CN113735303B - Method and system for removing calcium hardness and soluble organic matters in nanofiltration concentrated water - Google Patents
Method and system for removing calcium hardness and soluble organic matters in nanofiltration concentrated water Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- C02F2209/21—Dissolved organic carbon [DOC]
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Abstract
The invention discloses a method for removing calcium hardness and soluble organic matters in nanofiltration concentrated water, which comprises the following steps: pumping cold rolling nanofiltration concentrated water to be treated into a modified porous zeolite adsorption tower through a water inlet pump, wherein modified porous zeolite is placed in the modified porous zeolite adsorption tower, and the modified porous zeolite accounts for 85-90% of the volume of the adsorption tower; the residence time of cold rolling nanofiltration concentrated water in the modified porous zeolite adsorption tower is 45-70 min; cold rolling nanofiltration concentrated water enters a modified resin adsorption tower through a lifting pump, modified styrene resin is arranged in the tower, the modified styrene resin occupies 80-90% of the whole volume of the adsorption tower, and the adsorption residence time of the nanofiltration concentrated water in the modified resin is 50-70 min; cold rolling nanofiltration concentrated water is discharged through a water outlet pump after passing through a modified resin adsorption reaction tower or enters a wastewater zero discharge system; a system for carrying out the method is also disclosed. According to the water quality and water quantity of cold-rolled nanofiltration concentrated water, an economic and efficient pollutant treatment process is developed, and calcium ions and soluble organic matters can be effectively removed.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for removing calcium hardness and soluble organic matters in nanofiltration concentrated water.
Background
As a basic industry in China, the steel industry is rapidly developed since the innovation is opened, and in recent years, the steel industry is always in a high-speed development stage, and the annual steel yield is increased by 15% -22%. However, the iron and steel industry is an industry with high energy consumption, high resources and high pollution, and the water resource consumption is huge and accounts for about 14% of the water consumption of the national industry.
The cold rolling dilute alkali wastewater mainly comes from oil warehouse drainage of each unit such as a rolling mill unit, a grinding roll unit, a strip steel degreasing unit and the like. The cold rolling dilute alkali wastewater after conventional treatment is discharged after reaching the standard. In order to reduce the wastewater discharge, the nanofiltration technology is adopted to treat cold-rolled dilute alkali wastewater which is discharged after reaching the standard, the nanofiltration water produced can be applied to production, and the content of calcium ions and soluble organic matters (DOC, dissolved organic carbon) in the nanofiltration concentrated water is high, so that the nanofiltration concentrated water is difficult to be further recycled.
However, a treatment method and a treatment process for simultaneously removing calcium ions and soluble organic matters in cold-rolled nanofiltration concentrated water are not available so far.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems of developing an economic and efficient pollutant treatment process according to the water quality and quantity of cold-rolled nanofiltration concentrated water, taking recycling and energy conservation and emission reduction as main tasks, reducing environmental pollution and actively coping with increasingly strict environmental protection regulations.
The technical scheme of the invention is that the method for removing calcium hardness and soluble organic matters in nanofiltration concentrated water comprises the following steps:
a. pumping cold rolling nanofiltration concentrated water to be treated into a modified porous zeolite adsorption tower through a water inlet pump, wherein modified porous zeolite is placed in the modified porous zeolite adsorption tower, and the modified porous zeolite accounts for 85-90% of the volume of the adsorption tower; the residence time of cold rolling nanofiltration concentrated water in the modified porous zeolite adsorption tower is 45-70 min;
b. then cold rolling nanofiltration concentrated water enters a modified resin adsorption tower through a lifting pump, modified styrene resin is arranged in the modified resin adsorption tower, the modified styrene resin accounts for 80-90% of the whole volume of the adsorption tower, and nanofiltration concentrated water is arranged in the modified resin adsorption tower
The middle residence time is 50-70 min;
c. the cold rolling nanofiltration concentrated water is discharged through a water outlet pump after passing through a modified resin adsorption reaction tower or enters a wastewater zero discharge system;
the preparation method of the modified porous zeolite comprises the following steps:
1) Selecting porous zeolite with granularity of 73-82%, soluble salt with mass fraction of 0.3-1.2%, calcium ion exchange capacity of 16-23 mg/g and DOC adsorption saturation of 6-13 mg/g;
2) Preparing a sodium carbonate solution with the concentration of 3.5-6.7 mol/L and a sodium sulfate solution with the concentration of 2.3-3.1 mol/L, mixing the two solutions, adding 2.3-7.5 mg of cetyltrimethylammonium bromide into each liter of the solution, and uniformly stirring to form a mixed solution;
3) Immersing the porous zeolite into the mixed solution according to the solid-liquid ratio of 1:5-8, immersing for 10-13 h in the mixed solution, and then carrying out microwave reaction on the porous zeolite and the mixed solution for 45-75 min;
4) Filtering porous zeolite, drying at 100-110 deg.c for 2-4 hr, cooling, heating in a heater to 130-160 deg.c at 5-8 deg.c/min, maintaining the temperature for 4-6 hr, and cooling to form modified porous zeolite.
The modified porous zeolite is prepared according to the characteristics of nanofiltration concentrated water, and can efficiently remove calcium ions and DOC in the nanofiltration concentrated water.
The calcium ion exchange capacity of the obtained modified porous zeolite is 21-39 mg/g, and the DOC adsorption saturation amount is 11-23 mg/g.
According to the method for removing calcium hardness and soluble organic matters in nanofiltration concentrated water, preferably, the water quality of the cold-rolled nanofiltration concentrated water to be treated is characterized in that the conductivity is 23410-42570 mg/L, sulfate ions are 1230-2145 mg/L, calcium ions are 134-289 mg/L and DOC is 56-78 mg/L;
the calcium ions in the cold rolling nanofiltration concentrated water are 54-93 mg/L and the DOC is 17-31 mg/L through a modified porous zeolite adsorption tower;
after the cold rolling nanofiltration concentrated water is treated, the calcium ions are 4-9 mg/L, and the DOC is 7-12 mg/L.
According to the method for removing calcium hardness and soluble organic matters in nanofiltration concentrated water, the particle size of the porous zeolite in the step 1) is preferably 30-50 meshes.
According to the method for removing calcium hardness and soluble organic matters in nanofiltration concentrated water, preferably, the two solutions in the step 2) are mixed according to the volume ratio of 0.5-1:0.5-1; the stirring speed in the step 2) is 50-70 rpm, and the stirring time is 5-10 min.
According to the method for removing calcium hardness and soluble organic matters in nanofiltration concentrated water, preferably, in the microwave reaction in the step 3), the microwave power is 400-500W, and the reaction temperature is 40-50 ℃; step 4) the drying equipment at 100-110 ℃ is a forced air drying oven.
The heating means is preferably a muffle furnace.
According to the method for removing calcium hardness and soluble organic matters in nanofiltration concentrated water, preferably, the preparation method of the modified styrene resin in the step b is as follows:
1) Selecting polystyrene-divinylbenzene resin polymer, wherein the crosslinking degree is 7-9%;
2) Placing the N, N-dimethylformamide solution in a reaction kettle, adding 760-820 mg of polystyrene-divinylbenzene resin polymer, 260-342 mg of gelatin, 45-89 mg of cellulose and 25-32 ml of benzoyl peroxide into each liter of the N, N-dimethylformamide solution according to the volume, heating the reaction kettle to 85-95 ℃ in a nitrogen protection atmosphere, and stirring for 2-5 h, wherein the stirring speed is 65-75 revolutions per minute;
3) Cooling and filtering the modified polystyrene-divinylbenzene resin mixture obtained after the reaction is finished, cleaning the mixture with petroleum ether for 3 to 5 times, cleaning the mixture with sodium hydroxide solution for 4 to 5 times, cleaning the mixture with dilute hydrochloric acid for 3 to 6 times, and cleaning the mixture with clear water for 3 to 5 times; then vacuum drying for 3-4 hours, immersing the polystyrene-divinylbenzene resin mixture in 6.3-8.9 mol/L sodium sulfamate aqueous solution according to the solid-to-liquid ratio of 1:2-3, heating to 78-93 ℃ in a reaction kettle, uniformly stirring, reacting for 12-15 hours, cooling, filtering, and vacuum drying for 3-4 hours at 55-65 ℃ to obtain the modified styrene resin.
The cation exchange capacity of the obtained modified styrene resin is 1.7-2.8 mmol/g, and the modified styrene resin has strong adsorption displacement capacity for calcium ions and DOC. The modified styrene resin is prepared according to the characteristics of nanofiltration concentrated water.
Further, the mass concentration of the sodium hydroxide solution in the step 3) is 0.5-5%; the mass concentration of the dilute hydrochloric acid is 0.8-3%.
Further, the vacuum drying temperature in the step 3) is 50-60 ℃; and 3) stirring at a speed of 85-100 rpm.
The invention also provides a cold rolling nanofiltration concentrated water treatment system, which comprises a water inlet pump, a modified porous zeolite adsorption tower, modified porous zeolite and a lifting pump, wherein the modified resin adsorption tower, modified resin and a water outlet pump;
the modified porous zeolite adsorption tower is connected with the water inlet pump, the modified porous zeolite is arranged in the modified porous zeolite adsorption tower, an outlet at the top of the modified porous zeolite adsorption tower is connected with a lifting pump, the lifting pump is connected with a modified resin adsorption tower, and the modified styrene resin is arranged in the modified resin adsorption tower; the outlet of the modified resin adsorption tower is connected with a water outlet pump;
the modified porous zeolite accounts for 85-90% of the volume of the modified porous zeolite adsorption tower;
the modified styrene resin accounts for 80-90% of the whole modified resin adsorption tower.
The beneficial effects of the invention are as follows:
according to the water quality and water quantity condition of the cold-rolled nanofiltration concentrated water, an economic and efficient pollutant treatment process is developed, and the specific modified porous zeolite and the modified styrene resin are arranged, so that calcium ions and soluble organic matters in the cold-rolled nanofiltration concentrated water can be removed simultaneously according to the characteristics of the cold-rolled nanofiltration concentrated water. After the cold rolling nanofiltration concentrated water is treated, the calcium ions are 4-9 mg/L, and the DOC is 7-12 mg/L.
Drawings
FIG. 1 is a diagram of a cold rolling nanofiltration concentrate treatment system of the present invention.
In the figure, a water inlet pump 1, a modified porous zeolite adsorption tower 2, a modified porous zeolite 3, a lift pump 4, a modified resin adsorption tower 5, a modified resin 6 and a water outlet pump 7 are shown.
Detailed Description
Example 1:
a cold rolling nanofiltration concentrated water treatment system comprises a water inlet pump, a modified porous zeolite adsorption tower, a modified porous zeolite and a lifting pump, wherein the modified porous zeolite adsorption tower, the modified resin and the water outlet pump (see figure 1).
The cold rolling nanofiltration concentrated water has the water quality characteristics of 28990mg/L of conductivity, 1760mg/L of sulfate ions, 156mg/L of calcium ions and 66mg/L of DOC.
And pumping the cold-rolled nanofiltration concentrated water into a modified porous zeolite adsorption tower through a water inlet pump, placing modified porous zeolite in the modified porous zeolite adsorption tower, wherein the volume of the modified porous zeolite in the adsorption tower is 90 percent. The residence time of cold rolling nanofiltration concentrated water in the modified porous zeolite adsorption tower is 60min.
The modified porous zeolite is prepared according to the characteristics of nanofiltration concentrated water, and can efficiently remove calcium ions and DOC in the nanofiltration concentrated water. The preparation method comprises 1) selecting porous zeolite with particle size of 40 mesh, wherein the particle size is 77%, the mass fraction of soluble salt is 0.8%, the calcium ion exchange capacity is 18mg/g, and DOC adsorption saturation amount is 9mg/g. 2) Preparing a sodium carbonate solution with the concentration of 4.7mol/L and a sodium sulfate solution with the concentration of 2.7mol/L, mixing the two solutions according to the volume ratio of 1:1, adding 4.6mg of cetyltrimethylammonium bromide into each liter of solution, and stirring for 7min at the stirring speed of 65 revolutions per minute to form a mixed solution; 3) Immersing porous zeolite into the mixed solution according to the solid-to-liquid ratio of 1:6, immersing the porous zeolite in the mixed solution for 12h, and then carrying out microwave reaction on the mixed solution for 55 minutes under the condition that the microwave power is 450W and the temperature is 45 ℃; 4) Filtering the porous zeolite, drying for 3 hours in a 105 ℃ forced air drying oven, cooling, then placing into a muffle furnace, heating the muffle furnace to 145 ℃ at a speed of 6 ℃/min, keeping the temperature for 5 hours, and cooling to form the modified porous zeolite. The calcium ion exchange capacity of the obtained modified porous zeolite is 29mg/g, and the DOC adsorption saturation amount is 16mg/g.
The calcium ions in the cold rolling nanofiltration concentrated water are 67mg/L and the DOC is 22mg/L through a modified porous zeolite adsorption tower.
And then, cold rolling nanofiltration concentrated water enters a modified resin adsorption tower through a lifting pump, modified styrene resin is arranged in the modified resin adsorption tower, the volume of the modified styrene resin in the whole adsorption tower is 90%, and the adsorption residence time of the nanofiltration concentrated water in the modified resin is 70min.
The modified styrene resin is prepared according to the characteristics of nanofiltration concentrated water. 1) Selecting polystyrene-divinylbenzene resin polymer, wherein the crosslinking degree is 8%; 2) Placing the N, N-dimethylformamide solution into a stainless steel reaction kettle, adding 790mg of polystyrene-divinylbenzene resin polymer, 311mg of gelatin, 77mg of cellulose and 29ml of benzoyl peroxide into each liter of the N, N-dimethylformamide solution according to the volume, and heating the reaction kettle to 90 ℃ in a nitrogen protection atmosphere, and stirring for 4 hours at a stirring speed of 70 revolutions per minute; 3) Cooling the modified polystyrene-divinylbenzene resin mixture obtained after the reaction is finished, filtering, cleaning with petroleum ether for 4 times, cleaning with 1% sodium hydroxide for 5 times, cleaning with 2% dilute hydrochloric acid for 5 times, and cleaning with clear water for 4 times; then vacuum drying for 4 hours at 55 ℃, immersing the polystyrene-divinylbenzene resin mixture in 7.2mol/L sodium sulfamate aqueous solution according to the solid-to-liquid ratio of 1:2, heating to 86 ℃ in a reaction kettle, stirring at 90 r/min, reacting for 14 hours, cooling, filtering, and vacuum drying for 4 hours at 60 ℃ to obtain the modified styrene resin. The modified styrene resin has cation exchange capacity of 2.1mmol/g and strong adsorption displacement capacity for calcium ions and DOC.
After the cold rolling nanofiltration concentrated water is treated, the calcium ions are 7mg/L, and the DOC is 10mg/L.
And the cold rolling nanofiltration concentrated water is discharged through a water outlet pump after passing through the modified resin adsorption reaction tower or enters a wastewater near zero discharge system.
Example 2:
a cold rolling nanofiltration concentrated water treatment system comprises a water inlet pump, a modified porous zeolite adsorption tower, a modified porous zeolite, a lifting pump, a modified resin adsorption tower, modified resin and a water outlet pump.
The cold rolling nanofiltration concentrated water has the water quality characteristics of 37700mg/L of conductivity, 1890mg/L of sulfate ions, 233mg/L of calcium ions and 61mg/L of DOC.
And pumping the cold-rolled nanofiltration concentrated water into a modified porous zeolite adsorption tower through a water inlet pump, placing modified porous zeolite in the modified porous zeolite adsorption tower, wherein the volume of the modified porous zeolite in the adsorption tower is 85 percent. The residence time of cold rolling nanofiltration concentrated water in the modified porous zeolite adsorption tower is 50min.
The modified porous zeolite is prepared according to the characteristics of nanofiltration concentrated water, and can efficiently remove calcium ions and DOC in the nanofiltration concentrated water. The preparation method comprises 1) selecting porous zeolite with particle size of 50 mesh, wherein the particle size is 81%, the mass fraction of soluble salt is 1.0%, the calcium ion exchange capacity is 17mg/g, and DOC adsorption saturation amount is 7mg/g. 2) Preparing a sodium carbonate solution with the concentration of 3.7mol/L and a sodium sulfate solution with the concentration of 2.4mol/L, mixing the two solutions according to the volume ratio of 1:1, adding 3.1mg of cetyltrimethylammonium bromide into each liter of solution, and stirring for 6min at the stirring speed of 50 revolutions per minute to form a mixed solution; 3) Immersing porous zeolite into the mixed solution according to the solid-to-liquid ratio of 1:5, immersing for 11h in the mixed solution, and then carrying out microwave reaction on the mixed solution for 45 minutes under the condition that the microwave power is 450W and the temperature is 45 ℃; 4) Filtering the porous zeolite, drying for 2 hours in a 105 ℃ forced air drying oven, cooling, then placing into a muffle furnace, heating the muffle furnace to 145 ℃ at a speed of 5 ℃/min, keeping the temperature for 4 hours, and cooling to form the modified porous zeolite. The calcium ion exchange capacity is 23mg/g, and the DOC adsorption saturation amount is 13mg/g.
The calcium ions in the cold rolling nanofiltration concentrated water are 59mg/L and the DOC is 19mg/L through a modified porous zeolite adsorption tower.
And then, cold rolling nanofiltration concentrated water enters a modified resin adsorption tower through a lifting pump, modified styrene resin is arranged in the modified resin adsorption tower, 80% of the volume of the modified styrene resin in the whole adsorption tower, and the adsorption residence time of the nanofiltration concentrated water in the modified resin is 55min.
The modified styrene resin is prepared according to the characteristics of nanofiltration concentrated water. 1) Selecting polystyrene-divinylbenzene resin polymer, wherein the crosslinking degree is 7%; 2) Putting the N, N-dimethylformamide solution into a stainless steel reaction kettle, adding 780mg of polystyrene-divinylbenzene resin polymer, 295mg of gelatin, 49mg of cellulose and 26ml of benzoyl peroxide into each liter of the N, N-dimethylformamide solution according to the volume, heating the reaction kettle to 88 ℃ in a nitrogen protection atmosphere, and stirring for 3 hours at a stirring speed of 65 revolutions per minute; 3) Cooling the modified polystyrene-divinylbenzene resin mixture obtained after the reaction is finished, filtering, cleaning with petroleum ether for 3 times, cleaning with 1% sodium hydroxide for 4 times, cleaning with 2% dilute hydrochloric acid for 3 times, and cleaning with clear water for 4 times; then vacuum drying for 3 hours at 55 ℃, immersing the polystyrene-divinylbenzene resin mixture in 6.8mol/L sodium sulfamate aqueous solution according to a solid-to-liquid ratio of 1:2, heating to 82 ℃ in a reaction kettle, stirring at 90 r/min, reacting for 13 hours, cooling, filtering, and vacuum drying for 3 hours at 60 ℃ to obtain the modified styrene resin. The modified styrene resin has cation exchange capacity of 1.9mmol/g and strong adsorption displacement capacity for calcium ions and DOC.
After the cold rolling nanofiltration concentrated water is treated, the calcium ions are 5mg/L, and the DOC is 9mg/L.
And the cold rolling nanofiltration concentrated water is discharged through a water outlet pump after passing through the modified resin adsorption reaction tower or enters a wastewater zero discharge system.
Example 3
The cold rolling nanofiltration concentrated water has the water quality characteristics of 41200mg/L of conductivity, 1921mg/L of sulfate ions, 275mg/L of calcium ions and 70mg/L of DOC.
The modified porous zeolite is prepared according to the characteristics of nanofiltration concentrated water, and can efficiently remove calcium ions and DOC in the nanofiltration concentrated water. The preparation method comprises 1) selecting porous zeolite with particle size of 50 mesh, wherein the particle size is 81%, the mass fraction of soluble salt is 0.9%, the calcium ion exchange capacity is 19mg/g, and DOC adsorption saturation amount is 9mg/g. 2) Preparing a sodium carbonate solution with the concentration of 5.2mol/L and a sodium sulfate solution with the concentration of 2.7mol/L, mixing the two solutions according to the volume ratio of 0.8:1, adding 5.4mg of cetyltrimethylammonium bromide into each liter of solution, and stirring for 8min at the stirring speed of 55 revolutions per minute to form a mixed solution; 3) Immersing porous zeolite into the mixed solution according to the solid-to-liquid ratio of 1:7, immersing the porous zeolite in the mixed solution for 12h, and then carrying out microwave reaction on the mixed solution for 55 minutes under the condition that the microwave power is 480W and the temperature is 48 ℃; 4) Filtering the porous zeolite, drying for 2 hours in a 105 ℃ forced air drying oven, cooling, then placing into a muffle furnace, heating the muffle furnace to 150 ℃ at the speed of 7 ℃/min, keeping the temperature for 4.5 hours, and cooling to form the modified porous zeolite. The calcium ion exchange capacity is 25mg/g, and the DOC adsorption saturation amount is 18mg/g.
Through a modified porous zeolite adsorption tower, the calcium ions in cold rolling nanofiltration concentrated water are 65mg/L, and the DOC is 24mg/L.
After the cold rolling nanofiltration concentrated water is treated, the calcium ions are 6mg/L, and the DOC is 11mg/L.
Otherwise, the same as in example 1 was conducted.
In summary, the invention provides a treatment process scheme of calcium ions and DOC in cold-rolled nanofiltration concentrated water for the first time, so that the invention belongs to a green and environment-friendly production process system of 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 (9)
1. A method for removing calcium hardness and soluble organic matters in nanofiltration concentrated water is characterized in that: the method comprises the following steps:
a. pumping cold rolling nanofiltration concentrated water to be treated into a modified porous zeolite adsorption tower through a water inlet pump, wherein modified porous zeolite is placed in the modified porous zeolite adsorption tower, and the modified porous zeolite accounts for 85-90% of the volume of the adsorption tower; the residence time of cold rolling nanofiltration concentrated water in the modified porous zeolite adsorption tower is 45-70 min;
b. then cold rolling nanofiltration concentrated water enters a modified resin adsorption tower through a lifting pump, modified styrene resin is arranged in the modified resin adsorption tower, the modified styrene resin accounts for 80-90% of the whole volume of the adsorption tower, and the retention time of the nanofiltration concentrated water in the modified resin adsorption tower is 50-70 min; the preparation method of the modified styrene resin comprises the following steps:
1) Selecting polystyrene-divinylbenzene resin polymer, wherein the crosslinking degree is 7-9%;
2) Placing the N, N-dimethylformamide solution in a reaction kettle, adding 760-820 mg of polystyrene-divinylbenzene resin polymer, 260-342 mg of gelatin, 45-89 mg of cellulose and 25-32 ml of benzoyl peroxide into each liter of the N, N-dimethylformamide solution according to the volume, heating the reaction kettle to 85-95 ℃ in a nitrogen protection atmosphere, and stirring for 2-5 h, wherein the stirring speed is 65-75 revolutions per minute;
3) Cooling and filtering the modified polystyrene-divinylbenzene resin mixture obtained after the reaction is finished, cleaning the mixture with petroleum ether for 3 to 5 times, cleaning the mixture with sodium hydroxide solution for 4 to 5 times, cleaning the mixture with dilute hydrochloric acid for 3 to 6 times, and cleaning the mixture with clear water for 3 to 5 times; then vacuum drying for 3-4 hours, immersing the polystyrene-divinylbenzene resin mixture in 6.3-8.9 mol/L sodium sulfamate aqueous solution according to the solid-to-liquid ratio of 1:2-3, heating to 78-93 ℃ in a reaction kettle, uniformly stirring, reacting for 12-15 hours, cooling, filtering, and vacuum drying for 3-4 hours at 55-65 ℃ to obtain the modified styrene resin;
c. the cold rolling nanofiltration concentrated water is discharged through a water outlet pump after passing through a modified resin adsorption reaction tower or enters a wastewater zero discharge system;
the preparation method of the modified porous zeolite comprises the following steps:
1) Selecting porous zeolite with granularity of 73-82%, soluble salt with mass fraction of 0.3-1.2%, calcium ion exchange capacity of 16-23 mg/g and soluble organic matter adsorption saturation amount of 6-13 mg/g;
2) Preparing a sodium carbonate solution with the concentration of 3.5-6.7 mol/L and a sodium sulfate solution with the concentration of 2.3-3.1 mol/L, mixing the two solutions, adding 2.3-7.5 mg of cetyltrimethylammonium bromide into each liter of the solution, and uniformly stirring to form a mixed solution;
3) Immersing the porous zeolite into the mixed solution according to the solid-liquid ratio of 1:5-8, immersing for 10-13 h in the mixed solution, and then carrying out microwave reaction on the porous zeolite and the mixed solution for 45-75 min;
4) Filtering porous zeolite, drying at 100-110 deg.c for 2-4 hr, cooling, heating in a heater to 130-160 deg.c at 5-8 deg.c/min, maintaining the temperature for 4-6 hr, and cooling to form modified porous zeolite.
2. The method for removing calcium hardness and soluble organics from nanofiltration concentrated water according to claim 1, wherein the method comprises the steps of: the cold rolling nanofiltration concentrated water to be treated is characterized by having the water quality characteristics of 23410-42570 mg/L of conductivity, 1230-2145 mg/L of sulfate ions, 134-289 mg/L of calcium ions and 56-78 mg/L of soluble organic matters;
through a modified porous zeolite adsorption tower, the calcium ions in cold rolling nanofiltration concentrated water are 54-93 mg/L, and the soluble organic matters are 17-31 mg/L.
3. The method for removing calcium hardness and soluble organics from nanofiltration concentrated water according to claim 1, wherein the method comprises the steps of: in the preparation method of the modified porous zeolite, the particle size of the porous zeolite in the step 1) is 30-50 meshes.
4. The method for removing calcium hardness and soluble organics from nanofiltration concentrated water according to claim 1, wherein the method comprises the steps of: in the preparation method of the modified porous zeolite, in the step 2), the two solutions are mixed according to the volume ratio of 0.5-1:0.5-1; the stirring speed in the step 2) is 50-70 rpm, and the stirring time is 5-10 min.
5. The method for removing calcium hardness and soluble organics from nanofiltration concentrated water according to claim 1, wherein the method comprises the steps of: in the preparation method of the modified porous zeolite, in the step 3), in the microwave reaction, the microwave power is 400-500W, and the reaction temperature is 40-50 ℃; step 4) the drying equipment at 100-110 ℃ is a forced air drying oven.
6. The method for removing calcium hardness and soluble organics from nanofiltration concentrated water according to claim 1, wherein the method comprises the steps of: in the preparation method of the modified styrene resin, the mass concentration of the sodium hydroxide solution in the step 3) is 0.5-5%; the mass concentration of the dilute hydrochloric acid is 0.8-3%.
7. The method for removing calcium hardness and soluble organics from nanofiltration concentrated water according to claim 1, wherein the method comprises the steps of: in the preparation method of the modified styrene resin, the vacuum drying temperature in the step 3) is 50-60 ℃.
8. The method for removing calcium hardness and soluble organics from nanofiltration concentrated water according to claim 1, wherein the method comprises the steps of: in the preparation method of the modified styrene resin, the stirring speed in the step 3) is 85-100 rpm.
9. The cold rolling nanofiltration concentrated water treatment system for implementing the method of claim 1, wherein:
the modified porous zeolite adsorption tower is connected with the water inlet pump, the modified porous zeolite is arranged in the modified porous zeolite adsorption tower, an outlet at the top of the modified porous zeolite adsorption tower is connected with a lifting pump, the lifting pump is connected with a modified resin adsorption tower, and the modified styrene resin is arranged in the modified resin adsorption tower; the outlet of the modified resin adsorption tower is connected with a water outlet pump;
the modified porous zeolite accounts for 85-90% of the volume of the modified porous zeolite adsorption tower;
the modified styrene resin accounts for 80-90% of the whole modified resin adsorption tower.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102908986A (en) * | 2012-10-29 | 2013-02-06 | 北京科技大学 | Method for modifying ammonia nitrogen adsorption material by means of microwave radiation combined with auxiliary |
| CN203402929U (en) * | 2013-05-03 | 2014-01-22 | 广东顺德弘顺达环保产业技术投资有限公司 | Production system for producing vegetative fulvic acid, potassium sulfate concentrated solution and vegetative organic bacterial manure by alcohol biological wastewater |
| CN108676269A (en) * | 2018-05-14 | 2018-10-19 | 和县伊迈炭业有限责任公司 | A kind of cellular polystyrol foam material and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102908986A (en) * | 2012-10-29 | 2013-02-06 | 北京科技大学 | Method for modifying ammonia nitrogen adsorption material by means of microwave radiation combined with auxiliary |
| CN203402929U (en) * | 2013-05-03 | 2014-01-22 | 广东顺德弘顺达环保产业技术投资有限公司 | Production system for producing vegetative fulvic acid, potassium sulfate concentrated solution and vegetative organic bacterial manure by alcohol biological wastewater |
| CN108676269A (en) * | 2018-05-14 | 2018-10-19 | 和县伊迈炭业有限责任公司 | A kind of cellular polystyrol foam material and its application |
Non-Patent Citations (1)
| Title |
|---|
| "超声-微波法合成粉煤灰分子筛及吸附性能研究";孟桂花等;《合成材料老化与应用》;20150228;第44卷(第1期);第74-76页 * |
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