CN209456248U - Chemical plating waste water processing and reclaiming system - Google Patents

Abstract

The utility model provides a kind of processing of chemical plating waste water and reclaiming system, it is related to environmental project water pollution control and resource circulation utilization technical field, including ozone supply system, Multi-level deflector catalytic ozonation pond, reaction tank, pH on-line monitoring combined control equipment, level-one bag filter, second level accurate filter and membrane bioreactor.The ozone supply system is connected with Multi-level deflector catalytic ozonation bottom of pond portion aerator；The connection of the water inlet of Multi-level deflector catalytic ozonation pond water outlet and reaction tank, the water outlet pipe road in Multi-level deflector catalytic ozonation pond are provided with pH on-line monitoring combined control equipment.Reaction tank is sequentially connected level-one bag filter, second level accurate filter and membrane bioreactor.Chemical plating waste water provided by the utility model processing and reclaiming system, it is ensured that obtain standard water discharge discharge or the reuse after further conventional treatment, occupied area is small, adaptable, can overall-in-one control schema, sludge output is few, and operating cost is low.

Description

Chemical plating waste water processing and reclaiming system

Technical field

The utility model relates to environmental project technical field of water pollution control, more particularly, to a kind of processing of chemical plating waste water And reclaiming system.

Background technique

In recent years, electroplating industry development in China's is swift and violent.But it needs that a large amount of organic or inorganic waste water are discharged in the plating process, In include the difficult heavy metal complex such as nickeliferous, copper, cyanide and strong acid, strong base substance etc., water quality is complicated, and pollution is tight Weight.It is horizontal for Dao Bi enterprise raising environment protection treating, 2012, Guangdong Province environmental protection Room issued document (Guangdong ring (2012) 83 Text), it is desirable that the Pearl River Delta area newly-built, renovating and enlarging project of electroplating industry further executes tightened up discharge standard.Wherein The special emission limit of water pollutant (table 3) of " discharge standard for electroplating pollutants " (GB21900-2008) is to all kinds of discharge indexs Stringent regulation is made.Continue publication " plating pollution discharge standard " (DB44-1597-2015) in June, 2015, On the basis of guaranteeing that emission limit adds tight, specific implementation area and time are adjusted.Even, energy is carried in environment The weak some sensitizing ranges of power, local government propose the super strict demand of plating industrial district wastewater zero discharge.And it is electroplated useless Heavy metal contaminants and biological pollution in water exist simultaneously, to electroplating wastewater processing and its further reuse bring compared with Big challenge.

For electroplating wastewater according to its electroplating technology difference, water outlet can simply be divided into heavy metal wastewater thereby containing ionic state, containing network Close state heavy metal wastewater thereby and other high salt waste water.Wherein, chemical plating waste water, due to the special coupling of chemical plating medicament, So that be coupled into stable complex compound between organic matter and heavy metal ion, cause to be difficult to become existing by general oxidizing One of field waste water difficult to deal with.The molecular weight that chemical plating generates heavy metal complex is big, water quality biochemical oxygen demand (BOD) is low, not easy-to-use The method of physical absorption and biological decomposition is handled.In addition, in this kind of waste water in addition to the nickel for having high-content, also containing a large amount of Complexing agent, stabilizer etc., this is the main source of the pollutants such as COD, BOD and nitrogen, phosphorus.

Currently, chemical plating waste water basic handling thinking is as follows: (1) for the heavy metal in waste water, first with oxidant by portion Divide oxidation operation so that organic group is separated with heavy metal, the heavy metal of free state passes through chemical precipitation again and removes, technique Simply, low in cost.But often there is concentration is low and stability is high heavy metal complex (especially in electroplating wastewater water outlet Nickel) so that water outlet is difficult to stably reaching standard discharge.Pollutant is complexed for low-concentration heavy metal, further treatment technique (hand over by ion Change, electrolysis method, membrane separation technique, absorption method, bioanalysis, advanced oxidation etc.) it is current market and research hotspot, some has been answered For Practical Project, but existing advanced treatment process operating cost is high, and Operation and Maintenance is complicated, easily shows the feelings such as water unstable Condition often performs practically no function.(2) for the biochemical pollutant index in waste water, industrial park is often pre- by each stock waste water sub-prime After processing, it is integrated into and anaerobic/anoxic/aerobic equal biochemical process is then used to be handled together.But often because of waste water itself Biodegradability is poor, and front end heavy-metal residual concentration is high, and pollution toxicity is big, causes the biochemical system operating cost of rear end high and effect It is highly unstable.

Can every heavy metal and biological pollution index ensure continual and steady qualified discharge in electroplating wastewater, be environment The basic demand of protection, while being also the basis that industrial park waste water can further obtain resource circulation utilization and reuse.

Utility model content

The purpose of this utility model is to provide chemical plating waste water processing and reclaiming systems, to solve chemical plating waste water processing It is difficult to up to standard or even reuse, wherein remaining heavy metal complex difficult to degrade directly influences the stability of subsequent biochemical technique again And the technical issues of validity.

The utility model patent provides a kind of processing of chemical plating waste water and reclaiming system includes ozone supply system, multistage folding It is raw to flow catalytic ozonation pond, reaction tank, pH on-line monitoring combined control equipment, level-one bag filter, second level accurate filter and film Object reactor.

Further, the ozone supply system is used for the ozone supply into Multi-level deflector catalytic ozonation pond；Further Ground, ozone in Multi-level deflector catalytic ozonation pond to waste water carry out catalysis oxidation, the waste water after oxidation successively flow into reaction tank, Level-one bag filter, second level accurate filter and membrane bioreactor.

Further, the pH on-line monitoring probe of the pH on-line monitoring combined control equipment is mounted on the Multi-level deflector catalysis The water outlet in pond is ozonized, the signal output line of the pH on-line monitoring probe is connected with electric cabinet, and the output of electric cabinet refers to Feedback signal line is enabled to be connected with ozone supply pipeline air volume regulating valve；The pH value of waste water after being pre-processed by detection oxidation contact break, On-line control ozone supply tolerance, linkage control pretreating effect.

Further, Multi-level deflector catalytic ozonation pond includes at least 1 grade of baffling, 2 reaction zones.

Lower liquid is connected for normal pressure between the reaction zone, and upper gaseous phase separation can pressurize adjusting；The reaction zone Inlet and outlet are all had, and the water inlet is located at the upper end of the reaction zone, the water outlet is located at the reaction The lower end in area, waste water flow upwardly into reaction zone described in next stage by baffling slot from the outflow of the lower end water outlet of the reaction zone Upper end water inlet.

Further, aerator is separately provided in the bottom of the reaction zone in the catalytic ozonation pond；It is smelly Oxygen supply system connects the aeration in the first reaction zone in Multi-level deflector catalytic ozonation pond by ozone supply pipe Device；Tail gas recycle pipe is provided between the adjacent reaction zone, the tail gas recycle pipe is used for will be anti-described in upper level It answers the exhaust collection in area and is passed through in the aerator of reaction zone described in next stage；Tail gas is provided on the tail gas recycle pipe Control valve；Gas pressure reduces step by step between the reaction zone；Each reaction zone is equipped with safety valve and pressure gauge, passes through pressure Pressure in Li Ji observing response area, operating pressure in safe valve regulation reaction zone；There are security personnel to filter in the waste water supply pipe Device；The filtering accuracy of the cartridge filter is 0.5~1.0mm.

Further, the upper end position in Multi-level deflector catalytic ozonation pond is provided with exhaust emission tube, Tail gas decomposer is provided on exhaust emission tube, the tail gas decomposer is for handling evolution ozone.

The reaction zone series of the catalytic ozonation reaction tank is discharged in tail gas according in the last exhaust emission tube Ozone residual quantity flexible setting ensures finally to be discharged as far as possible ozone residual quantity in tail gas and is preferably minimized.

Further, the ozone supply system includes ozone generator, ozone supply pipe, air volume regulating valve and gas stream Meter；The ozone generator is connect with ozone supply pipe, is provided with air volume regulating valve and gas on the ozone supply pipe Flowmeter.

Further, in the reaction zone in Multi-level deflector catalytic ozonation pond, in the upper of the aerator Portion position is separately provided with catalyst fixed bed；It is described it is catalyst fixed bed on be provided with spherical solid catalyst.

Further, the solid catalyst particle partial size is 2~8mm, and bulk density is 1.3~1.8kg/L；It is described to urge Agent fixed bed loading is 30%~60%, and the solid catalyst is described catalyst fixed bed to hold with a thickness of 0.2~0.8m Hold in the palm layer with a thickness of 0.1~0.2m.

Further, the reaction tank is at least arranged between two reaction zones, and the first reaction interval is caught for adding heavy metal For adding dephosphorization agent between collection agent, second reaction zone.Adding of agent and stirring are correspondingly provided in the upper position of reaction interval Equipment；The top of first reaction interval is equipped with water inlet, connects between the lower part and second reaction zone of first reaction interval Logical, the top between the second reaction zone is equipped with water outlet；The water outlet of the reaction tank passes through booster pump and level-one pocket type mistake The water inlet of filter is connected.

Further, the water outlet of the level-one bag filter continue through booster pump and second level accurate filter into The mouth of a river is connected；The water outlet of the second level accurate filter is connected with the water inlet of the membrane bioreactor；Described one The filtration media pore diameters of grade bag hose are 10~50 μm；The filtration media pore diameters of the second level accurate filter are 0.5~3 μm； The level-one bag filter and second level accurate filter are equipped with back purge system.

Further, membrane separation assemblies, including plate membrane, doughnut are set inside the denitrification membrane bioreactor At least one of film, tubular membrane etc., membrane aperture≤0.2 μm of the membrane separation assemblies；On the membrane bioreactor outlet pipe Flowing water Valve, pressure vacuum ga(u)ge and Vacuum suction pump are set；According to actual motion condition, flowing water Valve is automatically closed, opens clear Valve is washed, starts to clean membrane separation assemblies.

Further, the chemical plating waste water includes the heavy metal wastewater thereby of chemical plating production technology discharge, through conventional materialization Still below standard chemical plating waste water after treatment process；Heavy metal in the chemical plating waste water mainly exists in the form of complex state.

Further, after the filtering of further conventional ultrafiltration film, water outlet can be back to for the membrane bioreactor pond water outlet On-site rinses ground, flushes the toilet, rinses vehicle and green irrigation；The membrane bioreactor pond water outlet is through further conventional super After filter, nanofiltration membrane and reverse osmosis treatment, water outlet can be back to electroplating enterprise industrial water.

Chemical plating waste water processing provided by the utility model and reclaiming system occupied area are small, and operation is simple, can integration Control, adaptable, without adjusting pH value repeatedly, sludge output is few, and operating cost is low.Using Multi-level deflector catalytic ozonation skill Art, lower liquid phase connection is normal pressure between each reaction zone, and upper gaseous phase separation can pressurize adjusting.Each reaction zone gas-liquid anisotropic flow has Effect contact, and individually gas chamber is effectively pressurized, and is conducive to improve gas-liquid mass transfer rate and chemical reaction rate to a greater degree；Using Flexible reaction of high order setting, the as far as possible residual ozone in effective use higher level's tail gas, ozone utilization rate, which maximizes, to be improved, discharge Tail gas cleaning.And system uses the mild controllable catalytic ozonation technology of high-efficiency cleaning, by the complex compound macromolecular of high stable state Preliminary exposition is easy unstability complex state small molecule, it is ensured that the small molecule heavy metal complex of generation can be by subsequent heavy metals trapping Agent effectively traps, and creates conditions for direct biological denitrification fast denitrogenation.Height is converted by substances such as phosphorus, nitrogen in waste water simultaneously Positive phosphorus acid ion, the nitrate ion of valence state create conditions for subsequent direct chemical dephosphorization, biological denitrification fast denitrogenation. In addition, anti-nitration reaction need to carry out under the conditions of simultaneous oxygen, and water inlet need to keep specific since denitrifying bacterium is generally chemoheterotrophic bacteria Small molecule carbon source, the quantity of carbon source and quality directly affect the distribution and effect of filler flora.Therefore, the catalysis ozone of front end Change technology can supplement available low molecule carbon source for it, and after step effectively filters, it is simultaneous that end introduces membrane bioreactor progress Oxygen denitrification carries out SS, TP, the COD etc. being filtered to remove in water that effectively degrade in fast denitrogenation, globally for weight in waste water simultaneously The heavy metals such as metal, COD, total phosphorus, total nitrogen, ammonia nitrogen and biological pollution index can make it continually and steadily reach even low The limit value requirement of table 3 in national emission standard, it is ensured that the discharge of pollutant index overall up to standard is established for subsequent Treatment for Reuse Basis.

Detailed description of the invention

It, below will be right in order to illustrate more clearly of specific embodiment of the present invention or technical solution in the prior art Specific embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, it is described below In attached drawing be that some embodiments of the utility model are not paying creativeness for those of ordinary skill in the art Under the premise of labour, it is also possible to obtain other drawings based on these drawings.

Other attached drawings are obtained according to these attached drawings.

Fig. 1 is the structural schematic diagram of chemical plating waste water provided by the embodiment of the utility model processing and reclaiming system；

Fig. 2 is that chemical plating waste water shown in FIG. 1 is handled and the ozone supply system of reclaiming system, pH monitor joint control dress on-line Set the structural schematic diagram with Multi-level deflector catalytic ozonation pond；

Fig. 3 is the structural schematic diagram of the membrane bioreactor of chemical plating waste water shown in FIG. 1 processing and reclaiming system.

Icon: 100- ozone supply system；200- Multi-level deflector catalytic ozonation pond；300- reaction tank；400- electricity Control case；500- membrane bioreactor；600- ozone generator；700- gas flowmeter；800- ozone supply pipe；900- PH on-line monitoring probe；110- aerator；120- is catalyst fixed bed；130- solid catalyst；140- tail gas recycle Pipe；150- safety valve；160- pressure gauge；170- exhaust emission tube；180- tail gas decomposer；190- adding of agent with Mixing plant；The first reaction interval of 210-；Between the second reaction zone 220-；230- level-one bag filter；240- second level essence Close filter；250- membrane separation assemblies；260- Vacuum suction pump；270- flowing water Valve；280- wash-out valve；290- is useless Water supplying pipe；310- cartridge filter；320- pressure vacuum ga(u)ge；330- signal output line；340- feedback signal line； 350- air volume regulating valve；360- first order reaction area；370- second order reaction area；380- third-order reaction area.

Specific embodiment

The technical solution of the utility model is clearly and completely described below in conjunction with attached drawing, it is clear that described Embodiment is the utility model a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, originally Field those of ordinary skill every other embodiment obtained without making creative work belongs to practical Novel protected range.

It is in the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", " perpendicular Directly ", the orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" is to be based on the orientation or positional relationship shown in the drawings, and is only For ease of description the utility model and simplify description, rather than the device or element of indication or suggestion meaning must have it is specific Orientation, be constructed and operated in a specific orientation, therefore should not be understood as limiting the present invention.In addition, term " the One ", " second ", " third " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance.

In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " is pacified Dress ", " connected ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integrally Connection；It can be mechanical connection, be also possible to be electrically connected；Can be directly connected, can also indirectly connected through an intermediary, It can be the connection inside two elements.For the ordinary skill in the art, above-mentioned art can be understood with concrete condition The concrete meaning of language in the present invention.

As shown in Figure 1-Figure 3, a kind of chemical plating waste water processing provided by the utility model and reclaiming system, including ozone Feed system 100, Multi-level deflector catalytic ozonation pond 200, reaction tank 300, pH monitor combined control equipment, level-one bag type filtering on-line Device 230, second level accurate filter 240 and membrane bioreactor 500；

Further, the ozone supply system 100 includes ozone generator 600, ozone supply pipe 800, tolerance adjusting Valve 350 and gas flowmeter 700；The ozone generator 600 of ozone supply system 100 is for generating ozone.Gas flowmeter 700 For calculating the supply amount of observation ozone, air volume regulating valve 350 is for controlling ozone flow.The ozone supply system 100 is used In the ozone supply into Multi-level deflector catalytic ozonation pond 200.

Ozone carries out catalysis oxidation to waste water in Multi-level deflector catalytic ozonation pond 200, and the waste water after oxidation successively flows Enter reaction tank 300, level-one bag filter, second level accurate filter and membrane bioreactor 500；

Multi-level deflector catalytic ozonation pond 200 includes at least 1 grade of baffling, 2 reaction zones；Under between the reaction zone Portion's liquid communication is normal pressure, and upper gaseous phase separates the adjusting that can pressurize.The reaction zone all has inlet and outlet, and institute State the upper end that water inlet is located at the reaction zone, the water outlet is located at the lower end of the reaction zone, and waste water is from the reaction zone The outflow of lower end water outlet flow upwardly into the upper end water inlet of reaction zone described in next stage by baffling slot；

Aerator 110 is separately provided in the bottom of the reaction zone in the catalytic ozonation pond；Ozone supply System 100 connects the exposure in the first reaction zone in Multi-level deflector catalytic ozonation pond 200 by ozone supply pipe 800 Device of air 110；Be provided with tail gas recycle pipe 140 between the adjacent reaction zone, the tail gas recycle pipe 140 be used for by The exhaust collection of reaction zone described in level-one is simultaneously passed through in the aerator 110 of reaction zone described in next stage；The tail gas recycle pipe Tail gas control valve is provided on 140；Gas pressure reduces step by step between the reaction zone；Each reaction zone is equipped with safety Valve 150 and pressure gauge 160, by pressure in 160 observing response area of pressure gauge, safety valve 150 adjusts operating pressure in reaction zone； 0.5~1.0mm cartridge filter 310 is arranged in the water inlet in Multi-level deflector catalytic ozonation pond 200.

In some embodiments, the ozone supply system 100 of chemical plating waste water processing and reclaiming system is urged to Multi-level deflector Change ozone supply in ozonisation pond 200；The ozone supply pipe 800 of ozone supply system 100 is catalyzed with setting in Multi-level deflector smelly Aerator 110 in the first order reaction area 360 of oxidation pond 200 connects, and ozone enters reaction zone by aerator 110 It is interior；Aerator 110 is located at the lower end of reaction zone, the small ozone-air bubble come out from the dispersion of aerator 110, by solid After catalyst 130 is catalyzed, reacted rapidly with the polluter in water；The ozone for having not enough time to reaction, by tail gas recycle pipe 140 Collect enter second order reaction area 370 aerator 110 in, be dispersed into waste water again, again with the pollutant in water After catalysis reaction, unreacted ozone continues through the collection of next stage tail gas recycle pipe 140, enters in next reaction zone, Until tail gas enters in the aerator 110 in end reaction area, after sufficiently reacting, collects and set into end reaction area top The exhaust emission tube 170 set is discharged after the tail gas decomposer 180 on exhaust emission tube 170 is handled.

Tail is discharged according in the last exhaust emission tube 170 in the reaction zone series of the catalytic ozonation reaction tank 300 Ozone residual quantity flexible setting in gas ensures finally to be discharged as far as possible ozone residual quantity in tail gas and is preferably minimized.In end Exhaust emission tube 170, tail gas decomposer of the tail gas by the setting on exhaust emission tube 170 are provided on catalysis oxidation pond 180 processing, protect environment.

By tail gas recycle pipe 140, the circulating repetition in Multi-level deflector catalytic ozonation pond 200 utilizes ozone, and described anti- Answering between area lower liquid phase connection is normal pressure, and upper gaseous phase separation can pressurize adjusting, and ozone utilization rate can reach 99% or more, smelly Coefficient of oxygen utilization, which maximizes, to be improved, and cost is greatly saved.

As shown in Fig. 2, further including pH on-line monitoring combined control equipment, institute further based on the above embodiment on basis The pH on-line monitoring probe 900 for stating pH on-line monitoring combined control equipment is mounted on going out for Multi-level deflector catalytic ozonation pond 200 At the mouth of a river, the signal output line 330 of the pH on-line monitoring probe 900 is connected with electric cabinet 400, and the output of electric cabinet 400 refers to Feedback signal line 340 is enabled to be connected with 800 road air volume regulating valve 350 of ozone supply pipe；By giving up after detection oxidation contact break pretreatment The pH value of water, on-line control ozone supply tolerance, linkage control pretreating effect；

The decreasing value of pH and ozone oxidation have it is close contact, the installation that pH monitors combined control equipment on-line can be with real-time detection The variation for the pH being discharged after oxidation judges ozone oxidation effect.In general, the pH of untreated waste water is on 9.0~11.0 left sides The right side, the pH after the pH on-Line Monitor Device detects oxidation then indicate oxidation effectiveness qualification 7.0~8.0 or so, can be direct Subsequent processing is carried out, otherwise, ozone oxidation effect can be reinforced by increasing the modes such as ozone dosage, so that the pH after oxidation In 7.0~8.0 ranges, keep oxidation effectiveness qualified, achievees the purpose that aoxidize contact break.

Based on the above embodiment on basis, further, catalytic ozonation pond is the hollow cube shape of sealing, normally When work, the upper gas section of each reaction zone in catalytic ozonation pond is sealed by respective lower aqueous, and being can independent control Gas pressure section；In order to make the pressure controllable of gas phase in each reaction zone in catalytic ozonation pond, it is arranged on tail gas recycle pipe 140 Safety valve 150 and pressure gauge 160 is separately provided on each reaction zone top in air volume regulating valve 350.It is smelly that source is adjusted by joint Operating pressure in the air demand and supply gas pressure of oxygen supply system 100, independent reaction zone, make in each reaction zone gaseous pressure by Grade is successively decreased.First reaction zone pressure state modulator guarantees that each reaction zone internal oxidition stabilised efficiency is efficient in 0.2~0.3MPa.

Based on the above embodiment on basis, further, each of described Multi-level deflector catalysis ozone reaction tank 300 is anti- It answers and is provided with catalyst fixed bed 120 in area, spherical solid catalyst 130 is provided on described catalyst fixed bed 120；

The solid catalyst 130 is with a thickness of 0.2~0.8m；Catalyst fixed bed 120 supporting layer is with a thickness of 0.1 ~0.2m；Catalyst fixed bed 120 loading is 30%~60%；The solid catalyst 130 is that titanium manganese base binary is urged Agent, major metal oxide effective component be iron oxide, manganese dioxide, titanium dioxide it is one or more；Its percentage composition Respectively 5~15%, 5~10%, 5~10%.130 grain diameter of solid catalyst be 2~8mm, bulk density be 1.3~ 1.8kg/L, loading are 30%~60%.

In some embodiments, the material in Multi-level deflector catalytic ozonation pond 200 is glass reinforced plastic, stainless steel, titanium steel, carbon steel Deng preferably using glass reinforced plastic；Catalyst fixed bed 120 flexibly multistage settings, substantially increase ozone, catalyst and waste water Contact area, reaction rate and oxidation rate.

Based on the above embodiment on basis, further, the reaction tank 300 include be sequentially communicated it is at least first anti- It answers 220 between section 210, second reaction zone, the first reaction interval 210 is for adding 220 between heavy metal chelating agent, second reaction zone For adding dephosphorization agent, the upper position of each reaction interval is separately installed with corresponding adding of agent and mixing plant 190；

The top of first reaction interval 210 is equipped with water inlet, and the lower part of first reaction interval 210 is anti-with second Section 220 is answered to be connected to, 220 top is equipped with water outlet between the second reaction zone.The water outlet of the reaction tank 300 passes through increasing Press pump is connected to the water inlet of level-one bag filter 230.

In some embodiments, the fluid of first reaction interval 210 is flow to from top to bottom 220 between second reaction zone, 220 fluid is flowed out by the water outlet of reaction tank 300 from bottom to top between second reaction zone, and 220 go out between the second reaction zone The mouth of a river is located at the top of reaction tank 300；

The heavy metal chelating agent is DTC class heavy metal chelating agent；

The dephosphorization agent can be with calcium salt, magnesium salts, aluminium salt dephosphorization agent, it is preferable that calcium salt dephosphorization agent selects calcium chloride.

According to the utility model, reaction tank 300 includes between the first reaction interval 210 being sequentially communicated and second reaction zone 220, water (flow) direction flows from top to down in 300 first reaction interval 210 of reaction tank, then between second reaction zone 220 again under Up baffling, finally 220 tops are discharged between second reaction zone.Further, 300 first reaction interval 210 of reaction tank adds Heavy metal chelating agent, 300 first reaction interval of reaction tank, 210 top is equipped with water inlet, into 300 first reaction interval of reaction tank 210 water is flow to from top to bottom 220 between 300 second reaction zone of reaction tank, in the type of flow of the upper entering and lower leaving from density current In, heavy metal chelating agent is more abundant with metal ion-chelant；220 add dephosphorization agent between 300 second reaction zone of reaction tank；Reaction tank 220 tops are discharged between 300 second reaction zone, are flowed out from bottom to top by the water outlet of reaction tank 300；The reaction tank 300 adds Sequence, the mode of fluid flowing of medicament help to stablize to be precipitated at more reliable complex compound with metal ion-chelant not dissolving Heavy metal chelate and phosphate substances.

At least there are two section of connecting, the installation of each section top of reaction tank 300 corresponds to the reaction tank 300 of the utility model The adding of agent and mixing plant of specification；The top water outlet of reaction tank 300 passes through booster pump and level-one bag filter 230 Water inlet connection.

The heavy metal chelating agent of the utility model is a kind of heavy metal for containing sulfydryl (dithiocar-bamate) functional group Trapping agent, the Long carbon chain DTC (dithiocar-bamate) class heavy metal chelating agent have stronger sequestering power, with small point Sub- complex state heavy metal ion carries out contraposition competition chelatropic reaction, has to the complex copper in cupric, nickel waste water, complexing nickel good Stable removal effect.

It should be noted that the utility model for the specific type of DTC class heavy metal chelating agent and included at Divide grade not do specifically limited, each DTC class heavy metal chelating agent well-known to those skilled in the art can be used.

Based on the above embodiment on basis, further, the water outlet of the level-one bag filter 230 is continued through Booster pump is connected with the water inlet of second level accurate filter 240；The water outlet and the film of the second level accurate filter 240 The water inlet of bioreactor 500 is connected.The filtration media pore diameters of the level-one bag hose are 10~50 μm；The second level essence The filtration media pore diameters of close filter 240 are 0.5~3 μm.The level-one bag filter 230 and second level accurate filter 240 It is equipped with back purge system.

According to the utility model, the small heavy metal precipitate and calcium phosphate precipitation after reaction together with liquid, convey into Enter in two-stage filter.Bag hose (10~50 μm), accurate filter (0.5~3 μm) double-filtration are set.Equipment backwash week Phase further extends, and reduces head loss.Heavy metal is effectively removed in supernatant, and total copper content stabilization in water outlet is lower than 0.3mg/L, total nickel content, which is stablized, is lower than 0.1mg/L.This method occupied area is small, and inflow-rate of water turbine is big, and processing speed is fast, without extra Chemical agent adds, and sludge output substantially reduces, and for subsequent bio strengthened denitrification reaction removal heavy metal toxicity, provides preferable water Matter.

After secondary filtration, the supernatant flowed out from accurate filter is flowed into membrane bioreactor 500；

As shown in figure 3, further, being arranged inside the membrane bioreactor 500 on basis based on the above embodiment Membrane separation assemblies 250, the membrane separation assemblies 250 include at least one of plate membrane, hollow-fibre membrane, tubular membrane etc., described Membrane aperture≤0.2 μm of membrane separation assemblies 250.

Preferably, flowing water Valve 270, pressure vacuum ga(u)ge 320 and vacuum are set on 500 outlet pipe of membrane bioreactor Suction pump 260, the membrane separation assemblies 250 work negative pressure as 0~-20kPa；When water outlet pressure vacuum ga(u)ge 320 shows the film When 250 operating pressure of separation assembly is lower than -25kPa, flowing water Valve 270 is closed, opens wash-out valve, starts membrane separation assemblies 250 cleanings.

After the removal of useless Organic substance in water is by multistage catalytic ozonisation pretreatment, by the heavy metal of high stable state While the preparatory preliminary exposition of complex compound macromolecular is easy unstability complex state small molecule, the substances such as phosphorus, nitrogen in waste water are converted Positive phosphorus acid ion, nitrate ion for high-valence state, it is fast for subsequent heavy metals trapping removal, chemical dephosphorization, biological denitrification Fast denitrogenation creates conditions.In addition, the organic matter of macromolecular is oxidized to the organic matter of small molecule low carbon chain in waste water, it is subsequent straight It connects biological denitrification fast denitrogenation and carbon source is provided；Heterotrophic denitrification denitrogenation is carried out in the membrane bioreactor 500, utilizes biology Organic matter in further degrading waste water is acted on, so that it is guaranteed that after by handling above, heavy metal, biological pollution in waste water Index overall up to standard.

In a preferred embodiment, the chemical plating waste water includes that the heavy metal of chemical plating production technology discharge is useless Water, chemical plating waste water still below standard after conventional materializing strategy technique；Heavy metal in the chemical plating waste water is mainly with network State form is closed to exist.

Preferably, in the chemical plating waste water nickel concentration be≤10mg/L, copper concentration be≤20mg/L, COD concentration≤ 300mg/L, total phosphorus concentration≤60mg/L, total nitrogen concentration≤180mg/L, ammonia nitrogen concentration≤40mg/L.

Preferably, after processing, the concentration of nickel is≤0.1mg/L in the water outlet of membrane bioreactor 500, and copper concentration is ≤ 0.3mg/L, COD concentration≤50mg/L, total phosphorus concentration≤1mg/L, total nitrogen concentration≤15mg/L, ammonia nitrogen concentration≤8mg/L.

In a preferred embodiment, the water outlet of membrane bioreactor 500 is after the filtering of further conventional ultrafiltration film, out Water can be back to on-site and rinse ground, flush the toilet, rinse the miscellaneous waters such as vehicle, greening.The water outlet of membrane bioreactor 500 warp After further conventional ultrafiltration, nanofiltration membrane and reverse osmosis treatment, water outlet can be back to electroplating enterprise industrial water.

Chemical plating waste water processing provided by the utility model and reclaiming system occupied area are small, and operation is simple, subtracts as far as possible Few added amount of chemical, can overall-in-one control schema, adaptable, without adjusting pH value repeatedly, sludge output is few, and the processing disposition of sludge takes With substantially reducing, operating cost is low.

This method uses Multi-level deflector catalytic ozonation to pre-process chemical plating waste water first, and step control oxidation is broken High stability, macromolecular heavy metal complex in waste water are decomposed into easy unstability, small molecule heavy metal complex, reached by network process To the purpose for pre-oxidizing just contact break；Some organic pollutants are decomposed in simultaneous oxidation, reduce the TOC and COD of waste water, are subsequent biochemical Reaction member provides low molecule carbon source；The substances such as phosphorus, nitrogen in waste water are completely converted into the positive phosphorus acid ion of high-valence state, nitre Acid ion provides condition for subsequent dephosphorization, denitrification.Then, the heavy metal chelating agent with highly effective chelating group is added, with Heavy metal ion in small molecule heavy metal complex carries out contraposition competition chelatropic reaction.Connect and, add chemical dephosphorization medicament, will Phosphorus in waste water is converted into precipitable state phosphorus-containing compound.Connect and, filtered using step, remove waste water in heavy metal precipitate With calcium phosphate precipitation object.Finally, carrying out simultaneous oxygen denitrification fast denitrogenation using membrane bioreactor 500, while by further UF membrane retention filtering fine particulate material, removes the pollutants such as remaining COD, TOC, TP, TN in waste water, it is ensured that pollution comprehensively The discharge of object index overall up to standard, lays the foundation for further reuse.

Application example 1

Chemical plating waste water (also known as burnt copper waste water) in seven strands of waste water of Dongguan garden electroplating wastewater processing factory, through conventional one After grade dosing precipitation process, the waste water is taken to be tested.

Such as Fig. 1-Fig. 3, waste water flows into Multi-level deflector catalytic ozonation pond 200 by 1.0mm cartridge filter 310 In first order reaction area 360, the ozone generator 600 of ozone supply system 100 generates ozone, is passed through by 800 tunnel of ozone supply pipe Aerator 110 is crossed to be blown into the first order reaction area 360 in Multi-level deflector catalytic ozonation pond 200.

Ozone and waste water anisotropic flow haptoreaction, after solid catalyst 130 further catalysis, by the high stable in waste water The heavy metal complex macromolecular preliminary exposition of state is easy unstability complex state small molecule, and the substances such as phosphorus, nitrogen in waste water is turned Turn to positive phosphorus acid ion, the nitrate ion of high-valence state.

The unreacted risen from water is complete to be collected containing ozone tail gas by tail gas recycle pipe 140, into catalytic ozonation In the second order reaction area 370 in pond, continue to blast in waste water by aerator 110, until ozone is imported by tail gas recycle pipe 140 In the third-order reaction area 380 in catalytic ozonation pond, then from exhaust emission tube 170 through the discharge of tail gas decomposer 180.

3 order reaction areas are arranged in Multi-level deflector catalytic ozonation pond, and thoroughly, the ozone in tail gas maximizes benefit for reaction at this time With.

It is provided with the pressure gauge 160 of observation pressure on catalytic ozonation pond, and prevents pressure in catalytic ozonation pond Excessively high safety valve 150.Air volume regulating valve 350 is set on tail gas recycle pipe 140.

The pH on-line monitoring combined control equipment is provided at the wastewater outlet in Multi-level deflector catalytic ozonation pond 200.To The variation of pH, judges oxidation effectiveness after detection oxidation contact break pretreatment, in time online linkage regulation.

Reaction tank 300 includes 220 between the first reaction interval 210 being sequentially communicated and second reaction zone, being respectively used to add Heavy metal chelating agent and dephosphorization agent, each section top are separately installed with corresponding adding of agent and mixing plant 190；First is anti- The fluid in section 210 is answered to be flow to 220 between second reaction zone from top to bottom, 220 water outlet is located at reaction tank between second reaction zone 300 top；The water outlet of reaction tank 300 is connected to by booster pump with the entrance of level-one bag hose 230.Multi-level deflector catalytic ozonation Catalyst fixed bed 120 loading of each reaction zone is 45% in pond 200.

The water outlet of level-one bag hose 230 continues through booster pump and is connected to the entrance of second level accurate filter 240.The filter of level-one bag The filtration media pore diameters of device and second level accurate filter are respectively 50 μm and 1 μm.

Waste water enters in membrane bioreactor 500 from the water outlet of second level accurate filter 240.Membrane bioreactor Hollow fiber film assembly is used in 500.Waste water carries out heterotrophic denitrification reaction in membrane bioreactor with denitrogenation, and passes through film Separation removes the pollutants such as remaining organic matter, total phosphorus, uses the discharge of water pollutant overall up to standard, establishes base for further reuse Plinth.

A kind of processing of chemical plating waste water and reclaiming system, further comprising the steps of:

Waste water to be processed is filled in Multi-level deflector catalytic ozonation pond 200, is opened 600 air air pump of ozone generator and is opened It closes, stablizes 2 minutes to air inlet, unlatching circulating water cooling device, 15 DEG C of control loop coolant-temperature gage.It is smelly to ensure that cooling water stablizes inflow After 600 generator tube of Oxygen Generator, ozone switch is opened, adjusting carrier gas flux, ozone supply gas pressure and ozone dosage respectively is 1L/min, 0.1MPa and 100mg/L are filled with a large amount of micro-bubble in Multi-level deflector catalytic ozonation pond 200 at this time.To smelly After oxidation stability output, suction pump is opened, control flow of inlet water is 120L/h, and gas-liquid mixed ratio is 1:2.

By the air volume regulating valve 350 on tail gas recycle pipe 140, Multi-level deflector catalytic ozonation reaction tank 200 is adjusted The gaseous pressure of each reaction zone reduces step by step, and can guarantee and continue to blast gas by the aerator 110 in next stage reaction zone Bubble.

By the pretreated waste water in Multi-level deflector catalytic ozonation pond, into the first reaction interval of reaction tank 300 210, open the first reaction interval 210 of reaction tank 300 connected adding of agent and mixing plant 190, the heavy metal configured The concentration that adds of trapping agent is 85mg/L, adjusts mixing plant revolving speed about 200r/min, makes heavy metal chelating agent and metal ion Sufficiently carry out chelatropic reaction.

It is flowed into after chelatropic reaction 220 between the second reaction zone of reaction tank 300, between opening 300 second reaction zone of reaction tank The concentration that adds of 220 connected adding of agent and mixing plant, the dephosphorization agent configured is 55mg/L, adjusts mixing plant revolving speed About 100r/min.

To the chemical plating waste water water quality before the present embodiment processing, effluent quality is detected with treated.Total copper, total nickel Detection method: atomic absorption spectrophotometry；PH detection method: pH detector；COD detection method: rapid sealing catalysis Resolution method；TN: potassium persulfate oxidation ultraviolet spectrophotometry；NH3-N: Berthelot spectrophotometry；TP: the anti-light splitting of molybdenum antimony Photometry (detection method of following embodiments is identical with this).

Testing result is as shown in table 1:

The pollutant concentration variation (mg/L) before and after the processing of 1 chemical plating waste water of table

Project	pH	COD	TN	NH3- N	TP	Ni	Cu
								Before processing	9.7	257	215	32.5	35	3.75	2.43
After processing	7.3	34	12	7.8	0.3	0.07	0.05

Application example 2

Chemical plating waste water (also known as burnt copper waste water) in seven strands of waste water of Dongguan garden electroplating wastewater processing factory, through conventional two After grade dosing precipitation process, the waste water is taken to be tested.

The difference from embodiment 1 is that in the present embodiment:

It is 1mm that precision, which is arranged, in cartridge filter；

3 order reaction areas are arranged in Multi-level deflector catalytic ozonation pond；

Catalyst fixed bed loading is 45%；

Membrane bioreactor membrane module is hollow fiber film assembly；

Control flow of inlet water is 180L/h；

Ozone supply gas pressure is 0.1MPa；

Ozone dosage is 80mg/L；

Gas-liquid mixed ratio is 1:4；

The concentration that adds of heavy metal chelating agent is 75mg/L；

The concentration that adds of dephosphorization agent is 45mg/L.

To the chemical plating waste water water quality before the present embodiment processing, effluent quality is detected with treated, and testing result is such as Shown in table 2:

The pollutant concentration variation (mg/L) before and after the processing of 2 chemical plating waste water of table

Project	pH	COD	TN	NH3- N	TP	Ni	Cu
								Before processing	9.3	227	220	30.4	36.5	1.25	1.65
After processing	7.7	34	13	7.2	0.2	0.05	0.05

Application example 3

The chemical plating waste water of the independent categorised collection of Qingyuan City garden electroplating wastewater processing factory, takes the waste water to be tested.

Difference with embodiment 1,2 is, in the present embodiment:

It is 0.5mm that precision, which is arranged, in cartridge filter；

4 order reaction areas are arranged in Multi-level deflector catalytic ozonation pond；

Catalyst fixed bed loading is 55%；

Membrane bioreactor membrane module is plate film assembly；

Control flow of inlet water is 180L/h；

Ozone supply gas pressure is 0.2MPa；

Ozone dosage is 145mg/L；

Gas-liquid mixed ratio is 1:1；

The concentration that adds of heavy metal chelating agent is 95mg/L；

The concentration that adds of dephosphorization agent is 75mg/L.

To the chemical plating waste water water quality before the present embodiment processing, effluent quality is detected with treated, and testing result is such as Shown in table 3:

The pollutant concentration variation (mg/L) before and after the processing of 3 chemical plating waste water of table

Project	pH	COD	TN	NH3- N	TP	Ni	Cu
								Before processing	10.6	327	260	45.6	41.2	5.85	7.65
After processing	8.3	48	14	7.5	0.3	0.09	0.15

Finally, it should be noted that the above various embodiments is only to illustrate the technical solution of the utility model, rather than it is limited System；Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should Understand: it is still possible to modify the technical solutions described in the foregoing embodiments, or to some or all of Technical characteristic is equivalently replaced；And these are modified or replaceed, it does not separate the essence of the corresponding technical solution, and this is practical new The range of each embodiment technical solution of type.

Claims (10)

1. a kind of chemical plating waste water processing and reclaiming system, which is characterized in that smelly including ozone supply system, Multi-level deflector catalysis Oxidation pond, reaction tank, pH on-line monitoring combined control equipment, level-one bag filter, second level accurate filter and membrane bioreactor；

The ozone supply system is connect with the aerator of the Multi-level deflector catalytic ozonation bottom of pond portion, ozone supply；Institute It states Multi-level deflector catalytic ozonation pond water outlet to connect with the water inlet of the reaction tank, Multi-level deflector catalytic ozonation pond Water outlet pipe road be provided with pH on-line monitoring combined control equipment；The water outlet of the reaction tank and the level-one pocket type mistake The connection of filter water inlet, the level-one bag filter water outlet are connect with the second level accurate filter water inlet, and described two Grade accurate filter water outlet is connected with the membrane bioreactor.

2. chemical plating waste water processing according to claim 1 and reclaiming system, which is characterized in that the pH on-line monitoring connection The pH on-line monitoring probe of control device is mounted on the water outlet in Multi-level deflector catalytic ozonation pond, the pH on-line monitoring The signal output line of probe is connected with electric cabinet, and the output order feedback signal line and ozone supply pipeline tolerance of electric cabinet are adjusted Valve is connected；Pass through the pH value of waste water after detection oxidation contact break pretreatment, on-line control ozone supply tolerance, linkage control pretreatment Effect.

3. chemical plating waste water processing according to claim 1 and reclaiming system, which is characterized in that the Multi-level deflector catalysis It ozonizes pond and includes at least 1 grade of baffling and two reaction zones；Lower liquid phase connection is normal pressure, top between two reaction zones Gas phase separates the adjusting that can pressurize；The reaction zone all has inlet and outlet, and the water inlet is located at the reaction zone Upper end, the water outlet is located at the lower end of the reaction zone, and waste water is flowed out from the lower end water outlet of the reaction zone by folding Chute flows upwardly into the upper end water inlet of reaction zone described in next stage；

Aerator is separately provided in the bottom of the reaction zone in the catalytic ozonation pond；The ozone supply system The aerator in the first reaction zone in Multi-level deflector catalytic ozonation pond is connected by ozone supply pipe；Adjacent The reaction zone between be provided with tail gas recycle pipe, the tail gas recycle pipe is used to receive in the tail gas of reaction zone described in upper level Collect and is passed through in the aerator of reaction zone described in next stage；Tail gas control valve is provided on the tail gas recycle pipe；Institute State gas pressure between reaction zone reduces step by step；Each reaction zone is equipped with safety valve and pressure gauge, is observed by pressure gauge anti- Answer pressure in area, operating pressure in safe valve regulation reaction zone；

Cartridge filter is equipped in the waste water supply pipe；The filtering accuracy of the cartridge filter is 0.5~1.0mm；? The upper end in Multi-level deflector catalytic ozonation pond is provided with exhaust emission tube, is provided with tail on the exhaust emission tube Gas decomposer.

4. chemical plating waste water processing according to claim 1 and reclaiming system, which is characterized in that the ozone supply system Including ozone generator, ozone supply pipe, air volume regulating valve and gas flowmeter；The ozone generator and the ozone supply Pipe connects, and is provided with the air volume regulating valve and the gas flowmeter on the ozone supply pipe.

5. chemical plating waste water processing according to claim 3 and reclaiming system, which is characterized in that urged in the Multi-level deflector Change ozonisation pond the reaction zone in, be separately provided in the upper position of the aerator it is catalyst fixed bed, It is described it is catalyst fixed bed on be provided with spherical solid catalyst.

6. chemical plating waste water processing according to claim 1 and reclaiming system, which is characterized in that the reaction tank is at least set Between setting two reaction zones, two reaction intervals are respectively first reaction between the first reaction interval and second reaction zone Section is used to add dephosphorization agent between the second reaction zone for adding heavy metal chelating agent；In each reaction interval Upper position is correspondingly provided with adding of agent and mixing plant；

The top of first reaction interval is equipped with water inlet, between the lower part and the second reaction zone of first reaction interval It is connected to, the top between the second reaction zone is equipped with water outlet；The water outlet of the reaction tank passes through booster pump and the level-one The water inlet of bag filter is connected.

7. chemical plating waste water processing according to claim 1 and reclaiming system, which is characterized in that the level-one bag type filtering The water outlet of device continues through booster pump and is connected with the water inlet of the second level accurate filter；The second level accurate filter Water outlet be connected with the water inlet of the membrane bioreactor；The filtration media pore diameters of the level-one bag hose are 10~50 μm；The filtration media pore diameters of the second level accurate filter are 0.5~3 μm；The level-one bag filter and second level essence Close filter is equipped with back purge system.

8. chemical plating waste water processing according to claim 1 and reclaiming system, which is characterized in that the membrane bioreactor Inside setting membrane separation assemblies, at least one including plate membrane, hollow-fibre membrane, tubular membrane etc., the membrane separation assemblies Membrane aperture≤0.2 μm；Flowing water Valve, pressure vacuum ga(u)ge and Vacuum suction pump are set on the membrane bioreactor outlet pipe；Root According to actual motion condition, flowing water Valve is automatically closed, opens wash-out valve, starts to clean membrane separation assemblies.

9. described in any item chemical plating waste water processing and reclaiming system according to claim 1~8, which is characterized in that describedization Learning waste electroplating includes the heavy metal wastewater thereby of chemical plating production technology discharge, chemistry still below standard after conventional materializing strategy technique Waste electroplating；Heavy metal in the chemical plating waste water mainly exists in the form of complex state.

10. chemical plating waste water processing according to claim 9 and reclaiming system, which is characterized in that the membrane biological reaction After the filtering of further conventional ultrafiltration film, water outlet can be back to on-site and rinse ground, flush the toilet, rinse vehicle and greening for device water outlet It irrigates；

After further conventional ultrafiltration, nanofiltration membrane and reverse osmosis treatment, water outlet can reuse for the membrane bioreactor water outlet In electroplating enterprise industrial water.