CN106186427A - The process technique of a kind of chemical nickel plating waste solution and device - Google Patents
The process technique of a kind of chemical nickel plating waste solution and device Download PDFInfo
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- CN106186427A CN106186427A CN201610672265.5A CN201610672265A CN106186427A CN 106186427 A CN106186427 A CN 106186427A CN 201610672265 A CN201610672265 A CN 201610672265A CN 106186427 A CN106186427 A CN 106186427A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/38—Gas flow rate
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/40—Liquid flow rate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to process technique and the device of a kind of chemical nickel plating waste solution, this technique is to be collected by chemical nickel plating waste solution in pH regulator groove, regulation chemical nickel plating waste solution pH value is between 4.5 6.0, is then sent in advanced oxidation reaction unit by the chemical nickel plating waste solution after regulation pH value；Chemical nickel plating waste solution after oxidation processes is discharged into nickel recovery pond, and after precipitation reclaims nickel ion, supernatant enters dephosphorization pond again, adds calcium oxide and carry out precipitating dephosphorization in dephosphorization pond, and after dephosphorization, supernatant enters rear end sewage disposal system.Present invention process uses the chemical nickel plating waste solution of the method process circuit plate of a kind of ozone/hydrogen peroxide solution coupling heterogeneous catalytic oxidation, realize destroying Organic substance and chelating agent, release nickel ion, the phosphorus making different shape is converted into orthophosphate form, and then precipitation removes nickel and phosphorus makes waste liquid reach discharge standard.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to the catalysis oxidation of a kind of circuit board plant chemical nickel plating waste solution
Processing technique and device, this technique uses ozone/hydrogen peroxide solution coupling heterogeneous catalytic oxidation method Treatment of Electroless Nickel Plating Wastewater, broken
Bad Organic substance and chelating agent, reclaim nickel ion so that the phosphorus of different shape is converted into the precipitated removal of orthophosphate form.
Background technology
The kind of waste water of wiring board manufacturing enterprise discharge is more, but the high-concentration waste liquid of discharge is mainly five kinds, organic
Development moves back film waste liquid, acid waste liquid, alkaline waste liquor, micro-corrosion liquid, nickeliferous waste liquid, although these discharging of waste liquid amounts are total at enterprise wastewater
In amount, accounting is relatively low, but its pollutant contribution rate is more than 85%, and pollutant kind is many, concentration is high, difficult, wherein with nickeliferous
The chemical nickel plating waste solution of the nickel chemical plating technology discharge in waste liquid is most difficult to process, and calls it as chemical nickel plating waste solution in the application,
Chemical nickel plating waste solution also exists the nickel complex with stronger complexing, a large amount of buffer agents such as acetic acid, succinic acid etc., reproducibility
Hypophosphites and phosphite, also brightener and stabilizer, the large amount of organic and the reducing substances that exist cause plating solution
COD value is up to hundreds of thousands mg/L, and total phosphorus reaches several ten thousand mg/L.This type of chemical nickel plating waste solution enters the sewage disposal system band of garden
Carry out huge impact load, cause the total phosphorus in effluent quality and nickel is regular exceeds standard, and nickeliferous chemical nickel plating waste solution belongs to
In first kinds of pollution matter, needing to entrust the enterprise with qualification to carry out recycling disposal, the waste liquid disposal costs per ton having reaches nearly ten thousand
Unit, brings bigger financial burden and environmental protection pressure to enterprise.If mishandling, serious environmental pollution more can be brought to ask
Topic.
In recent years, the nickeliferous waste liquid method of disposal research for circuit board plant is more, and mainly two class methods, one is by
Recycling after suitably processing, such as, " chemical nickel plating waste solution processing equipment up to standard (CN204607752U) " utility model is special
Profit describes a kind of U.S. Oak Ridge K-25 institute and develops EVNIR-CP chemical nickel-plating liquid regeneration technology.This technique is at groove
While set up a periodicity and continuous way except the bypath system of sodium phosphite, exist controlling plating solution phosphorous acid sodium and sodium sulfate
Relatively low concentration level, keeps the composition of chemical nickel-plating liquid and stablizing of plating speed.The most with good grounds ion exchange principle or electric osmose
Analysis principle removes sodium phosphite, makes the process research of nickel-plating waste liquid regeneration.Due to the complicated component of electroplating effluent,
The plating solution of regeneration does not often reach the highest wiring board coating standard-required, so, wiring board enterprise does not the most use
Regeneration plating solution.Two is that qualified discharge after nickel is reclaimed in harmless treatment, and this type of technology category is more, (1) sedimentation method, broken in oxidation
After network, add and dissociate Ni2+In conjunction with the reagent generating precipitation.By adding NaOH, CaO, sulfide etc., nickel ion is made to generate
Precipitation, and nickel ion is removed from waste liquid.(2) oxidation-reduction method, after chemical oxidation contact break, adds reducing agent, by nickel ion
It is reduced to nickel remove.Conventional reducing agent has sodium borohydride etc..(3) ion exchange, after oxidation contact break, utilizes amberlite
In fat, the cation on active group exchanges with the nickel ion in waste water, is fixed on exchanger resin by nickel ion and makes waste water obtain
To the method purified.(4) other method, such as electrolysis and absorption method etc..In order to obtain preferable coating, at chemical nickel-plating liquid
In must add chelating agent, and nickel ion complexation, prevent nickel ion from generating precipitation with orthophosphite ions.But, this makes
When no matter which kind of method Treatment of Electroless Nickel Plating Wastewater to reclaim nickel ion by, it is necessary first to oxidation contact break.Conventional oxidant have ozone,
Potassium permanganate, sodium hypochlorite, hydrogen peroxide etc..Chelating agent main in plating solution is orthophosphite and hypophosphorous acid root, needs him
Be converted into orthophosphoric acid root after can be only achieved the effect of contact break, it addition, the removal of phosphorus is also required to emphasis and closes in chemical nickel plating waste solution
Note, otherwise can increase subsequent biochemical and process load, and maximally effective phosphorus removing method uses phosphate radical to produce phosphoric acid with calcium ion exactly
The sedimentation method of calcium, therefore, oxidation contact break is not only advantageous to the recovery of nickel ion and can assist the removal of phosphorus.But, chemistry
There is competitive oxidation relation in the reproducibility compositions such as the Organic substance in nickel-plating waste liquid and chelating agent, if to reach preferable contact break effect
Fruit is necessary for initial oxidation and decomposes major part Organic substance, the COD value of chemical nickel plating waste solution is reduced to below 6000mg/L, ability
Reach preferable contact break effect.But certain oxidant of single use, can not reach preferable contact break effect.Therefore, grind
The person of studying carefully uses the Fenton oxidation method of high-level oxidation technology to carry out contact break (CN104386874A, CN204607752U), applicant
Company is also using the method to carry out chemical nickel plating waste solution process, but from the point of view of the actual running results, contact break efficiency is only at 55-
Between 65%, waste liquid causes water outlet nickel and phosphorus often to exceed standard after entering rear end biochemical treatment system.And Fenton oxidation method needs
Use substantial amounts of iron filings and acid-base reagent, discharge a large amount of sludge silt (hazardous waste), be unfavorable for that follow-up nickel ion reclaims, it is seen then that
The contact break effect of Fenton oxidation method can not meet liquid waste processing requirement, is badly in need of the oxidation contact break method that exploitation is new.
Summary of the invention
It is an object of the invention to provide the process technique of a kind of chemical nickel plating waste solution, this technique uses a kind of ozone/dioxygen
The chemical nickel plating waste solution of the method process circuit plate of water coincidence heterogeneous catalytic oxidation, it is achieved destroy Organic substance and chelating agent, release
Put nickel ion so that the phosphorus of different shape is converted into orthophosphate form, and then precipitation removes nickel and phosphorus makes waste liquid reach discharge
Standard.It is a further object to provide the processing means of a kind of chemical nickel plating waste solution.
The present invention is achieved by the following technical solutions: the process technique of a kind of chemical nickel plating waste solution, and this technique is passed through
Following steps realize:
1., by chemical nickel plating waste solution collecting in pH regulator groove, the sulfuric acid solution or the concentration that add concentration 5%-30% are 5%-
The sodium hydroxide solution of 15% or concentration are the sodium carbonate liquor of 5%-10%, and regulation chemical nickel plating waste solution pH value is 4.5-6.0
Between, then the chemical nickel plating waste solution after regulation pH value is sent into advanced oxidation reaction unit；
2. the advanced oxidation retort that is first fed on advanced oxidation reaction unit of chemical nickel plating waste solution, after regulation pH value, opens
Open ozonator and spontaneous imbibition booster pump, by the flow of the Valve controlling ozone that ozone emitters carries, make the smelly of overflow area
Oxygen concentration is between 0.5-2.5mg/L；Add inbound traffics by Valve controlling hydrogen peroxide, make the hydrogen peroxide concentration of overflow area exist
Between 0.1-0.5mL/L；Chemistry after gas-liquid mixed district in advanced oxidation retort, hydrogen peroxide, ozone and regulation pH value
Nickel-plating waste liquid carries out hybrid concurrency raw Heterogeneous oxidation reaction, then at the beds of advanced oxidation retort, hydrogen peroxide,
Ozone with regulation pH value after chemical nickel plating waste solution carry out heterogeneous catalytic oxidation reaction, the chemical plating after oxidation processes
Nickel waste liquid is collected from the downflow weir of advanced oxidation retort and is entered nickel recovery pond through discharging tube, with the sodium hydroxide of concentration 5%-15%
The sodium carbonate liquor heightening pH value of solution or concentration 5%-10% is between 11.5-12.5, and precipitation reclaims nickel ion；Supernatant is arranged
Entering dephosphorization pond, add calcium oxide and carry out precipitating dephosphorization in dephosphorization pond, the addition of calcium oxide is 90～150g/ liters, generation
Calcium phosphate can carry out reuse as the phosphate fertilizer source of manure, and after dephosphorization, supernatant enters rear end sewage disposal system.
Described advanced oxidation reaction unit includes advanced oxidation retort, ozonator and hydrogen peroxide storage tank, wherein, high
Level oxidation reaction tank is the tank body of a cylindrical shape, and tank interior arranges the air and liquid mixer of a vertebral body shape, described
Air and liquid mixer is inlaid with porous air distribution plate by draw-in groove, and advanced oxidation retort is divided into upper end and urges by described porous air distribution plate
Change zoneofoxidation and overflow area, gas-liquid mixed district, lower end；The lower end of described air and liquid mixer is air and liquid mixer outlet, described gas-liquid
At least three support column is installed on mixer outlet, outside the upper end of described advanced oxidation retort, is provided with downflow weir and connection
Discharging tube below downflow weir, described hydrogen peroxide storage tank is by pipeline and valve, effusion meter and the self-priming being arranged on pipeline
Booster pump is connected with advanced oxidation retort top；Described ozonator by pipeline and the effusion meter that is arranged on pipeline with
Advanced oxidation retort top connects, and chemical nickel plating waste solution sends into advanced oxidation retort from the top inlet of air and liquid mixer.
In order to keep beds stable, the diameter of the pore on porous air distribution plate is less than catalyst particle diameter, gas
10 centimetres, the bottom of liquid mixer outlet distance advanced oxidation retort.
Advanced oxidation retort is divided into gas-liquid mixed district, catalysis zoneofoxidation, drainage region by the present invention.In gas-liquid mixed district
In, under streams of ozone agitation, waste liquid mixes with hydrogen peroxide, obtains ozone, waste liquid and hydrogen peroxide gas-liquid mixture, Er Qiesan
Heterogeneous oxidation reaction occurring between person, then enters catalysis zoneofoxidation from the bottom of air and liquid mixer, gas-liquid mixture is through too much
Hole air distribution plate, even into catalyst layer, carries out sufficient heterogeneous catalytic oxidation reaction, and major part ozone and dioxygen are consumed
Falling, waste liquid flows into overflow area, and remaining ozone and dioxygen are completely consumed, and the waste liquid after process separates with catalyst, then
Flow out from downflow weir, enter nickel recovery pond.
The technical scheme that the present invention provides has the advantage that
(1) the advanced oxidation reaction unit of present invention design, it is possible to make oxidant and waste liquid be sufficiently mixed reaction, oxidation efficiency and
Oxidant utilization significantly improves, and oxidation reaction speed is accelerated, it is possible to more thoroughly destroy the complex of nickel, by orthophosphite,
The phosphorus-containing compounds such as hypophosphorous acid root are oxidized to orthophosphoric acid root.The different shape nickel in waste liquid is made to be converted into nickel ion, phosphorous chemical combination
Thing is converted into phosphate, beneficially nickel, the recovery of phosphorus and removal.
(2) the advanced oxidation reaction unit of present invention design has advanced oxidation function, can be with oxidation Decomposition chemical nickel plating
Most of reducing substances in waste liquid, is substantially reduced the COD of chemical nickel plating waste solution, alleviates follow-up sewage disposal work
Skill load.
(3) the process unit unit capacity of present invention design significantly improves, and under same treatment Capability Requirement, originally sets
Standby floor space is less, may be mounted at the discharging of waste liquid of workshop, it is also possible to be installed to Sewage Disposal, easy and simple to handle.
(4) present invention is that chemical nickel plating waste solution processes technique and the device providing complete set, it is possible to solve currentization
Learning the difficult problem that nickel-plating waste liquid processes, treatment effect meet the requirement of environmental protection, equipment investment and operating cost are low, the nickel of recovery and phosphoric acid
Salt can recycle, and has obvious economic worth, can compensate the expense of liquid waste processing, reduce chemical nickel plating waste solution further
Processing cost.
Accompanying drawing explanation
Fig. 1 is the processing technological flow figure of chemical nickel plating waste solution of the present invention.
Fig. 2 is advanced oxidation reaction unit structural representation of the present invention.
Fig. 3 is air and liquid mixer and porous air distribution plate structural representation in Fig. 2 of the present invention.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with concrete to the present invention of accompanying drawing
Embodiment is described in further detail.
As shown in Figure 1: the process technique of a kind of chemical nickel plating waste solution, this technique is realized by following steps: by chemical plating
Nickel waste collection is in pH regulator groove A, and the sulfuric acid solution or the sodium hydroxide that concentration is 5%-15% that add concentration 5%-30% are molten
Liquid or concentration are the sodium carbonate liquor of 5%-10%, and regulation chemical nickel plating waste solution pH value is between 4.5-6.0, then will regulation
Chemical nickel plating waste solution after pH value sends into advanced oxidation reaction unit B.
As shown in Figure 2: the chemical nickel plating waste solution after regulation pH value is first fed into the senior oxygen on advanced oxidation reaction unit B
Change retort B1, open ozonator B9 and spontaneous imbibition booster pump B18, the Valve controlling ozone carried by ozone emitters B9
Flow (effusion meter B16 instruction), make the ozone concentration of overflow area B21 between 0.5-2.5mg/L；Controlled by valve B11
Hydrogen peroxide add inbound traffics (effusion meter B15 instruction), make the hydrogen peroxide concentration of overflow area B21 between 0.1-0.5mL/L；At height
Gas-liquid mixed district B19 in level oxidation reaction tank B1, hydrogen peroxide, ozone mix with the chemical nickel plating waste solution after regulation pH value
And occur Heterogeneous oxidation to react, then at the beds B3 of advanced oxidation retort B1, hydrogen peroxide, ozone with regulation
Chemical nickel plating waste solution after pH value carries out heterogeneous catalytic oxidation reaction, and the chemical nickel plating waste solution after oxidation processes is from senior
The downflow weir B17 of oxidation reaction tank B1 collects and enters nickel recovery pond C through discharging tube B7, with the sodium hydroxide solution of concentration 5%-15%
Or the sodium carbonate liquor heightening pH value of concentration 5%-10% is between 11.5-12.5, precipitation reclaims nickel ion；Supernatant enters and removes
Phosphorus pond D, adds calcium oxide in the D of dephosphorization pond and carries out precipitating dephosphorization, and the addition of calcium oxide is 90～150g/ liters, the phosphorus of generation
Acid calcium can carry out reuse as the phosphate fertilizer source of manure, and after dephosphorization, supernatant enters rear end sewage disposal system.
As shown in Figure 2,3, described advanced oxidation reaction unit B include advanced oxidation retort B1, ozonator B9 and
Hydrogen peroxide storage tank B10, wherein, advanced oxidation retort B1 is 304 rustless steels or the plastic material of a cylindrical shape
Tank body, tank interior is arranged the air and liquid mixer B5 of a vertebral body shape, described air and liquid mixer B5 and is inlaid with by draw-in groove B12
On porous air distribution plate B6, advanced oxidation retort B1 is divided into upper end catalysis zoneofoxidation B20 and overflows by described porous air distribution plate B6
Stream district B21, gas-liquid mixed district, lower end B19；The lower end of described air and liquid mixer B5 is that air and liquid mixer exports B8, and described gas-liquid is mixed
On clutch outlet B8, at least three support column B14 is installed, outside the upper end of described advanced oxidation retort B1, is provided with downflow weir
B17 and is arranged on pipeline by pipeline with being connected to the discharging tube B7 below downflow weir B17, described hydrogen peroxide storage tank B10
Valve B11, effusion meter B15 and spontaneous imbibition booster pump B18 are connected with advanced oxidation retort B1 top；Described ozonator B9 leads to
Crossing pipeline and the effusion meter B16 being arranged on pipeline is connected with advanced oxidation retort B1 top, chemical nickel plating waste solution is from gas-liquid
Top inlet B2 of blender B8 sends into advanced oxidation retort B1.In order to keep beds B3 stable, porous air distribution plate
The diameter of the pore B13 on B6 is less than catalyst B4 particle diameter, and air and liquid mixer outlet B8 installs support column B14, makes gas-liquid
10 centimetres, the bottom of mixer outlet B8 distance advanced oxidation retort.
Heretofore described and ozonator be commercially available any air source of the gas ozonator, ozone produce
Amount reaches more than 10g/h.
Heretofore described and hydrogen peroxide storage tank be commercially available any one resistance to hydrogen peroxide corrosion plastics medicine-adding bin, hold
Amass between 20-100L.Hydrogen peroxide storage tank by pipeline successively with spontaneous imbibition booster pump, valve, effusion meter, advanced oxidation retort
It is connected.
Heretofore described and nickel recovery pond C, dephosphorization pond D structure identical, use integration Pool body design, including adding
Medicine reaction zone, tube settling district, clear liquid area and sludge discharging area, use existing any integration flocculation precipitation reaction pond equal
Can, it is prior art construction, the most no longer illustrates.
In order to be described more fully the actual effect of the present invention, illustrated by specific embodiment:
Embodiment 1, the application present invention processes the chemical nickel plating waste solution of first enterprise discharge
Chemical nickel plating waste solution is collected pH regulator pond A, with sulphuric acid or the sodium carbonate liquor regulation pH of concentration 10% of concentration 15%
Value is 5.1, and the chemical nickel plating waste solution regulating pH pumps into advanced oxidation retort B1, opens ozonator B9 and self-absorption pressurizing
Pump B18, the registration of the effusion meter B16 of regulation and control ozone is 2.5L/min, and keeping overflow area B21 ozone concentration is 1.2mg/L, regulation and control
The registration of the effusion meter B15 of hydrogen peroxide is 0.5L/min, and keeping overflow area B21 hydrogen peroxide concentration is 0.2mg/L.Through senior oxygen
Change the chemical nickel plating waste solution after retort B1 catalytic oxidation and enter nickel recovery pond C, add the sodium carbonate liquor of 10%, regulation
PH is 11.9, stops reaction 2 hours, and precipitation reclaims, and supernatant enters dephosphorization pond D, adds 100g calcium oxide in every liter of supernatant,
Precipitation 3 hours, Chinese effluent.After above-mentioned technique, the main water quality index of water outlet is: COD value is 120mg/L, total nickel
For 0.1mg/L, total phosphorus is 0.6mg/L.
Embodiment 2, the application present invention processes the chemical nickel plating waste solution of second enterprise discharge
Chemical nickel plating waste solution is collected pH regulator pond A, with sulphuric acid or the sodium hydroxide solution regulation of concentration 10% of concentration 10%
PH value is 5.9, and the chemical nickel plating waste solution regulating pH pumps into advanced oxidation retort B1, opens ozonator B9 and self-priming increases
Press pump B18, the registration of the effusion meter 16 of regulation and control ozone is 2.0L/min, and keeping overflow area B21 ozone concentration is 0.6mg/L, adjusts
The registration of the effusion meter 15 of control hydrogen peroxide is 0.75L/min, and keeping overflow area B21 hydrogen peroxide concentration is 0.4mg/L.Through senior
Chemical nickel plating waste solution after oxidation reaction tank B1 catalytic oxidation enters nickel recovery pond C, adds the sodium hydroxide solution of 10%,
Regulation pH is 12.2, stops reaction 3 hours, and precipitation reclaims, and supernatant enters dephosphorization pond D, adds 110g oxygen in every liter of supernatant
Change calcium, precipitation 5 hours, Chinese effluent.After above-mentioned technique, the main water quality index of water outlet is: COD value is 96mg/L,
Total nickel is 0.02mg/L, and total phosphorus is 0.4mg/L.
Embodiment 3, the application present invention processes the chemical nickel plating waste solution of the third enterprise discharge
Chemical nickel plating waste solution is collected pH regulator pond A, with sulphuric acid or the sodium hydroxide solution regulation of concentration 15% of concentration 20%
PH value is 4.6, and the chemical nickel plating waste solution regulating pH pumps into advanced oxidation retort B1, opens ozonator B9 and self-priming increases
Press pump B18, the registration of the effusion meter 16 of regulation and control ozone is 3.0L/min, and keeping overflow area B21 ozone concentration is 1.5mg/L, adjusts
The registration of the effusion meter 15 of control hydrogen peroxide is 1.2L/min, and keeping overflow area B21 hydrogen peroxide concentration is 0.45mg/L.Through senior
Chemical nickel plating waste solution after oxidation reaction tank B1 catalytic oxidation enters nickel recovery pond C, adds the sodium hydroxide solution of 15%,
Regulation pH is 12.3, stops reaction 4 hours, and precipitation reclaims, and supernatant enters dephosphorization pond D, adds 120g oxygen in every liter of supernatant
Change calcium, precipitation 4 hours, Chinese effluent.After above-mentioned technique, the main water quality index of water outlet is: COD value is 88mg/L,
Total nickel is 0.02mg/L, and total phosphorus is 0.2mg/L.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope that the invention discloses, the change that can readily occur in or replacement,
All should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of the claims
It is as the criterion.
Claims (3)
1. the process technique of a chemical nickel plating waste solution, it is characterised in that: this technique is realized by following steps:
1., by chemical nickel plating waste solution collecting in pH regulator groove, the sulfuric acid solution or the concentration that add concentration 5%-30% are 5%-
The sodium hydroxide solution of 15% or concentration are the sodium carbonate liquor of 5%-10%, and regulation chemical nickel plating waste solution pH value is 4.5-6.0
Between, then the chemical nickel plating waste solution after regulation pH value is sent into advanced oxidation reaction unit；
2. the advanced oxidation retort that is first fed on advanced oxidation reaction unit of chemical nickel plating waste solution, after regulation pH value, opens
Open ozonator and spontaneous imbibition booster pump, by the flow of the Valve controlling ozone that ozone emitters carries, make the smelly of overflow area
Oxygen concentration is between 0.5-2.5mg/L；Add inbound traffics by Valve controlling hydrogen peroxide, make the hydrogen peroxide concentration of overflow area exist
Between 0.1-0.5mL/L；Chemistry after gas-liquid mixed district in advanced oxidation retort, hydrogen peroxide, ozone and regulation pH value
Nickel-plating waste liquid carries out hybrid concurrency raw Heterogeneous oxidation reaction, then at the beds of advanced oxidation retort, hydrogen peroxide,
Ozone with regulation pH value after chemical nickel plating waste solution carry out heterogeneous catalytic oxidation reaction, the chemical plating after oxidation processes
Nickel waste liquid is collected from the downflow weir of advanced oxidation retort and is entered nickel recovery pond through discharging tube, with the sodium hydroxide of concentration 5%-15%
The sodium carbonate liquor heightening pH value of solution or concentration 5%-10% is between 11.5-12.5, and precipitation reclaims nickel ion；Supernatant is arranged
Entering dephosphorization pond, add calcium oxide and carry out precipitating dephosphorization in dephosphorization pond, the addition of calcium oxide is 90～150g/ liters, generation
Calcium phosphate can carry out reuse as the phosphate fertilizer source of manure, and after dephosphorization, supernatant enters rear end sewage disposal system.
2. advanced oxidation reaction unit as claimed in claim 1, it is characterised in that: described advanced oxidation reaction unit includes height
Level oxidation reaction tank, ozonator and hydrogen peroxide storage tank, wherein, advanced oxidation retort is the tank of a cylindrical shape
Body, tank interior arranges the air and liquid mixer of a vertebral body shape, and described air and liquid mixer is inlaid with porous gas distribution by draw-in groove
On plate, advanced oxidation retort is divided into upper end catalysis zoneofoxidation and overflow area, lower end gas-liquid mixed by described porous air distribution plate
District；The lower end of described air and liquid mixer is air and liquid mixer outlet, and the upper at least three of installing of described air and liquid mixer outlet supports
Post, is provided with downflow weir and is connected to the discharging tube below downflow weir outside the upper end of described advanced oxidation retort, described double
Oxygen water storage tank is connected with advanced oxidation retort top by pipeline and valve, effusion meter and the spontaneous imbibition booster pump being arranged on pipeline
Connect；Described ozonator is connected with advanced oxidation retort top by pipeline and the effusion meter being arranged on pipeline, chemistry
Nickel-plating waste liquid sends into advanced oxidation retort from the top inlet of air and liquid mixer.
3. advanced oxidation response system as claimed in claim 2, it is characterised in that: in order to keep beds stable, many
The diameter of the pore on the air distribution plate of hole is less than catalyst particle diameter, the end of air and liquid mixer outlet distance advanced oxidation retort
10 centimetres of portion.
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| CN107265730A (en) * | 2017-06-26 | 2017-10-20 | 嘉兴英施特环保科技有限公司 | Chemical nickel waste liquid waste water treatment process and equipment |
| CN107954542A (en) * | 2017-11-21 | 2018-04-24 | 常州亚环环保科技有限公司 | A kind of device and its application process that phosphorus is recycled from phosphorous electroplating wastewater |
| CN108178428A (en) * | 2017-12-26 | 2018-06-19 | 深圳市绿沁投资有限公司 | The treating method and apparatus of electroplating wastewater |
| CN108275809A (en) * | 2018-01-31 | 2018-07-13 | 常州市武进天工机械制造有限公司 | Chemical nickel plating, electroplated zinc nickel alloy wastewater treatment method |
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| CN111072179A (en) * | 2019-12-27 | 2020-04-28 | 江苏中科瑞尔汽车科技有限公司 | Chemical nickel plating waste water treatment method |
| CN111573883A (en) * | 2020-04-21 | 2020-08-25 | 生态环境部华南环境科学研究所 | Method for treating chemical nickel plating waste liquid through iron-based catalyst |
| CN112624432A (en) * | 2020-12-31 | 2021-04-09 | 惠州金茂源环保科技有限公司 | Electroplating wastewater ozone oxidation advanced treatment method |
| CN113511744A (en) * | 2020-04-10 | 2021-10-19 | 鹏鼎控股(深圳)股份有限公司 | Treatment method and treatment system for nickel plating waste liquid |
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| CN107954542A (en) * | 2017-11-21 | 2018-04-24 | 常州亚环环保科技有限公司 | A kind of device and its application process that phosphorus is recycled from phosphorous electroplating wastewater |
| CN108178428A (en) * | 2017-12-26 | 2018-06-19 | 深圳市绿沁投资有限公司 | The treating method and apparatus of electroplating wastewater |
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| CN112624432A (en) * | 2020-12-31 | 2021-04-09 | 惠州金茂源环保科技有限公司 | Electroplating wastewater ozone oxidation advanced treatment method |
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