CN105000711A - Nickel-containing combined electroplating wastewater treatment device and method - Google Patents
Nickel-containing combined electroplating wastewater treatment device and method Download PDFInfo
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- CN105000711A CN105000711A CN201510415865.9A CN201510415865A CN105000711A CN 105000711 A CN105000711 A CN 105000711A CN 201510415865 A CN201510415865 A CN 201510415865A CN 105000711 A CN105000711 A CN 105000711A
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Abstract
The present invention discloses a nickel-containing combined electroplating wastewater treatment device and method. The device comprises a combination pool, a regulating pool, a first sedimentation tank, a second sedimentation tank, a cyanide breaking tank, and an ion-exchange column; an air flotation machine is arranged between the combination pool and the regulating pool; the regulating pool is connected with the first sedimentation tank, and a first reaction tank is arranged between the regulation pool and the first sedimentation tank; the first sedimentation tank is connected with the second sedimentation tank, and a second reaction tank is arranged between the first sedimentation tank and the second sedimentation tank; the second sedimentation tank is connected with the cyanide breaking tank; and the cyanide breaking tank is connected with the ion-exchange column. The method mainly comprises: using hypophosphorous acid removal agent to reduce the total amount of phosphorus; adopting a similar oxygen method to remove the heavy metal ions in the comprehensive waste water; and finally using an ion exchange method to remove the chemical nickel in the comprehensive waste water through adsorption so that the comprehensive waste water can meet the discharge standard. The nickel-containing combined electroplating wastewater treatment device and method has advantages of being simple in technique, high in efficiency of treating nickel-containing combined electroplating wastewater, low in treatment cost, stable in effluent, and strong in applicability.
Description
Technical field
The present invention relates to technical field of sewage, especially relate to the device and method of a kind of process containing the electroplating comprehensive waste water of chemical nickel.
Background technology
Along with widespread use and the contribution industrially of electroplating technology, electroplating wastewater also brings serious problem of environmental pollution, and electroplating wastewater is very complicated, except containing except cyanogen waste water and acidic and alkaline waste water, heavy metal wastewater thereby is the great waste water classification of Electroplating Operations potentially dangerous.Therefore, Electroplating Wastewater Treatment problem receives the concern of numerous people, existing multiple Treatment process, by by poisonous improvement be nontoxic, harmful be converted into harmless, reclaim heavy metal, who the measure such as to recycle and eliminates or reduce the quantity discharged of heavy metal, make electroplating wastewater reach the emission standard of country, traditional treatment process has chemical method, ion exchange method, electrolytic process etc.
But, in current electroplating comprehensive waste water, major part all contains chemical nickel plating rinse water, the total phosphorous in electroplating comprehensive waste water is caused to increase, the shortcomings such as electroplating comprehensive waste water treatment technology existence of the prior art is difficult to hypophosphite and the phosphite in removal chemical nickel plating or processing cost is too high, technique is too complicated.
Summary of the invention
The problems such as high are crossed containing the electroplating comprehensive waste water of chemical nickel and processing cost for being difficult in above-mentioned prior art remove, the invention provides the device and method of a kind of process containing the electroplating comprehensive waste water of chemical nickel, its object is to by the process that combined by use class oxysome method and ion exchange method, the electroplating comprehensive waste water heavy metal ion containing chemical nickel is not only made to reach the standard of discharge, and can active adsorption chemical nickel ion.
To achieve these goals, the invention provides a kind of process containing the device of the electroplating comprehensive waste water of chemical nickel, it is characterized in that, comprising: comprehensive pool, equalizing tank, the first settling tank, the second settling tank, broken cyanide pond and ion exchange column.
Air floatation machine is provided with between described comprehensive pool and equalizing tank.
Described equalizing tank is connected with the first settling tank, is provided with the first reaction tank between equalizing tank and the first settling tank.
Described first settling tank is connected with the second settling tank, is provided with the second reaction tank between the first settling tank and the second settling tank.
Described second settling tank is connected with broken cyanide pond; Broken cyanide pond is connected with ion exchange column.
As preferably, between described comprehensive pool and air floatation machine, be provided with lift pump; Impeller pump is provided with between described air floatation machine and equalizing tank.
Present invention also offers the method for a kind of process containing the electroplating comprehensive waste water of chemical nickel, it is characterized in that, the method comprises the following steps:
A, comprehensive wastewater remove suspended substance and oil slick;
Comprehensive wastewater PH to 3-4 after b, adjustment above-mentioned steps a process;
C, to add in comprehensive wastewater except time phosphorus agent and hydrogen peroxide stir simultaneously, regulate PH to 6-7, after precipitation, removing time phosphorus and sub-phosphorus;
Add reductive agent Sodium Pyrosulfite in d, comprehensive wastewater after above-mentioned removal time phosphorus and sub-phosphorus, Cr6+ is reduced into Cr3+;
E, drop into molysite again, form ferrite; Or input Fenton reagent, regulate pH value to 3-4;
F, comprehensive wastewater after above-mentioned steps e process drop into alkali lye, carry out pH value adjustment, regulate pH value to 9-10;
G, logical oxygen stirring is carried out to the comprehensive wastewater after above-mentioned steps f process;
H, comprehensive wastewater after above-mentioned steps g process add appropriate clorox broken cyanide compound;
I, the comprehensive wastewater after above-mentioned steps h process entered successively chemical nickel ion, deammoniation nitrogen and go the resin-column of COD to adsorb; Or the comprehensive wastewater after above-mentioned steps h process is added clorox again, then remove COD and ammonia nitrogen; Make water outlet can reach national up-to-date emission standard.
As preferably, the oil removal rate in described step a reaches 70%-90%, and removal efficiency reaches 50%-80%.
As preferably, the stirring duration that the comprehensive wastewater in described step c adds except time phosphorus agent is half hour.
As preferably, in described step g, logical oxygen stirs the oxygen passed into is atmospheric oxidation Fe2+ and Fe3+; The pH value of this comprehensive wastewater is 10.
As preferably, in described step h, the pH value of comprehensive wastewater is slightly acidic.
As preferably, the resin-column of chemical nickel that goes in described step I is ion-exchange-chelate resin exchange column; The resin-column of deammoniation nitrogen is remove the macropore H type resin that ammonia nitrogen has good result; The resin-column of COD is gone to be the macropore chelate resin exchange column that loading capacity is larger.
Compared with prior art, adopt the beneficial effect that the present invention produces: process provided by the invention, containing the method for the electroplating comprehensive waste water of chemical nickel, adopts time phosphorus agent to reduce total phosphorus content; Adopt the heavy metal ion in class oxysome method removal comprehensive wastewater; The chemical nickel Adsorption finally using ion exchange method will to contain in comprehensive wastewater, makes comprehensive wastewater reach the standard of discharge.Treatment process disclosed by the invention, namely simply, efficiently, processing cost is low again, and stable water outlet, be applicable to various big, medium-sized and small enterprises and use.
Accompanying drawing explanation
Fig. 1 is the schema of a kind of process of the present invention containing the device and method of the electroplating comprehensive waste water of chemical nickel.
Embodiment
Below in conjunction with specification drawings and specific embodiments, substantive distinguishing features of the present invention is further described.
As shown in Figure 1, a kind of process provided by the invention is containing the device of the electroplating comprehensive waste water of chemical nickel, and it comprises: comprehensive pool, equalizing tank, the first settling tank, the second settling tank, broken cyanide pond and ion exchange column; Be provided with air floatation machine between comprehensive pool and equalizing tank, this air floatation machine is jet air float oil removal machine, is mainly used in removing the oil and suspended substance that contain in most of sewage; Equalizing tank is connected with the first settling tank, is provided with the first reaction tank between equalizing tank and the first settling tank; First settling tank is connected with the second settling tank, is provided with the second reaction tank between the first settling tank and the second settling tank; Second settling tank is connected with broken cyanide pond; Broken cyanide pond is connected with ion exchange column.Be provided with lift pump between comprehensive pool and air floatation machine, by lift pump, comprehensive wastewater delivered in air floatation machine; Be provided with impeller pump between air floatation machine and equalizing tank, by impeller pump, comprehensive wastewater delivered in equalizing tank.
Present invention also offers the method for a kind of process containing the electroplating comprehensive waste water of chemical nickel, the method comprises the following steps:
A, comprehensive wastewater remove suspended substance and oil slick;
Comprehensive wastewater PH to 3-4 after b, adjustment above-mentioned steps a process;
C, to add in comprehensive wastewater except time phosphorus agent and hydrogen peroxide stir simultaneously, regulate PH to 6-7, after precipitation, removing time phosphorus and sub-phosphorus;
Add reductive agent Sodium Pyrosulfite in d, comprehensive wastewater after above-mentioned removal time phosphorus and sub-phosphorus, Cr6+ is reduced into Cr3+;
E, drop into molysite again, form ferrite; Or input Fenton reagent, regulate pH value to 3-4;
F, comprehensive wastewater after above-mentioned steps e process drop into alkali lye, carry out pH value adjustment, regulate pH value to 9-10;
G, logical oxygen stirring is carried out to the comprehensive wastewater after above-mentioned steps f process;
H, comprehensive wastewater after above-mentioned steps g process add appropriate clorox broken cyanide compound;
I, the comprehensive wastewater after above-mentioned steps h process entered successively chemical nickel ion, deammoniation nitrogen and go the resin-column of COD to adsorb; Or the comprehensive wastewater after above-mentioned steps h process is added clorox again, then remove COD and ammonia nitrogen; Make water outlet can reach national up-to-date emission standard.
In step a, in Waste Water Centralized discharge band waste water comprehensive pool, lift pump is used to deliver in air floatation machine.This air floatation machine is jet gas
Floating oil removal machine, its Main Function is the equipment removing oil and the suspended substance contained in sewage, its main operational principle utilizes the mode of jet by absorption of air in water system by water circulating pump (jet-pump), form mixing wastewater with air state, mixing wastewater with air liquid enters four aerating regulation devices more respectively through dissolving and turns back in equipment by release head, more tiny by the bubble diameter after release head process, make it adhere to flco and emerge, thus isolate water pollutant.Pollutent is concentrated and is discharged into lower oil groove or mechanical settling tank after the different positions of equipment is collected, water after elite is reusable, air-float purification facility have advanced jetting type air dissolving system, achieve plural serial stage tandem type flotation, improve the clearance of oil and suspended substance.According to kind and the emulsification degree of sewage, after the multistage flotation of jet air float oil removal machine, export sewage non-emulsified oil oil removal rate can reach 70%-90%, and removal efficiency can reach 50%-80%.
In step c, comprehensive wastewater is delivered in reaction tank and is added except time phosphorus agent and hydrogen peroxide stir simultaneously, add except time phosphorus agent be a kind of special adjustment, add except the test result of time phosphorus agent is as table one.
Table one: the comprehensive wastewater in step c, adds except total phosphorous before and after time phosphorus agent.
| Title | Total phosphorus |
| Before process | 38.7 |
| After process | 0.17 |
Containing the electroplating comprehensive waste water of chemical nickel after step a-c process, use class oxidation style to proceed process, metal ion free in waste water major part is removed, as Fe, Mg, Zn, Mn, Ni, Ca, Cu, Hg, Cr6+, Cr3+ etc.
More specifically, the process of class ferrite process containing the principle of chemical nickel waste water is: in waste water, add molysite or ferrous salt, heavy metal ion under certain condition in handsome waste water and molysite generate stable ferrite, adopt solid-liquid separation technique, reach the object of heavy-metal ion removal.
The process of class ferrite process specifically comprises steps d to step f, class ferrite process process first-selection must have enough Fe2+ and Fe3+, although more or less containing iron ion in electroplating wastewater, can not meet and produce ferritic requirement, extra supplementary iron ion, can add Fe S04 or Fe C12.For ensureing ferritic formation and quality, reductive agent Sodium Pyrosulfite being added to waste water before treatment Cr6+ is reduced into Cr3+.
In step f, comprehensive wastewater is delivered in settling tank, in settling tank, drop into alkali lye, and carry out pH value adjustment, regulate pH value to 9-10.
In step g, the oxygen that leads to be atmospheric oxidation Fe2+ be Fe3+, will consider to blast the speed of air and flow etc. in addition, under normal temperature condition, metal ion is deadlocked shape precipitation of hydroxide, and after logical oxygen stirs, in comprehensive wastewater, the reaction principle of metal ion is as follows:
Cr3++30H=Cr(OH)3↓
Fe3++30H=Fe(OH)3↓
Cu2++20H=Cu(OH)2↓
Zn2++20H=Zn(OH)2↓
Ni2++20H=Zn(OH)2↓
After step g process, comprehensive wastewater is blackish green, and comprehensive wastewater pH value is retained in about 10.Remove the detected result of metal ion in the rear comprehensive wastewater of major part precipitation as shown in Table 2.
Table two: the content of metal ion before and after class ferrite process process process.
| Title | Cu | Ni | Cr6+ | Fe | Zn |
| Before process | 91 | 71.5 | 25.6 | 16.6 | 161 |
| After process | 0.13 | 0.1 | 0.1 | 0.1 | 0.2 |
The test result of Cn content before and after appropriate clorox broken cyanide compound is added as shown in Table 3 in step h.
Table three.
| Title | Cn |
| Before process | 37 |
| After process | <0.1 |
Step I can only process the heavy metal ion such as the free nickel in waste water due to class ferrite process, the ion exchange treatment that the complex compound nickel for chemical nickel in electroplating wastewater still cannot be accomplished qualified discharge and carry out.
More specifically, ion exchange method mainly utilizes the cation exchange groups in ion-exchange carry out exchanging with some ion in electroplating wastewater and removed, make the method that waste water is purified, ion exchange technique contacts with metallic solution with a kind of Solid-state Ion-exchange agent with ion-exchange performance, make to enter multinomial replacement(metathesis)reaction between the ion of object in solution and exchanger, and optionally enter in solid phase exchanger, then with the object ion that suitable reagent desorb is adsorbed, make it to reenter solution.
In this preferred embodiment, ion-exchange-chelate resin and nickel is selected to generate the very high chelate of stability, low dense useless nickel-containing waste water can be processed, there is adsorbed ion exchange and chelating triple role, stable chelate can be formed when Adsorption of Heavy Metals waste water, nickel and ion-exchange-chelate resin can be reclaimed again by resolving, there is the performance more excellent than chelating precipitation agent, sorbent material and ion exchange resin.The concrete mode of ion-exchange-chelating absorption be chelating group is loaded to porous organic polymer and inorganic adsorbent on.Find containing different heteroatomic chelating gene in research, can show good effect in selective adsorption nickel, such as, utilize hsab theory to design chelating gene, be the basis to nickel absorption, when processing single nickel waste water, trend towards sulphur and phosphorus atom in the choice; Increase the wetting ability of chelating group, the chelating speed of resin to nickel can be improved; Increase chelating group number and reduce the sterically hindered loading capacity that all can increase chelating gene pairs nickel.
Selectivity is one of most important index of ion-exchange-chelate resin, and when designing the chelate resin of absorbed Ni, what follow is the optionally principle improving absorbed Ni ion.From hsab theory, intermediary's acid, nitrogen, sulphur atom have good coordination to nickel, can improve the selectivity of absorbed Ni.
Therefore select should meet the following conditions during chelate resin: have the skeleton that stability is strong, this skeleton, when meeting mechanical property, has large specific surface area and good aperture as much as possible as far as possible; Selectivity is good and large to object ion loading capacity; When trace concentration and analysis, carboxylic benzene, the function bases such as azo-group can increase wetting ability, strengthen rate of adsorption; The good stability of the chelating gene imported, use repeatly rate is high.
The resin-column of chemical nickel that goes in above-mentioned steps i is ion-exchange-chelate resin exchange column; Deammoniation nitrogen resin-column is macropore H type resin removal ammonia nitrogen to good result; Go COD resin-column to be the macropore chelate resin exchange column that loading capacity is larger, this COD resin-column water outlet COD can reach 50mg/L.
In addition, Fenton process can also be used in above-mentioned steps e to remove metal cations Fe free in waste water, Mg, Zn, Mn, Ni, Ca, Cu, Hg, Cr6+, Cr3+ etc.The Fenton reagent used is the oxidation system that Fe2+ and H2O2 forms jointly.
By again adding clorox in step h waste water, removal chemical nickel can also be carried out, then carry out COD and deammoniation nitrogen, making this comprehensive wastewater reach emission standard in above-mentioned steps i.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; technical scheme of the present invention is modified or equivalent replacement, all belong to protection scope of the present invention.
Claims (8)
1. process is containing a device for the electroplating comprehensive waste water of chemical nickel, it is characterized in that comprising: comprehensive pool, equalizing tank, the first settling tank, the second settling tank, broken cyanide pond and ion exchange column;
Air floatation machine is provided with between described comprehensive pool and equalizing tank;
Described equalizing tank is connected with the first settling tank, is provided with the first reaction tank between equalizing tank and the first settling tank;
Described first settling tank is connected with the second settling tank, is provided with the second reaction tank between the first settling tank and the second settling tank;
Described second settling tank is connected with broken cyanide pond; Broken cyanide pond is connected with ion exchange column.
2. a kind of process according to claim 1 is containing the device of the electroplating comprehensive waste water of chemical nickel, it is characterized in that: be provided with lift pump between described comprehensive pool and air floatation machine; Impeller pump is provided with between described air floatation machine and equalizing tank.
3. process is containing a method for the electroplating comprehensive waste water of chemical nickel, and it is characterized in that, the method comprises the following steps:
A, comprehensive wastewater remove suspended substance and oil slick;
Comprehensive wastewater PH to 3-4 after b, adjustment above-mentioned steps a process;
C, to add in comprehensive wastewater except time phosphorus agent and hydrogen peroxide stir simultaneously, regulate PH to 6-7, after precipitation, removing time phosphorus and sub-phosphorus;
Add reductive agent Sodium Pyrosulfite in d, comprehensive wastewater after above-mentioned removal time phosphorus and sub-phosphorus, Cr6+ is reduced into Cr3+;
E, drop into molysite again, form ferrite; Or input Fenton reagent, regulate pH value to 3-4;
F, comprehensive wastewater after above-mentioned steps e process drop into alkali lye, carry out pH value adjustment, regulate pH value to 9-10;
G, logical oxygen stirring is carried out to the comprehensive wastewater after above-mentioned steps f process;
H, comprehensive wastewater after above-mentioned steps g process add appropriate clorox broken cyanide compound;
I, the comprehensive wastewater after above-mentioned steps h process entered successively chemical nickel ion, deammoniation nitrogen and go the resin-column of COD to adsorb; Or the comprehensive wastewater after above-mentioned steps h process is added clorox again, then remove COD and ammonia nitrogen; Make water outlet can reach national up-to-date emission standard.
4. a kind of process according to claim 3 is containing the method for the electroplating comprehensive waste water of chemical nickel, it is characterized in that: the oil removal rate in described step a reaches 70%-90%, and removal efficiency reaches 50%-80%.
5. a kind of process according to claim 3 is containing the method for the electroplating comprehensive waste water of chemical nickel, it is characterized in that: the stirring duration that the comprehensive wastewater in described step c adds except time phosphorus agent is half hour.
6. a kind of process according to claim 3 is containing the method for the electroplating comprehensive waste water of chemical nickel, it is characterized in that: in described step g, logical oxygen stirs the oxygen passed into is atmospheric oxidation Fe2+ and Fe3+; The pH value of this comprehensive wastewater is 10.
7. a kind of process according to claim 3 is containing the method for the electroplating comprehensive waste water of chemical nickel, and it is characterized in that: in described step h, the pH value of comprehensive wastewater is slightly acidic.
8. a kind of process according to claim 3 is containing the method for the electroplating comprehensive waste water of chemical nickel, it is characterized in that: the resin-column of chemical nickel that goes in described step I is ion-exchange-chelate resin exchange column; The resin-column of deammoniation nitrogen is remove the macropore H type resin that ammonia nitrogen has good result; The resin-column of COD is gone to be the macropore chelate resin exchange column that loading capacity is larger.
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