation reaction tank is for generating in little granule by the secondary waste water coming from Fenton reactor and the containing of colloidal Three grades of waste water of one or more mixture in nickel hydroxide, nickelous carbonate and nickel sulfide；

Flocculation tank comprises in described nickel hydroxide, nickelous carbonate and nickel sulfide for being formed by described three grades of waste water Kind or several mixture at the level Four waste water of interior big colloidal solid；

Sedimentation tank generates supernatant to be discharged for carrying out separating to inflow described level Four waste water therein and comprises institute State one or more mixture in nickel hydroxide, nickelous carbonate and nickel sulfide at interior precipitate；

Precipitate in this sedimentation tank is carried out mud-water separation process, isolated high nickel-containing waste water is pumped into recovery profit again Collecting tank in；

Ion exchange column is for carrying out further adsorption treatment to the free state nickel of residual in described supernatant.

Device used in described contact break pretreatment pool is polynary micro-electrolysis device, three-dimensional electrolysis device or photocatalytic degradation Any one of device or combination.

Coagulant used in described coagulation reaction tank is polyacrylamide.

Described ion exchange column uses cationic resin, includes but not limited to strong-acid type or weak-type.

Compared with prior art, processing system of the present utility model passes through contact break pretreatment treatment technology, by strong complex state Nickel contact break form free state nickel, the organic molecule chain of difficult oxidative degradation is interrupted destruction simultaneously, forms tractable little point Sub-compound, then by Fenton's reaction further exhaustive oxidation Organic substance, discharges the nickel ion of complex state, exists afterwards Coagulating link uses and adds liquid caustic soda and a small amount of coagulant makes to be in the nickel ion of mineralized and generates the hydrogen of big colloidal solid shape Nickel oxide/nickelous carbonate/nickel sulfide, is removed the nickel ion in waste water again, more afterwards by flocculation, precipitation link Overwhelming majority nickel ion is precipitated, after removing precipitate, supernatant is pumped into resin cation exchange device by filtration system Again by the free state nickel ion absorption of residual in this supernatant.On the one hand method of the present utility model can make anodic oxidation sealing of hole The discharge of nickel-containing waste water reaches national grade one discharge standard sustainedly and stably, stops nickel contamination risk, on the other hand can make nickeliferous Organic pollution in waste water effectively aoxidizes, decomposes and removal effect.This utility model can thoroughly solve anodic oxidation Sealing of hole nickel-containing waste water cannot be the most up to standard a difficult problem.

Accompanying drawing explanation

Fig. 1 is the schematic flow sheet of processing method in this utility model.

Fig. 2 is processing system structural representation of the present utility model.

Detailed description of the invention

As it is shown in figure 1, this utility model flow process is as follows:

Step S1, utilizes nickel-containing waste water collecting tank collect nickel-containing waste water and nickel-containing waste water pumps into contact break pretreatment pool.

Step S2, in contact break pretreatment pool, add acid until pH value in described contact break pretreatment pool 2.0-5.0 it Between, the response time is at 60min-90min；After contact break pretreatment so that in waste water, the structure of difficult degradation complex is able to Changing, the primary wastewater after processing flows into Fenton reactor.

Step S3, during successively adding ferrous sulfate and hydrogen peroxide, Fenton's reaction, controls water inlet in this Fenton reactor PH value be between 2.0-6.0, process produce substantial amounts of hydroxyl radical free radical, now by mechanical agitation in this primary wastewater Organic substance carries out aoxidizing, resolution process, and the response time is 15min-90min (the preferably response time is at 60min-90min), it After, this is processed the secondary waste water comprising described float and enters coagulation reaction tank.

Described ferrous sulfate accounts for the 0.01%-0.6% of nickel-containing waste water weight；Described hydrogen peroxide accounts for nickel-containing waste water weight 0.05%-2.0%.

Step S4, adds caustic alkali/soda/dissolvable sulfide, by the pH value of secondary waste water in described coagulation reaction tank It is adjusted between 9.0-13.0；Then add a little coagulant be reacted to form substantial amounts of comprise newly-generated nickel hydroxide or Nickelous carbonate or nickel sulfide or its mixture are at interior little granule and colloid, and the response time is 25min-40min, afterwards, by this Three grades of waste water with a large amount of little granules and colloid after process enter flocculation tank.Described coagulant is preferably polypropylene Amide.

Step S5, in described flocculation tank add flocculant be reacted to form comprise described sized nickel hydroxide/carbon acid nickel/ Nickel sulfide at interior big colloidal solid, response time 30min-40min, afterwards, after this is processed with big colloidal solid Level Four waste water enter sedimentation tank.

Step S6, after level Four waste water precipitates 150min-230min in sedimentation tank, filters direct for supernatant therein pump System, utilizes this filtration system to filter out a small amount of float in described supernatant, afterwards, by described supernatant remaining Whole waste water is sent into and is removed the nickel ion of residual in this waste water in ion exchange column further；To this sedimentation tank comprises described hydrogen-oxygen Change nickel carbon acid nickel/nickel sulfide and carry out mud-water separation process at interior precipitate, isolated high nickel-containing waste water is pumped into recovery again In the collecting tank utilized.

Step S7, uses the cationic resin of free state nickel ion exchange present in water body in ion exchange column (preferably efficiently chelate resin) carries out ion exchange to described supernatant, is normally arranged by the waste water up to standard discharged through ion exchange column Put；Wherein nickel ion content is less than 80mg/L less than 0.1mg/L, COD.

As in figure 2 it is shown, the following processing means of method selection of the present utility model is carried out:

Anodic oxidation sealing of hole nickel-containing waste water processing equipment 200 includes that sealing of hole nickel-containing waste water collecting tank 210, first promotes Pump 211, contact break pretreatment pool the 220, the oneth pH detector the 221, first dosing pump 222, Fenton reactor 230, mechanical agitator 231, the second dosing pump the 232, the 3rd dosing pump 233, coagulation reaction tank the 240, the 2nd pH detector the 241, the 4th dosing pump 242, 5th dosing pump 243, flocculation tank the 250, the 6th dosing pump 251, sedimentation tank the 260, second elevator pump 261, pneumatic diaphragm pump 262, pressure filter 263, ion exchange column 270, filter 271, backwashing pump 272 and control system 280.

Specifically, sealing of hole nickel-containing waste water collecting tank 210 is used for collecting sealing of hole nickel-containing waste water, such as anodic oxidation sealing of hole workshop Rinse water and sealing of hole waste liquid can be flowed in sealing of hole nickel-containing waste water collecting tank 210 by pipe special.At sealing of hole Nickel-bearing Waste Water collecting groove 210 is provided with liquid level detector for detecting the liquid level in sealing of hole nickel-containing waste water collecting tank 210, when flowing into Nickel-bearing Waste When the liquid level of water exceedes liquid level detector presetting value, liquid level detector sends signal, control system to control system 280 After 280 receive signal, send instruction to the first elevator pump 211 and make the first elevator pump 211 operate.First elevator pump 211 is by nickeliferous Waste water pumps into contact break pretreatment pool.

Sealing of hole Nickel-bearing Waste tank 210 is connected with contact break pretreatment pool 220 by the first elevator pump 211, the first elevator pump 211 are used for being delivered in contact break pretreatment pool waste water in sealing of hole Nickel-bearing Waste tank 210.Can be by regulating the first elevator pump 211 speed controlling conveying, thus control the time that nickel-containing waste water reacts in contact break pretreatment pool 220.Wherein contact break is located in advance In reason pond, device used is any one or group of polynary micro-electrolysis device or three-dimensional electrolysis device or photocatalytic degradation device Close.

Oneth pH detector 221 and the first dosing pump 222 are connected with contact break pretreatment pool 220.A wherein pH detector 221 for detecting the pH value of waste liquid in contact break pretreatment pool 220.First dosing pump 222 is for adding in contact break pretreatment pool 220 Liquid feeding acid such as sulfuric acid solution until a pH detector 221 detects that in contact break pretreatment pool 220, pH value is between 2-5.Nickeliferous Waste water response time in contact break pretreatment pool 220 is 60-90 minute, and the response time can pass through flow velocity and contact break pretreatment pool Volume regulates and controls.Nickel-containing waste water enters Fenton reactor 230 afterwards.

Mechanical agitator the 231, second dosing pump 232 is connected with Fenton reactor 230 with the 3rd dosing pump 233.Wherein Mechanical agitator 231 is used for stirring the nickel-containing waste water in Fenton reactor 230, the second dosing pump 232 and the 3rd dosing Pump 233 adds quantitative ferrous sulfate and hydrogen peroxide respectively in Fenton reactor 230, thus carries out Fenton oxidation degraded.Logical The nickel-containing waste water crossing Fenton reactor 230 flows in coagulation reaction tank 240.

2nd pH detector the 241, the 4th dosing pump 242 is connected with coagulation reaction tank 240 with the 5th dosing pump 243.Its In the 2nd pH detector 241 for detecting the pH value of waste liquid in coagulation reaction tank 240.4th dosing pump 242 is for anti-to coagulation Annex solution in pond 240 is answered to subtract such as sodium hydroxide solution until the 2nd pH detector 241 detects that in coagulation reaction tank 24, pH value exists Between 10-11.5th dosing pump 243 is for adding coagulant such as polyacrylamide (PAM) in coagulation reaction tank 240.Pass through The nickel-containing waste water of coagulation reaction tank 240 flows in flocculation tank 250.

6th dosing pump 251 is connected with flocculation tank 250.6th dosing pump 251 is for adding to flocculation tank 250 Add flocculant.Flowed in sedimentation tank 260 by flocculation tank 250 nickel-containing waste water.

Second elevator pump 261 is connected with sedimentation tank 260 with pneumatic diaphragm pump 262.Wherein the second elevator pump 261 is for inciting somebody to action Supernatant waste liquid in sedimentation tank 260 is delivered in filter 271 filter.Pneumatic diaphragm pump 262 is in by heavy in sedimentation tank 260 Shallow lake thing is delivered in pressure filter 263 carry out mud-water separation.Pressure filter 263 isolated waste liquid again flows into sealing of hole Nickel-bearing Waste tank In 210.

Filter 271 is for filtering out a small amount of float in the supernatant waste water of sedimentation tank 260, to guarantee discharge of wastewater Up to standard.Flowed in ion exchange column 270 by the waste water of filter 271.

Ion exchange column 270 is filled with efficient chelate resin, removes, for adsorbing, the nickel ion precipitated the most completely, from And further ensure that wastewater to reach standard.Backwashing pump 272 is connected in ion exchange column 270.Wherein backwashing pump 272 is for handing over ion Changing post 270 to regenerate, the available nickeliferous water of high concentration, such that it is able to carry out resource.The most also regeneration can be obtained highly concentrated Spend nickeliferous water to flow into again in sealing of hole Nickel-bearing Waste tank 210.

Method of the present utility model preferably employs following processing system and carries out the process of nickel-containing waste water.

This system includes: sealing of hole nickel-containing waste water collecting tank, the first elevator pump, contact break pretreatment pool, a pH detector, One dosing pump, the second dosing pump, the 3rd dosing pump, Fenton reactor, mechanical agitator, coagulation reaction tank, the 2nd pH detector, 4th dosing pump, the 5th dosing pump, flocculation tank, the 6th dosing pump, sedimentation tank, the second elevator pump, filter, pneumatic every Membrane pump, pressure filter, ion exchange column, backwashing pump: wherein,

Described sealing of hole nickel-containing waste water collecting tank is used for collecting sealing of hole nickel-containing waste water；

Described first elevator pump is placed between described sealing of hole nickel-containing waste water collecting tank and described contact break pretreatment pool, and being used for will Nickel-containing waste water in described sealing of hole nickel-containing waste water pumps in described contact break pretreatment pool；

A described pH detector, the first dosing pump are connected with described contact break pretreatment pool；A described pH detector For monitoring waste water information in contact break pretreatment pool；Described first dosing pump is for automatically adding in described contact break pretreatment pool Acid is until a described pH detector display pH value is between 2-5；

Described second dosing pump, the 3rd dosing pump, mechanical agitator are connected with described Fenton reactor；Described mechanical agitation Device is for stirring waste liquid in described Fenton reactor；Described second dosing pump is for adding in described Fenton reactor Ferrous sulfate；Described 3rd dosing pump is for adding hydrogen peroxide in described Fenton reactor；

Described 2nd pH detector, the 4th dosing pump, the 5th dosing pump are connected with described coagulation reaction tank；Described 2nd pH Detector is used for monitoring waste water information in coagulation reaction tank；Described 4th dosing pump is for automatically adding in described coagulation reaction tank Add caustic alkali/soda/dissolvable sulfide until described 2nd pH detector display pH value is between 10-11；Described slender acanthopanax Teat pipette is for adding coagulant in described coagulation reaction tank；

Described 6th dosing pump is for adding flocculant in described flocculation tank；

Described pneumatic diaphragm pump is for being delivered to described pressure filter by the precipitate in described sedimentation tank；

Described pressure filter for carrying out mud liquid separation to described precipitate；

Described second elevator pump is placed between sedimentation tank and filter, for the supernatant in described sedimentation tank is pumped into institute State in filter；

Described filter is connected with described ion exchange column；Described backwashing pump is connected with stating ion exchange column；Described backwash Pump is for regenerating described ion exchange column.

In five embodiments of the present utility model, relevant parameter see table:

。

Claims (4)

1. a processing system for the nickel-containing waste water that anodic oxidation sealing of hole produces, including nickel-containing waste water collecting tank, some liquid Elevator pump, contact break pretreatment pool and some dosing pumps, it is characterised in that: also include Fenton reactor, coagulation reaction tank, flocculation Reaction tank, sedimentation tank and ion exchange column, wherein,

Contact break pretreatment pool is for becoming the nickel of free state and few portion by the strong complex state nickel contact break of the Ni-EDTA form in collecting tank Divide the little molecule of weak complex state；

Fenton reactor for carrying out aoxidizing by the one-level nickel-containing waste water that contact break pretreatment pool flows into, resolution process to be to generate containing little The partly precipitated thing of molecular organic and nickel compound is at the interior secondary waste water in float；

Coagulation reaction tank for by come from Fenton reactor secondary waste water generate in little granule and colloidal containing hydrogen-oxygen Three grades of waste water of one or more mixture in change nickel, nickelous carbonate and nickel sulfide；

Flocculation tank for described three grades of waste water are formed comprise the one in described nickel hydroxide, nickelous carbonate and nickel sulfide or Several mixture are at the level Four waste water of interior big colloidal solid；

Sedimentation tank generates supernatant to be discharged for carrying out separating to inflow described level Four waste water therein and comprises described hydrogen One or more mixture in nickel oxide, nickelous carbonate and nickel sulfide are at interior precipitate；

Precipitate in this sedimentation tank is carried out mud-water separation process, isolated high nickel-containing waste water is pumped into recycling In collecting tank；

Ion exchange column is for carrying out further adsorption treatment to the free state nickel of residual in described supernatant.

The processing system of the nickel-containing waste water that anodic oxidation sealing of hole the most according to claim 1 produces, it is characterised in that: described Device used in contact break pretreatment pool is any in polynary micro-electrolysis device, three-dimensional electrolysis device or photocatalytic degradation device One or combination.

The processing system of the nickel-containing waste water that anodic oxidation sealing of hole the most according to claim 1 produces, it is characterised in that: Coagulant used in described coagulation reaction tank is polyacrylamide.

The processing system of the nickel-containing waste water that anodic oxidation sealing of hole the most according to claim 1 produces, it is characterised in that: described Ion exchange column in use cationic resin, include but not limited to strong-acid type or weak-type.