CN110950400B - Method for removing total nickel and dissolved organic matters in cold rolling nickel-containing wastewater - Google Patents
Method for removing total nickel and dissolved organic matters in cold rolling nickel-containing wastewater Download PDFInfo
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Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a method for removing total nickel and Dissolved Organic Matters (DOM) in cold-rolling nickel-containing wastewater, which comprises the following steps: the cold-rolled nickel-containing wastewater enters a modified converter steel slag adsorption tower, and the retention time in the modified converter steel slag adsorption tower is 16-32 min; the modified converter steel slag adsorbent accounts for 75-88% of the internal volume of the modified converter steel slag adsorption tower; then, the mixture enters a pH adjusting tank, dilute hydrochloric acid is added, the retention time is 12-18 minutes, and the pH value of effluent is 6.6-8.2; after passing through the regulating reservoir, the cold-rolled nickel-containing wastewater enters a modified resin adsorption tower, ethanolamine modified chelating resin is filled in the modified resin adsorption tower, and the cold-rolled nickel-containing wastewater passes through the modified resin adsorption tower and is discharged after reaching the standard. The effluent water quality after the treatment by the method is 0.06-0.09 mg/L of total nickel, 9-13 mg/L of DOM and 6.8-8.1 of pH.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a process and a method for efficiently removing total nickel and dissolved organic matters in cold rolling nickel-containing wastewater.
Background
After the cold-rolling nickel electroplating process, the surface of the strip steel needs to be washed by pure water, and most of the waste water after the strip steel washing is discharged to a waste water station because nickel ions and Dissolved Organic Matters (DOM) exist.
So far, no treatment process aiming at total nickel and DOM in the cold rolling nickel-containing wastewater exists. The invention aims to develop a technical scheme for removing total nickel and soluble organic matters in cold rolling nickel-containing wastewater according to the water quality and water quantity condition of cold rolling nickel-containing wastewater, takes green process and energy conservation and emission reduction as main tasks, reduces environmental pollution, and actively deals with increasingly strict environmental protection regulations.
Disclosure of Invention
The invention aims to provide a method for removing total nickel and DOM in cold-rolled nickel-containing wastewater.
The technical scheme of the invention is as follows:
a method for removing total nickel and DOM in cold rolling nickel-containing wastewater is characterized by comprising the following steps: .
The cold-rolled nickel-containing wastewater enters a modified converter steel slag adsorption tower, and the retention time in the modified converter steel slag adsorption tower is 16-32 min; the modified converter steel slag adsorbent accounts for 75-88% of the internal volume of the modified converter steel slag adsorption tower;
the modified converter steel slag adsorbent is prepared by the following steps according to the water quality of the cold rolling nickel-containing wastewater: (1) the modified converter steel slag comprises, by mass, 39.9-51.2% of CaO, 12.5-19.8% of TFe, and SiO216.9 to 27.8% of Al2O32.8 to 6.7 percent of MgO, 6.3 to 9.8 percent of Mn, 1.7 to 8.6 percent of Mn and 1.8 to 11.2 percent of C; after ball milling, screening to obtain particles with the particle size of 80-250 meshes, cleaning with 0.1-0.3 mol/L dilute hydrochloric acid, cleaning with 0.05-0.08 mol/L dilute sulfuric acid, and cleaning with industrial water with the conductivity of 350-620 mu s/cm; (2) putting the steel slag into 3.5-4.9 mol/L sodium chloride solution, soaking for 8-11 hours, taking out, and drying in a 105 ℃ blast drying oven; (3) fully mixing the dried steel slag, the granular activated carbon and the ferric chloride according to the mass ratio of 11-19: 2: 1; (4) putting the mixture into a muffle furnace, heating to 380-410 ℃ at a heating rate of 6-8 ℃/min, then keeping the temperature for 35-55 min, and cooling to prepare a modified converter steel slag adsorbent;
cold-rolled nickel-containing wastewater enters a pH adjusting tank after passing through a converter steel slag adsorption tower, dilute hydrochloric acid is added, the retention time is 12-18 minutes, and the pH of effluent is 6.6-8.2;
after passing through a regulating reservoir, cold-rolled nickel-containing wastewater enters a modified resin adsorption tower, ethanolamine modified chelating resin is filled in the modified resin adsorption tower, and the ethanolamine modified chelating resin accounts for 75-90% of the volume of the whole modified resin adsorption tower; and the cold-rolled nickel-containing wastewater passes through the modified resin adsorption tower and then is discharged after reaching the standard.
According to the method for removing the total nickel and DOM in the cold rolling nickel-containing wastewater, before treatment, the water quality of the cold rolling nickel-containing wastewater is 1.7-8.5 mg/L of the total nickel, 45-67 mg/L of the DOM and 6.5-7.9 of the pH value.
Further, the density of the modified converter steel slag adsorbent is 3.15-3.98 g/cm3The specific adsorption surface area is 4.11-5.23 cm2And the stability expansion rate is 12-15%, so that the capacity of adsorbing total chromium and DOM is greatly improved.
Further, after the cold-rolled nickel-containing wastewater passes through a converter steel slag adsorption tower, the effluent quality is that the total nickel is 0.4-0.9 mg/L, the DOM is 15-27 mg/L, and the pH is 8.5-10.1.
According to the method for removing total nickel and DOM in cold-rolled nickel-containing wastewater, the ethanolamine modified chelating resin is prepared according to the characteristics of the cold-rolled nickel-containing wastewater: 1) performing polymerization reaction, namely putting 2, 4-dihydroxybenzene, formaldehyde, oxalic acid and citric acid into a reaction kettle according to the molar ratio of 1: 1.3-1.9: 1.4-1.7: 0.05-0.12, heating the reaction kettle to 98-105 ℃ under normal pressure, and reacting for 12-20 hours; 2) cleaning the chelate resin, namely naturally cooling the chelate resin to room temperature after the reaction is finished, filtering, cleaning the chelate resin with dichloromethane for 2-3 times, cleaning the chelate resin with petroleum ether for 2-3 times, cleaning the chelate resin with clear water for 3-5 times, and drying in a forced air drying oven at 50-55 ℃ for 3-4 hours; 3) and (3) modifying the polymer, namely cooling the chelate resin, putting the chelate resin, ethanolamine and dichloromethane in a volume ratio of 1-3: 0.2: 30-45 into a mechanical stirrer, reacting for 80-100 min in the stirrer at a rotating speed of 45-65 r/min, filtering after the reaction is finished, drying for 2 hours in a forced air drying oven at 50-55 ℃, and cooling to obtain the ethanolamine modified group chelate resin.
Furthermore, the mass fraction of the oxalic acid is 2 percent, and the mass fraction of the citric acid is 5 percent.
Further, the ethanolamine-modified chelating resin has a water swelling rate of 1.32 to 1.53 and can react with Ni at 25 DEG C2+The adsorption capacity is 0.528-0.895 mmol/g.
Further, after cold rolling nickel-containing wastewater passes through a modified resin adsorption tower, the effluent quality is that the total nickel is 0.06-0.09 mg/L, the DOM is 9-13 mg/L, and the pH is 6.8-8.1. The cold rolling nickel-containing waste water is then discharged through a drain pump.
Detailed description of the invention:
a process system for removing total nickel and DOM in cold-rolled nickel-containing wastewater comprises a primary lift pump, a modified converter steel slag adsorption tower, modified converter steel slag, a secondary lift pump, a pH adjusting tank, a tertiary lift pump, a modified resin adsorption tower, ethanolamine modified chelate resin and a drainage pump.
The water quality of the cold rolling nickel-containing wastewater is that the total nickel is 1.7-8.5 mg/L, the DOM is 45-67 mg/L, and the pH is 6.5-7.9.
And the cold-rolled nickel-containing wastewater enters the modified converter steel slag adsorption tower through a primary lift pump, and the retention time in the modified converter steel slag adsorption tower is 16-32 min. The modified converter steel slag accounts for 75-88% of the internal volume of the modified converter steel slag adsorption tower. The modified converter steel slag is loose and porous, has a large specific surface area, contains active groups on the surface, and has strong adsorption performance. Compared with other adsorbents, active sites on the surface of the steel slag are negatively charged, and generate electrostatic adsorption on cations and organic matters with the cations in the solution; the surface ions of oxides such as silicon, aluminum, iron and the like on the surface of the steel slag particles are not coordinated and unsaturated, and are coordinated with water in an aqueous solution, the water is dissociated and desorbed to form a hydroxylated group, and the group can generate a surface coordination complex with metal cations, so that heavy metal ions and DOM are adsorbed.
The modified converter steel slag is prepared and synthesized according to the water quality of the cold rolling nickel-containing wastewater. (1) The modified converter steel slag comprises, by mass, 39.9-51.2% of CaO, 12.5-19.8% of TFe, and SiO216.9 to 27.8% of Al2O32.8 to 6.7 percent of MgO, 6.3 to 9.8 percent of Mn, 1.7 to 8.6 percent of Mn and 1.8 to 11.2 percent of C. After ball milling, screening the powder with the particle size of 80-250 meshes, washing the powder for 3 times by using 0.1-0.3 mol/L dilute hydrochloric acid, then washing the powder for 3 times by using 0.05-0.08 mol/L dilute sulfuric acid, and then washing the powder for 3-5 times by using industrial water with the conductivity of 350-620 mu s/cm. (2) The steel slag is placed into 3.5-4.9 mol/L sodium chloride solution to be soaked for 8-11 hours, and the steel slag is taken out and dried in a blast drying oven at 105 ℃. (3) The dried steel slag, the granular active carbon and the ferric chloride are mixed according to the mass ratio of 11 to up toMix well in a ratio of 19:2: 1. (4) And (3) putting the mixture into a muffle furnace, heating to 380-410 ℃ at a heating rate of 6-8 ℃/min, then keeping the temperature for 35-55 min, and cooling to prepare the modified converter steel slag adsorbent. After the preparation process, the density of the modified converter steel slag adsorbent is 3.15-3.98 g/cm3The specific adsorption surface area is 4.11-5.23 cm2And the stability expansion rate is 12-15%, so that the capacity of adsorbing total chromium and DOM is greatly improved.
After cold rolling nickel-containing wastewater passes through a converter steel slag adsorption tower, the effluent quality is that the total nickel is 0.4-0.9 mg/L, the DOM is 15-27 mg/L, and the pH is 8.5-10.1. The pH value of the effluent is obviously increased, and because the steel slag is alkaline, the cold rolling nickel-containing wastewater needs to enter a pH adjusting tank to adjust the pH value to be neutral again.
And pumping the cold-rolled nickel-containing wastewater into a pH adjusting tank by using a secondary lift pump, adding dilute hydrochloric acid into the pH adjusting tank, and determining the addition amount of the dilute hydrochloric acid by using a sensor and an automatic control system. The retention time of the cold rolling nickel-containing wastewater in the pH adjusting tank is 12-18 minutes, and the pH of the final effluent is 6.6-8.2.
After passing through the regulating reservoir, the cold-rolled nickel-containing wastewater is pumped into a modified resin adsorption tower by a three-level lift pump, and total nickel and DOM are further removed. Ethanolamine modified chelating resin is filled in the modified resin adsorption tower, and accounts for 75-90% of the volume of the whole modified resin adsorption tower.
The ethanolamine modified chelating resin is prepared according to the characteristics of cold-rolled nickel-containing wastewater. 1) A step of polymerization, in which 2, 4-dihydroxybenzene, formaldehyde, oxalic acid (mass fraction is 2%) and citric acid (mass fraction is 5%) are put into a reaction kettle according to the molar ratio of 1: 1.3-1.9: 1.4-1.7: 0.05-0.12, the reaction kettle is heated to 98-105 ℃ under normal pressure, and the reaction lasts for 12-20 hours; 2) cleaning the chelate resin, namely naturally cooling the chelate resin to room temperature after the reaction is finished, filtering, cleaning the chelate resin with dichloromethane for 2-3 times, cleaning the chelate resin with petroleum ether for 2-3 times, cleaning the chelate resin with clear water for 3-5 times, and drying in a forced air drying oven at 50-55 ℃ for 3-4 hours; 3) modifying the polymer, namely cooling the chelate resin, and mechanically stirring the chelate resin, ethanolamine and dichloromethane in a volume ratio of 1-3: 0.2: 30-45And (3) reacting in a stirrer with the rotating speed of 45-65 r/min for 80-100 min, filtering after the reaction is finished, drying in a forced air drying oven at 50-55 ℃ for 2 h, and cooling to obtain the ethanolamine modified chelating resin. The water swelling rate of the ethanolamine modified chelating resin is 1.32-1.53, and the reaction temperature is 25 ℃ for Ni2+The adsorption capacity is 0.528-0.895 mmol/g (standard solution test).
After cold rolling nickel-containing wastewater passes through a modified resin adsorption tower, the effluent quality is that the total nickel is 0.06-0.09 mg/L, the DOM is 9-13 mg/L, and the pH is 6.8-8.1. The cold rolling nickel-containing waste water is then discharged through a drain pump.
The invention also provides a process system for removing total nickel and DOM in cold-rolled nickel-containing wastewater, which comprises a primary lifting pump, a modified converter steel slag adsorption tower, modified converter steel slag, a secondary lifting pump, a pH adjusting tank, a tertiary lifting pump, a modified resin adsorption tower, ethanolamine modified chelate resin and a drainage pump.
The beneficial technical effects are as follows:
the invention provides a treatment scheme for removing total nickel and DOM in cold rolling nickel-containing wastewater, and the technical scheme effectively solves the problem that the cold rolling nickel-containing wastewater pollutes the environment. The effluent water quality treated by the method is 0.06-0.09 mg/L of total nickel, 9-13 mg/L of DOM and 6.8-8.1 of pH, belongs to an environment-friendly production process of steel and has good social and environmental benefits.
Drawings
FIG. 1 is a process flow for removing total nickel and dissolved organic matters in cold rolling nickel-containing wastewater,
wherein: the device comprises a primary lift pump-1, a modified converter steel slag adsorption tower-2, modified converter steel slag-3, a secondary lift pump-4, a pH adjusting tank-5, a tertiary lift pump-6, a modified resin adsorption tower-7, ethanolamine modified chelating resin-8 and a drainage pump-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.
Example 1:
a process system for removing total nickel and DOM in cold-rolled nickel-containing wastewater comprises a primary lift pump, a modified converter steel slag adsorption tower, modified converter steel slag, a secondary lift pump, a pH adjusting tank, a tertiary lift pump, a modified resin adsorption tower, ethanolamine modified chelate resin and a drainage pump.
The water quality of the cold rolling nickel-containing wastewater is that the total nickel is 8.2mg/L, the DOM is 63mg/L, and the pH is 7.7.
And the cold-rolled nickel-containing wastewater enters the modified converter steel slag adsorption tower through a primary lift pump, and the retention time in the modified converter steel slag adsorption tower is 28 min. The modified converter steel slag accounts for 85% of the internal volume of the modified converter steel slag adsorption tower. The modified converter steel slag is loose and porous, has a large specific surface area, contains active groups on the surface, and has strong adsorption performance. Compared with other adsorbents, active sites on the surface of the steel slag are negatively charged, and generate electrostatic adsorption on cations and organic matters with the cations in the solution; the surface ions of oxides such as silicon, aluminum, iron and the like on the surface of the steel slag particles are not coordinated and unsaturated, and are coordinated with water in an aqueous solution, the water is dissociated and desorbed to form a hydroxylated group, and the group can generate a surface coordination complex with metal cations, so that heavy metal ions and DOM are adsorbed.
The modified converter steel slag is prepared and synthesized according to the water quality of the cold rolling nickel-containing wastewater. (1) The modified converter steel slag comprises, by mass, 43.2% of CaO, 14.7% of TFe and SiO223.2% of Al2O34.9%, MgO 5.2%, Mn 4.7%, C4.1%. After ball milling, the particle size is screened to be 180 meshes, the solution is washed for 3 times by using 0.3mol/L dilute hydrochloric acid, then washed for 3 times by using 0.07mol/L dilute sulfuric acid, and then washed for 5 times by using industrial water with the conductivity of 590 mu s/cm. (2) The steel slag is put into 4.7mol/L sodium chloride solution to be soaked for 11 hours, and then is taken out to be dried in a blast drying oven at 105 ℃. (3) And fully mixing the dried steel slag, the granular activated carbon and the ferric chloride according to the mass ratio of 19:2: 1. (4) And (3) putting the mixture into a muffle furnace, heating to 410 ℃ at the heating rate of 8 ℃/min, keeping the temperature for 55min, and cooling to prepare the modified converter steel slag adsorbent. After the preparation process, the density of the modified converter steel slag adsorbent is 3.69g/cm3Specific surface area of adsorptionThe product is 4.78cm2And/kg, the stability expansion rate is 15%, and the capacity of adsorbing total chromium and DOM is greatly improved.
After cold-rolled nickel-containing wastewater passes through a converter steel slag adsorption tower, the effluent quality is that the total nickel is 0.5mg/L, the DOM is 19mg/L, and the pH is 9.7. The pH value of the effluent is obviously increased, and because the steel slag is alkaline, the cold rolling nickel-containing wastewater needs to enter a pH adjusting tank to adjust the pH value to be neutral again.
And pumping the cold-rolled nickel-containing wastewater into a pH adjusting tank by using a secondary lift pump, adding dilute hydrochloric acid into the pH adjusting tank, and determining the addition amount of the dilute hydrochloric acid by using a sensor and an automatic control system. The retention time of the cold rolling nickel-containing wastewater in the pH adjusting tank is 16 minutes, and the pH of the final effluent is 7.8.
After passing through the regulating reservoir, the cold-rolled nickel-containing wastewater is pumped into a modified resin adsorption tower by a three-level lift pump, and total nickel and DOM are further removed. Ethanolamine modified chelating resin is filled in the modified resin adsorption tower, and accounts for 85% of the volume of the whole modified resin adsorption tower.
The ethanolamine modified chelating resin is prepared according to the characteristics of cold-rolled nickel-containing wastewater. 1) A step of polymerization, in which 2, 4-dihydroxybenzene, formaldehyde, oxalic acid (mass fraction of 2%) and citric acid (mass fraction of 5%) are put into a reaction kettle according to the mol ratio of 1:1.8:1.7:0.07, the reaction kettle is heated to 99 ℃ under normal pressure, and the reaction lasts for 18 hours; 2) cleaning the chelate resin, namely naturally cooling the chelate resin to room temperature after the reaction is finished, filtering, cleaning the chelate resin with dichloromethane for 2 times, cleaning the chelate resin with petroleum ether for 3 times, cleaning the chelate resin with clear water for 5 times, and drying the chelate resin in a forced air drying oven at the temperature of 52 ℃ for 4 hours; 3) and (3) modifying the polymer, namely cooling the chelate resin, putting the chelate resin into a mechanical stirrer according to the volume ratio of 3:0.2:40 of the chelate resin to ethanolamine to dichloromethane, reacting for 90min in the stirrer at the rotating speed of 65 r/min, filtering after the reaction is finished, drying for 2 h in an air drying oven at the temperature of 55 ℃, and cooling to prepare the ethanolamine modified group chelate resin. The water swelling rate of the ethanolamine modified chelating resin is 1.41, and the reaction temperature is 25 ℃ for Ni2+The adsorption capacity was 0.7.82mmol/g (standard solution test).
After cold-rolled nickel-containing wastewater passes through a modified resin adsorption tower, the effluent quality is that the total nickel is 0.08mg/L, the DOM is 12mg/L, and the pH is 7.8. The cold rolling nickel-containing waste water is then discharged through a drain pump.
Example 2:
a process system for removing total nickel and DOM in cold-rolled nickel-containing wastewater comprises a primary lift pump, a modified converter steel slag adsorption tower, modified converter steel slag, a secondary lift pump, a pH adjusting tank, a tertiary lift pump, a modified resin adsorption tower, ethanolamine modified chelate resin and a drainage pump.
The water quality of the cold rolling nickel-containing wastewater is that the total nickel is 3.6mg/L, the DOM is 51mg/L, and the pH is 6.9.
And the cold-rolled nickel-containing wastewater enters the modified converter steel slag adsorption tower through a primary lift pump, and the retention time in the modified converter steel slag adsorption tower is 18 min. The modified converter steel slag accounts for 82% of the internal volume of the modified converter steel slag adsorption tower. The modified converter steel slag is loose and porous, has a large specific surface area, contains active groups on the surface, and has strong adsorption performance. Compared with other adsorbents, active sites on the surface of the steel slag are negatively charged, and generate electrostatic adsorption on cations and organic matters with the cations in the solution; the surface ions of oxides such as silicon, aluminum, iron and the like on the surface of the steel slag particles are not coordinated and unsaturated, and are coordinated with water in an aqueous solution, the water is dissociated and desorbed to form a hydroxylated group, and the group can generate a surface coordination complex with metal cations, so that heavy metal ions and DOM are adsorbed.
The modified converter steel slag is prepared and synthesized according to the water quality of the cold rolling nickel-containing wastewater. (1) The modified converter steel slag comprises, by mass, 45.8% of CaO, 15.5% of TFe and SiO219.7% of Al2O34.1%, MgO 7.9%, Mn 3.7%, C3.3%. After ball milling, the particle size is screened to be 150 meshes, the powder is washed for 3 times by using 0.1mol/L dilute hydrochloric acid, then washed for 3 times by using 0.06mol/L dilute sulfuric acid, and then washed for 4 times by using industrial water with the conductivity of 410 mu s/cm. (2) The steel slag is put into 3.7mol/L sodium chloride solution to be soaked for 9 hours, and then is taken out to be dried in a blast drying oven at 105 ℃. (3) Fully mixing the dried steel slag, the granular activated carbon and the ferric chloride according to the mass ratio of 13:2: 1. (4) Placing the mixture in a muffle furnace and heating at 6 deg.C/minHeating to 380 ℃ at a speed, then keeping the temperature for 41min, and cooling to prepare the modified converter steel slag adsorbent. After the preparation process, the density of the modified converter steel slag adsorbent is 3.71g/cm3The specific adsorption surface area is 5.05cm2The expansion rate of stability is 14 percent per kg, and the capacity of adsorbing total chromium and DOM is greatly improved.
After cold-rolled nickel-containing wastewater passes through a converter steel slag adsorption tower, the effluent quality is that the total nickel is 0.5mg/L, the DOM is 19mg/L, and the pH is 8.9. The pH value of the effluent is obviously increased, and because the steel slag is alkaline, the cold rolling nickel-containing wastewater needs to enter a pH adjusting tank to adjust the pH value to be neutral again.
And pumping the cold-rolled nickel-containing wastewater into a pH adjusting tank by using a secondary lift pump, adding dilute hydrochloric acid into the pH adjusting tank, and determining the addition amount of the dilute hydrochloric acid by using a sensor and an automatic control system. The retention time of the cold rolling nickel-containing wastewater in the pH adjusting tank is 12-18 minutes, and the pH of the final effluent is 7.1.
After passing through the regulating reservoir, the cold-rolled nickel-containing wastewater is pumped into a modified resin adsorption tower by a three-level lift pump, and total nickel and DOM are further removed. Ethanolamine modified chelating resin is filled in the modified resin adsorption tower, and accounts for 88% of the volume of the whole modified resin adsorption tower.
The ethanolamine modified chelating resin is prepared according to the characteristics of cold-rolled nickel-containing wastewater. 1) A step of polymerization, in which 2, 4-dihydroxybenzene, formaldehyde, oxalic acid (mass fraction of 2%) and citric acid (mass fraction of 5%) are put into a reaction kettle according to the mol ratio of 1:1.4:1.6:0.09, the reaction kettle is heated to 99 ℃ under normal pressure, and the reaction lasts for 15 hours; 2) cleaning the chelate resin, namely naturally cooling the chelate resin to room temperature after the reaction is finished, filtering, cleaning the chelate resin with dichloromethane for 2 times, cleaning the chelate resin with petroleum ether for 2 times, cleaning the chelate resin with clear water for 3 times, and drying in a forced air drying oven at 50 ℃ for 3 hours; 3) and (3) modifying the polymer, namely cooling the chelate resin, putting the chelate resin into a mechanical stirrer according to the volume ratio of the chelate resin to the ethanolamine to the dichloromethane of 2:0.2:35, reacting for 90min in the stirrer at the rotating speed of 45 r/min, filtering after the reaction is finished, drying for 2 h in an air drying oven at the temperature of 50 ℃, and cooling to prepare the ethanolamine modified group chelate resin. Ethanolamine modified chelating resin in waterSwelling ratio of 1.33, Ni at 25 ℃2+The adsorption capacity was 0.788mmol/g (standard solution test).
After cold-rolled nickel-containing wastewater passes through a modified resin adsorption tower, the effluent quality is that the total nickel is 0.07mg/L, the DOM is 12mg/L, and the pH is 7.0. The cold rolling nickel-containing waste water is then discharged through a drain pump.
In conclusion, the method for removing the total nickel and DOM in the cold-rolling nickel-containing wastewater has low one-time investment; the treatment effect is stable; the production and operation cost is low; high automation degree and simple operation. The invention fully embodies the effects of energy conservation and emission reduction, and is an environment-friendly green steel production process.
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 (7)
1. A method for removing total nickel and DOM in cold rolling nickel-containing wastewater is characterized by comprising the following steps:
the cold-rolled nickel-containing wastewater enters a modified converter steel slag adsorption tower, and the retention time in the modified converter steel slag adsorption tower is 16-32 min; the modified converter steel slag adsorbent accounts for 75-88% of the internal volume of the modified converter steel slag adsorption tower;
the modified converter steel slag adsorbent is prepared by the following steps according to the water quality of the cold rolling nickel-containing wastewater: (1) the modified converter steel slag comprises, by mass, 39.9-51.2% of CaO, 12.5-19.8% of TFe, and SiO216.9 to 27.8% of Al2O32.8 to 6.7 percent of MgO, 6.3 to 9.8 percent of Mn, 1.7 to 8.6 percent of Mn and 1.8 to 11.2 percent of C; after ball milling, screening to obtain particles with the particle size of 80-250 meshes, cleaning with 0.1-0.3 mol/L dilute hydrochloric acid, cleaning with 0.05-0.08 mol/L dilute sulfuric acid, and cleaning with industrial water with the conductivity of 350-620 mu s/cm; (2) putting the steel slag into 3.5-4.9 mol/L sodium chloride solution, soaking for 8-11 hours, taking out, and drying in a 105 ℃ blast drying oven; (3) mixing the dried steel slag, granular active carbon and ferric chlorideFully mixing the components in a ratio of 11-19: 2: 1; (4) putting the mixture into a muffle furnace, heating to 380-410 ℃ at a heating rate of 6-8 ℃/min, then keeping the temperature for 35-55 min, and cooling to prepare a modified converter steel slag adsorbent;
cold-rolled nickel-containing wastewater enters a pH adjusting tank after passing through a modified converter steel slag adsorption tower, dilute hydrochloric acid is added, the retention time is 12-18 minutes, and the pH of effluent is 6.6-8.2;
after passing through a regulating reservoir, cold-rolled nickel-containing wastewater enters a modified resin adsorption tower, wherein ethanolamine modified chelating resin is filled in the modified resin adsorption tower, and the ethanolamine modified chelating resin accounts for 75-90% of the volume of the whole modified resin adsorption tower; cold rolling nickel-containing wastewater passes through a modified resin adsorption tower and then is discharged after reaching the standard;
the ethanolamine modified chelating resin is prepared according to the characteristics of cold-rolled nickel-containing wastewater: 1) performing polymerization reaction, namely putting 2, 4-dihydroxybenzene, formaldehyde, oxalic acid and citric acid into a reaction kettle according to the molar ratio of 1: 1.3-1.9: 1.4-1.7: 0.05-0.12, heating the reaction kettle to 98-105 ℃ under normal pressure, and reacting for 12-20 hours; 2) cleaning the chelate resin, namely naturally cooling the chelate resin to room temperature after the reaction is finished, filtering, cleaning the chelate resin with dichloromethane for 2-3 times, cleaning the chelate resin with petroleum ether for 2-3 times, cleaning the chelate resin with clear water for 3-5 times, and drying in a forced air drying oven at 50-55 ℃ for 3-4 hours; 3) and (3) modifying the polymer, namely cooling the chelate resin, putting the chelate resin, ethanolamine and dichloromethane in a volume ratio of 1-3: 0.2: 30-45 into a mechanical stirrer, reacting for 80-100 min in the stirrer at a rotating speed of 45-65 r/min, filtering after the reaction is finished, drying for 2 hours in a forced air drying oven at 50-55 ℃, and cooling to obtain the ethanolamine modified group chelate resin.
2. The method for removing total nickel and DOM in cold rolling nickel-containing wastewater according to claim 1, wherein the method comprises the following steps: before treatment, the water quality of the cold rolling nickel-containing wastewater is that the total nickel is 1.7-8.5 mg/L, the DOM is 45-67 mg/L, and the pH is 6.5-7.9.
3. The method for removing total nickel and DOM in cold rolling nickel-containing wastewater according to claim 1, wherein the method comprises the following steps: improvement ofThe density of the steel slag adsorbent of the converter is 3.15-3.98 g/cm3The specific adsorption surface area is 4.11-5.23 cm2And the stability expansion rate is 12-15%, so that the capacity of adsorbing total chromium and DOM is greatly improved.
4. The method for removing total nickel and DOM in cold rolling nickel-containing wastewater according to claim 1, wherein the method comprises the following steps: after cold-rolled nickel-containing wastewater passes through the modified converter steel slag adsorption tower, the effluent quality is that the total nickel is 0.4-0.9 mg/L, the DOM is 15-27 mg/L, and the pH is 8.5-10.1.
5. The method for removing total nickel and DOM in cold rolling nickel-containing wastewater according to claim 1, wherein the method comprises the following steps: the mass fraction of the oxalic acid is 2 percent, and the mass fraction of the citric acid is 5 percent.
6. The method for removing total nickel and DOM in cold rolling nickel-containing wastewater according to claim 1, wherein the method comprises the following steps: the ethanolamine modified chelating resin has a water swelling rate of 1.32-1.53 and can react with Ni at 25 DEG C2+The adsorption capacity is 0.528-0.895 mmol/g.
7. The method for removing total nickel and DOM in cold rolling nickel-containing wastewater according to claim 1, wherein the method comprises the following steps: after cold rolling nickel-containing wastewater passes through a modified resin adsorption tower, the water quality of effluent is that the total nickel is 0.06-0.09 mg/L, DOM is 9-13 mg/L, and the pH is 6.8-8.1, and then the cold rolling nickel-containing wastewater is discharged through a drainage pump.
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| CN108554379A (en) * | 2018-05-16 | 2018-09-21 | 辽宁大学 | Adsorbent and its preparation method and application based on discarded slag |
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| DD234412A1 (en) * | 1985-02-04 | 1986-04-02 | Zeiss Jena Veb Carl | METHOD FOR REMOVING NICKELIONS FROM CHEMICAL NICKEL SOLUTIONS |
| CN103524710A (en) * | 2013-09-22 | 2014-01-22 | 湖南师范大学 | Method for preparing metal chelating agent by modifying bromo-epoxy resin waste |
| CN106315909A (en) * | 2015-06-29 | 2017-01-11 | 宝山钢铁股份有限公司 | Device and method for removing COD and two heavy metals (iron and nickel) in cold rolling dilute alkali wastewater |
| CN107235570A (en) * | 2016-03-28 | 2017-10-10 | 宝山钢铁股份有限公司 | A kind of cold rolling acid waste water is up to standard and method and system of reuse |
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