CN113562906A - Zero-emission method and system for high-salt chromium-containing concentrated water - Google Patents
Zero-emission method and system for high-salt chromium-containing concentrated water Download PDFInfo
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- CN113562906A CN113562906A CN202010349498.8A CN202010349498A CN113562906A CN 113562906 A CN113562906 A CN 113562906A CN 202010349498 A CN202010349498 A CN 202010349498A CN 113562906 A CN113562906 A CN 113562906A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 262
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 185
- 239000011651 chromium Substances 0.000 title claims abstract description 185
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 87
- 229920005989 resin Polymers 0.000 claims abstract description 87
- 238000004062 sedimentation Methods 0.000 claims abstract description 52
- 238000001179 sorption measurement Methods 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 45
- 238000005189 flocculation Methods 0.000 claims abstract description 31
- 230000016615 flocculation Effects 0.000 claims abstract description 31
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 30
- 239000012528 membrane Substances 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims abstract description 19
- 230000008020 evaporation Effects 0.000 claims abstract description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 230000014759 maintenance of location Effects 0.000 claims description 16
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229920002401 polyacrylamide Polymers 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000010802 sludge Substances 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 7
- 229940106681 chloroacetic acid Drugs 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N propylene glycol methyl ether Substances COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 7
- -1 propylene glycol methyl ether ester Chemical class 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052791 calcium Inorganic materials 0.000 abstract description 25
- 239000011575 calcium Substances 0.000 abstract description 25
- 229910000831 Steel Inorganic materials 0.000 abstract description 6
- 239000010959 steel Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 description 15
- 208000028659 discharge Diseases 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 238000010612 desalination reaction Methods 0.000 description 5
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
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Classifications
-
- 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
-
- 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
- C02F1/52—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
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a zero-emission method and a zero-emission system for high-salt chromium-containing concentrated water. The zero emission method comprises the following steps: the high-salt chromium-containing concentrated water enters a high-density sedimentation tank, the high-density sedimentation tank is divided into a mixing tank, a flocculation tank and a sedimentation tank, and after passing through the high-density sedimentation tank, the calcium hardness of the high-salt chromium-containing concentrated water is 5-13 mg/L; and then the high-salt chromium-containing concentrated water enters a modified resin adsorption tower, and then the high-salt chromium-containing concentrated water is pumped into a high-pressure reverse osmosis membrane by a high-pressure water inlet pump, the pressure of the high-pressure water inlet pump is 40-55 MPa, and the high-salt chromium-containing concentrated water enters an evaporation crystallizer, and finally sodium chloride miscellaneous salt is formed in the high-salt chromium-containing concentrated water. The invention provides a technical scheme for zero discharge of high-salt chromium-containing concentrated water, effectively solves the problem that the high-salt chromium-containing concentrated water pollutes the environment, belongs to a green and environment-friendly production process of steel, and has good social benefit and environmental benefit.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a zero-emission method and a zero-emission system for high-salt chromium-containing concentrated water.
Background
After the working procedures of cold rolling chromium-containing passivation and nickel electroplating, the surface of the strip steel needs to be washed by pure water, and most of the waste water after the strip steel is washed is discharged to a waste water station due to the chromium ions and organic matters. After the chromium-containing wastewater is treated by a traditional biological method or a two-stage reduction method in a wastewater station, the chromium-containing wastewater in cold rolling cannot reach the discharge standard. Therefore, the concentration technology is adopted to treat the cold rolling chromium-containing wastewater, the produced water can be applied to production, and the high-salinity concentrated water can be used for wastewater zero-discharge treatment.
At present, the treatment process mainly adopted by the chromium-containing wastewater is mainly a sodium bisulfite two-stage reduction and precipitation technology, but the effluent quality can hardly meet the requirements of new national standards. The nanofiltration and the reverse osmosis are adopted to treat the chromium-containing wastewater, and no technical report is found in the high-salinity concentrated water treatment scheme.
The chemical reduction precipitation method is the earliest and most extensive method for treating chromium-containing wastewater at home and abroad. The treatment technology generally comprises the steps of firstly adjusting the pH value of wastewater to be 2-3 under an acidic condition by using sulfuric acid, then reducing hexavalent chromium in a solution to trivalent chromium by using a chemical reducing agent, then adjusting the pH value to be 7-9 by using sodium hydroxide or lime milk, and separating insoluble trivalent chromium precipitate generated by the trivalent chromium precipitate from a water body to achieve the aim of removing chromium. The invention patent with the application number of CN104030478A discloses a method for treating chromium-containing wastewater. The method comprises (1) adding acid into chromium-containing wastewater, and adjusting pH to 2-3; (2) adding a reducing agent into the acidic chromium-containing wastewater to reduce hexavalent chromium ions into trivalent chromium ions; (3) and c, adding alkali into the solution treated in the step b, adjusting the pH value to be between 8 and 9, and converting trivalent chromium ions into chromium hydroxide precipitates. However, this invention does not focus on the removal of COD.
However, up to now, there has been no zero-emission treatment scheme for high-salt chromium-containing concentrated water.
Disclosure of Invention
The invention aims to develop an economical and efficient zero-emission treatment process according to the water quality and water quantity condition of high-salt chromium-containing concentrated water, takes the cyclic utilization, energy conservation and emission reduction as main tasks, reduces environmental pollution, and actively deals with increasingly strict environmental protection regulations. The invention provides a zero discharge method and a zero discharge system for high-salt chromium-containing concentrated water, belonging to an environment-friendly production process system for steel.
The technical scheme adopted by the invention is as follows:
a zero discharge method of high-salt chromium-containing concentrated water comprises the following steps:
(1) the high-salt chromium-containing concentrated water enters a high-density sedimentation tank, and the high-density sedimentation tank is divided into a mixing tank, a flocculation tank and a sedimentation tank; firstly, high-salt chromium-containing concentrated water enters a mixing tank, sodium carbonate is added into the mixing tank, the adding amount is 345-678 mg/L, preferably 378-560 mg/L, meanwhile, anionic polyacrylamide is added, the adding amount is 0.5-2 mg/L, preferably 1-1.6 mg/L, and the retention time of the high-salt chromium-containing concentrated water in the mixing tank is 2.5-4.5 min; then the sewage enters a flocculation tank, the flow velocity in a guide cylinder barrel is 0.5-1.1 m/s, the flow velocity in a water outlet area is 0.01-0.06 m/s, and the sludge reflux amount is 2-3%; allowing the high-salt chromium-containing concentrated water to flow into a sedimentation tank from a flocculation tank water outlet zone, and keeping for 15-35 min; after passing through a high-density sedimentation tank, the calcium hardness of the high-salt chromium-containing concentrated water is 5-13 mg/L;
(2) the high-salt chromium-containing concentrated water enters a modified resin adsorption tower, modified resin is placed in the modified resin adsorption tower, and the modified resin accounts for 85-95% of the volume of the whole modified resin adsorption tower;
(3) then pumping high-salt chromium-containing concentrated water into a high-pressure reverse osmosis membrane by using a high-pressure water inlet pump, wherein the pressure of the high-pressure water inlet pump is 40-55 MPa, preferably 48-50 MPa, the conductivity of the high-salt chromium-containing concentrated solution is 54120-71200 muS/cm, the calcium hardness is 7-25 mg/L, and the total chromium is 0.8-3.4 mg/L;
(4) and finally, the high-salt chromium-containing concentrated solution enters an evaporation crystallizer, and finally the high-salt chromium-containing concentrated water forms sodium chloride mixed salt.
According to the zero emission method of the high-salt chromium-containing concentrated water, in the step (2), the modified resin is prepared according to the water quality characteristics of the cold-rolled high-salt chromium-containing concentrated water, and the zero emission method is prepared by the following steps: 1) putting the polymethyl acrylate resin into a reaction kettle, filling the reaction kettle with an ethylenediamine solution, swelling for 8-10 h in the reaction kettle, then heating the reaction kettle to 110-125 ℃, keeping the temperature for 12-14 h, cooling to form propylene glycol monomethyl ether acetate, filtering, washing the product to be neutral with water, and drying; 2) mixing propylene glycol methyl ether ester and chloroacetic acid according to a molar ratio of 4-6: 1, putting the mixture into a reaction kettle, adjusting the pH value of the solution to 8.9-9.8, heating the reaction kettle to 65-75 ℃, starting a stirrer at a stirring speed of 65-85 rpm, reacting for 12-16 h, and cooling to form modified polyacrylamide ethylamine resin, namely the modified resin.
According to the zero emission method of the high-salt chromium-containing concentrated water, further, in the modified resin preparation step 1), the product is washed to be neutral by deionized water and is dried in vacuum at 50-65 ℃.
According to the zero emission method of the high-salt chromium-containing concentrated water, disclosed by the invention, further, in the step (1), the stirring speed of the mixing tank is 75-85 revolutions per minute.
According to the zero emission method of the high-salt chromium-containing concentrated water, disclosed by the invention, further, the hydraulic retention time of the flocculation tank in the step (1) is 7-9 min.
According to the zero emission method of the high-salt chromium-containing concentrated water, further, in the step (1), the diameter of an inclined tube in the sedimentation tank is 55-75 mm, the inclination angle of the inclined tube is 55-58 degrees, the inclined length of the inclined tube is 1200-1450 mm, and the surface load is 10.5-13.5 m3/m2H, the height of the clear water area is 0.5-0.8 m.
According to the zero emission method of the high-salt chromium-containing concentrated water, provided by the invention, the high-salt chromium-containing concentrated water stays in the modified resin adsorption tower for 25-35 min.
According to the zero emission method of the high-salt chromium-containing concentrated water, further, after the high-salt chromium-containing concentrated water in the step (2) passes through the modified resin adsorption tower, the hardness of calcium in the high-salt chromium-containing concentrated water is 3-10 mg/L, and the total chromium is 0.3-1.2 mg/L.
According to the zero emission method of the high-salt chromium-containing concentrated water, further, in the step (3), the salt rejection rate of a high-pressure reverse osmosis membrane is 99.2-99.5%, and the water yield is 60%; after the high-salt chromium-containing concentrated water passes through the high-pressure reverse osmosis membrane, the conductivity of produced water is 230-890 mu S/cm, and the produced water is directly recycled for production.
According to the zero emission method of the high-salt chromium-containing concentrated water, provided by the invention, further, in the step (4), the high-salt chromium-containing concentrated solution enters an evaporation crystallizer, and the evaporation temperature is 80-90 ℃.
The invention also provides a system applied to the zero emission method of the high-salt chromium-containing concentrated water, which comprises a water inlet pump 1, a high-density sedimentation tank 2, a primary water inlet pump 3, a modified resin adsorption tower 4, a high-pressure water inlet pump 6, a high-pressure reverse osmosis 7, a secondary water inlet pump 8 and an evaporation crystallizer 9 which are sequentially connected; the high-density sedimentation tank 2 comprises a mixing tank, a flocculation tank and a sedimentation tank; modified resin 5 is placed in the modified resin adsorption tower 4, and the modified resin accounts for 85-95% of the volume of the whole modified resin adsorption tower.
Detailed description of the invention:
the technical scheme of the high-salt chromium-containing concentrated water comprises a water inlet pump, a high-density sedimentation tank, a primary water inlet pump, a modified resin adsorption tower, modified resin, a high-pressure water inlet pump, high-pressure reverse osmosis, a secondary water inlet pump and an evaporative crystallizer.
The high-salt chromium-containing concentrated water is characterized by having a pH value of 6-9, an electric conductivity of 26890-34980 mu s/cm, total chromium of 11.2-34.2 mg/L and calcium hardness of 75-256 mg/L.
The high-salt chromium-containing concentrated water enters a high-density sedimentation tank through a water inlet pump, and the high-density sedimentation tank is divided into a mixing tank, a flocculation tank and a sedimentation tank. The high-salt chromium-containing concentrated water firstly enters a mixing tank, sodium carbonate is added into the mixing tank, the adding amount is 345-678 mg/L, and meanwhile, anionic polyacrylamide is added, and the adding amount is 0.5-2 mg/L. The stirring speed of the mixing tank is 75-85 r/min, and the residence time of the high-salt chromium-containing concentrated water in the mixing tank is 2.5-4.5 min. And then the sludge enters a flocculation tank, the hydraulic retention time of the flocculation tank is 7-9 min, the flow velocity in the guide cylinder barrel is 0.5-1.1 m/s, the flow velocity in a water outlet area is 0.01-0.06 m/s, and the sludge reflux amount is 2-3%. The high-salt chromium-containing concentrated water flows into the sedimentation tank from the water outlet zone of the flocculation tank, the diameter of an inclined tube is 55-75 mm, the inclination angle of the inclined tube is 55-58 degrees, the inclined length of the inclined tube is 1200-1450 mm, and the surface load is 10.5-13.5 m3/m2H, the height of the clear water area is 0.5-0.8 m, and the retention time is 15-35 min. After passing through the high-density sedimentation tank, the calcium hardness of the high-salt chromium-containing concentrated water is 5-13 mg/L.
The high-salt chromium-containing concentrated water enters a modified resin adsorption tower through a primary lift pump, modified resin is placed in the modified resin adsorption tower, the modified resin accounts for 85-95% of the volume of the whole modified resin adsorption tower, and the high-salt chromium-containing concentrated water stays in the modified resin adsorption tower for 25-35 min. After passing through the modified resin adsorption tower, the hardness of calcium in the high-salt chromium-containing concentrated water is 3-10 mg/L, and the total chromium is 0.3-1.2 mg/L.
The modified resin is specially synthesized and prepared according to the water quality characteristics of cold-rolled high-salt chromium-containing concentrated water. 1) Putting the polymethyl acrylate resin into a reaction kettle, filling the reaction kettle with an ethylenediamine solution, swelling for 8-10 h in the reaction kettle, then heating the reaction kettle to 115 ℃, keeping the temperature for 12-14 h, cooling to form propylene glycol monomethyl ether acetate, filtering, washing a product to be neutral by using deionized water, and carrying out vacuum drying at 55 ℃. 2) Mixing propylene glycol methyl ether ester and chloroacetic acid according to a molar ratio of 4-6: 1, putting the mixture into a reaction kettle, adjusting the pH of the solution to 9.5, heating the reaction kettle to 65-75 ℃, starting a stirrer, stirring at a speed of 65-85 rpm, and reacting for 12-16 h. And cooling to form the modified polyacrylamide ethylamine resin.
Then the high-pressure water inlet pump pumps the high-salt chromium-containing concentrated water into the high-pressure reverse osmosis membrane. The pressure of the high-pressure water inlet pump is 40-55 MPa. The desalination rate of the high-pressure reverse osmosis membrane is 99.2-99.5%, and the water yield is 60%. After the high-salt chromium-containing concentrated water passes through the high-pressure reverse osmosis membrane, the conductivity of produced water is 230-890 mu S/cm, and the produced water is directly recycled for production. The high-salt chromium-containing concentrated solution has the conductivity of 54120-71200 mu S/cm, the calcium hardness of 7-25 mg/L and the total chromium of 0.8-3.4 mg/L. The lower the contaminating component, the higher the purity of the final evaporated crystalline salt and the better the quality. If the chromium content is high, the chromium content in the crystallized salt may be high, and the crystallized salt is a hazardous waste.
And then pumping the high-salt chromium-containing concentrated solution into an evaporation crystallizer by a secondary water inlet pump, wherein the evaporation temperature is 80-90 ℃, and finally, forming sodium chloride mixed salt by the high-salt chromium-containing concentrated water.
Advantageous technical effects
The invention provides a technical scheme for zero discharge of high-salt chromium-containing concentrated water, effectively solves the problem that the high-salt chromium-containing concentrated water pollutes the environment, belongs to a green and environment-friendly production process of steel, and has good social benefit and environmental benefit.
By applying the method and the system for zero discharge of the high-salt chromium-containing concentrated water, the conductivity of produced water is 230-890 mu S/cm, and the produced water is directly recycled for production; the high-salt chromium-containing concentrated solution has the conductivity of 54120-71200 mu S/cm, the calcium hardness of 7-25 mg/L and the total chromium of 0.8-3.4 mg/L, and enters an evaporation crystallizer to form sodium chloride miscellaneous salt, so that zero emission is realized.
Drawings
FIG. 1 is a flow chart of a high-salt chromium-containing concentrated water zero-discharge process;
wherein, the water inlet pump-1, the high-density sedimentation tank-2, the first-stage water inlet pump-3, the modified resin adsorption tower-4, the modified resin-5, the high-pressure water inlet pump-6, the high-pressure reverse osmosis-7, the second-stage water inlet pump-8 and the evaporative crystallizer-9.
Detailed Description
The present invention is further illustrated below with reference to examples, which are understood by those skilled in the art to be illustrative only and not to constitute any limitation to the present invention.
The following detailed description of the process of the invention is given with reference to FIG. 1:
example 1:
a technical scheme of high-salt chromium-containing concentrated water comprises a water inlet pump, a high-density sedimentation tank, a primary water inlet pump, a modified resin adsorption tower, modified resin, a high-pressure water inlet pump, high-pressure reverse osmosis, a secondary water inlet pump and an evaporative crystallizer.
The high-salt chromium-containing concentrated water is characterized in that the pH value is 7.2, the conductivity is 29620 mu S/cm, the total chromium content is 21.2mg/L, and the calcium hardness is 137 mg/L.
The high-salt chromium-containing concentrated water enters a high-density sedimentation tank through a water inlet pump, and the high-density sedimentation tank is divided into a mixing tank, a flocculation tank and a sedimentation tank. The high-salt chromium-containing concentrated water firstly enters a mixing tank, sodium carbonate is added into the mixing tank, the adding amount is 378mg/L, and meanwhile, anionic polyacrylamide is added, and the adding amount is 1 mg/L. The stirring speed of the mixing tank is 75 revolutions per minute, and the retention time of the high-salt chromium-containing concentrated water in the mixing tank is 3 min. Then the wastewater enters a flocculation tank, the hydraulic retention time of the flocculation tank is 8min, the flow velocity in a draft tube barrel is 0.8m/s, and the water flows in a water outlet areaThe speed is 0.03m/s, and the sludge reflux amount is 2 percent. The high-salt chromium-containing concentrated water flows into a sedimentation tank from a water outlet zone of the flocculation tank, the diameter of an inclined pipe is 55mm, the inclination angle of the inclined pipe is 58 degrees, the inclined length of the inclined pipe is 1350mm, and the surface load is 11.2m3/m2H, height of clear water zone 0.6m, residence time 22 min. After passing through the high-density sedimentation tank, the calcium hardness of the high-salt chromium-containing concentrated water is 6 mg/L.
The high-salt chromium-containing concentrated water enters a modified resin adsorption tower through a primary lift pump, modified resin is placed in the modified resin adsorption tower, the modified resin accounts for 95% of the volume of the whole modified resin adsorption tower, and the high-salt chromium-containing concentrated water stays in the modified resin adsorption tower for 35 min. After passing through the modified resin adsorption tower, the calcium hardness of the high-salt chromium-containing concentrated water is 4mg/L, and the total chromium is 0.9 mg/L.
The modified resin is specially synthesized and prepared according to the water quality characteristics of cold-rolled high-salt chromium-containing concentrated water. 1) Putting the polymethyl acrylate resin into a reaction kettle, filling the reaction kettle with an ethylenediamine solution, swelling for 8h in the reaction kettle, then heating the reaction kettle to 110 ℃, keeping the temperature for 12h, cooling to form propylene glycol monomethyl ether acetate, filtering, washing a product to be neutral by deionized water, and drying in vacuum at the temperature of 65 ℃. 2) Mixing propylene glycol methyl ether ester and chloroacetic acid according to a molar ratio of 4:1, putting into a reaction kettle, adjusting the pH of the solution to 9.8, heating the reaction kettle to 65 ℃, starting a stirrer, stirring at a speed of 65 revolutions per minute, and reacting for 12 hours. And cooling to form the modified polyacrylamide ethylamine resin.
Then the high-pressure water inlet pump pumps the high-salt chromium-containing concentrated water into the high-pressure reverse osmosis membrane. The pressure of the high-pressure water inlet pump is 50 MPa. The desalination rate of the high-pressure reverse osmosis membrane is 99.3 percent, and the water yield is 60 percent. After the high-salt chromium-containing concentrated water passes through the high-pressure reverse osmosis membrane, the conductivity of the produced water is 450 mu S/cm, and the produced water is directly recycled for production. The high-salt chromium-containing concentrated solution has the conductivity of 67420 mu S/cm, the calcium hardness of 13mg/L and the total chromium of 2.2 mg/L.
Then pumping the high-salt chromium-containing concentrated solution into an evaporation crystallizer by a secondary water inlet pump, wherein the evaporation temperature is 85 ℃, and finally forming sodium chloride mixed salt by the high-salt chromium-containing concentrated water.
Example 2:
the technical scheme of the high-salt chromium-containing concentrated water comprises a water inlet pump, a high-density sedimentation tank, a primary water inlet pump, a modified resin adsorption tower, modified resin, a high-pressure water inlet pump, high-pressure reverse osmosis, a secondary water inlet pump and an evaporative crystallizer.
The high-salt chromium-containing concentrated water is characterized in that the pH value is 8.1, the conductivity is 31290 mu s/cm, the total chromium content is 31.1mg/L, and the calcium hardness is 211 mg/L.
The high-salt chromium-containing concentrated water enters a high-density sedimentation tank through a water inlet pump, and the high-density sedimentation tank is divided into a mixing tank, a flocculation tank and a sedimentation tank. The high-salt chromium-containing concentrated water firstly enters a mixing tank, sodium carbonate is added into the mixing tank, the adding amount is 678mg/L, and meanwhile, anionic polyacrylamide is added, and the adding amount is 2 mg/L. The stirring speed of the mixing tank is 85 r/min, and the retention time of the high-salt chromium-containing concentrated water in the mixing tank is 3.5 min. Then the sewage enters a flocculation tank, the hydraulic retention time of the flocculation tank is 9min, the flow velocity in a guide cylinder barrel is 1.1m/s, the flow velocity of a water outlet area is 0.06m/s, and the sludge reflux amount is 2%. The high-salt chromium-containing concentrated water flows into a sedimentation tank from a flocculation tank water outlet zone, the diameter of an inclined tube is 55mm, the inclination angle of the inclined tube is 58 degrees, the inclined length of the inclined tube is 1450mm, and the surface load is 12.5m3/m2H, height of clear water zone 0.8m, residence time 22 min. After passing through the high-density sedimentation tank, the calcium hardness of the high-salt chromium-containing concentrated water is 11 mg/L.
The high-salt chromium-containing concentrated water enters a modified resin adsorption tower through a primary lift pump, modified resin is placed in the modified resin adsorption tower, the modified resin accounts for 85% of the volume of the whole modified resin adsorption tower, and the high-salt chromium-containing concentrated water stays in the modified resin adsorption tower for 31 min. After passing through the modified resin adsorption tower, the calcium hardness of the high-salt chromium-containing concentrated water is 9mg/L, and the total chromium is 0.4 mg/L.
The modified resin is specially synthesized and prepared according to the water quality characteristics of cold-rolled high-salt chromium-containing concentrated water. 1) Putting the polymethyl acrylate resin into a reaction kettle, filling the reaction kettle with the ethylenediamine solution, swelling for 8h in the reaction kettle, then heating the reaction kettle to 125 ℃, keeping the temperature for 12h, cooling to form propylene glycol monomethyl ether acetate, filtering, washing the product to be neutral by deionized water, and vacuum-drying at 50 ℃. 2) Mixing propylene glycol methyl ether ester and chloroacetic acid according to a molar ratio of 4:1, putting into a reaction kettle, adjusting the pH value of the solution to 9.1, heating the reaction kettle to 75 ℃, starting a stirrer, stirring at a speed of 65 r/min, and reacting for 12 h. And cooling to form the modified polyacrylamide ethylamine resin.
Then the high-pressure water inlet pump pumps the high-salt chromium-containing concentrated water into the high-pressure reverse osmosis membrane. The pressure of the high-pressure water inlet pump is 55 MPa. The desalination rate of the high-pressure reverse osmosis membrane is 99.4 percent, and the water yield is 60 percent. After the high-salt chromium-containing concentrated water passes through the high-pressure reverse osmosis membrane, the conductivity of the produced water is 530 mu S/cm, and the produced water is directly recycled for production. The high-salt chromium-containing concentrate has the conductivity of 63240 mu S/cm, the calcium hardness of 22mg/L and the total chromium of 3.1 mg/L.
Then pumping the high-salt chromium-containing concentrated solution into an evaporation crystallizer by a secondary water inlet pump, wherein the evaporation temperature is 85 ℃, and finally forming sodium chloride mixed salt by the high-salt chromium-containing concentrated water.
Example 3:
the technical scheme of the high-salt chromium-containing concentrated water comprises a water inlet pump, a high-density sedimentation tank, a primary water inlet pump, a modified resin adsorption tower, modified resin, a high-pressure water inlet pump, high-pressure reverse osmosis, a secondary water inlet pump and an evaporative crystallizer.
The high-salt chromium-containing concentrated water is characterized in that the pH value is 8.0, the conductivity is 30190 mu s/cm, the total chromium content is 30.1mg/L, and the calcium hardness is 198 mg/L.
The high-salt chromium-containing concentrated water enters a high-density sedimentation tank through a water inlet pump, and the high-density sedimentation tank is divided into a mixing tank, a flocculation tank and a sedimentation tank. The high-salt chromium-containing concentrated water firstly enters a mixing tank, sodium carbonate is added into the mixing tank, the adding amount is 345mg/L, and meanwhile, anionic polyacrylamide is added, and the adding amount is 0.5 mg/L. The stirring speed of the mixing tank is 80 r/min, and the retention time of the high-salt chromium-containing concentrated water in the mixing tank is 4.5 min. Then the sewage enters a flocculation tank, the hydraulic retention time of the flocculation tank is 7min, the flow velocity in a guide cylinder barrel is 0.5m/s, the flow velocity of a water outlet area is 0.01m/s, and the sludge reflux amount is 3%. The high-salt chromium-containing concentrated water flows into a sedimentation tank from a flocculation tank water outlet zone, the diameter of an inclined pipe is 75mm, the inclination angle of the inclined pipe is 55 degrees, the inclined length of the inclined pipe is 1200mm, and the surface load is 13.5m3/m2H, height of clear water zone 0.5m, retention time 35 min. After passing through the high-density sedimentation tank, the calcium hardness of the high-salt chromium-containing concentrated water is 10 mg/L.
The high-salt chromium-containing concentrated water enters a modified resin adsorption tower through a primary lift pump, modified resin is placed in the modified resin adsorption tower, the modified resin accounts for 85% of the volume of the whole modified resin adsorption tower, and the high-salt chromium-containing concentrated water stays in the modified resin adsorption tower for 32 min. After passing through the modified resin adsorption tower, the calcium hardness of the high-salt chromium-containing concentrated water is 5mg/L, and the total chromium is 0.4 mg/L.
The modified resin is specially synthesized and prepared according to the water quality characteristics of cold-rolled high-salt chromium-containing concentrated water. 1) Putting the polymethyl acrylate resin into a reaction kettle, filling the reaction kettle with an ethylenediamine solution, swelling for 10 hours in the reaction kettle, then heating the reaction kettle to 115 ℃, keeping the temperature for 14 hours, cooling to form propylene glycol monomethyl ether acetate, filtering, washing a product to be neutral by deionized water, and drying in vacuum at 55 ℃. 2) Mixing propylene glycol methyl ether ester and chloroacetic acid according to a molar ratio of 5:1, putting into a reaction kettle, adjusting the pH of the solution to 9.5, heating the reaction kettle to 70 ℃, starting a stirrer, stirring at a speed of 85 revolutions per minute, and reacting for 12 hours. And cooling to form the modified polyacrylamide ethylamine resin.
Then the high-pressure water inlet pump pumps the high-salt chromium-containing concentrated water into the high-pressure reverse osmosis membrane. The pressure of the high-pressure water inlet pump is 40 MPa. The desalination rate of the high-pressure reverse osmosis membrane is 99.5 percent, and the water yield is 60 percent. After the high-salt chromium-containing concentrated water passes through the high-pressure reverse osmosis membrane, the conductivity of the produced water is 340 mu S/cm, and the produced water is directly recycled for production. The high-salt chromium-containing concentrate has the conductivity of 66120 mu S/cm, the calcium hardness of 7mg/L and the total chromium of 0.8 mg/L.
Then pumping the high-salt chromium-containing concentrated solution into an evaporation crystallizer by a secondary water inlet pump, wherein the evaporation temperature is 90 ℃, and finally forming sodium chloride mixed salt by the high-salt chromium-containing concentrated water.
Example 4:
the technical scheme of the high-salt chromium-containing concentrated water comprises a water inlet pump, a high-density sedimentation tank, a primary water inlet pump, a modified resin adsorption tower, modified resin, a high-pressure water inlet pump, high-pressure reverse osmosis, a secondary water inlet pump and an evaporative crystallizer.
The high-salt chromium-containing concentrated water is characterized in that the pH value is 7.0, the conductivity is 34300 mu s/cm, the total chromium content is 32.1mg/L, and the calcium hardness is 210 mg/L.
The high-salt chromium-containing concentrated water is pumped in by a water inlet pumpAnd (4) entering a high-density sedimentation tank, wherein the high-density sedimentation tank is divided into a mixing tank, a flocculation tank and a sedimentation tank. The high-salt chromium-containing concentrated water firstly enters a mixing tank, sodium carbonate is added into the mixing tank, the adding amount is 385mg/L, and meanwhile, anionic polyacrylamide is added, and the adding amount is 1.5 mg/L. The stirring speed of the mixing tank is 85 r/min, and the retention time of the high-salt chromium-containing concentrated water in the mixing tank is 4.5 min. Then the sewage enters a flocculation tank, the hydraulic retention time of the flocculation tank is 8min, the flow velocity in a guide cylinder barrel is 0.5m/s, the flow velocity of a water outlet area is 0.01m/s, and the sludge reflux amount is 3%. The high-salt chromium-containing concentrated water flows into a sedimentation tank from a water outlet zone of the flocculation tank, the diameter of an inclined pipe is 65mm, the inclination angle of the inclined pipe is 58 degrees, the inclined length of the inclined pipe is 1350mm, and the surface load is 11.5m3/m2H, height of clear water zone 0.7m, retention time 30 min. After passing through the high-density sedimentation tank, the calcium hardness of the high-salt chromium-containing concentrated water is 9 mg/L.
The high-salt chromium-containing concentrated water enters a modified resin adsorption tower through a primary lift pump, modified resin is placed in the modified resin adsorption tower, the modified resin accounts for 83% of the volume of the whole modified resin adsorption tower, and the high-salt chromium-containing concentrated water stays in the modified resin adsorption tower for 32 min. After passing through the modified resin adsorption tower, the calcium hardness of the high-salt chromium-containing concentrated water is 6mg/L, and the total chromium is 0.5 mg/L.
The modified resin is specially synthesized and prepared according to the water quality characteristics of cold-rolled high-salt chromium-containing concentrated water. 1) Putting the polymethyl acrylate resin into a reaction kettle, filling the reaction kettle with an ethylenediamine solution, swelling for 9 hours in the reaction kettle, then heating the reaction kettle to 115 ℃, keeping the temperature for 14 hours, cooling to form propylene glycol monomethyl ether acetate, filtering, washing a product to be neutral by deionized water, and drying in vacuum at 55 ℃. 2) Mixing propylene glycol methyl ether ester and chloroacetic acid according to a molar ratio of 5:1, putting into a reaction kettle, adjusting the pH of the solution to 9.5, heating the reaction kettle to 70 ℃, starting a stirrer, stirring at 75 r/min, and reacting for 12 h. And cooling to form the modified polyacrylamide ethylamine resin.
Then the high-pressure water inlet pump pumps the high-salt chromium-containing concentrated water into the high-pressure reverse osmosis membrane. The pressure of the high-pressure water inlet pump is 49 MPa. The desalination rate of the high-pressure reverse osmosis membrane is 99.5 percent, and the water yield is 60 percent. After the high-salt chromium-containing concentrated water passes through the high-pressure reverse osmosis membrane, the conductivity of produced water is 348 mu S/cm, and the produced water is directly recycled for production. The high-salt chromium-containing concentrate has the conductivity of 62250 mu S/cm, the calcium hardness of 8mg/L and the total chromium of 0.8 mg/L.
Then pumping the high-salt chromium-containing concentrated solution into an evaporation crystallizer by a secondary water inlet pump, wherein the evaporation temperature is 90 ℃, and finally forming sodium chloride mixed salt by the high-salt chromium-containing concentrated water.
In conclusion, the invention firstly provides a complete technical scheme of zero discharge of the high-salt chromium-containing concentrated water, and the problem of environmental pollution caused by chromium-containing heavy metals is solved systematically, so the invention belongs to an environment-friendly production process system for steel.
Of course, those skilled in the art should recognize that the above-described embodiments are illustrative only, and not limiting, and that changes and modifications can be made within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A zero discharge method of high-salt chromium-containing concentrated water is characterized by comprising the following steps: the method comprises the following steps:
(1) the high-salt chromium-containing concentrated water enters a high-density sedimentation tank, and the high-density sedimentation tank is divided into a mixing tank, a flocculation tank and a sedimentation tank; firstly feeding the high-salt chromium-containing concentrated water into a mixing tank, adding sodium carbonate in an amount of 345-678 mg/L into the mixing tank, and simultaneously adding anionic polyacrylamide in an amount of 0.5-2 mg/L, wherein the retention time of the high-salt chromium-containing concentrated water in the mixing tank is 2.5-4.5 min; then the sewage enters a flocculation tank, the flow velocity in a guide cylinder barrel is 0.5-1.1 m/s, the flow velocity in a water outlet area is 0.01-0.06 m/s, and the sludge reflux amount is 2-3%; allowing the high-salt chromium-containing concentrated water to flow into a sedimentation tank from a flocculation tank water outlet zone, and keeping for 15-35 min;
(2) the high-salt chromium-containing concentrated water enters a modified resin adsorption tower, modified resin is placed in the modified resin adsorption tower, and the modified resin accounts for 85-95% of the volume of the whole modified resin adsorption tower;
(3) then pumping high-salt chromium-containing concentrated water into a high-pressure reverse osmosis membrane by using a high-pressure water inlet pump, wherein the pressure of the high-pressure water inlet pump is 40-55 MPa;
(4) and finally, the high-salt chromium-containing concentrated solution enters an evaporation crystallizer, and finally the high-salt chromium-containing concentrated water forms sodium chloride mixed salt.
2. The method for zero emission of high-salt chromium-containing concentrated water according to claim 1, which is characterized in that: in the step (2), the modified resin is prepared according to the water quality characteristics of the cold-rolled high-salt chromium-containing concentrated water, and is prepared by the following steps: 1) putting the polymethyl acrylate resin into a reaction kettle, filling the reaction kettle with an ethylenediamine solution, swelling for 8-10 h in the reaction kettle, then heating the reaction kettle to 110-125 ℃, keeping the temperature for 12-14 h, cooling to form propylene glycol monomethyl ether acetate, filtering, washing the product to be neutral with water, and drying; 2) mixing propylene glycol methyl ether ester and chloroacetic acid according to a molar ratio of 4-6: 1, putting the mixture into a reaction kettle, adjusting the pH value of the solution to 8.9-9.8, heating the reaction kettle to 65-75 ℃, starting a stirrer at a stirring speed of 65-85 rpm, reacting for 12-16 h, and cooling to obtain the modified polyacrylamide ethylamine resin.
3. The method for zero emission of the high-salt chromium-containing concentrated water according to claim 2, which is characterized in that: in the modified resin preparation step 1), the product is washed to be neutral by deionized water and is dried in vacuum at 50-65 ℃.
4. The method for zero emission of high-salt chromium-containing concentrated water according to claim 1, which is characterized in that: in the step (1), the stirring speed of the mixing pool is 75-85 r/min.
5. The method for zero emission of high-salt chromium-containing concentrated water according to claim 1, which is characterized in that: and (2) in the step (1), the hydraulic retention time of the flocculation tank is 7-9 min.
6. The method for zero emission of high-salt chromium-containing concentrated water according to claim 1, which is characterized in that: in the step (1), the diameter of an inclined tube in the sedimentation tank is 55-75 mm, the inclination angle of the inclined tube is 55-58 degrees, the inclined length of the inclined tube is 1200-1450 mm, and the surface load is 10.5-13.5 m3/m2H, the height of the clear water area is 0.5-0.8 m.
7. The method for zero emission of high-salt chromium-containing concentrated water according to claim 1, which is characterized in that: in the step (2), the high-salt chromium-containing concentrated water stays in the modified resin adsorption tower for 25-35 min.
8. The method for zero emission of high-salt chromium-containing concentrated water according to claim 1, which is characterized in that: in the step (3), the salt rejection rate of the high-pressure reverse osmosis membrane is 99.2-99.5%, and the water yield is 60%; after the high-salt chromium-containing concentrated water passes through the high-pressure reverse osmosis membrane, the conductivity of produced water is 230-890 mu S/cm, and the produced water is directly recycled for production.
9. The method for zero emission of high-salt chromium-containing concentrated water according to claim 1, which is characterized in that: and (4) feeding the high-salt chromium-containing concentrated solution in the step (4) into an evaporation crystallizer, wherein the evaporation temperature is 80-90 ℃.
10. A system for use in the zero emission method of high-salt chromium-containing concentrated water according to any one of claims 1 to 9, characterized in that: comprises a water inlet pump (1), a high-density sedimentation tank (2), a primary water inlet pump (3), a modified resin adsorption tower (4), a high-pressure water inlet pump (6), a high-pressure reverse osmosis (7), a secondary water inlet pump (8) and an evaporative crystallizer (9) which are connected in sequence; the high-density sedimentation tank (2) comprises a mixing tank, a flocculation tank and a sedimentation tank; modified resin (5) is placed in the modified resin adsorption tower (4), and the modified resin accounts for 85-95% of the volume of the whole modified resin adsorption tower.
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