CN109851132A - A method of recycling ice crystal, fluorite and ammonium sulfate from the high ammonia nitrogen acid waste water of high fluorine - Google Patents
A method of recycling ice crystal, fluorite and ammonium sulfate from the high ammonia nitrogen acid waste water of high fluorine Download PDFInfo
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Abstract
The method that the invention discloses a kind of to recycle ice crystal, fluorite and ammonium sulfate from the high ammonia nitrogen acid waste water of high fluorine, described method includes following steps: (1) pH that acid-base reagent adjusts the high ammonia nitrogen acid waste water of high fluorine is added, waste water is heated, aluminum sulfate is added to be stirred to react, sodium sulphate is added to be stirred to react, filtering, obtains ice crystal and solution A；(2) reagent is added and the pH of solution A is adjusted to 8~9, add calcium sulfate, be stirred to react, filter to obtain calcium fluoride precipitate and solution B；(3) aluminum sulfate is added in solution B, is stirred to react 2h, filters, obtains precipitating S1 and solution C；(4) pH in solution C is adjusted to 5~6 with sulfuric acid, ammonium sulfate crystallization can be obtained in concentration.The present invention provides not only a kind of new high fluorine fluoride waste technique of processing, has that process conditions are simple, are easy to control, it can be achieved that workshop handles mass.
Description
Technical field
The present invention relates to high fluoric acid field of waste water treatment, return from the high ammonia nitrogen acid waste water of high fluorine more particularly, to one kind
The method of ice collection spar, fluorite and ammonium sulfate.
Background technique
With the development of industry, the discharge amount of fluoride waste is more and more, brings more harm to environment.It is related to fluorine-containing
The industry of waste water mainly includes the traditional industries such as metal smelt, plating, pesticide, and the fluorine in these fluoride wastes is mainly with fluorination
The forms such as object, hydrofluoric acid and fluosilicic acid exist, and fluorinated volume height is different in all kinds of waste water.A large amount of rows of industrial fluoride waste
It puts, not only pollutes environment, can also jeopardize the growth and development of plant and animal, it is strong that human body is finally jeopardized finally by food chain
Health.If it is excessively high to take in fluorine content, it will lead to fluorine spot odontopathy, fluorosis of bone, cause injury of kidney.In order to avoid fluorine is caused by human body
Strict control has been done to fluorinated volume in industrial wastewater by harm, China, and industrial discharge fluorine in wastewater content must not exceed 6mg/L.
The processing method of fluoride waste mainly includes the methods of chemical precipitation method, absorption method, reverse osmosis and electrodialysis.Change
The precipitation method are learned using more mainly calcium precipitation, that is, adds calcium salt and forms calcium fluoride precipitate into fluoride waste and reach
Except F-Purpose, but need to be added excessive calcium salt in the method treatment process, the precipitating sludge formed after reaction is more and is mixed
Sludge is closed, is worth low；Absorption method is to utilize F in adsorbent absorption fluoride waste-, since adsorbance is limited, can only handle lower
The fluoride waste of concentration, and being passed through again using needs for adsorbent is reprocessed；Hyperfiltration be under conditions of enough pressure,
Water is separated from fluoride waste using reverse osmosis membrane, electrodialysis is made under the action of external electric field using permselective membrane
F in waste water-Pass through, to achieve the purpose that fluorine removal, both the above method equipment investment cost is big, more demanding to film.
Ice crystal is mainly used as the fluxing agent of aluminium metallurgy, the wear-resistant filler of rubber, grinding wheel, enamel opalizer, glass and wards off
The opacifier and fluxing agent of porcelain production, the agrochemical of crops；Fluorite mainly produces fluorochemical on chemical industry
Primary raw material, such as hydrofluoric acid, aluminum fluoride, in addition to this, fluorite is widely used in the works such as metallurgy, cement, glass, ceramics
Industry；Ammonium sulfate is mainly the raw materials of industry such as agricultural fertilizer and chemical industry, dyeing and weaving, medicine, leather, also acts as fertilizer, welding agent, fabric
Fireproof agent, pharmaceutically makees salting-out agents, osmotic pressure regulator etc., and the sulphur ammonium (ammonium sulfate) of purification can be used for the manufacture of beer.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides one kind from the high ammonia nitrogen acid waste water of high fluorine
The method of middle recycling ice crystal, fluorite and ammonium sulfate.The present invention provides not only a kind of new processing fluoride waste technique, simultaneously
It can be recycled in treatment process and obtain valuable ice crystal, fluorite and ammonium sulfate.The present invention is simple with process conditions, is easy control
System is, it can be achieved that workshop handles mass.
Technical scheme is as follows:
A method of recycling ice crystal, fluorite and ammonium sulfate from the high ammonia nitrogen acid waste water of high fluorine, the method includes
Following steps:
(1) acid-base reagent is added and the pH of the high ammonia nitrogen acid waste water of high fluorine is adjusted to certain end point values, waste water is heated, be added
It after aluminum sulfate is stirred to react a period of time, adds sodium sulphate and is stirred to react, filter, obtain ice crystal and solution A；
(2) reagent is added and the pH of solution A is adjusted to 8~9, then calcium sulfate is added in solution A, be stirred to react, make solution A
In free F-It is converted into calcium fluoride precipitate and solution B；
(3) aluminum sulfate is added in solution B, is stirred to react, for residual F in adsorbent solution-, filter, obtain precipitating S1
And solution C；
(4) pH in solution C is adjusted to 5~6 with sulfuric acid, ammonium sulfate crystallization can be obtained in concentration.
Step (1) the soda acid agent is ammonium hydroxide or sulfuric acid, and the selection of ammonium hydroxide or sulfuric acid depends on stoste pH value.
Step (1) endpoint pH is 3~4.
Step (1) heating temperature is 70~80 DEG C.
Step (1) described aluminum sulfate be stirred to react the time be 15~20min, sodium sulphate be stirred to react the time be 45~
60min。
Aluminum sulfate described in step (1) and fluorine in wastewater molar ratio are 1:12；Sodium sulphate and fluorine in wastewater molar ratio are 1:
4。
Addition reagent described in step (2) is ammonium hydroxide；The time is stirred to react after calcium sulfate is added as 2h.
The dosage of calcium sulfate described in step (2) is added according to molar ratio F:Ca=1:1.
The dosage of aluminum sulfate described in step (3) is added according to molar ratio F:Al=1:6, reaction time 2h.
The present invention is beneficial to be had the technical effect that
The present invention makes full use of the F in high ammonia nitrogen and high fluorine waste water-And NH4 +, reagent is added by substep and obtains corresponding product,
It not only disposes waste water effectively, while realizing that waste water reclaiming obtains value product；Compared to traditional fluorine removal side
Method, the used amount of reagent of the method is less, and cost of disposal is low, and treatment process is simple, and batch processing may be implemented；Fluorine removal process
The ice crystal of middle generation is the cosolvent for smelting aluminium, will not only generate fluoride pollution caused by secondary fluorine-containing sludge, also solve
Current ice crystal problem in short supply.
Detailed description of the invention
Fig. 1 is present invention process flow diagram.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1
Water sample component index is handled in the implementation case are as follows: F concentration is 25.28g/L, pH 3.7, and ammonia-nitrogen content is
26.575g/L specific processing step is as follows.
(1) water sample pH is adjusted to 3 with sulfuric acid, is heated to 70 DEG C, addition 36.9g aluminum sulfate is stirred to react after 15min to be added again
Enter 23.61g sodium sulphate and be stirred to react 45min, 46.7g ice crystal (aqueous) and solution A are obtained after filtering；
(2) pH of solution A is adjusted to 9 with ammonium hydroxide, 7.1g calcium sulfate (F:Ca=1:1) is added in solution A, is stirred to react
2h makes the free F in solution A-It is converted into calcium fluoride precipitate, 8.93g calcirm-fluoride and solution B can be obtained in filtering；
(3) 5.89g aluminum sulfate (F:Al=1:6) is added in solution B and is stirred to react residual F in 2h adsorbent solution B-, mistake
Filter obtains precipitating S1 and solution C, measures the residual F in solution C-Content is 1.23ppm；
(4) 2ml sulfuric acid is added, the pH of solution C is adjusted to 6,129.28g ammonium sulfate crystallization can be obtained in evaporation, and ammonium sulfate is pure
Degree is 99%；
(5) after step (1) and step (2) processing, the fluorine in wastewater rate of recovery is up to 98%.
Embodiment 2
Water sample component index is handled in the implementation case are as follows: F concentration is 25.28g/L, pH 3.7, and ammonia-nitrogen content is
26.575g/L specific processing step is as follows.
(1) it keeps the original pH of waste water constant, is heated to 75 DEG C, be added after 36.9g aluminum sulfate is stirred to react 15min and add
23.61g sodium sulphate is stirred to react 50min, and 46.7g ice crystal (aqueous) and solution A are obtained after filtering；
(2) pH of solution A is adjusted to 8 with concentrated ammonia liquor, 7.1g calcium sulfate (F:Ca=1:1) is added in solution A, stirring is anti-
2h is answered, the free F in solution A is made-It is converted into calcium fluoride precipitate, 8.93g calcirm-fluoride and solution B can be obtained in filtering；
(3) 5.89g aluminum sulfate (F:Al=1:6) is added in solution B and is stirred to react residual F in 2h adsorbent solution B-, mistake
Filter obtains precipitating S1 and solution C, measures the residual F in solution C-Content is 1.5ppm；
(4) 2.5ml sulfuric acid is added, the pH of solution C is adjusted to 5.5,129.28g ammonium sulfate crystallization, sulfuric acid can be obtained in evaporation
Ammonium purity is 99%；
(5) after step (1) and step (2) processing, the fluorine in wastewater rate of recovery is up to 98%.
Embodiment 3
Water sample component index is handled in the implementation case are as follows: F concentration is 25.28g/L, pH 3.7, and ammonia-nitrogen content is
26.575g/L specific processing step is as follows.
(1) pH of water sample is adjusted to 4 or so with ammonium hydroxide, is heated to 80 DEG C, 36.9g aluminum sulfate is added and is stirred to react 20min
After add 23.61g sodium sulphate be stirred to react 60min filtering after obtain 46.7g ice crystal (aqueous) and solution A；
(2) pH of solution A is adjusted to 9 with concentrated ammonia liquor, 7.1g calcium sulfate (F:Ca=1:1) is added in solution A, stirring is anti-
2h is answered, the free F in solution A is made-It is converted into calcium fluoride precipitate, 8.93g calcirm-fluoride and solution B can be obtained in filtering；
(3) 5.89g aluminum sulfate (F:Al=1:6) is added in solution B and is stirred to react residual F in 2h adsorbent solution B-, mistake
Filter obtains precipitating S1 and solution C, measures the residual F in solution C-Content is 1.3ppm；
(4) 3ml sulfuric acid is added, the pH of solution C is adjusted to 5,129.28g ammonium sulfate crystallization can be obtained in evaporation, and ammonium sulfate is pure
Degree is 99%；
(5) after step (1) and step (2) processing, the fluorine in wastewater rate of recovery is up to 98%.
Claims (9)
1. a kind of method for recycling ice crystal, fluorite and ammonium sulfate from the high ammonia nitrogen acid waste water of high fluorine, which is characterized in that described
Method includes the following steps:
(1) acid-base reagent is added and the pH of the high ammonia nitrogen acid waste water of high fluorine is adjusted to certain end point values, waste water is heated, sulfuric acid is added
It after aluminium is stirred to react a period of time, adds sodium sulphate and is stirred to react, filter, obtain ice crystal and solution A；
(2) reagent is added and the pH of solution A is adjusted to 8~9, then calcium sulfate is added in solution A, be stirred to react, make in solution A
Free F-It is converted into calcium fluoride precipitate and solution B；
(3) aluminum sulfate is added in solution B, is stirred to react, for residual F in adsorbent solution-, filter, obtain precipitating S1 and solution
C；
(4) pH in solution C is adjusted to 5~6 with sulfuric acid, ammonium sulfate crystallization can be obtained in concentration.
2. the method according to claim 1, wherein step (1) the soda acid agent be ammonium hydroxide or sulfuric acid, ammonium hydroxide or
The selection of sulfuric acid depends on stoste pH value.
3. the method according to claim 1, wherein step (1) endpoint pH is 3~4.
4. the method according to claim 1, wherein step (1) heating temperature is 70~80 DEG C.
5. the method according to claim 1, wherein step (1) described aluminum sulfate be stirred to react the time be 15~
20min, sodium sulphate are stirred to react the time as 45~60min.
6. the method according to claim 1, wherein aluminum sulfate described in step (1) and fluorine in wastewater molar ratio
For 1:12；Sodium sulphate and fluorine in wastewater molar ratio are 1:4.
7. the method according to claim 1, wherein addition reagent described in step (2) is ammonium hydroxide；Sulfuric acid is added
It is 2h that the time is stirred to react after calcium.
8. the method according to claim 1, wherein the dosage of calcium sulfate described in step (2) is according to molar ratio
F:Ca=1:1 addition.
9. the method according to claim 1, wherein the dosage of aluminum sulfate described in step (3) is according to molar ratio
F:Al=1:6 addition, reaction time 2h.
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Cited By (3)
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| CN110937742A (en) * | 2019-12-05 | 2020-03-31 | 无锡中天固废处置有限公司 | Method for treating and recycling high-fluorine high-ammonia nitrogen waste liquid |
| CN112520924A (en) * | 2020-10-12 | 2021-03-19 | 九江学院 | Recycling and resource treatment method for alkaline wastewater in tantalum-niobium hydrometallurgy |
| CN113501599A (en) * | 2021-08-11 | 2021-10-15 | 龙岩学院 | Method for treating fluorine-containing wastewater |
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Application publication date: 20190607 |