CN109250842A - A kind of method and process system of fluorine-containing industrial waste water with high ammoniac nitrogen circular treatment - Google Patents
A kind of method and process system of fluorine-containing industrial waste water with high ammoniac nitrogen circular treatment Download PDFInfo
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- CN109250842A CN109250842A CN201811170338.6A CN201811170338A CN109250842A CN 109250842 A CN109250842 A CN 109250842A CN 201811170338 A CN201811170338 A CN 201811170338A CN 109250842 A CN109250842 A CN 109250842A
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- fluorine
- ammonia
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- industrial waste
- magnesium
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/586—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The present invention provides a kind of circular treatment new method for removing fluorine ion and ammonia in fluorine-containing industrial waste water with high ammoniac nitrogen simultaneously, fluorine removal medicament reduces dosing type simultaneously for precipitating except ammonia provides phosphorus source, and it is low to be discharged remaining phosphorus concentration.Old brine is magnesium source after thermal power plant's magnesium processes desulfurization wastewater or salt lake can be used to mention potassium, and instead of conventional magnesium salts medicament, other industrial wastewaters are recycling in deamination technique by the treatment of wastes with processes of wastes against one another, realize the circular economy processing technique of sustainable development.Meanwhile the system of fluorine-containing industrial waste water with high ammoniac nitrogen circular treatment is provided, microwave radiation replaces traditional heating process, heating rate is fast, homogeneous heating, substantially shortens the pyrolysis time of guanite, it is high to decompose the ammonia concentration obtained, after acid recovery, can get the ammonia salt solution of higher concentration.The investment of a whole set of fluorine-containing industrial waste water with high ammoniac nitrogen circulating treating system of the invention and operating cost are low, are discharged fluorine ion after processing and ammonia nitrogen concentration stability, fluoride ion removing rate can reach 98%, ammonia nitrogen removal frank is up to 97% or more.
Description
Technical field
The present invention relates to Industrial Wastewater Treatment environmental technology fields, and in particular to a kind of fluorine-containing industrial waste water with high ammoniac nitrogen circulation
Processing method and process system, while flocculation sedimentation fluorine ion and guanite, recycle after microwave-heating, realize fluorine-containing height
The resource recycling of ammonia nitrogen industrial wastewater is handled.
Background technique
China's rapid economic development at present, the huge consumption of the simultaneous energy, environmental problem are also got worse.In order to
Current environment situation is set to be improved, country is also increasingly tighter to the management of " three wastes ".Fluoride pollution is main next in water environment
Source is fluorine-containing " three wastes " of industrial production discharge, and being related to industry mainly has aluminium electroloysis, steel, cement, brick and tile, ceramics, phosphate fertilizer, glass
Glass, semiconductor, pharmacy etc..Although fluorine is one of the essential trace elements of the human body, however, Excess free enthalpy will lead to fluorine poisoning, table
It is now different pathological changes, such as osteosclerosis, osteoporosis, osteomalacia and Secondary hyperparathyroidism osseous lesion
Deng.On the other hand, with industry sizes such as China's chemistry manufacturing industry, smelting and processing of metals industry, petrochemical processing industry and textile industries
It is rapidly developed, the discharge amount of ammonia nitrogen waste water also increasingly increases.Ammonia nitrogen is the common contaminant of water pollution, the presence of ammonia nitrogen
The oxygen in water can be largely consumed, water eutrophication is caused, leads to algae mass propagation, fish are a large amount of dead due to anoxic
It dies, to influence the development of living environment and aquatic products industry.
Such as, in the rare high-melting-point non-ferrous metal metallurgy such as tantalum, niobium or fluorine-containing coal mine drainage is a kind of to fluorine-containing ammonia nitrogen waste water
Compared with the complex industrial waste water that difficulty is set, usually using individual treatment process.The administering method of simple fluoride waste mainly has
Chemical precipitation method, absorption method, and freezing, ion exchange resin method for removing fluor, active carbon method for removing fluor, ultrafiltration method for removing fluor, electrodialysis
Because at high cost, low efficiency, Technical Economy are poor, less popularization.Processing to ammonia nitrogen waste water, blow-off method, ion are handed over
Changing method, biochemical method, chemical oxidization method, absorption method and chemical precipitation method etc. has many reports, especially magnesium phosphate ammonia precipitation (birds droppings
Stone) except the method for ammonia, it is the technology that the good feasibility of effect is high in practice.But the comprehensive treatment technique of fluorine-containing ammonia nitrogen waste water is answered
With being still short of, the adding of agent higher cost and poor continuity of technique are removed.
Summary of the invention
The contents of the present invention are to provide one kind can go Natural zeolite and the process integration except ammonia, the treatment of wastes with processes of wastes against one another, resource simultaneously
Change and mentions the old brine deamination of potassium using thermal power plant's magnesium processes desulfurization wastewater or salt lake；Cooperate microwave pyrolytic process simultaneously, realizes processing work
The cycle applications of skill.To solve the technical issues of fluorine-containing industrial waste water with high ammoniac nitrogen is handled simultaneously, the present invention uses a kind of fluorine-containing height
Ammonia nitrogen industrial wastewater circulating disposal process system, this system include raw water conditioning tank, Ca salt device, Mg salt device, mechanical acceleration
Clarifying basin, soda ash device, box microwave reactor, ammonia recycling device；For the operation steady in a long-term for guaranteeing this process system, go back
Including related matched cleaning system, dosing stocking system, suction pump, electrical system and blind controller system, it is characterised in that:
Raw water conditioning tank (101), Ca salt device (102), Mg salt device (103), effluent storage jar (104), mechanical acceleration are clear
Clear pond (105), clear water reserviors (106), soda ash device (107), box microwave reactor (108), ammonia recycling device (109) string
Connection can be taken off using same medicament realization precipitating fluorine removal and to provide phosphorus source except ammonia by adding magnesium salts or introducing thermal power plant's magnesium processes
Old brine after sulphur waste water/salt lake Potassium process provides magnesium source, generates magnesium ammonium phosphate (guanite) precipitating.
The technical scheme is that
(1) fluorine-containing high ammonia-nitrogen wastewater is introduced into conditioning tank (101) first, soda ash is added and adjusts wastewater pH to 8~10, will adjust later
It saves waste water in pond and introduces mechanical accelerating purifying pool (105), two water phosphorus are added by Ca salt device (102) and Mg salt device (103)
Sour hydrogen calcium (CaHPO4•2H2O) and magnesium salts, or introduce thermal power plant's magnesium processes desulfurization wastewater or salt lake mention after potassium old brine (104) and
Dicalcium phosphate dihydrate is added in waste water after being sufficiently mixed, adding of agent molar ratio is Ca2+:F-:Mg2+:NH4 +=(5~5.5): 1:(2
~2.5): 2, mechanical stirring accelerates 30~90 min of reaction, and reaction equation is as follows:
10CaHPO4•2H2O + 2F- → Ca10(PO4)6F2↓+ 4HPO4 2- + 6H+ + 20H2O (reaction 1)
Mg2+ + NH4 + + HPO4 2- + 6H2O → MgNH4PO4•6H2O + 6H+(reaction 2)
It ramps up by isolated clear water, is flowed out through catch basin, it is anti-that the solidliquid mixture of sinking by pump is transferred to box microwave
Answer device (108).
(2) after solidliquid mixture is placed in fluidisation microwave reactor, NH in molar ratio4 +:OH-=1:1 is added soda ash (107) and stirs
Microwave reactor is opened after mixing mixing, power setting is 0.4~0.5 KW, 10~20 min of microwave radiation, and mixture is dry to be divided
It solves the ammonia generated and recycling (109) in acid solution is passed through by the gas-guide tube of microwave reactor upper end.
The invention has the following advantages over the prior art:
(1) new method that is a kind of while removing fluorine ion and ammonia is provided, fluorine removal medicament subtracts simultaneously for precipitating except ammonia provides phosphorus source
It is low to be discharged remaining phosphorus concentration for few dosing type.
(2) old brine is magnesium source after the present invention mentions potassium using thermal power plant's magnesium processes desulfurization wastewater or salt lake, instead of conventional magnesium salts medicine
Other industrial wastewaters are recycling in deamination technique by agent, the treatment of wastes with processes of wastes against one another, realize the circular economy processing skill of sustainable development
Art.
(3) the present invention provides the system of fluorine-containing industrial waste water with high ammoniac nitrogen circular treatment, microwave radiation replaces traditional heating
Process, heating rate is fast, homogeneous heating, substantially shortens the pyrolysis time of guanite, and the ammonia concentration for decomposing acquisition is high, through peracid
After recycling, the ammonia salt solution of higher concentration can get.
(4) investment of a whole set of fluorine-containing industrial waste water with high ammoniac nitrogen circulating treating system and operating cost are low, and fluorine is discharged after processing
Ion and ammonia nitrogen concentration stability, fluoride ion removing rate can reach 98%, and ammonia nitrogen removal frank can reach 95% or more.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1.
First by 1 m3Ammonia nitrogen concentration is 500 mg/L, F-Concentration is that the waste water of 250 mg/L is added in raw water conditioning tank, so
PH to 8 is adjusted afterwards, waste water in conditioning tank is introduced into mechanical accelerating purifying pool later, by Ca2+:F-:Mg2+:NH4 +=5:1:2.5:2
90 min of medicament mechanic whirl-nett reaction is added, ramps up by isolated clear water, is flowed out through catch basin, the solidliquid mixture of sinking
Box microwave reactor is transferred to by pump.After the solidliquid mixture being pumped into is placed in fluidisation microwave reactor, NH in molar ratio4 +:
OH-=1:1, which is added after soda ash is stirred, opens microwave reactor, and power setting is 0.4 KW, 10 min of microwave radiation, mixing
The dry ammonia for decomposing generation of object is passed through in acid solution by the gas-guide tube of microwave reactor upper end to be recycled.It is tested through analysis, clearly
Ammonia nitrogen removal frank is up to 95%, F in water-For removal rate up to 92%, remaining phosphorus concentration is lower than 3%, ammonia release rate when magnesium ammonium phosphate microwave decomposition
It is 98%.
Embodiment 2.
First by 1 m3Ammonia nitrogen concentration is 500 mg/L, F-Concentration is that the waste water of 250 mg/L is added in raw water conditioning tank, so
PH to 10 is adjusted afterwards, waste water in conditioning tank is introduced into mechanical accelerating purifying pool later, by Ca2+:F-:Mg2+:NH4 +=5.5:1:
90 min of medicament mechanic whirl-nett reaction is added in 2.5:2, ramps up by isolated clear water, flows out through catch basin, the solid-liquid of sinking
Mixture is transferred to box microwave reactor by pump.The solidliquid mixture being pumped into be placed in fluidisation microwave reactor after, by mole
Compare NH4 +:OH-=1:1, which is added after soda ash is stirred, opens microwave reactor, and power setting is 0.4 KW, microwave radiation 10
Min, the dry ammonia for decomposing generation of mixture is passed through in acid solution by the gas-guide tube of microwave reactor upper end to be recycled.Through analyzing
Test, ammonia nitrogen removal frank is up to 97%, F in clear water-For removal rate up to 98%, remaining phosphorus concentration is lower than 3%, when magnesium ammonium phosphate microwave decomposition
Ammonia release rate is 98%.
Embodiment 3.
First by 1 m3Ammonia nitrogen concentration is 500 mg/L, F-Concentration is that the waste water of 250 mg/L is added in raw water conditioning tank, so
PH to 8 is adjusted afterwards, waste water in conditioning tank is introduced into mechanical accelerating purifying pool later, by Ca2+:F-:NH4 +Medicine is added in=5.5:1:2
Agent stirring, while introducing heat-engine plant wet flue gas magnesium processes desulfurization wastewater (Mg2+Concentration is 6532 mg/L) about 100 L, mechanical stirring
90 min are reacted, ramps up by isolated clear water, is flowed out through catch basin, the solidliquid mixture of sinking is transferred to box by pump
Microwave reactor.After the solidliquid mixture being pumped into is placed in fluidisation microwave reactor, NH in molar ratio4 +:OH-=1:1 is added soda ash and stirs
Microwave reactor is opened after mixing mixing, power setting is 0.4 KW, 10 min of microwave radiation, and mixture is dry to decompose the ammonia generated
Gas is passed through in acid solution by the gas-guide tube of microwave reactor upper end and is recycled.It is tested through analysis, ammonia nitrogen removal frank reaches in clear water
90%, F-For removal rate up to 95%, remaining phosphorus concentration is lower than 5%, and ammonia release rate is 98% when magnesium ammonium phosphate microwave decomposition.
Embodiment 4.
First by 1 m3Ammonia nitrogen concentration is 500 mg/L, F-Concentration is that the waste water of 250 mg/L is added in raw water conditioning tank, so
PH to 8 is adjusted afterwards, waste water in conditioning tank is introduced into mechanical accelerating purifying pool later, by Ca2+:F-:NH4 +Medicament is added in=5.5:1:2
Stirring, while introducing salt lake and mentioning the high old brine (Mg of magnesium after potassium2+Concentration is 461 g/L) about 1.4 L, mechanic whirl-nett reaction 90
Min is ramped up by isolated clear water, is flowed out through catch basin, and it is anti-that the solidliquid mixture of sinking by pump is transferred to box microwave
Answer device.After the solidliquid mixture being pumped into is placed in fluidisation microwave reactor, NH in molar ratio4 +:OH-=1:1 is added soda ash and is stirred
After open microwave reactor, power setting is 0.4 KW, 10 min of microwave radiation, and the dry ammonia generated that decomposes of mixture passes through
The gas-guide tube of microwave reactor upper end, which is passed through in acid solution, to be recycled.It is tested through analysis, ammonia nitrogen removal frank is up to 90%, F in clear water-It goes
Except rate is up to 95%, remaining phosphorus concentration is lower than 5%, and ammonia release rate is 98% when magnesium ammonium phosphate microwave decomposition.
Claims (3)
1. a kind of fluorine-containing industrial waste water with high ammoniac nitrogen circulation process method, which comprises the following steps:
(1) fluorine-containing high ammonia-nitrogen wastewater is introduced into conditioning tank, soda ash is added and adjusts wastewater pH to 8~10；
(2) waste water in conditioning tank is introduced into mechanical accelerating purifying pool, hydrogen phosphate dihydrate is added by Ca salt device and Mg salt device
Calcium (CaHPO4•2H2O) and magnesium salts, adding of agent molar ratio are Ca2+:F-:Mg2+:NH4 +=(5~5.5): 1:(2~2.5): 2, machine
Tool stirring accelerates 30~90 min of reaction to ramp up by isolated clear water, flow out through catch basin after reaction；
(3) solidliquid mixture to sink is transferred to box microwave reactor by pump, in molar ratio NH4 +:OH-Soda ash is added in=1:1
Microwave reactor is opened after mixing evenly, and power setting is 0.4~0.5 kW, 10~20 min of microwave radiation, mixture drying
It decomposes the ammonia generated and ammonia recycling device is passed through by the gas-guide tube of microwave reactor upper end.
2. a kind of fluorine-containing industrial waste water with high ammoniac nitrogen circulation process method as described in claim 1, which is characterized in that step (2)
In magnesium salts be that thermal power plant's magnesium processes desulfurization wastewater or salt lake mention one of old brine (being not less than 15% containing magnesium) after potassium.
3. a kind of fluorine-containing industrial waste water with high ammoniac nitrogen circulating treating system, it is characterised in that: raw water conditioning tank (101), Ca salt device
(102), Mg salt device (103), effluent storage jar (104), mechanical accelerating purifying pool (105), clear water reserviors (106), soda ash dress
Set (107), box microwave reactor (108), ammonia recycling device (109) series connection.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109516631A (en) * | 2019-01-28 | 2019-03-26 | 湖南工业大学 | A kind of processing method of fluorine-containing ammonia nitrogen waste water |
| CN110282783A (en) * | 2019-07-23 | 2019-09-27 | 格丰科技材料有限公司 | A kind of processing system and processing method of phosphorus ammonium wastewater from chemical industry |
| CN110563198A (en) * | 2019-09-04 | 2019-12-13 | 广西长润环境工程有限公司 | Chemical fertilizer wastewater treatment method and treatment equipment |
| CN113087266A (en) * | 2021-04-30 | 2021-07-09 | 北京首钢国际工程技术有限公司 | Control method suitable for zero discharge of sintering pellet desulfurization and denitrification acid making wastewater |
| CN114149077A (en) * | 2021-11-27 | 2022-03-08 | 浙江沃乐环境科技有限公司 | Integrated wastewater synchronous denitrification and defluorination reactor device and use method thereof |
| CN114229985A (en) * | 2021-12-15 | 2022-03-25 | 湖南有色郴州氟化学有限公司 | Novel method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride |
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| CN105858995A (en) * | 2016-04-15 | 2016-08-17 | 燕山大学 | Method for removing ammonia through magnesium ammonium phosphate microwave radiation decomposition and cycling |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109516631A (en) * | 2019-01-28 | 2019-03-26 | 湖南工业大学 | A kind of processing method of fluorine-containing ammonia nitrogen waste water |
| CN110282783A (en) * | 2019-07-23 | 2019-09-27 | 格丰科技材料有限公司 | A kind of processing system and processing method of phosphorus ammonium wastewater from chemical industry |
| CN110282783B (en) * | 2019-07-23 | 2021-10-22 | 格丰科技材料有限公司 | Ammonium phosphate chemical wastewater treatment system and method |
| CN110563198A (en) * | 2019-09-04 | 2019-12-13 | 广西长润环境工程有限公司 | Chemical fertilizer wastewater treatment method and treatment equipment |
| CN110563198B (en) * | 2019-09-04 | 2022-04-01 | 广西长润环境工程有限公司 | Chemical fertilizer wastewater treatment method and treatment equipment |
| CN113087266A (en) * | 2021-04-30 | 2021-07-09 | 北京首钢国际工程技术有限公司 | Control method suitable for zero discharge of sintering pellet desulfurization and denitrification acid making wastewater |
| CN114149077A (en) * | 2021-11-27 | 2022-03-08 | 浙江沃乐环境科技有限公司 | Integrated wastewater synchronous denitrification and defluorination reactor device and use method thereof |
| CN114149077B (en) * | 2021-11-27 | 2023-02-14 | 浙江沃乐环境科技有限公司 | Integrated wastewater synchronous denitrification and defluorination reactor device and use method thereof |
| CN114229985A (en) * | 2021-12-15 | 2022-03-25 | 湖南有色郴州氟化学有限公司 | Novel method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride |
| CN114229985B (en) * | 2021-12-15 | 2023-09-19 | 湖南有色郴州氟化学有限公司 | Method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride |
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Address after: 100039 6th floor, building 1, yard 16, West Fourth Ring Middle Road, Haidian District, Beijing Applicant after: Guoneng Lang Xinming Environmental Protection Technology Co.,Ltd. Address before: 100039 6th floor, building 1, yard 16, West Fourth Ring Middle Road, Haidian District, Beijing Applicant before: BEIJING LUCENCY ENVIRO-TECH Co.,Ltd. |
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