CN105858995A - Method for removing ammonia through magnesium ammonium phosphate microwave radiation decomposition and cycling - Google Patents
Method for removing ammonia through magnesium ammonium phosphate microwave radiation decomposition and cycling Download PDFInfo
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- CN105858995A CN105858995A CN201610238023.5A CN201610238023A CN105858995A CN 105858995 A CN105858995 A CN 105858995A CN 201610238023 A CN201610238023 A CN 201610238023A CN 105858995 A CN105858995 A CN 105858995A
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- ammonium phosphate
- magnesium ammonium
- ammonia
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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
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5254—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using magnesium compounds and phosphoric acid for removing ammonia
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for removing ammonia through magnesium ammonium phosphate microwave radiation decomposition and cycling. The method comprises the main steps that ammonia-nitrogen wastewater is added into a magnesium ammonium phosphate settling pond, a decomposition product with active magnesium and phosphorus produced through decomposition of a magnesium ammonium phosphate microwave decomposition reactor is added into the settling pond, stirring reaction is performed for 50-100 min, the solution stands for 60-120 min, liquid supernatant is drained out of a water outlet of the settling pond, and the magnesium ammonium phosphate solid-liquid mixture settled at the bottom of the settling pond is transferred to the magnesium ammonium phosphate microwave decomposition reactor through a pump for decomposition; after the magnesium ammonium phosphate solid-liquid mixture is completely transferred into the decomposition reactor, sodium hydroxide is added, then, a microwave radiator is started for radiation decomposition, ammonia gas produced through radiation decomposition is recycled through a follow-up ammonia absorption system, and a magnesium ammonium phosphate decomposition product produced through decomposition is added into the magnesium ammonium phosphate settling pond to be cycled. The method is easy to operate, low in treating cost, capable of efficiently removing ammonia nitrogen in water and high in economic and environmental benefit.
Description
Technical field
The invention belongs to environmental technology field, particularly to the preprocess method of a kind of ammonia nitrogen waste water.
Background technology
At present, the major issue that China's Water ecoenvironment faces is that ammonia nitrogen discharge capacity is far super by Na Shui
The environmental carrying capacity of body, ammonia nitrogen has become more than COD affects the primary pollutant of China's surface water environment quality.
Showing according to China Environmental State Bulletin in 2014, whole nation ammonia nitrogen in waste water discharge capacity reaches 238.5 ten thousand tons, is equivalent to be subject to
Receive nearly 8 times of water body environment capacity.Ammonia nitrogen (NH3And NH4 +) it is to water ecological environment in all kinds of nitrogen-containing compound
Impact and the maximum a kind of existing forms of harm, compared with the nitrogen of other forms, it is to the harm of water body more
Extensively, complicated and lasting.And in following a very long time, China will be in urbanization and industrialization is " double
Quickly " developmental stage, pollutant emission incremental pressure is huge, needs raising ammonia nitrogenous wastewater treatment technology level badly.
The ammonia nitrogen processing method of current industrial application mainly has bioanalysis and the big class of chemical method two.Bioanalysis goes
Except ammonia nitrogen is effective, expense is low, but this technology is by factors shadows such as ammonia nitrogen in waste water concentration, water temperature and carbon sources
Ringing, the waste water being generally used for the little 500mg/L of ammonia nitrogen concentration processes, and needs rational C/N ratio in processing procedure.Change
Method mainly has ammonia still process method, breakpoint chlorination and magnesium ammonium phosphate sediment etc. except ammonia.Ammonia still process method is generally used for high concentration
The process of ammonia nitrogen waste water, although its deamination is respond well, but there have that equipment investment is big, waste water processes energy consumption to be high
And the problems such as fluctuation of service；Breakpoint chlorination is generally used for Low Concentration Ammonia Containing Wastewater process or drinking water disappears
Poison, owing to the easy generation in application process of this technology has the chlorine-containing organic compounds of carcinogenesis,
The less industrial treatment for waste water.Magnesium ammonium phosphate sediment is to enjoy Chinese scholars extensive concern in recent years
A kind of waste water high-efficiency ammonia-removal method.This technology, compared with bioanalysis, ammonia still process method and breakpoint chlorination, does not exists
Disadvantages mentioned above, and possess simple to operate, be swift in response and the plurality of advantages such as product precipitate and separate performance is good, be
A kind of waste water ammonia-removal technology having applications well prospect.
Ammoniomagnesium phosphate, (MgNH4PO4·6H2O, Magnesium Ammonium Phosphate, MAP), be
A kind of indissoluble white crystal mineral.Research shows at optimum pH scope (9-10.7), as Mg in aqueous solution2+、
NH4 +And PO4 3–When hybrid ionic concentration exceedes its dissolubility limit value, ammoniomagnesium phosphate can be sent out according to following reaction equation
Raw crystallization, thus reach to remove the purpose of ammonia nitrogen in waste water.
Mg2++NH4 ++HPO4 3–+6H2O→MgNH4PO4·6H2O↓+H+ (1)
Existing research report the most extensively confirms that applying the MAP sedimentation method to process all kinds of ammonia nitrogen waste waters is completely may be used technically
Row, ammonia nitrogen removal frank is up to more than 90%.But regrettably, due to past in many ammonia nitrogen waste waters
Toward lacking the Mg being available for precipitation2+And PO4 3–, need to add a large amount of phosphorus and magnesium in magnesium ammonium phosphate sediment processing procedure
Salt so that cost for wastewater treatment is high, less economical, seriously constrains the method in Ammonia Wastewater Treatment field
Popularization and application.The current MAP of solution precipitation is to use cheap magnesium source and phosphorus except the main path of ammonia high cost
Acid ammonium magnesium recycles.But, regrettably use cheap magnesium source to reduce magnesium ammonium phosphate sediment processing cost
Amplitude is extremely limited, and ammoniomagnesium phosphate to recycle be to reduce the conventional of magnesium ammonium phosphate sediment cost at present and have
The approach of effect.But existing realize NaOH pyrolysis and two kinds of sides of high-temperature direct thermal solution that ammoniomagnesium phosphate recycles
Formula easily produces by-product Mg2P2O7, there is also simultaneously decomposition the most long (generally need time-consuming 3 hours with
On), seriously hinder the industrial applications of ammoniomagnesium phosphate recycle utilization.
Summary of the invention
In place of the invention aims to solve above-mentioned the deficiencies in the prior art, it is provided that a kind of phosphoric acid
Ammonium magnesium microwave radiation Decomposition Cycle ammonia-removal method.The present invention not only can reach and avoids ammoniomagnesium phosphate decomposing
Journey produces by-product Mg2P2O7Purpose, ammoniomagnesium phosphate catabolic process can be accelerated again simultaneously, reduce and decompose
Time consumption.
Technical scheme is as follows:
A, first ammonia nitrogen waste water is joined in magnesium ammonium phosphate sediment pond, be subsequently adding and divided by ammoniomagnesium phosphate microwave
Solve reactor decompose produce containing activated carbon and the catabolite of phosphorus, control waste water in magnesium ammonium phosphate sediment pond
Mg:N:P mol ratio, at 1.5～1:1:1.1～0.9 scope, subsequent start-up agitator, regulates magnesium ammonium phosphate sediment pond
Middle wastewater pH is to 8.5～9, and stirring reaction 50～100min, after question response terminates, reaction solution stands 60～120
Min, in magnesium ammonium phosphate sediment pond, supernatant discharges from magnesium ammonium phosphate sediment pond outlet, magnesium ammonium phosphate sediment pond
The ammoniomagnesium phosphate solidliquid mixture of bottom precipitation is transferred to ammoniomagnesium phosphate microwave decomposition reactor by pump to be carried out point
Solve；
B, after ammoniomagnesium phosphate solidliquid mixture is transferred in ammoniomagnesium phosphate microwave decomposition reactor completely, press
OH–:NH4 +Mol ratio is the ratio addition sodium hydroxide of 1.3～1:1, then starts microwave radiometer, radiation
Stopping radiation after reacting 200～900 seconds, the ammonia that radiolysis produces reclaims through follow-up ammonia absorption system, point
Solve the ammoniomagnesium phosphate catabolite produced and then join recycling in magnesium ammonium phosphate sediment pond.
The know-why of the present invention
1) magnesium ammonium phosphate sediment pond: in this reaction tank, ammoniomagnesium phosphate catabolite (the most phosphorous and magnesium
Compound) with waste water in ammonia nitrogen can react rapidly generation magnesium ammonium phosphate sediment, when magnesium ammonium phosphate sediment mix
Bottom thing sedimentation sedimentation tank, then can be transferred in ammoniomagnesium phosphate decomposition reactor by pump.
2) ammoniomagnesium phosphate decomposition reactor: the most unstable due to ammoniomagnesium phosphate in this process,
Ammonium radical ion can parse from ammoniomagnesium phosphate solid, at heat effect and the work of non-thermal effect of microwave radiation
Under with, the ammonia discharged departs from reaction system rapidly and realizes the decomposition of ammoniomagnesium phosphate solid.
The present invention compared with prior art has the advantage that
1) stable through this technical finesse water outlet ammonia nitrogen concentration, ammonia nitrogen removal frank is up to 90-95%, water outlet residual phosphorus
Concentration can process as subsequent biochemical and supplement phosphorus in several milligrams per liter scopes, residual phosphorus, save subsequent biochemical and process
Cost.
2) in ammoniomagnesium phosphate, ammonia release rate is high, up to more than 95%；Catabolic process avoids by-product
Mg2P2O7Generation, the most relatively conventional ammoniomagnesium phosphate decomposition method, ammoniomagnesium phosphate microwave radiation of the present invention divides
Solution method can shorten the ammoniomagnesium phosphate resolving time greatly.
3) ammoniomagnesium phosphate microwave decomposition reactor steams the ammonia concentration height in gas, after sulfuric acid solution absorbs,
In absorbent solution, amounts of ammonium salt is up to about 20%, compares ammonia still process method and has higher recovery value.
4) consistent reliably except ammonia, simple to operate, engineering investment cost is low, and processing cost is low, can be used for
The pretreatment of all kinds ammonia nitrogen waste water.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the present invention.
Detailed description of the invention
Embodiment 1
According to the ammoniomagnesium phosphate microwave radiation Decomposition Cycle ammonia-removal method flow process shown in Fig. 1, first by 1m3
Ammonia nitrogen concentration is that the ammonia nitrogen waste water 5 of 1000mg/L joins magnesium ammonium phosphate sediment pond 2, is subsequently adding by phosphoric acid
Ammonium magnesium microwave decomposition reactor 1 decomposes the catabolite 3 containing activated carbon and phosphorus produced, and controls ammoniomagnesium phosphate and sinks
In pond, shallow lake, waste water Mg:N:P mol ratio is the ratio of 1.5:1:1.1, subsequent start-up agitator, regulates ammoniomagnesium phosphate
In sedimentation tank, wastewater pH is to 8.5, and after question response terminates, reaction solution stands 60min, magnesium ammonium phosphate sediment
In pond, supernatant discharges from sedimentation tank outlet 6, and through analyzing test, ammonia nitrogen removal frank reaches 95%, residual phosphorus
Concentration is 8mg/L；The ammoniomagnesium phosphate solidliquid mixture 7 of magnesium ammonium phosphate sediment pond bottom precipitation is shifted by pump
Decompose to ammoniomagnesium phosphate microwave decomposition reactor.Treat that ammoniomagnesium phosphate solidliquid mixture is transferred to phosphoric acid completely
After in ammonium magnesium microwave decomposition reactor, by OH–:NH4 +Mol ratio is that the ratio of 1.3:1 adds sodium hydroxide,
Then starting microwave radiometer, radioreaction stopped radiation after 200 seconds, through analyzing test, in ammoniomagnesium phosphate
Ammonia release rate is 95%, and the ammonia 4 that radiolysis produces reclaims through follow-up ammonia absorption system, decomposes generation
Ammoniomagnesium phosphate catabolite adds recycling in magnesium ammonium phosphate sediment pond.
Embodiment 2
First by 1m3Ammonia nitrogen concentration is that the ammonia nitrogen waste water of 1000mg/L joins magnesium ammonium phosphate sediment pond, so
Rear addition decomposed by ammoniomagnesium phosphate microwave decomposition reactor produce containing activated carbon and the catabolite of phosphorus, control
In magnesium ammonium phosphate sediment pond, waste water Mg:N:P mol ratio is the ratio of 1.5:1:1.1, subsequent start-up agitator, adjusts
In joint magnesium ammonium phosphate sediment pond 2, wastewater pH is to 9, stirring reaction 100min, after question response terminates, and reaction
Solution left standstill 120min, in magnesium ammonium phosphate sediment pond, supernatant discharges from sedimentation tank outlet, through analyzing test,
Ammonia nitrogen removal frank reaches 94%, and residual phosphorus concentration is 5mg/L；The ammonium phosphate of magnesium ammonium phosphate sediment pond bottom precipitation
Magnesium solidliquid mixture is transferred to ammoniomagnesium phosphate microwave decomposition reactor by pump and decomposes；Treat that ammoniomagnesium phosphate is solid
After liquid mixture is transferred in ammoniomagnesium phosphate microwave decomposition reactor completely, by OH–:NH4 +Mol ratio is at 1:1
Scope adds sodium hydroxide, then starts microwave radiometer, and radioreaction stopped radiation after 900 seconds, through dividing
Analysis test, in ammoniomagnesium phosphate, ammonia release rate is 98%, and the ammonia that radiolysis produces is through follow-up ammonia absorption system
Reclaim, decompose the ammoniomagnesium phosphate catabolite produced and add recycling in magnesium ammonium phosphate sediment pond.
Embodiment 3
First by 1m3Ammonia nitrogen concentration is that the ammonia nitrogen waste water of 1000mg/L joins magnesium ammonium phosphate sediment pond, so
Rear addition decomposed by ammoniomagnesium phosphate microwave decomposition reactor produce containing activated carbon and the catabolite of phosphorus, control
In magnesium ammonium phosphate sediment pond, waste water Mg:N:P mol ratio is 1:1:0.9, subsequent start-up agitator, regulates ammonium phosphate
In magnesium precipitate pond, wastewater pH is to 8.5, and stirring reaction 50min, after question response terminates, reaction solution stands 60
Min, in magnesium ammonium phosphate sediment pond, supernatant discharges from sedimentation tank outlet, through analyzing test, ammonia nitrogen removal frank
Reaching 90%, residual phosphorus concentration is 3mg/L；The ammoniomagnesium phosphate solid-liquid mixing of magnesium ammonium phosphate sediment pond bottom precipitation
Thing is transferred to ammoniomagnesium phosphate microwave decomposition reactor by pump and decomposes；Treat that ammoniomagnesium phosphate solidliquid mixture is complete
Total transfer is to after in ammoniomagnesium phosphate microwave decomposition reactor, by OH–:NH4 +Mol ratio is that the ratio of 1.3:1 adds
Entering sodium hydroxide, then start microwave radiometer, radioreaction stopped radiation after 200 seconds, through analyzing test,
In ammoniomagnesium phosphate, ammonia release rate is 99%, and the ammonia that radiolysis produces reclaims through follow-up ammonia absorption system, point
Solve the ammoniomagnesium phosphate catabolite produced and add recycling in magnesium ammonium phosphate sediment pond.
Embodiment 4
First by 1m3Ammonia nitrogen concentration is that the ammonia nitrogen waste water of 1000mg/L joins magnesium ammonium phosphate sediment pond, so
The magnesium ammonium phosphate sediment pond containing activated carbon and phosphorus produced is decomposed in rear addition by ammoniomagnesium phosphate microwave decomposition reactor
Middle wastewater pH is to 9, and stirring reaction 100min, after question response terminates, reaction solution stands 120min, phosphorus
In acid ammonium magnesium precipitate pond, supernatant discharges from sedimentation tank outlet, and through analyzing test, ammonia nitrogen removal frank reaches 91%,
Residual phosphorus concentration is 4mg/L；The ammoniomagnesium phosphate solidliquid mixture of magnesium ammonium phosphate sediment pond bottom precipitation passes through pump
It is transferred to ammoniomagnesium phosphate microwave decomposition reactor decompose；Treat that ammoniomagnesium phosphate solidliquid mixture is transferred to completely
After in ammoniomagnesium phosphate microwave decomposition reactor, by OH–:NH4 +Mol ratio adds sodium hydroxide in the ratio of 1:1,
Then starting microwave radiometer, radioreaction stopped radiation after 900 seconds, through analyzing test, in ammoniomagnesium phosphate
Ammonia release rate is 97%, and the ammonia that radiolysis produces reclaims through follow-up ammonia absorption system, decomposes the phosphorus produced
Acid ammonium magnesium catabolite adds recycling in magnesium ammonium phosphate sediment pond.
Embodiment 5
First by 1m3Ammonia nitrogen concentration is that the ammonia nitrogen waste water of 1500mg/L joins magnesium ammonium phosphate sediment pond, so
Rear addition by ammoniomagnesium phosphate microwave decomposition reactor 3 decompose generation containing activated carbon and the catabolite of phosphorus, control
In magnesium ammonium phosphate sediment pond processed, waste water Mg:N:P mol ratio is 1:1:1, subsequent start-up agitator, regulates phosphoric acid
In ammonium magnesium precipitate pond 2, wastewater pH is to 9, and stirring reaction 70min, after question response terminates, reaction solution stands
90min, in magnesium ammonium phosphate sediment pond, supernatant discharges from sedimentation tank outlet, through analyzing test, ammonia nitrogen removal
Rate reaches 92.5%, and residual phosphorus concentration is 4.5mg/L；The ammoniomagnesium phosphate solid-liquid of magnesium ammonium phosphate sediment pond bottom precipitation
Mixture is transferred to ammoniomagnesium phosphate microwave decomposition reactor by pump and decomposes；Treat that ammoniomagnesium phosphate solid-liquid mixes
After thing is transferred in ammoniomagnesium phosphate microwave decomposition reactor completely, by OH–:NH4 +Mol ratio is in the ratio of 1:1
Adding sodium hydroxide, then start microwave radiometer, radioreaction stops radiation after 750 seconds, surveys through analyzing
Examination, in ammoniomagnesium phosphate, ammonia release rate is 98%, and the ammonia that radiolysis produces reclaims through follow-up ammonia absorption system,
Decompose the ammoniomagnesium phosphate catabolite produced and add recycling in magnesium ammonium phosphate sediment pond.
Embodiment 6
First by 1m3Ammonia nitrogen concentration is that the ammonia nitrogen waste water of 1500mg/L joins magnesium ammonium phosphate sediment pond, so
Rear addition decomposed by ammoniomagnesium phosphate microwave decomposition reactor produce containing activated carbon and the catabolite of phosphorus, control
In magnesium ammonium phosphate sediment pond, waste water Mg:N:P mol ratio is 1:1:1, subsequent start-up agitator, regulates ammonium phosphate
In magnesium precipitate pond, wastewater pH is to 8.7, and stirring reaction 78min, after question response terminates, reaction solution stands 85
Min, in magnesium ammonium phosphate sediment pond, supernatant discharges from sedimentation tank outlet, through analyzing test, ammonia nitrogen removal frank
Reaching 90.6%, residual phosphorus concentration is 3.8mg/L；The ammoniomagnesium phosphate solid-liquid of magnesium ammonium phosphate sediment pond bottom precipitation mixes
Compound is transferred to ammoniomagnesium phosphate microwave decomposition reactor by pump and decomposes；Treat ammoniomagnesium phosphate solidliquid mixture
After being transferred to completely in ammoniomagnesium phosphate microwave decomposition reactor, by OH–:NH4 +Mol ratio is in the ratio of 1.2:1
Adding sodium hydroxide, then start microwave radiometer, radioreaction stops radiation after 550 seconds, surveys through analyzing
Examination, in ammoniomagnesium phosphate, ammonia release rate is 96.8%, and the ammonia that radiolysis produces reclaims through follow-up ammonia absorption system,
Decompose the ammoniomagnesium phosphate catabolite produced and add recycling in magnesium ammonium phosphate sediment pond.
Claims (1)
1. an ammoniomagnesium phosphate microwave radiation Decomposition Cycle ammonia-removal method, it is characterised in that it includes following
Step:
A, first ammonia nitrogen waste water is joined in magnesium ammonium phosphate sediment pond, be subsequently adding and divided by ammoniomagnesium phosphate microwave
Solve reactor decompose produce containing activated carbon and the catabolite of phosphorus, control waste water in magnesium ammonium phosphate sediment pond
Mg:N:P mol ratio is 1.5～1:1:1.1～0.9, subsequent start-up agitator, useless in regulation magnesium ammonium phosphate sediment pond
Water pH to 8.5～9, stirring reaction 50～100min, after question response terminates, reaction solution stands 60～120min,
In magnesium ammonium phosphate sediment pond, supernatant discharges from sedimentation tank outlet, the phosphorus of magnesium ammonium phosphate sediment pond bottom precipitation
Acid ammonium magnesium solidliquid mixture is transferred to ammoniomagnesium phosphate microwave decomposition reactor by pump and decomposes；
B, after ammoniomagnesium phosphate solidliquid mixture is transferred in ammoniomagnesium phosphate microwave decomposition reactor completely, press
OH–:NH4 +Mol ratio is the ratio addition sodium hydroxide of 1.3～1:1, then starts microwave radiometer, radiation
Stopping radiation after reacting 200～900 seconds, the ammonia that radiolysis produces reclaims through follow-up ammonia absorption system, point
Solve the ammoniomagnesium phosphate catabolite produced and then join recycling in magnesium ammonium phosphate sediment pond.
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Cited By (1)
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