CN107235601A - A kind of integrated electroplating treatment method for waste water, processing system and application - Google Patents

A kind of integrated electroplating treatment method for waste water, processing system and application Download PDF

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CN107235601A
CN107235601A CN201710446987.3A CN201710446987A CN107235601A CN 107235601 A CN107235601 A CN 107235601A CN 201710446987 A CN201710446987 A CN 201710446987A CN 107235601 A CN107235601 A CN 107235601A
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water
reverse osmosis
membrane
stage reverse
concentration
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CN107235601B (en
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韩全
张恒
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Guangdong Shangchen Environmental Technology Co ltd
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Guangdong Yeanovo Environmental Protection Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/05Conductivity or salinity
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/08Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/10Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/28Anaerobic digestion processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/341Consortia of bacteria
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/347Use of yeasts or fungi
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124Water desalination
    • Y02A20/131Reverse-osmosis

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention provides a kind of integrated electroplating treatment method for waste water, it is characterised in that the processing method sequentially includes:(1) integrative electroplating waste is pre-processed, obtains pretreated water;(2) pretreated water for obtaining step (1) carries out biochemical treatment, obtains biochemical treatment water;(3) the biochemical treatment water for obtaining step (2) carries out concentration, obtains concentration high salt concentrated water and recycle-water;(4) the concentration high salt concentrated water that step (3) is obtained is evaporated crystallization treatment, obtains recycle-water and crystal;Wherein recycle water standard is:PH 68, electrical conductivity≤50, COD≤30, turbidity≤1;This method is simple to operate, stable, with low cost, treatment effeciency is high, so that the zero-emission or low emission of plating production integrative electroplating waste are reached, while realizing the recovery of higher degree to each metal ion in waste water.

Description

A kind of integrated electroplating treatment method for waste water, processing system and application
Technical field
The present invention relates to a kind of processing method of waste water and processing system, and in particular to a kind of processing of integrative electroplating waste Method and its processing system.
Background technology
Integrative electroplating waste processing is in handling process often using chemical precipitation method, electrolysis, conventional ion exchange process etc. Processing method.But above-mentioned processing method has some limitations and can not accomplish zero-emission.
Chemical precipitation method is the method that present processing integrative electroplating waste is commonly used, and this method needs to add substantial amounts of acid Alkali, while need to add ferrous sulfate, aluminium polychloride, so that the saliferous rate of water discharge is added, and the metal remained in water The discharge of ion is still difficult to reach standard.Therefore, because controlled substance content is extremely low as defined in wastewater discharge standard, row is reached The standard of putting is needed to put into the chemicals of excess, and cost is high, and waste water can not be reclaimed as process water and used.In addition, chemical Sedimentation can not directly be reclaimed to the metal ion in waste water, while will also produce in substantial amounts of sludge, sludge containing big Metal ion is measured, sludge need to be handled again, cause secondary pollution.
The handling process of electrolysis is ripe, stable, but because controlled substance content as defined in discharge standard is extremely low, so Processing method power consumption in electrolysis wastewater is larger, and processing cost is high, and is also easy to produce toxic gas, it is difficult to which processing is arrived up to standard Discharge.
Conventional ion exchange process uses organic backbone ion exchange resin, can effectively remove in waste water it is various be harmful to from Son, while water can be with reuse, but the resin demand required for the processing method is big, and regenerated liquid processing is difficult, need to consume a large amount of Soda acid, processing cost is high;And resin is in regenerative process, because regeneration, the contraction of generation of resin cause tree with expansion A large amount of ruptures of fat, economy is not high.Reverse osmosis membrane concentration electroplating wastewater is such as used, while pure water reuse, but the work Skill is only applied to the waste water system processing of single high valence ion, so using there is its limitation.
As can be seen that there are problems in the various processing methods currently for integrative electroplating waste, even if to each electricity The existing equipment of plating factory makes full use of the largely or entirely reuse for being still unable to reach waste water, and to valuable in waste water Value metal can not be effectively separated and reclaim.
The content of the invention
It is an object of the invention to overcome produced problem in the prior art and defect, there is provided a kind of simple to operate, operation The high integrated electroplating treatment method for waste water of stable, with low cost, treatment effeciency and corresponding processing system, so as to reach plating life The zero-emission or low emission of integrative electroplating waste are produced, while realizing the recovery of higher degree to each metal ion in waste water, is saved Electroplating industry industrial water amount, substantially reduces pollution of the electroplating industry to environment, reduces the usage amount of soda acid, effectively save can provide Source reduces production cost and realizes the recovery of equipment investment, promotes and promote the cleanly production and sustainable development of electroplating industry Exhibition.
The purpose of the present invention is achieved through the following technical solutions:
The present invention provides a kind of integrated electroplating treatment method for waste water, it is characterised in that the processing method sequentially includes:
(1) integrative electroplating waste is pre-processed, obtains pretreated water;
(2) pretreated water for obtaining step (1) carries out biochemical treatment, obtains biochemical treatment water;
(3) the biochemical treatment water for obtaining step (2) carries out concentration, obtains concentration high salt concentrated water and reuse Water;
(4) the concentration high salt concentrated water that step (3) is obtained is evaporated crystallization treatment, obtains recycle-water and crystallization Thing;
Wherein recycle water standard is:PH 6-8, electrical conductivity≤50, COD≤30, turbidity≤1.
Preferably, in the step (1),
The integrative electroplating waste pH 3-6, it contains zinc, SS and COD;
Preferably, the step of pretreatment is:
Integrative electroplating waste is introduced pH regulating reservoirs by (1-1), and addition sodium hydroxide to pH is 9-12;
Waste water after step (1-1) processing is introduced chemical reaction pond by (1-2), adds coagulant, flocculant is added afterwards, is stirred Mix 20-30min;
Waste water after step (1-2) processing is introduced accurate control High-rate sedimentation system by (1-3);
Preferably, in the step (1-1), it is 10% sodium hydroxide solution regulation pH to add concentration;
Preferably, in the step (1-2), the coagulant is inorganic coagulant, more preferably FeCl3
Preferably, the flocculant is organic flocculant, more preferably PAM;Preferably, the addition coagulant and flocculation Time interval between agent is 20-40min;
Preferably, the wastewater pH handled through step (1-2) is 8-9;
Preferably, in the step (1-3), the accurate control High-rate sedimentation system by water distribution system, precipitation process pond, Inclined tube, effluent weir, sludge bucket are sequentially connected composition;Preferably, the waste water after step (1-2) processing is introduced into the water distribution successively System, precipitation process pond, inclined tube;Supernatant after above-mentioned processing obtains pretreated water into effluent weir, and obtained sludge sinks Enter sludge bucket;Preferably, the pressure in the precipitation process pond is 2-3Mpa.
Preferably, in the step (2), the biochemical treatment step is:The pretreated water that step (1) is obtained enters successively Enter anaerobic pond, Aerobic Pond, membrane bioreactor;
Preferably, anaerobic bacteria is included in the anaerobic pond;Preferably, the anaerobic bacteria is selected from saccharomycete, nitrate bacterium, shuttle One or more in bacillus or bacteroid;
Preferably, the saccharomycete, nitrate bacterium, Fusobacterium or bacteroid make it have salt tolerance through domestication;
Preferably, aerobic microbiological is included in the Aerobic Pond;
Preferably, one or more of the oxygen animalcule in bacillus, rhizobium, nitrifier or mould;
Preferably, the bacillus, rhizobium, nitrifier or mould make it have salt tolerance through domestication;
Preferably, the membrane bioreactor is made up of hollow fiber film assembly and membrane cisterna;Preferably, the doughnut Membrane module is located in the membrane cisterna;
Preferably, the doughnut membrane aperture is 0.01-0.1 μm;
Preferably, pH is 6-8 after the biochemical treatment.
Preferably, in the step (3), the concentration step is:The biochemical treatment water that step (2) is obtained is successively By one-level nanofiltration system, first-stage reverse osmosis system, two-stage reverse osmosis system;
Preferably, the one-level nanofiltration system is sequentially connected and constituted by accurate filter and one-level NF membrane;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the precise microfiltration device is 5 μm;
Preferably, the one-level NF membrane is technical grade equipment with high desalinization NF membrane;
Preferably, the aperture of the one-level NF membrane is 1-2nm;
Preferably, the one-level NF membrane is 50-70% to the rejection of sodium ion;
Preferably, the rejection > 97% of the one-level NF membrane heavy metal ion and salinity;
Preferably, the film pressure of entering of the one-level nanofiltration system is 1.0-1.5Mpa;
Preferably, the relative molecular mass retention scope of the one-level nanofiltration system is 150-300 dalton;
Preferably, the pH of the water of the entrance one-level nanofiltration system is 6-8;
Preferably, the permeate of the one-level nanofiltration system can be used as recycle-water;
Preferably, the concentrate of the one-level nanofiltration system enters first-stage reverse osmosis system.
Preferably, in the step (3), the first-stage reverse osmosis system by accurate filter and first-stage reverse osmosis film successively Connection composition;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the precise microfiltration device is 5 μm;
Preferably, the first-stage reverse osmosis film is bitter reverse osmosis membrane;
Preferably, the rejection > 98% of the first-stage reverse osmosis film heavy metal ion and salinity;
Preferably, the aperture of the first-stage reverse osmosis film is 0.1-1nm;
Preferably, the film pressure of entering of the first-stage reverse osmosis system is 1.8Mpa;
Preferably, the pH of the water of the entrance first-stage reverse osmosis system is 5-6;
Preferably, pH is adjusted by adding hydrochloric acid in the first-stage reverse osmosis system;
Preferably, the salt acid for adjusting pH that concentration is 0.2-0.5% is added;
Preferably, the permeate of the first-stage reverse osmosis system returns to one-level nanofiltration system;
Preferably, the concentrate of the first-stage reverse osmosis system enters two-stage reverse osmosis system.
Preferably, in the step (3), the two-stage reverse osmosis system by accurate filter and two-pass reverse osmosis film successively Connection composition;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the precise microfiltration device is 5 μm;
Preferably, the two-pass reverse osmosis film is seawater reverse osmosis membrane;
Preferably, the rejection > 99.5% of the two-pass reverse osmosis film heavy metal ion and salinity;
Preferably, the aperture of the two-pass reverse osmosis film is 0.1-1nm;
Preferably, the film pressure of entering of the two-stage reverse osmosis system is 4-5Mpa;
Preferably, the pH of the water of the entrance two-stage reverse osmosis system is 6-8;
Preferably, pH is adjusted by adding hydrochloric acid in the two-stage reverse osmosis system;
Preferably, the concentration of the hydrochloric acid is 0.2-0.5%;
Preferably, the permeate of the two-stage reverse osmosis system returns to one-level nanofiltration system;
Preferably, the concentrate of the two-stage reverse osmosis system is the high salt concentrated water.
Preferably, in the step (4), the evaporative crystallization process step is:The high salt concentrated water that step (3) is obtained according to Secondary process heat exchanger, concentration evaporator, crystallizing evaporator;
Preferably, the operation temperature of the heat exchanger is 80-100 DEG C;
Preferably, the operating pressure of the heat exchanger is 0.05-0.1MPa;
Preferably, the concentration evaporator is sequentially connected group by heating chamber, separation chamber, circular chamber, liquid distributor, demister Into;
Preferably, the crystallizing evaporator is sequentially connected and constituted by separation chamber, salt leg, thickener, crystallization kettle;
Preferably, condensed water of the high salt concentrated water after concentration evaporator returns to the two-stage reverse osmosis system;
Preferably, the high salt concentrated water obtains concentrating high salt concentrated water after concentration evaporator;
Preferably, the salt content of the concentration high salt concentrated water is 30-35%;
Preferably, the concentration high salt concentrated water obtains crystal and condensed water after crystallizing evaporator;Preferably, it is described Crystal is sodium sulphate and/or sodium chloride;Preferably, the condensed water is used as recycle-water.
The present invention also provides a kind of processing system of integrated electroplating treatment method for waste water of the present invention, it is characterised in that The system includes pretreatment unit, biochemical treatment unit, concentration unit and the evaporative crystallization processing unit being sequentially communicated.
Preferably, the pH regulating reservoirs, chemical reaction pond, accurate control that the pretreatment unit includes being sequentially communicated are efficiently heavy Shallow lake system;The accurate control High-rate sedimentation system is connected successively by water distribution system, precipitation process pond, inclined tube, effluent weir, sludge bucket Connect composition.
Preferably, the biochemical treatment unit includes anaerobic pond, Aerobic Pond, the membrane bioreactor being sequentially communicated;
Preferably, the membrane bioreactor is made up of hollow fiber film assembly and membrane cisterna;
Preferably, the hollow fiber film assembly is located in the membrane cisterna;
Preferably, the doughnut membrane aperture is 0.01-0.1 μm.
Preferably, the concentration unit include be sequentially communicated one-level nanofiltration system, first-stage reverse osmosis system, two grades Counter-infiltration system.
Preferably, the one-level nanofiltration system is sequentially connected and constituted by accurate filter and one-level NF membrane;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the accurate filter is 5 μm;
The one-level NF membrane is technical grade equipment with high desalinization NF membrane;
Preferably, the aperture of the one-level NF membrane is 1-2nm;
Preferably, the one-level NF membrane is 50-70% to the rejection of sodium ion;
Preferably, the rejection > 97% of the one-level NF membrane heavy metal ion and salinity;
Preferably, the film pressure of entering of the one-level nanofiltration system is 1.0-1.5Mpa;
Preferably, the relative molecular mass retention scope of the one-level nanofiltration system is 150-300 dalton;
Preferably, the pH of the water of the entrance one-level nanofiltration system is 6-8.
Preferably, the first-stage reverse osmosis system is sequentially connected and constituted by accurate filter and first-stage reverse osmosis film;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the accurate filter is 5 μm;
Preferably, the first-stage reverse osmosis film is bitter reverse osmosis membrane;
Preferably, the rejection > 98% of the first-stage reverse osmosis film heavy metal ion and salinity;
Preferably, the aperture of the first-stage reverse osmosis film is 0.1-1nm;
Preferably, the film pressure of entering of the first-stage reverse osmosis system is 1.8Mpa;
Preferably, the pH of the water of the entrance first-stage reverse osmosis system is 5-6;
Preferably, pH is adjusted by adding hydrochloric acid in the first-stage reverse osmosis system;
Preferably, the concentration of the hydrochloric acid is 0.2-0.5%.
Preferably, the two-stage reverse osmosis system is sequentially connected and constituted by accurate filter and two-pass reverse osmosis film;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the accurate filter is 5 μm;
Preferably, the two-pass reverse osmosis film is seawater reverse osmosis membrane;
Preferably, the rejection > 99.5% of the two-pass reverse osmosis film heavy metal ion and salinity;
Preferably, the aperture of the two-pass reverse osmosis film is 0.1-1nm;
Preferably, the film pressure of entering of the two-stage reverse osmosis system is 4-5Mpa;
Preferably, the pH of the water of the entrance two-stage reverse osmosis system is 6-8;
Preferably, pH is adjusted by adding hydrochloric acid in the two-stage reverse osmosis system;
Preferably, the concentration of the hydrochloric acid is 0.2-0.5%.
Preferably, the evaporative crystallization unit includes heat exchanger, concentration evaporator, the crystallizing evaporator being sequentially communicated;
Preferably, the operation temperature of the heat exchanger is 80-100 DEG C;
Preferably, the operating pressure of the heat exchanger is 0.05-0.1MPa;
Preferably, the concentration evaporator is sequentially connected group by heating chamber, separation chamber, circular chamber, liquid distributor, demister Into;
Preferably, the crystallizing evaporator is sequentially connected and constituted by separation chamber, salt leg, thickener, crystallization kettle.
Integrated electroplating treatment method for waste water of the present invention or integrated electroplating treatment method for waste water processing system of the present invention The application united in processing integrative electroplating waste.
The present invention for overcome defect present in the processing of integrative electroplating waste in the prior art there is provided integrative electroplating waste Processing method be:
Integrative electroplating waste pollutant sources analysis of the present invention:Integrative electroplating waste is mainly derived from after zinc-plated process The rinse water that the processes such as plating piece cleaning, filter cleaning, the cleaning of pole plate are produced, it mainly contains the dirts such as zinc ion, SS, COD Contaminate thing.
Integrative electroplating waste pretreating process of the present invention:
The integrative electroplating waste need to consider the influence interacted when pH value control condition and metal ion coexist, and this is comprehensive Close in electroplating wastewater containing the metal ions such as copper, a small amount of nickel, zinc, when adjusting wastewater pH to 9-12, dosing coagulant and wadding Solidifying agent, catches, builds bridge etc. that effect makes copper and the metal ion such as a small amount of nickel, zinc flocculate instead by the net of coagulant and flocculant Should, inorganic precipitation flco is formed, then be separated by accurate control High-rate sedimentation system.
Integrative electroplating waste is introduced into pH regulating reservoirs, addition sodium hydroxide to pH is 9-12;Waste water after processing is introduced Chemical reaction pond, adds coagulant, and flocculant is added afterwards, stirs 20-30min;Waste water after processing is introduced into accurate control high Imitate settling system;The accurate control High-rate sedimentation system by water distribution system, precipitation process pond, inclined tube, effluent weir, sludge bucket according to Secondary connection composition;Waste water after processing is introduced into the water distribution system, precipitation process pond, inclined tube successively;After above-mentioned processing Supernatant obtains pretreated water into effluent weir, and sludge sinks to sludge bucket;Above-mentioned precision controls High-rate sedimentation system to increase Desilting area, the shortening sedimentation time, improves deposition efficiency, by the waterpower water distribution of accurate control High-rate sedimentation system, efficiently sinks The effect such as drop, efficient precipitation flco and SS, while in setting the inclined tube in pond, making jetsam not by doing that current stabilization is influenceed Disturb, reach rapid precipitation effect, the disposal ability of the accurate control High-rate sedimentation system is bigger than general sedimentation basin 3-7 times, The sludge of bottom of pond is discharged into sludge-tank by the static pressure mud discharging device of setting and further concentrated, and is then pumped into sludge filter press press filtration, Mud cake is reprocessed according to property, can remove about 80% suspension, 40-70% oils, and makes delivery turbidity<30NTU, COD Decline 40-60% etc.;
Integrative electroplating waste biochemical processing process of the present invention:Pretreated water is sequentially entered into anaerobic pond, Aerobic Pond, film Bioreactor;By A/O/MBR biodegradation, the material such as most COD, ammonia nitrogen and SS in waste water is removed;This The anaerobic technique is invented under without dissolved oxygen conditions or under anoxia condition, using the effect of anaerobic bacteria, organic matter is occurred water Solution, acidifying, remove the organic matter in waste water, improve the biodegradability of sewage, are conducive to follow-up aerobic treatment process;The present invention The aerobic process is organic matter oxidation Decomposition in the presence of aerobic microbiological under aerobic conditions, and organic concentration declines, Microbial biomass increase, the organic matter in sewage is attracted to activated sludge and biofilm surface first, and with microbial cell table Face is contacted, and the organic matter of small molecule can be directed through cell membrane into microbial body, and larger molecular organicses then must be It is hydrolyzed to after small molecule be taken in cell body by microorganism again in the presence of exoenzyme-hydrolase.Organic matter is finally divided Solution is into CO2And H2O;Membrane bioreactor of the present invention is made up of hollow fiber film assembly and membrane cisterna;Preferably, it is described hollow Fiber film component is located in the membrane cisterna;Membrane module is positioned in membrane cisterna, is aerated in pond, because hollow-fibre membrane is less than Zoogloea and free bacteria, all can be retained in membrane cisterna by 0.1 micron of aperture, so that mud-water separation is reached, it is various outstanding Floating particles, bacterium, algae, turbidity and organic matter are effectively removed, it is ensured that go out aqueous suspension close to zero it is excellent go out Water water quality.The efficient crown_interception of membrane bioreactor, can be smoothed out nitration reaction, effectively with effectively catching nitrifier Remove ammonia nitrogen;The larger molecular organicses for being difficult to degraded can be retained simultaneously, are extended its residence time in biochemical reaction tank, are made Decomposed to greatest extent.
Integrative electroplating waste concentration technique of the present invention:By biochemical treatment water sequentially pass through one-level nanofiltration system, First-stage reverse osmosis system, two-stage reverse osmosis system;The present invention is to realize the zero-emission of zinc-containing water, in biochemical treatment system rear end Concentrating and treating system is set, for handling the strong brine of biochemical treatment system generation;Concentrating and treating system of the present invention is many The technique that level concentration, nanofiltration/reverse osmosis concentration are combined, by the concentration step by step of film, makes the water of high content of salt waste water gradually drop Low (the high salt concentrated water salt content obtained is 40-60g/L) is so as to reduce investment and the running cost of subsequent evaporation crystal system With;The concentration technique to need strong brine to be processed in follow-up evaporation and crystallization system, than conventional concentration system System reduces 80%, makes the cost of investment of whole Waste Water Treatment and reduces 20-30%, the operating cost of wastewater treatment is reduced 30-40%, improves the automaticity of system.
Integrative electroplating waste evaporative crystallization handling process of the present invention:The high salt concentrated water that concentration is obtained is passed through successively Cross heat exchanger, concentration evaporator, crystallizing evaporator;The present invention accomplishes fully recovering after wastewater treatment to evaporative crystallization stage The zero-emission of zinc-containing water;Waste water is introduced into the heat exchanger in the evaporation and crystallization system, by heat exchange, is removed in waste water O2And CO2Gas, the waste water after heat exchange, which enters in concentration evaporator, is evaporated concentration, when waste water salt concentration to 30-35% When produce sodium sulphate and sodium chloride crystallization before, the waste water is delivered into crystallizing evaporator, crystal and condensed water is obtained, it is cold Solidifying water is used as recycle-water.Evaporation and crystallization system of the present invention causes the negative of waste water evaporation section using mechanical temperature raising device Pressure, can save the energy, and the waste steam through overcompression heats supercharging and entered outside the pipe of concentration evaporator, and latent heat is passed to Pipe, itself condenses into condensed water, while the brine waste evaporation in pipe.The characteristics of evaporation and crystallization system of the present invention is Small volume, takes up an area less, energy consumption is low, and the thermal efficiency is high, and the power consumption of general one ton of waste water is 16-20kwh, and its thermal efficiency is that single-action is dodged 27 times of steaming system, are 7 times of quadruple effect flash system, are current state-of-the-art evaporation concentration system, the crystal produced by it Can be through handling or sending relevant departments' purification to utilize, its main component is sodium sulphate and sodium chloride.
The advantage of above-mentioned evaporation and crystallization system is as follows:(1) system makes identical water tonnage device of making using mixed journey feedwater Ton water power consumes more external technique and reduces 40-50%;(2) it is dense by the high salt of concentrating and treating system because the system mixes journey feedwater Water sequentially enters low temperature effect from the high temperature effect of evaporation and crystallization system, and concentration is gradually risen, and temperature is gradually reduced.Avoid external work In skill, imitated from low temperature to being raised caused by high temperature effect make-up cooling water in high temperature effect feed water concentration, be effectively reduced the knot of high temperature effect Dirt and corrosion condition;(3) it is evenly distributed by the high salt concentrated water of concentrating and treating system on concentration evaporator, it is to avoid existing steaming Send out the uneven susceptible to plugging shortcoming of spray nozzle type feedwater in crystal system;(4) vacuum system uses differential pressure air extractor, accurate between each effect Really form design pressure difference so that the system run all right is reliable.
The processing system of integrated electroplating treatment method for waste water of the present invention, using programmable logic controller (PLC), while real Now electric and instrument automatic control and monitoring, using industrial computer, operation process state and operational factor to system are monitored. In addition, the membranous system in the system periodically uses permeate to rinse to rinse the pollutant of film surface, diaphragm;And set up online Chemical cleaning system, it is ensured that system is long-term, stably, Effec-tive Function.
At present, the Technology development in the prior art on integrative electroplating waste has chemical precipitation technology, biological treatment Technology and membrane separation technique, routine techniques essentially according to " qualified discharge " highway route design, with the present invention compared with exist it is following not Foot:
(1) routine techniques system wastewater recycle rate is 60%, wherein, water resource is not recycled fully, after wastewater treatment Discharge adds the load of surrounding enviroment;
(2) microorganism is to the poor resistance of salinity in routine biochemistry treatment technology, and sludge concentration is generally 3000mg/L, this The sludge concentration of inventive technique mesophytization system is 7000-8000mg/L.
(3) heavy metal ion not yet 100% is removed, and environmental pollution is still present;
(4) concentrated water that film concentration systems are produced need to be handled again, otherwise can cause two layers of pollution;
(5) routine techniques reuse water conductivity is 200-300 μ S/cm, the μ S/ of the technology of the present invention reuse water conductivity≤50 cm。
The beneficial effect of integrated electroplating treatment method for waste water of the present invention, processing system:
(1) condition that integrative electroplating waste pretreating process of the present invention reacts according to various heavy metal ion is different, Using online monitoring instruments such as pH, ORP, measuring pump quantitative dosing is automatically controlled, medicament is added and is fully reacted with waste water, and pass through Precision control High-rate sedimentation system carries out separation of solid and liquid processing, and removal of heavy metal ions rate is up to 99.99%.
(2) integrative electroplating waste biochemical process of the present invention uses A/O/MBR techniques, and system is by biochemistry pool, membrane module With membrane cisterna composition, activated sludge can be all retained in membrane cisterna, the various pollutions such as various suspended particulates, bacterium, organic matter The thing residence time is long, so as to be sufficiently removed, it is ensured that effluent quality is excellent, SS is almost nil.This process volume load is high, right Water quality and quantity adaptive faculty is strong, using through taming the extraordinary microorganism with salt tolerant to salt content height and being given up containing difficult degradation COD Water removal efficiency is high, and denitrification effect is good.
(3) integrative electroplating waste concentration technology of the present invention using special membrane concentration technique by the salinity in waste water according to The technology that desalination and concentration and smart desalination and concentration are combined is by more than 30 times of Waste water concentrating, and the production water of advanced treatment system can direct reuse In production.Special membrane concentration technique still with efficient salt rejection rate, with higher mechanical strength and uses the longevity under with high flow rate Life, good, the characteristics of cost performance is high of waving function, chemical stability can be being issued compared with low operating pressure.
(4) integrative electroplating waste evaporative crystallization of the present invention is using the extraordinary both vapor compression technology of Germany, by distillation hydro-thermal Exchanger, concentration evaporator, crystallizer and centrifuge etc. are constituted, when evaporator handles waste water, the heat energy needed for evaporating waste water Release heat energy is provided when steam condenses and condenses water cooling again, and in the process of running, the loss without latent heat realizes waste water Low-temperature negative-pressure evaporates.In compressor compresses, pressure and temperature is lifted, and high enthalpy steam can fully reclaim steaming as thermal source again Distilled water and dope heat, save energy consumption.Evaporated during evaporation using pipe is outer, not only never incrustation in efficiency high and pipe.
Brief description of the drawings
Hereinafter, embodiment of the present invention is described in detail with reference to accompanying drawing, wherein:
Fig. 1 is integrative electroplating waste processing system schematic diagram of the present invention.
Embodiment
Illustrate the present invention referring to specific embodiment.It will be appreciated by those skilled in the art that these embodiments are only For illustrating the present invention, it does not limit the scope of the present invention in any way.
Experimental method in following embodiments, is conventional method unless otherwise specified.Original used in following embodiments Material, reagent material etc., unless otherwise specified, are commercially available products.
First, integrative electroplating waste pollutant sources analysis of the present invention:Integrative electroplating waste is mainly derived from galvanizer The rinse water that the process such as plating piece cleaning, filter cleaning, cleaning of pole plate is produced after sequence, it mainly contains zinc ion, SS, COD Deng pollutant.
2nd, integrative electroplating waste pretreating process of the present invention:Integrative electroplating waste is introduced into pH regulating reservoirs, hydrogen is added Sodium oxide molybdena to pH be 9-12;Waste water after processing is introduced into chemical reaction pond, coagulant is added, flocculant is added afterwards, 20- is stirred 30min;Waste water after processing is introduced into accurate control High-rate sedimentation system;The accurate control High-rate sedimentation system is by with water system System, precipitation process pond, inclined tube, effluent weir, sludge bucket are sequentially connected composition;Waste water after processing is introduced described with water system successively System, precipitation process pond, inclined tube;Supernatant after above-mentioned processing obtains pretreated water into effluent weir, and sludge sinks to sludge bucket; Above-mentioned accurate control High-rate sedimentation system shortens the sedimentation time, improves deposition efficiency to increase desilting area, passes through precision control Waterpower water distribution, high-efficiency sedimentation of High-rate sedimentation system processed etc. are acted on, efficient precipitation flco and SS, while described in setting in pond Inclined tube, the interference for making jetsam not influenceed by current stabilization reaches rapid precipitation effect, the accurate control High-rate sedimentation system Disposal ability is bigger than general sedimentation basin 3-7 times, and the sludge of bottom of pond is discharged into sludge-tank by the static pressure mud discharging device of setting and enters one Step concentration, is then pumped into sludge filter press press filtration, mud cake is reprocessed according to property, can remove about 80% suspension, 40-70% Oils, and make delivery turbidity<30NTU, COD decline 40-60% etc.;
3rd, integrative electroplating waste biochemical processing process of the present invention:Pretreated water is sequentially entered into anaerobic pond, it is aerobic Pond, membrane bioreactor;By A/O/MBR biodegradation, the thing such as most COD, ammonia nitrogen and SS in waste water is removed Matter;Anaerobic technique of the present invention, using the effect of anaerobic bacteria, sends out organic matter under without dissolved oxygen conditions or under anoxia condition Unboiled water solution, acidifying, remove the organic matter in waste water, improve the biodegradability of sewage, are conducive to follow-up aerobic treatment process;This It is organic matter oxidation Decomposition in the presence of aerobic microbiological, organic concentration under aerobic conditions to invent the aerobic process Decline, microbial biomass increase, the organic matter in sewage is attracted to activated sludge and biofilm surface, and and microorganism first Cell surface is contacted, and the organic matter of small molecule can be directed through cell membrane and enter in microbial body, and larger molecular organicses are then It must be hydrolyzed to after small molecule be taken in cell body by microorganism again in the presence of exoenzyme-hydrolase.Organic matter is most CO is broken down into eventually2And H2O;Membrane bioreactor of the present invention is made up of hollow fiber film assembly and membrane cisterna;Preferably, institute Hollow fiber film assembly is stated in the membrane cisterna;Membrane module is positioned in membrane cisterna, is aerated in pond, due to doughnut Film is less than 0.1 micron of aperture, can all be retained in zoogloea and free bacteria in membrane cisterna, so that mud-water separation is reached, Various suspended particulates, bacterium, algae, turbidity and organic matter are effectively removed, it is ensured that go out aqueous suspension close to zero Excellent effluent quality.The efficient crown_interception of membrane bioreactor, can be such that nitration reaction smoothly enters with effectively catching nitrifier OK, ammonia nitrogen is effectively removed;The larger molecular organicses for being difficult to degraded can be retained simultaneously, extend its stop in biochemical reaction tank Time, it is allowed to be decomposed to greatest extent.
4th, integrative electroplating waste concentration technique of the present invention:Biochemical treatment water is sequentially passed through into one-level nanofiltration system System, first-stage reverse osmosis system, two-stage reverse osmosis system;The present invention is to realize the zero-emission of zinc-containing water, in biochemical treatment system Rear end sets concentrating and treating system, for handling the strong brine of biochemical treatment system generation;Concentrating and treating system of the present invention The technique combined for multistage concentration, nanofiltration/reverse osmosis concentration, by the concentration step by step of film, make the water of high content of salt waste water by Gradually reduction (the high salt concentrated water salt content obtained is 40-60g/L) is so as to reduce investment and the fortune of subsequent evaporation crystal system Row expense;The concentration technique to need strong brine to be processed in follow-up evaporation and crystallization system, at conventional concentration Reason system reduces 80%, makes the cost of investment of whole Waste Water Treatment and reduces 20-30%, the operating cost of wastewater treatment 30-40% is reduced, the automaticity of system is improved.
5th, integrative electroplating waste evaporative crystallization handling process of the present invention:The high salt concentrated water that concentration is obtained according to Secondary process heat exchanger, concentration evaporator, crystallizing evaporator;The present invention by fully recovering after wastewater treatment to evaporative crystallization stage, Accomplish the zero-emission of zinc-containing water;Waste water is introduced into the heat exchanger in the evaporation and crystallization system, by heat exchange, is removed useless O in water2And CO2Gas, the waste water after heat exchange, which enters in concentration evaporator, is evaporated concentration, when waste water salt concentration to 30- When 35% before sodium sulphate and sodium chloride crystallization is produced, the waste water is delivered into crystallizing evaporator, crystal and condensation is obtained Water, condensed water is used as recycle-water.Evaporation and crystallization system of the present invention causes waste water evaporation part using mechanical temperature raising device The negative pressure divided, can save the energy, and the waste steam through overcompression heats supercharging and entered outside the pipe of concentration evaporator, latent heat Pipe is passed to, itself condenses into condensed water, while the brine waste evaporation in pipe.Evaporation and crystallization system of the present invention Feature is small volume, is taken up an area less, energy consumption is low, and the thermal efficiency is high, and the power consumption of general one ton of waste water is 16-20kwh, and its thermal efficiency is 27 times of single-action flash system, are 7 times of quadruple effect flash system, are current state-of-the-art evaporation concentration systems, produced by it Crystal can be through handling or sending relevant departments' purification to utilize, and its main component is sodium sulphate and sodium chloride.
The technological process of following examples of the present invention, its basic handling flow is:Electroplating integrated electroplating wastewater → pretreatment Technique → biochemical processing process → entrance anaerobic pond → entrance Aerobic Pond → membrane bioreactor → supercharging → one-level NF membrane point From → supercharging → first-stage reverse osmosis UF membrane → supercharging → two-pass reverse osmosis UF membrane, high salt concentrated water enters evaporative crystallization after separation System;In evaporation and crystallization system, high salt concentrated water handles the condensed water produced by concentration evaporator, can meet workshop recycle-water Water quality requirement.
Embodiment 1
(1) integrative electroplating waste is pre-processed, and obtains pretreated water
Take integrative electroplating waste first, the comprehensive wastewater be mainly derived from after zinc-plated process plating piece cleaning, filter cleaning, The rinse water that the processes such as the cleaning of pole plate are produced, it mainly contains the pollutants such as zinc ion, SS, COD.
Integrative electroplating waste is introduced into pH regulating reservoirs, the sodium hydroxide solution that addition concentration is 10% to pH is 9-12;Will Waste water after processing introduces chemical reaction pond, adds coagulant FeCl3, it is rear to add flocculant PAM, stir 20-30min;Will place Waste water after reason introduces accurate control High-rate sedimentation system;The accurate control High-rate sedimentation system is by water distribution system, place of settling Reason pond, inclined tube, effluent weir, sludge bucket are sequentially connected composition;Waste water after processing is introduced into the water distribution system, place of settling successively Manage pond, inclined tube;Supernatant after above-mentioned processing obtains pretreated water into effluent weir, and sludge sinks to sludge bucket;Above-mentioned precision Control High-rate sedimentation system shortens the sedimentation time to increase desilting area, improves deposition efficiency, efficiently heavy by precision control Waterpower water distribution, high-efficiency sedimentation of shallow lake system etc. are acted on, efficient precipitation flco and SS, while in setting the inclined tube in pond, making The interference that jetsam is not influenceed by current stabilization, reaches rapid precipitation effect, the processing energy of the accurate control High-rate sedimentation system Power is bigger than general sedimentation basin 3-7 times, and the sludge of bottom of pond is discharged into sludge-tank by the static pressure mud discharging device of setting and further concentrated, Sludge filter press press filtration is then pumped into, mud cake is reprocessed according to property, can remove about 80% suspension, 40-70% oils, And make delivery turbidity<30NTU, COD decline 40-60% etc.;
(2) pretreated water is subjected to biochemical treatment, obtains biochemical treatment water
The pretreated water is sequentially entered into anaerobic pond, Aerobic Pond, membrane bioreactor;Wherein, include and detest in anaerobic pond Oxygen bacterium, one or more of the anaerobic bacteria in saccharomycete, nitrate bacterium, Fusobacterium or bacteroid;The saccharomycete, nitre Hydrochlorate bacterium, Fusobacterium or bacteroid make it have salt tolerance through domestication;Aerobic microbiological is included wherein in Aerobic Pond;It is described aerobic The one or more bacillus of the microorganism in bacillus, rhizobium, nitrifier or mould, rhizobium, nitrification Bacterium or mould make it have salt tolerance through domestication;Enter membrane bioreactor afterwards, the membrane bioreactor is by hollow-fibre membrane (aperture of hollow-fibre membrane is 0.01-0.1 μm) component and membrane cisterna composition;Membrane module is positioned in membrane cisterna, is exposed in pond Gas, pH is 6-8 after the biochemical treatment, can remove the material such as most COD, ammonia nitrogen and SS in waste water;It is of the present invention to detest Oxygen technique is under without dissolved oxygen conditions or under anoxia condition, using the effect of anaerobic bacteria, organic matter is occurred hydrolysis, acidifying, goes Except the organic matter in waste water, the biodegradability of sewage is improved, is conducive to follow-up aerobic treatment process;Aerobic work of the present invention Skill is organic matter oxidation Decomposition in the presence of aerobic microbiological under aerobic conditions, and organic concentration declines, and microbial biomass increases Plus, the organic matter in sewage is attracted to activated sludge and biofilm surface first, and is contacted with microbial cell surface, small The organic matter of molecule can be directed through cell membrane into microbial body, and larger molecular organicses then must exoenzyme- It is hydrolyzed to after small molecule be taken in cell body by microorganism again in the presence of hydrolase.Organic matter is finally broken down into CO2With H2O;Membrane bioreactor of the present invention is made up of hollow fiber film assembly and membrane cisterna, and membrane module is positioned in membrane cisterna, Yu Chi It is middle to be aerated, because hollow-fibre membrane is less than 0.1 micron of aperture, zoogloea and free bacteria can be all retained in film Chi Zhong, so as to reach mud-water separation, various suspended particulates, bacterium, algae, turbidity and organic matter are effectively removed, and are protected Aqueous suspension is demonstrate,proved close to zero excellent effluent quality.The efficient crown_interception of membrane bioreactor, can be with effectively catching nitre Change bacterium, be smoothed out nitration reaction, effectively remove ammonia nitrogen;The larger molecular organicses for being difficult to degraded, extension can be retained simultaneously Its residence time in biochemical reaction tank, it is allowed to be decomposed to greatest extent.
(3) the biochemical treatment water is subjected to concentration, obtains high salt concentrated water and recycle-water
Biochemical treatment water is sequentially passed through into one-level nanofiltration system, first-stage reverse osmosis system, two-stage reverse osmosis system;Described one Level nanofiltration system is sequentially connected and constituted by accurate filter and one-level NF membrane, and wherein the filter core of accurate filter is fusion-jet type PP Cotton, the aperture of precise microfiltration device is 5 μm, and the aperture of the one-level NF membrane is 1nm, and pending water passes through one-level NF membrane When, the rejection to sodium ion is 50%, and the rejection of heavy metal ion and salinity is 98%;Afterwards by one-level nanofiltration system System, pH is 6-8, enters film pressure for 1.5Mpa;The relative molecular mass retention scope of the one-level nanofiltration system is 300 dalton; The permeate of the one-level nanofiltration system can be continuing with through ion exchange as recycle-water;
Concentrate of the above-mentioned processing water Jing Guo one-level nanofiltration system enters first-stage reverse osmosis system, the first-stage reverse osmosis system System is sequentially connected composition by accurate filter and first-stage reverse osmosis film (bitter reverse osmosis membrane, aperture is 0.1-1nm), and one-level is anti- The film pressure of entering of osmosis system is 1.8Mpa, and it is 5-6 to adjust pH by 0.2% hydrochloric acid, by the first-stage reverse osmosis film, counterweight The rejection of metal ion and salinity is 99%;Permeate of the above-mentioned processing water Jing Guo first-stage reverse osmosis system returns to one-level nanofiltration System, its concentrate enters two-stage reverse osmosis system.The two-stage reverse osmosis system is by accurate filter and two-pass reverse osmosis film (seawater reverse osmosis membrane, aperture is 0.1-1nm) is sequentially connected composition;The film pressure of entering of two-stage reverse osmosis system is 5Mpa, is passed through 0.2% hydrochloric acid adjustment pH is 6-8, by the two-pass reverse osmosis film, and the rejection of heavy metal ion and salinity is 99.9%; Above-mentioned processing water returns to one-level nanofiltration system by the permeate of two-stage reverse osmosis system, and its concentrate is high salt concentrated water, high salt The salt content of concentrated water is 40g/L.
The present invention is to realize the zero-emission of integrative electroplating waste, and concentrating and treating system is set in biochemical treatment system rear end, For handling the strong brine of biochemical treatment system generation;Concentrating and treating system of the present invention is multistage concentration, nanofiltration/counter-infiltration The technique combined is concentrated, by the concentration step by step of film, making the water of high content of salt waste water gradually reduces (the high salt concentrated water obtained Salt content is 40g/L) so as to reduce investment and the operating cost of subsequent evaporation crystal system;After the concentration technique causes Strong brine to be processed is needed in continuous evaporation and crystallization system, 80% is reduced than conventional concentrating and treating system, makes whole waste water The cost of investment of processing system reduces 30%, and the operating cost of wastewater treatment reduces 40%, makes the automaticity of system Improve.Above-mentioned zinc-containing water concentration technique, carries out pre-concentration through accurate filter and one-level nanofiltration system, is received by one-level The permeate of filter system can be used as recycle-water after ion exchange, and the concentrate of the one-level nanofiltration system is anti-into one-level Osmosis system;The permeate of the first-stage reverse osmosis system returns to one-level nanofiltration system, the concentration of the first-stage reverse osmosis system Liquid enters two-stage reverse osmosis system;The permeate of the two-stage reverse osmosis system returns to one-level nanofiltration system, two grades of reverse osmosis The concentrate of permeable system is the high salt concentrated water.
(4) the high salt concentrated water is evaporated crystallization treatment, obtains recycle-water and crystal
Above-mentioned high salt concentrated water is sequentially passed through into heat exchanger, concentration evaporator, crystallizing evaporator;The operation temperature of the heat exchanger Spend for 80-100 DEG C;The operating pressure of the heat exchanger is 0.05-0.1MPa;The concentration evaporator by heating chamber, separation chamber, Circular chamber, liquid distributor, demister are sequentially connected composition;The crystallizing evaporator by separation chamber, salt leg, thickener, crystallization kettle according to Secondary connection composition;Condensed water of the above-mentioned high salt concentrated water after concentration evaporator returns to above-mentioned two-stage reverse osmosis system;High salt is dense The concentrate that water is obtained after concentration evaporator is concentration high salt concentrated water, and salt content is 40-60g/L;The concentration high salt concentrated water Crystal and condensed water are obtained after crystallizing evaporator;Obtained crystal is sodium sulphate and/or sodium chloride;And condensed water is made Workshop is returned to for recycle-water to be continuing with.
Wherein, the concentration evaporator is made up of the multiple evaporators being serially connected, and (90 DEG C or so) heating of low temperature are steamed Vapour is introduced into the first effect, heats feed liquid therein, feed liquid is produced the almost equivalent evaporation lower than vapor (steam) temperature.The steam of generation The second effect is introduced into as heating steam, makes the feed liquid of the second effect with than the first effect lower temperature evaporation.This process is always Repeat to last effect.The solidifying water of first effect is returned at thermal source, and other each solidifying water of effect are exported after collecting as desalination water, a steaming Vapour is put into, and the water that can evaporate many times comes out.Meanwhile, feed liquid is passed through by the concentration successively of the first effect to most end effect, in most end Effect reaches supersaturation and crystallizes and separate out.It is achieved in the separation of solid and liquid of feed liquid.
The technical parameter of the evaporation and crystallization system processing concentrated water is as follows:
(1) desalination water salt content (TDS) is less than 10ppm
(2) ton desalination water steam consumption quantity=(1/ effect number)/90%t/t
(3) 2~4kwh/t of ton desalination water power consumption
A kind of integrated electroplating treatment method for waste water of the present invention not only improves wastewater recycle rate relative to prior art To 99.67%, while processing cost, the metal ion recycling reduced in solid waste yield and waste water can be greatly reduced, thoroughly Realize the zero-emission of waste water.
Comparative example 1
(1) integrative electroplating waste is taken first, its pH 3-6, it contains zinc, SS and COD;Integrative electroplating waste is introduced into pH Regulating reservoir, adds sodium hydroxide regulation pH, and its reaction time is 20-25min;Waste water is introduced into chemical reaction pond afterwards, added mixed Solidifying agent PAC and flocculant PAM, stirs 25min.Waste water is introduced into settling system again and carries out mud-water separation, sludge enters at sludge Reason system, supernatant enters biochemical system.
(2) pretreated water is sequentially entered into anaerobic pond, Aerobic Pond, biochemical sedimentation basin;Wherein, include and detest in anaerobic pond Aerobic microbiological is included in oxygen bacterium, wherein Aerobic Pond;Enter biochemical sedimentation basin afterwards, the biochemical sedimentation basin is by water distributing area, sludge Area, Disengagement zone and effluent weir composition;Biochemical sedimentation basin water outlet SS is 30mg/L, and COD is 50mg/L, and biochemistry pool water outlet 40% is up to standard Discharge, 60% enters film concentration systems.
(3) water outlet after biochemistry is sequentially passed through into accurate filter, reverse osmosis membrane apparatus;The filter core of wherein accurate filter is PP cottons, the aperture of precise microfiltration device is 5 μm;The film pressure of entering of counter-infiltration system is 1.2-1.6Mpa, is adjusted by hydrochloric acid PH is 5-6, by the reverse osmosis membrane, and the rejection of heavy metal ion and salinity is 99%;The concentrate of reverse osmosis membrane is returned Pretreatment system is handled again, reverse osmosis membrane permeate electrical conductivity 200-300 μ S/cm, accounts for the 60% of total waste water, permeate It is used as reuse Water circulation to production line.
In a word, specific description of embodiments of the present invention is not intended to limit the present invention for the above, and those skilled in the art can be with It is variously modified or is deformed according to the present invention, without departing from the spirit of the present invention, all should belong to right appended by the present invention will The scope asked.

Claims (16)

1. a kind of integrated electroplating treatment method for waste water, it is characterised in that the processing method sequentially includes:
(1) integrative electroplating waste is pre-processed, obtains pretreated water;
(2) pretreated water for obtaining step (1) carries out biochemical treatment, obtains biochemical treatment water;
(3) the biochemical treatment water for obtaining step (2) carries out concentration, obtains concentration high salt concentrated water and recycle-water;
(4) the concentration high salt concentrated water that step (3) is obtained is evaporated crystallization treatment, obtains recycle-water and crystal;
Wherein recycle water standard is:PH 6-8, electrical conductivity≤50, COD≤30, turbidity≤1.
2. processing method according to claim 1, it is characterised in that in the step (1), the integrative electroplating waste pH 3-6, it contains zinc, SS and COD;
Preferably, the step of pretreatment is:
Integrative electroplating waste is introduced pH regulating reservoirs by (1-1), and addition sodium hydroxide to pH is 9-12;
Waste water after step (1-1) processing is introduced chemical reaction pond by (1-2), adds coagulant, flocculant is added afterwards, is stirred 20-30min;
Waste water after step (1-2) processing is introduced accurate control High-rate sedimentation system by (1-3);
Preferably, in the step (1-1), it is 10% sodium hydroxide solution regulation pH to add concentration;
Preferably, in the step (1-2), the coagulant is inorganic coagulant, more preferably FeCl3;Preferably, the wadding Solidifying agent is organic flocculant, more preferably PAM;Preferably, the time interval added between coagulant and flocculant is 20- 40min;
Preferably, the wastewater pH handled through step (1-2) is 8-9;
Preferably, in the step (1-3), the accurate control High-rate sedimentation system is by water distribution system, precipitation process pond, tiltedly Pipe, effluent weir, sludge bucket are sequentially connected composition;Preferably, the waste water after step (1-2) processing is introduced described with water system successively System, precipitation process pond, inclined tube;Supernatant after above-mentioned processing obtains pretreated water into effluent weir, and obtained sludge is sunk to Sludge bucket;Preferably, the pressure in the precipitation process pond is 2-3Mpa.
3. processing method according to claim 1 or 2, it is characterised in that in the step (2), the biochemical treatment step Suddenly it is:The pretreated water that step (1) is obtained sequentially enters anaerobic pond, Aerobic Pond, membrane bioreactor;
Preferably, anaerobic bacteria is included in the anaerobic pond;Preferably, the anaerobic bacteria is selected from saccharomycete, nitrate bacterium, Fusobacterium Or the one or more in bacteroid;
Preferably, the saccharomycete, nitrate bacterium, Fusobacterium or bacteroid make it have salt tolerance through domestication;
Preferably, aerobic microbiological is included in the Aerobic Pond;
Preferably, one or more of the oxygen animalcule in bacillus, rhizobium, nitrifier or mould;
Preferably, the bacillus, rhizobium, nitrifier or mould make it have salt tolerance through domestication;
Preferably, the membrane bioreactor is made up of hollow fiber film assembly and membrane cisterna;Preferably, the hollow-fibre membrane group Part is located in the membrane cisterna;
Preferably, the doughnut membrane aperture is 0.01-0.1 μm;
Preferably, pH is 6-8 after the biochemical treatment.
4. processing method according to any one of claim 1 to 3, it is characterised in that described dense in the step (3) Contracting process step is:The biochemical treatment water that step (2) is obtained sequentially passes through one-level nanofiltration system, first-stage reverse osmosis system, two Level counter-infiltration system;
Preferably, the one-level nanofiltration system is sequentially connected and constituted by accurate filter and one-level NF membrane;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the precise microfiltration device is 5 μm;
Preferably, the one-level NF membrane is technical grade equipment with high desalinization NF membrane;
Preferably, the aperture of the one-level NF membrane is 1-2nm;
Preferably, the one-level NF membrane is 50-70% to the rejection of sodium ion;
Preferably, the rejection > 97% of the one-level NF membrane heavy metal ion and salinity;
Preferably, the film pressure of entering of the one-level nanofiltration system is 1.0-1.5Mpa;
Preferably, the relative molecular mass retention scope of the one-level nanofiltration system is 150-300 dalton;Preferably, it is described PH into the water of one-level nanofiltration system is 6-8;
Preferably, the permeate of the one-level nanofiltration system can be used as recycle-water;
Preferably, the concentrate of the one-level nanofiltration system enters first-stage reverse osmosis system.
5. processing method according to any one of claim 1 to 4, it is characterised in that in the step (3), described one Level counter-infiltration system is sequentially connected and constituted by accurate filter and first-stage reverse osmosis film;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the precise microfiltration device is 5 μm;
Preferably, the first-stage reverse osmosis film is bitter reverse osmosis membrane;
Preferably, the rejection > 98% of the first-stage reverse osmosis film heavy metal ion and salinity;
Preferably, the aperture of the first-stage reverse osmosis film is 0.1-1nm;
Preferably, the film pressure of entering of the first-stage reverse osmosis system is 1.8Mpa;
Preferably, the pH of the water of the entrance first-stage reverse osmosis system is 5-6;
Preferably, pH is adjusted by adding hydrochloric acid in the first-stage reverse osmosis system;
Preferably, the salt acid for adjusting pH that concentration is 0.2-0.5% is added;
Preferably, the permeate of the first-stage reverse osmosis system returns to one-level nanofiltration system;
Preferably, the concentrate of the first-stage reverse osmosis system enters two-stage reverse osmosis system.
6. processing method according to any one of claim 1 to 5, it is characterised in that in the step (3), described two Level counter-infiltration system is sequentially connected and constituted by accurate filter and two-pass reverse osmosis film;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the precise microfiltration device is 5 μm;
Preferably, the two-pass reverse osmosis film is seawater reverse osmosis membrane;
Preferably, the rejection > 99.5% of the two-pass reverse osmosis film heavy metal ion and salinity;
Preferably, the aperture of the two-pass reverse osmosis film is 0.1-1nm;
Preferably, the film pressure of entering of the two-stage reverse osmosis system is 4-5Mpa;
Preferably, the pH of the water of the entrance two-stage reverse osmosis system is 6-8;
Preferably, pH is adjusted by adding hydrochloric acid in the two-stage reverse osmosis system;
Preferably, the concentration of the hydrochloric acid is 0.2-0.5%;
Preferably, the permeate of the two-stage reverse osmosis system returns to one-level nanofiltration system;
Preferably, the concentrate of the two-stage reverse osmosis system is the high salt concentrated water.
7. processing method according to any one of claim 1 to 6, it is characterised in that in the step (4), described to steam Sending out crystallization treatment step is:The high salt concentrated water that step (3) is obtained sequentially passes through heat exchanger, concentration evaporator, crystallizing evaporator;
Preferably, the operation temperature of the heat exchanger is 80-100 DEG C;
Preferably, the operating pressure of the heat exchanger is 0.05-0.1MPa;
Preferably, the concentration evaporator is sequentially connected by heating chamber, separation chamber, circular chamber, liquid distributor, demister and constituted;
Preferably, the crystallizing evaporator is sequentially connected and constituted by separation chamber, salt leg, thickener, crystallization kettle;
Preferably, condensed water of the high salt concentrated water after concentration evaporator returns to the two-stage reverse osmosis system;
Preferably, the high salt concentrated water obtains concentrating high salt concentrated water after concentration evaporator;
Preferably, the salt content of the concentration high salt concentrated water is 30-35%;
Preferably, the concentration high salt concentrated water obtains crystal and condensed water after crystallizing evaporator;Preferably, the crystallization Thing is sodium sulphate and/or sodium chloride;Preferably, the condensed water is used as recycle-water.
8. the processing system of integrated electroplating treatment method for waste water as any one of claim 1 to 7, it is characterised in that institute State pretreatment unit, biochemical treatment unit, concentration unit and evaporative crystallization processing unit that system includes being sequentially communicated.
9. processing system according to claim 8, it is characterised in that the pH that the pretreatment unit includes being sequentially communicated is adjusted Save pond, chemical reaction pond, accurate control High-rate sedimentation system;The accurate control High-rate sedimentation system is by water distribution system, precipitation Processing pond, inclined tube, effluent weir, sludge bucket are sequentially connected composition.
10. processing system according to claim 8 or claim 9, it is characterised in that the biochemical treatment unit includes being sequentially communicated Anaerobic pond, Aerobic Pond, membrane bioreactor;
Preferably, the membrane bioreactor is made up of hollow fiber film assembly and membrane cisterna;
Preferably, the hollow fiber film assembly is located in the membrane cisterna;
Preferably, the doughnut membrane aperture is 0.01-0.1 μm.
11. the processing system according to any one of claim 8 to 10, it is characterised in that the concentration unit bag Include the one-level nanofiltration system being sequentially communicated, first-stage reverse osmosis system, two-stage reverse osmosis system.
12. the processing system according to any one of claim 8 to 11, it is characterised in that the one-level nanofiltration system by Accurate filter and one-level NF membrane are sequentially connected composition;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the accurate filter is 5 μm;
The one-level NF membrane is technical grade equipment with high desalinization NF membrane;
Preferably, the aperture of the one-level NF membrane is 1-2nm;
Preferably, the one-level NF membrane is 50-70% to the rejection of sodium ion;
Preferably, the rejection > 97% of the one-level NF membrane heavy metal ion and salinity;
Preferably, the film pressure of entering of the one-level nanofiltration system is 1.0-1.5Mpa;
Preferably, the relative molecular mass retention scope of the one-level nanofiltration system is 150-300 dalton;
Preferably, the pH of the water of the entrance one-level nanofiltration system is 6-8.
13. the processing system according to any one of claim 8 to 12, it is characterised in that the first-stage reverse osmosis system It is sequentially connected and is constituted by accurate filter and first-stage reverse osmosis film;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the accurate filter is 5 μm;
Preferably, the first-stage reverse osmosis film is bitter reverse osmosis membrane;
Preferably, the rejection > 98% of the first-stage reverse osmosis film heavy metal ion and salinity;
Preferably, the aperture of the first-stage reverse osmosis film is 0.1-1nm;
Preferably, the film pressure of entering of the first-stage reverse osmosis system is 1.8Mpa;
Preferably, the pH of the water of the entrance first-stage reverse osmosis system is 5-6;
Preferably, pH is adjusted by adding hydrochloric acid in the first-stage reverse osmosis system;
Preferably, the concentration of the hydrochloric acid is 0.2-0.5%.
14. the processing system according to any one of claim 8 to 13, it is characterised in that the two-stage reverse osmosis system It is sequentially connected and is constituted by accurate filter and two-pass reverse osmosis film;
Preferably, the filter core of the accurate filter is fusion-jet type PP cottons;
Preferably, the filter core aperture of the accurate filter is 5 μm;
Preferably, the two-pass reverse osmosis film is seawater reverse osmosis membrane;
Preferably, the rejection > 99.5% of the two-pass reverse osmosis film heavy metal ion and salinity;
Preferably, the aperture of the two-pass reverse osmosis film is 0.1-1nm;
Preferably, the film pressure of entering of the two-stage reverse osmosis system is 4-5Mpa;
Preferably, the pH of the water of the entrance two-stage reverse osmosis system is 6-8;
Preferably, pH is adjusted by adding hydrochloric acid in the two-stage reverse osmosis system;
Preferably, the concentration of the hydrochloric acid is 0.2-0.5%.
15. the processing system according to any one of claim 8 to 14, it is characterised in that the evaporative crystallization unit bag Include the heat exchanger being sequentially communicated, concentration evaporator, crystallizing evaporator;
Preferably, the operation temperature of the heat exchanger is 80-100 DEG C;
Preferably, the operating pressure of the heat exchanger is 0.05-0.1MPa;
Preferably, the concentration evaporator is sequentially connected by heating chamber, separation chamber, circular chamber, liquid distributor, demister and constituted;
Preferably, the crystallizing evaporator is sequentially connected and constituted by separation chamber, salt leg, thickener, crystallization kettle.
16. the processing any one of processing method or claim 8 to 15 as any one of claim 1 to 7 Application of the system in processing integrative electroplating waste.
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CN108017230A (en) * 2017-11-27 2018-05-11 广东莞绿环保工程有限公司 A kind of heavy metal waste water treatment system and method
CN108059309A (en) * 2018-01-30 2018-05-22 深圳职业技术学院 A kind of plating method for processing organic wastewater and device
CN108726806A (en) * 2018-06-21 2018-11-02 南通曙光机电工程有限公司 A kind of Integral low-energy high-salt wastewater processing system
CN110386720A (en) * 2019-06-25 2019-10-29 广州安赛化工有限公司 A kind of purifying of plating high-salt wastewater and salt separation system and treatment process
CN110697998A (en) * 2019-11-12 2020-01-17 东江环保股份有限公司 Treatment method of copper oxide production wastewater
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CN112225392A (en) * 2020-09-11 2021-01-15 广东闻扬环境科技有限公司 Treatment method and treatment system for electroplating cleaning wastewater
CN113292193A (en) * 2021-06-08 2021-08-24 苏州融和福天宝环保科技有限责任公司 Method for comprehensively treating electroplating comprehensive wastewater
CN114620889A (en) * 2022-03-07 2022-06-14 李鹏 Electroplating comprehensive wastewater zero-discharge treatment system and process thereof
CN115448549A (en) * 2022-10-20 2022-12-09 倍杰特集团股份有限公司 Zero-emission treatment system and method
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