CN109607909A - A kind of high ammonia nitrogen uranium containing manganese wastewater treatment method - Google Patents
A kind of high ammonia nitrogen uranium containing manganese wastewater treatment method Download PDFInfo
- Publication number
- CN109607909A CN109607909A CN201811425983.8A CN201811425983A CN109607909A CN 109607909 A CN109607909 A CN 109607909A CN 201811425983 A CN201811425983 A CN 201811425983A CN 109607909 A CN109607909 A CN 109607909A
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- Prior art keywords
- ammonia nitrogen
- wastewater treatment
- treatment method
- containing manganese
- uranium
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Classifications
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
-
- 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
- C02F2101/006—Radioactive compounds
Abstract
The present invention relates to a kind of high ammonia nitrogen uranium containing manganese wastewater treatment methods, comprising the following steps: (1) mixes quick lime with water, stir into even slurry shape and obtain lime slurry；(2) step (1) resulting sediment is returned again into step (1) in subsequent operation；(3) soluble carbonate salt is added into supernatant obtained by step (1), removes a certain amount of calcium ion；(4) by after the resulting filtrate ultrafiltration of step (3), it is passed through gaseous state film device；(5) step (4) resulting absorbing liquid is evaporated after being concentrated into saturated solution, crystallization obtains corresponding ammonium salt product, and crystalline mother solution merges evaporating, concentrating and crystallizing again with absorbing liquid next time.The present invention had both realized the removal of the harmful elements such as Manganese in Waste Water, uranium, ensure that the qualified discharge of waste water；The byproducts such as ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium phosphate and ammonium hydroxide can be made in the ammonia nitrogen in waste water again, realize the purpose of the recycling of waste.
Description
Technical field
The invention belongs to uranium resources to extract technical field of three-waste treatment, and in particular to a kind of high ammonia nitrogen uranium containing manganese wastewater treatment
Method.
Background technique
In the production technology of natural uranium, produce core pure compound from ore, by the broken mill of ore, leach, extract and
All multi-process such as purifying purification, can generate a large amount of radioactive wastewater.Often containing ammonia nitrogen, manganese ion, uranium element etc. in waste water
Objectionable impurities, and ammonia nitrogen concentration is higher sometimes, can reach 500mg/L or more, can neither return to production technology use, it can not
It is directly discharged into water pollution environment.Processing for such waste water also lacks cost-effective means at present, causes a large amount of height
The accumulation of ammonia nitrogen radioactive wastewater forms certain environmental risk.
Processing for uranium-bearing radioactive wastewater has membrane processing method, biological treatment, zeroth order iron-deoxidize, chemical precipitation
Method etc., but current membrane separating method, uranium concentration could be down to outlet standard by generally requiring multistage, and application cost is caused to increase
Add, and the concentrated water after gained separation also needs to be further processed；The main function of biomaterial is absorption, although one can be played
Fixed effect, but it is also only at the experimental study stage at present, it is difficult to fairly large application in a short time；Zero-valent Iron is suitable for micro
The removal of uranium, but it is higher to uranium-containing waste water water quality requirement, and also action time is relatively slow, and iron is also noted that in use process
Excessive oxidation.More mature at present, what is industrially generallyd use is mostly flocculent precipitation, i.e., is added into waste water solvable
Property molysite, add milk of lime, adjust the pH of waste water, make molysite formed flocculate, milk of lime sediment and molysite flocculate are common
Radioactive element uranium in absorption carrier band waste water, to reach removal effect, but it is generally higher to neutralize pH, so can generate a large amount of
Sediment.
Processing for high-concentration ammonia nitrogen in waste water, it is more mature at present using it is more be air stripping method and air lift
Method.Mechanism is that the pH of waste water is adjusted to alkalinity, converts ion state ammonium to free molecular state ammonia, and then passing to air will
Ammonia aeration carries away.In comparison, air- extraction uses steam, and stripping temperature is higher, and efficiency is higher, but energy consumption also substantially increases
Add.But two methods are typically only capable to the ammonia nitrogen in waste water being down to a certain concentration, it is difficult to directly reach outlet standard, it is also necessary to and
Other low-concentration ammonia-nitrogen processing methods combine, and lead to the tediously long complexity of process flow.And ammonia nitrogen removal efficiency impact factor is more,
Especially in winter, since temperature is lower, efficiency will be greatly reduced blow-off method, often will affect the normal operation of technique.Separately
Outside, the gas containing ammonia nitrogen cannot be directly discharged into atmosphere, it is necessary to be absorbed using absorbent, to guarantee that ammonia nitrogen is dense in efflux gas
That spends is up to standard, further increases the complexity of technique.
In general, the processing of the radioactive wastewater at present for not only uranium-bearing, manganese, but also containing ammonia nitrogen in high density lacks corresponding
Research, even more no molding processing technological flow cause the processing of such waste water to be difficult to implement, with the accumulation of rate of water added, ring
Border risk also gradually increases, and proposes further challenge to the construction of China's green uranium mine.
Summary of the invention
It is an object of the invention to: not only contain in ammonia nitrogen in high density, but also the Spent Radioactive water process of uranium-bearing for China and exists
The problem of, a kind of high ammonia nitrogen is developed from the introducing of new material in conjunction with the exploitation of new process and the optimization of traditional handicraft
The treatment process of uranium-containing waste water, guarantee discharged wastewater met the national standard while, realize waste water in useful constituent recycling, be China this
The processing of class radioactive wastewater provides a new way, to promote the construction of China's green uranium mine.
Technical scheme is as follows: a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, comprising the following steps:
(1) quick lime is mixed with water, stirs into even slurry shape and obtains lime slurry；Institute is added into handled waste water
Lime slurry is stated, pH to 11.5 or more is adjusted, is stirred to react 10min or more, slurry sedimentation separation respectively obtains supernatant and sinks
Slag；
(2) step (1) resulting sediment is returned again to step (1) in subsequent operation, utilization is wherein unreacted effective
Ingredient reduces reagent consumption, while being aged to sediment, reduces volume；After ageing 4 times, since the 5th, according to each
It is aged newly generated sediment quality, the sediment of corrresponding quality is discharged；
(3) soluble carbonate salt is added into supernatant obtained by step (1), removes a certain amount of calcium ion, keep calcium from
Sub- concentration is no more than 400mg/L, is stirred to react 10min, obtains slurry；Gained slurry by filtration is separated, filtrate and filter residue are obtained,
Filter residue is discharged；
(4) it after the resulting filtrate ultrafiltration of step (3), will be passed through gaseous state film device, both sides differential pressure of membrane is greater than 0.005Mpa, behaviour
Make temperature and maintain 5 DEG C or more, film absorbs side and makees absorbent with corresponding reagent；The absorbing liquid of high-concentration ammonia-nitrogen is obtained after processing and is gone
Except the waste water of ammonia nitrogen, ammonia nitrogen concentration is down to 10mg/L in waste water, utilizes outlet after sulphur acid for adjusting pH to 6-9；
(5) step (4) resulting absorbing liquid is evaporated after being concentrated into saturated solution, crystallization obtains corresponding ammonium salt and produces
Product, crystalline mother solution merge evaporating, concentrating and crystallizing again with absorbing liquid next time.
Preferably, in step (1), the Lime Quality percentage is 10%~20%.
Preferably, in step (1), in supernatant uranium concentration be down to 0.04mg/L hereinafter, manganese concentration be down to 0.5mg/L with
Under.
Preferably, in step (3), the soluble carbonate salt is sodium carbonate.
Preferably, in step (3), the soluble carbonate salt is potassium carbonate.
Preferably, in step (3), the additional amount of the soluble carbonate salt is to make the complete sedimentation theory dosage of calcium ion
1.0-1.5 times.
Preferably, in step (4), the gaseous state film device uses polypropylene hollow fiber membrane.
Preferably, in step (4), the gaseous state film device uses polytetrafluoroethylhollow hollow fiber membrane.
Preferably, in step (4), the corresponding solution is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, water.
Preferably, the evaporation and concentration uses mechanical steam recompression technology, controlled at 100 DEG C -110 DEG C.
Remarkable result of the invention is: high ammonia nitrogen uranium waste water precipitates pretreatment-clear liquid gas using invented lime white
State UF membrane ammonia nitrogen-ammonia nitrogen absorbing liquid MVR condensing crystallizing treatment process, in processed waste water uranium concentration be down to 0.04mg/L with
Under, manganese concentration is down to 0.5mg/L hereinafter, ammonia nitrogen concentration is down to 10mg/L or less.Both the harmful elements such as Manganese in Waste Water, uranium had been realized
Removal, ensure that the qualified discharge of waste water；Ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium phosphate can be made in the ammonia nitrogen in waste water again
And the byproducts such as ammonium hydroxide, realize the purpose of the recycling of waste.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of high ammonia nitrogen uranium containing manganese wastewater treatment method of the present invention.
Specific embodiment
With reference to the accompanying drawing and specific embodiment is to a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method work of the present invention
It is further described.
The present invention is first turned up wastewater pH, manganese ion is made to be converted into manganous hydroxide for waste water not only uranium-bearing but also the characteristic containing manganese,
Again by stirring action, manganous hydroxide is quickly oxidized to hydrated manganese oxide flocky precipitate using oxygen, and the pH being added is adjusted
Agent-milk of lime carries the uranium in removal waste water jointly, to together remove uranium manganese from solution.Ammonia nitrogen in waste water at this time
As the raising of pH has been converted into free NH3, free NH will be contained3Waste water introduce hydrophobic gas film, by film two sides NH3Point
Pressure difference makes free NH3It is diffused into the other side from high concentration side across gas film, recycles respective absorption agent to absorb, absorbs
Concentrated solution afterwards is concentrated using mechanical steam recompression technology (MVR) and corresponding product is made, thus complete the removal of ammonia nitrogen with
Recycling.
A kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, comprising the following steps:
(1) quick lime is mixed with water, stirs into even slurry shape and obtains lime slurry；Institute is added into handled waste water
Lime slurry is stated, pH to 11.5 or more is adjusted, is stirred to react 10min or more, slurry sedimentation separation respectively obtains supernatant and sinks
Slag；
(2) step (1) resulting sediment is returned again to step (1) in subsequent operation, utilization is wherein unreacted effective
Ingredient reduces reagent consumption, while being aged to sediment, reduces volume；After ageing 4 times, since the 5th, according to each
It is aged newly generated sediment quality, the sediment of corrresponding quality is discharged；
(3) soluble carbonate salt is added into supernatant obtained by step (1), removes a certain amount of calcium ion, keep calcium from
Sub- concentration is no more than 400mg/L, is stirred to react 10min, obtains slurry；Gained slurry by filtration is separated, filtrate and filter residue are obtained,
Filter residue is discharged；
(4) it after the resulting filtrate ultrafiltration of step (3), will be passed through gaseous state film device, both sides differential pressure of membrane is greater than 0.005Mpa, behaviour
Make temperature and maintain 5 DEG C or more, film absorbs side and makees absorbent with corresponding reagent；The absorbing liquid of high-concentration ammonia-nitrogen is obtained after processing and is gone
Except the waste water of ammonia nitrogen, ammonia nitrogen concentration is down to 10mg/L in waste water, utilizes outlet after sulphur acid for adjusting pH to 6-9；
(5) step (4) resulting absorbing liquid is evaporated after being concentrated into saturated solution, crystallization obtains corresponding ammonium salt and produces
Product, crystalline mother solution merge evaporating, concentrating and crystallizing again with absorbing liquid next time.
Preferably, in step (1), the Lime Quality percentage is 10%~20%.
Preferably, in step (1), in supernatant uranium concentration be down to 0.04mg/L hereinafter, manganese concentration be down to 0.5mg/L with
Under.
Preferably, in step (3), the soluble carbonate salt is sodium carbonate.
Preferably, in step (3), the soluble carbonate salt is potassium carbonate.
Preferably, in step (3), the additional amount of the soluble carbonate salt is to make the complete sedimentation theory dosage of calcium ion
1.0-1.5 times.
Preferably, in step (4), the gaseous state film device uses polypropylene hollow fiber membrane.
Preferably, in step (4), the gaseous state film device uses polytetrafluoroethylhollow hollow fiber membrane.
Preferably, in step (4), the corresponding solution is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, water.
Preferably, the evaporation and concentration uses mechanical steam recompression technology, controlled at 100 DEG C -110 DEG C.
Specific embodiment
The present invention is described further with reference to the accompanying drawings and examples.Respectively different to component three in implementation process
Class waste water has carried out treatment research, and the concrete composition of waste water is shown in Table 1.The sediment return of waste water lime sedimentation gained follows in treatment process
After recycling 4 times, since the 5th, later by newly generated sediment quality is recycled every time, corrresponding quality sediment is discharged in ring；Carbonic acid
Salt deliming is stirred to react the time as 10min；Except ammonia nitrogen gaseous state membrane area 1.5m2, 100-110 DEG C of MVR thickening temperature, remaining technique
Condition and it the results are shown in Table 2.
1 waste water main component mg/L of table
| Component | Ammonia nitrogen | Na+ | Mg2+ | Ca2+ | Mn2+ | U | SO4 2- | NO3 - |
| 1 class | 4256 | 182 | 81.4 | 558 | 45 | 2.45 | 1483 | 19725 |
| 2 classes | 1483 | 134 | 58 | 480 | 34 | 1.61 | 1443 | 6929 |
| 3 classes | 515 | 95 | 62 | 510 | 21 | 0.82 | 1340 | 2788 |
The high ammonia nitrogen uranium-bearing manganese wastewater treatment test condition of table 2 and result
Above-described embodiment is only of the invention more excellent as a result, still the present invention is not limited to above-described embodiment,
It within the knowledge of a person skilled in the art, can also be in the premise for not departing from present inventive concept
Under make corresponding combination variation.
Claims (10)
1. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, which comprises the following steps:
(1) quick lime is mixed with water, stirs into even slurry shape and obtains lime slurry；The stone is added into handled waste water
Grey slurry adjusts pH to 11.5 or more, is stirred to react 10min or more, slurry sedimentation separation respectively obtains supernatant and sediment；
(2) step (1) resulting sediment is returned again to step (1) in subsequent operation, utilization wherein unreacted effective component,
Reagent consumption is reduced, while sediment is aged, reduces volume；It is new according to each ageing since the 5th after ageing 4 times
The sediment quality of generation, is discharged the sediment of corrresponding quality；
(3) soluble carbonate salt is added into supernatant obtained by step (1), removes a certain amount of calcium ion, keep calcium ion dense
Degree is no more than 400mg/L, is stirred to react 10min, obtains slurry；Gained slurry by filtration is separated, filtrate and filter residue are obtained, will be filtered
Slag discharge；
(4) it after the resulting filtrate ultrafiltration of step (3), will be passed through gaseous state film device, both sides differential pressure of membrane is greater than 0.005Mpa, operation temperature
Degree maintains 5 DEG C or more, and film absorbs side and makees absorbent with corresponding reagent；The absorbing liquid and removal ammonia of high-concentration ammonia-nitrogen are obtained after processing
The waste water of nitrogen, ammonia nitrogen concentration is down to 10mg/L in waste water, utilizes outlet after sulphur acid for adjusting pH to 6-9；
(5) step (4) resulting absorbing liquid being evaporated after being concentrated into saturated solution, crystallization obtains corresponding ammonium salt product,
Crystalline mother solution merges evaporating, concentrating and crystallizing again with absorbing liquid next time.
2. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, it is characterised in that: in step (1), the Lime Quality percentage
Than being 10%~20%.
3. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, it is characterised in that: in step (1), uranium concentration is down in supernatant
0.04mg/L is hereinafter, manganese concentration is down to 0.5mg/L or less.
4. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, it is characterised in that: in step (3), the soluble carbonate salt is
Sodium carbonate.
5. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, it is characterised in that: in step (3), the soluble carbonate salt is
Potassium carbonate.
6. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, it is characterised in that: in step (3), the soluble carbonate salt
Additional amount is 1.0-1.5 times for making the complete sedimentation theory dosage of calcium ion.
7. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, it is characterised in that: in step (4), the gaseous state film device is used
Polypropylene hollow fiber membrane.
8. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, it is characterised in that: in step (4), the gaseous state film device is used
Polytetrafluoroethylhollow hollow fiber membrane.
9. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, it is characterised in that: in step (4), the corresponding solution be sulfuric acid,
Hydrochloric acid, nitric acid, phosphoric acid, water.
10. a kind of high ammonia nitrogen uranium containing manganese wastewater treatment method, it is characterised in that: in step (5), the evaporation and concentration uses machine
Tool formula steam recompression technology, controlled at 100 DEG C -110 DEG C.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018223A (en) * | 2019-12-26 | 2020-04-17 | 湖南中核金原新材料有限责任公司 | Method for realizing zero discharge of wastewater in process of producing rare earth chloride from monazite |
| CN111115934A (en) * | 2019-12-20 | 2020-05-08 | 中轻建设(安徽)设计工程有限公司 | Desulfurization ammonia nitrogen wastewater treatment method |
| CN111606487A (en) * | 2020-05-27 | 2020-09-01 | 长沙矿冶研究院有限责任公司 | Method for continuously treating and recycling manganese and ammonia nitrogen resources from electrolytic manganese wastewater |
| CN111635086A (en) * | 2020-07-14 | 2020-09-08 | 常州时升环境工程科技有限公司 | Zero discharge system for producing ammonium salt from ammonia nitrogen-containing wastewater and treatment process thereof |
| CN113526635A (en) * | 2021-08-27 | 2021-10-22 | 南华大学 | Method for treating uranium tailing pond percolation water by recycling neutralized precipitation slag |
| CN113707352A (en) * | 2021-01-12 | 2021-11-26 | 核工业北京化工冶金研究院 | Method for treating radioactive comprehensive wastewater |
| CN113955872A (en) * | 2021-08-31 | 2022-01-21 | 江西盖亚环保科技有限公司 | Harmless and resource recycling treatment process for electrolytic manganese slag leachate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115934A (en) * | 2019-12-20 | 2020-05-08 | 中轻建设(安徽)设计工程有限公司 | Desulfurization ammonia nitrogen wastewater treatment method |
| CN111018223A (en) * | 2019-12-26 | 2020-04-17 | 湖南中核金原新材料有限责任公司 | Method for realizing zero discharge of wastewater in process of producing rare earth chloride from monazite |
| CN111606487A (en) * | 2020-05-27 | 2020-09-01 | 长沙矿冶研究院有限责任公司 | Method for continuously treating and recycling manganese and ammonia nitrogen resources from electrolytic manganese wastewater |
| CN111635086A (en) * | 2020-07-14 | 2020-09-08 | 常州时升环境工程科技有限公司 | Zero discharge system for producing ammonium salt from ammonia nitrogen-containing wastewater and treatment process thereof |
| CN113707352A (en) * | 2021-01-12 | 2021-11-26 | 核工业北京化工冶金研究院 | Method for treating radioactive comprehensive wastewater |
| CN113526635A (en) * | 2021-08-27 | 2021-10-22 | 南华大学 | Method for treating uranium tailing pond percolation water by recycling neutralized precipitation slag |
| CN113955872A (en) * | 2021-08-31 | 2022-01-21 | 江西盖亚环保科技有限公司 | Harmless and resource recycling treatment process for electrolytic manganese slag leachate |
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Application publication date: 20190412 |
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| RJ01 | Rejection of invention patent application after publication |