CN111233237A - Method for realizing zero discharge of high-concentration brine in steel production enterprise - Google Patents
Method for realizing zero discharge of high-concentration brine in steel production enterprise Download PDFInfo
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- 239000012267 brine Substances 0.000 title claims abstract description 39
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 25
- 239000010959 steel Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- 238000005189 flocculation Methods 0.000 claims abstract description 29
- 230000016615 flocculation Effects 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 26
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 230000008020 evaporation Effects 0.000 claims abstract description 14
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013505 freshwater Substances 0.000 claims abstract description 11
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000013522 chelant Substances 0.000 claims abstract description 6
- 239000010802 sludge Substances 0.000 claims abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000003860 storage Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 5
- 239000002351 wastewater Substances 0.000 claims description 61
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 5
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
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- 239000000126 substance Substances 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 3
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- 238000011084 recovery Methods 0.000 abstract description 6
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 11
- 239000007788 liquid Substances 0.000 description 5
- 238000010612 desalination reaction Methods 0.000 description 4
- 238000009292 forward osmosis Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/444—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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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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
- 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
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Abstract
The invention relates to a method for zero discharge of high-concentration brine in iron and steel production enterprises, wherein the high-concentration brine firstly enters an adjusting tank, alkali liquor is added while stirring, and the effluent of the adjusting tank enters a first ozone oxidation tower and enters an electric flocculation device; the discharged sludge enters a sludge treatment system for treatment; the effluent of the electric flocculation enters an electric adsorption device, the produced water after the electric adsorption treatment enters a sand filtration device, the effluent enters an ultrafiltration device, the concentrated water of the ultrafiltration device flows back to an adjusting tank for circular treatment, the ultrafiltration produced water enters chelate ion exchange resin, the effluent enters a two-stage reverse osmosis system RO for concentration and separation, the produced water enters a fresh water storage tank, high-salt water enters a second ozone oxidation tower, and high-purity sodium chloride and sodium sulfate crystal salt are obtained through evaporation and crystallization. The advantages are that: the recovery of high-concentration metallurgical salt water is realized in the treatment process, the crystallized solid salt reaches the industrial salt standard, the energy consumption of the process is low, the cost is low, and the treatment effect is stable.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a method for realizing zero discharge of high-concentration brine in steel production enterprises.
Background
The unit water consumption of the steel enterprises in China is still higher than the level of the advanced steel enterprises in China, so that the new water consumption per ton of steel of the steel enterprises is further reduced, the cyclic utilization rate of water of the steel enterprises is improved, and the comprehensive treatment and recycling of wastewater of the steel enterprises are enhanced, which is one of the keys for realizing sustainable development of the steel enterprises.
The reuse of wastewater is the final target of wastewater treatment, but after the wastewater is subjected to reverse osmosis treatment, most of primary pure water is obtained, and simultaneously, a large proportion of high-salinity concentrated water is also produced, the concentrated water is an inevitable product of a reverse osmosis desalination process, contains high organic matters and salt concentration, and the concentrated water content is about 25% of the reverse osmosis treatment water content. For the high-salinity concentrated water, the treatment method at the present stage is basically direct discharge, which causes a great deal of resource waste and environmental pollution.
In the prior art, the Chinese patent application number: 201010283192.3, discloses a process for desalting strong brine by pervaporation technology and recovers purified water. The process can concentrate strong brine to the maximum extent, and has high desalting rate and low effluent conductivity. Meanwhile, the heat recovery technology is combined, the overall energy consumption of the system is greatly reduced, and the system can be used for desalting wastewater such as reverse osmosis concentrated drainage, circulating cooling sewage and the like. The technology has high operation energy consumption, needs to heat the strong brine to more than 60 ℃, can only remove salt in the strong brine, and can not remove COD in the strong brine.
Chinese patent application No.: 201110212189.7 discloses a strong brine processing system, this scheme can not get rid of ammonia nitrogen and nitre nitrogen in the strong brine, and the structure is complicated moreover, is difficult for operation management.
Chinese patent application No.: 200910070804.8, a forward osmosis membrane module is adopted, the seawater desalination strong brine is used as a drawing liquid, fresh water is used as a feeding liquid, part of the fresh water which permeates the seawater desalination strong brine at the permeation side of the forward osmosis membrane module and the feeding liquid side is mixed into diluted standard salt water and then is discharged out of the forward osmosis membrane module, and the rest of the feeding liquid is discharged out of the forward osmosis membrane module. The technology can only be used for treating the seawater strong brine, and is not suitable for the strong brine process in the metallurgical industry.
Chinese patent publication No.: CN1030773143B discloses a strong brine zero-discharge treatment process of a steel plant, which adopts a three-stage reverse osmosis process to concentrate wastewater and then carries out evaporation crystallization. The concentration of the three-stage reverse osmosis has high operation cost, and the process does not consider the problems of organic matter pollution, inorganic matter scaling and the like of the reverse osmosis membrane, so that the popularization and the application are limited.
Chinese patent publication No.: CN1030773143B discloses a high-efficiency liquid zero-discharge wastewater treatment method and system, which has the advantages of low energy consumption and high efficiency, but the obtained mixed salt cannot be disposed to become secondary pollutants, even dangerous waste, and thus the problem of recycling solid salts is not solved.
Chinese patent publication No.: CN104370396B discloses a sea water desalination strong brine zero-discharge treatment method and device, mainly adopting electrodialysis to carry out the reconcentration of waste water, reaching the state close to saturated salt, the process has very high operation cost and complex operation, and is not beneficial to large-scale popularization and application.
In conclusion, the existing metallurgical wastewater treatment process has the defects of poor treatment effect, serious membrane pollution, low water yield of a system and overhigh process operation cost. Therefore, the development of an efficient method for zero discharge of the high-concentration salt water of the steel can greatly reduce the adverse effect of the discharge of the comprehensive waste water of the steel on the environment of the surrounding water area, and the resource utilization of the production waste water is a new benefit growth point.
Disclosure of Invention
Aiming at the strong brine discharged by steel enterprises, the strong brine is sequentially subjected to ozone oxidation, electric flocculation, electric adsorption, sand filtration, ultrafiltration, softening resin, reverse osmosis, ozone oxidation and multiple-effect evaporation treatment, so that the metallurgical high-concentration brine is recycled, and simultaneously, the evaporated crystal salt reaches the industrial salt standard, and the aim of zero discharge of the metallurgical high-concentration brine is fulfilled.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for realizing zero discharge of high-concentration brine in steel production enterprises comprises the following steps:
1) high-concentration salt water firstly enters an adjusting tank, alkali liquor is added while stirring, the pH value of the wastewater is controlled to be 9.5-10.5, the effluent of the adjusting tank enters a first ozone oxidation tower, the adding amount of ozone is 20-24mg/L, under the strong oxidation effect of ozone, organic matters which cannot be biodegraded in the wastewater are oxidized into micromolecule organic matters which are easy to biodegrade or are partially mineralized by the ozone, and the effluent of the first ozone oxidation tower enters an electric flocculation device;
2) the electric flocculation device utilizes the high salinity characteristic of the wastewater to reduce the electric quantity consumption required by electric flocculation, an aluminum-iron polar plate is selected as an electrode material of the electric flocculation device, the reaction voltage is controlled to be 3V-4V, the distance between the polar plates is 2cm-3cm, the reaction time is 25min-35min, the pH value of the wastewater is 7.0-8.0, the power supply adopts a periodic reversing power supply, the cathode and the anode of the electric flocculation are exchanged in a certain period, and the reversing period is 8s-10 s; sludge discharged by the electric flocculation device enters a sludge treatment system for treatment, and is reduced after electric flocculation treatment, so that suspended matters and calcium and magnesium metal ions in wastewater are effectively reduced;
3) the effluent of the electric flocculation enters electric adsorption equipment, and the electric adsorption technology is to utilize a charged electrode to adsorb ions and charged particles in water, so that dissolved salts and other charged substances are enriched and concentrated on the surface of the electrode to realize wastewater purification. Controlling the voltage of a polar plate to be 1.0-1.4V, the distance between polar plates to be 1cm-2cm, the pH value of wastewater to be 7.0-8.0, returning electro-adsorption concentrated water to a front-end regulating reservoir, feeding produced water after electro-adsorption treatment into a sand filter device, adopting a single-layer quartz sand homogeneous filter material, further reducing the turbidity and suspended matters of the filtered effluent water, feeding sand filter backwash water into a front-end regulating reservoir, feeding the effluent water into an ultrafiltration device, controlling the pH value of the wastewater to be 6.2-6.6, further intercepting the suspended matters and colloidal pollutants in the wastewater through an ultrafiltration membrane, feeding the concentrated water of the ultrafiltration device back to the regulating reservoir for cyclic treatment, feeding the ultrafiltration produced water into chelate ion exchange resin, adsorbing residual metal ions in the wastewater through the exchange performance of the resin, feeding regenerated wastewater of the ion exchange resin back to the regulating reservoir for cyclic treatment, feeding the resin effluent water into a two-stage reverse osmosis system (RO) for concentration, intercepting most of salt and micromolecule organic matters in the wastewater, enabling water produced by the RO of the second-stage reverse osmosis system to enter a fresh water storage tank for being reused by fresh water users, enabling high-salt water produced by the RO of the second-stage reverse osmosis system to enter a second ozone oxidation tower, controlling the pH of the wastewater to be 9.5-10.5, enabling the adding amount of ozone to be 24-28mg/L, further degrading the concentrated organic matters of the RO of the second-stage reverse osmosis system, enabling the water discharged from the second ozone oxidation tower to enter a multi-effect evaporation device, and obtaining high-purity sodium chloride and sodium sulfate crystal salt through evaporation and crystallization.
The high-concentration brine is produced by a reverse osmosis process for steel production, wherein the pH value is 7.0-8.5, the conductivity is 8.0-9.0ms/cm, the COD is 70-100mg/L, and the total hardness is 1200-1400 mg/L.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an integrated process treatment method consisting of ozone oxidation, electric flocculation, electric adsorption, sand filtration, ultrafiltration, resin softening, reverse osmosis, ozone oxidation and multiple-effect evaporation for high-concentration brine of steel enterprises, the recovery of metallurgy high-concentration brine is realized in the treatment process, the crystallized solid salt reaches the industrial salt standard, and a new benefit growth point is formed.
Drawings
FIG. 1 is a process flow diagram of a zero discharge method of high-concentration brine in steel manufacturing enterprises.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1
Referring to FIG. 1, the high-concentration brine is the high-concentration brine produced by the reverse osmosis process for steel production, wherein the pH value is 7.0-8.5, the conductivity is 8.0-9.0mS/cm, the COD is 70-100mg/L, and the total hardness is 1200-1400 mg/L.
During treatment, high-concentration brine firstly enters an adjusting tank, alkali liquor is added while stirring, the pH value of wastewater is controlled to be 9.5, effluent of the adjusting tank enters a first ozone oxidation tower, the adding amount of ozone is 20mg/L, effluent of the first ozone oxidation tower enters an electric flocculation device, an aluminum-iron polar plate is selected as an electrode material of the electric flocculation device, the reaction voltage is controlled to be 3V, the distance between polar plates is 2cm, the reaction time is 25min, the pH value of the wastewater is 7.0, a periodic reversing power supply is adopted as the power supply, and the reversing period is 8 s. The effluent of the electric flocculation enters electric adsorption equipment, the voltage of a polar plate is controlled to be 1.0V, the distance between the polar plates is 1cm, the pH value of the wastewater is 7.0, and the electric adsorption concentrated water returns to a front-end regulating reservoir.
The product water after the electro-adsorption treatment gets into sand filtration device, adopts the homogeneity filter material of individual layer quartz sand, and the play water turbidity and suspended solid further reduce after the filtration, and sand filtration backwash water gets into the front end equalizing basin, and play water gets into ultrafiltration device, and control waste water pH is 6.2, further holds back suspended solid, colloid class polluting substances in the waste water through the milipore filter, and ultrafiltration device's dense water flows back to the equalizing basin and carries out circulation treatment.
The ultrafiltration produced water enters chelate ion exchange resin, residual calcium and magnesium metal ions in the wastewater are adsorbed by the exchange performance of the resin, the regeneration wastewater of the ion exchange resin flows back to a regulating tank for circulation treatment, the resin effluent enters a two-stage reverse osmosis system (RO) for concentration and separation, most of salt, micromolecule organic matters and the like in the wastewater are intercepted, the produced water of the two-stage RO system (the conductance is less than 80 mus/cm, the COD is less than 5mg/L and the total hardness is less than 0.1mg/L) enters a fresh water storage tank for being reused by fresh water users, the total recovery rate of the system reaches 91 percent, high-salt water produced by the two-stage RO system enters a second ozone oxidation tower, the pH of the wastewater is controlled to be 9.5, the ozone adding amount is 24mg/L, and the high-salt waterThe RO concentrated organic matter is further degraded, the effluent of the second ozone oxidation tower enters a multi-effect evaporation device, and industrial sodium chloride and industrial sodium sulfate crystal salt are obtained through evaporation and crystallization, wherein the industrial NaCl reaches the secondary standard of industrial dry salt of GB/T5462-2003 Industrial salt, and the industrial Na reaches the secondary standard of industrial dry salt2SO4Reaches class II first-class standard of GB/T6009-2014.
Example 2
Referring to FIG. 1, the high-concentration brine is the high-concentration brine produced by the reverse osmosis process for steel production, wherein the pH value is 7.0-8.5, the conductivity is 8.0-9.0mS/cm, the COD is 70-100mg/L, and the total hardness is 1200-1400 mg/L.
During treatment, high-concentration brine firstly enters an adjusting tank, alkali liquor is added while stirring, the pH value of wastewater is controlled to be 10.0, effluent of the adjusting tank enters a first ozone oxidation tower, the adding amount of ozone is 22mg/L, effluent of the first ozone oxidation tower enters an electric flocculation device, an aluminum-iron polar plate is selected as an electrode material of the electric flocculation device, the reaction voltage is controlled to be 3.5V, the distance between polar plates is 2.5cm, the reaction time is 30min, the pH value of the wastewater is 7.5, a periodic reversing power supply is adopted as the power supply, and the reversing period is 9 s. The effluent of the electric flocculation enters electric adsorption equipment, the voltage of a polar plate is controlled to be 1.2V, the distance between the polar plates is controlled to be 1.5cm, the pH value of wastewater is 7.5, and the electric adsorption concentrated water returns to a front-end regulating tank.
The product water after the electro-adsorption treatment gets into sand filtration device, adopts the homogeneity filter material of individual layer quartz sand, and the play water turbidity and suspended solid further reduce after the filtration, and sand filtration backwash water gets into the front end equalizing basin, and play water gets into ultrafiltration device, and control waste water pH is 6.4, further holds back suspended solid, colloid class polluting substances in the waste water through the milipore filter, and ultrafiltration device's dense water flows back to the equalizing basin and carries out circulation treatment.
The ultrafiltration produced water enters chelate ion exchange resin, residual calcium and magnesium metal ions in the wastewater are adsorbed by the exchange performance of the resin, the regeneration wastewater of the ion exchange resin flows back to a regulating tank for circulation treatment, the resin effluent enters a two-stage reverse osmosis system (RO) for concentration and separation, most of salt, micromolecular organic matters and the like in the wastewater are intercepted, the produced water of the two-stage RO system (the conductance is less than 80 mu s/cm, the COD is less than 5mg/L, and the total hardness is less than 0.1mg/L) enters new waterThe water storage pool is reused for new water users, the total recovery rate of the system reaches 92 percent, high-salt water generated by the two-stage RO system enters a second ozone oxidation tower, the pH value of the wastewater is controlled to be 10.0, the ozone adding amount is 26mg/L, the organic matters concentrated by the two-stage RO system are further degraded, the water discharged from the second ozone oxidation tower enters a multi-effect evaporation device, industrial sodium chloride and industrial sodium sulfate crystal salt are obtained through evaporation and crystallization, wherein the industrial NaCl reaches the industrial dry salt secondary standard of GB/T5462-2003 'industrial salt', and the industrial Na reaches the industrial dry salt secondary standard2SO4Reaches class II first-class standard of GB/T6009-2014.
Example 3
Referring to FIG. 1, the high-concentration brine is the high-concentration brine produced by the reverse osmosis process for steel production, wherein the pH value is 7.0-8.5, the conductivity is 8.0-9.0mS/cm, the COD is 70-100mg/L, and the total hardness is 1200-1400 mg/L.
During treatment, high-concentration brine firstly enters an adjusting tank, hydrochloric acid is added while stirring, the pH value of wastewater is controlled to be 10.5, the effluent of the adjusting tank enters a first ozone oxidation tower, the adding amount of ozone is 24mg/L, the effluent of the first ozone oxidation tower enters an electric flocculation device, an aluminum-iron polar plate is selected as an electrode material of the electric flocculation device, the reaction voltage is controlled to be 4.0V, the distance between polar plates is 3.0cm, the reaction time is 35min, the pH value of the wastewater is 8.0, a periodic reversing power supply is adopted as the power supply, and the reversing period is 10 s. The effluent of the electric flocculation enters electric adsorption equipment, the voltage of a polar plate is controlled to be 1.4V, the distance between the polar plates is 2.0cm, the pH value of the wastewater is 8.0, and the concentrated electric adsorption water returns to a front-end regulating reservoir.
The product water after the electro-adsorption treatment gets into sand filtration device, adopts the homogeneity filter material of individual layer quartz sand, and the play water turbidity and suspended solid further reduce after the filtration, and sand filtration backwash water gets into the front end equalizing basin, and play water gets into ultrafiltration device, and control waste water pH is 6.6, further holds back suspended solid, colloid class polluting substances in the waste water through the milipore filter, and ultrafiltration device's dense water flows back to the equalizing basin and carries out circulation treatment.
The ultrafiltration produced water enters chelate ion exchange resin, residual calcium and magnesium metal ions in the wastewater are adsorbed by the exchange performance of the resin, and the regeneration wastewater of the ion exchange resin flows back to the regulating tank for circular treatment. Resin outThe water enters a two-stage reverse osmosis system (RO) for concentration and separation, most of salt, micromolecular organic matters and the like in the wastewater are intercepted, the water produced by the two-stage RO system (the conductance is less than 80 mu s/cm, the COD is less than 5mg/L, the total hardness is less than 0.1mg/L) enters a fresh water storage tank for reuse in fresh water users, the total recovery rate of the system reaches 90 percent, high-salt water generated by the two-stage RO system enters a second ozone oxidation tower, the pH of the wastewater is controlled to be 10.5, the ozone adding amount is 28mg/L, the organic matters concentrated by the two-stage RO are further degraded, the water discharged from the second ozone oxidation tower enters a multi-effect evaporation device, and industrial sodium chloride and industrial sodium sulfate crystal salt are obtained through evaporation and crystallization, wherein the industrial NaCl reaches the industrial dry salt secondary standard of GB/T5462-2SO4Reaches class II first-class standard of GB/T6009-2014.
Claims (2)
1. A method for realizing zero discharge of high-concentration brine in steel production enterprises is characterized by comprising the following steps:
1) high-concentration salt water firstly enters an adjusting tank, alkali liquor is added while stirring, the pH value of the wastewater is controlled to be 9.5-10.5, the effluent of the adjusting tank enters a first ozone oxidation tower, the adding amount of ozone is 20-24mg/L, under the strong oxidation effect of ozone, organic matters which cannot be biodegraded in the wastewater are oxidized into micromolecule organic matters which are easy to biodegrade or are partially mineralized by the ozone, and the effluent of the first ozone oxidation tower enters an electric flocculation device;
2) the electric flocculation device utilizes the high salinity characteristic of the wastewater to reduce the electric quantity consumption required by electric flocculation, an aluminum-iron polar plate is selected as an electrode material of the electric flocculation device, the reaction voltage is controlled to be 3V-4V, the distance between the polar plates is 2cm-3cm, the reaction time is 25min-35min, the pH value of the wastewater is 7.0-8.0, the power supply adopts a periodic reversing power supply, the cathode and the anode of the electric flocculation are exchanged in a certain period, and the reversing period is 8s-10 s; sludge discharged by the electric flocculation device enters a sludge treatment system for treatment, and is reduced after electric flocculation treatment, so that suspended matters and calcium and magnesium metal ions in wastewater are effectively reduced;
3) the effluent of the electric flocculation enters electric adsorption equipment, and the electric adsorption technology is to utilize a charged electrode to adsorb ions and charged particles in water, so that dissolved salts and other charged substances are enriched and concentrated on the surface of the electrode to realize wastewater purification. Controlling the voltage of a polar plate to be 1.0-1.4V, the distance between polar plates to be 1cm-2cm, the pH value of wastewater to be 7.0-8.0, returning electro-adsorption concentrated water to a front-end regulating reservoir, feeding produced water after electro-adsorption treatment into a sand filter device, adopting a single-layer quartz sand homogeneous filter material, further reducing the turbidity and suspended matters of the filtered effluent water, feeding sand filter backwash water into a front-end regulating reservoir, feeding the effluent water into an ultrafiltration device, controlling the pH value of the wastewater to be 6.2-6.6, further intercepting the suspended matters and colloidal pollutants in the wastewater through an ultrafiltration membrane, feeding the concentrated water of the ultrafiltration device back to the regulating reservoir for cyclic treatment, feeding the ultrafiltration produced water into chelate ion exchange resin, adsorbing residual metal ions in the wastewater through the exchange performance of the resin, feeding regenerated wastewater of the ion exchange resin back to the regulating reservoir for cyclic treatment, feeding the resin effluent water into a two-stage reverse osmosis system (RO) for concentration, intercepting most of salt and micromolecule organic matters in the wastewater, enabling water produced by the RO of the second-stage reverse osmosis system to enter a fresh water storage tank for being reused by fresh water users, enabling high-salt water produced by the RO of the second-stage reverse osmosis system to enter a second ozone oxidation tower, controlling the pH of the wastewater to be 9.5-10.5, enabling the adding amount of ozone to be 24-28mg/L, further degrading the concentrated organic matters of the RO of the second-stage reverse osmosis system, enabling the water discharged from the second ozone oxidation tower to enter a multi-effect evaporation device, and obtaining high-purity sodium chloride and sodium sulfate crystal salt through evaporation and crystallization.
2. The method for zero discharge of high-concentration brine in steel enterprises as claimed in claim 1, wherein the high-concentration brine is produced by a reverse osmosis process for steel production, and has a pH of 7.0-8.5, an electrical conductivity of 8.0-9.0ms/cm, a COD of 70-100mg/L, and a total hardness of 1200-1400 mg/L.
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