Resourceful treatment device and treatment method for high-salinity wastewater

[0087] Example 1

[0088] The main water quality characteristics of the coal chemical high salt wastewater treated in this embodiment are: pH = 7.5, the concentration of the solubility total solid (TDS) is 10,000 mg / L, CL - The concentration of 4000mg / L, SO 4 2- The concentration of 2000mg / L, Mg 2+ CA 2+ The concentration is 50 mg / L, the concentration of solubilis is 50 mg / L, F - The concentration is 50mg / L, HCO 3 -The concentration of 300 mg / L, the concentration of COD was 80 mg / L.

[0089] Process figure 1 As shown, the specific steps include:

[0090] Step 1, high salt wastewater enters efficient division filtration unit for processing. First, calcium chloride and magnesium chloride were added to the primary reaction pool, and the added concentration was 0.8 g / L, the reaction time was 15 min, and the water overflowing into the secondary reaction tank, sodium carbonate and polymerized aluminum chloride were added, and sodium carbonate was added. The concentration of 1.0 g / L, polymerized aluminum chloride was added to 0.1 g / L; then sodium hydroxide was added, and the pH of the wastewater was adjusted to 10.8, the reaction time was 15 min, and the water entered the primary precipitation pool to produce calculus, magnesium, silicon A variety of precipitates such as acid salts, fluoride, and their complexes, the first-stage precipitation pool effluent enters the filtration unit to form high-efficiency removal filtration water; film filter unit filter pressure is 0.08 MPa, membrane material is polytetrafluoroethylene, The film aperture is 0.15 μm; the filter residue is concentrated after curing;

[0091] Under this condition, the film flux of the film filter unit is controlled at 400L / m. 2 H h left and right; membrane filter unit exuberant (SS) is less than 0.5 mg / L, the water calcium ion concentration is less than 10 mg / L, the magnesium ion concentration is less than 10 mg / L, the solissa concentration is less than 20 mg / L, the fluorogenic concentration is less than 20 mg / L;

[0092] Step 2, efficient removal of hard filtration water into ozone catalytic oxidation unit treatment, ozone catalytic oxidation unit employ activated carbon-based catalyst, operating conditions: water pH is 7.5, water supply temperature 15 ° C, residence time 1 h, ozone concentration 150 mg / L .

[0093] Under this condition, ozone catalytic oxidation water COD is around 30 mg / L;

[0094] Step 3, ozone catalytic oxidation effluent into the ultrafiltration unit treatment, the ultrafiltration unit employs pressure ultrafiltration, the assembly employs the outer pressure hollow fiber ultrafiltration membrane assembly, the filtration pressure is 0.08 MPa;

[0095] Under this condition, the ultrafiltration is less than 0.1 NTU; the ultrafiltration concentrated phase is concentrated after dehydrating curing;

[0096] Step 4, ultrafiltration water into high pressure reverse osmosis unit processing, high pressure reverse osmosis unit adopts a roll reverse osmosis membrane assembly, operating conditions: operating pressure is 4 MPa, water pH is 7.5;

[0097] Under this condition, the film flux of the high pressure reverse osmosis unit is 13 ~ 15L / m. 2 · H, the recovery rate of high pressure reverse osmosis unit is 60%, and the high pressure reverse osmosis is about 25000mg / L;

[0098] Step 5, high pressure reverse osmosis concentrated water into the two-stage nanofiltration unit treatment, two-stage nanofiltration unit, first-stage nanofiltration, using the disc tube nanofiltration membrane assembly, run, 50% of the first-stage nanofiltration concentrated water returned to one The graded noodles filtered water and the water mixed were used as one-stage nanofiltration in water. The operating conditions of the primary nanofiltration are: operating pressure is 3 MPa, water pH is 7.5; the secondary nanofiltration is used with a roll-filtered filter assembly, the operating conditions of the secondary nanofiltration are: operating pressure is 2MPa, the water pH is 7.5;

[0099] Under this condition, the film flux of the primary nation is 13 to 15 l / m. 2 · H, the recovery rate is 70% ~ 75%; the film flux of the secondary nanofiltration is 18 ~ 20L / m 2 H, the recovery rate is 75 ~ 80%; the mass ratio of chloride ions and sulfate ions in the secondary nano filter production is 55: 1; the mass ratio of sulfate ions and chloride ions in the primary nanofiltration concentrated water is 15: 1 ;

[0100] Step 6, the secondary nanofiltration water enters the roll reverse osmosis unit treatment, the roll reverse osmosis adopts a roll reverse osmosis membrane assembly, operating conditions: operating pressure 3MPa, water pH is 7.5;

[0101] Under this condition, the film flux of the roll of reverse osmosis unit is 16 ~ 18L / m. 2 · H, the recovery of the roll reverse osmosis unit is 60%;

[0102] Step 7, the primary nation filter concentrated water enters the evaporation crystallization unit to evaporate crystallization treatment, to obtain sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, 98%, to GB / T6009-2014 "industry Class II first-class standards in the sodium sulfate sodium sulfate;

[0103] Step 8, the roll-type reverse osmosis water enters the evaporation crystallization unit for evaporation crystallization treatment, to obtain a sodium chloride salt and evaporation crystal water, the resulting sodium chloride is separated by 98%, reaching GB / T5462-2015 Refining Industrial Salt First Class Standard in "Industrial Salt" Standard.

[0104] Among them, high-pressure reverse osmotic water, roll reverse osmosis water and evaporative crystal production water after mixing, water conductivity <1200μs / cm, COD <60mg / L, CL - <200mg / L, meet the reuse requirements of the everlament of the ever.

[0105] Example 2

[0106] The main water quality characteristics of the coal chemical high salt wastewater treated in this embodiment: pH = 8, the concentration of the dissolved total solid (TDS) is 15000 mg / L, CL - The concentration is 5500mg / L, SO 4 2- The concentration of 3000mg / L, MG 2+ The concentration is 60mg / L, CA 2+ The concentration is 100 mg / L, the concentration of solubilis is 100 mg / L, F - The concentration is 60mg / L, HCO 3 - The concentration of 400 mg / L, the concentration of the COD was 100 mg / L.

[0107] The specific steps include:

[0108] Step 1, high salt wastewater enters efficient division filtration unit for processing. First, calcium chloride and magnesium chloride are added to the primary reaction pool, and the concentration is 1.1 g / l and 1.5 g / L, the reaction time is 20 min, and the water overflow to the secondary reaction cell, sodium carbonate and polymerization Aluminum, sodium carbonate, concentration of 1.5 g / L, polymerized aluminum chloride added concentration of 0.2 g / L; then sodium hydroxide, adjusting the pH of the wastewater is 11.2, the reaction time is 20 min, and the water enters the primary precipitation pool to produce calculus , Magnesium hard, silicate, fluoride and its complex, etc., the first-stage precipitation pool effluent into the filtration unit to form high-efficiency removal filtration water; film filter unit filter pressure is 0.12 MPa, membrane material is Polytetrafluoroethylene, membrane pore size is 0.2 μm; the filter residue is concentrated after curing;

[0109] Under this condition, the film flux of the film filter unit is controlled at 300L / m. 2 · H and where the membrane filter unit is less than 0.5 mg / L, the water calcium ion concentration is less than 10 mg / L, the magnesium ion concentration is less than 10 mg / L, the solissa concentration is less than 20 mg / L, the fluorogenic ion concentration is less than 20 mg / L;

[0110] Step 2, efficiently removed the hard filtration water into the ozone catalytic oxidation unit treatment, ozone catalytic oxidation unit employ activated carbon-based catalyst, operating conditions: inlet pH 8, water temperature 20 ° C, residence time 1.5H, ozone concentration 170mg / L.

[0111] Under this condition, ozone catalytic oxidation water COD is around 40 mg / L;

[0112] Step 3, ozone catalytic oxidation effluent into the ultrafiltration unit treatment, the ultrafiltration unit employs pressure ultrafiltration, the assembly uses an outer pressure hollow fiber ultrafiltration membrane assembly, and the filtration pressure is 0.1 MPa;

[0113] Under this condition, the ultrafiltration is less than 0.1 NTU; the ultrafiltration concentrated phase is concentrated after dehydrating curing;

[0114] Step 4, ultrafiltration water into high pressure reverse osmosis unit processing, high pressure reverse osmosis unit employs a roll reverse osmosis membrane assembly, operating conditions: operating pressure is 5 MPa, water pH is 8;

[0115] Under this condition, the film flux of the high pressure reverse osmosis unit is 12 to 14 l / m. 2 · H, the recovery rate of high pressure reverse osmosis unit is 55%, and the high pressure reverse osmosis is about 33000mg / L;

[0116] Step 5, high pressure reverse osmosis concentrated water into the two-stage nanofiltration unit treatment, two-stage nanofiltration units in the two-stage nanofiltration unit use the disc tubular nanofiltration membrane assembly, run, 55% of the primary nanofiltration concentrated water returned to one The graded noodles filtered water and the water mixed were used as one-stage nanofiltration in water. The operating conditions of the primary nanofiltration are: operating pressure is 3.5 MPa, water pH is 8; the secondary nanofiltration is used with roll-based nanofiltration membrane assemblies, and the operating conditions of the secondary nanofiltration are: operating pressure is 2.5MPa, into the water PH is 8;

[0117] Under this condition, the membrane flux of the primary nation was 11 to 13 l / m. 2 · H, the recovery rate is 72%, the film flux of the secondary nation is 16 ~ 18L / m 2 H, the recovery rate is 78%; the mass ratio of chloride ions and sulfate ions in the secondary nano filter production is 57: 1; the mass ratio of sulfate ions and chloride ions in the primary nanofiltration concentrated water is 17: 1;

[0118] Step 6, the secondary nanofiltration water into the roll-type reverse osmosis unit treatment, the roll-type reverse osmosis adopts a roll reverse osmosis membrane assembly, operating conditions are: operating pressure 4MPa, water pH is 8;

[0119] Under this condition, the film flux of the roll of reverse osmosis unit is 15 to 17L / m. 2 · H, the recovery of the roll reverse osmosis unit is 56%;

[0120] Step 7, the primary nation filter concentrated water enters the evaporation crystallization unit to evaporate crystallization treatment, to obtain sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, 98%, to GB / T6009-2014 "industry Class II first-class standards in the sodium sulfate sodium sulfate;

[0121] Step 8, the roll-type reverse osmosis water enters the evaporation crystallization unit for evaporation crystallization treatment, to obtain a sodium chloride salt and evaporation crystal water, the resulting sodium chloride is separated by 98%, reaching GB / T5462-2015 Refining Industrial Salt First Class Standard in "Industrial Salt" Standard.

[0122] Among them, high-pressure reverse osmotic water, roll reverse osmosis water and evaporative crystal production water after mixing, water conductivity <1200μs / cm, COD <60mg / L, CL - <200mg / L, meet the reuse requirements of the everlament of the ever.

[0123] Example 3

[0124] The main water quality characteristics of the coal chemical high salt wastewater treated in this embodiment: pH = 8.5, the concentration of solubility total solid (TDS) is 20000mg / L, CL - The concentration is 7000mg / L, SO 4 2- The concentration is 4000 mg / L, MG 2+ The concentration is 90mg / L, CA 2+ The concentration of 150 mg / L, the concentration of solubilis is 150mg / L, F - The concentration is 80mg / L, HCO 3 - The concentration of 500 mg / L, the concentration of COD was 120 mg / L.

[0125] The specific steps include:

[0126] Step 1, high salt wastewater enters efficient division filtration unit for processing. First, calcium hydroxide and magnesium oxide is added to the primary reaction pool, and the concentration is 1.5 g / l and 2.0 g / l, and the reaction time is 30 min, and the water overflows to the secondary reaction cell, sodium carbonate and polymer chlorine Aluminum, sodium carbonate, concentration of 1.8 g / L, polymerized aluminum chloride added concentration of 0.3 g / L; then sodium hydroxide, adjusting the pH of the wastewater is 11.5, the reaction time is 30 min, and the water enters the primary precipitation pool to produce calcium Hard, magnesium hard, silicate, fluoride and its complex, etc. For the polytetrafluoroethylene, the film aperture is 0.25 μm; the filter residue is concentrated after curing;

[0127] Under this condition, the film flux of the film filter unit is controlled at 200 L / m. 2 · H and where the membrane filter unit is less than 0.5 mg / L, the water calcium ion concentration is less than 10 mg / L, the magnesium ion concentration is less than 10 mg / L, the solissa concentration is less than 20 mg / L, the fluorogenic ion concentration is less than 20 mg / L;

[0128] Step 2, efficiently removed the hard filtration water into the ozone catalytic oxidation unit treatment, ozone catalytic oxidation unit employ the activated carbon-based catalyst, operating conditions: in water pH is 8.5, water intake temperature 30 ° C, residence time 2 h, ozone concentration 200mg / L .

[0129] Under this condition, ozone catalytic oxidation water COD is around 60 mg / L;

[0130] Step 3, ozone catalytic oxidation water enters the ultrafiltration unit treatment, the ultrafiltration unit employs pressure ultrafiltration, and the assembly uses an outer pressure hollow fiber ultrafiltration membrane assembly, and the filtration pressure is 0.12 MPa;

[0131] Under this condition, the ultrafiltration is less than 0.1 NTU; the ultrafiltration concentrated phase is concentrated after dehydrating curing;

[0132] Step 4, ultrafiltration water into high pressure reverse osmosis unit processing, high pressure reverse osmosis unit employs a roll reverse osmosis membrane assembly, operating conditions: operating pressure is 6 MPa, water pH is 8.5;

[0133] Under this condition, the membrane flux of the high pressure reverse osmosis unit is 10 ~ 12L / m. 2 · H, the recovery rate of high pressure reverse osmosis unit is 50%, and the high pressure reverse osmosis is about 40000mg / L;

[0134] Step 5, high pressure reverse osmosis concentrated water into the two-stage nanofiltration unit treatment, two-stage nanofiltration units in the two-stage nanofiltration unit use the disc tubular nanofiltration membrane assembly, run, 55% of the primary nanofiltration concentrated water returned to one The graded noodles filtered water and the water mixed were used as one-stage nanofiltration in water. The operating conditions of the primary nanofiltration are: operating pressure is 4 MPa, the water pH is 8.5; the secondary nanofiltration is used with a roll nanofiltration membrane assembly, the operating conditions of the secondary nanofiltration are: operating pressure is 3 MPa, the water pH is 8.5;

[0135] Under this condition, the film flux of the primary nation is 8 ~ 10L / m. 2 · H, the recovery rate is 70%, the film flux in the secondary nation is 13 ~ 15L / m 2 H, the recovery rate is 75%; the mass ratio of chloride ions and sulfate ions in the secondary nano filter production is 60: 1; the mass ratio of sulfate ions and chloride ions in the primary nanofiltration concentrated water is 18: 1;

[0136] Step 6, the secondary nanofiltration water into the roll-type reverse osmosis unit treatment, the roll-type reverse osmosis adopts a roll reverse osmosis membrane assembly, operating conditions are: operating pressure 5MPa, water pH is 8.5;

[0137] Under this condition, the film flux of the roll reverse osmosis unit is 13 to 15 l / m. 2 · H, the recovery of the roll reverse osmosis unit is 50%;

[0138] Step 7, the primary nation filter concentrated water enters the evaporation crystallization unit for evaporation crystallization treatment to obtain sodium sulfate and evaporated crystalline water, the resulting sodium sulfate is separated by 98%, reaching GB / T 6009-2014 " II first-class standards in the sodium industrial anhydrous sulfate "standard;

[0139] Step 8, the roll-on reverse osmosis water enters the evaporation of the crystallization unit to evaporate crystallization treatment, to obtain a sodium chloride salt and evaporation crystalline water, the resulting sodium chloride salt is separated by 98%, reaching GB / T 5462- The refining industrial salt level standard in the "Industrial Salt" standard.

[0140] Among them, high-pressure reverse osmotic water, roll reverse osmosis water and evaporative crystal production water after mixing, water conductivity <1200μs / cm, COD <60mg / L, CL - <200mg / L, meet the reuse requirements of the everlament of the ever.