CN105906154A - Resourceful treatment and recycling method of circuit board wastewater - Google Patents
Resourceful treatment and recycling method of circuit board wastewater Download PDFInfo
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- CN105906154A CN105906154A CN201610412345.7A CN201610412345A CN105906154A CN 105906154 A CN105906154 A CN 105906154A CN 201610412345 A CN201610412345 A CN 201610412345A CN 105906154 A CN105906154 A CN 105906154A
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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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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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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- 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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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/105—Phosphorus compounds
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- C02F2301/04—Flow arrangements
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- C02F3/30—Aerobic and anaerobic processes
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- C02F3/308—Biological phosphorus removal
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Abstract
The invention relates to a resourceful treatment and recycling method of circuit board wastewater. The resourceful treatment and recycling method comprises the following steps of 1, precipitation breaking and copper removal, wherein pH of the circuit board wastewater is adjusted to 2-4, the circuit board wastewater is put into a precipitation breaking and copper removal reactor filled with ferric carbon filler, an aeration reaction is performed, the pH of outlet water of the reactor is adjusted, a flocculating agent is added, a stirring coagulating reaction is performed, and solid-liquid separation is performed; 2, cyanide breaking and nickel removal, wherein the pH of a supernate obtained in the step 1 is adjusted to 2-4, the supernate is put into a cyanide breaking and nickel removal reactor, and an aeration reaction is performed, the pH of outlet water of the reactor is adjusted to 8-9, a stirring coagulating reaction is performed, and solid liquid separation is performed; 3, filter material biological filter pond treatment, wherein the supernate obtained in the step 2 is added into a filter material biochemical treatment system with a cyanide breaking and nickel removal filter material, cyanide breaking and nickel removal are performed, and the final outlet water is obtained. Compared with the prior art, the method is simple in flow, compact, stable, efficient, low in operation cost, applicable to wastewater with the high heavy metal concentration and particularly suitable for circuit board wastewater treatment, and has the high popularization and application value.
Description
Technical field
The present invention relates to belong to advanced treatment of industrial waste water field, especially relate to a kind of contact break copper removal, broken cyanide removes
The method that the recycling treatment of nickel coupling two-stage Novel filter material biofilter process circuit plate waste water reclaims, particularly locates
The method that the recycling treatment of the board wastewater that the content of beary metal such as reason copper nickel are higher reclaims.
Background technology
Printed wiring board (PCB) waste water is to produce a large amount of waste water containing heavy metal during printed wiring board and have
Machine waste water, contaminated wastewater species is many, complicated component, intractability are big, processing cost is high.At printed circuit board
In the technological process of production, containing copper ion in the waste water of the operation discharges such as nog plate, weak burn into electro-coppering；Erosion plate,
Containing copper ion and chelating agent EDTA and sodium potassium tartrate tetrahydrate etc. in the waste water of the operation discharges such as electroless copper plating；In plating
Containing nickel ion in the waste water of nickel operation discharge；Chelating agent is easily formed with the heavy metal such as copper under certain condition and chelates
Thing, conventional method of wastewater treatment is very difficult to remove.Most domestic printed substrate enterprise uses sodium sulfide
Or heavy metal chelating agent carries out contact break process, but a large amount of chelating agent contained in waste water are difficult to effectively be abolished, copper network
Compound stability is relatively strong, and conventional coagulation neutralization precipitation is very difficult to except complex state copper, so that water outlet tends not to up to standard
Discharge.Three grades of materializing strategy the most multistage of two-stage, the knot that such way causes is taked for contact break effect is undesirable
Fruit is that operating cost is higher, complex operation, and after multistage materializing strategy, conductivity of waste water raises follow-up biochemistry
It is unfavorable to process, and biochemical effects is very poor, and ultimately resulting in water outlet can not stably reaching standard.Giving up containing plurality of heavy metal ion
Water not only causes serious water body soil pollution, brings drinking water safety problem and ecological environment problem, simultaneously containing big
The direct discharging of waste water of amount heavy metal is also a kind of wasting of resources.The most effectively remove board wastewater pollutant load
The heavy metal ion such as the copper nickel bigger with harm, reclaim the heavy metal of waste water, water outlet heavy metal concentration and other pollutions
The discharge of thing stably reaching standard is the difficult point of process circuit plate waste water.
Catalyzed internal electrocatalysis method, also known as micro-electrolysis method, ultimate principle is to utilize the ferrum in iron filings and carbon molten at electrolyte
Liquid constitutes countless small galvanic element, complicated redox reaction occurs.This method is anti-based on the battery in electrochemistry
Should, course of reaction is mainly concerned with the multiple effect associations such as oxidoreduction, electricity enrichment, physical absorption and flocculating sedimentation
With completing.Under acid medium and aerobic conditions, the nascent state [H] of Inner electrolysis generation and Fe2+Can be permitted in waste water
Many materials generation redox reaction, thus destroy the structure of chelating agent so that it is lose or reduce the ability of complex copper,
The ferrous hydroxide that synkaingenesis becomes has good flocculation adsorption activity, can adsorb the small suspension in waste water
Thing and colloidality material, remove Pollutants in Wastewater further.Additionally ferrum can replace the copper of waste water intermediate ion state,
Copper in waste water is replaced into elemental copper, and the removal effect that Inner electrolysis heavy metal is excellent can reduce waste water to micro-life
The toxic action of thing, improves biochemical efficiency.Microelectrolysis process generates nascent state [H], O2、·OH、Fe2+And Fe3+
There is complicated redox reaction with the polluter in waste water in isoreactivity material, the difficult degradation in waste water is divided greatly
Sub-Organic substance is converted into degradable small-molecule substance, improves the biodegradability of waste water.Process based on catalyzed internal electrocatalysis
Feature, this method is frequently utilized for the pretreatment stage of waste water, along with the further research to the method, catalyzed internal electrocatalysis
The advantage that method can not be fully achieved this method as a kind of single technology.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and a kind of board wastewater is provided
Recycling treatment reclaim method.
The purpose of the present invention can be achieved through the following technical solutions:
The method that the recycling treatment of a kind of board wastewater reclaims, comprises the following steps:
(1) contact break copper removal
Adjusting circuit plate wastewater pH=2～4, then put into equipped with in the contact break copper-stripping reaction device of ferrum carbon filler, aeration is anti-
Should, regulate reactor water outlet pH=8～9, add flocculant, stir coagulating, staticly settle, solid-liquid separation,
Upper strata the first supernatant enters next step and processes, and lower sediment reclaims；
(2) broken cyanide removes nickel
The first supernatant pH=2～4 that regulating step (1) obtains, then put into the broken cyanide equipped with ferrum carbon filler except nickel
In reactor, aerated reaction, regulate reactor water outlet pH=8～9, add flocculant, stir coagulating, Gu
Liquid separates, and upper strata the second supernatant enters next step and processes, and lower sediment reclaims；
(3) filtrate biofilter processes
The second supernatant that step (2) obtains is joined the filtrate biochemical treatment system equipped with denitrogenation dephosphorizing filtrate
In, carry out denitrogenation dephosphorizing process, i.e. obtain final outflow water.
Contact break copper-stripping reaction device and broken cyanide remove the addition of the ferrum carbon filler in nickel reactant device and press reactor dischargeable capacity
It is calculated as 0.05～0.15kg/L.Ferrum carbon filler is preferably ferrum carbon Pall ring filler.
Described ferrum carbon filler is made by the following method: the iron filings after weighing by acid-wash activation, Powdered Activated Carbon and
The filler body of rare earth metal powder composition, adds zinc powder and titanium dioxide, compressing, at isolation air ring
Calcine under border, quenching, i.e. prepare ferrum carbon filler.
The mass ratio of iron filings, Powdered Activated Carbon and rare earth metal powder three after acid-wash activation is (80～88):
(11～18): (0.01～2)；
The dosage of described zinc powder is the 0.05～0.2% of ferrum carbon filler gross weight；
The dosage of described titanium dioxide is the 0.008～0.015% of ferrum carbon filler gross weight.
The process conditions of calcining are to calcine 90～100min at 1050～1200 DEG C.
Flocculant described in step (1) and step (2) is Flokal B polyacrylamide, its dosage
It is 0.3～0.8mg/L waste water.
The condition of the aerated reaction in step (1) and step (2) is: oxygen in water in aeration control reactor
Concentration is 2.5～4mg/L, and reactor residence time is 0.5～1.5h；
The process conditions of stirring coagulating are: under the rotating speed of 60～100rpm, react 5～20min.
Described filtrate biochemical treatment system is composed in series by anaerobic biofilter and two filter tanks of BAF,
Filtrate stacking volume in two filter tanks shares equally the 30～50% of the total dischargeable capacity in respective filter tank, described Anaerobe
The hydraulic detention time in filter tank is 2～4h, and the hydraulic detention time of BAF is 5～7h.
Described denitrogenation dephosphorizing filtrate is made by the following method:
Weigh the dispensing being uniformly mixed so as to obtain by comminuted steel shot, iron powder, zeolite powder, activated carbon and cement, limit in hollow float
Water spray limit spills into dispensing, obtains wrapping up the filtrate ball of dispensing, maintenance, i.e. prepares denitrogenation dephosphorizing filtrate.
The mass ratio of comminuted steel shot, iron powder, zeolite powder, activated carbon and cement is (40～50): (8～12): (18～25):
(10～12): (12～16)；
Curing condition: temperature is 15 DEG C～25 DEG C, and relative humidity is 40%～60%, and curing time is 7～10 days.
The present invention is respectively provided with two-stage catalyzed internal electrocatalysis reactor in technique front end, effect be respectively contact break copper removal and
The heavy metal almost all such as broken cyanide removes nickel, the Cu in waste water nickel before entering biochemical system are transferred in mud, to dirt
In mud, heavy metal carries out resource recovery, reduces the heavy metal in waste water toxic action to microorganism simultaneously, improves
Subsequent biochemical treatment effeciency, additionally Inner electrolysis reactor is to CODCr, ammonia nitrogen also have certain removal effect；Biochemical
System uses anaerobism+BAF reactor, and built-in novel synchronous denitrogenation dephosphorizing filtrate, to total nitrogen, total phosphorus
It is respectively provided with excellent removal effect: the filtrate in anaerobic biofilter has invigoration effect to denitrifying microorganism, by force
Change denitrification effect, in the case of low ratio of carbon to ammonium can also efficient denitrification, simultaneously denitrification consume carbon source will waste water have
Machine thing is removed；Owing to Organic substance most in waste water is removed by Inner electrolysis reactor and anaerobic biofilter, enter
The content of organics entering aerobic biofilter is the lowest, and low organic concentration environment promotes the increasing of nitrifier
Long, ammonia nitrogen is converted into nitrate nitrogen, simultaneously part COD in aerobic biofilterCrAlso it is removed；Novel filter
The removal of phosphorus is mainly realized by material biofilter by biotic induce chemical precipitation, when environment exists free H+Time
Filtrate separates out free iron and generates precipitation with phosphate reaction, is removed with the biomembrane form come off, biological and chemical
Synergism realizes efficient dephosphorization.Total copper=0.05 of final outflow water～0.10mg/L, total nickel after treatment by using the treatment method
=0.01～0.02mg/L, CODCr=30～40mg/L, ammonia nitrogen=0.5～2.0mg/L, total nitrogen=10～13mg/L, total phosphorus
=0.1～0.2mg/L, effluent quality can stably reach GB 18918-2002, and " urban wastewater treatment firm pollutant are arranged
Put standard " one-level emission standard A.
To reduce copper removal in " contact break copper removal " reactor, nickel is had a small amount of removal effect simultaneously.This be because of
For, copper belongs to inert metal, and copper ion reduction can be generated by the Zero-valent Iron in Inner electrolysis filler by metathesis
Elemental copper, the copper that additionally oxidation-reduction potential is higher preferentially participates in electrochemical reaction, then relies on flocculation adsorption coprecipitated
Copper is removed by shallow lake effect, and " contact break copper removal " water outlet total copper concentration is up to one-level emission standard A；Nickel belongs to more active
Metal, before movable metallic table comes ferrum, Zero-valent Iron does not reacts, and the removal of this part of nickel relies primarily on newly
The hydrated ferric oxide. flocculation adsorption that ecological iron ion hydrolysis obtains is removed, and the total nickel concentration of water outlet can not reach one-level A row
Putting standard, therefore water outlet enters " broken cyanide removes nickel " reactor further except nickel." broken cyanide removes nickel " reactor water inlet
Content of copper ion is the lowest, although the most also can remove part copper ion, but with by light electrolysis, oxidoreduction
It is main for acting on flocculation adsorption etc. and removing nickel ion in waste water, and the total nickel concentration of reactor water outlet reaches one-level A discharge mark
Accurate.
In sum, " contact break copper removal " and " broken cyanide removes nickel " reactor is to carry out to copper, nickel removal effect simultaneously
, but owing to going removing heavy metals difference, cutting mechanisms also difference to cause Inner electrolysis reactor preferentially to remove copper removal, work as copper
Ion is reduced to start the most afterwards and nickel reactant.Nickel, based on contact break copper removal, is had on a small quantity by " contact break copper removal "
Remove；" broken cyanide removes nickel " except nickel, also has a small amount of removal effect based on broken cyanide to copper；Final outflow water can be protected
Card copper nickel ion all can reach one-level emission standard A.
Compared with prior art, the invention have the advantages that
(1) the whole processing system of the present invention is removed nickel reactant device and two-stage biological filter by contact break copper-stripping reaction device, broken cyanide
Pond is constituted, and first based on catalyzed internal electrocatalysis, the Heavy Metals ion in waste water carries out contact break copper removal and breaks
Cyanogen processes except nickel, heavy metal is transferred in mud carry out resource recycling, avoids heavy metal ion pair simultaneously
The inhibitory action of subsequent biochemical system, additionally Inner electrolysis process can be by the macromolecular complex of difficult degradation in board wastewater
Matter is converted into the small-molecule substance that microorganism is degradable, improves biodegradability, simultaneously to CODCr, ammonia nitrogen also have one
Fixed removal effect, then utilizes two-stage novel synchronous denitrogenation dephosphorizing filtrate biofilter to carry out efficient organics removal
With synchronous denitrification dephosphorizing effect, it is ensured that final outflow water can stably reaching standard, there is flow process simple, height compact, stable
Effect, operating cost is low, it is adaptable to the waste water particularly board wastewater that heavy metal concentration is higher processes, and has higher
The advantage of popularization and application.
(2) contact break copper removal of the present invention and broken cyanide remove nickel and utilize ferrum carbon Pall ring filler, based on internal electrolysis principle
Processing board wastewater, catalyzed internal electrocatalysis method has electrochemical reaction, oxidoreduction, absorption, electricity simultaneously
The synergism such as cohesion and flocculation, effectively destroy the chelating agent in board wastewater, by heavy metals such as Cu in waste water nickel
Ion-transfer realizes resource recycling to mud, significantly weakens heavy metal ion simultaneously and makees the murder by poisoning of microorganism
With, additionally can change structure and the form of hardly degraded organic substance in waste water, the macromolecular substances of difficult degradation is converted
For degradable small-molecule substance, improve wastewater biodegradability.
(4) the novel synchronous denitrogenation dephosphorizing filtrate that two-stage biofilter of the present invention adds can remove with enhanced biological nitrogen removal
Phosphorus effect, filtrate is free in acid condition to tap a blast furnace and phosphate reaction realizes biochemistry and coordinates dephosphorization function, with
Shi Tie has certain facilitation to the activity of microorganism, overcomes microorganism denitrogenation effect under the conditions of low ratio of carbon to ammonium
Contradiction between the poorest and synchronous denitrification dephosphorizing, effluent quality can be with stably reaching standard.
(5) catalyzed internal electrocatalysis of the present invention also serves as the pretreatment unit of biochemical system, improves wastewater biodegradability, carries
High biochemical system shock resistance meets ability, overcomes traditional method and adds a large amount of contact break medicament and cause waste water salinity mistake
Height causes the defect that Biochemical Treatment is undesirable, makes whole system run more stable, and stable effluent quality is excellent,
All can stably reach GB 18918-2002 " urban wastewater treatment firm pollutant emission standard " one-level A discharge mark
Accurate.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the present invention.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Take from certain circuit board plant comprehensive pool waste water (total copper=180～200mg/L, total nickel=0.9～1.5mg/L,
CODCr=450～550mg/L, ammonia nitrogen=35～45mg/L, total nitrogen=65～75mg/L, total phosphorus=3.8～4.5mg/L),
Flow process as shown in Figure 1 processes.
First, certain circuit board plant comprehensive pool wastewater pH=3～4 is taken from regulation, pumps into contact break copper-stripping reaction with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.1kg/L in reactor, and reactor bottom is provided with aerator
Carry out aeration, control oxygen in water concentration 2.5～4.0mg/L, time of staying 1h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to contact break copper-stripping reaction device water outlet, then add commercially available
Flokal B polyacrylamide (PAM), the dosage of PAM is 0.5mg/L, stirs coagulating 10min
Afterwards (rotating speed is 80r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures the total copper of supernatant
=0.10～0.15mg/L；
The supernatant obtained to above-mentioned steps adds sulphuric acid regulation pH=3～4, pumps into broken cyanide except nickel reactant with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.1kg/L in reactor, and reactor bottom is provided with aerator
Carry out aeration, control oxygen in water concentration 2.5～4mg/L, time of staying 1h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to broken cyanide except nickel reactant device water outlet, then add commercially available
The dosage of Flokal B PAM, PAM is 0.5mg/L, and after stirring coagulating 10min, (rotating speed is
80r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures total nickel=0.01 of supernatant～0.02mg/L；
Supernatant above-mentioned steps obtained with dosing pump pumps into two-stage Novel filter material biofilter biochemical treatment system,
This system is in series by anaerobic biofilter and BAF, adds novel synchronous denitrogenation dephosphorizing inside filter tank
Filtrate, filtrate stacking volume accounts for the 30%～50% of the total dischargeable capacity in filter tank, anaerobic biofilter and aeration and biological
Filter tank hydraulic detention time is respectively 3h and 6h, and BAF nitrification liquid is back to anaerobic biofilter, returns
Flow ratio is 200%, after measured, total copper=0.05 of final outflow water～0.10mg/L, total nickel=0.01～0.02mg/L,
CODCr=30～40mg/L, ammonia nitrogen=0.5～2.0mg/L, total nitrogen=10～13mg/L, total phosphorus=0.1～0.2mg/L, go out
Water water quality can stably reach GB 18918-2002 " urban wastewater treatment firm pollutant emission standard " one-level A row
Put standard；
Total copper=180 of comprehensive wastewater～200mg/L, the total copper of supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction
=0.10～0.15mg/L, this factory's comprehensive wastewater about 7000t/d, every day recyclable copper about 1400kg；Total nickel=0.9～1.5
Mg/L, through total nickel=0.01 of supernatant that broken cyanide obtains except coagulating sedimentation after nickel reactant～0.02mg/L, every day is recyclable
Nickel about 10kg, has higher resource recycling and is worth.
Embodiment 2
Take from certain circuit board plant comprehensive pool waste water (total copper=180～200mg/L, total nickel=0.9～1.5mg/L,
CODCr=450～550mg/L, ammonia nitrogen=35～45mg/L, total nitrogen=65～75mg/L, total phosphorus=3.8～4.5mg/L),
Flow process as shown in Figure 1 processes.
First, certain circuit board plant comprehensive pool wastewater pH=3～4 is taken from regulation, pumps into contact break copper-stripping reaction with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.05kg/L in reactor, and reactor bottom is provided with aeration
Device carries out aeration, controls oxygen in water concentration 2.5～4.0mg/L, time of staying 1.5h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to contact break copper-stripping reaction device water outlet, then add commercially available
Flokal B polyacrylamide (PAM), the dosage of PAM is 0.8mg/L, stirs coagulating 20min
Afterwards (rotating speed is 60r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures the total copper of supernatant
=0.10～0.15mg/L；
The supernatant obtained to above-mentioned steps adds sulphuric acid regulation pH=3～4, pumps into broken cyanide except nickel reactant with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.15kg/L in reactor, and reactor bottom is provided with aeration
Device carries out aeration, controls oxygen in water concentration 2.5～4mg/L, time of staying 0.5h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to broken cyanide except nickel reactant device water outlet, then add commercially available
The dosage of Flokal B PAM, PAM is 0.3mg/L, and after stirring coagulating 15min, (rotating speed is
80r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures total nickel=0.01 of supernatant～0.02mg/L；
Supernatant above-mentioned steps obtained with dosing pump pumps into two-stage Novel filter material biofilter biochemical treatment system,
This system is in series by anaerobic biofilter and BAF, adds novel synchronous denitrogenation dephosphorizing inside filter tank
Filtrate, filtrate stacking volume accounts for the 30%～50% of the total dischargeable capacity in filter tank, anaerobic biofilter and aeration and biological
Filter tank hydraulic detention time is respectively 4h and 7h, and BAF nitrification liquid is back to anaerobic biofilter, returns
Flow ratio is 200%, after measured, total copper=0.05 of final outflow water～0.10mg/L, total nickel=0.01～0.02mg/L,
CODCr=30～40mg/L, ammonia nitrogen=0.5～2.0mg/L, total nitrogen=10～13mg/L, total phosphorus=0.1～0.2mg/L, go out
Water water quality can stably reach GB 18918-2002 " urban wastewater treatment firm pollutant emission standard " one-level A row
Put standard；
Total copper=180 of comprehensive wastewater～200mg/L, the total copper of supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction
=0.10～0.15mg/L, this factory's comprehensive wastewater about 7000t/d, every day recyclable copper about 1450kg；Total nickel=0.9～1.5
Mg/L, through total nickel=0.01 of supernatant that broken cyanide obtains except coagulating sedimentation after nickel reactant～0.02mg/L, every day is recyclable
Nickel about 12kg, has higher resource recycling and is worth.
In above-mentioned processing method:
Ferrum carbon filler is prepared by the following method and forms: live with the hydrochloric acid solution pickling iron filings that mass percent is 5%
Change 30min, by iron filings: Powdered Activated Carbon: rare earth metal powder=85%:14.95%:0.05% mass percent
Measure, add zinc powder as binding agent and titanium dioxide as catalyst, raw material blending is placed on Pall ring shape
In model, with powder press under 200kN compressing, the demoulding take out blank, blank is completely cut off air and exists
Take out quenching under the conditions of 1050 DEG C after 100min, prepare ferrum carbon Pall ring filler；Wherein zinc powder and titanium dioxide
Dosage is respectively the 0.1% and 0.01% of ferrum carbon filler gross weight.
Denitrogenation dephosphorizing filtrate, preparation method is: first slag, iron filings, zeolite are crushed, then according to quality
Percentage ratio measures comminuted steel shot: iron powder: zeolite powder: activated carbon: cement=45%:10%:20%:10%:15%,
It is uniformly mixed so as to obtain dispensing；Being sprinkled into the plastic hollow ball float of a diameter of 10mm in seed-coating machine, water spray limit, limit is sprinkled into joins
Material, obtains the filtrate wrapped；The filtrate wrapped is put in natural curing room, temperature 15 DEG C～25 DEG C and phase
It is maintenance 7～10 days under the conditions of 40%～60% to humidity, i.e. prepares nitrogen and phosphorus removal bio filter.
Embodiment 3
Take from certain circuit board plant comprehensive pool waste water (total copper=180～200mg/L, total nickel=0.9～1.5mg/L,
CODCr=450～550mg/L, ammonia nitrogen=35～45mg/L, total nitrogen=65～75mg/L, total phosphorus=3.8～4.5mg/L),
Flow process as shown in Figure 1 processes.
First, certain circuit board plant comprehensive pool wastewater pH=3～4 is taken from regulation, pumps into contact break copper-stripping reaction with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.15kg/L in reactor, and reactor bottom is provided with aeration
Device carries out aeration, controls oxygen in water concentration 2.5～4.0mg/L, time of staying 0.5h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to contact break copper-stripping reaction device water outlet, then add commercially available
Flokal B polyacrylamide (PAM), the dosage of PAM is 0.3mg/L, stirs coagulating 10min
Afterwards (rotating speed is 100r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures the total copper of supernatant
=0.10～0.15mg/L；
The supernatant obtained to above-mentioned steps adds sulphuric acid regulation pH=3～4, pumps into broken cyanide except nickel reactant with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.15kg/L in reactor, and reactor bottom is provided with aeration
Device carries out aeration, controls oxygen in water concentration 2.5～4mg/L, time of staying 0.5h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to broken cyanide except nickel reactant device water outlet, then add commercially available
The dosage of Flokal B PAM, PAM is 0.3mg/L, and after stirring coagulating 15min, (rotating speed is
100r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures the total nickel of supernatant
=0.01～0.02mg/L；
Supernatant above-mentioned steps obtained with dosing pump pumps into two-stage Novel filter material biofilter biochemical treatment system,
This system is in series by anaerobic biofilter and BAF, adds novel synchronous denitrogenation dephosphorizing inside filter tank
Filtrate, filtrate stacking volume accounts for the 30%～50% of the total dischargeable capacity in filter tank, anaerobic biofilter and aeration and biological
Filter tank hydraulic detention time is respectively 2h and 5h, and BAF nitrification liquid is back to anaerobic biofilter, returns
Flow ratio is 200%, after measured, total copper=0.05 of final outflow water～0.10mg/L, total nickel=0.01～0.02mg/L,
CODCr=30～40mg/L, ammonia nitrogen=0.5～2.0mg/L, total nitrogen=10～13mg/L, total phosphorus=0.1～0.2mg/L, go out
Water water quality can stably reach GB 18918-2002 " urban wastewater treatment firm pollutant emission standard " one-level A row
Put standard；
Total copper=180 of comprehensive wastewater～200mg/L, the total copper of supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction
=0.10～0.15mg/L, this factory's comprehensive wastewater about 7000t/d, every day recyclable copper about 1450kg；Total nickel=0.9～1.5
Mg/L, through total nickel=0.01 of supernatant that broken cyanide obtains except coagulating sedimentation after nickel reactant～0.02mg/L, every day is recyclable
Nickel about 12kg, has higher resource recycling and is worth.
In above-mentioned processing method:
Ferrum carbon filler is prepared by the following method and forms: live with the hydrochloric acid solution pickling iron filings that mass percent is 5%
Change 30min, by iron filings: Powdered Activated Carbon: rare earth metal powder=88%:11%:1% mass percent measures,
Add zinc powder as binding agent and titanium dioxide as catalyst, raw material blending is placed on Pall ring shape
In, with powder press under 200kN compressing, the demoulding take out blank, blank is completely cut off air at 1200 DEG C
Under the conditions of take out quenching after 90min, prepare ferrum carbon Pall ring filler；Wherein zinc powder and titanium dioxide dosage divide
Not Wei ferrum carbon filler gross weight 0.2% and 0.008%.
Denitrogenation dephosphorizing filtrate, preparation method is: first slag, iron filings, zeolite are crushed, then according to quality
Percentage ratio measures comminuted steel shot: iron powder: zeolite powder: activated carbon: cement=40%:12%:25%:11%:16%,
It is uniformly mixed so as to obtain dispensing；Being sprinkled into the plastic hollow ball float of a diameter of 10mm in seed-coating machine, water spray limit, limit is sprinkled into joins
Material, obtains the filtrate wrapped；The filtrate wrapped is put in natural curing room, temperature 15 DEG C and relative humidity
It is maintenance 10 days under the conditions of 60%, i.e. prepares nitrogen and phosphorus removal bio filter.
Embodiment 4
Take from certain circuit board plant comprehensive pool waste water (total copper=180～200mg/L, total nickel=0.9～1.5mg/L,
CODCr=450～550mg/L, ammonia nitrogen=35～45mg/L, total nitrogen=65～75mg/L, total phosphorus=3.8～4.5mg/L),
Flow process as shown in Figure 1 processes.
First, certain circuit board plant comprehensive pool wastewater pH=3～4 is taken from regulation, pumps into contact break copper-stripping reaction with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.05kg/L in reactor, and reactor bottom is provided with aeration
Device carries out aeration, controls oxygen in water concentration 2.5～4.0mg/L, time of staying 1.5h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to contact break copper-stripping reaction device water outlet, then add commercially available
Flokal B polyacrylamide (PAM), the dosage of PAM is 0.8mg/L, stirs coagulating 5min
Afterwards (rotating speed is 60r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures the total copper of supernatant
=0.10～0.15mg/L；
The supernatant obtained to above-mentioned steps adds sulphuric acid regulation pH=3～4, pumps into broken cyanide except nickel reactant with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.05kg/L in reactor, and reactor bottom is provided with aeration
Device carries out aeration, controls oxygen in water concentration 2.5～4mg/L, time of staying 1.5h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to broken cyanide except nickel reactant device water outlet, then add commercially available
The dosage of Flokal B PAM, PAM is 0.8mg/L, and after stirring coagulating 5min, (rotating speed is
60r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures total nickel=0.01 of supernatant～0.02mg/L；
Supernatant above-mentioned steps obtained with dosing pump pumps into two-stage Novel filter material biofilter biochemical treatment system,
This system is in series by anaerobic biofilter and BAF, adds novel synchronous denitrogenation dephosphorizing inside filter tank
Filtrate, filtrate stacking volume accounts for the 45% of the total dischargeable capacity in filter tank, anaerobic biofilter and BAF
Hydraulic detention time is respectively 3h and 5h, and BAF nitrification liquid is back to anaerobic biofilter, reflux ratio
It is 200%, after measured, total copper=0.05 of final outflow water～0.10mg/L, total nickel=0.01～0.02mg/L,
CODCr=30～40mg/L, ammonia nitrogen=0.5～2.0mg/L, total nitrogen=10～13mg/L, total phosphorus=0.1～0.2mg/L, go out
Water water quality can stably reach GB 18918-2002 " urban wastewater treatment firm pollutant emission standard " one-level A row
Put standard；
Total copper=180 of comprehensive wastewater～200mg/L, the total copper of supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction
=0.10～0.15mg/L, this factory's comprehensive wastewater about 7000t/d, every day recyclable copper about 1450kg；Total nickel=0.9～1.5
Mg/L, through total nickel=0.01 of supernatant that broken cyanide obtains except coagulating sedimentation after nickel reactant～0.02mg/L, every day is recyclable
Nickel about 12kg, has higher resource recycling and is worth.
In above-mentioned processing method:
Ferrum carbon filler is prepared by the following method and forms: live with the hydrochloric acid solution pickling iron filings that mass percent is 5%
Change 30min, by iron filings: Powdered Activated Carbon: rare earth metal powder=80%:18%:2% mass percent measures,
Add zinc powder as binding agent and titanium dioxide as catalyst, raw material blending is placed on Pall ring shape
In, with powder press under 200kN compressing, the demoulding take out blank, blank is completely cut off air at 1200 DEG C
Under the conditions of take out quenching after 90min, prepare ferrum carbon Pall ring filler；Wherein zinc powder and titanium dioxide dosage divide
Not Wei ferrum carbon filler gross weight 0.05% and 0.008%.
Denitrogenation dephosphorizing filtrate, preparation method is: first slag, iron filings, zeolite are crushed, then according to quality
Percentage ratio measures comminuted steel shot: iron powder: zeolite powder: activated carbon: cement=50%:8%:18%:12%:12%,
It is uniformly mixed so as to obtain dispensing；Being sprinkled into the plastic hollow ball float of a diameter of 10mm in seed-coating machine, water spray limit, limit is sprinkled into joins
Material, obtains the filtrate wrapped；The filtrate wrapped is put in natural curing room, temperature 25 DEG C and relative humidity
It is maintenance 7 days under the conditions of 40%, i.e. prepares nitrogen and phosphorus removal bio filter.
Embodiment 5
Take from certain circuit board plant comprehensive pool waste water (total copper=180～200mg/L, total nickel=0.9～1.5mg/L,
CODCr=450～550mg/L, ammonia nitrogen=35～45mg/L, total nitrogen=65～75mg/L, total phosphorus=3.8～4.5mg/L),
Flow process as shown in Figure 1 processes.
First, certain circuit board plant comprehensive pool wastewater pH=3～4 is taken from regulation, pumps into contact break copper-stripping reaction with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.12kg/L in reactor, and reactor bottom is provided with aeration
Device carries out aeration, controls oxygen in water concentration 2.5～4.0mg/L, time of staying 0.8h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to contact break copper-stripping reaction device water outlet, then add commercially available
Flokal B polyacrylamide (PAM), the dosage of PAM is 0.6mg/L, stirs coagulating 12min
Afterwards (rotating speed is 80r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures the total copper of supernatant
=0.10～0.15mg/L；
The supernatant obtained to above-mentioned steps adds sulphuric acid regulation pH=3～4, pumps into broken cyanide except nickel reactant with dosing pump
Device, adds Pall ring filler by reactor dischargeable capacity 0.12kg/L in reactor, and reactor bottom is provided with aeration
Device carries out aeration, controls oxygen in water concentration 2.5～4mg/L, time of staying 0.8h；
Add the sodium hydroxide solution regulation pH=8～9 of 10% to broken cyanide except nickel reactant device water outlet, then add commercially available
The dosage of Flokal B PAM, PAM is 0.6mg/L, and after stirring coagulating 12min, (rotating speed is
80r/min), staticly settling 30min, solid-liquid separation obtains supernatant, measures total nickel=0.01 of supernatant～0.02mg/L；
Supernatant above-mentioned steps obtained with dosing pump pumps into two-stage Novel filter material biofilter biochemical treatment system,
This system is in series by anaerobic biofilter and BAF, adds novel synchronous denitrogenation dephosphorizing inside filter tank
Filtrate, filtrate stacking volume accounts for the 50% of the total dischargeable capacity in filter tank, anaerobic biofilter and BAF
Hydraulic detention time is respectively 3h and 5h, and BAF nitrification liquid is back to anaerobic biofilter, reflux ratio
It is 200%, after measured, total copper=0.05 of final outflow water～0.10mg/L, total nickel=0.01～0.02mg/L,
CODCr=30～40mg/L, ammonia nitrogen=0.5～2.0mg/L, total nitrogen=10～13mg/L, total phosphorus=0.1～0.2mg/L, go out
Water water quality can stably reach GB 18918-2002 " urban wastewater treatment firm pollutant emission standard " one-level A row
Put standard；
Total copper=180 of comprehensive wastewater～200mg/L, the total copper of supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction
=0.10～0.15mg/L, this factory's comprehensive wastewater about 7000t/d, every day recyclable copper about 1450kg；Total nickel=0.9～1.5
Mg/L, through total nickel=0.01 of supernatant that broken cyanide obtains except coagulating sedimentation after nickel reactant～0.02mg/L, every day is recyclable
Nickel about 12kg, has higher resource recycling and is worth.
In above-mentioned processing method:
Ferrum carbon filler is prepared by the following method and forms: live with the hydrochloric acid solution pickling iron filings that mass percent is 5%
Change 30min, by iron filings: Powdered Activated Carbon: rare earth metal powder=84%:15.99%:0.01% mass percent
Measure, add zinc powder as binding agent and titanium dioxide as catalyst, raw material blending is placed on Pall ring shape
In model, with powder press under 200kN compressing, the demoulding take out blank, blank is completely cut off air and exists
Take out quenching under the conditions of 1100 DEG C after 95min, prepare ferrum carbon Pall ring filler；Wherein zinc powder and titanium dioxide are thrown
Dosage is respectively the 0.18% and 0.015% of ferrum carbon filler gross weight.
Denitrogenation dephosphorizing filtrate, preparation method is: first slag, iron filings, zeolite are crushed, then according to quality
Percentage ratio measures comminuted steel shot: iron powder: zeolite powder: activated carbon: cement=46%:10%:20%:10%:14%,
It is uniformly mixed so as to obtain dispensing；Being sprinkled into the plastic hollow ball float of a diameter of 10mm in seed-coating machine, water spray limit, limit is sprinkled into joins
Material, obtains the filtrate wrapped；The filtrate wrapped is put in natural curing room, temperature 20 DEG C and relative humidity
It is maintenance 8 days under the conditions of 50%, i.e. prepares nitrogen and phosphorus removal bio filter.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and use to send out
Bright.These embodiments obviously easily can be made various amendment by person skilled in the art, and at this
The General Principle illustrated is applied in other embodiments without through performing creative labour.Therefore, the present invention does not limits
In above-described embodiment, those skilled in the art are according to the announcement of the present invention, without departing from changing that scope is made
Entering and revise all should be within protection scope of the present invention.
Claims (10)
1. the method that the recycling treatment of a board wastewater reclaims, it is characterised in that comprise the following steps:
(1) contact break copper removal
Adjusting circuit plate wastewater pH=2～4, then put in the reactor equipped with ferrum carbon filler, aerated reaction, regulation
Reactor water outlet pH=8～9, adds flocculant, stirs coagulating, staticly settles, solid-liquid separation, upper strata the
One supernatant enters next step and processes, and lower sediment reclaims；
(2) broken cyanide removes nickel
The first supernatant pH=2～4 that regulating step (1) obtains, then put in the reactor equipped with ferrum carbon filler,
Aerated reaction, regulation reactor water outlet pH=8～9, addition flocculant, stirring coagulating, solid-liquid separation, on
Layer the second supernatant enters next step and processes, and lower sediment reclaims；
(3) filtrate biofilter processes
The second supernatant that step (2) obtains is joined the filtrate biochemical treatment system equipped with denitrogenation dephosphorizing filtrate
In, carry out denitrogenation dephosphorizing process, i.e. obtain final outflow water.
The method that the recycling treatment of a kind of board wastewater the most according to claim 1 reclaims, its feature
It is, in step (1) and step (2): the addition of the ferrum carbon filler in reactor presses reactor dischargeable capacity
It is calculated as 0.05～0.15kg/L.
The method that the recycling treatment of a kind of board wastewater the most according to claim 1 and 2 reclaims, its
Being characterised by, described ferrum carbon filler is made by the following method: the iron filings after weighing by acid-wash activation, and powder is lived
Property charcoal and rare earth metal powder composition filler body, add zinc powder and titanium dioxide, compressing, isolation
Calcine under air ambient, quenching, i.e. prepare ferrum carbon filler.
The method that the recycling treatment of a kind of board wastewater the most according to claim 3 reclaims, its feature
Being, the mass ratio of iron filings, Powdered Activated Carbon and rare earth metal powder three after acid-wash activation is (80～88):
(11～18): (0.01～2)；
The dosage of described zinc powder is the 0.05～0.2% of ferrum carbon filler gross weight；
The dosage of described titanium dioxide is the 0.008～0.015% of ferrum carbon filler gross weight.
The method that the recycling treatment of a kind of board wastewater the most according to claim 3 reclaims, its feature
Being, the process conditions of calcining are to calcine 90～100min at 1050～1200 DEG C.
The method that the recycling treatment of a kind of board wastewater the most according to claim 1 reclaims, its feature
Being, the flocculant described in step (1) and step (2) is Flokal B polyacrylamide, and it adds
Amount is 0.3～0.8mg/L waste water.
The method that the recycling treatment of a kind of board wastewater the most according to claim 1 reclaims, its feature
Being, the condition of the aerated reaction in step (1) and step (2) is: dissolve in water in aeration control reactor
Oxygen concentration is 2.5～4mg/L, and reactor residence time is 0.5～1.5h；
The process conditions of stirring coagulating are: under the rotating speed of 60～100rpm, react 5～20min.
The method that the recycling treatment of a kind of board wastewater the most according to claim 1 reclaims, its feature
Being, described filtrate biochemical treatment system is by anaerobic biofilter and two filter tank series connection groups of BAF
Becoming, the filtrate stacking volume in two filter tanks shares equally the 30～50% of the total dischargeable capacity in respective filter tank, described anaerobism
The hydraulic detention time of biofilter is 2～4h, and the hydraulic detention time of BAF is 5～7h.
The method that the recycling treatment of a kind of board wastewater the most according to claim 1 reclaims, its feature
Being, described denitrogenation dephosphorizing filtrate is made by the following method:
Weigh the dispensing being uniformly mixed so as to obtain by comminuted steel shot, iron powder, zeolite powder, activated carbon and cement, limit in hollow float
Water spray limit spills into dispensing, obtains wrapping up the filtrate ball of dispensing, maintenance, i.e. prepares denitrogenation dephosphorizing filtrate.
The method that the recycling treatment of a kind of board wastewater the most according to claim 9 reclaims, its feature
Being, the mass ratio of comminuted steel shot, iron powder, zeolite powder, activated carbon and cement is (40～50): (8～12): (18～25):
(10～12): (12～16)；
Curing condition: temperature is 15 DEG C～25 DEG C, and relative humidity is 40%～60%, and curing time is 7～10 days.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108409003A (en) * | 2018-04-04 | 2018-08-17 | 深圳市深投环保科技有限公司 | The processing method and system of salt-containing organic wastewater after the recycling of PCB waste water copper |
| CN108911421A (en) * | 2018-08-17 | 2018-11-30 | 深圳市东森环境技术有限公司 | Tin-stripping wastewater integrated sewage disposal technique and system |
| CN109111048A (en) * | 2018-09-28 | 2019-01-01 | 章嘉华 | A kind of processing system of commercial metal waste water |
| CN109437471A (en) * | 2018-10-25 | 2019-03-08 | 深圳骏泽环保有限公司 | Board wastewater treatment process up to standard |
| CN109467262A (en) * | 2018-10-29 | 2019-03-15 | 深圳骏泽环保有限公司 | Board wastewater processing method based on special membrane |
| CN111233218A (en) * | 2020-01-16 | 2020-06-05 | 深圳市蓝清环境科技工程有限公司 | Catalytic FENTON wastewater treatment process |
| CN112759187A (en) * | 2020-12-28 | 2021-05-07 | 昆山至卓环保科技有限公司 | Method for treating industrial wastewater of electronic circuit board |
| CN113061730A (en) * | 2021-03-23 | 2021-07-02 | 北京佰利格瑞资源科技有限公司 | Method for removing iron in waste ternary lithium battery recovery process |
| CN113262786A (en) * | 2021-06-09 | 2021-08-17 | 广东工业大学 | Heterogeneous nano copper catalyst and preparation method and application thereof |
| CN113603309A (en) * | 2021-09-07 | 2021-11-05 | 安徽泉盛化工有限公司 | Treatment method of gas-making circulating wastewater |
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| CN108409003A (en) * | 2018-04-04 | 2018-08-17 | 深圳市深投环保科技有限公司 | The processing method and system of salt-containing organic wastewater after the recycling of PCB waste water copper |
| CN108911421A (en) * | 2018-08-17 | 2018-11-30 | 深圳市东森环境技术有限公司 | Tin-stripping wastewater integrated sewage disposal technique and system |
| CN109111048A (en) * | 2018-09-28 | 2019-01-01 | 章嘉华 | A kind of processing system of commercial metal waste water |
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| CN111233218A (en) * | 2020-01-16 | 2020-06-05 | 深圳市蓝清环境科技工程有限公司 | Catalytic FENTON wastewater treatment process |
| CN112759187A (en) * | 2020-12-28 | 2021-05-07 | 昆山至卓环保科技有限公司 | Method for treating industrial wastewater of electronic circuit board |
| CN113061730A (en) * | 2021-03-23 | 2021-07-02 | 北京佰利格瑞资源科技有限公司 | Method for removing iron in waste ternary lithium battery recovery process |
| CN113262786A (en) * | 2021-06-09 | 2021-08-17 | 广东工业大学 | Heterogeneous nano copper catalyst and preparation method and application thereof |
| CN113603309A (en) * | 2021-09-07 | 2021-11-05 | 安徽泉盛化工有限公司 | Treatment method of gas-making circulating wastewater |
| CN113603309B (en) * | 2021-09-07 | 2022-12-27 | 安徽泉盛化工有限公司 | Treatment method of gas-making circulating wastewater |
| CN114195288A (en) * | 2021-12-10 | 2022-03-18 | 中新联科环境科技(安徽)有限公司 | Method for purifying comprehensive nickel wastewater and copper-containing wastewater |
| CN115043548A (en) * | 2022-05-27 | 2022-09-13 | 常州大学 | Coal chemical wastewater integration processing apparatus |
| CN115043548B (en) * | 2022-05-27 | 2023-06-23 | 常州大学 | Integrated treatment device for coal chemical wastewater |
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