CN107253798B - Advanced treatment and reuse combined process for steel industrial wastewater - Google Patents

Advanced treatment and reuse combined process for steel industrial wastewater Download PDF

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CN107253798B
CN107253798B CN201710382593.6A CN201710382593A CN107253798B CN 107253798 B CN107253798 B CN 107253798B CN 201710382593 A CN201710382593 A CN 201710382593A CN 107253798 B CN107253798 B CN 107253798B
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nanofiltration
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CN107253798A (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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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/22—Treatment of water, waste water, or sewage by freezing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • C02F3/302—Nitrification and denitrification treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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

Abstract

The invention relates to a combined process for advanced treatment and recycling of steel industrial wastewater, and provides a method for desalting and recycling the steel industrial wastewater and treating the residual strong brine to reach the standard and discharge the residual strong brine. The method comprises the steps that after being treated by a cooling unit and an immersed ultrafiltration unit, the steel industrial wastewater firstly enters a reverse osmosis unit for primary desalination, the desalinated reverse osmosis produced water is sent to a water supply system for graded recycling, concentrated water produced by the reverse osmosis unit is sequentially treated by a softening clarification tank, an ozone oxidation tank, a nitrification-denitrification biofilter, a multi-medium filter, an external pressure type ultrafiltration unit and the like, then enters a nanofiltration unit for secondary desalination, the desalinated nanofiltration produced water is sent to the water supply system for graded recycling, and the concentrated water produced by the nanofiltration unit is sequentially treated by a Fenton oxidation tank, an ozone oxidation tank, an active carbon biofilter and a breakpoint chlorination tank and then is discharged after reaching the standard.

Description

Advanced treatment and reuse combined process for steel industrial wastewater
Technical Field
The invention belongs to the field of water treatment, and relates to a combined process for advanced treatment and recycling of steel industrial wastewater.
Background
The steel industry is water consumers and wastewater discharge consumers. Under the background that fresh water resources are in short supply and energy conservation and emission reduction are greatly promoted nationwide, the advanced treatment of the wastewater in the iron and steel industry is more and more emphasized. At present, most iron and steel enterprises have established a circulating treatment system to treat and recycle the wastewater in the iron and steel industry, but with the problems of corrosion, scaling, microorganism breeding and the like of the circulating water system caused by high concentration times of indexes such as salt, chloride ions and the like, the iron and steel enterprises still have to discharge a large amount of wastewater into the environment.
In recent years, with the decreasing investment and running cost of the whole membrane method water treatment system, part of steel enterprises have tried to apply the ultrafiltration and reverse osmosis dual-membrane method process to the preparation of desalted water of the enterprises, but because the desalted water preparation process can generate the concentrated brine with high pollutant concentration and high concentration multiple, the domestic concentrated brine with high concentration multiple is lack of a cost-effective treatment mode. If the evaporation crystallization zero-emission process is adopted, the problems of huge investment, high operation cost, difficult disposal of generated crystallized salt mud due to the characteristics of hazardous wastes and the like are often faced, and the common method of steel enterprises is to directly discharge strong brine or spray the material consumption in the enterprises, so that the steel enterprises are often not large in scale or low in water yield when using the double-membrane process, and the high-level water-saving recycling is difficult to really realize.
Disclosure of Invention
The invention aims to solve the technical problem of providing a combined process for advanced treatment and recycling of wastewater in the steel industry, so that a steel enterprise can improve the recovery rate of produced water, treat strong brine at low cost and discharge the strong brine up to the standard, thereby promoting the large-scale application of a whole membrane method in the steel enterprise.
The technical scheme adopted by the invention is as follows: provides an advanced treatment and reuse combined process for steel industrial wastewater, which comprises the following steps:
(1) a cooling unit: the cooling unit comprises a cooling tower, a regulating water tank and a plate type grid, and is used for cooling the steel industrial wastewater to be treated, regulating the water quantity and filtering fine particles;
(2) an immersed ultrafiltration unit: the immersed ultrafiltration unit comprises an immersed ultrafiltration membrane, an ultrafiltration water generating tank, a neutralization tank, a water collecting tank, a high-density sedimentation tank and a multi-medium filter. And the effluent of the cooling unit enters an immersed ultrafiltration membrane for filtration, and suspended matters and colloid in the wastewater are intercepted. The immersed ultrafiltration membrane cleaning and emptying water is subjected to neutralization treatment, sedimentation in a high-density sedimentation tank and filtration by a multi-medium filter, and the treated wastewater enters a regulating water tank in a cooling unit;
(3) a reverse osmosis unit: the reverse osmosis unit comprises two sections of reverse osmosis membranes, and the effluent of the immersed ultrafiltration unit enters the reverse osmosis unit for primary desalination to obtain reverse osmosis produced water and concentrated water;
(4) a reverse osmosis concentrated water treatment unit: comprises a softening clarification tank, an ozone oxidation tank, a nitrification and denitrification filter tank and a multi-media filter. Adding agents such as sodium hydroxide and sodium carbonate into the softening clarification tank, softening the reverse osmosis concentrated water, and removing heavy metals and partial fluorides in the concentrated water; the effluent of the softening and clarifying tank enters an ozone tank after the pH value of the effluent is adjusted to oxidize and degrade organic matters, so that the biodegradability of the concentrated water is improved, and the effluent enters a nitrification and denitrification biological filter to remove ammonia nitrogen and total nitrogen; and the effluent of the filter tank enters a clean water tank and is filtered by a multi-medium filter.
(5) External pressure type ultrafiltration unit: the effluent of the reverse osmosis concentrated water treatment unit enters an external pressure type ultrafiltration membrane for filtration, colloid, suspended matters and microorganisms are intercepted, and the backwash water and the concentrated water return to a softening clarification tank of the reverse osmosis concentrated water treatment unit;
(6) and (3) nanofiltration unit: the nanofiltration unit comprises two sections of nanofiltration membranes, and effluent water filtered by the external pressure type ultrafiltration unit enters the nanofiltration membrane unit for secondary desalination to obtain nanofiltration product water and concentrated water;
(7) a nanofiltration concentrated water treatment unit: comprises Fenton oxidation, ozone oxidation, an activated carbon biological filter and a break point chlorination tank. The nanofiltration concentrated water generated by the nanofiltration unit is firstly subjected to Fenton oxidation to remove COD in the concentrated waterCrSuspended matter and color; adding a polyaluminium chloride agent into the Fenton precipitation tank to remove fluoride; the effluent of the Fenton sedimentation tank enters an ozone contact oxidation tank to remove the COD which is difficult to degrade againCrImproving the biodegradability of nanofiltration concentrated water, and then entering an activated carbon biological filter for further removing CODCrAnd finally, adding sodium hypochlorite into the break point chlorination tank to further remove ammonia nitrogen in the concentrated water and then discharging.
The steel industrial wastewater treated by the method of the invention enters the system after being pretreated, and the water quality is characterized in that: the water temperature is 15-45 ℃, the pH value is 6.0-9.0, the conductivity is less than or equal to 3000 mu S/cm, and the total hardness (as CaCO)3Calculated) is less than or equal to 800 mg/L, total dissolved solids are less than or equal to 2000 mg/L, and Cl-Less than or equal to 500 mg/L, suspended matter less than or equal to 15mg/L，CODCrLess than or equal to 30 mg/L, less than or equal to 10 mg/L of ammonia nitrogen, less than or equal to 20 mg/L of total nitrogen, less than or equal to 2 mg/L of oil and less than or equal to 15 mg/L of fluoride.
And (2) a plate type grid is arranged in a regulating water tank of the cooling unit in the step (1) and particles larger than 100 microns in water are intercepted.
The immersed ultrafiltration membrane component of the immersed ultrafiltration unit in the step (2) adopts a hollow fiber curtain type membrane component, the material of the ultrafiltration membrane adopts Polytetrafluoroethylene (PTFE), and the aperture of the ultrafiltration membrane is 0.2 mu m.
And (3) the water quality SDI of the produced water of the immersed ultrafiltration unit in the step (2) is less than or equal to 3, and the turbidity is less than or equal to 0.2 NTU.
And (3) discharging cleaning water of an immersed ultrafiltration membrane tank of the immersed ultrafiltration unit in the step (2) to a neutralization tank through a pipeline, uniformly mixing the cleaning water in the neutralization tank through aeration, adding agents such as hydrochloric acid or sodium hydroxide to adjust the pH, pumping the cleaning water with the adjusted pH into a water collecting tank from the neutralization tank by a pump, then pumping the cleaning water from the water collecting tank to a high-density sedimentation tank by the pump, adding agents such as polyaluminum chloride and polyacrylamide into the high-density sedimentation tank for coagulating sedimentation, automatically flowing the effluent of the high-density sedimentation tank to a high-density production water tank, pumping the effluent of the high-density production water tank into a multi-media filter for filtering, wherein the pH of the filtered product water is 7.0-8.5, the SS is less than or equal to 5 mg/L, the turbidity is less than or equal to 5NTU, and returning the product water to an adjusting water tank.
And (3) the reverse osmosis membrane system of the reverse osmosis unit is divided into a first-stage membrane concentration and a second-stage membrane concentration, the yield recovery rate of the produced water of the reverse osmosis unit is more than or equal to 75%, the conductivity of the produced water is less than or equal to 100 mu S/cm, and the TDS is less than or equal to 50 mg/L.
And (3) adopting a medicament softening method to a softening clarification tank of the reverse osmosis concentrated water treatment unit in the step (4), adding medicaments comprising sodium hydroxide, sodium carbonate, polyaluminium chloride and polyacrylamide, and softening the reverse osmosis concentrated water to obtain reverse osmosis concentrated water with the hardness of less than or equal to 350 mg/L.
And (4) the pH value of the effluent of a softening and clarifying tank of the reverse osmosis concentrated water treatment unit in the step (4) is higher, a pH adjusting measure is arranged on the effluent of the softening and clarifying tank, the effluent is neutralized by adopting a medicament, the medicament is added to be hydrochloric acid, and the pH value of the effluent is adjusted to 7.0-8.0.
The step (4) is reversedThe nitrification denitrification filter of the osmotic concentrated water treatment unit adopts pre-nitrification and post-denitrification, and the volume load of the pre-nitrification filter is 0.58kgNH3-N/（m3D) filtration rate 3.0m3/（m2H); volume load of post denitrification filter tank is 3.10kgNO3-N/（m3D) filtration rate 9.0m3/（m2H), adding sodium acetate as a carbon source, inoculating and domesticating the nitrification and denitrification filter tank by adopting a high-salt-resistant and high-chloride-ion-resistant nitrification and denitrification strain, wherein the ammonia nitrogen in the effluent of the filter tank after domestication is less than or equal to 2 mg/L, and the total nitrogen is less than or equal to 5 mg/L.
And (5) adopting a hollow fiber membrane component as an external pressure type ultrafiltration membrane component of the external pressure type ultrafiltration unit, wherein the ultrafiltration membrane is made of polyvinylidene fluoride, and the nominal pore diameter of the ultrafiltration membrane is 0.03 mu m.
And (3) the nanofiltration membrane system of the nanofiltration unit in the step (6) is divided into a first stage and a second stage of membrane concentration, the yield of the nanofiltration produced water is more than or equal to 60 percent, the conductivity of the produced water is less than or equal to 900 mu S/cm, and the TDS is less than or equal to 450 mg/L.
And (3) the washing water of the reverse osmosis unit in the step (3) and the washing water of the nanofiltration unit in the step (6) come from a reverse osmosis water production tank. And (3) discharging acid and alkali cleaning wastewater for water production to a neutralization pond of the immersed ultrafiltration unit in the step (2) through a pipeline for treatment.
And (3) performing Fenton oxidation on the nanofiltration concentrated water treatment unit in the step (7), adopting a four-phase catalytic Fenton oxidation reactor, not needing to adjust the pH value before reaction, controlling the reaction pH value to be 5-7, adding medicaments such as hydrogen peroxide, ferrous sulfate, sodium hydroxide and polyacrylamide, and enabling the COD of the nanofiltration concentrated water subjected to Fenton treatment to be less than or equal to 50 mg/L.
And (3) performing Fenton oxidation on the nanofiltration concentrated water treatment unit in the step (7), and synchronously adding a polyaluminium chloride agent to remove fluoride, wherein the fluoride in the treated nanofiltration concentrated water is less than or equal to 10 mg/L.
And (3) after the effluent of the Fenton sedimentation tank of the nanofiltration concentrated water treatment unit in the step (7) enters an ozone contact oxidation tank and an activated carbon biological filter for treatment, the COD is less than or equal to 30 mg/L.
And (3) enabling the effluent of the active biological filter of the nanofiltration concentrated water treatment unit in the step (7) to enter a breakpoint chlorination tank, adding a sodium hypochlorite agent to further remove ammonia nitrogen, wherein the ammonia nitrogen of the treated nanofiltration concentrated water is less than or equal to 1 mg/L.
The nanofiltration concentrated water treated by the nanofiltration concentrated water treatment unit in the step (7) can meet various water quality index requirements specified in table 3 of 'water pollutant discharge Standard for iron and Steel industry' (GB 13456-2012), wherein the ammonia nitrogen is less than 1 mg/L, and the total nitrogen is less than 15 mg/L and less than 30 mg/L.
Drawings
FIG. 1 is a flow chart of the combined process for advanced treatment and recycling of wastewater from iron and steel industry of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The embodiment of the invention designs an advanced treatment and recycling combined process for steel industrial wastewater, which comprises the steps of treating the steel industrial wastewater by using an all-membrane method through an advanced treatment and recycling process combination, providing desalted water with different water qualities according to the requirements of users, enabling the total recycling rate of produced water to reach more than 85% under the condition that sludge is conveyed to the outside of a system for treatment, and enabling discharged concentrated brine to reach various water quality index requirements specified in table 3 of the discharge standard of pollutants for steel industrial water (GB 13456-2012) through a concentrated brine treatment process with lower cost. The invention solves the problem of high cost of the treatment of the strong brine by the double-membrane method, and is beneficial to the popularization of the double-membrane method.
The specific process flow is shown in figure 1 and comprises the following steps:
(1) a cooling unit: the cooling unit comprises a cooling tower, a regulating water tank and a plate type grid, and is used for cooling the steel industrial wastewater to be treated, regulating the water quantity and filtering fine particles;
(2) an immersed ultrafiltration unit: the immersed ultrafiltration unit comprises an immersed ultrafiltration membrane, an ultrafiltration water generating tank, a neutralization tank, a water collecting tank, a high-density sedimentation tank and a multi-medium filter. And the effluent of the cooling unit enters an immersed ultrafiltration membrane for filtration, and suspended matters and colloid in the wastewater are intercepted. Backwashing emptying water of the immersed ultrafiltration membrane is subjected to neutralization treatment, sedimentation in a high-density sedimentation tank and filtration by a multi-medium filter, and the treated wastewater enters a regulating water tank in a cooling unit;
(3) a penetration unit: the reverse osmosis unit comprises two sections of reverse osmosis membranes, and the effluent of the immersed ultrafiltration unit enters the reverse osmosis membrane unit for primary desalination to obtain reverse osmosis produced water and concentrated water;
(4) a reverse osmosis concentrated water treatment unit: comprises a softening clarification tank, an ozone oxidation tank, a nitrification and denitrification filter tank and a multi-media filter. Adding agents such as sodium hydroxide and sodium carbonate into the softening clarification tank, softening the reverse osmosis concentrated water, and removing heavy metals and partial fluorides in the concentrated water; after the pH of the effluent of the softening and clarifying tank is adjusted, the effluent enters an ozone tank to oxidize and degrade organic matters which are difficult to be biochemically degraded, the biodegradability of the concentrated water is improved, and the effluent enters a nitrification and denitrification biological filter to remove ammonia nitrogen and total nitrogen; and the effluent of the filter tank enters a clean water tank and is filtered by a multi-medium filter.
(5) External pressure type ultrafiltration unit: the effluent of the reverse osmosis concentrated water treatment unit enters an external pressure type ultrafiltration membrane for filtration, colloid, suspended matters and microorganisms are intercepted, and backwash water and concentrated water return to a softening clarification tank;
(6) and (3) nanofiltration unit: the nanofiltration unit comprises two sections of nanofiltration membranes, and effluent water filtered by the external pressure type ultrafiltration unit enters the nanofiltration membrane unit for secondary desalination to obtain nanofiltration product water and concentrated water;
(7) a nanofiltration concentrated water treatment unit: comprises Fenton oxidation, ozone oxidation, an activated carbon biological filter and a break point chlorination tank. Carrying out Fenton oxidation on nanofiltration concentrated water generated by the nanofiltration unit to remove organic matters, suspended matters and chromaticity in the concentrated water; adding a polyaluminium chloride agent into the Fenton precipitation tank to remove fluoride; the effluent of the Fenton sedimentation tank enters an ozone contact oxidation tank to remove organic matters difficult to degrade and improve the biodegradability of nanofiltration concentrated water, and then enters an activated carbon biological filter to further remove CODCrFinally adding chlorine through the break pointAnd adding sodium hypochlorite into the tank to remove ammonia nitrogen in the concentrated water and then discharging.
The invention is further illustrated by the following specific example. The example is an advanced treatment and recycling project constructed by a certain steel company by adopting the method, and the daily treated water amount is 2.5 ten thousand tons.
The process flow diagram is shown in figure 1.
The water quality characteristics of the steel industry wastewater in this example are as follows: water temperature of 45 deg.C, pH of 7.5, conductivity of 3000 μ S/cm, and total hardness (as CaCO)3Calculated) was 800 mg/L, total dissolved solids was 2000 mg/L, Cl-500 mg/L, suspension 15 mg/LCr30 mg/L, 10 mg/L ammonia nitrogen, 20 mg/L total nitrogen, 2 mg/L oil, 15 mg/L fluoride.
The method for carrying out advanced treatment and recycling on the steel industrial wastewater is described as follows:
the pretreated steel industrial wastewater is connected with an inlet of a cooling tower through a pipeline; the bottom of the cooling tower is a cooling tower water producing pool; a plate type grid is arranged at the outlet of the water producing pool of the cooling tower; the water outlet of the cooling tower is connected with the immersed ultrafiltration membrane pool through a pipeline and a flow channel; the immersed ultrafiltration membrane pool is connected with the ultrafiltration water production pool through a pipeline provided with a suction pump; the ultrafiltration water generating tank is connected with the immersed ultrafiltration membrane tank through a pipeline provided with a backwashing pump; the immersed ultrafiltration membrane pool is connected with the neutralization water collecting pool through a pipeline; the neutralization water collecting tank is connected with the high-density sedimentation tank through a pipeline provided with a lift pump; the inlet of the high-density sedimentation tank is provided with a dosing port; the water outlet of the high-density sedimentation tank is connected with a high-density production water tank through a pipeline; the high-density water production pond is connected with the multi-medium filter I through a pipeline provided with a booster pump; the water outlet of the multi-medium filter I is connected with a cooling tower water production pool through a pipeline; the ultrafiltration water producing tank is connected with the reverse osmosis device through a pipeline provided with a booster pump and a high-pressure pump; the water produced by the reverse osmosis device is connected with a water supply user through a pipeline; the water produced by the reverse osmosis device is connected with the cleaning water tank through a pipeline; the cleaning water tank is connected with the reverse osmosis device through a pipeline provided with a cleaning water pump; the reverse osmosis device is connected with the neutralization tank through a pipeline; the reverse osmosis concentrated water is connected with the softening clarification tank through a pipeline; the inlet and the outlet of the softening clarification tank are provided with a dosing port; the outlet of the softening and clarifying tank is connected with the ozone oxidation tank through a flow channel; the ozone oxidation tank is connected with the middle water tank through a water outlet; the middle water tank is connected with the nitrification denitrification filter tank through a pipeline provided with a lift pump; the nitrification and denitrification filter tank is provided with a carbon source feeding port; the effluent of the nitrification and denitrification filter tank is connected with a clean water tank through a pipeline; the clean water tank is connected with the nitrification denitrification filter tank through a pipeline provided with a backwashing water pump; backwashing drainage of the nitrification and denitrification filter tank is connected with a backwashing drainage tank I through a pipeline; the backwashing drainage tank is connected with the softening clarification tank through a pipeline provided with a lift pump; the clean water tank is connected with the multi-medium filter through a pipeline provided with a booster pump; the water outlet of the multi-medium filter II is connected with an external pressure type ultrafiltration raw water pool through a pipeline; the external pressure type ultrafiltration raw water pool is connected with external pressure type ultrafiltration through a pipeline provided with a booster pump; the external pressure type ultrafiltration produced water is connected with a nanofiltration raw water pool through a pipeline; the nanofiltration raw water tank is connected with external pressure type ultrafiltration through a pipeline provided with a backwashing water pump; the external pressure type ultrafiltration backwashing drainage is connected with a softening clarification tank through a pipeline; the nanofiltration raw water tank is connected with a nanofiltration device through a pipeline provided with a booster pump and a high-pressure pump; the nanofiltration water production tank is connected with a nanofiltration water production tank through a pipeline; the nanofiltration water producing tank is connected with a water supply user through a pipeline provided with a booster pump; the cleaning water tank is connected with the nanofiltration device through a pipeline provided with a cleaning water pump; the nanofiltration backwashing drainage is connected with a neutralization water collecting tank through a pipeline; the nanofiltration concentrated water is connected with a nanofiltration concentrated water tank through a pipeline; the nanofiltration concentrated water tank is connected with the Fenton reactor through a pipeline provided with a lift pump; the effluent of the Fenton reactor is connected with a Fenton sedimentation tank through a pipeline; the Fenton reactor and the Fenton sedimentation tank are provided with dosing ports; the effluent of the Fenton sedimentation tank is connected with an ozone oxidation tank through a flow channel; the ozone oxidation tank is connected with the activated carbon biological filter through a water outlet flow channel; the effluent of the activated carbon biological filter is connected with a break point chlorination tank through a flow channel; the break point chlorination tank is provided with a dosing port; the break point chlorination tank discharges the wastewater through a pipeline provided with a lift pump.
The daily treatment scale of the wastewater in the iron and steel industry treated by the method is 25000 tons, the process layout is compact, the occupied area is small, and the actual occupied area of the example is only 4656.39m2At a unit ofThe water treatment amount occupies only 0.19m of the floor area2/m3/d。
The method is adopted to treat the wastewater in the iron and steel industry, the nitrification and denitrification strains with high salt resistance and high chloride ion resistance are adopted in the nitrification and denitrification filter tank of the reverse osmosis concentrated water treatment unit for inoculation and domestication, the ammonia nitrogen in the effluent of the filter tank after the domestication is finished is less than or equal to 2 mg/L, and the total nitrogen is less than or equal to 5 mg/L.
After the method is adopted to treat the wastewater in the iron and steel industry, the reverse osmosis water yield of the embodiment is more than or equal to 76 percent, the water quality of the reverse osmosis water is less than or equal to 60 mu S/cm, the TDS is less than or equal to 35 mg/L, and the method can be supplied to iron and steel enterprises for producing soft water, desalted water and the like with strict requirements on water quality.
After the method is adopted to treat the wastewater in the iron and steel industry, the nanofiltration water yield of the embodiment is more than or equal to 65 percent, the nanofiltration water conductivity is less than or equal to 650 mu S/cm, the TDS is less than or equal to 350 mg/L, and the method can be used for supplying the water quality of iron and steel enterprises with general production recycling and fire fighting water.
After the method is adopted to treat the wastewater in the iron and steel industry, the reverse osmosis water production and the nanofiltration water production are recycled in a grading way by the process of the embodiment, so that the total water recovery rate of the whole system is more than or equal to 85 percent under the condition that the sludge is conveyed to the outside of the system for treatment.
After the method is adopted to treat the wastewater in the iron and steel industry, the discharge amount of concentrated water in the whole system is less than 10%, the water amount brought by discharged mud is less than 5%, the concentrated water treatment meets the requirements of various water quality indexes specified in table 3 of the discharge Standard of pollutants for Water in iron and steel industry (GB 13456-2012), wherein the ammonia nitrogen is less than 1 mg/L, and the total nitrogen is less than 15 mg/L and less than 30 mg/L.

Claims (18)

1. The combined process for advanced treatment and recycling of the wastewater in the steel industry is characterized by comprising the following steps of: (1) a cooling unit: the cooling unit comprises a cooling tower, a regulating water tank and a plate type grid, and is used for cooling the steel industrial wastewater to be treated, regulating the water quantity and filtering fine particles; (2) an immersed ultrafiltration unit: the immersed ultrafiltration unit comprises an immersed ultrafiltration membrane, an ultrafiltration water production tank, a neutralization tank, a water collecting tank, a high-density sedimentation tank and a multi-medium filter I, and the effluent of the cooling unit enters the immersed ultrafiltration membrane for carrying outFiltering, namely intercepting suspended matters and colloids in the wastewater, performing neutralization treatment on backwash emptying water of the immersed ultrafiltration membrane, precipitating in a high-density sedimentation tank, filtering by using a multi-medium filter I, and feeding the treated wastewater into a regulating water tank in a cooling unit; (3) a reverse osmosis unit: the reverse osmosis unit comprises two sections of reverse osmosis membranes, and the effluent of the immersed ultrafiltration unit enters the reverse osmosis membrane unit for primary desalination to obtain reverse osmosis produced water and concentrated water; (4) a reverse osmosis concentrated water treatment unit: the device comprises a softening clarification tank, an ozone oxidation tank, a nitrification and denitrification filter tank and a multi-media filter II, wherein sodium hydroxide and sodium carbonate are added into the softening clarification tank to soften the reverse osmosis concentrated water and remove heavy metals and partial fluoride in the concentrated water; after the pH of the effluent of the softening and clarifying tank is adjusted, the effluent enters an ozone oxidation tank to degrade organic matters, the biodegradability of concentrated water is improved, and the effluent enters a nitrification and denitrification biological filter to remove ammonia nitrogen and total nitrogen; the effluent of the filter tank enters a clean water tank and is filtered by a multi-media filter II, (5) an external pressure type ultrafiltration unit: the effluent of the reverse osmosis concentrated water treatment unit enters an external pressure type ultrafiltration membrane for filtration, colloid, suspended matters and microorganisms are intercepted, and the backwash water and the concentrated water return to a softening clarification tank of the reverse osmosis concentrated water treatment unit; (6) and (3) nanofiltration unit: the nanofiltration unit comprises two sections of nanofiltration membranes, and effluent water filtered by the external pressure type ultrafiltration unit enters the nanofiltration membrane unit for secondary desalination to obtain nanofiltration product water and concentrated water; (7) a nanofiltration concentrated water treatment unit: comprises Fenton oxidation, ozone oxidation, an active carbon biological filter and a break point chlorination tank, wherein nanofiltration concentrated water generated by a nanofiltration unit is subjected to Fenton oxidation to remove COD (chemical oxygen demand) in the concentrated waterCrSuspended matter and color; adding a polyaluminium chloride agent into the Fenton precipitation tank to remove fluoride; the effluent of the Fenton sedimentation tank enters an ozone contact oxidation tank to remove the COD which is difficult to degrade againCrImproving the biodegradability of nanofiltration concentrated water, and then entering an activated carbon biological filter for further removing CODCrAnd finally, sodium hypochlorite is added into the breaking point chlorination tank to further remove ammonia nitrogen in the concentrated water, and the concentrated water is discharged after reaching the standard.
2. The combined process for advanced treatment and recycling of wastewater from iron and steel industry as claimed in claim 1, wherein the combined process comprisesThe water quality of the steel industrial wastewater treated by the method after pretreatment is characterized by comprising the following steps: the water temperature is 15-45 ℃, the pH value is 6.0-9.0, the conductivity is less than or equal to 3000 mu S/cm, and the total hardness (as CaCO)3Calculated) is less than or equal to 800 mg/L, total dissolved solids are less than or equal to 2000 mg/L, and Cl-Less than or equal to 500 mg/L, and less than or equal to 15 mg/L of suspended mattersCrLess than or equal to 30 mg/L, less than or equal to 10 mg/L of ammonia nitrogen, less than or equal to 20 mg/L of total nitrogen, less than or equal to 2 mg/L of oil and less than or equal to 15 mg/L of fluoride.
3. The integrated process for advanced treatment and recycling of wastewater from iron and steel industry as claimed in claim 1, wherein the conditioning water tank of the cooling unit of step (1) is provided with a grid of plates to trap particles larger than 100 μm in water.
4. The combined process for advanced treatment and recycling of wastewater in iron and steel industry according to claim 1, wherein the immersed ultrafiltration membrane module of the immersed ultrafiltration unit in the step (2) is a hollow fiber curtain membrane module, the ultrafiltration membrane material is Polytetrafluoroethylene (PTFE), and the aperture of the ultrafiltration membrane is 0.2 μm.
5. The combined process for advanced treatment and recycling of wastewater in iron and steel industry according to claim 1, wherein the immersed ultrafiltration unit in the step (2) has a water quality SDI less than or equal to 3 and a turbidity less than or equal to 0.2 NTU.
6. The combined process for advanced treatment and recycling of wastewater in the iron and steel industry according to claim 1, characterized in that the cleaning water in the immersed ultrafiltration membrane tank of the immersed ultrafiltration unit in the step (2) is discharged to a neutralization tank through a pipeline, the neutralization tank is uniformly mixed by aeration, hydrochloric acid or sodium hydroxide is added to adjust the pH value, the cleaning water after the pH adjustment is pumped into a water collecting tank from the neutralization tank by a pump, the cleaning water is lifted to a high-density sedimentation tank from the water collecting tank by a pump, polyaluminium chloride and polyacrylamide are added to the high-density sedimentation tank for coagulating sedimentation, the effluent of the high-density sedimentation tank flows automatically to a high-density production water tank, the effluent is pumped into a multi-medium filter from the high-density production water tank for filtration, the pH value of the filtered production water is 7.0-8.5, the SS is less than or equal to 5 mg/L, the turbidity is less than or equal to 5U, and the production water returns to the adjustment water tank.
7. The combined process for the advanced treatment and recycling of wastewater in the iron and steel industry as claimed in claim 1, wherein the reverse osmosis membrane system of the reverse osmosis unit in the step (3) is divided into a first stage and a second stage for membrane concentration, the recovery rate of the produced water of the reverse osmosis unit is more than or equal to 75%, the conductivity of the produced water is less than or equal to 100 μ S/cm, and the TDS is less than or equal to 50 mg/L.
8. The combined process for advanced treatment and recycling of wastewater in the iron and steel industry according to claim 1, wherein the softening and clarifying tank of the reverse osmosis concentrated water treatment unit in the step (4) adopts a medicament softening method, wherein medicaments such as sodium hydroxide, sodium carbonate, polyaluminum chloride and polyacrylamide are added, and the hardness of the reverse osmosis concentrated water after softening treatment is less than or equal to 350 mg/L.
9. The combined process for advanced treatment and recycling of wastewater in iron and steel industry according to claim 1, wherein the softening and clarifying tank of the reverse osmosis concentrated water treatment unit in the step (4) has a high pH value of the effluent, a pH adjustment measure is provided on the effluent of the softening and clarifying tank, the effluent is neutralized by a medicament, hydrochloric acid is added into the softening and clarifying tank, and the pH value of the effluent is adjusted to 7.0-8.0.
10. The combined process for advanced treatment and recycling of wastewater in iron and steel industry according to claim 1, wherein the nitrification-denitrification filter tank of the reverse osmosis concentrated water treatment unit in the step (4) adopts pre-nitrification and post-denitrification, and the volume load of the pre-nitrification filter tank is 0.58kgNH3-N/(m3D) filtration rate 3.0m3/(m2H); volume load of post denitrification filter tank is 3.10kgNO3-N/(m3D) filtration rate 9.0m3/(m2H), adding sodium acetate as a carbon source, inoculating and domesticating the nitrification-denitrification filter tank by adopting a high-salt-resistant and high-chloride-ion-resistant nitrification-denitrification strain, wherein the ammonia nitrogen in the effluent of the filter tank after domestication is less than or equal to 2 mg/L, and the total nitrogen is less than or equal to 5 mg/L.
11. The combined process for advanced treatment and recycling of wastewater in iron and steel industry according to claim 1, wherein the external-pressure type ultrafiltration membrane module of the external-pressure type ultrafiltration unit in the step (5) is a hollow fiber membrane module, the ultrafiltration membrane is made of polyvinylidene fluoride, and the nominal pore diameter of the ultrafiltration membrane is 0.03 μm.
12. The combined process for the advanced treatment and recycling of wastewater in the iron and steel industry as claimed in claim 1, wherein the nanofiltration membrane system of the nanofiltration unit in the step (6) is divided into a first stage and a second stage for membrane concentration, the recovery rate of the nanofiltration produced water is not less than 60%, the conductivity of the produced water is not more than 900 μ S/cm, and the TDS is not more than 450 mg/L.
13. The combined process for advanced treatment and recycling of wastewater in iron and steel industry according to claim 1, wherein the cleaning water of the reverse osmosis unit in the step (3) and the nanofiltration unit in the step (6) comes from a reverse osmosis water production tank, and the generated acid-base cleaning wastewater is discharged to the neutralization tank of the submerged ultrafiltration unit in the step (2) through a pipeline for treatment.
14. The combined process for advanced treatment and recycling of wastewater in iron and steel industry according to claim 1, wherein the step (7) of Fenton oxidation of the nanofiltration concentrated water treatment unit adopts a four-phase catalytic Fenton reactor, the pH is not required to be adjusted before the Fenton reaction, the reaction pH is controlled to be 5-7, and the reagents are hydrogen peroxide, ferrous sulfate, sodium hydroxide and polyacrylamide, and the Fenton treated nanofiltration concentrated water COD is treated by FentonCr≤50mg/L。
15. The combined process for advanced treatment and recycling of wastewater in iron and steel industry according to claim 1, wherein the Fenton oxidation unit of the nanofiltration concentrated water treatment unit in the step (7) is synchronously added with polyaluminum chloride to remove fluoride, and the treated nanofiltration concentrated water has fluoride content of less than or equal to 10 mg/L.
16. The combined process for the advanced treatment and recycling of wastewater in the iron and steel industry according to claim 1, wherein COD is less than or equal to 30 mg/L after the effluent of the Fenton precipitation tank of the nanofiltration concentrated water treatment unit in the step (7) enters the ozone contact oxidation tank and the activated carbon biological filter for treatment.
17. The combined process for advanced treatment and recycling of wastewater in the iron and steel industry according to claim 1, wherein the outlet water of the active biofilter of the nanofiltration concentrated water treatment unit in the step (7) enters a break point chlorination tank, sodium hypochlorite is added to further remove ammonia nitrogen, and the ammonia nitrogen of the treated nanofiltration concentrated water is less than or equal to 1 mg/L.
18. The combined process for advanced treatment and recycling of wastewater in iron and steel industry according to claim 1, wherein the nanofiltration concentrated water treated by the nanofiltration concentrated water treatment unit in the step (7) meets the requirements of various water quality indexes specified in table 3 of the emission standard of pollutants for water in iron and steel industry (GB 13456-2012), wherein the ammonia nitrogen is less than 1 mg/L, and the total nitrogen is less than 15 mg/L and less than 30 mg/L.
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