CN114751541A - Device and method for continuously and deeply treating fluorine-containing wastewater - Google Patents
Device and method for continuously and deeply treating fluorine-containing wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 143
- 239000011737 fluorine Substances 0.000 title claims abstract description 53
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 53
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 102
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 47
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 38
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 19
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- 229910001868 water Inorganic materials 0.000 claims description 132
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- 238000009826 distribution Methods 0.000 claims description 67
- 238000004062 sedimentation Methods 0.000 claims description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 28
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910001424 calcium ion Inorganic materials 0.000 claims description 18
- 239000010802 sludge Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 238000005649 metathesis reaction Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 8
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 59
- -1 fluorine ions Chemical class 0.000 description 21
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- 239000002244 precipitate Substances 0.000 description 14
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 11
- 229910001634 calcium fluoride Inorganic materials 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
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- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a device and a method for continuously and deeply treating fluorine-containing wastewater. The device comprises a first reaction tank, a second reaction tank and a third reaction tank; the wastewater after defluorination by the method provided by the invention enters a subsequent wastewater treatment device through a wastewater lifting pump to remove COD, BOD and ammonia nitrogen in the wastewater, and is discharged after being qualified. According to the technical scheme provided by the invention, the fluorine content in the fluorine-containing wastewater after the pH value is adjusted is less than 1ppm after primary defluorination, double decomposition reaction and secondary defluorination. According to the invention, a 33% liquid calcium chloride solution, solid sodium carbonate, a secondary defluorinating agent with a certain concentration and an auxiliary agent thereof are adopted, so that accurate control can be realized, the stability of treating the fluorine-containing wastewater is greatly improved, and the long-period stable operation can be ensured; meanwhile, the solid waste amount is greatly reduced; the device provided by the invention improves the automation degree of wastewater treatment, greatly reduces the labor intensity of workers and also saves human resources.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a device and a method for continuously and deeply treating fluorine-containing wastewater.
Background
In industry, the deterioration and pollution phenomena of water environment are increasingly attracting attention, and wastewater discharged by industries such as fluorine-containing ore mining, fluorine chemical industry, metal smelting, aluminum processing, coke, glass, electronics, electroplating, chemical fertilizers, pesticides and the like often contains high-concentration fluoride.
Scientific research finds that fluorine has strong affinity to calcium and phosphorus in a human body, can destroy the normal metabolism of the calcium and the phosphorus in the body, and can inhibit the activity of certain enzymes, so that a series of diseases such as dental fluorosis, fluoroossium, kidney, liver and brain damage, immunologic dysfunction, pulmonary edema, pulmonary hemorrhage, children intelligence decline and the like can be caused. If not treated, the method not only poses harm to human health, but also harms the ecological environment. Therefore, the wastewater containing fluorine must be discharged after being subjected to harmless treatment so as to avoid harm to human and environment. In order to reduce the harm of fluoride to human bodies, the state sets a strict industrial fluorine-containing wastewater discharge standard:
the discharge standards of surface water, domestic drinking water, sewage and fluorine-containing industrial wastewater are shown in table 1.
TABLE 1
At present, the adopted fluorine-containing wastewater treatment technology is simple primary physical and chemical precipitation, and by testing the pH value, fluorine ions in the wastewater are converted into calcium fluoride while the pH value of the wastewater is adjusted by adding acid and lime milk. If the dosage is excessive, the dosage is large, the produced sludge is large, the operation cost is high, and if the dosage is insufficient, the reaction efficiency is low, the removal rate of fluorine ions is low, the discharged fluorine-containing wastewater cannot reach the standard, and the wastewater causes harm to people and environment. Although calcium fluoride is difficult to dissolve in water, the calcium fluoride still has certain solubility in water, the solubility of the calcium fluoride at 18 ℃ is 0.0016g, and the concentration of the calcium fluoride is converted into 7.79ppm of fluoride ions, and the fluoride-containing wastewater can hardly reach the standard stably by using the traditional method for treating the fluoride-containing wastewater. Therefore, it is urgently required to design a fluorine-containing wastewater treatment system for solving the above-mentioned phenomenon.
Disclosure of Invention
Aiming at the problems of the prior fluorine-containing wastewater treatment technology, the invention provides a device and a method for continuously and deeply treating fluorine-containing wastewater.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the invention provides a device for continuously and deeply treating fluorine-containing wastewater, which comprises a first reaction tank, a second reaction tank and a third reaction tank, wherein the first reaction tank is connected with the second reaction tank;
the first reaction tank is connected with the pH adjusting tank through a wastewater metering pump, the first reaction tank is connected with the second reaction tank through a bottom through hole through a 33% calcium chloride solution metering pump and a 33% calcium chloride solution metering tank, and wastewater in the first reaction tank flows into the bottom of the second reaction tank through a potential difference;
the second reaction tank is connected with the polyaluminium chloride solution metering tank through a polyaluminium chloride solution metering pump, the second reaction tank is connected with the third reaction tank through a middle through hole, and wastewater in the second reaction tank flows into the middle of the third reaction tank through the potential difference;
the third reaction tank is connected with the polyacrylamide solution metering tank a through a polyacrylamide solution metering pump a, the third reaction tank is connected with the first water distribution tank through a middle through hole, and wastewater in the third reaction tank flows into the middle of the first water distribution tank through the potential difference;
the first water distribution tank is connected with the first inclined plate sedimentation tank through a bottom through hole, and wastewater in the first water distribution tank flows into the lower part of the first inclined plate sedimentation tank through the potential difference;
the first inclined plate sedimentation tank overflows to a first intermediate water tank through an upper overflow port, the liquid levels of the first reaction tank, the second reaction tank, the third reaction tank and the first water distribution tank are determined by the height of the overflow port, and the first inclined plate sedimentation tank is connected with a plate-and-frame filter press through a sludge delivery pump;
the first intermediate water tank is connected with the double decomposition reaction tank through an overflow port;
a sodium carbonate metering and feeding device is arranged at the upper part of the double decomposition reaction tank, is connected with a polyacrylamide solution metering tank b through a polyacrylamide metering pump b, and is connected with a second water distribution tank through a lower through hole;
the second water distribution tank is connected with the second inclined plate sedimentation tank through a bottom through hole, and wastewater in the second water distribution tank flows into the lower part of the second inclined plate sedimentation tank through potential difference;
the second inclined plate sedimentation tank overflows to a second intermediate water tank through an upper overflow port, the liquid levels of the double decomposition reaction tank and the second inclined plate water distribution tank are determined by the height of the overflow port, and the second inclined plate sedimentation tank is connected with the plate-and-frame filter press through a sludge delivery pump;
the second intermediate water tank is connected with the secondary defluorination reaction tank through an overflow port;
the second-stage defluorination reaction tank is connected with the second-stage defluorination agent metering tank through a second-stage defluorination agent metering pump and is connected with the third water distribution tank through a lower through hole;
the third water distribution tank is connected with a third inclined plate sedimentation tank through a bottom through hole, and wastewater in the third water distribution tank flows into the lower part of the third inclined plate sedimentation tank through the potential difference;
and the third inclined plate sedimentation tank overflows to a third middle water tank through an upper overflow port, the liquid levels of the secondary defluorination reaction tank and the third water distribution tank are determined by the height of the overflow port, and the third inclined plate sedimentation tank is connected with the plate-and-frame filter press through a sludge delivery pump.
The invention also provides a method for continuously and deeply treating fluorine-containing wastewater by using the device, which comprises the following steps:
(1) conveying the fluorine-containing wastewater neutralized to pH 6-8 to a first reaction tank through a wastewater metering pump, continuously pumping a metered 33% calcium chloride solution into the first reaction tank through a 33% calcium chloride solution metering pump under stirring, and after reaction, allowing the wastewater to enter a second reaction tank through a through hole at the bottom of the first reaction tank;
(2) in the second reaction tank, fully mixing with a metered polyaluminium chloride (PAC) solution continuously added by a polyaluminium chloride (PAC) solution metering pump under stirring, then entering a third reaction tank through a middle through hole of the second reaction tank, fully mixing with a metered polyacrylamide solution continuously added by a Polyacrylamide (PAM) solution metering pump a under stirring, entering a first water distribution tank through a middle through hole, distributing water by the first water distribution tank, then flowing into a first inclined plate sedimentation tank, and overflowing to the first middle water tank through an overflow cofferdam;
(3) the wastewater flows into a double decomposition reaction tank from a first intermediate water tank, reacts with metered sodium carbonate under stirring, is added with a certain amount of polyacrylamide solution through a polyacrylamide metering pump b, is connected with a second water distribution tank through a lower through hole, and then enters a second inclined plate sedimentation tank and a second intermediate water tank through the second water distribution tank;
(4) and the wastewater flows into the second-stage defluorination reaction tank from the second intermediate water tank, further reacts with the second-stage defluorination agent under stirring, and overflows to a third intermediate water tank after being settled by a third water distribution tank and a third inclined plate settling tank.
Further, in the step (1), the concentration of calcium ions is excessive by 1500ppm to 5000 ppm; preferably, the excess is 2300-2600 ppm.
Further, in the step (2), the mass concentration of the polyaluminium chloride solution is 10%; the adding amount of the polyaluminium chloride solution is 0.015-0.025 percent of the total amount of the wastewater.
Further, 3-5g of ethylene bis stearamide per L of the polyaluminum chloride solution is added.
Further, in the step (2), the concentration of the polyacrylamide solution is 0.1%, and the addition amount of the polyacrylamide solution is 0.0015% -0.0030% of the total amount of the wastewater.
Further, in the step (3), the adding amount of sodium carbonate in the double decomposition reaction tank is calculated according to the following formula:
m1=[(m2×c)/40]×106
wherein m is1-the amount of sodium carbonate added, kg/h;
M2-flow of waste water, kg/h;
c- -Ca in wastewater2+Concentration,%;
the concentration of the polyacrylamide solution is 0.1%, and the addition amount of the polyacrylamide solution is 0.0015% -0.0030% of the total amount of the wastewater.
Further, in the step (4), the secondary defluorinating agent is prepared from crystalline aluminum chloride: ferric chloride: sodium silicate according to the mass ratio of 18: 10: 8, preparing a mixture; the addition amount of the secondary defluorinating agent is 0.15-0.25%, preferably 0.2% of the flow amount of the wastewater.
The fluorine-containing wastewater treated by the method is the fluorine-containing wastewater generated in the industrial production process. The wastewater after defluorination by the method provided by the invention enters a subsequent wastewater treatment device through a wastewater lifting pump to remove COD, BOD and ammonia nitrogen in the wastewater, and is discharged after being qualified.
The invention enables the content of the fluorinion in the wastewater to be less than 1ppm through the procedures of primary defluorination, secondary defluorination and the like, and excessive calcium ion removal by multi-component separation. And then the wastewater is discharged after reaching the standard after COD, BOD, ammonia nitrogen and other substances in the wastewater are removed by a subsequent wastewater treatment device.
In the primary defluorination process, 33% calcium chloride solution is used as a main defluorination agent, so that the addition of 33% calcium chloride solution is conveniently and accurately controlled, the calcium ion concentration in a primary reactor is over 1500ppm, preferably over 2000ppm, and the fluorine ion concentration in wastewater is not more than 8 ppm. Through the synergistic effect of adding polyaluminium chloride solution (PAC) and polyacrylamide solution (PAM), suspended calcium fluoride precipitate particles are subjected to flocculation precipitation, and then are subjected to sedimentation and clarification in a primary inclined plate sedimentation tank, so that the content of calcium fluoride in wastewater is not higher than 8 ppm.
After the first-stage defluorination, according to the content of calcium ions in the wastewater and the flow rate of the wastewater, continuously and accurately adding metered polyacrylamide and solid sodium carbonate to ensure that the calcium ions in the wastewater are precipitated out of a wastewater system by calcium carbonate. In the process, firstly, solid sodium carbonate is added, so that the total amount of wastewater is not increased; secondly, the calcium carbonate precipitate is combined with trace soluble calcium fluoride in the solution to generate a coprecipitate, so that the concentration of fluorine ions in the wastewater is further reduced, and the concentration of the fluorine ions is generally reduced to 2-3ppm from 7-8 ppm.
The procedures of removing excessive calcium ions by multi-component separation, secondary defluorination and the like are carried out, so that the content of fluorine ions in the wastewater is less than 2ppm, preferably less than 1 ppm; and performing flocculation precipitation on the wastewater subjected to double decomposition, and adding 0.2% of secondary defluorinating agent into the supernatant. The secondary defluorinating agent mainly comprises the following components: crystalline aluminum chloride, ferric chloride, sodium silicate and water are prepared into colloidal aqueous solution with the solid content of 30%, the colloidal aqueous solution is added into wastewater with the fluorine ion content of less than 8ppm, fluorine ions in the water body and high-valence cations form a fluorine-containing complex which is more insoluble, and the colloidal aqueous solution is settled under the flocculation effect to achieve the purpose of removing the fluorine ions, so that the fluorine content in the wastewater is less than 1 ppm.
The invention has the beneficial effects that:
(1) according to the technical scheme provided by the invention, the fluorine content in the fluorine-containing wastewater after the pH value is adjusted is less than 1ppm after primary defluorination, double decomposition reaction and secondary defluorination. The technology adopts 33 percent of liquid calcium chloride solution, solid sodium carbonate, a fixed-concentration secondary defluorinating agent and an auxiliary agent thereof, so that accurate control can be realized, the stability of treating the fluorine-containing wastewater is greatly improved, and the long-period stable operation can be ensured; meanwhile, the solid waste amount is greatly reduced;
(2) the device provided by the invention improves the automation degree of wastewater treatment, greatly reduces the labor intensity of workers and also saves human resources.
Drawings
FIG. 1 is a schematic view of an apparatus for continuous advanced treatment of wastewater containing fluorine according to the present invention;
wherein, 7 is a pH value adjusting tank, 8 is a wastewater metering pump, 1 is a polyacrylamide solution metering tank a, 2 is a polyacrylamide solution metering pump a, 3 is a polyaluminum chloride solution metering tank, 4 is a polyaluminum chloride solution metering pump, 5 is a 33% calcium chloride solution metering tank, 6 is a 33% calcium chloride solution metering pump, 9 is a first reaction tank, 10 is a second reaction tank, 11 is a third reaction tank, 12 is a first water distribution tank, 13 is a first inclined plate sedimentation tank, 14 is a first intermediate water tank, 26 is a sludge conveying pump, 25 is a plate-and-frame filter press, 15 is a double decomposition reaction tank, 28 is a polyacrylamide solution metering tank b, 27 is a polyacrylamide solution metering pump b, 16 is a second water distribution tank, 17 is a second inclined plate sedimentation tank, 18 is a second intermediate water tank, 19 is a second defluorination reaction tank, 23 is a second defluorination agent metering pump, 24 is a second defluorination agent metering tank, 2 is a second defluorination agent metering tank, A third water distribution tank 20, a third inclined plate sedimentation tank 21 and a third middle water tank 22.
Detailed Description
In order to make the technical solutions of the present invention better understood, the following description is provided clearly and completely, and other similar embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present application based on the embodiments in the present application.
A device for continuously and deeply treating fluorine-containing wastewater is shown in figure 1 and comprises a pH value adjusting tank 7, a wastewater metering pump 8, a polyacrylamide solution metering tank 1, a polyacrylamide solution metering pump a 2, a polyaluminum chloride solution metering tank a 3, a polyaluminum chloride solution metering pump 4, a 33% calcium chloride solution metering tank 5, a 33% calcium chloride solution metering pump 6, a first reaction tank 9, a second reaction tank 10, a third reaction tank 11, a first water distribution tank 12, a first inclined plate sedimentation tank 13, a first intermediate water tank 14, a sludge conveying pump 26, a plate-and-frame filter press 25, a double decomposition reaction tank 15, a polyacrylamide solution metering pump b 27, a polyacrylamide solution metering tank b 28, a second water distribution tank 16, a second inclined plate sedimentation tank 17, a second intermediate water tank 18, a secondary defluorination reaction tank 19, a secondary defluorination agent metering pump 23, a secondary defluorination agent metering tank 24, A third water distribution tank 20, a third inclined plate sedimentation tank 21 and a third middle water tank 22.
Wherein the first reaction tank 9 is connected with the pH adjusting tank 7 through a wastewater metering pump 8, the first reaction tank 9 is connected with the second reaction tank 10 through a bottom through hole through a metering pump 4 of 33 percent calcium chloride solution and a metering tank 5 of 33 percent calcium chloride solution, and wastewater in the first reaction tank 9 flows into the bottom of the second reaction tank 10 through a potential difference.
The second reaction tank 10 is connected with the polyaluminium chloride solution metering tank 3 through a polyaluminium chloride solution metering pump 4, the second reaction tank 10 is connected with the third reaction tank 11 through a middle through hole, and wastewater in the second reaction tank 10 flows into the middle of the third reaction tank 11 through potential difference.
The third reaction tank 11 is connected with the polyacrylamide solution metering tank 1 through a polyacrylamide solution metering pump 2, the third reaction tank 11 is connected with the first water distribution tank 12 through a middle through hole, and wastewater in the third reaction tank 11 flows into the middle of the first water distribution tank 12 through potential difference.
The first water distribution tank 12 is connected with the first inclined plate sedimentation tank 13 through a bottom through hole, and wastewater in the first water distribution tank 12 flows into the lower part of the first inclined plate sedimentation tank 13 through potential difference.
The first inclined plate sedimentation tank 13 overflows to a first middle water tank 14 through an upper overflow port, the liquid levels of the first reaction tank 9, the second reaction tank 10, the third reaction tank 11 and the first water distribution tank 12 are determined by the height of the overflow port, and the first inclined plate sedimentation tank 13 is connected with a plate-and-frame filter press 25 through a sludge delivery pump 26.
The first intermediate water reservoir 14 is connected to a metathesis reaction reservoir 15 via an overflow.
The upper part of the double decomposition reaction tank 15 is provided with a sodium carbonate metering and feeding device which is connected with a polyacrylamide solution metering tank b 28 through a polyacrylamide solution metering pump b 27 and is connected with a second water distribution tank 16 through a lower through hole.
The second water distribution tank 16 is connected with the second inclined plate sedimentation tank 17 through a bottom through hole, and the wastewater in the second water distribution tank 16 flows into the lower part of the second inclined plate sedimentation tank 17 through potential difference.
The second inclined plate sedimentation tank 17 overflows to a second intermediate water tank 18 through an upper overflow port, the liquid levels of the double decomposition reaction tank 15 and the second water distribution tank 16 are determined by the height of the overflow port, and the second inclined plate sedimentation tank 17 is connected with a plate-and-frame filter press 25 through a sludge delivery pump 26.
The second intermediate water tank 18 is connected with the second-stage defluorination reaction tank 19 through an overflow port.
The second-stage defluorination reaction tank 19 is connected with a second-stage defluorination agent metering tank 24 through a second-stage defluorination agent metering pump 23 and is connected with a third water distribution tank 20 through a lower through hole.
The third water distribution tank 20 is connected with the third inclined plate sedimentation tank 21 through a bottom through hole, and wastewater in the third water distribution tank 20 flows into the lower part of the third inclined plate sedimentation tank 21 through the potential difference.
The third inclined plate sedimentation tank 21 overflows to a third intermediate water tank 22 through an upper overflow port, the liquid levels of the secondary defluorination reaction tank 19 and the third water distribution tank 20 are determined by the height of the overflow port, and the third inclined plate sedimentation tank 21 is connected with a plate-and-frame filter press 25 through a sludge delivery pump 26.
Example 1
(1) Neutralizing: 6-8 fluorine-containing wastewater is metered by a wastewater metering pump 8 and then is continuously conveyed to a first reaction tank 9, a metered 33% calcium chloride solution is continuously pumped into the fluorine-containing wastewater through a 33% calcium chloride solution metering pump 6 under stirring, equivalent calcium chloride is added according to the content of fluoride ions in the fluorine-containing wastewater, and the amount of excessive 2500ppm calcium ions is added, so that the fluoride ions in the wastewater react with the calcium chloride to generate calcium fluoride precipitate, the amount of the excessive 2500ppm calcium ions is enabled to pass through a through hole at the bottom of the first reaction tank 9, and then the calcium ions enter a second reaction tank 10.
(2) In the second reaction tank 10, 10% of polyaluminum chloride (PAC) solution containing 5g of ethylene bis stearamide per L continuously added by a polyaluminum chloride (PAC) solution metering pump 4 is fully mixed with the polyaluminum chloride (PAC) solution under stirring, the adding amount of the polyaluminum chloride (PAC) is 0.02% of the total amount of the wastewater, and the mixture enters a third reaction tank 11 through a through hole in the middle of the second reaction tank 10, continuously adding 0.1 percent of Polyacrylamide (PAM) solution into the wastewater by a Polyacrylamide (PAM) solution metering pump 2 under stirring, wherein the adding amount of the Polyacrylamide (PAM) is 0.0020 percent of the total amount of the wastewater, fully mixing, enters the first water distribution tank 12 through the middle through hole, flows into the first inclined plate sedimentation tank 13 after being distributed with water by the first water distribution tank 12, overflows to the first middle water tank 14 through the overflow cofferdam, and is sampled and analyzed from the first middle water tank 14, wherein the fluorine ion content is 7.9 ppm.
(3) The wastewater flows to a double decomposition reaction tank 15 from a first intermediate water tank 14, metered sodium carbonate solid is added under stirring for reaction, excessive calcium ions and sodium carbonate generate calcium carbonate precipitation, 0.1 percent of Polyacrylamide (PAM) solution is continuously added through a Polyacrylamide (PAM) solution metering pump 2 under stirring, the adding amount of the Polyacrylamide (PAM) is 0.0020 percent of the total amount of the wastewater, and then the wastewater enters a second inclined plate sedimentation tank 17 and a second intermediate water tank 18 through a second water distribution tank 16, and the content of fluorine ions is 2.59ppm by sampling and analyzing from the second intermediate water tank 18.
(4) The wastewater flows from the second intermediate water tank 18 to the second-stage defluorination reaction tank 19, the second-stage defluorination agent accounting for 0.2 percent of the total amount of the wastewater is added under stirring, trace fluorine ions in the wastewater further react with the second-stage defluorination agent to generate complex precipitates, the complex precipitates are settled by the third water distribution tank 20 and the third inclined plate settling tank 21, the supernatant overflows to the third intermediate water tank 22, and the fluorine ion content of the complex precipitates is analyzed to be 0.78ppm by sampling from the third intermediate water tank 22.
The defluorinated wastewater enters a subsequent wastewater treatment device through a wastewater lifting pump to remove COD, BOD and ammonia nitrogen in the wastewater, and is discharged after being qualified.
Example 2
(1) Neutralizing: 6-8 of fluoride-containing wastewater is metered by a wastewater metering pump 8 and then is continuously conveyed to a first reaction tank 9, a metered 33% calcium chloride solution is continuously injected into the fluoride-containing wastewater through a 33% calcium chloride solution metering pump 6 under stirring, equivalent calcium chloride is added according to the content of fluoride ions in the fluoride-containing wastewater, and the amount of 5000ppm excessive calcium ions is added, so that the fluoride ions in the wastewater react with the calcium chloride to generate calcium fluoride precipitate, and the calcium ions are excessive by 5000ppm and enter a second reaction tank 10 through a through hole at the bottom of the first reaction tank 9.
(2) In the second reaction tank 10, 10% of polyaluminum chloride (PAC) solution containing 5g of ethylene bis stearamide per L continuously added by a polyaluminum chloride (PAC) solution metering pump 4 is fully mixed with the polyaluminum chloride (PAC) solution under stirring, the adding amount of the polyaluminum chloride (PAC) is 0.025 percent of the total amount of the wastewater, and the mixture enters a third reaction tank 11 through a through hole in the middle of the second reaction tank 10, continuously adding 0.1 percent of Polyacrylamide (PAM) solution into the wastewater by a Polyacrylamide (PAM) solution metering pump 2 under stirring, wherein the adding amount of the Polyacrylamide (PAM) is 0.0020 percent of the total amount of the wastewater, fully mixing, enters the first water distribution tank 12 through the middle through hole, flows into the first inclined plate sedimentation tank 13 after being distributed with water by the first water distribution tank 12, overflows to the first middle water tank 14 through the overflow cofferdam, and is sampled and analyzed from the first middle water tank 14, wherein the fluorine ion content is 7.8 ppm.
(3) The wastewater flows to a double decomposition reaction tank 15 from a first intermediate water tank 14, metered sodium carbonate solid is added under stirring for reaction, excessive calcium ions and sodium carbonate generate calcium carbonate precipitation, 0.1 percent of Polyacrylamide (PAM) solution is continuously added through a Polyacrylamide (PAM) solution metering pump 2 under stirring, the adding amount of the Polyacrylamide (PAM) is 0.0025 percent of the total amount of the wastewater, and then the wastewater enters a second inclined plate sedimentation tank 17 and a second intermediate water tank 18 through a second water distribution tank 16, and the content of fluorine ions is 2.53ppm by sampling and analyzing from the second intermediate water tank 18.
(4) The wastewater flows from the second intermediate water tank 18 to the second-stage defluorination reaction tank 19, the second-stage defluorination agent accounting for 0.25 percent of the total amount of the wastewater is added under stirring, trace fluorine ions in the wastewater further react with the second-stage defluorination agent to generate complex precipitates, the complex precipitates are settled by the third water distribution tank 20 and the third inclined plate settling tank 21, the supernatant overflows to the third intermediate water tank 22, and the fluorine ion content of the complex precipitates is 0.76ppm by sampling and analyzing the third intermediate water tank 22.
The defluorinated wastewater enters a subsequent wastewater treatment device through a wastewater lifting pump to remove COD, BOD and ammonia nitrogen in the wastewater, and is discharged after being qualified.
Example 3
(1) Neutralizing: 6-8 fluorine-containing wastewater is metered by a wastewater metering pump 8 and then is continuously conveyed to a first reaction tank 9, a metered 33% calcium chloride solution is continuously pumped into the fluorine-containing wastewater through a 33% calcium chloride solution metering pump 6 under stirring, equivalent calcium chloride is added according to the content of fluoride ions in the fluorine-containing wastewater, and the amount of excessive 2500ppm calcium ions is added, so that the fluoride ions in the wastewater react with the calcium chloride to generate calcium fluoride precipitate, the amount of the excessive 2500ppm calcium ions is enabled to pass through a through hole at the bottom of the first reaction tank 9, and then the calcium ions enter a second reaction tank 10.
(2) In the second reaction tank 10, continuously adding 10% polyaluminium chloride (PAC) solution through a polyaluminium chloride (PAC) solution metering pump 4 under stirring, wherein the adding amount of the polyaluminium chloride (PAC) is 0.02% of the total amount of the wastewater, fully mixing, then entering a third reaction tank 11 through a through hole in the middle of the second reaction tank 10, continuously adding 0.1% Polyacrylamide (PAM) solution through a Polyacrylamide (PAM) solution metering pump 2 under stirring, wherein the adding amount of the Polyacrylamide (PAM) is 0.0020% of the total amount of the wastewater, fully mixing, then entering a first water distribution tank 12 through a through hole in the middle, distributing water through the first water distribution tank 12, then flowing into a first inclined plate sedimentation tank 13, overflowing to a first middle water tank 14 through an overflow cofferdam, and sampling and analyzing the content of fluoride ions in the first middle water tank 14 to be 8.6 ppm.
(3) The wastewater flows to a double decomposition reaction tank 15 from a first intermediate water tank 14, metered sodium carbonate solid is added under stirring for reaction, excessive calcium ions and sodium carbonate generate calcium carbonate precipitation, 0.1 percent of Polyacrylamide (PAM) solution is continuously added through a Polyacrylamide (PAM) solution metering pump 2 under stirring, the adding amount of the Polyacrylamide (PAM) is 0.0020 percent of the total amount of the wastewater, and then the wastewater enters a second inclined plate sedimentation tank 17 and a second intermediate water tank 18 through a second water distribution tank 16, and the content of fluorine ions is 2.59ppm by sampling and analyzing from the second intermediate water tank 18.
(4) The wastewater flows from the second intermediate water tank 18 to the second-stage defluorination reaction tank 19, the second-stage defluorination agent accounting for 0.2 percent of the total amount of the wastewater is added under stirring, trace fluorine ions in the wastewater further react with the second-stage defluorination agent to generate complex precipitates, the complex precipitates are settled by the third water distribution tank 20 and the third inclined plate settling tank 21, the supernatant overflows to the third intermediate water tank 22, and the fluorine ion content of the complex precipitates is 0.89ppm by sampling and analyzing the third intermediate water tank 22.
The defluorinated wastewater enters a subsequent wastewater treatment device through a wastewater lifting pump to remove COD, BOD and ammonia nitrogen in the wastewater, and is discharged after being qualified.
Claims (8)
1. A device for continuously and deeply treating fluorine-containing wastewater comprises a first reaction tank, a second reaction tank and a third reaction tank, and is characterized in that,
the first reaction tank (9) is connected with the pH adjusting tank (7) through a wastewater metering pump (8), the first reaction tank (9) is connected with the second reaction tank (10) through a bottom through hole through a 33% calcium chloride solution metering pump (4) and a 33% calcium chloride solution metering tank (5), and wastewater in the first reaction tank (9) flows into the bottom of the second reaction tank (10) through potential difference;
the second reaction tank (10) is connected with the polyaluminium chloride solution metering tank (3) through a polyaluminium chloride solution metering pump (4), the second reaction tank (10) is connected with the third reaction tank (11) through a middle through hole, and wastewater in the second reaction tank (10) flows into the middle of the third reaction tank (11) through potential difference;
the third reaction tank (11) is connected with the polyacrylamide solution metering tank a (1) through a polyacrylamide solution metering pump a (2), the third reaction tank (11) is connected with the first water distribution tank (12) through a middle through hole, and wastewater in the third reaction tank (11) flows into the middle of the first water distribution tank (12) through potential difference;
the first water distribution tank (12) is connected with the first inclined plate sedimentation tank (13) through a bottom through hole, and wastewater in the first water distribution tank (12) flows into the lower part of the first inclined plate sedimentation tank (13) through the potential difference;
the first inclined plate sedimentation tank (13) overflows to a first middle water tank (14) through an upper overflow port, the liquid levels of the first reaction tank (9), the second reaction tank (10), the third reaction tank (11) and the first water distribution tank (12) are determined by the height of the overflow port, and the first inclined plate sedimentation tank (13) is connected with a plate-and-frame filter press (25) through a sludge delivery pump (26);
the first intermediate water tank (14) is connected with the double decomposition reaction tank (15) through an overflow port;
a sodium carbonate metering and feeding device is arranged at the upper part of the double decomposition reaction tank (15), is connected with a polyacrylamide solution metering tank b (28) through a polyacrylamide metering pump b (27), and is connected with a second water distribution tank (16) through a lower through hole;
the second water distribution tank (16) is connected with a second inclined plate sedimentation tank (17) through a bottom through hole, and wastewater in the second water distribution tank (16) flows into the lower part of the second inclined plate sedimentation tank (17) through the potential difference;
the second inclined plate sedimentation tank (17) overflows to a second intermediate water tank (18) through an upper overflow port, the liquid levels of the double decomposition reaction tank (15) and the second inclined plate water distribution tank (16) are determined by the height of the overflow port, and the second inclined plate sedimentation tank (17) is connected with a plate-and-frame filter press (25) through a sludge delivery pump (26);
the second intermediate water tank (18) is connected with the secondary defluorination reaction tank (19) through an overflow port;
the secondary defluorination reaction tank (19) is connected with a secondary defluorination agent metering tank (24) through a secondary defluorination agent metering pump (23) and is connected with a third water distribution tank (20) through a lower through hole;
the third water distribution tank (20) is connected with a third inclined plate sedimentation tank (21) through a through hole at the bottom, and wastewater in the third water distribution tank (20) flows into the lower part of the third inclined plate sedimentation tank (21) through the potential difference;
the third inclined plate sedimentation tank (21) overflows to a third middle water tank (22) through an upper overflow port, the liquid level of the secondary defluorination reaction tank (19) and the liquid level of the third water distribution tank (20) are determined by the height of the overflow port, and the third inclined plate sedimentation tank (21) is connected with a plate-and-frame filter press (25) through a sludge delivery pump (26).
2. A method for continuously and deeply treating fluorine-containing wastewater by using the device of claim 1, which is characterized by comprising the following steps:
(1) conveying the fluorine-containing wastewater neutralized to pH 6-8 to a first reaction tank (9) through a wastewater metering pump (8), continuously pumping the fluorine-containing wastewater into a metered 33% calcium chloride solution through a 33% calcium chloride solution metering pump (4) under stirring, and after reaction, allowing the wastewater to enter a second reaction tank (10) through a through hole at the bottom of the first reaction tank (9);
(2) in a second reaction tank (10), fully mixing with a metered polyaluminium chloride (PAC) solution continuously added through a polyaluminium chloride (PAC) solution metering pump (4) under stirring, then entering a third reaction tank (11) through a middle through hole of the second reaction tank (10), fully mixing with a metered Polyacrylamide (PAM) solution continuously added through a Polyacrylamide (PAM) solution metering pump a (2) under stirring, then entering a first water distribution tank (12) through the middle through hole, distributing water through the first water distribution tank (12), then flowing into a first inclined plate sedimentation tank (13), and overflowing to a first middle water tank (14) through an overflow cofferdam;
(3) the wastewater flows into a double decomposition reaction tank (15) from a first intermediate water tank (14), reacts with metered sodium carbonate under stirring, is added with a certain amount of polyacrylamide solution through a polyacrylamide metering pump b (27), is connected with a second water distribution tank (16) through a lower through hole, and then enters into a second inclined plate sedimentation tank (17) and a second intermediate water tank (18) through the second water distribution tank (16);
(4) the wastewater flows from the second intermediate water tank (18) to the secondary defluorination reaction tank (19), is further reacted with the secondary defluorination agent under stirring, is settled by the third water distribution tank (20) and the third inclined plate settling tank (21), and then supernatant overflows to the third intermediate water tank (22).
3. The method according to claim 2, wherein in the step (1), the calcium ion concentration is in excess of 1500ppm to 5000 ppm; preferably, the excess amounts 2300 and 2600 ppm.
4. The method according to claim 2, wherein in the step (2), the mass concentration of the polyaluminum chloride solution is 10%; the adding amount of the polyaluminum chloride solution is 0.015-0.025 percent of the total amount of the wastewater.
5. The method of claim 4, wherein 3 to 5g of ethylene bis stearamide per L is added to the polyaluminum chloride solution.
6. The method of claim 2, wherein in the step (2), the concentration of the polyacrylamide solution is 0.1%, and the amount of the polyacrylamide solution added is 0.0015% -0.0030% of the total amount of the wastewater.
7. The process of claim 2 or 3, wherein in step (3), the amount of sodium carbonate added to the metathesis reaction tank is calculated according to the following formula:
m1=[(m2×c)/40]×106
wherein m is1-the amount of sodium carbonate added, kg/h;
M2-flow of waste water, kg/h;
c- -Ca in wastewater2+Concentration,%;
the concentration of the polyacrylamide solution is 0.1 percent, and the addition amount is 0.0015 to 0.0030 percent of the total amount of the wastewater.
8. The process according to claim 2, wherein in step (4), the secondary defluorinating agent is a crystalline aluminum chloride: iron chloride: sodium silicate according to the mass ratio of 18: 10: 8, preparing a mixture; the addition amount of the secondary defluorinating agent is 0.15-0.25 percent of the flow amount of the wastewater, and the preferred addition amount is 0.2 percent.
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