CN209815855U - Fluorine-containing wastewater deep purification and recovery system - Google Patents
Fluorine-containing wastewater deep purification and recovery system Download PDFInfo
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- CN209815855U CN209815855U CN201920514320.7U CN201920514320U CN209815855U CN 209815855 U CN209815855 U CN 209815855U CN 201920514320 U CN201920514320 U CN 201920514320U CN 209815855 U CN209815855 U CN 209815855U
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Abstract
The utility model discloses a fluorine-containing wastewater deep purification and recovery system, which comprises a wastewater adjusting tank, an ion exchange column, a desorbent tank, a regenerant tank, a desorption liquid tank, a precipitant tank and a crystallization reaction tank, wherein the wastewater adjusting tank, the desorbent tank and the regenerant tank are respectively connected with an inlet of the ion exchange column through a first valve, a second valve and a third valve; the outlet of the ion exchange column is provided with a drain valve, the outlet is also connected with a desorption liquid tank through a fourth valve, and the bottom of the desorption liquid tank is connected with the interior of the crystallization reaction tank through a fifth valve; the precipitator groove is connected with the inner part of the crystallization reaction groove through a sixth valve, a drain valve is arranged on a drain outlet at the bottom of the crystallization reaction groove, and the lower part of the side surface of the crystallization reaction groove is communicated with the wastewater adjusting groove through a seventh valve. The utility model aims at providing a fluoride waste water deep purification and recovery system, ion exchange column goes out water discharge to reach standard in the system, makes the fluorine in desorbent and the regeneration raffinate then change into cryolite product retrieval and utilization simultaneously, carries out deep purification to fluoride waste water and handles.
Description
Technical Field
The utility model belongs to the technical field of sewage treatment, specifically be a fluoride waste water deep purification and recovery system.
Background
Fluorine (chemical symbol F) is a nonmetallic chemical element, is closely related to human health, and a proper amount of fluorine can promote calcification of teeth and bones and is beneficial to nerve excitation conduction and metabolism of enzymes in vivo, but excessive fluorine has serious harm to human bodies, soil and animals and plants. At present, the treatment method of the fluorine-containing wastewater mainly comprises a chemical precipitation method, a flocculation precipitation method, an adsorption method, a fluidized bed crystallization method, a reverse osmosis method, an electrocoagulation method and an ion exchange method. As early as the national emission Standard for pollutants from the inorganic chemical industry (GB 31573-2015) newly issued in 2015, the limit of the emission of fluoride ions in water is reduced from 10mg/L to 6 mg/L. Obviously, the traditional chemical precipitation and flocculation precipitation system cannot meet new discharge standards.
In addition, ion exchange is a common fluorine-containing wastewater deep purification system, but the existing ion exchange defluorination system has the key problems of poor resin adsorption selectivity, small adsorption capacity, difficult desorption liquid recycling, poor cycle performance and the like, and is not widely applied to the field of industrial fluorine-containing wastewater treatment. Therefore, an efficient and economic fluorine-containing wastewater deep purification system is urgently needed to be developed, and the concentration of fluorine ions in the effluent is ensured to be stably lower than 6mg/L so as to meet the increasingly strict requirements of the fluorine ion discharge standard.
SUMMERY OF THE UTILITY MODEL
The utility model aims at above problem, provide a fluoride waste water deep purification and recovery system, ion exchange column goes out water discharge to reach standard in this system, makes the fluorine in desorbent and the regeneration raffinate then change into cryolite product retrieval and utilization simultaneously, carries out deep purification to fluoride waste water and handles, solves the problem of knowing imbibition retrieval and utilization difficulty.
In order to realize the above purpose, the utility model adopts the technical scheme that: the system comprises a wastewater adjusting tank, an ion exchange column, a desorbent tank, a regenerant tank, a desorption liquid tank, a precipitant tank and a crystallization reaction tank, wherein the bottom of the wastewater adjusting tank is connected with an inlet pipeline of the ion exchange column through a first valve, the bottom of the desorbent tank is connected with the inlet pipeline of the ion exchange column through a second valve, and the bottom of the regenerant tank is connected with the inlet pipeline of the ion exchange column through a third valve; a drain valve is arranged on an outlet pipeline of the ion exchange column, the outlet is also connected with a desorption liquid tank pipeline through a fourth valve, and the bottom of the desorption liquid tank is connected with an internal pipeline above the crystallization reaction tank through a fifth valve; the precipitator groove is connected with an internal pipeline above the crystallization reaction groove through a sixth valve, a drain valve is arranged on a drain outlet pipeline at the bottom of the crystallization reaction groove, and the lower part of the side surface of the crystallization reaction groove is communicated with the wastewater adjusting groove through a seventh valve.
Further, the aluminum-loaded chelating resin filled in the ion exchange column is iminodiacetic acid type or aminophosphonic acid type resin.
Further, the desorbent contained in the desorbent tank is sodium hydroxide solution.
Further, the regenerant contained in the regenerant tank is one or more of an aluminum chloride solution and an aluminum sulfate solution.
Further, the precipitator contained in the precipitator tank is a mixed solution of sodium hydroxide and aluminum hydroxide.
Further, be equipped with agitating unit on the crystallization reaction tank, agitating unit includes motor and stirring thick liquid, the motor sets up in crystallization reaction tank top, the stirring thick liquid sets up in the crystallization reaction tank, and is connected with motor output shaft transmission through the pivot of vertical setting.
Further, the stirring paddle is spiral stirring paddle, and is arranged two layers from top to bottom in sequence on the rotating shaft, and the rotating directions are opposite, the acting force on the liquid is downward when the upper spiral stirring paddle is stirred, and the acting force on the liquid is upward when the lower spiral stirring paddle is stirred.
The utility model has the advantages that: effluent of an ion exchange column in the system reaches the standard and is discharged, and meanwhile, fluorine in the desorbent and the regenerated residual liquid is converted into cryolite products for recycling, so that the fluorine-containing wastewater is subjected to deep purification treatment, and the problem of difficulty in knowing imbibition recycling is solved.
1. The utility model discloses well ion exchange resin desorption is thorough, and recycling performance is good.
2. The utility model discloses well water fluoride ion concentration is stable discharges up to standard, satisfies the requirement of 6mg/L in the new standard.
3. The utility model discloses the fluorinion in the well fluoride waste water is finally retrieved with the form that the cryolite depositd, and fluorine recycle reaches 100%.
Drawings
Fig. 1 is a schematic view of the structure of the present invention.
The text labels in the figures are represented as: 1. a wastewater conditioning tank; 2. an ion exchange column; 3. a desorbent tank; 4. a regenerant tank; 5. a desorption liquid tank; 6. a precipitant tank; 7. a crystallization reaction tank; 8. a sewage inlet valve; 9. a first valve; 10. a second valve; 11. a third valve; 12. a fifth valve; 13. a sixth valve; 14. a seventh valve; 15. a drain valve; 16. a fourth valve; 17. a blowoff valve; 18. a motor; 19. and (4) stirring the slurry.
Detailed Description
In order to make the technical solution of the present invention better understood, the present invention is described in detail below with reference to the accompanying drawings, and the description of the present invention is only exemplary and explanatory, and should not be construed as limiting the scope of the present invention.
As shown in fig. 1, the specific structure of the present invention is: a fluorine-containing wastewater deep purification and recovery system comprises a wastewater adjusting tank 1, an ion exchange column 2 (which adopts a cylindrical exchange column, wherein a solution is introduced from one end of the column and is fully contacted with a fixed ion exchange resin layer in a compact state or an ion exchange resin bed in a flowing state to perform ion exchange), a desorbent tank 3, a regenerant tank 4, a desorption liquid tank 5, a precipitator tank 6 and a crystallization reaction tank 7, wherein the upper part of the wastewater adjusting tank 1 is connected with a fluorine-containing wastewater source pipeline through a sewage inlet valve 8, the bottom of the wastewater adjusting tank is connected with an inlet pipeline of the ion exchange column 2 through a first valve 9, aluminum-loaded chelating resin is filled in the ion exchange column 2, the bottom of the desorbent tank 3 is connected with the inlet pipeline of the ion exchange column 2 through a second valve 10, and the bottom of the regenerant tank 4 is connected with the inlet pipeline of the ion exchange column 2 through a third valve 11; a drain valve 15 is arranged on an outlet pipeline of the ion exchange column 2, the outlet is also connected with a desorption liquid tank 5 through a fourth valve 16, and the bottom of the desorption liquid tank 5 is connected with an internal pipeline above the crystallization reaction tank 7 through a fifth valve 12; the precipitator tank 6 is connected with an internal pipeline above the crystallization reaction tank 7 through a sixth valve 13, a drain valve 17 is arranged on a drain outlet pipeline at the bottom of the crystallization reaction tank 7, the lower part of the side surface (communicated with the inside) is communicated with the wastewater adjusting tank 1 through a seventh valve 14, and a conveying pump is preferably arranged on all connecting pipelines.
Preferably, the aluminum-loaded chelating resin filled in the ion exchange column 2 is an iminodiacetic acid type or an aminophosphonic acid type resin. The iminodiacetic acid or the aminophosphoric acid has stronger matching capacity with aluminum, and the stability of the resin loaded with aluminum is better.
Preferably, the desorbent contained in the desorbent tank 3 is sodium hydroxide solution. The sodium hydroxide solution can completely desorb the fluoride ions adsorbed on the aluminum-loaded resin into desorption liquid in the form of fluorine-aluminum complex, and the desorption liquid contains Al3+、F-And Na+Is compatible with cryolite (Na)3AlF6) So that the desorption liquid can be used for recovering the cryolite.
Preferably, the regenerant contained in the regenerant tank 4 is one or more of an aluminum chloride solution and an aluminum sulfate solution. The regenerant must be an aluminum-containing solution, wherein the aluminum chloride and aluminum sulfate solutions are cheap, readily available and easy to prepare and are suitable as the regenerant.
Preferably, the precipitant contained in the precipitant tank 6 is a mixed solution of sodium hydroxide and aluminum hydroxide. The desorption liquid contains F in large amount-And a small amount of Al3+、Na+The precipitant is reacted with the desorption solution to form cryolite (Na)3AlF6) Precipitating, the precipitant must be supplemented with cationic Al3+And Na+And does not contain Cl-、SO4 2-And the precipitant can only be prepared by mixing sodium hydroxide and aluminum hydroxide.
Preferably, a stirring device is arranged on the crystallization reaction tank 7 and comprises a motor 18 and a stirring paddle 19, the motor 18 is arranged above the crystallization reaction tank 7, and the stirring paddle 19 is arranged in the crystallization reaction tank 7 and is in transmission connection with an output shaft of the motor 18 through a vertically arranged rotating shaft. When the output shaft of the motor 18 drives the stirring paddle 19 to rotate, the solution is stirred to fully react.
Preferably, the stirring paddle 19 is a spiral stirring paddle, and is sequentially provided with two layers from top to bottom on the rotating shaft, and the rotating directions are opposite, the acting force on the liquid is downward when the upper layer spiral stirring paddle is stirred, and the acting force on the liquid is upward when the lower layer spiral stirring paddle is stirred. When stirring, the upper and lower layer solutions form convection, so that the reaction is more complete and thorough.
When the system is used specifically, the operation process of the system is as follows: a. an adsorption stage; b. a desorption phase; c. a regeneration stage; d. and (5) a crystallization recycling stage. Wherein, the stages a to c are a cycle operation process, and the stage d is a batch operation process.
a. An adsorption stage: the ion exchange column 2 is filled with iminodiacetic acid type aluminum-carrying chelating resin, a second valve 10, a third valve 11 and a fourth valve 16 which are connected with the ion exchange column 2 are closed, the fluorine-containing wastewater in the wastewater adjusting tank 1 enters from the upper part of the ion exchange column 2 through a first valve 9, the flow rate of the fluorine-containing wastewater is controlled to be 6m/h, the fluorine-containing wastewater is treated by utilizing the ion exchange column 2 filled with the aluminum-carrying chelating resin, the high-efficiency and selective adsorption of fluorine in the aqueous solution is realized by depending on the strong matching capability between aluminum ions and fluorine ions, the concentration of fluorine ions in the effluent is ensured to reach the standard and be discharged, and the effluent reaching the standard is discharged from a drain valve 15 at the lower part of the ion exchange column.
b. A desorption stage: closing the third valve 11 and the drain valve 15, opening the second valve 10 and the fourth valve 16, filling the sodium hydroxide solution in the desorbent tank 3, wherein the sodium hydroxide solution enters from the upper part of the ion exchange column 2 through the second valve 10, controlling the flow rate of the desorbent to be 1m/h, the aluminum loaded on the aluminum-loaded chelating resin can be completely desorbed and enter into the desorption mixed solution, fully desorbing fluorine on the resin into the solution through the sodium hydroxide, ensuring the complete desorption of the resin, and discharging the desorption mixed solution from the fourth valve 16 at the lower part of the ion exchange column 2 and entering into the desorption liquid tank 5.
c. A regeneration stage: closing the first valve 9, the second valve 10 and the drain valve 15, opening the third valve 11 and the fourth valve 16, filling the regenerant (aluminum chloride solution) in the regenerant tank 4, regenerating the aluminum salt solution to saturate the aluminum on the resin, feeding the regenerant from the upper part of the ion exchange column 2 through the third valve 11, controlling the flow rate of the regenerant to be 1m/h, leading the aluminum ions on the aluminum-loaded chelate resin to reach the reloading saturation and to reach the use requirement of the adsorption stage, and discharging the regenerated residual liquid formed as a result from the fourth valve 16 at the lower part of the ion exchange column 2 into the desorption liquid tank 5.
d. A crystallization recycling stage: a precipitator (a mixed solution of sodium hydroxide and aluminum hydroxide, the molar ratio of the mixed solution Na to Al is 3.3: 1) is filled in the precipitator tank 6, the solutions in the desorption liquid tank 5 and the precipitator tank 6 are respectively added into the crystallization reaction tank 7 through a fifth valve 12 and a sixth valve 13, a double-layer stirring paddle 19 is arranged in the crystallization reaction tank 7, the stirring time is controlled for 2 hours, the reaction pH =5, after the reaction is finished, cryolite sludge and clear liquid are obtained, the stirring is stopped, the cryolite sludge is discharged from a drain valve 17 at the bottom of the crystallization reaction tank 7, and the clear liquid at the upper layer flows back into the wastewater adjusting tank 1 through a seventh valve 14, so that the closed-loop circulation treatment is realized.
Through above-mentioned system for fluoride waste water has obtained effective treatment, and 2 play water of ion exchange column discharge up to standard, and simultaneously, the fluorine in desorption liquid and the regeneration raffinate then changes into cryolite product retrieval and utilization, solves the problem of understanding imbibition retrieval and utilization difficulty, has realized the thorough recycle of fluorine.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The principles and embodiments of the present invention have been explained herein using specific examples, which are presented only to assist in understanding the methods and their core concepts. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes can be made without departing from the principle of the present invention, and the above technical features can be combined in a proper manner; the application of these modifications, variations or combinations, or the application of the concepts and solutions of the present invention in other contexts without modification, is not intended to be considered as a limitation of the present invention.
Claims (7)
1. The fluorine-containing wastewater deep purification and recovery system comprises a wastewater adjusting tank (1), an ion exchange column (2), a desorbent tank (3), a regenerant tank (4), a desorbent tank (5), a precipitant tank (6) and a crystallization reaction tank (7), and is characterized in that the bottom of the wastewater adjusting tank (1) is connected with an inlet pipeline of the ion exchange column (2) through a first valve (9), the bottom of the desorbent tank (3) is connected with the inlet pipeline of the ion exchange column (2) through a second valve (10), and the bottom of the regenerant tank (4) is connected with the inlet pipeline of the ion exchange column (2) through a third valve (11); a drain valve (15) is arranged on an outlet pipeline of the ion exchange column (2), the outlet is also connected with a desorption liquid tank (5) through a fourth valve (16), and the bottom of the desorption liquid tank (5) is connected with an internal pipeline above the crystallization reaction tank (7) through a fifth valve (12); the precipitator groove (6) is connected with an internal pipeline above the crystallization reaction groove (7) through a sixth valve (13), a drain valve (17) is arranged on a drain outlet pipeline at the bottom of the crystallization reaction groove (7), and the lower part of the side surface of the crystallization reaction groove is communicated with the wastewater adjusting groove (1) through a seventh valve (14).
2. The system for deeply purifying and recovering fluorine-containing wastewater according to claim 1, wherein the aluminum-loaded chelating resin filled in the ion exchange column (2) is an iminodiacetic acid type or an aminophosphonic acid type resin.
3. The system for deeply purifying and recovering fluorine-containing wastewater as claimed in claim 1, wherein the desorbent contained in the desorbent tank (3) is sodium hydroxide solution.
4. The system for deeply purifying and recovering fluorine-containing wastewater as claimed in claim 1, wherein the regenerant contained in the regenerant tank (4) is one or more of an aluminum chloride solution and an aluminum sulfate solution.
5. The system for deeply purifying and recycling fluorine-containing wastewater as claimed in claim 1, wherein the precipitant contained in said precipitant tank (6) is a mixed solution of sodium hydroxide and aluminum hydroxide.
6. The fluorine-containing wastewater deep purification and recovery system according to claim 1, wherein a stirring device is arranged on the crystallization reaction tank (7), the stirring device comprises a motor (18) and a stirring paddle (19), the motor (18) is arranged above the crystallization reaction tank (7), and the stirring paddle (19) is arranged in the crystallization reaction tank (7) and is in transmission connection with an output shaft of the motor (18) through a vertically arranged rotating shaft.
7. The system for deeply purifying and recycling fluorine-containing wastewater according to claim 6, wherein the stirring paddle (19) is a spiral stirring paddle, two layers are sequentially arranged on the rotating shaft from top to bottom, the rotating directions of the two layers are opposite, the acting force on the liquid is downward when the upper layer of spiral stirring paddle is stirred, and the acting force on the liquid is upward when the lower layer of spiral stirring paddle is stirred.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201920514320.7U CN209815855U (en) | 2019-04-16 | 2019-04-16 | Fluorine-containing wastewater deep purification and recovery system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201920514320.7U CN209815855U (en) | 2019-04-16 | 2019-04-16 | Fluorine-containing wastewater deep purification and recovery system |
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| CN209815855U true CN209815855U (en) | 2019-12-20 |
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| CN201920514320.7U Expired - Fee Related CN209815855U (en) | 2019-04-16 | 2019-04-16 | Fluorine-containing wastewater deep purification and recovery system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624387A (en) * | 2020-10-15 | 2021-04-09 | 北京朗新明环保科技有限公司 | Intelligent efficient defluorination system for mine water |
| CN112708776A (en) * | 2020-12-08 | 2021-04-27 | 长沙环境保护职业技术学院 | Method for simultaneously removing fluorine and chlorine from zinc electrolyte |
-
2019
- 2019-04-16 CN CN201920514320.7U patent/CN209815855U/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624387A (en) * | 2020-10-15 | 2021-04-09 | 北京朗新明环保科技有限公司 | Intelligent efficient defluorination system for mine water |
| CN112708776A (en) * | 2020-12-08 | 2021-04-27 | 长沙环境保护职业技术学院 | Method for simultaneously removing fluorine and chlorine from zinc electrolyte |
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Granted publication date: 20191220 |