CN111233245A - Fluorine wastewater desalination and concentration device and method - Google Patents
Fluorine wastewater desalination and concentration device and method Download PDFInfo
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- CN111233245A CN111233245A CN202010143165.XA CN202010143165A CN111233245A CN 111233245 A CN111233245 A CN 111233245A CN 202010143165 A CN202010143165 A CN 202010143165A CN 111233245 A CN111233245 A CN 111233245A
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
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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
- 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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Abstract
The invention discloses a fluorine wastewater desalination and concentration device and a fluorine wastewater desalination and concentration method. Compared with the traditional treatment mode for treating the fluorine-containing wastewater by a precipitation method, the technical scheme of the invention adopts the mode that ions are directionally migrated under the driving of an external electric field to treat the fluorine-containing wastewater, a large amount of chemicals are not needed, and the fluorine wastewater desalting and concentrating device only uses the original water tank, the polar water tank, the concentrated water tank, the charge membrane module and the positive and negative electrodes, so that the structure is simple, and the fluorine wastewater treatment cost is reduced.
Description
Technical Field
The invention relates to the wastewater treatment industry, in particular to a fluorine wastewater desalination and concentration device and a method.
Background
Fluoride is a toxicological indicator of water quality and widely exists in water in nature. In industry, metallurgy industry, glass etching industry, chemical industry and electroplating industry, a large amount of high-concentration fluoride wastewater is often generated, the water quality condition of the surrounding environment is seriously influenced, and the human health is influenced. At present, most of domestic manufacturers mostly adopt a fluorine-containing wastewater treatment mode of a traditional precipitation method, but the mode cannot fully utilize medicines, wastes the medicines excessively and increases the cost. Meanwhile, the generated villiaumite precipitate is difficult to be pumped out of mud, and the precipitate cannot be discharged for a long time, and is easy to be caked, so that various problems of a sedimentation tank are caused.
Disclosure of Invention
The method adopts the charge membrane to concentrate and recycle the mixed wastewater of ammonium fluoride and ammonium sulfate generated in the production and manufacturing process of rare metals. The mixed wastewater produced by the original production adopts a precipitation process, and a large amount of lime is adopted for precipitation, so that the fluorine salt cannot be reused. The mixed solution of ammonium fluoride and ammonium sulfate concentrated by the method is returned to production and used for next process production, and the desalted water can be returned to production again to be used as cleaning water. Not only realizes the recycling of fluoride salt, but also does not cause any pollution to the environment, and really realizes the zero discharge of waste water.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a fluorine wastewater desalination and concentration device comprises a raw water tank, a polar water tank, a concentrated water tank and a charge membrane assembly, wherein the raw water tank, the polar water tank and the concentrated water tank are respectively provided with a filter.
Further, the raw water tank is provided with a raw water circulation pipeline, the concentrated water tank is provided with a concentrated water circulation pipeline, the pole water tank is provided with a pole water circulation pipeline, the raw water circulation pipeline, the concentrated water circulation pipeline and the pole water circulation pipeline are all provided with a water pump, and the filter is arranged on each circulation pipeline.
Furthermore, the raw water circulating pipeline and the concentrated water circulating pipeline are both provided with concentration detection elements.
Further, the device also comprises a reaction box, and the concentrated water box is connected with the reaction box.
The invention also discloses a method for desalting and concentrating by using the fluorine wastewater desalting and concentrating device, which comprises the following steps: firstly, preparing a sodium chloride solution, pouring the sodium chloride solution into a water tank, pouring an ammonium sulfate and ammonium fluoride wastewater mixed solution into a raw water tank, pouring a receiving solution into a concentrated water tank, and electrifying; secondly, after the power is switched on, transferring fluorine ions to a concentrated water tank through a charge membrane assembly, periodically recording the content of the fluorine ions in the ammonium sulfate-ammonium fluoride wastewater mixed solution, when the content of the fluorine ions in the ammonium sulfate-ammonium fluoride wastewater mixed solution is less than 1g/L and the concentration of the fluorine ions in a receiving solution is more than 20g/L, recording the content of F, turning off a power supply, discharging the receiving solution, and performing two-stage desalination; and thirdly, pouring the receiving liquid into the concentrated water tank again, turning on the power supply, recording the numerical value when the content of the fluorine ions in the ammonium sulfate-ammonium fluoride wastewater mixed liquid is less than 0.15g/L, turning off the power supply, and discharging and flushing the receiving liquid.
Further, the receiving liquid in the concentrated water tank is discharged into the reaction tank, and magnesium is added into the reaction tank to react with the receiving liquid to generate magnesium fluoride.
Furthermore, before the power is on, the water pump is started, and the solutions in the raw water tank, the pole water tank and the concentrated water tank are respectively circulated to discharge gas.
Further, the pressure values of the water pumps in the raw water tank, the extreme water tank and the concentrated water tank are respectively 0.05Mpa, 0.04Mpa and 0.05Mpa, and the voltage value is 64V.
Further, the receiving liquid is ammonium sulfate and ammonium fluoride waste water mixed liquid.
From the above description of the present invention, it can be seen that the advantages of the present invention over the prior art are:
compared with the traditional treatment mode for treating the fluorine-containing wastewater by a precipitation method, the technical scheme of the invention adopts the mode that ions are directionally migrated under the driving of an external electric field to treat the fluorine-containing wastewater, a large amount of chemicals are not needed, and the fluorine wastewater desalting and concentrating device only uses the original water tank, the polar water tank, the concentrated water tank, the charge membrane module and the positive and negative electrodes, so that the structure is simple, and the fluorine wastewater treatment cost is reduced.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Fig. 2 is a data diagram of embodiment 1 of the present invention.
FIG. 3 is a data graph of example 1 of the present invention.
FIG. 4 is a graph showing data on the change in the F content of the dope of example 1 of the present invention.
Fig. 5 is a data diagram of embodiment 2 of the present invention.
FIG. 6 is a data graph of example 2 of the present invention.
FIG. 7 is a data graph showing the change in the F content of the dope of example 2 of the present invention.
Fig. 8 is a data diagram of embodiment 3 of the present invention.
FIG. 9 is a data graph of example 3 of the present invention.
FIG. 10 is a data graph showing the change in the F content of the dope of example 3 of the present invention.
Detailed Description
Referring to fig. 1, the fluorine wastewater desalination and concentration device comprises a raw water tank 1, an electrode water tank 2, a concentrated water tank 3 and a charge membrane module 4, wherein the raw water tank 1, the electrode water tank 2 and the concentrated water tank 3 are respectively provided with a filter 5. When the device is used, ammonium sulfate and ammonium fluoride waste water mixed liquor is poured into the raw water tank 1, electrolyte is poured into the polar water tank 2, the ammonium sulfate and ammonium fluoride waste water mixed liquor and the electrolyte remove impurities through the filter 5, then the device is powered on, under the action of an external electric field, fluorine ions in the ammonium sulfate and ammonium fluoride waste water mixed liquor are transferred into the concentrated water tank 3 through the charge membrane assembly 4 until the fluorine ions in the ammonium sulfate and ammonium fluoride waste water mixed liquor meet the standard.
Referring to fig. 1, the raw water tank 1 of the present technical solution is provided with a raw water circulation pipeline 11, the concentrated water tank 3 is provided with a concentrated water circulation pipeline 31, the polar water tank 2 is provided with a polar water circulation pipeline 21, the raw water circulation pipeline 11, the concentrated water circulation pipeline 21 and the polar water circulation pipeline 21 are all provided with a water pump 6, and the filter 5 is arranged on each circulation pipeline. Before the power is on, the water pump 6 is firstly turned on, so that the solution in the raw water tank 1, the polar water tank 2 and the concentrated water tank 3 continuously circulates in the tank body and the circulating pipeline of the raw water tank 1, the polar water tank 2, the concentrated water tank 3 and the circulating pipeline, the gas in the raw water tank 1, the polar water tank 2, the concentrated water tank 3 and the circulating pipeline is discharged, and the device is prevented from being burnt out after the power is on. The filter 5 is disposed in the circulation line, and can filter impurities in the solution for a plurality of times.
Referring to fig. 1, the raw water circulation line 11 and the concentrated water circulation line 31 of the present embodiment are both provided with a concentration detection element 7. The arrangement of the concentration detection element 7 is convenient for monitoring the concentration of the fluorine ions in the raw water tank 1 and the concentrated water tank 3 in real time.
Referring to fig. 1, the desalination and concentration device for fluorine wastewater of the present embodiment further includes a reaction tank (not shown), and the concentrate tank 3 is connected to the reaction tank (not shown). The fluorine waste water in the concentrated water tank 3 is discharged to a reaction tank (not shown in the figure), and magnesium is added into the reaction tank (not shown in the figure) to react with the fluorine waste water to generate magnesium fluoride product for reuse.
The invention also discloses a method for desalting and concentrating by using the fluorine wastewater desalting and concentrating device, which comprises the following steps: preparing a 3% sodium chloride solution, pouring the sodium chloride solution into an ultra-water tank, pouring an ammonium sulfate and ammonium fluoride wastewater mixed solution into a raw water tank, pouring a receiving solution into a concentrated water tank, and electrifying; secondly, after the power is switched on, fluorine ions migrate to a concentrated water tank through a charge membrane module, the content of the fluorine ions in the ammonium sulfate-ammonium fluoride wastewater mixed liquid is recorded periodically, when the content of the fluorine ions in the ammonium sulfate-ammonium fluoride wastewater mixed liquid is less than 1g/L, the concentration of the fluorine ions in the receiving liquid is more than 20g/L, the content of F is recorded, a power supply is turned off, the receiving liquid is discharged, and two-stage desalination is carried out; and thirdly, pouring the receiving liquid into the concentrated water tank again, turning on the power supply, recording the numerical value when the content of the fluorine ions in the ammonium sulfate-ammonium fluoride wastewater mixed liquid is less than 0.15g/L, turning off the power supply, and discharging and flushing the receiving liquid.
In the method, the receiving liquid of the concentrated water tank is discharged into the reaction tank, and magnesium is added into the reaction tank to react with the receiving liquid to generate magnesium fluoride.
In the method, before the power is on, the water pump is started, and the solutions in the raw water tank, the pole water tank and the concentrated water tank are respectively circulated to discharge gas.
In the method, the pressure values of the water pumps in the original water tank, the extreme water tank and the concentrated water tank are respectively 0.05Mpa, 0.04Mpa and 0.05Mpa, and the adopted voltage value is 64V. The charged membrane migrates ions by an applied voltage. The voltage is large, the current value is large, the migration of ions is faster, but the energy consumption is high, and the maximum economic benefit can be realized by adopting the pressure intensity and the voltage value of the value.
In the method, the receiving liquid is ammonium sulfate and ammonium fluoride waste water mixed liquid. The mixed liquid of the ammonium sulfate and the ammonium fluoride is waste, so that the treatment cost is not increased.
Example 1
Referring to fig. 2 to 4, the content of the ammonium sulfate-ammonium fluoride wastewater mixed liquor F in the raw water tank 1 is 7.9g/L, the initial wastewater amount is 1T, the content of the ammonium sulfate-ammonium fluoride wastewater mixed liquor F in the concentrated water tank is 7.9g/L, the initial wastewater amount is 30L, and the voltage is set to 64V. And (4) carrying out charge migration under the action of an electrodialysis system, and enriching ions in the concentrated water tank. The first stage took 55 minutes to remove the F content from 7.9g/L to 1.6g/L, leaving a volume of 840L, the F content in the concentrate tank reached 21g/L, and the volume was 190L. And (3) replacing the ammonium sulfate-ammonium fluoride wastewater mixed liquor in the concentrated water tank, taking 30L of the ammonium sulfate-ammonium fluoride wastewater mixed liquor with the F content of 7.9g/L, pouring into the concentrated water tank, and starting two-stage desalination. The voltage is 64V, the content of the stock solution F is 1.5g/L, the stock solution F is continuously removed to 0.09g/L, the volume of the raw water is 765L, the content of the concentrated solution F is 4.4g/L, and the volume is 105L.
Fluorine-containing waste water 1T squeezes into the circulating line at former water tank through the drive power of water pump, gets rid of impurity through the filter, and fluorine-containing waste water returns former water tank through the circulating line again, so in the past constantly circulate. The fluorine-containing wastewater 30L is pumped into the circulating pipe in the concentrated water tank by the driving force of the water pump, impurities are removed by the filter, and the filtrate returns to the concentrated water tank again through the circulating pipe, so that the previous process is continuously circulated. The 3% sodium chloride 100L is squeezed into the circulating pipeline through the driving force of the water pump in the polar water tank, impurities are removed through the filter, and the filtrate returns to the polar water tank again through the circulating pipeline, so that the previous continuous circulation is realized.
Example 2
Referring to fig. 5 to 7, the content of the ammonium sulfate-ammonium fluoride wastewater mixed liquor F in the raw water tank 1 is 7.2g/L, the initial wastewater amount is 1T, the content of the ammonium sulfate-ammonium fluoride wastewater mixed liquor F in the concentrated water tank is 7.2g/L, the initial wastewater amount is 30L, and the voltage is set to 64V. And (4) carrying out charge migration under the action of an electrodialysis system, and enriching ions in the concentrated water tank. In the first stage, it took 55 minutes to remove 7.2g/L to 1.6g/L, leaving 840L of fluoride ions in the concentrate tank to 23g/L and 190L of fluoride ions in the concentrate tank. And (3) replacing the ammonium sulfate-ammonium fluoride wastewater mixed liquor in the concentrated water tank, taking 30L of the ammonium sulfate-ammonium fluoride wastewater mixed liquor with the F content of 7.2g/L, pouring the mixed liquor into the concentrated water tank, and starting two-stage desalination with the voltage of 64V. The F content in the raw water tank is 1.6g/L, the volume of the raw water is 740L, the F content in the concentrated water tank is 6g/L, and the volume is 100L.
Example 3
The content of the ammonium sulfate-ammonium fluoride waste water mixed liquor F in the raw water tank is 7.3g/L, the initial waste water amount is 1T, the content of the ammonium sulfate-ammonium fluoride waste water mixed liquor F in the concentrated water tank is 7.3g/L, the initial water amount is 30L, and the voltage is set to be 64V. And (3) carrying out charge migration under the action of an electrodialysis system, and enriching ions in the concentration chamber. In the first stage, the content of the ammonium sulfate-ammonium fluoride waste water mixed liquor F in the raw water tank is removed from 7.3g/L to 1.6g/L within 55 minutes, the volume of the mixed liquor is 840L, and the fluorine ions in the concentrated water tank reach 20g/L and 190L. And (3) replacing ammonium sulfate and ammonium fluoride waste water mixed liquor in the concentrated water tank, pouring 30L of ammonium sulfate and ammonium fluoride waste water mixed liquor with the F content of 7.3g/L into the concentrated water tank, starting secondary desalination, wherein the voltage is 64V, the F content of 1.6g/L in the raw water tank is continuously removed downwards to the volume of 739L of 0.098g/L of the raw water tank, the F content of 5.55g/L in the concentrated water tank and the volume is 101L.
The above description is only an embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modifications made by using the design concept should fall within the scope of infringing the present invention.
Claims (9)
1. A fluorine waste water desalination enrichment facility which characterized in that: the device comprises a raw water tank, a polar water tank, a concentrated water tank and a charge membrane assembly, wherein the raw water tank, the polar water tank and the concentrated water tank are respectively provided with a filter.
2. The desalination and concentration device for fluorine waste water according to claim 1, characterized in that: the raw water tank is provided with a raw water circulation pipeline, the concentrated water tank is provided with a concentrated water circulation pipeline, the pole water tank is provided with a pole water circulation pipeline, the raw water circulation pipeline, the concentrated water circulation pipeline and the pole water circulation pipeline are all provided with a water pump, and the filter is arranged on each circulation pipeline.
3. The desalination and concentration device for fluorine waste water according to claim 2, characterized in that: the raw water circulating pipeline and the concentrated water circulating pipeline are both provided with concentration detection elements.
4. The desalination and concentration device for fluorine waste water according to claim 3, characterized in that: the device also comprises a reaction box, and the concentrated water box is connected with the reaction box.
5. A method for desalination and concentration by using the apparatus for desalination and concentration of fluorine wastewater according to claim 4, characterized in that: the method comprises the following steps: firstly, preparing a sodium chloride solution, pouring the sodium chloride solution into a water tank, pouring an ammonium sulfate and ammonium fluoride wastewater mixed solution into a raw water tank, pouring a receiving solution into a concentrated water tank, and electrifying; secondly, after the power is switched on, transferring fluorine ions to a concentrated water tank through a charge membrane assembly, periodically recording the content of the fluorine ions in the ammonium sulfate-ammonium fluoride wastewater mixed solution, when the content of the fluorine ions in the ammonium sulfate-ammonium fluoride wastewater mixed solution is less than 1g/L and the concentration of the fluorine ions in a receiving solution is more than 20g/L, recording the content of F, turning off a power supply, discharging the receiving solution, and performing two-stage desalination; and thirdly, pouring the receiving liquid into the concentrated water tank again, turning on the power supply, recording the numerical value when the content of the fluorine ions in the ammonium sulfate-ammonium fluoride wastewater mixed liquid is less than 0.15g/L, turning off the power supply, and discharging and flushing the receiving liquid.
6. The desalination and concentration method of fluorine wastewater according to claim 5, characterized in that: and discharging the receiving liquid in the concentrated water tank into the reaction tank, adding magnesium into the reaction tank, and reacting with the receiving liquid to generate magnesium fluoride.
7. The desalination and concentration method of fluorine wastewater according to claim 5, characterized in that: the receiving liquid is ammonium sulfate and ammonium fluoride waste water mixed liquid.
8. The desalination and concentration method of fluorine wastewater according to claim 5, characterized in that: before the power is on, the water pump is started, and the solutions in the raw water tank, the pole water tank and the concentrated water tank are respectively circulated to discharge gas.
9. The desalination and concentration method of fluorine wastewater according to claim 5, characterized in that: the pressure values of the water pumps in the original water tank, the extreme water tank and the concentrated water tank are respectively 0.05Mpa, 0.04Mpa and 0.05Mpa, and the voltage value is 64V.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047558A (en) * | 2020-07-17 | 2020-12-08 | 福建龙氟化工有限公司 | Fluorine-containing wastewater treatment device and treatment method |
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| CN101193823A (en) * | 2005-06-09 | 2008-06-04 | 株式会社荏原制作所 | Electrodialyzer, waste water treatment method, and fluorine treatment system |
| WO2014083716A1 (en) * | 2012-11-30 | 2014-06-05 | 株式会社 東芝 | Method for treating fluorine-containing wastewater, and apparatus for treating fluorine-containing wastewater |
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2020
- 2020-03-04 CN CN202010143165.XA patent/CN111233245A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101193823A (en) * | 2005-06-09 | 2008-06-04 | 株式会社荏原制作所 | Electrodialyzer, waste water treatment method, and fluorine treatment system |
| WO2014083716A1 (en) * | 2012-11-30 | 2014-06-05 | 株式会社 東芝 | Method for treating fluorine-containing wastewater, and apparatus for treating fluorine-containing wastewater |
Non-Patent Citations (1)
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| 董凯等: "电渗析法脱除氨法烟气脱硫浆液中的氟离子", 《化工环保》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047558A (en) * | 2020-07-17 | 2020-12-08 | 福建龙氟化工有限公司 | Fluorine-containing wastewater treatment device and treatment method |
| CN112047558B (en) * | 2020-07-17 | 2023-05-09 | 福建省龙氟新材料有限公司 | Fluorine-containing wastewater treatment device and treatment method |
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