CN105906154B - A kind of method of the recycling treatment recycling of board wastewater - Google Patents
A kind of method of the recycling treatment recycling of board wastewater Download PDFInfo
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- CN105906154B CN105906154B CN201610412345.7A CN201610412345A CN105906154B CN 105906154 B CN105906154 B CN 105906154B CN 201610412345 A CN201610412345 A CN 201610412345A CN 105906154 B CN105906154 B CN 105906154B
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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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- 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
- C02F1/46—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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- 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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- 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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- C02F2101/00—Nature of the contaminant
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- C02F2101/105—Phosphorus compounds
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- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C02F2101/10—Inorganic compounds
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- C02F2101/30—Organic compounds
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- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C02F3/00—Biological treatment of water, waste water, or sewage
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- C02F3/302—Nitrification and denitrification treatment
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/308—Biological phosphorus removal
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Abstract
本发明涉及一种线路板废水的资源化处理回收的方法，包括以下步骤：(1)破络除铜：调节线路板废水pH＝2～4，再投入装有铁碳填料的破络除铜反应器中，曝气反应，调节反应器出水pH＝8～9，加入絮凝剂，搅拌混凝反应，固液分离；(2)破氰除镍：调节步骤(1)得到的上清液pH＝2～4，再投入装有铁碳填料的破氰除镍反应器中，曝气反应，调节反应器出水pH＝8～9，加入絮凝剂，搅拌混凝反应，固液分离；(3)滤料生物滤池处理：将步骤(2)得到的上清液加入到装有脱氮除磷滤料的滤料生化处理系统中，脱氮除磷，即得到最终出水。与现有技术相比，本发明流程简单，紧凑、稳定高效，运行成本低，适用于重金属浓度较高的废水特别是线路板废水处理，具有较高推广应用价值等。
The invention relates to a method for recycling circuit board waste water, comprising the following steps: (1) decoupling and removing copper: adjusting the pH of the circuit board waste water to be 2-4, and then putting into the decoupling and copper removal equipped with iron-carbon fillers In the reactor, the aeration reaction is carried out, the pH of the effluent of the reactor is adjusted to be 8-9, the flocculant is added, the coagulation reaction is stirred, and the solid-liquid separation is performed; (2) cyanide breaking and nickel removal: adjusting the pH of the supernatant liquid obtained in step (1) = 2 to 4, then put into a cyanide-breaking and nickel-removing reactor equipped with iron-carbon fillers, aeration reaction, adjust the pH of the effluent from the reactor = 8-9, add a flocculant, stir and coagulate reaction, and separate solid-liquid; (3 ) filter material biological filter tank treatment: the supernatant obtained in step (2) is added to the filter material biochemical treatment system equipped with denitrification and phosphorus removal filter material, and the final effluent is obtained by denitrification and phosphorus removal. Compared with the prior art, the invention has the advantages of simple process, compactness, stability and high efficiency, low operation cost, suitable for the treatment of wastewater with high heavy metal concentration, especially circuit board wastewater, and has high popularization and application value.
Description
Technical field
The present invention relates to advanced treatment of industrial waste water field is belonged to, nickel coupling is removed more particularly, to a kind of contact break copper removal, broken cyanide
The method for closing the recycling treatment recycling of two-stage Novel filter material biofilter process circuit plate waste water, the especially weight such as processing cupro-nickel
The method of the recycling treatment recycling of the higher board wastewater of tenor.
Background technique
Printed wiring board (PCB) waste water is that largely waste water and organic waste containing heavy metal are generated during printed wiring board
Water, contaminated wastewater species are more, complicated component, processing difficulty is big, processing cost is high.In the printed circuit board technological process of production
In, contain copper ion in the waste water of the processes such as nog plate, weak burn into electro-coppering discharge；In the processes discharge such as erosion plate, electroless copper plating
Contain copper ion and complexing agent EDTA and sodium potassium tartrate tetrahydrate etc. in waste water；Contain nickel ion in the waste water of nickel plating process discharge；
Complexing agent easily forms chelate with heavy metals such as copper under certain condition, and conventional wastewater treatment method is difficult to remove.State at present
Interior overwhelming majority printed wiring board enterprise carries out contact break processing using vulcanized sodium or heavy metal chelating agent, but contains in waste water big
Amount complexing agent is difficult to effectively be abolished, and copper complex stability is stronger, and conventional coagulation neutralization precipitation is difficult to remove complex state copper,
So that water outlet tends not to qualified discharge.The even multistage materializing strategy of two-stage three-level is taken for contact break effect is undesirable, in this way
Way caused by the result is that operating cost is higher, complex operation, conductivity of waste water is increased to rear after multistage materializing strategy
Continuous biochemical treatment is unfavorable, and biochemical effects are very poor, eventually leads to water outlet and is unable to stably reaching standard.It is useless containing plurality of heavy metal ion
Water not only causes serious water body soil pollution, brings drinking water safety problem and ecological environment problem, while containing an a large amount of huge sum of moneys
The direct discharging of waste water of category is also a kind of wasting of resources.How to effectively remove board wastewater pollutant load and endangers biggish
The heavy metal ion such as cupro-nickel recycle the heavy metal of waste water, and water outlet heavy metal concentration and the discharge of other pollutant stably reaching standards are places
Manage the difficult point of board wastewater.
Catalyzed internal electrocatalysis method, also known as micro-electrolysis method, basic principle be using in iron filings iron and carbon in electrolyte solution
Countless small primary batteries are constituted, complicated redox reaction occurs.The method is based on the cell reaction in electrochemistry, reaction process
In be mainly concerned with a variety of effects collaboration completions such as redox, electricity enrichment, physical absorption and flocculating setting.In acid medium and
Under aerobic conditions, nascent state [H] and Fe that Inner electrolysis generates2+Redox reaction can occur with substances many in waste water, thus
Destroy complexing agent structure, the ability for making it lose or reduce complex copper, synkaingenesis at ferrous hydroxide have well
Flocculation-adsorption activity can adsorb small suspended matter and colloidality substance in waste water, further remove Pollutants in Wastewater.
In addition iron can replace the copper of waste water intermediate ion state, the copper in waste water is replaced into elemental copper, Inner electrolysis is excellent to heavy metal
Removal effect can reduce toxic action of the waste water to microorganism, improve biochemical efficiency.Microelectrolysis process generation nascent state [H],
O2、·OH、Fe2+And Fe3+Complicated redox reaction occurs for the polluter in isoreactivity substance and waste water, will be in waste water
Larger molecular organics difficult to degrade are converted into degradable small-molecule substance, improve the biodegradability of waste water.At catalyzed internal electrocatalysis
The characteristics of reason, the method are frequently utilized for the pretreatment stage of waste water, and with the further research to this method, catalyzed internal electrocatalysis method is made
The advantages of method cannot be fully achieved for a kind of single technology.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of board wastewaters
The method of recycling treatment recycling.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of method of the recycling treatment recycling of board wastewater, comprising the following steps:
(1) contact break copper removal
Adjusting circuit plate wastewater pH=2~4, then put into the contact break copper-stripping reaction device equipped with iron carbon filler, aeration reaction,
It adjusts reactor and is discharged pH=8~9, flocculant is added, stir coagulating, staticly settle, be separated by solid-liquid separation, the first supernatant of upper layer
Liquid enters to be handled in next step, lower sediment recycling；
(2) broken cyanide removes nickel
The first supernatant pH=2~4 that regulating step (1) obtains, then the broken cyanide equipped with iron carbon filler is put into except nickel reactant
In device, aeration reaction adjusts reactor and is discharged pH=8~9, flocculant is added, stir coagulating, is separated by solid-liquid separation, upper layer the
Two supernatants enter to be handled in next step, lower sediment recycling；
(3) filtrate biofilter is handled
The second supernatant that step (2) obtains is added in the filtrate biochemical treatment system equipped with denitrogenation dephosphorizing filtrate,
Denitrogenation dephosphorizing processing is carried out to get final outflow water is arrived.
Contact break copper-stripping reaction device and broken cyanide are except the additive amount of the iron carbon filler in nickel reactant device is based on reactor dischargeable capacity
For 0.05~0.15kg/L.Iron carbon filler is preferably iron carbon Pall ring filler.
The iron carbon filler is made by the following method: weighing by the iron filings after acid-wash activation, Powdered Activated Carbon and dilute
The filler body of earth metal powder constituent adds zinc powder and titanium dioxide, and compression moulding is calcined in the case where completely cutting off air environment,
Quenching, obtains iron 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 the zinc powder is the 0.05~0.2% of iron carbon filler total weight；
The dosage of the titanium dioxide is the 0.008~0.015% of iron carbon filler total weight.
The process conditions of calcining are that 90~100min is calcined at 1050~1200 DEG C.
Flocculant described in step (1) and step (2) is Flokal B polyacrylamide, dosage 0.3
~0.8mg/L waste water.
The condition of step (1) and the aeration reaction in step (2) are as follows: oxygen in water concentration is in aeration control reactor
2.5~4mg/L, reactor residence time are 0.5~1.5h；
Stir the process conditions of coagulating are as follows: under the revolving speed of 60~100rpm, react 5~20min.
The filtrate biochemical treatment system is composed in series by two filter tanks of anaerobic biofilter and biological aerated filter, and two
Filtrate stacking volume in a filter tank shares equally the 30~50% of the total dischargeable capacity in respective filter tank, the water of the anaerobic biofilter
The power residence time is 2~4h, and the hydraulic detention time of biological aerated filter is 5~7h.
The denitrogenation dephosphorizing filtrate is made by the following method:
The ingredient being uniformly mixed so as to obtain by comminuted steel shot, iron powder, zeolite powder, active carbon and cement is weighed, side is sprayed water into hollow float
While spilling into ingredient, the filtrate ball of package ingredient is obtained, maintenance obtains denitrogenation dephosphorizing filtrate.
Comminuted steel shot, iron powder, zeolite powder, active carbon and cement mass ratio be (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.
Two-stage catalyzed internal electrocatalysis reactor is respectively set in technique front end in the present invention, and effect is respectively contact break copper removal and broken cyanide
Except nickel, into biochemical system before the heavy metals almost all such as Cu in waste water nickel be transferred in sludge, to Heavy Metals in Sludge
Resource utilization is carried out, while reducing toxic action of the heavy metal in waste water to microorganism, improves subsequent biochemical treatment effeciency,
In addition Inner electrolysis reactor is to CODCr, ammonia nitrogen also have certain removal effect；Biochemical system is anti-using anaerobism+biological aerated filter
Device is answered, built-in novel synchronous denitrogenation dephosphorizing filtrate all has excellent removal effect to total nitrogen, total phosphorus: in anaerobic biofilter
Filtrate to denitrifying microorganism have invigoration effect, strengthened denitrification effect, in low ratio of carbon to ammonium can also with efficient denitrification,
Denitrification consumes carbon source for organic matter removal in waste water simultaneously；Since organic matter most in waste water is by Inner electrolysis reactor
It is removed with anaerobic biofilter, the content of organics into aerobic biofilter is very low, and low organic concentration environment promotees
Into the growth of nitrifier, ammonia nitrogen is converted into nitrate nitrogen, while part COD in aerobic biofilterCrAlso it is removed；It is novel
Filtrate biofilter mainly passes through biological induced chemical precipitating to the removal of phosphorus and realizes, when environment has free H+When filtrate analyse
Free iron and phosphate reaction, which generate, out precipitates, and is removed with the biological form membrane to fall off, biological and chemical synergistic effect is realized
Efficient dephosphorization.Total copper=0.05 of final outflow water~0.10mg/L after treatment by using the treatment method, 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, effluent quality
GB 18918-2002 " urban wastewater treatment firm pollutant emission standard " level-one emission standard A can be stably reached.
To restore based on copper removal in " contact break copper removal " reactor, while there is a small amount of removal to act in nickel.This is because copper category
Zero-valent Iron in inert metal, Inner electrolysis filler, which can be restored copper ion by metathesis, generates elemental copper, in addition oxygen
Change the higher copper of reduction potential and preferentially participate in electrochemical reaction, then removes copper by flocculation adsorption co-precipitation, " contact break
Copper removal " is discharged total copper concentration up to level-one emission standard A；Nickel belongs to compared with active metal, before movable metallic table comes iron, zero
Valence iron does not react, and the removal of this part of nickel relies primarily on the iron hydroxide flocculation adsorption that nascent state iron ion hydrolyzes and goes
It removes, level-one emission standard A cannot be reached by being discharged total nickel concentration, therefore is discharged into " broken cyanide removes nickel " reactor and is further removed nickel.
" broken cyanide removes nickel " reactor water inlet content of copper ion is very low, although can also remove part copper ion at this time, by micro-
In the effects of electrolysis, redox and flocculation adsorption removal waste water based on nickel ion, reactor is discharged total nickel concentration and arranges up to level-one A
Put standard.
In conclusion " contact break copper removal " and " broken cyanide removes nickel " reactor carry out copper, nickel removal effect simultaneously, but by
Removing heavy metals are different, also difference causes Inner electrolysis reactor preferentially to remove copper removal to cutting mechanisms in going, when copper ion is reduced to centainly
Beginning and nickel reactant after degree." contact break copper removal " has a small amount of removal based on contact break copper removal, to nickel；" broken cyanide removes nickel " is removed with broken cyanide
Based on nickel, a small amount of removal effect is also had to copper；Final outflow water can guarantee cupro-nickel ion and can achieve level-one A discharge mark
It is quasi-.
Compared with prior art, the invention has the following advantages that
(1) the entire processing system of the present invention removes nickel reactant device and two-stage biofilter structure by contact break copper-stripping reaction device, broken cyanide
At, first based on catalyzed internal electrocatalysis, contact break copper removal and broken cyanide are carried out except nickel is handled to the Heavy Metals ion in waste water,
Heavy metal is transferred to progress resource utilization utilization in sludge, while avoiding inhibition of the heavy metal ion to subsequent biochemical system
Effect, in addition Inner electrolysis processing can convert macromolecular substances difficult to degrade in board wastewater to degradable small of microorganism
Molecular substance improves biodegradability, while to CODCr, ammonia nitrogen also have certain removal effect, then utilize two-stage novel synchronous
Denitrogenation dephosphorizing filtrate biofilter carries out efficiently removal organic matter and synchronous denitrification dephosphorizing effect, guarantees that final outflow water can be stablized
It is up to standard, have process simple, compact, stability and high efficiency, operating cost is low, is suitable for the higher waste water of heavy metal concentration especially line
Road plate wastewater treatment, has the advantages that higher popularization and application.
(2) contact break copper removal and broken cyanide of the present invention are except nickel is using iron carbon Pall ring filler, to line based on internal electrolysis principle
Road plate waste water is handled, and catalyzed internal electrocatalysis method has electrochemical reaction, redox, absorption, electrocoagulation and flocculation etc. simultaneously
Synergistic effect effectively destroys the complexing agent in board wastewater, the heavy metal ion such as Cu in waste water nickel is transferred in sludge real
Existing resource recycling, while weakening toxic action of the heavy metal ion to microorganism significantly, it is difficult in waste water in addition to can change
The structure and form of degradation of organic substances convert macromolecular substances difficult to degrade to degradable small-molecule substance, improve waste water
Biodegradability.
(4) the novel synchronous denitrogenation dephosphorizing filtrate that two-stage biofilter of the present invention adds can be imitated with strengthening biological carbon and phosphorous removal
Fruit, free tapping and phosphate reaction realize that biochemistry coordinates dephosphorization function to filtrate in acid condition, while iron is to micro- life
The activity of object has certain facilitation, overcomes microorganism denitrification effect difference and simultaneous denitrification under the conditions of low ratio of carbon to ammonium and removes
Contradiction between phosphorus, effluent quality can be with stably reaching standards.
(5) catalyzed internal electrocatalysis of the present invention also serves as the pretreatment unit of biochemical system, improves wastewater biodegradability, improves life
Change system shock resistance meets ability, and overcoming conventional method and adding a large amount of contact break medicaments causes waste water salinity is excessively high to cause biochemical place
The undesirable defect of effect is managed, keeps whole system operation more stable, stable effluent quality is excellent, can stably reach GB
18918-2002 " urban wastewater treatment firm pollutant emission standard " level-one emission standard A.
Detailed description of the invention
Fig. 1 is flow diagram of the invention.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
It is derived 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), as shown in Figure 1
Process handled.
It is derived from certain circuit board plant comprehensive pool wastewater pH=3~4 firstly, adjusting, is pumped into contact break copper-stripping reaction device with metering pump,
Pall ring filler is added by reactor dischargeable capacity 0.1kg/L in reactor, reactor bottom is equipped with aerator and is aerated, and controls
Oxygen in water concentration processed 2.5~4.0mg/L, residence time 1h；
The sodium hydroxide solution for being added 10% to the water outlet of contact break copper-stripping reaction device adjusts pH=8~9, then adds commercially available yin
Ionic flocculant polyacrylamide (PAM), the dosage of PAM are 0.5mg/L, stir (revolving speed 80r/ after coagulating 10min
Min), 30min is staticly settled, separation of solid and liquid obtains supernatant, measures total copper=0.10 of supernatant~0.15mg/L；
The supernatant obtained to above-mentioned steps is added sulfuric acid and adjusts pH=3~4, is pumped into broken cyanide with metering pump and removes nickel reactant
Device, reactor is interior to add Pall ring filler by reactor dischargeable capacity 0.1kg/L, and reactor bottom is equipped with aerator and is exposed
Gas controls 2.5~4mg/L of oxygen in water concentration, residence time 1h；
To broken cyanide except the sodium hydroxide solution that the water outlet of nickel reactant device is added 10% adjusts pH=8~9, commercially available yin is then added
The dosage of ionic flocculant PAM, PAM are 0.5mg/L, are stirred after coagulating 10min (revolving speed 80r/min), and it is heavy to stand
Shallow lake 30min, separation of solid and liquid obtain supernatant, measure total nickel=0.01 of supernatant~0.02mg/L；
It is pumped into two-stage Novel filter material biofilter biochemical treatment system with the supernatant that metering pump obtains above-mentioned steps, it should
System is in series by anaerobic biofilter and biological aerated filter, and novel synchronous denitrogenation dephosphorizing filtrate is added inside filter tank, filter
Material stacking volume accounts for about the 30%~50% of the total dischargeable capacity in filter tank, when anaerobic biofilter and biological aerated filter hydraulic retention
Between be respectively 3h and 6h, biological aerated filter nitrification liquid is back to anaerobic biofilter, reflux ratio 200%, after measured, finally
It is discharged total copper=0.05~0.10mg/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, effluent quality can stably reach GB 18918-2002
" urban wastewater treatment firm pollutant emission standard " level-one emission standard A；
Total copper=180 of comprehensive wastewater~200mg/L, the total copper of the supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction=
Copper about 1400kg can be recycled in 0.10~0.15mg/L, factory's comprehensive wastewater about 7000t/d daily；Total nickel=0.9~1.5mg/L,
Total nickel=0.01 of supernatant~0.02mg/L that coagulating sedimentation obtains after broken cyanide is except nickel reactant, can be recycled nickel about 10kg daily,
Resource recycling value with higher.
Embodiment 2
It is derived 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), as shown in Figure 1
Process handled.
It is derived from certain circuit board plant comprehensive pool wastewater pH=3~4 firstly, adjusting, is pumped into contact break copper-stripping reaction device with metering pump,
Pall ring filler is added by reactor dischargeable capacity 0.05kg/L in reactor, reactor bottom is equipped with aerator and is aerated,
Control 2.5~4.0mg/L of oxygen in water concentration, residence time 1.5h；
The sodium hydroxide solution for being added 10% to the water outlet of contact break copper-stripping reaction device adjusts pH=8~9, then adds commercially available yin
Ionic flocculant polyacrylamide (PAM), the dosage of PAM are 0.8mg/L, stir (revolving speed 60r/ after coagulating 20min
Min), 30min is staticly settled, separation of solid and liquid obtains supernatant, measures total copper=0.10 of supernatant~0.15mg/L；
The supernatant obtained to above-mentioned steps is added sulfuric acid and adjusts pH=3~4, is pumped into broken cyanide with metering pump and removes nickel reactant
Device, reactor is interior to add Pall ring filler by reactor dischargeable capacity 0.15kg/L, and reactor bottom is equipped with aerator and is exposed
Gas controls 2.5~4mg/L of oxygen in water concentration, residence time 0.5h；
To broken cyanide except the sodium hydroxide solution that the water outlet of nickel reactant device is added 10% adjusts pH=8~9, commercially available yin is then added
The dosage of ionic flocculant PAM, PAM are 0.3mg/L, are stirred after coagulating 15min (revolving speed 80r/min), and it is heavy to stand
Shallow lake 30min, separation of solid and liquid obtain supernatant, measure total nickel=0.01 of supernatant~0.02mg/L；
It is pumped into two-stage Novel filter material biofilter biochemical treatment system with the supernatant that metering pump obtains above-mentioned steps, it should
System is in series by anaerobic biofilter and biological aerated filter, and novel synchronous denitrogenation dephosphorizing filtrate is added inside filter tank, filter
Material stacking volume accounts for about the 30%~50% of the total dischargeable capacity in filter tank, when anaerobic biofilter and biological aerated filter hydraulic retention
Between be respectively 4h and 7h, biological aerated filter nitrification liquid is back to anaerobic biofilter, reflux ratio 200%, after measured, finally
It is discharged total copper=0.05~0.10mg/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, effluent quality can stably reach GB 18918-2002
" urban wastewater treatment firm pollutant emission standard " level-one emission standard A；
Total copper=180 of comprehensive wastewater~200mg/L, the total copper of the supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction=
Copper about 1450kg can be recycled in 0.10~0.15mg/L, factory's comprehensive wastewater about 7000t/d daily；Total nickel=0.9~1.5mg/L,
Total nickel=0.01 of supernatant~0.02mg/L that coagulating sedimentation obtains after broken cyanide is except nickel reactant, can be recycled nickel about 12kg daily,
Resource recycling value with higher.
In above-mentioned processing method:
Iron carbon filler is prepared by the following method: being activated with the hydrochloric acid solution pickling iron filings that mass percent is 5%
30min, by iron filings: Powdered Activated Carbon: rare earth metal powder=85%:14.95%:0.05% mass percent measures, and is added
Zinc powder, as catalyst, raw material mixing is placed in Pall ring shape, with powder pressure as binder and titanium dioxide
Blank is taken out in the compression moulding at 200kN of power machine, demoulding, and blank isolation air is taken out after 100min under the conditions of 1050 DEG C and is quenched
Iron carbon Pall ring filler is made in fire；Wherein zinc powder and titanium dioxide dosage are respectively 0.1% He of iron carbon filler total weight
0.01%.
Denitrogenation dephosphorizing filtrate, the preparation method comprises the following steps: being first crushed steel slag, iron filings, zeolite, then according to mass percent
Measure comminuted steel shot: iron powder: zeolite powder: active carbon: cement=45%:10%:20%:10%:15% is uniformly mixed so as to obtain ingredient；It is wrapping
It is sprinkled into the plastic hollow floating ball that diameter is 10mm in clothing machine, is sprinkled into ingredient in water spray, the filtrate wrapped；It will wrap
Filtrate be put in natural curing room, 15 DEG C~25 DEG C of temperature and relative humidity conserve 7~10 days under the conditions of being 40%~60%, i.e.,
Nitrogen and phosphorus removal bio filter is prepared.
Embodiment 3
It is derived 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), as shown in Figure 1
Process handled.
It is derived from certain circuit board plant comprehensive pool wastewater pH=3~4 firstly, adjusting, is pumped into contact break copper-stripping reaction device with metering pump,
Pall ring filler is added by reactor dischargeable capacity 0.15kg/L in reactor, reactor bottom is equipped with aerator and is aerated,
Control 2.5~4.0mg/L of oxygen in water concentration, residence time 0.5h；
The sodium hydroxide solution for being added 10% to the water outlet of contact break copper-stripping reaction device adjusts pH=8~9, then adds commercially available yin
Ionic flocculant polyacrylamide (PAM), the dosage of PAM are 0.3mg/L, and (revolving speed is after stirring coagulating 10min
100r/min), 30min is staticly settled, separation of solid and liquid obtains supernatant, measures total copper=0.10 of supernatant~0.15mg/L；
The supernatant obtained to above-mentioned steps is added sulfuric acid and adjusts pH=3~4, is pumped into broken cyanide with metering pump and removes nickel reactant
Device, reactor is interior to add Pall ring filler by reactor dischargeable capacity 0.15kg/L, and reactor bottom is equipped with aerator and is exposed
Gas controls 2.5~4mg/L of oxygen in water concentration, residence time 0.5h；
To broken cyanide except the sodium hydroxide solution that the water outlet of nickel reactant device is added 10% adjusts pH=8~9, commercially available yin is then added
The dosage of ionic flocculant PAM, PAM are 0.3mg/L, are stirred after coagulating 15min (revolving speed 100r/min), and it is heavy to stand
Shallow lake 30min, separation of solid and liquid obtain supernatant, measure total nickel=0.01 of supernatant~0.02mg/L；
It is pumped into two-stage Novel filter material biofilter biochemical treatment system with the supernatant that metering pump obtains above-mentioned steps, it should
System is in series by anaerobic biofilter and biological aerated filter, and novel synchronous denitrogenation dephosphorizing filtrate is added inside filter tank, filter
Material stacking volume accounts for about the 30%~50% of the total dischargeable capacity in filter tank, when anaerobic biofilter and biological aerated filter hydraulic retention
Between be respectively 2h and 5h, biological aerated filter nitrification liquid is back to anaerobic biofilter, reflux ratio 200%, after measured, finally
It is discharged total copper=0.05~0.10mg/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, effluent quality can stably reach GB 18918-2002
" urban wastewater treatment firm pollutant emission standard " level-one emission standard A；
Total copper=180 of comprehensive wastewater~200mg/L, the total copper of the supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction=
Copper about 1450kg can be recycled in 0.10~0.15mg/L, factory's comprehensive wastewater about 7000t/d daily；Total nickel=0.9~1.5mg/L,
Total nickel=0.01 of supernatant~0.02mg/L that coagulating sedimentation obtains after broken cyanide is except nickel reactant, can be recycled nickel about 12kg daily,
Resource recycling value with higher.
In above-mentioned processing method:
Iron carbon filler is prepared by the following method: being activated with the hydrochloric acid solution pickling iron filings that mass percent is 5%
30min, by iron filings: Powdered Activated Carbon: rare earth metal powder=88%:11%:1% mass percent measures, and zinc powder is added and makees
It is binder and titanium dioxide as catalyst, raw material mixing is placed in Pall ring shape, is existed with powder press
Blank is taken out in compression moulding under 200kN, demoulding, and blank isolation air is taken out after 90min under the conditions of 1200 DEG C and is quenched, is made
Iron carbon Pall ring filler；Wherein zinc powder and titanium dioxide dosage are respectively the 0.2% and 0.008% of iron carbon filler total weight.
Denitrogenation dephosphorizing filtrate, the preparation method comprises the following steps: being first crushed steel slag, iron filings, zeolite, then according to mass percent
Measure comminuted steel shot: iron powder: zeolite powder: active carbon: cement=40%:12%:25%:11%:16% is uniformly mixed so as to obtain ingredient；It is wrapping
It is sprinkled into the plastic hollow floating ball that diameter is 10mm in clothing machine, is sprinkled into ingredient in water spray, the filtrate wrapped；It will wrap
Filtrate be put in natural curing room, 15 DEG C of temperature and relative humidity conserve 10 days under the conditions of being 60%, that is, denitrogenation is prepared and removes
Phosphorus filter material for biological filter.
Embodiment 4
It is derived 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), as shown in Figure 1
Process handled.
It is derived from certain circuit board plant comprehensive pool wastewater pH=3~4 firstly, adjusting, is pumped into contact break copper-stripping reaction device with metering pump,
Pall ring filler is added by reactor dischargeable capacity 0.05kg/L in reactor, reactor bottom is equipped with aerator and is aerated,
Control 2.5~4.0mg/L of oxygen in water concentration, residence time 1.5h；
The sodium hydroxide solution for being added 10% to the water outlet of contact break copper-stripping reaction device adjusts pH=8~9, then adds commercially available yin
Ionic flocculant polyacrylamide (PAM), the dosage of PAM are 0.8mg/L, stir (revolving speed 60r/ after coagulating 5min
Min), 30min is staticly settled, separation of solid and liquid obtains supernatant, measures total copper=0.10 of supernatant~0.15mg/L；
The supernatant obtained to above-mentioned steps is added sulfuric acid and adjusts pH=3~4, is pumped into broken cyanide with metering pump and removes nickel reactant
Device, reactor is interior to add Pall ring filler by reactor dischargeable capacity 0.05kg/L, and reactor bottom is equipped with aerator and is exposed
Gas controls 2.5~4mg/L of oxygen in water concentration, residence time 1.5h；
To broken cyanide except the sodium hydroxide solution that the water outlet of nickel reactant device is added 10% adjusts pH=8~9, commercially available yin is then added
The dosage of ionic flocculant PAM, PAM are 0.8mg/L, stir after coagulating 5min (revolving speed 60r/min), staticly settle
30min, separation of solid and liquid obtain supernatant, measure total nickel=0.01 of supernatant~0.02mg/L；
It is pumped into two-stage Novel filter material biofilter biochemical treatment system with the supernatant that metering pump obtains above-mentioned steps, it should
System is in series by anaerobic biofilter and biological aerated filter, and novel synchronous denitrogenation dephosphorizing filtrate is added inside filter tank, filter
Material stacking volume accounts for about the 45% of the total dischargeable capacity in filter tank, and anaerobic biofilter and biological aerated filter hydraulic detention time are distinguished
For 3h and 5h, biological aerated filter nitrification liquid is back to anaerobic biofilter, and reflux ratio 200%, after measured, final outflow water is total
Copper=0.05~0.10mg/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, effluent quality can stably reach GB 18918-2002, and " cities and towns are dirty
Water treatment plant's pollutant emission standard " level-one emission standard A；
Total copper=180 of comprehensive wastewater~200mg/L, the total copper of the supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction=
Copper about 1450kg can be recycled in 0.10~0.15mg/L, factory's comprehensive wastewater about 7000t/d daily；Total nickel=0.9~1.5mg/L,
Total nickel=0.01 of supernatant~0.02mg/L that coagulating sedimentation obtains after broken cyanide is except nickel reactant, can be recycled nickel about 12kg daily,
Resource recycling value with higher.
In above-mentioned processing method:
Iron carbon filler is prepared by the following method: being activated with the hydrochloric acid solution pickling iron filings that mass percent is 5%
30min, by iron filings: Powdered Activated Carbon: rare earth metal powder=80%:18%:2% mass percent measures, and zinc powder is added and makees
It is binder and titanium dioxide as catalyst, raw material mixing is placed in Pall ring shape, is existed with powder press
Blank is taken out in compression moulding under 200kN, demoulding, and blank isolation air is taken out after 90min under the conditions of 1200 DEG C and is quenched, is made
Iron carbon Pall ring filler；Wherein zinc powder and titanium dioxide dosage are respectively the 0.05% and 0.008% of iron carbon filler total weight.
Denitrogenation dephosphorizing filtrate, the preparation method comprises the following steps: being first crushed steel slag, iron filings, zeolite, then according to mass percent
Measure comminuted steel shot: iron powder: zeolite powder: active carbon: cement=50%:8%:18%:12%:12% is uniformly mixed so as to obtain ingredient；It is being coated
It is sprinkled into the plastic hollow floating ball that diameter is 10mm in machine, is sprinkled into ingredient in water spray, the filtrate wrapped；By what is wrapped
Filtrate is put in natural curing room, and 25 DEG C of temperature and relative humidity conserve 7 days under the conditions of being 40%, that is, it is raw that denitrogenation dephosphorizing is prepared
Object filter.
Embodiment 5
It is derived 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), as shown in Figure 1
Process handled.
It is derived from certain circuit board plant comprehensive pool wastewater pH=3~4 firstly, adjusting, is pumped into contact break copper-stripping reaction device with metering pump,
Pall ring filler is added by reactor dischargeable capacity 0.12kg/L in reactor, reactor bottom is equipped with aerator and is aerated,
Control 2.5~4.0mg/L of oxygen in water concentration, residence time 0.8h；
The sodium hydroxide solution for being added 10% to the water outlet of contact break copper-stripping reaction device adjusts pH=8~9, then adds commercially available yin
Ionic flocculant polyacrylamide (PAM), the dosage of PAM are 0.6mg/L, stir (revolving speed 80r/ after coagulating 12min
Min), 30min is staticly settled, separation of solid and liquid obtains supernatant, measures total copper=0.10 of supernatant~0.15mg/L；
The supernatant obtained to above-mentioned steps is added sulfuric acid and adjusts pH=3~4, is pumped into broken cyanide with metering pump and removes nickel reactant
Device, reactor is interior to add Pall ring filler by reactor dischargeable capacity 0.12kg/L, and reactor bottom is equipped with aerator and is exposed
Gas controls 2.5~4mg/L of oxygen in water concentration, residence time 0.8h；
To broken cyanide except the sodium hydroxide solution that the water outlet of nickel reactant device is added 10% adjusts pH=8~9, commercially available yin is then added
The dosage of ionic flocculant PAM, PAM are 0.6mg/L, are stirred after coagulating 12min (revolving speed 80r/min), and it is heavy to stand
Shallow lake 30min, separation of solid and liquid obtain supernatant, measure total nickel=0.01 of supernatant~0.02mg/L；
It is pumped into two-stage Novel filter material biofilter biochemical treatment system with the supernatant that metering pump obtains above-mentioned steps, it should
System is in series by anaerobic biofilter and biological aerated filter, and novel synchronous denitrogenation dephosphorizing filtrate is added inside filter tank, filter
Material stacking volume accounts for about the 50% of the total dischargeable capacity in filter tank, and anaerobic biofilter and biological aerated filter hydraulic detention time are distinguished
For 3h and 5h, biological aerated filter nitrification liquid is back to anaerobic biofilter, and reflux ratio 200%, after measured, final outflow water is total
Copper=0.05~0.10mg/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, effluent quality can stably reach GB 18918-2002, and " cities and towns are dirty
Water treatment plant's pollutant emission standard " level-one emission standard A；
Total copper=180 of comprehensive wastewater~200mg/L, the total copper of the supernatant that coagulating sedimentation obtains after contact break copper-stripping reaction=
Copper about 1450kg can be recycled in 0.10~0.15mg/L, factory's comprehensive wastewater about 7000t/d daily；Total nickel=0.9~1.5mg/L,
Total nickel=0.01 of supernatant~0.02mg/L that coagulating sedimentation obtains after broken cyanide is except nickel reactant, can be recycled nickel about 12kg daily,
Resource recycling value with higher.
In above-mentioned processing method:
Iron carbon filler is prepared by the following method: being activated with the hydrochloric acid solution pickling iron filings that mass percent is 5%
30min, by iron filings: Powdered Activated Carbon: rare earth metal powder=84%:15.99%:0.01% mass percent measures, and is added
Zinc powder, as catalyst, raw material mixing is placed in Pall ring shape, with powder pressure as binder and titanium dioxide
Blank is taken out in the compression moulding at 200kN of power machine, demoulding, and blank isolation air is taken out after 95min under the conditions of 1100 DEG C and is quenched
Iron carbon Pall ring filler is made in fire；Wherein zinc powder and titanium dioxide dosage are respectively 0.18% He of iron carbon filler total weight
0.015%.
Denitrogenation dephosphorizing filtrate, the preparation method comprises the following steps: being first crushed steel slag, iron filings, zeolite, then according to mass percent
Measure comminuted steel shot: iron powder: zeolite powder: active carbon: cement=46%:10%:20%:10%:14% is uniformly mixed so as to obtain ingredient；It is wrapping
It is sprinkled into the plastic hollow floating ball that diameter is 10mm in clothing machine, is sprinkled into ingredient in water spray, the filtrate wrapped；It will wrap
Filtrate be put in natural curing room, 20 DEG C of temperature and relative humidity conserve 8 days under the conditions of being 50%, that is, denitrogenation dephosphorizing is prepared
Filter material for biological filter.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (6)
1. the method that a kind of recycling treatment of board wastewater recycles, which comprises the following steps:
(1) contact break copper removal
Adjusting circuit plate wastewater pH=2~4, then put into the contact break copper-stripping reaction device equipped with iron carbon filler, aeration reaction, it adjusts
Reactor be discharged pH=8~9, be added flocculant, stir coagulating, staticly settle, be separated by solid-liquid separation, the first supernatant of upper layer into
Enter and handles in next step, lower sediment recycling；
(2) broken cyanide removes nickel
The first supernatant pH=2~4 that regulating step (1) obtains, then put into the broken cyanide equipped with iron carbon filler and remove in nickel reactant device,
Aeration reaction adjusts reactor and is discharged pH=8~9, flocculant is added, stir coagulating, is separated by solid-liquid separation, the second supernatant of upper layer
Liquid enters to be handled in next step, lower sediment recycling；
(3) filtrate biofilter is handled
The second supernatant that step (2) obtains is added in the filtrate biochemical treatment system equipped with denitrogenation dephosphorizing filtrate, is carried out
Denitrogenation dephosphorizing handles to arrive final outflow water；
The additive amount that contact break copper-stripping reaction device and broken cyanide remove the iron carbon filler in nickel reactant device is calculated as by reactor dischargeable capacity
0.05~0.15kg/L；
The iron carbon filler is made by the following method: weighing by the iron filings after acid-wash activation, Powdered Activated Carbon and rare earth gold
The filler body for belonging to powder constituent, adds zinc powder and titanium dioxide, and compression moulding is calcined in the case where completely cutting off air environment, quenching,
Obtain iron 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 the zinc powder is the 0.05~0.2% of iron carbon filler total weight；
The dosage of the titanium dioxide is the 0.008~0.015% of iron carbon filler total weight；
The condition of step (1) and the aeration reaction in step (2) are as follows: oxygen in water concentration is 2.5 in aeration control reactor
~4mg/L, reactor residence time are 0.5~1.5h；
Stir the process conditions of coagulating are as follows: under the revolving speed of 60~100rpm, react 5~20min.
2. the method that a kind of recycling treatment of board wastewater according to claim 1 recycles, which is characterized in that calcining
Process conditions be at 1050~1200 DEG C calcine 90~100min.
3. the method that a kind of recycling treatment of board wastewater according to claim 1 recycles, which is characterized in that step
(1) and flocculant described in step (2) is Flokal B polyacrylamide, and dosage is useless for 0.3~0.8mg/L
Water.
4. the method that a kind of recycling treatment of board wastewater according to claim 1 recycles, which is characterized in that described
Filtrate biochemical treatment system be composed in series by two filter tanks of anaerobic biofilter and biological aerated filter, the filter in two filter tanks
Material stacking volume shares equally the 30~50% of the total dischargeable capacity in respective filter tank, and the hydraulic detention time of the anaerobic biofilter is
2~4h, the hydraulic detention time of biological aerated filter are 5~7h.
5. the method that a kind of recycling treatment of board wastewater according to claim 1 recycles, which is characterized in that described
Denitrogenation dephosphorizing filtrate be made by the following method:
The ingredient being uniformly mixed so as to obtain by comminuted steel shot, iron powder, zeolite powder, active carbon and cement is weighed, is dissipated into hollow float in water spray
Enter ingredient, obtain the filtrate ball of package ingredient, maintenance obtains denitrogenation dephosphorizing filtrate.
6. the method that a kind of recycling treatment of board wastewater according to claim 5 recycles, which is characterized in that steel
Powder, iron powder, zeolite powder, active carbon and cement mass ratio be (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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| CN108409003B (en) * | 2018-04-04 | 2020-11-13 | 深圳市深投环保科技有限公司 | Treatment method and system for salt-containing organic wastewater after PCB wastewater copper recovery |
| 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 |
| CN113262786B (en) * | 2021-06-09 | 2022-08-19 | 广东工业大学 | Heterogeneous nano copper catalyst and preparation method and application thereof |
| 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 |
| CN114195288B (en) * | 2021-12-10 | 2023-08-04 | 中新联科环境科技(安徽)有限公司 | Method for purifying comprehensive nickel-containing wastewater and copper-containing wastewater |
| CN115043548B (en) * | 2022-05-27 | 2023-06-23 | 常州大学 | An integrated treatment device for coal chemical wastewater |
| CN115353226B (en) * | 2022-08-23 | 2024-09-24 | 湖南皓志科技股份有限公司 | Rapid collecting and processing technology for invalid rare earth polishing solution |
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