CN107253798A - A kind of advanced treatment and reclamation group technology of wastewater of steel industry - Google Patents

A kind of advanced treatment and reclamation group technology of wastewater of steel industry Download PDF

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Publication number
CN107253798A
CN107253798A CN201710382593.6A CN201710382593A CN107253798A CN 107253798 A CN107253798 A CN 107253798A CN 201710382593 A CN201710382593 A CN 201710382593A CN 107253798 A CN107253798 A CN 107253798A
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water
wastewater
pond
unit
steel industry
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CN107253798B (en
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喻盛华
俞勇
方建
赵珺
何伟军
鲍震宇
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Zhejiang Fuchun Ziguang Environmental Protection Co Ltd
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Zhejiang Fuchun Ziguang 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
    • C02F1/22Treatment of water, waste water, or sewage by freezing
    • 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
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • 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
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • 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
    • 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
    • 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
    • C02F3/30Aerobic and anaerobic processes
    • C02F3/302Nitrification and denitrification treatment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • 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

Abstract

The present invention relates to a kind of advanced treatment and reclamation group technology of wastewater of steel industry there is provided it is a kind of to wastewater of steel industry carry out desalination recovery, and by remaining strong brine handle qualified discharge method.Wastewater of steel industry passes through cooling unit, after the processing of immersion ultra filtration unit, it is introduced into reverse osmosis units and carries out a desalination, reverse osmosis produced water after desalination delivers to water system grading recycle, the concentrated water that reverse osmosis units are produced passes sequentially through softening depositing reservoir, ozone oxidation pond, nitration denitrification biofilter, more medium filter, after the processing such as external-compression type ultra filtration unit, enter back into nano-filtration unit and carry out secondary desalination, nanofiltration production water after desalination send water system grading recycle, the concentrated water that nano-filtration unit is produced sequentially passes through Fenton oxidation again, ozone oxidation pond, qualified discharge after activated carbon bio-filter and the processing of break point chlorination pond.

Description

A kind of advanced treatment and reclamation group technology of wastewater of steel industry
Technical field
The invention belongs to water treatment field, it is related to a kind of advanced treatment and reclamation group technology of wastewater of steel industry.
Background technology
Steel and iron industry is to use water rich and influential family and discharge of wastewater rich and influential family.Freshwater resources it is in short supply, national carry forward vigorously energy-saving and emission-reduction Background under, the advanced treating of wastewater of steel industry is increasingly taken seriously.Currently, most of iron and steel enterprise, which has set up, follows Ring processing system, is handled wastewater of steel industry and is recycled, still, highly concentrated with indexs such as salinity and chlorions Demagnification number brought to the growth of the corrosion and scaling of circulation and microorganism the problems such as, iron and steel enterprise is still had to By substantial amounts of discharge of wastewater into environment.
In recent years, with the investment and the increasingly reduction of operating cost of membrane water treatment system, part iron enterprise is The desalted water that bi-membrane method technique through attempting ultrafiltration and counter-infiltration is applied to enterprise is produced, but is due to be produced in desalted water Cheng Zhong, can produce high pollution thing concentration, the strong brine of high concentration multiple, and the domestic strong brine to high concentration multiple lacks at present This economic processing mode.It is as high, generation in then often faced the huge, operating cost of investment using evaporative crystallization technique of zero discharge Salt slurry is crystallized because having the problems such as hazardous waste feature disposes difficult, the usual way of iron and steel enterprise be strong brine it is direct discharge or Person sprays supplies consumption in enterprise so that iron and steel enterprise using bi-membrane method technique when often small or producing water ratio not It is high, it is difficult to the real water saving reuse for realizing high level.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of advanced treatment and reclamation group technology of wastewater of steel industry, make Iron and steel enterprise can improve production Water Sproading rate, strong brine, and qualified discharge be handled at low cost, so as to promote full embrane method in steel Large-scale application in enterprise.
The technical solution adopted by the present invention is:A kind of advanced treatment and reclamation group technology of wastewater of steel industry is provided, wrapped Include following steps:
(1) cooling unit:Cooling unit includes cooling tower, balancing tank and board-like grid, to pending wastewater of steel industry Carry out cooling down, regulating pondage and filtering fine particle;
(2) immersion ultra filtration unit:Immersion ultra filtration unit includes submerged ultrafiltration, ultrafiltration production pond, neutralization pond, catchmented Pond, highly dense sedimentation basin and more medium filter.The water outlet of cooling unit enters submerged ultrafiltration and filtered, and retains waste water In suspension and colloid.Submerged ultrafiltration cleaning unwatering is by neutralisation treatment, highly dense sedimentation basin precipitation, multi-medium filtering Device is filtered, the balancing tank that the waste water after processing is entered back into cooling unit;
(3) reverse osmosis units:Reverse osmosis units include two sections of reverse osmosis membranes, and immersion ultra filtration unit water outlet enters reverse osmosis units A desalination is carried out, reverse osmosis produced water and concentrated water is obtained;
(4) reverse osmosis concentrated unit for treating water:Including softening depositing reservoir, ozone oxidation pond, nitration denitrification filter tank and multimedium mistake Filter.The medicaments such as sodium hydroxide, sodium carbonate are added in softening depositing reservoir, sofening treatment is carried out to reverse osmosis concentrated water, are removed simultaneously Heavy metal and partially fluorinated thing in concentrated water;Enter ozone pond oxidative degradation organic matter after softening depositing reservoir water outlet regulation pH, carry The biodegradability of high concentrated water, enters back into nitration denitrification biofilter and removes ammonia nitrogen and total nitrogen;The water outlet in filter tank enters clear water reserviors, Filtered again by more medium filter.
(5) external-compression type ultra filtration unit:Reverse osmosis concentrated unit for treating water water outlet is filtered into external pressure type ultra-filtration membrane, is cut Colloid, suspension and microorganism are stayed, backwash water and concentrated water return to the softening depositing reservoir of reverse osmosis concentrated unit for treating water;
(6) nano-filtration unit:Nano-filtration unit includes two sections of NF membranes, and the water outlet after the filtering of external-compression type ultra filtration unit enters NF membrane list Member carries out secondary desalination, obtains nanofiltration production water and concentrated water;
(7) nanofiltration concentrated water processing unit:Including Fenton oxidation, ozone oxidation, activated carbon bio-filter and break point chlorination pond.Receive The nanofiltration concentrated water that filter unit is produced first passes around the COD in Fenton oxidation removal concentrated waterCr, suspension and colourity;And it is heavy in Fenton Aluminium polychloride medicament is added in the pond of shallow lake and removes fluoride;The water outlet of Fenton sedimentation basin enters O3 contacted oxidation pond, removes again Difficult degradation CODCr, the biodegradability of nanofiltration concentrated water is improved, activated carbon bio-filter is entered back into and further removes CODCr, finally lead to Cross break point chlorination pond and add sodium hypochlorite and further remove in concentrated water and discharged after ammonia nitrogen.
The wastewater of steel industry of the described method processing using the present invention enters the system, its water quality after pretreatment It is characterized as:Water temperature is 15 DEG C~45 DEG C, and pH is 6.0~9.0, the μ S/cm of electrical conductivity≤3000, total hardness(With CaCO3Meter)≤ 800mg/L, total dissolved solidss≤2000mg/L, Cl-≤ 500mg/L, suspension≤15mg/L, CODCr≤ 30mg/L, ammonia nitrogen≤ 10mg/L, total nitrogen≤20mg/L, oil≤2mg/L, fluoride≤15mg/L.
Described step(1)In board-like grid, trap water more than 100 μm is provided with the balancing tank of cooling unit Grain.
Described step(2)The submerged ultrafiltration component of immersion ultra filtration unit uses hollow fiber form curtain type membrane group Part, the material of milipore filter uses polytetrafluoroethylene (PTFE)(PTFE), ultrafiltration membrane aperture is 0.2 μm.
Described step(2)Producing water water quality SDI≤3 of immersion ultra filtration unit, turbidity≤0.2NTU.
Described step(2)The rinse water of the immersed ultrafiltration membrane pond of immersion ultra filtration unit passes through discharge of pipes to neutralization Pond, it is well mixed by aeration in neutralization pond, the medicaments such as hydrochloric acid or sodium hydroxide regulation pH is added, pH rinse water has been adjusted Collecting-tank is squeezed into from neutralization pond with pump, then is lifted from collecting-tank with pump to highly dense sedimentation basin, polymerization is added in highly dense sedimentation basin The medicament such as aluminium chloride and polyacrylamide, carries out coagulating sedimentation, and highly dense sedimentation basin water outlet flows automatically to highly dense production pond, then from highly dense More medium filter filtering is squeezed into production pond with pump, and producing water water quality pH after filtering is 7.0~8.5, SS≤5mg/L, and turbidity≤ 5NTU, production water returns to step(1)The balancing tank of cooling unit.
Described step(3)The reverse osmosis membrane system of reverse osmosis units is divided into two sections of film concentrations of one-level, reverse osmosis units Produce Water Sproading rate >=75%, production water conductivity≤100 μ S/cm, TDS≤50mg/L.
Described step(4)The softening depositing reservoir of reverse osmosis concentrated unit for treating water uses medicament tenderizer, and adding medicament is Sodium hydroxide, sodium carbonate, aluminium polychloride and polyacrylamide, the reverse osmosis concentrated water hardness≤350mg/L after softened processing.
Described step(4)The water outlet pH value of the softening depositing reservoir of reverse osmosis concentrated unit for treating water is higher, in softening clarification Pond water outlet is neutralized provided with regulation pH measures using medicament, adds medicament for hydrochloric acid, water outlet pH value is adjusted to 7.0~8.0.
Described step(4)The nitration denitrification filter tank of reverse osmosis concentrated unit for treating water is using the preposition rearmounted anti-nitre of nitrification Change, the volumetric loading 0.58kgNH in preposition nitrification filter tank3-N/(m3·d), filtering velocity 3.0m3/(m2·h);Rear-mounted denitrification filter tank Volumetric loading 3.10kgNO3-N/(m3·d), filtering velocity 9.0m3/(m2·h), carbon source is added for sodium acetate.Nitration denitrification is filtered Pond is inoculated with and tamed using the nitration denitrification bacterial strain of the high chlorine resistant of resistance to high salt ion, the water outlet ammonia nitrogen in filter tank after the completion of domestication ≤ 2mg/L, total nitrogen≤5mg/L.
Described step(5)The external pressure type ultra-filtration membrane component of external-compression type ultra filtration unit uses hollow fiber film assembly, ultrafiltration The material of film uses Kynoar, and milipore filter nominal pore size is 0.03 μm.
Described step(6)The nanofiltration membrane system of nano-filtration unit is divided into two sections of film concentrations of one-level, the production Water Sproading rate of nanofiltration >=60%, production water conductivity≤900 μ S/cm, TDS≤450mg/L.
Described step(3)Reverse osmosis units and described step(6)The rinse water of nano-filtration unit, comes from reverse osmosis produced Pond.The soda acid cleaning waste water of water is produced, described step is discharged to by pipeline(2)The neutralization pond processing of immersion ultra filtration unit.
Described step(7)The Fenton oxidation of nanofiltration concentrated water processing unit, is mutually catalyzed Fenton oxidation reactor, instead using four PH need not be adjusted before answering, reaction pH controls add medicament for hydrogen peroxide, ferrous sulfate, sodium hydroxide and polypropylene 5~7 Acid amides, nanofiltration concentrated water COD≤50mg/L after being handled through Fenton.
Described step(7)The Fenton oxidation of nanofiltration concentrated water processing unit, synchronously adds aluminium polychloride medicament and goes fluorine removal Fluoride≤10mg/L in compound, the nanofiltration concentrated water through processing.
Described step(7)The Fenton sedimentation basin water outlet of nanofiltration concentrated water processing unit enters O3 contacted oxidation pond and activity After the processing of charcoal biofilter, COD≤30mg/L.
Described step(7)The activated biofiler water outlet of nanofiltration concentrated water processing unit enters break point chlorination pond, adds secondary Sodium chlorate medicament further goes to remove ammonia nitrogen, nanofiltration concentrated water ammonia nitrogen≤1mg/L after processing.
Described step(7)Nanofiltration concentrated water after nanofiltration concentrated water processing unit processes can reach《Steel and iron industry water pollution Thing discharge standard》(GB13456-2012)Every water quality index requirement as defined in table 3, wherein ammonia nitrogen is less than 1mg/L, and total nitrogen is small It is less than 30mg/L in 15mg/L, COD.
Brief description of the drawings
Fig. 1 is a kind of flow chart of the advanced treatment and reclamation group technology of wastewater of steel industry of the invention.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Embodiments of the present invention design a kind of advanced treatment and reclamation group technology of wastewater of steel industry, and this method passes through The process combination of advanced treatment and reclamation, is handled using full embrane method wastewater of steel industry, is required to provide different quality according to user Desalted water, sludge be delivered to outside system handle under conditions of, the total reclamation rate of production water is reached more than 85%, at the same by compared with The strong brine processing technology of low cost, reaches outer row's strong brine《Steel and iron industry pollution discharge standard》(GB13456- 2012)Every water quality index requirement as defined in table 3.The present invention solves the high Cost Problems of bi-membrane method strong brine processing, favorably In the popularization of bi-membrane method.
Its concrete technology flow process is as shown in figure 1, comprise the following steps:
(1) cooling unit:Cooling unit includes cooling tower, balancing tank and board-like grid, to pending wastewater of steel industry Carry out cooling down, regulating pondage and filtering fine particle;
(2) immersion ultra filtration unit:Immersion ultra filtration unit includes submerged ultrafiltration, ultrafiltration production pond, neutralization pond, catchmented Pond, highly dense sedimentation basin and more medium filter composition.The water outlet of cooling unit enters submerged ultrafiltration and filtered, retention Suspension and colloid in waste water.The backwash unwatering of submerged ultrafiltration is by neutralisation treatment, highly dense sedimentation basin precipitation, many Jie Mass filter is filtered, the balancing tank that the waste water after processing is entered back into cooling unit;
(3) permeation unit:Reverse osmosis units include two sections of reverse osmosis membranes, and immersion ultra filtration unit water outlet enters reverse osmosis membrane unit A desalination is carried out, reverse osmosis produced water and concentrated water is obtained;
(4) reverse osmosis concentrated unit for treating water:Including softening depositing reservoir, ozone oxidation pond, nitration denitrification filter tank and multimedium mistake Filter.The medicaments such as sodium hydroxide, sodium carbonate are added in softening depositing reservoir, sofening treatment is carried out to reverse osmosis concentrated water, are removed simultaneously Heavy metal and partially fluorinated thing in concentrated water;Soften after depositing reservoir water outlet regulation pH, into the difficult biochemical drop of ozone pond oxidative degradation Organic matter is solved, the biodegradability of concentrated water is improved, nitration denitrification biofilter is entered back into and removes ammonia nitrogen and total nitrogen;The water outlet in filter tank Into clear water reserviors, then by more medium filter filtering.
(5) external-compression type ultra filtration unit:Reverse osmosis concentrated unit for treating water water outlet is filtered into external pressure type ultra-filtration membrane, retention Colloid, suspension and microorganism, backwash water and concentrated water return to softening depositing reservoir;
(6) nano-filtration unit:Nano-filtration unit includes two sections of NF membranes, and the water outlet after the filtering of external-compression type ultra filtration unit enters NF membrane list Member carries out secondary desalination, obtains nanofiltration production water and concentrated water;
(7) nanofiltration concentrated water processing unit:Including Fenton oxidation, ozone oxidation, activated carbon bio-filter and break point chlorination pond.Receive The nanofiltration concentrated water that filter unit is produced passes through Fenton oxidation, removes organic matter, suspension and colourity in concentrated water;And in Fenton precipitation Aluminium polychloride medicament is added in pond and removes fluoride;The water outlet of Fenton sedimentation basin enters O3 contacted oxidation pond, removes difficult degradation Organic matter, improves the biodegradability of nanofiltration concentrated water, enters back into activated carbon bio-filter and further remove CODCr, finally by break Chlorination pond adds sodium hypochlorite and removes discharge after ammonia nitrogen in concentrated water.
The present invention is further illustrated below by a specific example.Example is certain iron company using the present invention's The advanced treatment and reclamation project that method is built, day processing water is 2.5 ten thousand tons.
Process flow diagram is shown in Fig. 1.
The water quality characteristic of wastewater of steel industry in this example is:Water temperature is 45 DEG C, and pH is 7.5, and electrical conductivity is 3000 μ S/ Cm, total hardness(With CaCO3Meter)For 800mg/L, total dissolved solidss are 2000mg/L, Cl-For 500mg/L, suspension is 15mg/ L, CODCrFor 30mg/L, ammonia nitrogen is 10mg/L, and total nitrogen is 20mg/L, and oil is 2mg/L, and fluoride is 15mg/L.
Advanced treatment and reclamation is carried out using the method for the present invention to wastewater of steel industry to be described as follows:
The pretreated wastewater of steel industry of described process is connected by the import of pipeline and cooling tower;The bottom of cooling tower is Cooling tower produces pond;Cooling tower production basin outlet has board-like grid;Cooling tower produces water out and passes through pipeline and stream canal and immersion Ultrafiltration membrane pool is connected;Immersed ultrafiltration membrane pond produces pond by the pipeline provided with suction pump and ultrafiltration and is connected;Ultrafiltration production pond leads to The pipeline provided with backwashing pump is crossed to be connected with immersed ultrafiltration membrane pond;Immersed ultrafiltration membrane pond is connected by pipeline with neutralizing collecting-tank Connect;Collecting-tank is neutralized to be connected with highly dense sedimentation basin by the pipeline provided with elevator pump;Highly dense sedimentation basin import is provided with dosing mouth;It is high Close sedimentation basin water outlet is connected by pipeline with highly dense production pond;Highly dense production pond passes through the pipeline provided with booster pump and multimedium mistake Filter I is connected;The water outlet of more medium filter I is produced pond by pipeline and cooling tower and is connected;Ultrafiltration production pond passes through provided with supercharging The pipeline of pump and high-pressure pump is connected with reverse osmosis unit;Reverse osmosis unit production water is connected by pipeline with water supply user;Counter-infiltration Device produces water and is connected by pipeline with cleaning pond;Pond is cleaned by the pipeline provided with flushing water pump and reverse osmosis unit to connect Connect;Reverse osmosis unit backwash draining is connected by pipeline with neutralization pond;Reverse osmosis concentrated water is connected by pipeline with softening depositing reservoir; The inlet and outlet for softening depositing reservoir is provided with dosing mouth;The outlet of softening depositing reservoir is connected by flowing canal with ozone oxidation pond;Ozone Oxidation pond is connected by delivery port with intermediate pool;Intermediate pool is connected by the pipeline provided with elevator pump and nitration denitrification filter tank Connect;Nitration denitrification filter tank adds mouth provided with carbon source;The water outlet in nitration denitrification filter tank is connected by pipeline with clear water reserviors;Clear water Pond is connected by the pipeline provided with backwash water pump with nitration denitrification filter tank;The backwash draining in nitration denitrification filter tank passes through pipeline It is connected with backwash blowoff basin I;Backwash blowoff basin is connected by the pipeline provided with elevator pump with softening depositing reservoir;Clear water reserviors are by setting The pipeline for having booster pump is connected with more medium filter;The water outlet of more medium filter II passes through pipeline and external-compression type ultrafiltration former pond Connection;External-compression type ultrafiltration former pond is connected by the pipeline provided with booster pump with external-compression type ultrafiltration;External-compression type ultrafiltration production water passes through Pipeline is connected with nanofiltration former pond;Nanofiltration former pond is connected by the pipeline provided with backwash water pump with external-compression type ultrafiltration;External-compression type Hyperfiltration reverse-rinsing draining is connected by pipeline with softening depositing reservoir;Nanofiltration former pond by the pipeline provided with booster pump and high-pressure pump with Nanofiltration device is connected;Nanofiltration is produced water and is connected by pipeline and nanofiltration production pond;Nanofiltration production pond passes through the pipeline provided with booster pump User is connected with water supply;Cleaning pond is connected by the pipeline provided with flushing water pump with nanofiltration device;Nanofiltration backwash draining passes through Pipeline is connected with neutralizing collecting-tank;Nanofiltration concentrated water is connected by pipeline with nanofiltration concentrated water pond;Nanofiltration concentrated water pond passes through provided with lifting The pipeline of pump is connected with Fenton reactor;Fenton reactor water outlet is connected by pipeline with Fenton sedimentation basin;Fenton reactor and Fenton sedimentation basin is provided with dosing mouth;The water outlet of Fenton sedimentation basin is connected by flowing canal with ozone oxidation pond;Ozone oxidation pond is by going out Current canal is connected with activated carbon bio-filter;Activated carbon bio-filter water outlet is connected by flowing canal with break point chlorination pond;Break adds Chlorine pond is provided with dosing mouth;Break point chlorination pond carries out outer arrange to waste water by the pipeline provided with elevator pump.
Use the wastewater of steel industry day treatment scale of method processing of the present invention for 25000 tons, process layout is compact, accounts for Ground area is small, and the actual floor space of this example is only 4656.39m2, processed in units water floor space only 0.19m2/m3/d。
Wastewater of steel industry is handled using the method for the present invention, reverse osmosis concentrated unit for treating water nitration denitrification filter tank is used The nitration denitrification bacterial strain of the high chlorine resistant of resistance to high salt ion is inoculated with and tamed, the water outlet ammonia nitrogen≤2mg/ in filter tank after the completion of domestication L, total nitrogen≤5mg/L.
After the method processing wastewater of steel industry of the present invention, reverse osmosis produced water rate >=76% of this example is reverse osmosis produced Water water quality is:Electrical conductivity≤60 μ S/cm, TDS≤35mg/L, can supply iron and steel enterprise's profit soft water strict to water quality requirement, Desalted water etc. produces water.
After the method processing wastewater of steel industry of the present invention, the nanofiltration producing water ratio of this example is >=65%, nanofiltration production water Electrical conductivity is≤650 μ S/cm, TDS≤350mg/L, can supply the production reuse and fire-fighting of iron and steel enterprise's water quality requirement typically Water.
After the method processing wastewater of steel industry of the present invention, by the technique of this example to reverse osmosis produced water and nanofiltration Produce moisture level to reclaim so that whole system is delivered to total yield Water Sproading rate >=85% under conditions of handling outside system in sludge.
After the method processing wastewater of steel industry of the present invention, the concentrated water drainage of whole system<10%, spoil disposal is taken out of Water<5%, concentrated water processing reaches《Steel and iron industry pollution discharge standard》(GB13456-2012)It is every as defined in table 3 Water quality index requirement, wherein ammonia nitrogen are less than 1mg/L, and total nitrogen is less than 15mg/L, and COD is less than 30mg/L.

Claims (18)

1. the advanced treatment and reclamation group technology of a kind of wastewater of steel industry, it is characterised in that including following steps:(1)It is cold But unit:Cooling unit includes cooling tower, balancing tank and board-like grid, and it is cold to carry out cooling to pending wastewater of steel industry But, regulating pondage and filtering fine particle;(2)Immersion ultra filtration unit:Immersion ultra filtration unit includes submerged ultrafiltration, surpassed Filter production pond, neutralization pond, collecting-tank, highly dense sedimentation basin and more medium filter I, the water outlet of cooling unit enter immersion and surpassed Filter membrane is filtered, and suspension and colloid in retention waste water, the backwash unwatering of submerged ultrafiltration pass through neutralisation treatment, height Close sedimentation basin precipitation, more medium filter I are filtered, the balancing tank that the waste water after processing is entered back into cooling unit;(3)Instead Permeation unit:Reverse osmosis units include two sections of reverse osmosis membranes, and the water outlet of immersion ultra filtration unit is carried out into reverse osmosis membrane unit Desalination, obtains reverse osmosis produced water and concentrated water;(4)Reverse osmosis concentrated unit for treating water:Including softening depositing reservoir, ozone oxidation The medicaments such as sodium hydroxide, sodium carbonate are added to reverse osmosis in pond, nitration denitrification filter tank and more medium filter II, softening depositing reservoir Saturating concentrated water carries out sofening treatment, while removing the heavy metal and partially fluorinated thing in concentrated water;Soften after depositing reservoir water outlet regulation pH, Into ozone oxidation pond degradation of organic substances, the biodegradability of concentrated water is improved, nitration denitrification biofilter is entered back into and removes ammonia nitrogen And total nitrogen;The water outlet in filter tank enters clear water reserviors, then is filtered by more medium filter II,(5)External-compression type ultra filtration unit:Counter-infiltration The water outlet of concentrated water processing unit is filtered into external pressure type ultra-filtration membrane, retention colloid, suspension and microorganism, backwash water and concentrated water Return to the softening depositing reservoir of reverse osmosis concentrated unit for treating water;(6)Nano-filtration unit:Nano-filtration unit includes two sections of NF membranes, external-compression type Water outlet after ultra filtration unit filtering enters nanofiltration film unit and carries out secondary desalination, obtains nanofiltration production water and concentrated water;(7)Nanofiltration concentrated water Processing unit:The nanofiltration produced including Fenton oxidation, ozone oxidation, activated carbon bio-filter and break point chlorination pond, nano-filtration unit Concentrated water first passes around the COD in Fenton oxidation removal concentrated waterCr, suspension and colourity;And polymerization chlorine is added in Fenton sedimentation basin Change aluminium medicament and remove fluoride;The water outlet of Fenton sedimentation basin enters O3 contacted oxidation pond, and difficult degradation COD is removed againCr, raising receives The biodegradability of concentrated water is filtered, activated carbon bio-filter is entered back into and further removes CODCr, added finally by break point chlorination pond secondary Sodium chlorate further removes qualified discharge after the ammonia nitrogen in concentrated water.
2. a kind of advanced treatment and reclamation group technology of wastewater of steel industry according to claim 1, it is characterised in that institute The wastewater of steel industry for the method processing using the present invention stated enters the system after pretreatment, and its water quality characteristic is:Water Temperature is 15 DEG C~45 DEG C, and pH is 6.0~9.0, the μ S/cm of electrical conductivity≤3000, total hardness(With CaCO3Meter)≤ 800mg/L, it is total molten Solve solid≤2000mg/L, Cl-≤ 500mg/L, suspension≤15mg/L, CODCr≤ 30mg/L, ammonia nitrogen≤10mg/L, total nitrogen≤ 20mg/L, oil≤2mg/L, fluoride≤15mg/L.
3. a kind of advanced treatment and reclamation group technology of wastewater of steel industry according to claim 1, it is characterised in that institute The step of stating(1)The particle in board-like lattice coral, trap water more than 100 μm is provided with the balancing tank of cooling unit.
4. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that described The step of(2)The submerged ultrafiltration component of immersion ultra filtration unit uses hollow fiber form curtain type film assembly, ultrafiltration membrane material Using polytetrafluoroethylene (PTFE)(PTFE), ultrafiltration membrane aperture is 0.2 μm.
5. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that described The step of(2)Producing water water quality SDI≤3 of immersion ultra filtration unit, turbidity≤0.2NTU.
6. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that described The step of(2)The rinse water of the immersed ultrafiltration membrane pond of immersion ultra filtration unit is by discharge of pipes to neutralization pond, in neutralization pond It is well mixed by aeration, the medicaments such as hydrochloric acid or sodium hydroxide regulation pH is added, pH rinse water pump has been adjusted from neutralization Collecting-tank is squeezed into pond, then is lifted from collecting-tank with pump to highly dense sedimentation basin, aluminium polychloride is added in highly dense sedimentation basin and poly- The medicaments such as acrylamide, carry out coagulating sedimentation, and highly dense sedimentation basin water outlet flows automatically to highly dense production pond, then from highly dense production pond pump More medium filter filtering is squeezed into, the producing water water quality pH after filtering is 7.0~8.5, SS≤5mg/L, turbidity≤5NTU, production water is returned To step(1)The balancing tank of cooling unit.
7. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that described The step of(3)The reverse osmosis membrane system of reverse osmosis units is divided into the concentration of two sections of films of one-level, and the production Water Sproading rates of reverse osmosis units >= 75%, production water conductivity≤100 μ S/cm, TDS≤50mg/L.
8. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that described The step of(4)The softening depositing reservoir of reverse osmosis concentrated unit for treating water, using medicament tenderizer, adds medicament for sodium hydroxide, carbon Sour sodium, aluminium polychloride and polyacrylamide, the reverse osmosis concentrated water hardness≤350mg/L after softened processing.
9. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that described The step of(4)The water outlet pH value of the softening depositing reservoir of reverse osmosis concentrated unit for treating water is higher, and pH is provided with softening depositing reservoir water outlet Regulation measure, is neutralized using medicament, adds medicament for hydrochloric acid, the pH value of water outlet is adjusted to 7.0~8.0.
10. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that institute The step of stating(4)The nitration denitrification filter tank of reverse osmosis concentrated unit for treating water uses preposition nitrification rear-mounted denitrification, preposition nitrification The volumetric loading 0.58kgNH in filter tank3-N/(m3·d), filtering velocity 3.0m3/(m2·h);The volumetric loading in rear-mounted denitrification filter tank 3.10kgNO3-N/(m3·d), filtering velocity 9.0m3/(m2·h), carbon source is added for sodium acetate, and nitration denitrification filter tank uses resistance to height The nitration denitrification bacterial strain of salt high chlorine resistant ion is inoculated with and tamed, the water outlet ammonia nitrogen≤2mg/L in filter tank after the completion of domestication, always Nitrogen≤5mg/L.
11. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that institute The step of stating(5)The external pressure type ultra-filtration membrane component of external-compression type ultra filtration unit uses hollow fiber film assembly, and the material of milipore filter is adopted With Kynoar, milipore filter nominal pore size is 0.03 μm.
12. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that institute The step of stating(6)The nanofiltration membrane system of nano-filtration unit is divided into two sections of film concentrations of one-level, and production Water Sproading rate >=60% of nanofiltration produces water Electrical conductivity≤900 μ S/cm, TDS≤450mg/L.
13. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that institute The step of stating(3)Reverse osmosis units and step(6)The rinse water of nano-filtration unit comes from reverse osmosis produced pond, and the soda acid of generation is clear Waste water is washed, passes through discharge of pipes to step(2)The neutralization pond processing of immersion ultra filtration unit.
14. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that institute The step of stating(7)The Fenton oxidation of nanofiltration concentrated water processing unit, is mutually catalyzed before Fenton reactor, Fenton's reaction without adjusting using four PH is saved, reaction pH controls add medicament for hydrogen peroxide, ferrous sulfate, sodium hydroxide and polyacrylamide, at Fenton 5~7 Nanofiltration concentrated water COD after reasonCr≤50mg/L。
15. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that institute The step of stating(7)The Fenton oxidation unit of nanofiltration concentrated water processing unit, synchronously adds aluminium polychloride medicament and removes fluoride, warp Nanofiltration concentrated water fluoride≤10mg/L after processing.
16. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that institute The step of stating(7)The Fenton sedimentation basin water outlet of nanofiltration concentrated water processing unit enters O3 contacted oxidation pond and activated carbon bio-filter After processing, COD≤30mg/L.
17. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that institute The step of stating(7)The activated biofiler water outlet of nanofiltration concentrated water processing unit enters break point chlorination pond, adds sodium hypochlorite medicament Further go to remove ammonia nitrogen, nanofiltration concentrated water ammonia nitrogen≤1mg/L after processing.
18. according to a kind of advanced treatment and reclamation group technology of wastewater of steel industry described in claim 1, it is characterised in that institute The step of stating(7)Nanofiltration concentrated water after nanofiltration concentrated water processing unit processes can reach《Steel and iron industry pollution discharge standard》 (GB13456-2012)Every water quality index requirement as defined in table 3, wherein ammonia nitrogen is less than 1mg/L, and total nitrogen is less than 15mg/L, COD Less than 30mg/L.
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