CN113562905B - Advanced treatment method and system for high-salinity wastewater - Google Patents
Advanced treatment method and system for high-salinity wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 163
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000001179 sorption measurement Methods 0.000 claims abstract description 73
- 238000000909 electrodialysis Methods 0.000 claims abstract description 56
- 238000004062 sedimentation Methods 0.000 claims abstract description 50
- 238000001471 micro-filtration Methods 0.000 claims abstract description 31
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 230000008020 evaporation Effects 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 58
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 239000003814 drug Substances 0.000 claims description 18
- 229960002089 ferrous chloride Drugs 0.000 claims description 17
- 239000011790 ferrous sulphate Substances 0.000 claims description 17
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 17
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 17
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 17
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- 229920002401 polyacrylamide Polymers 0.000 claims description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 14
- 239000011630 iodine Substances 0.000 claims description 14
- 229910052740 iodine Inorganic materials 0.000 claims description 14
- 230000014759 maintenance of location Effects 0.000 claims description 14
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 14
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical compound CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 claims description 8
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229960003194 meglumine Drugs 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 230000004907 flux Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000035699 permeability Effects 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 pH is 7-8 Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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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
- C02F1/02—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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F1/52—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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a high-salinity wastewater advanced treatment method and system, wherein the method comprises the following steps: the high-salt wastewater enters a modified activated carbon adsorption tower, modified activated carbon is placed in the modified activated carbon adsorption tower, and COD (chemical oxygen demand) of the high-salt wastewater after passing through the modified activated carbon adsorption tower is 8-23 mg/L; the high-salt wastewater enters a hard-removing dosing sedimentation tank, and passes through the hard-removing dosing sedimentation tank, wherein the pH value is 7-8, the COD is 8-23 mg/L, and the calcium hardness is 7-16 mg/L; the high-salt wastewater enters microfiltration through a secondary lifting pump, enters an electrodialysis system through a tertiary lifting pump, and after passing through the electrodialysis system, the produced water can be reused for production; the concentrated water generated by the method can be discharged by a drainage pump and enters an evaporation crystallization system to be directly evaporated to dryness to form crystalline salt. The invention is an economic and efficient advanced treatment technical scheme, reduces environmental pollution and actively meets increasingly strict environmental protection regulations.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a high-salinity wastewater advanced treatment method and system.
Background
The iron and steel industry is an industry with high energy consumption, high resource and high pollution, and the water resource consumption is huge and accounts for about 14 percent of the water consumption of the national industry.
The unit water consumption of the iron and steel enterprises in China is still higher than the level of the advanced iron and steel enterprises abroad, the new water consumption per ton of steel for the iron and steel enterprises is further reduced, the recycling rate of water for the iron and steel enterprises is improved, and the enhancement of the comprehensive treatment and recycling of wastewater of the iron and steel enterprises is one of the keys for realizing sustainable development of the iron and steel enterprises in China.
The organic pollutant and nitrate nitrogen in the high-salt wastewater generated by steel are high, and the direct (or neutral) discharge of the high-salt wastewater causes serious water pollution and resource waste. To date, there is no process or method for treating high-salt wastewater.
Disclosure of Invention
The invention aims to provide a high-salt wastewater advanced treatment method and a system according to the water quality and water quantity of high-salt wastewater, develop an economic and efficient advanced treatment technical scheme, reduce environmental pollution and actively cope with increasingly strict environmental protection regulations.
The invention provides a complete advanced treatment method for high-salt wastewater for the first time, and the system solves the pollution problem of the high-salt wastewater, and after the advanced treatment of the high-salt wastewater, the high-salt wastewater can reach the standard and be discharged and recycled for production, thereby belonging to a steel green and environment-friendly production process system.
The technical scheme adopted by the invention is as follows:
a high-salinity wastewater advanced treatment method comprises the following steps:
(1) The high-salt wastewater enters a modified activated carbon adsorption tower, modified activated carbon is placed in the modified activated carbon adsorption tower, and the modified activated carbon accounts for 75-90% of the volume of the whole adsorption tower; COD of the high-salt wastewater after passing through the modified activated carbon adsorption tower is 8-23 mg/L;
(2) The high-salt wastewater enters a hard-removing dosing sedimentation tank which is divided into two parts, wherein the front part is a stirring tank, and the rear part is a sedimentation tank; sodium carbonate and polyacrylamide are added into the front stirring pool, the adding amount of the sodium carbonate is 780-1010 mg/L, preferably 890-1000 mg/L, the polyacrylamide is anionic, and the adding amount is 0.5-2 mg/L, preferably 0.6-0.9 mg/L; the medicament and the high-salt wastewater are fully mixed and then enter a sedimentation tank, and the retention time in the sedimentation tank is 25-40 min; the mixture passes through a hard removal and dosing sedimentation tank, the pH value is 7-8, the COD is 8-23 mg/L, and the calcium hardness is 7-16 mg/L;
(3) The high-salt wastewater enters a microfiltration device, the pressure pump pressure of the microfiltration is 0.3-0.6 MPa, the aperture is 0.23-0.30 mu m, and the flux is 120-180L/m 2 H, the calcium hardness after microfiltration is 5-13 mg/L;
(4) The high-salt wastewater enters an electrodialysis system, the electrodialysis membrane thickness is 0.14-0.19 mm, the exchange capacity is 1.5-2.3 mol/kg, and the surface resistance is 2.0-10.5 ohm cm 2 The selective permeability of the whole electrodialysis system is 97-99%, and the water yield is 69-82%; after passing through the electrodialysis system, the produced water can be reused for production; the concentrated water produced by the method can enter an evaporative crystallization system to be directly evaporated to dryness to form crystalline salt.
According to the advanced treatment method of the high-salinity wastewater, the water quality characteristics of the high-salinity wastewater are as follows: pH is 7-8, COD is 34-89 mg/L, calcium hardness is 65-138 mg/L, and TDS is 13470-18900 mg/L.
According to the advanced treatment method of the high-salt wastewater, the modified activated carbon in the step (1) is prepared according to the water quality condition of the high-salt wastewater by the following steps: 1) Screening active carbon; 2) Preparing a solution: preparing a ferrous sulfate solution and a ferrous chloride solution, and mixing the ferrous sulfate solution and the ferrous chloride solution according to a volume ratio of 3-5:1 to form a ferrous solution; 3) Dipping: adding active carbon, zinc chloride, meglumine and polymethacrylic acid into a ferrous solution to form an active carbon-ferrous mixed solution, and carrying out ultrasonic treatment and impregnation; 4) Calcining: filtering, washing the activated carbon with clear water, drying, cooling, putting into a muffle furnace, heating to 260-310 ℃, keeping the temperature for 45-70 min, and cooling to form the modified activated carbon.
According to the advanced treatment method of the high-salt wastewater, the modified activated carbon medicament is prepared by the following specific steps according to the water quality condition of the high-salt wastewater: 1) Screening of activated carbon: selecting coal-made granular activated carbon with the grain diameter of 1.6-2.7 mm, preferably 1.8-2.2 mm; the strength is 92-94%, the specific surface area is 980-1210 cm 2 Preferably 990 to 1200cm per gram 2 Per gram, the iodine adsorption capacity is 810-950 mg/g, and the methylene blue adsorption capacity is 80-120 mg/g; 2) Preparing a solution: and (2) preparing.4 to 3.9mol/L ferrous sulfate solution, preferably 2.7 to 3.0 mol/L, 1.2 to 1.9mol/L ferrous chloride solution, preferably 1.5 to 1.7mol/L ferrous sulfate solution and ferrous chloride solution are prepared, and the ferrous sulfate solution and the ferrous chloride solution are mixed according to a volume ratio of 3 to 5:1 to form a ferrous solution; 3) Dipping: adding 35-67 g of active carbon, 1-3 g of zinc chloride, 4-12 g of meglumine and 1-3 mL of polymethacrylic acid into each liter of ferrous solution to form an active carbon-ferrous mixed solution, carrying out ultrasonic treatment at 200Hz for 10-25 min, and then soaking for 8-12 h; 4) Calcining: filtering, washing the activated carbon to be neutral by using clear water, drying in a cleaned activated carbon oven, cooling, then placing in a muffle furnace, heating to 260-310 ℃, keeping the temperature for 45-70 min, and cooling to form modified activated carbon;
according to the advanced treatment method of the high-salt wastewater, the retention time of the high-salt wastewater in the step (1) in the modified activated carbon adsorption tower is 20-35 min.
According to the advanced treatment method of the high-salt wastewater, in the step (2), the stirring speed of the stirring pool is 56-65 r/min; the residence time is 1-5 min.
According to the advanced treatment method of the high-salt wastewater, further, after the high-salt wastewater passes through an electrodialysis system, TDS of produced water is 234-1450 mg/L, and the produced water can be recycled for production; the high-salt wastewater is concentrated water TDS (total dissolved solids) generated by electrodialysis is 42450-98570 mg/L, and the high-salt wastewater can be discharged by a drainage pump and enters an evaporation crystallization system to be directly evaporated to form crystalline salt.
According to the advanced treatment method of the high-salt wastewater, the prepared modified activated carbon has the strength of 93-95% and the specific surface area of 1180-1410 cm 2 Per gram, the iodine adsorption quantity is 1050-1250 mg/g, and the methylene blue adsorption quantity is 132-155 mg/g.
According to the advanced treatment method of the high-salt wastewater, in the preparation step 4) of the modified activated carbon, the washed activated carbon is dried in an oven at 100-110 ℃ for 90-120 min.
According to the advanced treatment method of the high-salt wastewater, in the preparation step 4) of the modified activated carbon, the modified activated carbon is placed into a muffle furnace, and the temperature is increased to 260-310 ℃ at 5-6 ℃/min.
The invention also provides a treatment system applied to the advanced treatment method of the high-salinity wastewater, which comprises a water inlet pump 1, a modified activated carbon adsorption tower 2, a primary water inlet pump 4, a hard removal dosing sedimentation tank 5, a secondary lifting pump 6, a microfiltration 7, a tertiary water inlet pump 8, an electro dialysis 9, an electrodialysis membrane 10 and a drainage pump 11 which are connected in sequence; the modified activated carbon adsorption tower 2 is internally provided with modified activated carbon 3, and the modified activated carbon 3 accounts for 75-90% of the whole adsorption tower volume.
Detailed description of the invention:
a high-salinity wastewater advanced treatment system comprises a water inlet pump, a modified activated carbon adsorption tower, modified activated carbon, a primary water inlet pump, a hard removal dosing sedimentation tank, a secondary lifting pump, microfiltration, a tertiary water inlet pump, an electrodialysis system, a modified electrodialysis membrane and a drainage pump.
The high-salinity wastewater has the water quality characteristics that: pH is 7-8, COD is 34-89 mg/L, calcium hardness is 65-138 mg/L, and TDS is 13470-18900 mg/L.
The high-salt wastewater enters a modified activated carbon adsorption tower through a water inlet pump, modified activated carbon is placed in the modified activated carbon adsorption tower, the modified activated carbon accounts for 75-90% of the whole volume of the adsorption tower, and the retention time of the high-salt wastewater in the modified activated carbon adsorption tower is 20-35 min. COD of the high-salt wastewater after passing through the modified activated carbon adsorption tower is 8-23 mg/L. COD is removed, and organic pollution of electrodialysis membranes in the subsequent electrodialysis process is prevented.
The modified activated carbon medicament is prepared according to the water quality condition of high-salt wastewater. The preparation process of the modified activated carbon medicament comprises the following steps: 1) Screening of activated carbon: selecting coal granular active carbon with the grain diameter of 1.6-2.7 mm; the strength is 92-94%, the specific surface area is 980-1210 cm 2 The iodine adsorption amount is 810-950 mg/g, and the methylene blue adsorption amount is 80-120 mg/g. 2) Preparing a solution: preparing ferrous sulfate solution of 2.4-3.9 mol/L and ferrous chloride solution of 1.2-1.9 mol/L, and mixing the ferrous sulfate solution and the ferrous chloride solution according to the volume ratio of 3-5:1 to form the ferrous solution. 3) Dipping: adding 35-67 g of active carbon, 1-3 g of zinc chloride, 4-12 g of meglumine and 1-3 mL of polymethacrylic acid into each liter of ferrous solution to form active carbon-sub-categoryThe iron mixed solution is ultrasonically treated for 10 to 25 minutes at 200Hz, and then is immersed for 8 to 12 hours. 4) Calcining: filtering, washing the activated carbon to be neutral by using clear water, drying the washed activated carbon in an oven at 105 ℃ for 90-120 min, cooling, then placing in a muffle furnace, heating to 260-310 ℃ at 5-6 ℃ per minute, keeping the temperature for 45-70 min, and cooling to form the modified activated carbon. The strength is 93-95%, the specific surface area is 1180-1410 cm 2 Per gram, the iodine adsorption quantity is 1050-1250 mg/g, and the methylene blue adsorption quantity is 132-155 mg/g.
The high-salt wastewater enters a hard removal and dosing sedimentation tank through a primary lifting pump. The hard adding sedimentation tank is divided into two parts, wherein the front part is a stirring tank, and the rear part is a sedimentation tank. Sodium carbonate and polyacrylamide are added into a front stirring pool, the adding amount of the sodium carbonate is 780-1010 mg/L, the polyacrylamide is anionic, and the adding amount is 0.5-2 mg/L. The stirring speed of the stirring pool is 56-65 r/min, and the residence time is 1-5 min. The medicament and the high-salt wastewater are fully mixed and then enter a sedimentation tank, and the retention time in the sedimentation tank is 25-40 min. The pH value is 7-8, the COD is 8-23 mg/L, and the calcium hardness is 7-16 mg/L through a hard removal and dosing sedimentation tank.
The high-salt wastewater enters microfiltration through a secondary lift pump. The pressure and the pump pressure of the micro-filtration pressure are 0.3 to 0.6MPa, the pore diameter is 0.23 to 0.30 mu m, and the flux is 120 to 180L/m 2 H. The calcium hardness is 5-13 mg/L after microfiltration. In the hard removing and dosing sedimentation tank, suspended matters in the precipitated water are 56-234 mg/L, and high suspended matters enter an electrodialysis system to cause membrane fouling, so that a microfiltration device is needed, and after microfiltration, the suspended matters are lower than 5mg/L. The hardness of calcium is removed by a hard adding sedimentation tank and a microfiltration process, and the scaling trend of the electrodialysis membrane is reduced as much as possible.
The high-salt wastewater enters an electrodialysis system through a three-stage lift pump. The electrodialysis membrane thickness is 0.14-0.19 mm, the exchange capacity is 1.5-2.3 mol/kg, and the area resistance is 2.0-10.5 omega cm 2 The selective permeability of the whole electrodialysis system is 97-99%, and the water yield is 69-82%. After passing through an electro dialysis system, the TDS of the produced water is 234-1450 mg/L, and can be reused for production. The high-salt wastewater is generated by electrodialysis, the TDS of the concentrated water is 42450-98570 mg/L, and the concentrated water can be discharged into an evaporation crystallization system by a drainage pump to be directly introducedEvaporating to dryness to form crystalline salt.
The beneficial technical effects of the invention are as follows:
aiming at the water quality characteristics of high-salt wastewater, namely pH is 7-8, COD is 34-89 mg/L, calcium hardness is 65-138 mg/L and TDS is 13470-18900 mg/L, the invention provides a high-salt wastewater advanced treatment method and a high-salt wastewater advanced treatment system, after the high-salt wastewater advanced treatment method is used for treating the high-salt wastewater, the calcium hardness of water is 5-13 mg/L, and the TDS of produced water is 234-1450 mg/L, so that the high-salt wastewater can be reused for production. The high-salt wastewater is concentrated water TDS (total dissolved solids) generated by electrodialysis is 42450-98570 mg/L, and the high-salt wastewater can be discharged by a drainage pump and enters an evaporation crystallization system to be directly evaporated to form crystalline salt.
Drawings
FIG. 1 is a system flow diagram of advanced treatment of high-salinity wastewater;
wherein: comprises a water inlet pump-1, a modified activated carbon adsorption tower-2, modified activated carbon-3, a primary water inlet pump-4, a hard removal dosing sedimentation tank-5, a secondary lifting pump-6, a micro-filtration-7, a tertiary water inlet pump-8, an electrodialysis-9, a modified electrodialysis membrane-10 and a drainage pump-11.
Detailed Description
The invention is further illustrated below in connection with examples, which are to be understood by those skilled in the art as being illustrative only and not limiting in any way.
The implementation of the method of the present invention is described in detail below with reference to fig. 1:
example 1:
a high-salinity wastewater advanced treatment system comprises a water inlet pump, a modified activated carbon adsorption tower, modified activated carbon, a primary water inlet pump, a hard removal dosing sedimentation tank, a secondary lifting pump, microfiltration, a tertiary water inlet pump, an electrodialysis system, a modified electrodialysis membrane and a drainage pump.
The high-salinity wastewater has the water quality characteristics that: pH 7.2, COD 56mg/L, calcium hardness 76mg/L and TDS 15460mg/L.
The high-salt wastewater enters a modified activated carbon adsorption tower through a water inlet pump, modified activated carbon is placed in the modified activated carbon adsorption tower, the modified activated carbon accounts for 80% of the whole volume of the adsorption tower, and the retention time of the high-salt wastewater in the modified activated carbon adsorption tower is 35min. COD of the high-salt wastewater passing through the modified activated carbon adsorption tower is 21mg/L
The modified activated carbon medicament is prepared according to the water quality condition of high-salt wastewater. The preparation process of the modified activated carbon medicament comprises the following steps: 1) Screening of activated carbon: selecting coal-made granular activated carbon with the grain diameter of 1.8mm; strength 92%, specific surface area 990cm 2 Per gram, the iodine adsorption amount is 870mg/g, and the methylene blue adsorption amount is 85mg/g. 2) Preparing a solution: preparing a ferrous sulfate solution with the concentration of 2.7mol/L, preparing a ferrous chloride solution with the concentration of 1.7mol/L, and mixing the ferrous sulfate solution and the ferrous chloride solution according to the volume ratio of 5:1 to form a ferrous solution. 3) Dipping: 55g of activated carbon, 2g of zinc chloride, 6g of meglumine and 2mL of polymethacrylic acid are added into each liter of ferrous solution to form an activated carbon-ferrous mixed solution, ultrasonic treatment is carried out at 200Hz for 15min, and then dipping is carried out for 10h. 4) Calcining: filtering, washing the activated carbon to be neutral by using clear water, drying the washed activated carbon in an oven at 105 ℃ for 100min, cooling, then placing the activated carbon into a muffle furnace, heating to 285 ℃ at 5 ℃/min, keeping the temperature for 55min, and cooling to form the modified activated carbon. 94% strength and 1210cm specific surface area 2 Per gram, the iodine adsorption amount is 1120mg/g, and the methylene blue adsorption amount is 135mg/g.
The high-salt wastewater enters a hard removal and dosing sedimentation tank through a primary lifting pump. The hard adding sedimentation tank is divided into two parts, wherein the front part is a stirring tank, and the rear part is a sedimentation tank. Sodium carbonate and polyacrylamide are added into a front stirring pool, the adding amount of the sodium carbonate is 890mg/L, the adding amount of the polyacrylamide is anionic, and the adding amount of the polyacrylamide is 2mg/L. The stirring speed of the stirring tank was 62 rpm and the residence time was 5min. The medicament and the high-salt wastewater are fully mixed and then enter a sedimentation tank, and the retention time in the sedimentation tank is 30min. The pH value is 7.3, the COD is 22mg/L, and the calcium hardness is 14mg/L through a hard removal and dosing sedimentation tank.
The high-salt wastewater enters microfiltration through a secondary lift pump. The micro-filtration pressure pump pressure is 0.4MPa, the pore diameter is 0.24 mu m, and the flux is 135L/m 2 H. The calcium hardness after microfiltration was 11mg/L.
The high-salt wastewater enters an electrodialysis system through a three-stage lift pump. Electrodialysis membrane thickness of 0.15mm, exchange capacity of 1.8mol/kg, and area resistance of 3.5Ω cm 2 The selective permeability of the whole electrodialysis system is 98%, and the water yield is 80%. After passing through the electrodialysis system, the TDS of the produced water is 456mg/L, and can be recycled for production. The high-salt wastewater is concentrated water TDS (total dissolved solids) generated by electrodialysis is 77320mg/L, and the high-salt wastewater can be discharged by a drainage pump and enters an evaporation crystallization system to be directly evaporated to dryness to form crystalline salt.
Example 2:
a high-salinity wastewater advanced treatment system comprises a water inlet pump, a modified activated carbon adsorption tower, modified activated carbon, a primary water inlet pump, a hard removal dosing sedimentation tank, a secondary lifting pump, microfiltration, a tertiary water inlet pump, an electrodialysis system, a modified electrodialysis membrane and a drainage pump.
The high-salinity wastewater has the water quality characteristics that: pH 7.7, COD 72mg/L, calcium hardness 111mg/L, TDS 16780mg/L.
The high-salt wastewater enters a modified activated carbon adsorption tower through a water inlet pump, modified activated carbon is placed in the modified activated carbon adsorption tower, the modified activated carbon accounts for 85% of the whole volume of the adsorption tower, and the retention time of the high-salt wastewater in the modified activated carbon adsorption tower is 24min. COD of the high-salt wastewater passing through the modified activated carbon adsorption tower is 11mg/L
The modified activated carbon medicament is prepared according to the water quality condition of high-salt wastewater. The preparation process of the modified activated carbon medicament comprises the following steps: 1) Screening of activated carbon: selecting coal granular activated carbon with the grain diameter of 1.9mm; strength 93%, specific surface area 1120cm 2 Per gram, the iodine adsorption amount is 870mg/g, and the methylene blue adsorption amount is 91mg/g. 2) Preparing a solution: preparing a ferrous sulfate solution with the concentration of 3.1mol/L, preparing a ferrous chloride solution with the concentration of 1.7mol/L, and mixing the ferrous sulfate solution and the ferrous chloride solution according to the volume ratio of 3:1 to form a ferrous solution. 3) Dipping: 42g of active carbon, 1g of zinc chloride, 7g of meglumine and 2mL of polymethacrylic acid are added into each liter of ferrous solution to form an active carbon-ferrous mixed solution, ultrasonic treatment is carried out at 200Hz for 21min, and then dipping is carried out for 11h. 4) Calcining: filtering, washing the activated carbon to be neutral by using clear water, drying the washed activated carbon in an oven at 105 ℃ for 115min, cooling, then placing in a muffle furnace, heating to 310 ℃ at 6 ℃/min, keeping the temperature for 70min, and cooling to form the modified activated carbon. 94% strength and 1230cm specific surface area 2 Iodine absorberThe attached amount is 1150mg/g, and the methylene blue adsorption amount is 137mg/g.
The high-salt wastewater enters a hard removal and dosing sedimentation tank through a primary lifting pump. The hard adding sedimentation tank is divided into two parts, wherein the front part is a stirring tank, and the rear part is a sedimentation tank. Sodium carbonate and polyacrylamide are added into a front stirring pool, wherein the adding amount of sodium carbonate is 820mg/L, and the adding amount of polyacrylamide is 0.5mg/L. The stirring speed of the stirring tank was 60 rpm and the residence time was 3min. The medicament and the high-salt wastewater are fully mixed and then enter a sedimentation tank, and the retention time in the sedimentation tank is 30min. The mixture passes through a hard removal and dosing sedimentation tank, the pH is 7.9, the COD is 17mg/L, and the calcium hardness is 16mg/L.
The high-salt wastewater enters microfiltration through a secondary lift pump. The micro-filtration pressure pump pressure is 0.4MPa, the pore diameter is 0.30 mu m, and the flux is 155L/m 2 H. The calcium hardness after microfiltration was 9mg/L.
The high-salt wastewater enters an electrodialysis system through a three-stage lift pump. The electrodialysis membrane thickness is 0.19mm, the exchange capacity is 2.2mol/kg, and the area resistance is 3.4 Ω cm 2 The whole electrodialysis system has 97% of selective permeability and 77% of water yield. After passing through the electrodialysis system, the TDS of the produced water is 567mg/L, and can be reused for production. The high-salt wastewater is concentrated water TDS (total dissolved solids) generated by electrodialysis is 50900mg/L, and the high-salt wastewater can be discharged by a drainage pump and enters an evaporation crystallization system to be directly evaporated to dryness to form crystalline salt.
Example 3:
a high-salinity wastewater advanced treatment system comprises a water inlet pump, a modified activated carbon adsorption tower, modified activated carbon, a primary water inlet pump, a hard removal dosing sedimentation tank, a secondary lifting pump, microfiltration, a tertiary water inlet pump, an electrodialysis system, a modified electrodialysis membrane and a drainage pump.
The high-salinity wastewater has the water quality characteristics that: pH 7.3, COD 89mg/L, calcium hardness 138mg/L and TDS 17780mg/L.
The high-salt wastewater enters a modified activated carbon adsorption tower through a water inlet pump, modified activated carbon is placed in the modified activated carbon adsorption tower, the modified activated carbon occupies 90% of the whole volume of the adsorption tower, and the retention time of the high-salt wastewater in the modified activated carbon adsorption tower is 20min. COD of the high-salt wastewater passing through the modified activated carbon adsorption tower is 15mg/L
The modified activated carbon medicament is prepared according to the water quality condition of high-salt wastewater. The preparation process of the modified activated carbon medicament comprises the following steps: 1) Screening of activated carbon: selecting coal-made granular activated carbon with the grain diameter of 2.7mm; 94% strength and 1200cm specific surface area 2 Per gram, iodine adsorption of 950mg/g and methylene blue adsorption of 120mg/g. 2) Preparing a solution: preparing a ferrous sulfate solution with the concentration of 3.9mol/L, preparing a ferrous chloride solution with the concentration of 1.9mol/L, and mixing the ferrous sulfate solution and the ferrous chloride solution according to the volume ratio of 5:1 to form a ferrous solution. 3) Dipping: to each liter of the ferrous solution, 67g of activated carbon, 3g of zinc chloride, 12g of meglumine and 3mL of polymethacrylic acid were added to form an activated carbon-ferrous mixed solution, which was sonicated at 200Hz for 25min, and then immersed for 12 hours. 4) Calcining: filtering, washing the activated carbon to be neutral by using clear water, drying the washed activated carbon in an oven at 105 ℃ for 115min, cooling, then placing in a muffle furnace, heating to 260 ℃ at 6 ℃/min, keeping the temperature for 45min, and cooling to form the modified activated carbon. Strength 95% and specific surface area 1410cm 2 Per gram, iodine adsorption of 1250mg/g and methylene blue adsorption of 150mg/g.
The high-salt wastewater enters a hard removal and dosing sedimentation tank through a primary lifting pump. The hard adding sedimentation tank is divided into two parts, wherein the front part is a stirring tank, and the rear part is a sedimentation tank. Sodium carbonate and polyacrylamide are added into a front stirring pool, wherein the adding amount of sodium carbonate is 1010mg/L, and the adding amount of polyacrylamide is 0.6mg/L. The stirring speed of the stirring tank was 60 rpm and the residence time was 4min. The medicament and the high-salt wastewater are fully mixed and then enter a sedimentation tank, and the retention time in the sedimentation tank is 40min. The mixture passes through a hard removal and dosing sedimentation tank, the pH value is 7.5, the COD is 18mg/L, and the calcium hardness is 15mg/L.
The high-salt wastewater enters microfiltration through a secondary lift pump. The micro-filtration pressure pump pressure is 0.6MPa, the pore diameter is 0.30 mu m, and the flux is 180L/m 2 H. The calcium hardness after microfiltration was 7mg/L.
The high-salt wastewater enters an electrodialysis system through a three-stage lift pump. The electrodialysis membrane thickness is 0.15mm, the exchange capacity is 1.5mol/kg, and the area resistance is 10.5 Ω cm 2 Selective permeability of the overall electrodialysis System 99%, and the water yield is 82%. After passing through the electrodialysis system, the TDS of the produced water is 452mg/L, and can be recycled for production. The high-salt wastewater is subjected to direct evaporation to form crystalline salt by discharging concentrated water TDS (total dissolved solids) generated by electrodialysis into an evaporation crystallization system through a drainage pump at 61200 mg/L.
Example 4:
a high-salinity wastewater advanced treatment system comprises a water inlet pump, a modified activated carbon adsorption tower, modified activated carbon, a primary water inlet pump, a hard removal dosing sedimentation tank, a secondary lifting pump, microfiltration, a tertiary water inlet pump, an electrodialysis system, a modified electrodialysis membrane and a drainage pump.
The high-salinity wastewater has the water quality characteristics that: pH 7.2, COD 80mg/L, calcium hardness 130mg/L and TDS 17650mg/L.
The high-salt wastewater enters a modified activated carbon adsorption tower through a water inlet pump, modified activated carbon is placed in the modified activated carbon adsorption tower, the modified activated carbon accounts for 85% of the whole volume of the adsorption tower, and the retention time of the high-salt wastewater in the modified activated carbon adsorption tower is 35min. COD of the high-salt wastewater passing through the modified activated carbon adsorption tower is 10mg/L
The modified activated carbon medicament is prepared according to the water quality condition of high-salt wastewater. The preparation process of the modified activated carbon medicament comprises the following steps: 1) Screening of activated carbon: selecting coal-made granular activated carbon with the grain diameter of 2.5mm; strength 93%, specific surface area 1100cm 2 Per gram, iodine adsorption of 950mg/g and methylene blue adsorption of 120mg/g. 2) Preparing a solution: preparing a ferrous sulfate solution with the concentration of 3.9mol/L, preparing a ferrous chloride solution with the concentration of 1.9mol/L, and mixing the ferrous sulfate solution and the ferrous chloride solution according to the volume ratio of 5:1 to form a ferrous solution. 3) Dipping: to each liter of the ferrous solution, 67g of activated carbon, 3g of zinc chloride, 11g of meglumine and 3mL of polymethacrylic acid were added to form an activated carbon-ferrous mixed solution, which was sonicated at 200Hz for 20min, and then immersed for 10 hours. 4) Calcining: filtering, washing the activated carbon to be neutral by using clear water, drying the washed activated carbon in an oven at 105 ℃ for 115min, cooling, then placing in a muffle furnace, heating to 300 ℃ at 5.5 ℃/min, and cooling to form the modified activated carbon. Strength 95%, specific surface area 1320cm 2 Iodine adsorption capacity 1150mg/g, methylene blue adsorption capacity149mg/g。
The high-salt wastewater enters a hard removal and dosing sedimentation tank through a primary lifting pump. The hard adding sedimentation tank is divided into two parts, wherein the front part is a stirring tank, and the rear part is a sedimentation tank. Sodium carbonate and polyacrylamide are added into a front stirring tank, wherein the adding amount of sodium carbonate is 990mg/L, and the adding amount of polyacrylamide is 1.2mg/L. The stirring speed of the stirring tank was 60 rpm and the residence time was 5min. The medicament and the high-salt wastewater are fully mixed and then enter a sedimentation tank, and the retention time in the sedimentation tank is 40min. The pH value is 7.3, the COD is 11mg/L, and the calcium hardness is 12mg/L through a hard removal and dosing sedimentation tank.
The high-salt wastewater enters microfiltration through a secondary lift pump. The micro-filtration pressure pump pressure is 0.5MPa, the pore diameter is 0.28 mu m, and the flux is 170L/m 2 H. The calcium hardness after microfiltration was 9mg/L.
The high-salt wastewater enters an electrodialysis system through a three-stage lift pump. The electrodialysis membrane thickness is 0.18mm, the exchange capacity is 2.0mol/kg, and the area resistance is 8.5 Ω cm 2 The whole electrodialysis system has the advantages of 99% of selective permeability and 80% of water production rate. After passing through the electrodialysis system, the TDS of the produced water is 351mg/L, and can be reused for production. The high-salt wastewater is produced by electrodialysis to generate concentrated water TDS of 71200mg/L, and the concentrated water TDS can be discharged by a drainage pump to enter an evaporation crystallization system for direct evaporation to form crystalline salt.
In conclusion, the invention provides a complete advanced treatment technical scheme for high-salt wastewater for the first time, and the system solves the problem that the high-salt wastewater pollutes the environment, so that the invention belongs to an environment-friendly production process system for steel. It will of course be appreciated by those skilled in the art that the above-described embodiments are provided for illustration only and not as limitations of the present invention, and that variations and modifications of the above-described embodiments will fall within the scope of the appended claims.
Claims (5)
1. The advanced treatment method of the high-salinity wastewater is characterized by comprising the following steps of:
(1) The high-salt wastewater enters a modified activated carbon adsorption tower, modified activated carbon is placed in the modified activated carbon adsorption tower, and the modified activated carbon accounts for 75-90% of the whole volume of the adsorption tower; the retention time of the high-salt wastewater in the step (1) in the modified activated carbon adsorption tower is 20-35 min;
(2) The high-salt wastewater enters a hard-removing dosing sedimentation tank which is divided into two parts, wherein the front part is a stirring tank, and the rear part is a sedimentation tank; adding sodium carbonate and polyacrylamide into a front stirring tank, wherein the adding amount of the sodium carbonate is 780-1010 mg/L, and the adding amount of the polyacrylamide is 0.5-2 mg/L; the medicament and the high-salt wastewater are fully mixed and then enter a sedimentation tank, and the retention time in the sedimentation tank is 25-40 min;
(3) The high-salt wastewater enters a microfiltration device, the pressure pump pressure of the microfiltration is 0.3-0.6 MPa, the aperture is 0.23-0.30 mu m, and the flux is 120-180L/m 2 H, the calcium hardness after microfiltration is 5-13 mg/L;
(4) The high-salt wastewater enters an electrodialysis system, the electrodialysis membrane thickness is 0.14-0.19 mm, the exchange capacity is 1.5-2.3 mol/kg, and the surface resistance is 2.0-10.5 ohm cm 2 The selective permeability of the whole electrodialysis system is 97-99%, and the water yield is 69-82%; after passing through the electrodialysis system, the produced water can be reused for production; concentrated water generated by the method can enter an evaporation crystallization system to be directly evaporated to dryness to form crystalline salt;
the modified activated carbon in the step (1) is prepared according to the water quality condition of high-salt wastewater by the following steps: 1) Screening of activated carbon: selecting coal granular active carbon with the grain diameter of 1.6-2.7 mm; the strength is 92-94%, the specific surface area is 980-1210 cm 2 Per gram, the iodine adsorption capacity is 810-950 mg/g, and the methylene blue adsorption capacity is 80-120 mg/g; 2) Preparing a solution: preparing a ferrous sulfate solution with the concentration of 2.4-3.9 mol/L and a ferrous chloride solution with the concentration of 1.2-1.9 mol/L, and mixing the ferrous sulfate solution and the ferrous chloride solution according to the volume ratio of 3-5:1 to form a ferrous solution; 3) Dipping: adding 35-67 g of active carbon, 1-3 g of zinc chloride, 4-12 g of meglumine and 1-3 mL of polymethacrylic acid into each liter of ferrous solution to form an active carbon-ferrous mixed solution, carrying out ultrasonic treatment for 10-25 min, and then soaking for 8-12 h; 4) Calcining: filtering, washing the activated carbon with clear water to neutrality, drying in a cleaned activated carbon oven, cooling, placing into a muffle furnace, and heatingKeeping the temperature at 260-310 ℃ for 45-70 min, and cooling to form modified activated carbon; the strength of the prepared modified activated carbon is 93-95%, and the specific surface area is 1180-1410 cm 2 Per gram, the iodine adsorption quantity is 1050-1250 mg/g, and the methylene blue adsorption quantity is 132-155 mg/g.
2. The advanced treatment method of high-salt wastewater according to claim 1, which is characterized in that: in the step (2), the stirring speed of the stirring pool is 56-65 r/min; the residence time is 1-5 min.
3. The advanced treatment method of high-salt wastewater according to claim 1, which is characterized in that: after passing through the electrodialysis system, mg/L is produced, and the product can be discharged by a drainage pump and enter an evaporation crystallization system to be directly evaporated to dryness to form crystalline salt.
4. The advanced treatment method of high-salt wastewater according to claim 1, which is characterized in that: in the preparation step 4) of the modified activated carbon, the cleaned activated carbon is dried for 90-120 min in an oven at 100-110 ℃.
5. The advanced treatment method of high-salt wastewater according to claim 1, which is characterized in that: in the preparation step 4) of the modified activated carbon, the modified activated carbon is put into a muffle furnace and heated to 260-310 ℃ at 5-6 ℃/min.
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